200902793 九、發明說明： 【交互參考之相關申請案】 曰提出申請之申請序號 本申請案為於2〇〇3年12月u 1〇/733，Ul料之部份連續案。 【發明所屬之技術領域】 ^明係有關於—種半成品之染色方法，此半成品至 刀地被浸沒於1浴中，其包括：—種或多種染料、 水：至少-種載體(例如：乙二醇丁㈣、及一種二醇(例 如.^一乙二醉）。 10200902793 IX. Invention Description: [Reciprocal Reference Related Application] 申请 Application No. This application is part of the continuous case of U 1〇/733 in December, 2003. [Technical field to which the invention pertains] The invention relates to a method for dyeing a semi-finished product, which is immersed in a bath, comprising: - one or more dyes, water: at least one kind of carrier (for example: B Glycol butyl (tetra), and a diol (for example, .
【先前技術】 著色半成品可藉直接添加（例如：經由混料）顏料及/或 染料，製成產品之聚合材料中製備，此類直接添加的方法 導致著色射質上被分散遍佈於半成品。直接添加法對於 製備下列半成品並非特別適合：僅些微著色或帶色(例如： 少於不透明）者，例如：於㈣鏡片之案例。使用直接添加 法欲適當且充分分散製備些微著色或帶色的半成品所需求 之少量著色劑典型地不易達成。 雖然可使用染料與樹脂之母料，以使於混料及/或擠塑 輕序中可較佳地控制所添加的染料數量，但製備母料^要 額外的步驟。此外，母料之樹脂會被暴露於至少二個=循 環（一個於製備母料時，及另一個於製備已染色半成品 時），其可導致最終的半成品具有降級的物性。 藉施加一種染料組成物至半成品之表面以製備著色的 6 20 200902793 半成品為周知，此類染色方法較適合用於製備些微著色或 帶色的半成品，因為僅有少量及經控制之著色劑數量被加 入其表面中，染料組成物可為水性或非水性。 鑑於使用有機溶劑之環境顧慮，近期日益增加地強調 5 發展使用水性染料組成物之染色方法。使用水性染料組成 物之半成品染色方法，典型地遭受包括下者之缺點，例如： 不均勻及/或不適當的染色、及相同半成品之不同批次間不 一致程度的染色。 意欲發展新的半成品染色方法，其使用水性染料組成 10 物，並導致生成均勻地與充分地染色的產品。此外，亦意 欲此類新方法可提供經歷時間後一致程度的染色。 【發明内容】 發明概述 本發明係揭示一種半成品之染色方法，此方法包括： is (a)提供一種半成品，選自群組包括：粉末、粒料、及線 料，其包含至少一種熱塑性聚合物； (b)將該半成品浸沒於一染浴中，其包括： (i) 至少一種染料， (ii) 水， 20 (iii)至少一種以下列通式I代表之載體， (I) Rl[0(CR2)n]m0R2 其中R1與R2各自獨立地代表：氫、烷基、 苄基、苯曱酶基、或苯基基團，其芳族環可被烷 7 200902793 基及/或鹵素取代，η為2或3,及m為1至35, 及 (iv) —種二醇，選自至少一種線性或分支的C2-C20-脂肪族二醇、聚(C2-C4伸烷基二醇）、於環中具有 5 5至8個碳原子之環脂肪族二醇、單環芳族二醇， 雙酚、及經氫化雙酚； (c) 將該半成品保留於該浴中一段足以生成已染色半成品 .之時間；及 (d) 將該已染色半成品自該浴取出。 10 發明詳述 於本發明方法中所使用之染浴包括至少一種依式I之 載體，如本文先前所述者。式I中之R可為線性或分支的 烷基，其可選自包括，但非限於曱基、乙基、丙基、丁基、 15 戊基、己基、庚基、辛基、壬基、癸基、十一烧基、十二 烧基、十三炫基、十四烧基、十五烧基、十六烧基、十七 烷基、與十八烷基、及其結構異構物（例如：異-丙基、異-丁基、三級丁基等）。 再予參照式I，R亦可選自：苄基、苯甲醯基、與苯基 20 基團，其可各自獨立地及選擇地被1至5個基團所取代， 選自：鹵素基團（例如：氯、溴、與氟）、線性或分支的CrC9-燒基基團（例如：曱基、乙基、丙基、丁基、戊基、己基、 庚基、辛基、與壬基）、及芳族基團（例如：苯基）。 8 200902793 於本發明之一實例中，關於式I，η為2及R為選自： 正丁基、異丁基、及三級丁基。於本發明之一特佳實例中， η為2及R為正丁基。 載體於染浴中之存在量典型地為少於或等於30重量 5 %，以少於或等於25重量％為較佳，並以少於或等於20 重量％為更佳。載體於染浴中之存在量亦典型地為至少10 重量％，以至少15重量％為較佳，並以至少17重量％為更 佳。載體於浴中之存在量範圍可為介於這些較高與較低值 之任意組合之間，這些數值為包含於其内。例如：載體於 ίο 染浴中之存在量典型地自10至30重量％，更典型地自15 至25重量％，及益加典型地於一數量自17至20重量％， 於各案例中重量百分率係以染浴之總重為基準。 染浴亦另外包括一種二醇，選自至少一種線性或分支 的C2-C20-脂肪族二醇、聚(C2-C4伸烷基二醇）、於環中具有 15 5至8個碳原子之環脂肪族二醇、單環芳族二醇，雙酚、 及經氫化雙酚。線性或分支的C2-C2(r脂肪族二醇之實例包 括，但非限於乙二醇、丙二醇、1,3-丙二醇、1,2-與2,3-丁 二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇、癸二 醇、Η^ —院二醇、十二烧二醇、十三院二醇、十四炫二醇、 20 十五炫二醇、十六烧二醇、十七燒二醇、十八貌二醇、十 九烷二醇、及二十烷二醇。 二醇(iv)可選自聚(C2-C4)伸烷基二醇之實例包括，但非 限於二-、二-、四·、五-、及較尚的乙二醇、二-、三-、四-、 五-、及較高的丙二醇、與二-、三-、四-、五-、及較高的 9 200902793 丁二醇。具有自5至8個碳原子之環脂肪族二醇，其可用 作二醇(iv)者包括，但非限於環戊二醇、環己二醇、環庚二 醇、及裱辛二醇。可用作二醇(iv)之單環芳族二醇實例包 ^ ’但非限於苯二醇，例如：1,2-二羥基苯、及1,3·二經基 苯’ crC4烧基取代之苯二醇，例如：4_三級丁基-苯ί 二醇、4-曱基-苯-l，2-二醇、3_三級丁基_5_曱基―苯十]—二 醇、及3,4,5,6-四曱基-苯-1，2_二醇、經鹵素取代之苯二醇， 例如.3,5-二氯苯-1，2-二醇、3,4,5,6-四溴-苯-ΐ，2-二醇、及 3,4,5-三氯-苯_ι，2_二醇、及CrC：4烷基與經鹵素取代之苯二 醇，例如：3-溴-5-三級丁基-苯二醇、3,6_二氯曱基 -笨-1，2-二醇、3_溴-4,5-二甲基-苯-L2-二醇、及 3_氯_4,6_: -三級丁基-苯-1，2-二醇。 可用作一醇(iv)之雙紛與氫化雙紛可藉下列通式Η予 以代表，[Prior Art] The colored semi-finished product can be prepared by directly adding (e.g., by mixing) a pigment and/or a dye to a polymeric material of the product, and such a direct addition method causes the colored radiant to be dispersed throughout the semi-finished product. The direct addition method is not particularly suitable for the preparation of the following semi-finished products: only slightly colored or colored (for example: less than opaque), for example: in the case of (iv) lenses. The use of direct addition methods to properly and adequately disperse the small amount of colorant required to prepare micro-colored or colored semi-finished products is typically not readily achieved. While masterbatches of dyes and resins can be used to better control the amount of dye added in the compounding and/or extrusion process, the preparation of the masterbatch requires an additional step. In addition, the resin of the masterbatch will be exposed to at least two = cycle (one when preparing the masterbatch and the other when preparing the dyed semifinished product), which can result in degraded physical properties of the final semifinished product. It is well known to apply a dye composition to the surface of a semi-finished product to prepare a pigmented 6 20 200902793 semi-finished product. Such a dyeing method is more suitable for the preparation of micro-colored or colored semi-finished products because only a small amount of controlled coloring agent is The dye composition may be aqueous or non-aqueous, added to its surface. In view of the environmental concerns of using organic solvents, there has recently been an increasing emphasis on the development of dyeing methods using aqueous dye compositions. Semi-finished dyeing processes using aqueous dye compositions typically suffer from disadvantages including, for example, uneven and/or improper dyeing, and inconsistencies in dyeing of different batches of the same semi-finished product. It is intended to develop a new semi-finished dyeing process which uses an aqueous dye to make up 10 and results in a product that is uniformly and sufficiently dyed. In addition, it is intended that such new methods provide a consistent degree of staining after a period of time. SUMMARY OF THE INVENTION The present invention discloses a method of dyeing a semi-finished product, the method comprising: is (a) providing a semi-finished product selected from the group consisting of: a powder, a pellet, and a strand comprising at least one thermoplastic polymer (b) immersing the semi-finished product in a dye bath comprising: (i) at least one dye, (ii) water, 20 (iii) at least one carrier represented by the following formula I, (I) Rl [0 (CR2)n]m0R2 wherein R1 and R2 each independently represent a hydrogen, an alkyl group, a benzyl group, a benzoinyl group, or a phenyl group, the aromatic ring of which may be substituted by alkane 7 200902793 and/or halogen, η is 2 or 3, and m is 1 to 35, and (iv) a diol selected from at least one linear or branched C2-C20-aliphatic diol, poly(C2-C4 alkylene glycol) a cycloaliphatic diol having 5 to 8 carbon atoms in the ring, a monocyclic aromatic diol, a bisphenol, and a hydrogenated bisphenol; (c) retaining the semi-finished product in the bath for a sufficient amount The time at which the semifinished product is dyed; and (d) the dyed semifinished product is taken out of the bath. 10 DETAILED DESCRIPTION OF THE INVENTION The dyebath used in the method of the invention comprises at least one carrier according to formula I, as previously described herein. R in formula I may be a linear or branched alkyl group which may be selected from, but not limited to, anthracenyl, ethyl, propyl, butyl, 15 pentyl, hexyl, heptyl, octyl, decyl, Sulfhydryl, eleven alkyl, dodecyl, thirteen, tetradecyl, fifteen, hexadecane, heptadecyl, octadecyl, and structural isomers thereof (eg, iso-propyl, iso-butyl, tert-butyl, etc.). Referring again to Formula I, R may also be selected from the group consisting of: benzyl, benzhydryl, and phenyl 20 groups, which may each be independently and selectively substituted with from 1 to 5 groups, selected from: halo a group (eg, chlorine, bromine, and fluorine), a linear or branched CrC9-alkyl group (eg, fluorenyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and hydrazine) a group), and an aromatic group (for example: phenyl). 8 200902793 In an example of the invention, with respect to formula I, η is 2 and R is selected from the group consisting of: n-butyl, isobutyl, and tertiary butyl. In a particularly preferred embodiment of the invention, η is 2 and R is n-butyl. The carrier is typically present in the dyebath in an amount of less than or equal to 30% by weight, preferably less than or equal to 25% by weight, and more preferably less than or equal to 20% by weight. The carrier is also typically present in the dyebath in an amount of at least 10% by weight, preferably at least 15% by weight, and more preferably at least 17% by weight. The carrier may be present in the bath in an amount ranging between any combination of these higher and lower values, and such values are included therein. For example, the carrier is typically present in the ίο dyebath in an amount from 10 to 30% by weight, more typically from 15 to 25% by weight, and is typically added in an amount from 17 to 20% by weight, in each case weight The percentage is based on the total weight of the dyebath. The dyebath also additionally comprises a diol selected from at least one linear or branched C2-C20-aliphatic diol, poly(C2-C4 alkylene glycol) having 15 to 8 carbon atoms in the ring. A cycloaliphatic diol, a monocyclic aromatic diol, a bisphenol, and a hydrogenated bisphenol. Linear or branched C2-C2 (Examples of r aliphatic diols include, but are not limited to, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2- and 2,3-butanediol, pentanediol, Glycol, heptanediol, octanediol, decanediol, decanediol, hydrazine, diol, dodecadiol, thirteenth diol, tetradecane diol, hexadecanol , hexadecyl diol, heptadecane diol, octadecyl diol, pentadecane diol, and eicosyl diol. The diol (iv) may be selected from the group consisting of poly(C2-C4)alkylene Examples of alcohols include, but are not limited to, di-, di-, tetra-, five-, and more preferred ethylene glycol, di-, tri-, tetra-, penta-, and higher propylene glycol, and di-, Tri-, tetra-, five-, and higher 9 200902793 butanediol. A cycloaliphatic diol having from 5 to 8 carbon atoms, which may be used as a diol (iv), but not limited to a ring Pentandiol, cyclohexanediol, cycloheptanediol, and octylene glycol. Examples of monocyclic aromatic diols useful as diol (iv) include, but are not limited to, benzenediols, for example: 2-Dihydroxybenzene, and 1,3·di-diphenylbenzene 'crc4-substituted phenylene glycol, for example: 4_tertiary butyl-benzoate Glycol, 4-mercapto-benzene-l,2-diol, 3-3-tert-butyl-5-nonyl-benzene-10-diol, and 3,4,5,6-tetradecyl-benzene -1,2-diol, halogen-substituted benzenediol, such as .3,5-dichlorobenzene-1,2-diol, 3,4,5,6-tetrabromo-benzene-indole, 2- a diol, and 3,4,5-trichloro-benzene-, 2,diol, and a CrC:4 alkyl group and a halogen-substituted benzenediol, for example, 3-bromo-5-tertiary butyl- Benzene glycol, 3,6-dichloroindolyl-stup-1,2-diol, 3-bromine-4,5-dimethyl-benzene-L2-diol, and 3-chloro-4,6_: - Tert-butyl-benzene-1,2-diol. Both can be used as a monol (iv) and hydrogenation can be represented by the following formula:
通式IIFormula II
於式II中：R〗與R2各自獨立地，及對Ρ與q亦各自獨立 地選自：CrQ-烧基(例如：曱基、乙基、正丙基、異丙基、 正丁基、二級丁基、及三級丁基）、氯、及溴；p/與:各 自獨立地為一自0至4之整數；及_X_為二價連結基團，選 10 200902793 自：-Ο-、-S-、S(02)-、-C(O)-、-CH2-、-CH=CH-、-C(CH3)2-、 與-C(CH3)(C6H5)-;及In Formula II: R and R2 are each independently, and the pair of oximes and q are each independently selected from the group consisting of: CrQ-alkyl (eg, decyl, ethyl, n-propyl, isopropyl, n-butyl, Secondary butyl, and tertiary butyl), chlorine, and bromine; p/ and: each independently an integer from 0 to 4; and _X_ is a divalent linking group, selected 10 200902793 From:- Ο-, -S-, S(02)-, -C(O)-, -CH2-, -CH=CH-, -C(CH3)2-, and -C(CH3)(C6H5)-;
G 5 代表一苯環或環己烷環。可用作二醇(iv)之雙酚，其一實例 為4,4’-異亞丙基雙酚（亦即：雙酚A)，可用作二醇(iv)之氫 '化雙酚，其一實例為4,4’-異亞丙基二環己醇。 於本發明之一較佳實例中，二醇(iv)為一種聚(C2-C4伸 ίο 烧基二醇），選自：二乙二醇、三乙二醇、四乙二醇、五乙 二醇、及其混合物，特佳的二醇為乙二醇與二乙二醇。 二醇於染浴中之存在量典型地為少於或等於20重量 %，以少於或等於15重量％為較佳，並以少於或等於12 重量％為更佳。二醇於染浴中之存在量亦典型地為至少1 15 重量％，以至少5重量％為較佳，並以至少10重量％為更 佳。二醇於浴中之存在量範圍可為介於這些較高與較低值 之任意組合之間，這些數值為包含於其内。例如：二醇於 染浴中之存在量典型地自1至20重量％，以自5至15重 量％為更佳，更典型地於一數量自10至12重量％，於各案 20 例中重量百分率係以染浴之總重為基準。 存在於染浴中之染料可選自：靜態染料、光色染料、 及其組合物。於此及於申請專利範圍中所使用之詞“靜態染 料”意指··當暴露於（或被保護自）紫外光(UV)時，不會大幅 11 200902793 地改變顏色之染料。於此及於申請專利範圍中所使用之詞 “光色染料”意指：當暴露於紫外光時，會反轉地改變顏色 之染料，為此藝具通常知識者為習知。典型地，當暴露於 特別波長的紫外光時，光色染料會轉變至一種開啟或活化 5 的形態，其具有顏色（於可見光譜之一特殊部份内）.。當移 開紫外線光源時，此開啟/活化的光色染料回到一種關閉或 未活化的形態，則其為無色，或至少為比活化形態較淺的 顏色。 可包括於染浴中的靜態染料，包括例如：織物染料、 10 及分散染料、以及於此技藝中習知適合用於半成品，如： 熱塑性聚碳酸酯物件，之調色者。適合的分散染料之實例 . 包括，但非限於分散藍色3號、分散藍色14號、分散黃色 3號、分散紅色13號、分散紅色17號。於此所述靜態染 料之分類與命名係依照“色料索引”，第3版，由染料與色 15 料協會及美國紡織品化學家與著色家公會共同出版（1971 年），將其内容併入本文供參考。通常染料可被用作單一的 染料成份或為染料混合物之一組份，視所欲之顏色而定， 故於此所用之靜態染料一詞包括靜態染料之混合物。 靜態染料類習知為直接染料，可用於施行本發明，直 2〇 接染料之實例包括，但非限於溶劑藍色35號、溶劑綠色3 號、及啶橙色基底，然而已被觀察到：直接染料典型地不 會將半成品著色（調色/染色）至如分散染料般強烈（其先前 敘述於本文中）。 其他適合的靜態染料包括例如：非水溶性的偶氮、二 12 200902793 苯胺、及蒽醌化合物，特別適合的實例包括：醋酸染料、 分散性醋酸染料、分散染料、及散佈染料，如揭示於：色 料索引，第3版，第2冊，染色家與著色家公會，1971年， 分別於第2479頁及第2187至2743頁，將其内容皆併入本 5 文供參考。較佳的分散染料包括Dystar’s Palanil Blue E-R150(蒽醌/分散藍色）與DIANIX Orange E-3RN(偶氮染 料/色料索引分散橙色25)。已觀察到：於本方法中，當半 成品為熱塑性聚碳酸酯時，苯酚紅色與4-苯基偶氮苯酚無 法提供所欲之染色程度。 ίο 於施行本發明當半成品包含熱塑性聚碳酸酯時，習知 為直接染料之靜態染料及那些被稱為酸性染料者，被觀察 . 到提供一少於所欲程度之調色，然而酸性染料被觀察到對 於尼龍為有效。 可用於本發明方法之另一類適合的靜態染料包括非遷 15 移靜態染料（亦即：靜態染料，其已被化學地修飾，藉以最 小化或排除其由已被加入其中之半成品移出）。一種特殊類 別的非遷移靜態染料可藉下列式III予以代表：G 5 represents a benzene ring or a cyclohexane ring. It can be used as a bisphenol of diol (iv), an example of which is 4,4'-isopropylidene bisphenol (ie, bisphenol A), which can be used as a hydrogen diol of diol (iv) An example of this is 4,4'-isopropylidene dicyclohexanol. In a preferred embodiment of the present invention, the diol (iv) is a poly(C2-C4 stretching diol) selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, and five ethylene. The diols and mixtures thereof, particularly preferred glycols are ethylene glycol and diethylene glycol. The diol is typically present in the dyebath in an amount of less than or equal to 20% by weight, preferably less than or equal to 15% by weight, and more preferably less than or equal to 12% by weight. The diol is typically present in the dyebath in an amount of at least 1 15% by weight, preferably at least 5% by weight, and more preferably at least 10% by weight. The diol may be present in the bath in an amount ranging between any combination of these higher and lower values, and such values are included therein. For example, the amount of diol present in the dyebath is typically from 1 to 20% by weight, more preferably from 5 to 15% by weight, more typically from 10 to 12% by weight, in each case, 20 cases. The weight percentage is based on the total weight of the dyebath. The dye present in the dyebath may be selected from the group consisting of: static dyes, photochromic dyes, and combinations thereof. As used herein and in the scope of the patent application, the term "static dye" means that when exposed to (or protected from) ultraviolet light (UV), the dye of the color is not significantly changed. The term "photochromic dye" as used herein and in the scope of the patent application means that the dye which changes color reversibly when exposed to ultraviolet light is conventionally known to those skilled in the art. Typically, when exposed to ultraviolet light of a particular wavelength, the photochromic dye will transition to an open or activated 5 form having a color (within a particular portion of the visible spectrum). When the ultraviolet light source is removed, the open/activated photochromic dye returns to a closed or unactivated form, which is colorless, or at least a lighter color than the activated form. Static dyes which may be included in the dye bath include, for example, fabric dyes, 10 and disperse dyes, as well as those conventionally used in the art for semi-finished products such as thermoplastic polycarbonate articles. Examples of suitable disperse dyes include, but are not limited to, Disperse Blue No. 3, Disperse Blue No. 14, Disperse Yellow No. 3, Disperse Red No. 13, and Disperse Red No. 17. The classification and naming of the static dyes described herein is based on the “Colorant Index”, 3rd edition, published by the Dyes and Colors Association and the American Textile Chemist and the Coloring Association (1971). This article is for reference. Generally, the dye can be used as a single dye component or as a component of a dye mixture, depending on the desired color, so the term static dye used herein includes a mixture of static dyes. Static dyes are known as direct dyes and can be used in the practice of the present invention. Examples of straight dyes include, but are not limited to, Solvent Blue No. 35, Solvent Green No. 3, and pyridine orange substrates, however, it has been observed that: The dye typically does not color (color/dye) the semi-finished product as strongly as the disperse dye (which was previously described herein). Other suitable static dyes include, for example, water-insoluble azo, bis 12 200902793 aniline, and hydrazine compounds, and particularly suitable examples include: acetic acid dyes, disperse acetic acid dyes, disperse dyes, and disperse dyes, as disclosed in: Colorant Index, 3rd Edition, Volume 2, Dyeing and Coloring Association, 1971, respectively, on page 2479 and pages 2187 to 2743, the contents of which are incorporated herein by reference. Preferred disperse dyes include Dystar's Palanil Blue E-R150 (蒽醌/Disperse Blue) and DIANIX Orange E-3RN (Azo Dye/Color Index Disperse Orange 25). It has been observed that in the present process, when the semifinished product is a thermoplastic polycarbonate, phenol red and 4-phenylazophenol do not provide the desired degree of dyeing. Ίο In the practice of the present invention, when the semi-finished product comprises a thermoplastic polycarbonate, those known as direct dyes and those known as acid dyes are observed. To provide a lesser degree than desired, the acid dye is It was observed to be effective for nylon. Another class of suitable static dyes which can be used in the process of the invention include non-immobilized static dyes (i.e., static dyes which have been chemically modified to minimize or eliminate their removal from the semi-finished product to which they have been added). A special class of non-migratory static dyes can be represented by the following formula III:
III R5-(聚合的成份-Y)t 20 於式III中，R5代表一種有機的染料基團（或發色團基團）； 聚合的成份係針對每個⑴各自獨立地選自：聚(C2-C4伸烷 基氧化物）之均聚物、共聚物、及嵌段共聚物，例如：聚環 氧乙烷與聚環氧丙烷之均聚物、聚（環氧乙烷-環氧丙烷）共 13 200902793 聚物、及環氧乙烧與環氧丙烧之二-或較高嵌段的共聚物； ⑴可為一自1至6之整數；及(Y)針對每個⑴各自獨立地選 自：羥基、一級胺、二級胺、及硫醇基團。聚合的成份可 具有一分子量自例如：44至1500。（Y)可選自之染料基團 包括，但非限於亞确基、靖基、偶氮(例如：單偶氮、二偶 氮、及三偶氮）、二芳基甲烧、三芳基甲烧、氧雜蒽、吖啶、 甲川、噻唑、吲達胺、吖σ井、σ号畊、及蒽醌染料基團。以 式III代表之非遷移靜態染料被更詳細地敘述於美國專利 編號：4,284,729、4,640,690、及 4,812,141。 10 20 富依照本發明方法（例如：藉浸潰）經由吸收或擴散將 半成品染色時，已發現可使用非遷移靜態染料δ當經由吸 收加至半成品中時，過量的非遷移靜態染料可自半成品洗 除，僅有最小量的已吸收非遷移靜態染料被自半成品溶濾 出來。當依本發明方法將製自熱塑性聚胺基曱酸酯之半成 木色日年(例如.藉浸潰），發現非遷移靜態染料(例如： 式ΠΙ代表者)特別有用。 ^於本發明方法之光㈣料包括料此藝中 =者所習知者’適合的光色染料類別包括，但非限 (:口木嘛）萘十井、及螺（十朵琳）苯令井 心“ 專利伽觀中者）、及色稀，如：苯並終^於關 如·敘述於美國專利5,274，132中者）、及於二=南(例 亡：取代基之笨並吡喃、及-選擇地經取代的雜二，·位置 笨並噻嗯並或苯並呋喃並被稠合至苯並吡=如. (例如：敛述於美國專利5,429,774中者 5的部份 ”他頰別之光色 14 200902793 染料包括如：俘精_與俘精酸胺，> :3“夫喃基與3_嗟 嗯基俘精酸酐及俘精酸胺(例如：敛述於美國專利4,州，^ 中者）’將有關光色染料所引述翻之相關内人本文供 參考。 5 10 15 於本毛月方法中，光色染料或其混合物可單獨使用咬 與：種❹種靜態染料併合使用。典型地，吸收光色染料 至半成品中，例如：包含熱塑性聚碳酸酯之物件，導致— 種染色的半成品當其暴露於或被保護自紫外光時，不會 容易地改變顏色。雖然無意被任何理論所束縛，但基於手 邊的資訊，咸信：光色染料於熱塑性聚合物 陷入一種開啟或關_形態，然而較柔軟、較 合物’如：聚胺基曱酸酉旨，則為非常適合的母體，可供光 色染料於深色與淺色的狀態之間容易地轉換。 染料於染浴中之存在量可廣泛地變化，典型地染料於 染浴中存在-數量足轉致生成—㈣色的半成品，盆呈 有-種可被肉眼識別的顏色效應及/或—種光色效應^列 如：於光色染料之案例中為當暴露於紫外光時。 貝際士存在於染洛中之染料數量依染料於包括水、載 體、及二醇之混合物中的溶解度而定，染料於浴中之溶解 度，受染浴溫度的影響。於那些染料未完全地溶解於浴令 之貫例中，染浴被認為包含飽和量的轉，藉添加—數量 ，染料，其超過染料於財之飽和量(例如：加至—染 續，通過其_袋脑）’财染色操作_，染料於洛 之罝可被維持於齡量，染料㈣中之量(❹：飽和°量） 20 200902793 可藉如：熱失重分析或分光光度分析予以週期性地或連續 地測定。 典型地染料於染浴中之存在量為少於或等於15重量 %，更典型地為少於或等於5重量％，益加典型地為少於或 5 等於1重量％，最典型地為少於0.5重量％。染料於染浴中 之存在量亦典型地為至少0.001重量％，以至少0.005重量 %為較佳，並以至少0.01重量％為更佳。染料於浴中之存 在量範圍可為介於這些較高與較低值之任意組合之間，這 些數值為包含於其内。例如：染料於染浴中之存在量典型 ίο 地自0.001至15重量％，更典型地自0.005至5重量％，益 加典型地為於一數量自0.01至1重量％，最典型地為於一 數量自0.01至0.5重量％，於一實例中，染料於染浴中之 存在量為0.03重量％，於各案例中重量百分率係以染浴之 總重為基準。 15 於本發明之一較佳實例中，染浴包含：0.001至0.5重 量％之該染料、65至75重量％之水、15至25重量％之該 載體、及1至15重量％之該二醇，於各案例中重量百分率 係以染浴之總重為基準。 水於染浴中之存在量典型地為少於或等於85重量％， 2〇 以少於或等於80重量％為較佳，並以少於或等於75重量％ 為更佳。水於染浴中之存在量亦典型地為至少50或51重 量％，以至少60重量％為較佳，並以至少65重量％為更佳。 水於浴中.之存在量範圍可為介於這些較高與較低值之任意 組合之間，這些數值為包含於其内。例如：水於染浴中之 16 200902793 存在量典型地自50(或51)至85重量％，更典型地自60至 87重量％，及益加典型地為於一數量自65至75重量％， 於各案例中重量百分率係以染浴之總重為基準。 於本發明之一實例中，染浴另外包括一種界面活性劑 5 (或乳化劑），其相異於各載體及二醇。於本發明中之適合 界面活性劑，當其被倒入水中時可容易地分散，隨後於其 攪拌時生成一種乳狀的乳化物。界面活性劑可選自至少一 種陰離子界面活性劑、兩性界面活性劑、及一種非離子界 面活性劑，選自至少一種聚（c2-c4烷氧化的）c14-c18不飽和 ίο 脂肪酸、聚（c2-c4烷氧化的）苯酚、及聚（c2-c4烷氧化 的）C1-C9烧基取代之笨酉分。 可用於本發明之陰離子界面活性劑實例包括如：羧 酸、胺基磺酸、或磷酸之胺鹽或鹼鹽，例如：月桂基硫酸 鈉、月桂基硫酸銨、木質磺酸鹽、乙二胺四乙酸(EDTA)鈉 15 鹽、及胺類之酸鹽，如：月桂基胺氯化氫、或聚（氧基-1,2- 乙烷二基），α-磺基-Ω-羥基醚與苯酚1-(甲基苯基）乙基衍生 的敍鹽。 可存在於染浴之兩性界面活性劑包括如：月桂基磺甜 采驗、二輕基乙基燒基甜采驗、以挪子酸為基質之酸胺基 20 甜菜鹼、Ν-月桂基胺基丙酸二納、或二缓酸椰子衍生物之 鈉鹽。 聚（C2-C4纟完乳化的）Ci4_Ci8不飽和脂肪酸之貫例包 括：乙氧化、丙氧化、及/或丁氧化的十四碳烯基羧酸。聚 (c2-c4烷氧化的）苯酚之實例包括：乙氧化、丙氧化、及/ 17 200902793 或丁氧化的笨驗。聚(c2_c4燒氧化的)Ci_c9烧基取代之苯 紛包括：辛基苯氧基聚伸乙基氧基乙醇及聚(氧基]，2_乙烧 二基）’ CX-笨基_〇羥基，經笨乙烯化者。 視情況添加之界面活性劑（乳化劑）可被使用於一數 5 量，少於或等於5重量。/°，此視情況添加之界面活性劑於 染浴中之存在量以〇·5至5重量％為較佳，並以數量i至4 重1 /。為更佳，於各案例中重量百分率係以染浴之重量為 * 基準。 染浴可另外選擇地包括一種效能增強添加劑，選自至 10 少一種下者：紫外線穩定劑、光學增亮劑、脫模劑、抗靜 電劑、熱穩定劑、紅外線吸收劑、及抗微生物劑（物質或化 合物）。於染浴中包括一種或多種這些選擇地效能增強添加 劑’可改善染色半成品之物理效能/性能。除染料外，當選 擇地添加劑浸沒於染浴中時，亦可擴散、滲透、或者被吸 15 收至半成品之本體内，例如：於染浴中包括紫外線穩定劑 時，導致染色半成品具有改善的抗紫外線性能。脫模劑可 較有利地包括於染浴中，當半成品為選自熱塑性粒料、熱 塑性線料、或熱塑性粉末，隨後自其製備半成品者，本文 將進一步予以討論。選擇地效能增強添加劑可選自那些習 20 知用於製備熱塑性模塑物件者。 可用於依本發明染浴之UV(紫外線)穩定劑（或吸收劑） 種類包括，但非限於水楊酸UV吸收劑、二苯曱酮uv吸 收劑、苯並三唾UV吸收劑、氰基丙稀酸酯uv吸收劑 及其混合物。苯並***uv吸收劑之更明確的實例包括， 18 200902793 但非限於2-(2，-羥基_5，_甲基笨其 、III R5-(Polymerized component -Y) t 20 In Formula III, R5 represents an organic dye group (or chromophore group); the polymerized component is each independently selected from each of (1): poly( Homopolymers, copolymers, and block copolymers of C2-C4 alkylene oxides, for example, homopolymers of polyethylene oxide and polypropylene oxide, poly(ethylene oxide-propylene oxide) a total of 13 200902793 polymer, and a copolymer of ethylene bromide and propylene bromide - or higher block; (1) can be an integer from 1 to 6; and (Y) is independent for each (1) It is selected from the group consisting of hydroxyl groups, primary amines, secondary amines, and thiol groups. The polymerized component may have a molecular weight of, for example, from 44 to 1,500. (Y) Dyes selected from the group include, but are not limited to, arginyl, jing, azo (eg, monoazo, diazo, and trisazo), diarylmethyl, triaryl , xanthene, acridine, methine, thiazole, indamine, 吖σ well, σ cultivating, and anthraquinone dye groups. Non-migrating static dyes represented by Formula III are described in more detail in U.S. Patent Nos. 4,284,729, 4,640,690, and 4,812,141. 10 20 rich When dyeing a semi-finished product by absorption or diffusion according to the method of the invention (for example: by dipping), it has been found that a non-migrating static dye δ can be used when added to the semi-finished product via absorption, the excess non-migrating static dye can be self-semi-finished Washed out, only a minimal amount of absorbed non-migrating static dye was filtered from the semi-finished product. Non-migrating static dyes (e.g., representative of the formula) are found to be particularly useful when the method of the present invention is to be made from a semi-wood color of a thermoplastic polyamino phthalate (e.g., by dipping). ^ The light (four) material in the method of the present invention includes the material of the art. The suitable light color dye category includes, but is not limited to (: mouth wood) naphthalene ten well, and snail (ten lin) benzene The wells are "in the patent gaze", and the color is thin, such as: benzo and finally in the United States Patent 5,274,132), and in the second = South (in the case of death: the stupid base a pyran, and - a selectively substituted heterodimer, a position stupid and a thiol or a benzofuran fused to a benzopyr = such as (for example, a portion of 5 in US Patent 5,429,774) His cheeks are light color 14 200902793 Dyes include: Capsules _ with chlorinated amines, > : 3 "Famyl and 3 嗟 基 俘 精 精 及 及 及 及 ( ( ( ( ( U.S. Patent No. 4, the state of the United States, the entire disclosure of which is incorporated herein by reference. 5 10 15 In this method, the photochromic dye or a mixture thereof can be used alone: Mixing static dyes. Typically, absorbing photochromic dyes into semi-finished products, such as articles containing thermoplastic polycarbonate, resulting in dyeing The finished product does not change color easily when it is exposed to or protected from ultraviolet light. Although it is not intended to be bound by any theory, based on the information at hand, the letter: the color dye in the thermoplastic polymer falls into an open or close _ The form, however, is softer and more complex, such as polyamine phthalic acid, which is a very suitable precursor for light color dyes to be easily converted between dark and light colors. Dye in dye bath The amount of presence can vary widely, typically the dye is present in the dyebath - the amount of the semi-finished product that is produced by the amount of (four) color, the pot has a color effect that can be recognized by the naked eye and / or a light color effect ^ For example, in the case of photochromic dyes, when exposed to ultraviolet light, the amount of dye present in the dyeing dye depends on the solubility of the dye in a mixture including water, carrier, and glycol, and the dye is in the bath. The solubility in the dye bath is affected by the temperature of the dye bath. In those cases where the dye is not completely dissolved in the bath, the dye bath is considered to contain the amount of saturation, by adding - quantity, dye, which is more saturated than the dye (eg: add to - dyeing, through its _ bag brain) 'financial dyeing operation _, the dye can be maintained in the age, the amount of dye (four) (❹: saturation ° amount) 20 200902793 Thermogravimetric analysis or spectrophotometric analysis is determined periodically or continuously. Typically the dye is present in the dyebath in an amount of less than or equal to 15% by weight, more typically less than or equal to 5% by weight, Typically less than or 5 equals 1% by weight, most typically less than 0.5% by weight. The dye is typically present in the dyebath in an amount of at least 0.001% by weight, preferably at least 0.005% by weight, and preferably More preferably, at least 0.01% by weight. The dye may be present in the bath in an amount ranging between any combination of these higher and lower values, and such values are included therein. For example, the amount of dye present in the dyebath is typically from 0.001 to 15% by weight, more typically from 0.005 to 5% by weight, and is typically from 0.01 to 1% by weight, most typically from 0.01 to 1% by weight. A quantity is from 0.01 to 0.5% by weight. In one example, the dye is present in the dyebath in an amount of 0.03% by weight, and in each case the weight percentage is based on the total weight of the dyebath. In a preferred embodiment of the invention, the dyebath comprises: 0.001 to 0.5% by weight of the dye, 65 to 75% by weight of water, 15 to 25% by weight of the carrier, and 1 to 15% by weight of the two Alcohol, the weight percentage in each case is based on the total weight of the dyebath. The amount of water present in the dyebath is typically less than or equal to 85% by weight, 2 Torr is preferably less than or equal to 80% by weight, and more preferably less than or equal to 75% by weight. The amount of water present in the dyebath is also typically at least 50 or 51% by weight, preferably at least 60% by weight, and more preferably at least 65% by weight. The amount of water present in the bath may range between any combination of these higher and lower values, and these values are included therein. For example: water in the dye bath 16 200902793 is typically present in an amount from 50 (or 51) to 85% by weight, more typically from 60 to 87% by weight, and the benefit is typically in a quantity from 65 to 75% by weight. The weight percentage in each case is based on the total weight of the dyebath. In one embodiment of the invention, the dyebath additionally comprises a surfactant 5 (or emulsifier) which is different from the respective carriers and diols. A suitable surfactant in the present invention can be easily dispersed when it is poured into water, and then a milky emulsion is formed upon stirring. The surfactant may be selected from at least one anionic surfactant, an amphoteric surfactant, and a nonionic surfactant selected from at least one poly(c2-c4 alkoxylated) c14-c18 unsaturated ίο fatty acid, poly(c2). -c4 alkoxylated) phenol, and poly(c2-c4 alkoxylated) C1-C9 alkyl substituted abbreviated. Examples of the anionic surfactant which can be used in the present invention include, for example, a carboxylic acid, an aminosulfonic acid, or an amine or alkali salt of phosphoric acid, for example, sodium lauryl sulfate, ammonium lauryl sulfate, lignosulfonate, ethylenediamine. Tetraacetic acid (EDTA) sodium 15 salt, and amine acid salts, such as: laurylamine hydrogen chloride, or poly(oxy-1,2-ethanediyl), α-sulfo-Ω-hydroxy ether and phenol a 1-(methylphenyl)ethyl-derived salt. The amphoteric surfactants which may be present in the dye bath include, for example, a lauryl sulfonate test, a di-light ethyl ketone sweet test, an acid-based amino acid 20 betaine, and a guanidine-laurylamine. A sodium salt of di-nanopropionate or a di-acidic coconut derivative. Typical examples of poly(C2-C4 emulsified) Ci4_Ci8 unsaturated fatty acids include: ethoxylated, propoxylated, and/or butylated oxidized tetradecenylcarboxylic acids. Examples of poly(c2-c4 alkoxylated) phenols include: ethoxylation, propoxylation, and / 17 200902793 or butan oxidation. Poly(c2_c4 oxidized) Ci_c9 alkyl substituted benzene includes: octyl phenoxy polyethyl ethoxyethanol and poly(oxy), 2 ethanediyl) CX-stupyl hydrazine , stupidized by ethylene. The surfactant (emulsifier) to be added as the case may be used in an amount of 5 or less, or less than or equal to 5 parts by weight. /°, the surfactant to be added as the case may be present in the dyebath in an amount of from 5% to 5% by weight, and in an amount of from i to 4 by weight. For better, the weight percentage in each case is based on the weight of the dye bath. The dyebath may additionally comprise a performance enhancing additive selected from the group consisting of: less than one of: ultraviolet stabilizers, optical brighteners, mold release agents, antistatic agents, heat stabilizers, infrared absorbers, and antimicrobial agents. (substance or compound). The inclusion of one or more of these selectively potentiating additives in the dyebath can improve the physical performance/performance of the dyed semifinished product. In addition to the dye, when the selected additive is immersed in the dye bath, it may be diffused, infiltrated, or absorbed into the body of the semi-finished product, for example, when the ultraviolet stabilizer is included in the dye bath, the dyed semi-finished product is improved. UV resistance. The release agent may be advantageously included in the dyebath, and will be discussed further herein when the semifinished product is selected from the group consisting of thermoplastic pellets, thermoplastic strands, or thermoplastic powders, followed by the preparation of semi-finished products therefrom. The selective performance enhancing additive may be selected from those known for use in the preparation of thermoplastic molded articles. UV (ultraviolet) stabilizers (or absorbers) which can be used in the dye bath according to the invention include, but are not limited to, salicylic acid UV absorbers, benzophenone uv absorbers, benzotrisole UV absorbers, cyano groups Acrylate uv absorbers and mixtures thereof. More specific examples of benzotriazole uv absorbers include, 18 200902793 but are not limited to 2-(2,-hydroxy-5, _methyl stupid,
Tirmvin® P，得自汽巴公司，二唾（市售品 二-三級丁基_2’·經基苯基)各氯苯 ' 2_(3’，5’· @ 二級戊基苯基） 得自汽巴公司）、苯丙 327,得自汽巴公司）、2·(2，邊基市售品⑽種⑧ 本並二°坐（市售品Tinuvin 酸，3-(2H-苯並***_2_基）^…山二 ，一 分支的烷基酯（市售品Tinuvin® 3 土 土）_4羥基_，C7-9 2-(3,，5，-二（1-甲基+笨其乙幻2,、4 ’付自汽巴公司）、 隹口 T· . ®QnA本基土）-2 •殘基苯基）苯並***（市 10 15 = 得自汽巴公〜2__基_3_二甲基节 下者之混合物：聚(氧基-⑽完二 基苯並三唾_2_基）_5_(1山二曱基乙基)冰經基 本基]-1-乳基$基]-Ω-羥基與聚（氧基乙烷二 基），α-[3-[3-(2Η-笨並三嗤_2_基)_5_(1，κ二曱基乙基μ經基 苯基]-1-氧基丙基ΗΜΗΜΜ-笨並三哇_2基^似-二 曱基乙基Μ-經基苯基]小氧基㊉基]_(市 1130 ’得自汽巴公司）、與2_[4_[2，基_3_十三烧基氧基丙 基]氧基]-2-羥基苯基]-4,6-二（2,4-二甲基苯基^二^三 4、與2_[4_[2_經基_3_十二烧基氧基丙基]氧基]1經基笨 基]-4,6-一 (2,4-一曱基苯基)-1，3,5~三畊（市售品π·/ 400，知·自 >飞巴公司）。市售的二苯甲§同uv穩定劑之一實 例為2-羥基-4-(N-辛氧基)二苯曱市售品Lowilite® 22， 得自Great Lakes化學公司，West Lafayette，印第安那州）。 可用於本發明之市售UV穩定劑之其他實例包括，但 19 20 200902793 非限於以丁化羥基曱苯(於後稱為”βητ”)穩定之對-甲氧基 肉桂酸2-乙基己酯（市售品Uvinul MC 80，得自BASF公 司，Mount Olive ’新澤西州）、未經穩定之對-曱氧基肉桂 酸2-乙基己酯（市售品Uvinul MC 80 N，得自BASF公司）、 2-氰基-3,3-二苯基丙烯酸2’-乙基己酯（市售品Uvinul 539 T ’得自BASF公司）、2-羥基-4-(N-辛氧基)二苯曱酮（市售 品 Cyasorb UV-501，得自 Cytec 公司，West Paterson，新 澤西州）、2-(2’-羥基-3’,5，-二-三級戊基苯基）苯並***(市售 品 Cyasorb UV-2337，得自 Cytec 公司）、及 2_(2_羥基-5_三 10 15 級辛基本基）本並二σ坐（市售品Cyasorb UV-5411 PA，得自 Cytec 公司）。 可用於本發明方法之其他種類的1;乂穩定劑包括那些 使用至少一種聚（氧基伸烷基)鏈予以修飾者，此種以聚（氧 基伸烷基)鏈修飾之UV穩定劑，其特徵在於：一旦被吸收 (或擴散)至半成品中時，即具有低的遷移性能（例如：其不 易自已被吸入之半成品中溶濾出來）。聚(氧基伸烧基)鍵可 為-種均聚物、共聚物、或♦段共聚物，生成自c2_c 烧基氧化物W如：環氧乙烧、環氧狀、及環氧丁 反應。聚（氧基伸餘)基时具有下㈣基：羥基基團、 Ά cve2() g旨基團。以聚(氧 鏈修飾之w穩定難更詳細地敘述於如：Tirmvin® P, available from Ciba, two saliva (commercially available as di-tertiary butyl-2'- mercaptophenyl) chlorobenzene ' 2_(3',5'· @ II-pentylphenyl ) from Ciba), styrene-acrylic 327, obtained from Ciba), 2 (2, 8 products of edge-based products (10) and 2° sitting (commercially available Tinuvin acid, 3-(2H-benzene) And triazol_2_yl)^...Moss 2, a branched alkyl ester (commercial Tinuvin® 3 soil)_4 hydroxyl_, C7-9 2-(3,,5,-two (1-A Base + stupid illusion 2, 4 'paid from Ciba company), 隹口T· . ® QnA base soil) - 2 • residue phenyl) benzotriazole (city 10 15 = from Ciba Mixture of the public ~ 2__ base _3_ dimethyl sulphate: poly(oxy-(10) dinyl benzotris-2-yl)_5_(1 succinylethyl) ice base -1-lacyl group - yl-hydroxyl and poly(oxyethanediyl), α-[3-[3-(2Η- 并 嗤 嗤 _ _ _ _ _ _ _ _ 1 1 1 1 1 1 1 1 Base ethyl p-phenyl phenyl]-1- oxypropyl hydrazine - stupid and triacetate _2 yl-like bis-indenyl ethyl hydrazine - phenyl phenyl] small oxy decyl] _ (city 1130) 'from Ciba Company', with 2_[4_[2, _3_13-decyloxypropyl] Oxy]-2-hydroxyphenyl]-4,6-di(2,4-dimethylphenyl^di^3, and 2_[4_[2_trans-based_3_dodecanyloxy) Propyl]oxy]1 via phenyl]-4,6-mono(2,4-mercaptophenyl)-1,3,5~three tillage (commercial product π·/ 400, know · from >Finba Company. One example of a commercially available diphenyl § uv stabilizer is 2-hydroxy-4-(N-octyloxy) diphenyl hydrazine commercially available Lowilite® 22, available from Great Lakes Chemistry Company, West Lafayette, Indiana. Other examples of commercially available UV stabilizers useful in the present invention include, but 19 20 200902793 is not limited to a stable pair of butyl hydroxy benzene (hereinafter referred to as "βητ") 2-ethylhexyl oxycinnamate (commercial product Uvinul MC 80, available from BASF Corporation, Mount Olive 'New Jersey), unstabilized p-methoxy-cinnamic acid 2-ethylhexyl ester (commercially available) Uvinul MC 80 N, available from BASF, 2'-ethylhexyl 2-cyano-3,3-diphenylacrylate (commercial product Uvinul 539 T 'from BASF), 2-hydroxy- 4-(N-octyloxy)dibenzophenone (commercial product Cyasorb UV-501, available from Cytec Corporation, West Paterson, New Jersey) , 2-(2'-hydroxy-3',5,-di-tri-pentylphenyl)benzotriazole (commercial product Cyasorb UV-2337, available from Cytec), and 2_(2_hydroxy- 5_3 10 15 辛 basic base) Ben 二 σ sit (commercial Cyasorb UV-5411 PA, available from Cytec). Other types of oxime stabilizers which can be used in the process of the invention include those which are modified with at least one poly(oxyalkylene) chain, which are modified with a poly(oxyalkylene) chain, characterized by It is that once absorbed (or diffused) into the semi-finished product, it has low migration properties (for example, it is not easily leached out of the semi-finished product that has been inhaled). The poly(oxyalkylene) bond can be a homopolymer, a copolymer, or a ♦ segment copolymer formed from a c2_c alkyl oxide such as an epoxy bromide, an epoxy, or a butylene reaction. The poly(oxy) group has a lower (tetra) group: a hydroxyl group, and a Ά cve2() g group. It is difficult to describe in more detail the poly (oxygen chain modification w).
6,602,447 B2 中。 、 J 收====== 20 200902793 波長為550奈米或較低，以525奈米或較低為較佳。較佳 者為：發射的光為於可見光譜之藍色區域(例如：發射的光 具有一波長為至少約400奈米及高至約525奈 的光不多於約500奈米為最佳。 τ十）叫射 可用於本發明之光學增亮劑種類包括，但非限於苯並 哼唑衍生物及蕙衍生物，可用於本發明之市售苯並α等唑衍 生物實例包括，但非限於： 2,2’-(2,5-噻吩二基)二[5-三級丁基苯並噚唑](市售品如：得 自汽巴公司之Uvitex® ΟΒ)、苯並啐唑衍生物如： Blankophor® KLA(得自拜耳公司，於匹茲堡，賓夕法尼亞 州）、Hostalux® KCB(得自 Clariant 公司，於 Muttenz，瑞士）、 及Hostalux® KCU(得自Clariant公司）。市售葱衍生物之一 實例為4,4’-二(2-苯並十坐基）葱（市售品如：East〇brite® OB-1，得自Eastman公司，於Kingsport，田納西州）。可 用於本發明之其他種類的光學增亮劑包括，但非限於4,4，-*一月女基產< -2，2 - 一續酸之竹生物、香豆素衍生物（例如：4-曱基-7-二乙基胺基香豆素）、及二（苯乙稀基)二苯基。 可包括於染浴中之脫模劑種類包括，但非限於以碳氫 化合物為基質之脫模劑、以脂肪酸為基質之脫模劑、以脂 肪酸酸胺為基質之脫模劑、以醇為基質之脫模劑、以脂肪 酸酯為基質之脫模劑、以矽酮為基質之脫模劑、及其混合 物或組合物。以碳氫化合物為基質之脫模劑實例包括：合 成的鏈烷、聚乙烯蠟、及碳氟化合物。可使用之以脂肪酸 為棊質的脫模劑包括例如：硬脂酸及羥基硬脂酸。可使用 21 200902793 ^月曰肪酸_為基質的脫模劑包括例如：硬脂麵胺、 申乙基—硬脂醯胺、及伸烷基二脂肪酸醯胺。以醇為基質 劑實例包括：十八烧醇、十六烧醇、及聚經基醇，、 乙—醇、及聚丙二醉。可包括於染料中以脂肪酸 酉曰為基貝之一脫模劑實例為硬脂酸丁 s旨。 10 15 可包括於本發明方法染浴中之抗靜電劑包括，但非限 於非離子抗靜電劑’如那些包含碳氟化合物基團者、及石夕 酮油，如：BAYSIL0NE 〇1A(可構自拜耳ag公司，德國）。 可用於本發明方法之其他抗靜電劑實例包括：二硬脂基經 基胺、三笨胺、三正辛基軌化物、三苯基膦氧化物、 吡欠N-氧化物、及乙氧化的山梨糖醇酐單月桂酸酯。 可包括於本發明方法染浴中之熱（或耐熱）穩定劑之種 颁包括，但非限於苯酚穩定劑、有機的硫醚穩定劑、有機 的磷化物穩定劑、受阻的胺穩定劑、環氧化物穩定劑、及 其混合物。熱穩定劑之特殊實例包括，但非限於2,6_二_三 級丁基-對-曱紛、鄰-二級丁基-對_甲驗、四，(亞甲基_3_(3,5_ 二-三級丁基-4-羥基苯基）丙酸i旨）曱烷、β_萘胺、對_伸苯基 二胺、及硫二伸乙基二(3,5-二-三級丁基)_4_經基氫化肉桂 酸酯’可購自汽巴特用化學品公司，商品名為IRGAN〇x 1035熱穩定劑。 可用於本發明方法中之紅外線(IR户及收劑包括吸收光 譜的紅外線區域之染料’市售之紅外線吸收劑實例包括： CYASORB IR-99、IR-126、及 IR-165，可得自 Glendale 保 護技術公司’ Lakeland，佛羅里達州。 22 20 200902793 可包括於本發明方法染浴中之抗微生物劑包括例如： 對微生物具有抗菌活性之物質，> :引起麵的微生物。 於此及於申請專利範圍中所用之“抗微生物劑，，一詞亦包括 抗菌的、消毒的、及抗真菌的物質。此外，抗微生物^亦 可於-種預·活化的形態使用，❹：於—種形態，其不會 變成抗微生物地活化，直至發生一啟動事件，例如了 I 物於預-活化物質上之動作。 ’ 10 15 20 可包括於染浴中之抗微生物劑實例包括，但非限於啥 諾_，如：奈咬酸"比旅酸、西諾沙星、料沙星、氣^ 沙星、氧氟沙星、培氣沙星、及依諾沙星；胺基普類，如： ^大黴素、卡那黴素、艾米康絲菌素、西梭徵素、拉普徽 阿卉米^ ;大環内酯，如：紅黴素、克拉黴素、及 了奇斂素，夕胜類，如：枯草桿菌素、莫匹羅星、 thyrothricin、短桿菌肽、及短桿菌酪肽；林可霉素，如： 林可霉素、及克林達黴素；與抗微生_，如：立復黴素 (nfampicin)及夫西地酸(fusidic acid)。可用於 抗微生物劑實例包括：1G，1()，_氧基二苯氧基胂、2_正料 ^異噻唑啉-3-酮、2,4,4，-三氯-2，_經基二笨基蝌亦稱為5_ 乳-2-(2,4-二氯苯氧基)苯酚，一般稱為地丨。·)、N丁基 -u-苯異射琳各嗣、及N_(三氣曱基硫)駄醯胺。 若疋使用效能增強添加劑，其於染浴中典型地存在一 J於或等於15重量％之正總量，以少於或等於5重量％為 争乂佳，並以少於或等於丨重量％為更佳。效能增強添加劑 於染浴中亦典型地存在—至少為〇 〇〇1重量％之總量，以至 23 200902793 少0.005重量％為較佳，並以至少0.01重量％為更佳。效能 增強添加劑於浴中之總存在量範圍可為介於這些較高與較 低值之任意組合之間，這些列舉之數值為包含於其内。例 如：效能增強添加劑於染浴中之總存在量典型地自0.001 5 至15重量％，更典型地自0.005至5重量％，及益加典型 地為於一數量自0·01至1重量％，於各案例中重量百分率 係以染浴之總重為基準。 本發明方法涉及將一種半成品染色，於本發明說明書 中，半成品之定義為：一種中間的熱塑性產物，選自群組 10 包括：粒料、線料、及粉末，其經計算可進一步加工(再成 形）使生成一種成品，這些名稱對專業人士為熟知。適合用 於此新穎方法之熱塑性材料為一種熱塑性材料系統，其包 含至少一成員，選自群組包括：（共）聚酯、（共）聚碳酸醋、 聚酯聚碳酸酯共聚物、丙烯腈-丁二烯-苯乙烯(ABS)共聚 15 物、聚醯胺、聚胺基曱酸酯、聚烷基（曱基）丙烯酸酯（例如： 聚曱基丙烯酸曱酯）、及苯乙烯共聚物（例如：苯乙烯丙烯 腈共聚物）。這些：（共）聚酯、（共）聚碳酸酯、聚酯聚碳酸 酯共聚物可為脂肪族或芳族聚合物（例如：包含雙酚Α之殘 餘物）。 20 於此及於申請專利範圍中所使用之“熱塑性”一詞意指 一種具有軟化或熔化點之聚合物，而且其實質上不含三度 空間的交聯網絡，此網絡係由化學反應性基團，例如：活 性氫基團，與游離的異氰酸酯基團之間生成共價鍵所致。 可用於本發明中之熱塑性聚合物包括那些專業人士所習知 24 200902793 者’如：熱塑性(共）聚酯、熱塑性(共）聚碳酸酯、熱塑性聚 酯聚碳酸酯共聚物、熱塑性丙烯腈-丁二烯-苯乙烯(ABS)共 聚物、熱塑性聚醯胺、熱塑性聚胺基曱酸酯、熱塑性聚烷 ，基（甲基）丙烯酸酯、及熱塑性苯乙烯共聚物。 5 半成品可包含那些專業人士所習知的添加劑，此類添 加劑包括，但非限於脫模劑、填料、於纖維或薄片形態之 增強劑（例如：金屬薄月’如：I呂薄片）、防焰劑、顏料、 及遮蓋劑，如：二氧化鈦 '光漫射劑，如：聚四氟乙烯、 氧化鋅、Paralaoid EXL-5136，可得自 Rohm and Haas 公司， ίο 及交聯的聚甲基丙烯酸曱@旨微球（如：n-licrosphere，得自6,602,447 in B2. , J Receive ====== 20 200902793 The wavelength is 550 nm or lower, preferably 525 nm or lower. Preferably, the emitted light is in the blue region of the visible spectrum (e.g., the emitted light has a wavelength of at least about 400 nanometers and up to about 525 nanometers of light is preferably no more than about 500 nanometers. τ 十) 射射 The optical brightener types useful in the present invention include, but are not limited to, benzoxazole derivatives and anthracene derivatives, and examples of commercially available benzoa-alpha azole derivatives useful in the present invention include, but not Limited to: 2,2'-(2,5-thiophenediyl) bis[5-tris-butylbenzoxazole] (commercial products such as: Uvitex® from Ciba), benzoxazole Derivatives such as: Blankophor® KLA (available from Bayer, Pittsburgh, PA), Hostalux® KCB (available from Clariant, Muttenz, Switzerland), and Hostalux® KCU (from Clariant). An example of a commercially available onion derivative is 4,4'-bis(2-benzoxa-based) onion (commercially available as East 〇brite® OB-1, available from Eastman, Inc., Kingsport, Tennessee) . Other types of optical brighteners useful in the present invention include, but are not limited to, 4, 4, -* January female base < -2,2 - a sour bamboo organism, coumarin derivative (eg: 4-mercapto-7-diethylamino coumarin) and bis(styrene)diphenyl. The types of release agents that can be included in the dyebath include, but are not limited to, hydrocarbon-based release agents, fatty acid-based release agents, fatty acid amine-based release agents, and alcohols. a matrix release agent, a fatty acid ester-based release agent, an anthrone-based release agent, and mixtures or compositions thereof. Examples of the hydrocarbon-based release agent include: synthetic alkane, polyethylene wax, and fluorocarbon. Release agents which can be used in the form of fatty acids include, for example, stearic acid and hydroxystearic acid. It is possible to use 21 200902793 ^ Moon fatty acid_ as a matrix release agent including, for example, stearylamine, stearyl-stearylamine, and alkylamine fatty acid decylamine. Examples of the alcohol-based matrix agent include: octadecyl alcohol, hexadecanol, and polyalkyl alcohol, ethyl alcohol, and polypropylene. An example of a release agent which may be included in the dye as a base of fatty acid hydrazine is stearic acid. 10 15 Antistatic agents which may be included in the dye bath of the method of the invention include, but are not limited to, nonionic antistatic agents such as those containing fluorocarbon groups, and oleanol oils, such as: BAYSIL0NE 〇 1A (construction) From Bayer AG, Germany). Examples of other antistatic agents that can be used in the process of the invention include: distearyl vialamine, triptylamine, tri-n-octyl-orbital, triphenylphosphine oxide, pyridyl N-oxide, and ethoxylated Sorbitol monolaurate. Formulations of thermal (or heat resistant) stabilizers which may be included in the dye bath of the process of the invention include, but are not limited to, phenol stabilizers, organic thioether stabilizers, organic phosphide stabilizers, hindered amine stabilizers, rings Oxide stabilizers, and mixtures thereof. Specific examples of heat stabilizers include, but are not limited to, 2,6-di-tertiary butyl-p-anthracene, o-and-tertiary butyl-p-a-test, and tetra-(methylene_3_(3, 5_Di-tertiary butyl-4-hydroxyphenyl)propionic acid i) decane, β-naphthylamine, p-phenylenediamine, and thiodiethylidene (3,5-di-tri The quaternary butyl)_4_carbamic acid cinnamate is commercially available from the Gasbat Chemical Company under the trade name IRGAN® x 1035 heat stabilizer. Infrared rays that can be used in the method of the present invention (IR households and dyes comprising dyes in the infrared region of the absorption spectrum) are commercially available examples of infrared absorbers including: CYASORB IR-99, IR-126, and IR-165, available from Glendale Protection Technology Company' Lakeland, FL. 22 20 200902793 Antimicrobial agents that may be included in the dye bath of the method of the present invention include, for example, substances that have antibacterial activity against microorganisms, >: microorganisms that cause noodles. The term "antimicrobial agent" as used in the scope also includes antibacterial, disinfecting, and antifungal substances. In addition, antimicrobial agents can also be used in a pre-activated form, in the form of It does not become antimicrobially activated until an initiation event occurs, such as the action of the I substance on the pre-activated substance. ' 10 15 20 Examples of antimicrobial agents that may be included in the dye bath include, but are not limited to, Zino _, such as: Nai acid " than travel acid, cinoxacin, sand star, gas ^ sand star, ofloxacin, aerofloxacin, and enoxacin; amines, such as: Damycin Kanamycin, amoebicin, cisplatin, Lapu Hui A Hui Mi ^; macrolides, such as: erythromycin, clarithromycin, and odd-character, Xisheng, Such as: subtilisin, mupirocin, thyrothricin, gramicidin, and bacillus tyrosin; lincomycin, such as: lincomycin, and clindamycin; and anti-micro- _, such as: Nfampicin and fusidic acid. Examples of useful anti-microbial agents include: 1G, 1 (), oxydiphenoxy fluorene, 2 _ _ isothiazoline-3 -ketone, 2,4,4,-trichloro-2,-yl-based di-phenyl hydrazine, also known as 5-milk-2-(2,4-dichlorophenoxy)phenol, generally known as mantle. ), N butyl-u-phenylisoprene, and N_(trimethylsulfonylthio)guanamine. If a potency enhancing additive is used, it typically has a J of 15 or 15 weight in the dyebath. The positive total amount of % is preferably less than or equal to 5% by weight, and more preferably less than or equal to 5% by weight. The potency enhancing additive is also typically present in the dyebath - at least 〇〇〇1 The total weight%, up to 23 200902793, 0.005 wt% Preferably, and more preferably at least 0.01% by weight. The total amount of potency enhancing additive in the bath may range between any combination of these higher and lower values, and the recited values are included therein. For example, the total amount of potency enhancing additive in the dyebath is typically from 0.001 to 15% by weight, more typically from 0.005 to 5% by weight, and the weight is typically from 0. 01 to 1 weight. %, the weight percentage in each case is based on the total weight of the dyebath. The method of the invention involves dyeing a semi-finished product, in the description of the invention, the semi-finished product is defined as: an intermediate thermoplastic product selected from the group 10 including : Pellets, strands, and powders, which are calculated to be further processed (reformed) to produce a finished product, these names are well known to professionals. A thermoplastic material suitable for use in this novel method is a thermoplastic material system comprising at least one member selected from the group consisting of: (co)polyester, (co)polycarbonate, polyester polycarbonate copolymer, acrylonitrile - Butadiene-styrene (ABS) copolymer 15, polyamine, polyamino phthalate, polyalkyl (decyl) acrylate (eg polydecyl acrylate), and styrene copolymer (Example: styrene acrylonitrile copolymer). These: (co)polyester, (co)polycarbonate, polyester polycarbonate copolymer may be an aliphatic or aromatic polymer (e.g., a residue comprising bisphenolphthalein). 20 The term "thermoplastic" as used herein and in the scope of the patent application means a polymer having a softening or melting point, and which is substantially free of a three-dimensional network of cross-linking networks, which is chemically reactive. A group, for example, an active hydrogen group, is formed by a covalent bond with a free isocyanate group. Thermoplastic polymers useful in the present invention include those known to those skilled in the art. Such as: thermoplastic (co)polyester, thermoplastic (co)polycarbonate, thermoplastic polyester polycarbonate copolymer, thermoplastic acrylonitrile- Butadiene-styrene (ABS) copolymers, thermoplastic polyamides, thermoplastic polyaminophthalates, thermoplastic polyalkanes, based (meth)acrylates, and thermoplastic styrene copolymers. 5 Semi-finished products may contain additives known to those skilled in the art, such as, but not limited to, release agents, fillers, reinforcing agents in the form of fibers or flakes (eg, metal thin moons such as: Ilu thin sheets), Flame agents, pigments, and masking agents, such as: titanium dioxide 'light diffusing agents, such as: polytetrafluoroethylene, zinc oxide, Paralaoid EXL-5136, available from Rohm and Haas, ίο and crosslinked polymethacrylic acid曱@旨微球 (eg: n-licrosphere, derived from
Nagase America公司）、紫外線穩定劑、7jc解穩定劑、熱穩 定劑、及抗微生物劑。於一實例中，半成品包含至少一種 下者：顏料、交聯的聚甲基丙烯酸曱酯微球、玻璃微球、 及金屬薄片。 15 半成品之製備可使用專業-認可的方法，如：擠塑，用 於製造線料，及切割線料製成粒料。於本發明說明書中之 粉末，其製備可藉溶液喷霧乾燥’或藉將其聚合的溶液或 炫體沉厥’粉末有時以其顆粒之最大尺寸作為特徵，可於 高至約1000微米之範圍。於本發明之一實例中，半成品係 20 選自：粉末、粒料、及線料。熱塑性粒料與線料可使用專 業·•認可的方法，如：擠塑或溶融抽絲，製得，將熱塑性粒 料及/或線料染色’隨後可予以進一步加工。於本發明之一 實例中，已染色的熱塑性粒料及/或線料被熔化(例如：於一 擠塑機中）’使生成一種熔融的已染色熱塑性組成物，而後 25 200902793 將此熔融的已染色熱塑性組成物加入（例如：注射）一製模 中，製模内容物經冷卻後，開啟製模，並自其取出已染色 的成形成品。 此種進一步加工已染色半成品之方法，不同於前文中 5 所述之直接添加的方法，但為較佳。使用已染色的熱塑性 粒料及/或線料，染料已存在於熱塑性聚合物内（而非被個別 地加至聚合物），此容許對所欲及可再現的調色程度有更佳 的控制。 於依本發明方法中，將被著色的半成品浸沒於染浴中 10 經歷一段時間，並使用可至少足以提供下者之溫度：至少 將一些染料浸潰（擴散或吸入）至半成品的本體中，因而影 響其染色（或調色），所使用之時間與溫度典型地依半成品 的組成而定。浸沒時間典型地少於或等於8小時，以典型 地少於或等於4小時為更佳，並以典型地少於或等於1小 15 時為甚至更佳。浸沒時間亦典型地至少為5秒，以典型地 至少30秒為更佳，並以典型地至少1分鐘為甚至更佳，浸 沒時間可為介於任何這些較高與較低值之間，這些列舉之 數值為包含於其内。於本發明之一實例中，浸沒時間典型 地為自5秒至8小時，更典型地自15或30秒至4小時， 20 益加典型地自1分鐘至1小時(例如：1至15分鐘）。 於半成品浸沒期間，染浴溫度典型地至少於室溫（例 如：25°C)，與低於染浴之沸點及/或分解溫度，典型地染浴 溫度被維持於25°C至99°C之溫度，例如：自60°C至97°C 或自70°C至95°C。如本文先前所述，浸沒之時間與溫度至 26 200902793 少部份係依被染色半成品的種類而定，例如：對於熱塑性 芳族聚碳酸酯之半成品，染色可於90至99°C之溫度有效 地進行，使用一浸沒時間典型地少於1小時，更典型地於 1至15分鐘之範圍，隨後將經調色（或染色）的半成品自染 5 浴取出。 染浴之製備可藉將染料、水、載體、二醇、選擇地界 面活性劑、及選擇地效能增強添加劑以任意順序予以混 合，例如：載體與二醇可與染料混合在一起，隨後將此混 合物加至水或將水加至混合物。於一實例中，染浴之生成 1〇 係藉：⑴製備一種包括水、載體、與二醇之混合物；（ii)將 染料加入一過濾器中，及(iii)將混合物通過染料並穿越過濾 器，由此生成染浴。染浴，或至少其中一部份，隨後典型 地連續地通過過濾器。選擇地可將包括水、載體、與二醇 之混合物加熱，例如：加熱至一溫度為25°C至99°C，或 15 60°C至97°C，或70°C至95°C，而後將已加熱的混合物與 過濾器中的染料接觸。 i 染料被加至其中之過濾器可為任何專業人士所習知的 適合過濾器，一種較佳類型的過濾器為袋濾器。以此方式 製備及保持染浴，可確保浴中的染料數量被實質上維持於 20 一飽和的程度（如本文先前所述），此外，染浴連續地通過 袋濾器可自其中移除顆粒污染物（例如：未溶解的染料細 粒），其會玷污經由浸沒於染浴所製得之已染色半成品。 於另一實例中，染浴被連續地引入及取出一浸沒槽（或 容器），典型地，浸沒槽為環路的一部份，其包括一流體與 27 200902793 泵浦接觸之入口（經由入口導管），經由一出口導管泵浦於 槽的出口與流體接觸。此環路可選擇地包括至少一只過濾 器，例如：如本文中先前所述之袋濾器，座落於入口及/或 出口導管之線上，較佳者為：浸沒槽的入口及出口位於槽 5 内染浴液位之下。 浸沒槽之入口可包括一只具有多個穿孔的板片（例 如.政佈斋或散佈器板片）。藉通過一只具有多個穿孔的板 片連續地將染浴引入浸沒槽，可增加浸沒槽内滿流混合的 程度，而且可改善其中所浸沒半成品之染色效率及均勻 〇 度。於散佈器板片中之穿孔可具有任意適合的形狀，例如： 圓形、橢圓形、多角形、或其組合。散佈器板片之穿孔典 型地具有直徑自0.79毫米至12.70毫米，例如：自3.17毫 米至6.35毫米，散佈器板片可具有任意適合的結構，例如： 其可為平坦的、凹面、或凸面。 5 本發明方法之範疇包括其他的步驟，藉此染浴組成物 可予修飾，例如：起始的染料或諸染料可被一種後續的染 料或諸染料所取代。於本發明之一實例中，將染料與選擇 地效能增強添加劑自其他的染浴組份(例如：水、載體、、一 醇、及選擇地界面活性劑）分開，此分開對於環境有利，^ 0 魏許染浴中不含染_組份再度使用，例如^其他的染 料或诸染料，或與一種新鮮的染料(諸染料），戋者作為二 種用以沖洗自染浴取出的已染色半成品之沖洗组成物^ 外，若染浴之染料遭到破壞’例如：被氧化或改變性質時(例 如：由於溫度短暫驟升造成過熱），玎使用染料分開法。 28 200902793 染料分開法之進行可藉將染浴與微粒活性碳接觸，隨 後自其分離一種實質上不含染料的液體，其包含水、載體、 二醇、及選擇地界面活性劑，於實質上具有如分開步驟前 之相同的相對比率。此不含染料的液體隨後可與另外一種 5 染料混合以生成一種不同的染浴。藉將染浴連續地通過一 包含活性碳的床或管柱，此染浴可與活性碳接觸。 此活性碳典型地實質上留住染浴中所有的染料，及較 佳地少於最低數量的染浴中之有機液體組份(例如：載體、 二醇、及選擇地界面活性劑），然而有機液體組份可能有一 10 些蒸發，而需要經由隨後添加蒸發的組份藉以調整不含染 料的液體。業已發現：當染料分開步驟施行於包含染料、 水、載體、及二醇之染浴時(不存在選擇地界面活性劑與選 擇地效能增強添加劑），實質上無有機液體組份被保留於活 性碳上。此結果特別令人驚訝，因為使用活性碳將有機化 15 合物與水性組成物分開為習知，若是如此，則預期染料與 大量的有機液體組成物同時會被保留，但是令人驚訝地於 本案例中未被觀察到。 於本發明之一實例中，此方法另外涉及一種染料分離 程序，其包括： 20 (〇 將染浴與微粒活性碳接觸，使生成一種包括染浴與與 微粒活性碳之混合物； (ii) 自混合物分離一種包括：水、載體、與二醇之不含染 料的液體、及 (iii) 選擇地添加至少一種染料至不含.染料的液體，因此生 29 200902793 成一種其他的染浴。 .如本文先前所述，藉將染浴通過一只包含微粒活性碳 的床或管柱，染浴可與微粒活性碳相接觸。於染料分開法 中所分離之不含染料的液體，實質上不含染料，例如：經 5 由分光光度分析測知包含無法偵測數量的染料。微粒活性 碳典型地具有一顆粒尺寸為200網目（例如：顆粒尺寸為 0.075毫米）。可用於本發明之一種市售微粒活性碳實例為 得自 Calgon Carbon 公司之 Filtrasorb 200 活性碳。 達成染料分開所需之活性碳數量，部份地係依染浴溫 10 度而定，一般而言，達成染料分開所需之活性碳數量為·· 當染浴溫度下降時為減少，當染浴溫度上升時為增加。於 本發明之一實例中，染浴與活性碳於25°c之溫度下相接觸。 選擇地加至不含染料液體之染料可選自：靜態染料、 光色染料、及其組合物，可添加之靜態染料與及光色染料 15 包括那些於本文中先前所述之種類與實例。加至不含染料 液體之染料可為與自染浴移除之相同類型的染料，於此個 案中，其他的染浴為一種新鮮或回復新鮮的染浴。或者， 加至不含染料液體之染料可為不同於自染浴移除的染料， 於此個案例中，其他的染浴為一種新的或不同的染浴。 20 染料分開法可另外包括添加額外的物料至不含染料之 液體及/或其他的染浴，此類其他的額外物料包括例如：界 面活性劑及/或效能增強添加劑，其可個別選自那些於本文 中先前所述之種類與實例。 自染浴取出後，已染色半成品典型地被沖洗以自其中 30 200902793 移除過量的染浴物料，沖洗步驟之達成典型地藉將已染色 物件至少一部份的表面與下者接觸一種包括水、及選擇 地一種式I所代表的載體、及/或一種二醇的沖洗組成物。 沖洗組成物中之水可為去離子水或蒸餾水，可存在於沖洗 組成物中之載體及一醇為如本文中先前所敛述有關染浴 者，並可個別選自那些於本文中先前所述之種類與實例， 例如：於一實例中，載體為乙二醇單-丁基醚，及二醇為二 乙二醇。較佳地，沖洗組成物為由水、一種式丨所代表的 10 15 20 載體、與一種二醇(如本文中先前所敘述有關染浴中之二醇 (iv))所組成。 沖洗組成物可與已染色半成品之表面相接觸，經由例 如：浸沒（浸泡）、喷霧施加、及/或帘流施加。經與已染色 半成品之表面接觸後，沖洗組成物可被重複循環及被用於 沖洗其他的已染色物件，經過數次沖洗循環後，染料會典 型地積聚於重複循環的沖洗組成物中。積聚的染料可^重 複循環的沖洗組成物移除，藉將重複循環的沖洗組成物與 微粒活性碳相接觸，如本文中先前所敘述之有關染料分開 汁洗、'且成物興土地包含水於一數量，典型地自％(或 1〇0重量％，更典型地自60至87重量％，益加典型 地於一數量自65至75重量〇/〇，认欠安点，士‘ 於各案例中重量百分率係 以冲洗組成物之總重為基準。 數量 若是存在時，可存在於沖洗域物中之龍及/或二醇 ’可選自那些於本文中先前所述有關染浴之範圍及數 31 200902793 量。例如：可存在於沖洗組成物中之載體數量，典型地自 10至30重量％，更典型地自15至25重量％，益加典型地 於一數量自17至20重量％，於各案例中重量百分率係以 沖洗組成物之總重為基準。例如：可存在於沖洗組成物中 5 之二醇數量，典型地自1至20重量％，更典型地自5至15 重量％，益加典型地於一數量自10至12重量％，於各案例 中重量百分率係以沖洗組成物之總重為基準。 經沖洗後，已染色半成品在用於自其模塑或成形至完 工物件前，典型地予以乾燥。本發明於下列實例中予以更 10 明確地敘述，其僅意欲為說明性質，因為其中有許多的修 飾及變化對那些精於此方面技藝者為顯見，除非另外指 明，所有的份及百分率皆以重量計。 【實施方式】 實例 15 於下列實例中，染浴之製備係藉將去離子水、載體、 及二醇於混合槽中混合在一起，因而生成一種液體混合 物。此液體混合物於95°C之溫度下連續地通過一只其内已 置放50公克染料之袋濾器。將此包含染料之已加熱混合物 自混合槽循環通過袋濾器並回送至混合槽，經歷一段時間 20 足以使包括水、載體、及二醇之混合物飽和的染料，因而 生成染浴。 於下列實例中，染料於染浴中之數量為約0.1重量％， 此染浴包含約70重量％(重量份)去離子水、18重量份乙二 醇單丁基醚(作為載體）、及12重量份二乙二醇(作為二醇）， 32 200902793 重量百分率係以去離子水、載體、與二醇之總重為基準。 此液體混合物通過一只已加入50公克染料於其内之袋濾 器。 透明的聚碳酸酯粒料(Makrolon 3208，得自拜耳材料科 5 學公司）使用得自LanXess公司之Macrolex紅色G、藍色 3R、或黃色3R染料予以著色。將粒料（1.4公斤）置於一鋼 絲網籃中，此籃具有足夠的網目尺寸，其容許著色溶液環 繞粒料，同時可將粒料留存於籃中。此包含粒料之籃隨後 被浸沒於95°C的著色溶液中，經5分鐘後，使用不含染料 ίο 的著色溶液沖洗粒料，藉以自粒料表面移除過量的染料， 最後使用去離子水沖洗粒料。於一對流烘箱中予以徹底的 乾燥後，粒料被模塑成具有尺寸為5公分X 7.5公分X 0.25 公分的樣品。 數值 對照組 籃色3R 紅色G 黃色3R L 95.8 32.1 55.0 92.4 a -0.16 26.3 76.0 -14.6 b 1.32 -67.5 35.5 85.0 黃度指數 4.1 -665 112 89 %透射 90.3 2.3 24.4 84.0 %霧度 1.9 0.5 0.4 0.4 33 200902793 本發明已參照其特定實例之明確細節予以敘述，並非 意欲將此類細節視為對於本發明範疇之限制，而是將其包 括於隨附的申請專利範疇之範圍與程度内。 5 【圖式簡單說明】 無 【主要元件符號說明】 益 10 34Nagase America), UV stabilizers, 7jc destabilizers, thermal stabilizers, and antimicrobials. In one example, the semi-finished product comprises at least one of the following: pigments, crosslinked polymethacrylate microspheres, glass microspheres, and metal flakes. 15 Semi-finished products can be prepared using professional-approved methods such as extrusion, for the manufacture of strands, and cutting of strands into pellets. The powder in the specification of the present invention may be prepared by spray drying of the solution or by sinking the solution or blaze which polymerizes it. The powder is sometimes characterized by the largest size of the granules, and may be as high as about 1000 microns. range. In one embodiment of the invention, the semi-finished product 20 is selected from the group consisting of: powder, pellets, and strands. Thermoplastic pellets and strands can be further processed using professionally recognized methods such as extrusion or melt spinning to dye thermoplastic pellets and/or strands. In one embodiment of the invention, the dyed thermoplastic pellets and/or strands are melted (e.g., in an extruder) to produce a molten, dyed thermoplastic composition, and then 25 200902793 The dyed thermoplastic composition is added (e.g., injected) into a mold, and after molding, the molded contents are cooled, the mold is opened, and the dyed shaped product is taken out therefrom. This method of further processing the dyed semi-finished product is different from the direct addition method described in the above 5, but is preferred. Using dyed thermoplastic pellets and/or strands, the dye is already present in the thermoplastic polymer (rather than being added to the polymer individually), which allows for better control over the desired and reproducible level of toning. In the method according to the invention, the colored semi-finished product is immersed in the dyeing bath for a period of time, and the use is at least sufficient to provide the temperature of at least: some of the dye is impregnated (diffused or inhaled) into the body of the semi-finished product, Thus affecting its dyeing (or toning), the time and temperature used will typically depend on the composition of the semi-finished product. The immersion time is typically less than or equal to 8 hours, more preferably less than or equal to 4 hours, and even more preferably less than or equal to 1 small 15 hours. The immersion time is also typically at least 5 seconds, preferably at least 30 seconds, and preferably at least 1 minute, and the immersion time can be between any of these higher and lower values. The numerical values listed are included in them. In one embodiment of the invention, the immersion time is typically from 5 seconds to 8 hours, more typically from 15 or 30 seconds to 4 hours, and 20 is typically from 1 minute to 1 hour (eg, 1 to 15 minutes) ). During the immersion of the semi-finished product, the dye bath temperature is typically at least room temperature (eg, 25 ° C), and below the boiling point and/or decomposition temperature of the dye bath, typically the bath temperature is maintained at 25 ° C to 99 ° C. The temperature is, for example, from 60 ° C to 97 ° C or from 70 ° C to 95 ° C. As previously described herein, the immersion time and temperature to 26 200902793 are less dependent on the type of semi-finished product being dyed. For example, for semi-finished thermoplastic aromatic polycarbonate, dyeing can be effective at temperatures between 90 and 99 °C. The immersion time is typically less than one hour, more typically in the range of from 1 to 15 minutes, and the toned (or dyed) semi-finished product is then removed from the dyed 5 bath. The dye bath can be prepared by mixing the dye, water, carrier, glycol, selective surfactant, and optionally potency enhancing additive in any order, for example, the carrier and the diol can be mixed with the dye, and then The mixture is added to water or water is added to the mixture. In one example, the dye bath is formed by: (1) preparing a mixture comprising water, a carrier, and a diol; (ii) adding the dye to a filter, and (iii) passing the mixture through the dye and passing through the filter. , thereby generating a dye bath. The dye bath, or at least a portion thereof, then typically passes continuously through the filter. Optionally, the mixture comprising water, a carrier, and a diol may be heated, for example, to a temperature of 25 ° C to 99 ° C, or 15 60 ° C to 97 ° C, or 70 ° C to 95 ° C, The heated mixture is then contacted with the dye in the filter. The filter to which the i dye is added may be a suitable filter for any person skilled in the art, and a preferred type of filter is a bag filter. Preparing and maintaining the dyebath in this manner ensures that the amount of dye in the bath is substantially maintained at a level of 20-saturation (as previously described herein), and in addition, the dyebath continuously removes particulate contamination from the bag filter through it. A substance (for example, undissolved dye fines) which stains the dyed semi-finished product obtained by immersion in a dye bath. In another example, the dyebath is continuously introduced and removed into an immersion tank (or container), typically the immersion tank is part of a loop that includes a fluid inlet to the 27 200902793 pump (via the inlet) The conduit) is pumped to the fluid at the outlet of the tank via an outlet conduit. The loop optionally includes at least one filter, such as a bag filter as previously described herein, positioned on the inlet and/or outlet conduit, preferably: the inlet and outlet of the submerged tank are located in the tank 5 Under the dye bath level. The inlet of the immersion tank may include a sheet having a plurality of perforations (e.g., Zhengbuzhai or spreader sheets). By continuously introducing the dyebath into the immersion tank through a sheet having a plurality of perforations, the degree of full flow mixing in the immersion tank can be increased, and the dyeing efficiency and uniform enthalpy of the immersed semi-finished product can be improved. The perforations in the diffuser panel can have any suitable shape, such as: circular, elliptical, polygonal, or a combination thereof. The perforations of the diffuser sheets typically have diameters from 0.79 mm to 12.70 mm, for example from 3.17 mm to 6.35 mm, and the diffuser sheets can have any suitable configuration, for example: they can be flat, concave, or convex. 5 The scope of the process of the invention includes additional steps whereby the dyebath composition can be modified, for example, the starting dye or dyes can be replaced by a subsequent dye or dye. In one embodiment of the invention, the dye is selectively separated from other dye bath components (eg, water, carrier, monool, and optionally surfactant) from the selected performance enhancing additive, which is advantageous for the environment, ^ 0 Wei Xu dye bath does not contain dye _ components reuse, such as ^ other dyes or dyes, or with a fresh dye (dyes), as the two used to rinse the dyed bath to take out the dyed In addition to the rinsing composition of the semi-finished product, if the dye of the dye bath is destroyed, for example, when it is oxidized or changes its properties (for example, due to overheating due to a sudden temperature rise), the dye separation method is used. 28 200902793 Dye separation can be carried out by contacting the dyebath with particulate activated carbon and subsequently separating a substantially dye-free liquid comprising water, a carrier, a diol, and optionally a surfactant, substantially There is the same relative ratio as before the separation step. This dye-free liquid can then be mixed with another 5 dye to create a different dye bath. The dyebath can be contacted with activated carbon by continuously passing the dyebath through a bed or column containing activated carbon. The activated carbon typically retains substantially all of the dye in the dyebath, and preferably less than the minimum amount of organic liquid components in the dyebath (eg, carrier, glycol, and optionally surfactant), however The organic liquid component may have some evaporation, and the dye-free liquid needs to be adjusted via subsequent addition of the evaporated component. It has been found that when the dye separation step is applied to a dye bath comprising dye, water, carrier, and diol (there is no selective surfactant and selective potency enhancing additive), substantially no organic liquid component is retained in the activity. On carbon. This result is particularly surprising since it is conventional to separate the organic compound 15 from the aqueous composition using activated carbon, and if so, it is expected that the dye will be retained simultaneously with a large amount of the organic liquid composition, but surprisingly Not observed in this case. In one embodiment of the invention, the method further relates to a dye separation procedure comprising: 20 (contacting the dyebath with the particulate activated carbon to produce a mixture comprising a dyebath and particulate activated carbon; (ii) The mixture separates one comprising: water, a carrier, a dye-free liquid with the diol, and (iii) optionally adding at least one dye to the liquid that does not contain the dye, thus producing 29 200902793 as an alternative dye bath. As previously described herein, the dye bath is contacted with particulate activated carbon by passing the dyebath through a bed or column containing particulate activated carbon. The dye-free liquid separated in the dye separation process is substantially free. Dyes, for example, are determined by spectrophotometric analysis to contain an undetectable amount of dye. The particulate activated carbon typically has a particle size of 200 mesh (eg, a particle size of 0.075 mm). It is commercially available as a commercially available product. An example of a particulate activated carbon is the Fluidtrasorb 200 activated carbon from Calgon Carbon. The amount of activated carbon required to achieve dye separation is partially based on a dye bath temperature of 10 degrees. In general, the amount of activated carbon required to achieve dye separation is reduced as the dye bath temperature decreases, and increases as the dye bath temperature increases. In one example of the invention, the dye bath and activated carbon are Contact at a temperature of 25 ° C. Selectively added to the dye-free liquid dye can be selected from: static dyes, photochromic dyes, and combinations thereof, static dyes and photochromic dyes that can be added 15 including those in this paper The types and examples previously described. The dye added to the dye-free liquid may be the same type of dye removed from the dye bath, in which case the other dye bath is a fresh or fresh dye bath. Alternatively, the dye added to the dye-free liquid may be a dye that is different from the self-dyeing bath. In this case, the other dye bath is a new or different dye bath. 20 The dye separation method may additionally include adding Additional materials to dye-free liquids and/or other dyebathings, such additional materials including, for example, surfactants and/or performance enhancing additives, which may be individually selected from those previously described herein And after the self-dyeing bath is removed, the dyed semi-finished product is typically rinsed to remove excess dye bath material from 30 200902793, and the rinsing step is typically achieved by contacting at least a portion of the surface of the dyed article with the underside. A rinse composition comprising water, and optionally a carrier represented by the formula I, and/or a diol. The water in the rinse composition may be deionized water or distilled water, a carrier which may be present in the rinse composition and The monool is as previously described herein with respect to the dyebath, and may be individually selected from those of the types and examples previously described herein, for example, in one example, the carrier is ethylene glycol mono-butyl ether, And the diol is diethylene glycol. Preferably, the rinsing composition is 10 15 20 carrier represented by water, a formula, and a diol (as previously described herein in the dye bath) Iv)). The rinse composition can be contacted with the surface of the dyed semifinished product by, for example, immersion (soaking), spray application, and/or curtain flow application. Upon contact with the surface of the dyed semi-finished product, the rinse composition can be recycled and used to rinse other dyed articles. After several rinse cycles, the dye typically accumulates in the recirculating rinse composition. The accumulated dye can be repeatedly recycled by flushing the composition by contacting the recirculating rinse composition with the particulate activated carbon, as described herein before in relation to the dye separate juice wash, and the material contains water. In a quantity, typically from % (or 1 〇 0% by weight, more typically from 60 to 87% by weight, benefiting from a typical amount from 65 to 75 weight 〇 / 〇, owing to the point, the gentleman's The weight percentage in the case is based on the total weight of the rinse composition. If present, the amount of dragon and/or glycol present that may be present in the rinse zone may be selected from those previously described herein in relation to the dye bath. And number 31 200902793. For example: the amount of carrier which may be present in the rinsing composition, typically from 10 to 30% by weight, more typically from 15 to 25% by weight, typically added in an amount from 17 to 20 weight %, the weight percentage in each case is based on the total weight of the rinse composition. For example: the amount of diol which may be present in the rinse composition 5, typically from 1 to 20% by weight, more typically from 5 to 15 % by weight, Yi Jia is typically used in one The amount is from 10 to 12% by weight, and the weight percentage in each case is based on the total weight of the rinse composition. After rinsing, the dyed semi-finished product is typically dried before being used for molding or forming it from the finished article. The present invention is further described in the following examples, which are intended to be illustrative only, and since many modifications and variations are obvious to those skilled in the art, unless otherwise indicated, all parts and percentages [Examples] In the following examples, the dyebath was prepared by mixing deionized water, a carrier, and a diol in a mixing tank to thereby form a liquid mixture. Continuously pass a bag filter in which 50 grams of dye has been placed at a temperature of ° C. The heated mixture containing the dye is circulated from the mixing tank through the bag filter and returned to the mixing tank for a period of time 20 sufficient to include A dye saturated with a mixture of water, a carrier, and a diol, thereby forming a dyebath. In the following examples, the amount of the dye in the dyebath is about 0.1. 5% by weight, the dyebath contains about 70% by weight of deionized water, 18 parts by weight of ethylene glycol monobutyl ether (as a carrier), and 12 parts by weight of diethylene glycol (as a diol), 32 200902793 The weight percentage is based on the total weight of deionized water, carrier, and glycol. This liquid mixture is passed through a bag filter to which 50 grams of dye has been added. Transparent polycarbonate pellets (Makrolon 3208, available from Bayer MaterialScience 5) is coloured using Macrolex Red G, Blue 3R, or Yellow 3R dye from LanXess. The pellets (1.4 kg) are placed in a wire mesh basket with sufficient mesh size. It allows the coloring solution to surround the pellets while leaving the pellets in the basket. The basket containing the pellets is then immersed in a 95 ° C coloring solution. After 5 minutes, the pellets are rinsed with a dye-free solution, whereby excess dye is removed from the surface of the pellets, and finally deionized. Rinse the pellets with water. After thorough drying in a pair of flow ovens, the pellets were molded into samples having dimensions of 5 cm x 7.5 cm x 0.25 cm. Numerical control basket color 3R red G yellow 3R L 95.8 32.1 55.0 92.4 a -0.16 26.3 76.0 -14.6 b 1.32 -67.5 35.5 85.0 yellowness index 4.1 -665 112 89 % transmission 90.3 2.3 24.4 84.0 % haze 1.9 0.5 0.4 0.4 33 The present invention has been described with reference to the specific details of the specific examples thereof, and is not intended to be construed as limiting the scope of the invention. 5 [Simple description of the diagram] None [Key component symbol description] Benefit 10 34