TW200538281A - Weatherable multilayer articles and method for their preparation - Google Patents

Abstract

Disclosed are weatherable multilayer articles comprising (I) a coating layer comprising a block copolyestercarbonate comprising structural units derived from at least one 1,3-dihydroxybenzene and at least one aromatic dicarboxylic acid, (ii) a second layer comprising a polymer comprising carbonate structural units, (iii) a substrate layer comprising a polypropylene, and (iv) at least one adhesive layer comprising the reaction product of an amine-functionalized polypropylene and a polyurethane, wherein the coating layer is in contiguous contact with the second layer, and the adhesive layer is in contiguous contact with the second layer and the substrate layer. Also disclosed is a method for making the multilayer article.

Description

200538281 九、發明說明： 【發明所屬之技術領域】 本發明係關於耐候多層樹脂物件及其製備方法。更特定 地，本發明係關於包含保護性嵌段共聚醋碳酸酉旨塗層、包 括含有碳酸酯結構單元之聚合物之第二層、基片、及在該 第一層與基片間之至少一層黏著層之多層物件。 【先前技術】 各種樹脂物件皆有長期色彩不安定性之問題。其會導致 ♦ %合物樹脂黃化，在某些具體實施例中，該黃化現象會損 害其透明性及吸引力。光澤之損失亦可以是一項非所要之 長期現象。 聚合物之黃化通常由紫外線輻射之作用所引起，也就是 此種黃化現象為什麼通稱為”光化黃化”之原因。用以抑制 光化黃化現象之許多方法業經使用及提議。許多這些方法 包括將紫外線吸收化合物（UVA，s)併入聚合物内。對大部份 而言，UVA’s為低分子量化合物，且其使用量必需相當低（通 籲 常至多1重量％)，才能避免該聚合物之物理性質（例如，衝 擊強度及在熱變形溫度中顯示之高溫性質）的降解。該等含 量可能不足以提供充份的保護作用。 一種保護樹脂物件免於光化黃化及光澤損失之方法為施 用耐候第二聚合物塗料，如文令使用該名詞”耐候”表示對 此種現象之抗性。適於此種目的之耐候聚合物包括間苯二 酚異酞酸酯/對酞酸酯共聚芳化物。其係為C〇hen等人，j200538281 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a weather-resistant multilayer resin object and a preparation method thereof. More specifically, the present invention relates to a second layer comprising a protective block copolyacetate carbonate coating, a polymer including a carbonate structural unit, a substrate, and at least between the first layer and the substrate. A multi-layer object with an adhesive layer. [Prior art] Various resin objects have long-term color instability problems. It will cause yellowing of the compound resin. In some embodiments, the yellowing phenomenon will impair its transparency and attractiveness. Loss of gloss can also be an undesirable long-term phenomenon. The yellowing of polymers is usually caused by the action of ultraviolet radiation, which is why this yellowing phenomenon is commonly referred to as "photo yellowing". Many methods to suppress photo-yellowing have been used and proposed. Many of these methods include incorporating ultraviolet absorbing compounds (UVA, s) into the polymer. For the most part, UVA's are low-molecular-weight compounds and must be used in relatively low amounts (usually up to 1% by weight) in order to avoid the physical properties of the polymer (for example, impact strength and display at thermal deformation temperature High temperature properties). These levels may not be sufficient to provide adequate protection. One way to protect resin objects from photo-yellowing and loss of gloss is to apply a weather-resistant second polymer coating. The term "weather-resistant" as used in the text indicates resistance to this phenomenon. Weather-resistant polymers suitable for this purpose include resorcinol isophthalate / terephthalate co-aromatic compounds. It is Cohen et al., J

Poly. Sci·，Part A-1，9，3263-3299(1971)、及 M〇nsant〇 9881I.doc 200538281Poly. Sci., Part A-1, 9, 3263-3299 (1971), and Munsant 9881I.doc 200538281

Company之特定相關美國專利（其包括美國專利第 3,444，129唬、第 3,460,961號、第 3,492,261 號及第 3,503,779 號）之主題。普遍承認之美國專利第6,572,956號係關於具有 包含衍生自1，3_二羥基苯有機二羧酸酯之結構單元之塗層 的耐侯夕層物件。普遍承認之美國專利第6，鳩，5〇7號係關 於1、有I 3至少一層塗層於其上之塗層之耐候多層物件， / k層I括包含間苯二酚芳化物聚酯鏈部份（其實質上 不3可連接至少該聚合物鏈之至少兩個單體單元之酸野鍵 口物）之熱*疋性聚合物，該耐候多層物件係藉由界面法製 成。在某些具體實施例中，該含間苯二盼芳化物聚醋鍵部 份之聚合物係為共聚酯碳酸酯。 耐候共聚®1碳酸®旨通常可作為第二層上之塗層，咳第二 炭Γ結構單元之聚合物樹脂。當施用該耐候聚 :曰之組合至具有第二層之基片樹脂(其中該第 :層鄰接該基片）時’會產生一項特別的問題。當該基片具 咼非極性時（例如，聚丙稀基 、 〇 a k 〜在4含極性碳酸酯結構單 第層與該基片之間實際上並無黏著現象。因此，欲 ==為’研發製襟可用於各種目的(例如，戶㈣ 例如’汽車）之車身配件）之含聚丙烯基片之耐候多 =件的方法’且該耐候多層物件之各層之間具有適合勸 【發明内容】 本發明已發現具有塗声雜夕 層免於風名虫、並在各層之門呈=件可以保護其下面各 屢之間具有優異黏著性。在一項其具 98811.doc 200538281 體實施例中，本發明包括一多層物件，其包含⑴一塗層， 其包括含衍生自至少一種i，3-二羥基苯與至少一種芳香族 二觀酸之結構單元之嵌段共聚酯碳酸酯，（ii)第二層，其包 括含碳酸酯結構單元之聚合物，（iii)一基片層，其含有聚丙 稀’及（iv)至少一層黏著層，其含有經胺官能化聚丙烯與聚 胺基甲酸酯之反應產物；其中該塗層與第二層互相接觸， 而該黏著層與第二層及基片層互相接觸。 在另一項其具體實施例中，本發明包括製備該多層物件 • 之方法。 藉由參考以下說明文及附加申請專利範圍，可更瞭解本 發明之各種其它特徵、方面、及優點。 【貫施方式】 在以下專利說明書及其後之申請專利範圍，會參考許多 名詞，這些名詞之定義具有以下意義。除非本文另有清楚 指定，該等單數型”一”，"一種"及"該"包括複數指稱。，，可 _ 視需要選用”係意指後續描述之事項或情況可或可不發 生，且意指該說明文包括該事項發生之實例、及該事項不 會發生之實例。如文中使用，該名詞”層，，可以與該等名詞 ’’薄膜’’及’’薄片，，可互換使用。該等名詞，，黏著層，，及，，黏結層，, 可互換使用。 本發明該等多層物件中之共聚酯碳酸酯薄膜包含至少_ 種含交替碳酸酯及芳化物嵌段之嵌段共聚酯碳酸酯。該等 嵌段共聚酯碳酸酯包括含1，3_二羥基苯結構單元及芳香族 二羧酸結構單元之式（I)聚合物： 、 98811.doc 200538281Company's subject matter in certain relevant U.S. patents (including U.S. Patents 3,444,129, 3,460,961, 3,492,261, and 3,503,779). Generally accepted U.S. Patent No. 6,572,956 relates to weather-resistant layer articles having a coating comprising a structural unit derived from an organic dicarboxylic acid ester of 1,3-dihydroxybenzene. The generally accepted US Patent No. 6, Dove, No. 507 relates to a weather-resistant multilayer article having a coating layer on which at least one layer of I 3 is applied. The / k layer I includes a resorcinol aromatic polyester. A chain polymer (which is not substantially an acid-field bond capable of connecting at least two monomer units of the polymer chain). The weather-resistant multilayer article is made by an interface method. In some embodiments, the polymer containing the isophenylene phthalate aromatic moiety is a copolyestercarbonate. Weather-resistant copolymer 1 carbonic acid is usually used as a coating on the second layer, a polymer resin of the second carbon Γ structural unit. A particular problem arises when applying the weather-resistant poly: to a substrate resin having a second layer (where the first: layer is adjacent to the substrate). When the substrate is non-polar (for example, polypropylene, 〇ak ~ 4) there is actually no adhesion between the single layer containing a polar carbonate structure and the substrate. Therefore, the desire == for 'development The flap can be used for various purposes (for example, household parts such as 'automobile' body parts), weather-resistant polypropylene-based substrates, and the weather-resistant multi-layer object has suitable layers between each layer. [Summary of the Invention] This It has been found by the invention that the layer having the coating sound is free from wind insects, and the pieces on the door of each layer can protect the lower layer with excellent adhesion. In one embodiment of 98811.doc 200538281, the present invention includes a multi-layered article including a first coating including a derivative containing at least one i, 3-dihydroxybenzene and at least one aromatic diguanide. Block copolymer polyester carbonate of structural unit of acid, (ii) a second layer comprising a polymer containing carbonate structural unit, (iii) a substrate layer containing polypropylene 'and (iv) at least one layer The adhesive layer contains the reaction product of amine-functionalized polypropylene and polyurethane; wherein the coating layer and the second layer are in contact with each other, and the adhesive layer is in contact with the second layer and the substrate layer. In another specific embodiment thereof, the invention includes a method of making the multilayered object. Various other features, aspects, and advantages of the present invention can be better understood by referring to the following description and additional patent application scope. [Implementation method] In the following patent specification and the scope of patent application thereafter, many terms will be referred to. The definitions of these terms have the following meanings. Unless otherwise specified herein, such singular forms "a", "an" and "the" include plural referents. ，， 可 optionally as needed "means that the event or situation described later may or may not occur, and means that the description includes an instance where the event occurs and an instance where the event does not occur. If used in the text, the term "Layer" can be used interchangeably with the terms "film" and "sheet". These terms, adhesive layer, and, adhesive layer, are used interchangeably. The copolyestercarbonate film in the multilayer articles of the present invention includes at least one block copolyestercarbonate containing alternating carbonate and aryl block. These block copolyester carbonates include polymers of formula (I) containing 1,3-dihydroxybenzene structural units and aromatic dicarboxylic acid structural units: 98811.doc 200538281

-0-R2-0—C-0-R2-0—C

Ο) r I I 5Ο) r I I 5

其中Rl各獨立為鹵素或^^2烷基，p為〇至3，R2各獨立為 一饧有機基團，m為至少丨，且至少約4。在某些具體實 施例中，η為至少約10，在其它具體實施例中，η為至少約 20且在又其它具體實施例中，η為約3〇至150。在某此具 體實施例中，m為至少約3，在其它具體實施例中，瓜為至 V、力10，且在又其它具體實施例中，m為約20-200。在其它 具體實施例中，n介於約2〇與5〇之間。在本發明之文中， ’’交替碳酸醋及芳化物嵌段”意指該共聚酯碳酸酯包含至少 一個碳酸酯嵌段及至少一個芳化物嵌段。在特別具體實施 例中，嵌段共聚酯碳酸酯包含至少一個芳化物嵌段及至少 兩個碳酸酯嵌段。在其它特別具體實施例中，嵌段共聚酯 碳酸醋包含具有至少一個芳化物彼段（"Β”）與至少兩個碳酸 酯嵌段（’’Α，’）之Α-Β-Α結構。 該芳化物嵌段含有包含可未經取代或經取代之i，3-二羥 基苯分子團之結構單元。烷基取代基若存在時，通常為直 鏈或分支鏈烷基，且最常位於兩個氧原子之鄰位，但是亦 涵蓋其它環位置。適合之Cl·!2烷基包括（但不限於）甲基、乙 基、正·丙基、異丙基、丁基、異_ 丁基、第三_ 丁基、壬基、 癸基、及經芳基取代之烷基，其包括节基。在某些具體實 施例中，任一種烷基取代基為甲基。適合之齒素取代基包 括溴、氯、及氟。含烷基與鹵素取代基之混合物之丨，3_二羥 98811.doc 200538281 基苯分子團亦適合。在一項具體實施例中， T P值可以是0至 3，在另一項具體實施例中，p值為〇至2，而在又另一工呈 體實施例中，p值為⑷。在一項具體實施例中，= 基本分子團為2-甲基間苯二酚。在許多具體實施例中， ，經基苯分子團為未經取代之間苯為零。亦涵 蓋含1’3-二經基苯分子團之混合物（例#，未經取代之間苯 一盼與2-甲基間苯二盼之混合物）之聚合物。Wherein R1 is each independently a halogen or ^ 2 alkyl group, p is 0 to 3, R2 is each independently an organic group, m is at least 丨, and at least about 4. In certain embodiments, n is at least about 10, in other embodiments, n is at least about 20 and in still other embodiments, n is about 30 to 150. In a specific embodiment, m is at least about 3, in other specific embodiments, the melon is up to V, force 10, and in still other specific embodiments, m is about 20-200. In other specific embodiments, n is between about 20 and 50. In the context of the present invention, "alternating carbonate and arylate blocks" means that the copolyester carbonate comprises at least one carbonate block and at least one arylate block. In a particular embodiment, the blocks are The polyester carbonate includes at least one arylate block and at least two carbonate blocks. In other particular embodiments, the block copolyester carbonate contains at least one arylate segment (" B ") and A-B-A structure of at least two carbonate blocks ('' A, '). The arylate block contains a structural unit containing an i, 3-dihydroxybenzene molecular group which may be unsubstituted or substituted. Alkyl substituents, if present, are usually straight or branched chain alkyl groups and are most often located adjacent to two oxygen atoms, but other ring positions are also encompassed. Suitable Cl ·! 2 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, butyl, iso-butyl, tert-butyl, nonyl, decyl, and An aryl-substituted alkyl group includes a benzyl group. In certain embodiments, any of the alkyl substituents is methyl. Suitable halo substituents include bromine, chlorine, and fluorine. For mixtures containing alkyl and halogen substituents, 3-dihydroxy 98811.doc 200538281 is also suitable. In one embodiment, the value of T P may be 0 to 3, in another embodiment, the value of p is 0 to 2, and in yet another embodiment, the value of p is ⑷. In a specific embodiment, the = basic molecular group is 2-methylresorcinol. In many embodiments, the phenyl group is unsubstituted and the benzene is zero. It also covers polymers containing a mixture of 1'3-diacylbenzene molecules (eg, a mixture of unsubstituted m-phenylene and 2-methyl m-phenylene).

在芳化物結構單元中，該W二經基苯分子圏係與芳香族 二羧酸分子團結合，言亥芳㈣二羧酸分子團可以是單環分 子團，例如，異酞酸酯或對苯二甲酸酯或其經齒素取代之 衍^物；或多環分子團，其說明實例包括二苯基二㈣酉旨、 Τ苯基醚二羧酸酯，二苯基砜二羧酸酯、二苯基酮二羧酸 6曰、一苯基硫二羧酸酯、或萘二羧酸酯。在某些具體實施 =中，多環分子團包括萘_2,6_二羧酸酯；或單環及/或多環 芳香知一羧酸酯之混合物。在許多具體實施例中，該芳香 、幾酉文刀子團為異酞酸酯及/或對酜酸酯。可存在該等分 子團之一或兩者。在一項具體實施例中，異酞酸酯與對酞 酸酯係以在約0.20至5·〇: !範圍内之莫耳比存在，而在另一 項具體實施例中，異酞酸酯與對酞酸酯係以在約〇 25至 0 1範圍内之莫耳比存在。當該異酞酸酯與對酞酸酯之 莫耳比大於約4.0 : 1時，則在某些具體實施例中會形成不 月b接又之ί衣係寡聚物數量。當該異酞酸酯與對酞酸酯之莫 #比小於約〇·25 : 1時，則在某些其它具體實施例中會形成 不此接又之不可溶聚合物數量。在某些具體實施例中，該 98811.doc 200538281 異酉太酸酯與對酉太酸酯 夂酉曰之4耳比為約〇·4〇至2·5:丨，而在苴 具體實施例中，則為約G.67^5 ··丨。 ’、 ㈣d體實Μ例中，該共聚_碳酸®1中之芳化物嵌段 、、貫貝上不含可連接該聚合物鏈之至少兩個單體單元 之酸酐鍵合物。在太 〜 本文令’貫負上不含酸酐鍵合物意指一 1於約28(^29G°C溫度下加熱該共聚S旨碳酸S旨，費時5分 在某一 /、體實例中，該共聚酯碳酸酯之分子量減少小In the aromatic compound structural unit, the bis-acrylic acid molecule is combined with an aromatic dicarboxylic acid molecular group, and the aromatic dicarboxylic acid molecular group may be a monocyclic molecular group, for example, an isophthalate or Phthalates or derivatives thereof substituted with dentin; or polycyclic molecular groups, illustrative examples of which include diphenyldiamine, phenyl ether dicarboxylate, diphenylsulfone dicarboxylic acid Ester, diphenyl ketone dicarboxylic acid, monophenylthiodicarboxylic acid ester, or naphthalenedicarboxylic acid ester. In some embodiments, the polycyclic molecular group includes naphthalene-2,6-dicarboxylic acid ester; or a mixture of monocyclic and / or polycyclic aromatic monocarboxylic acid esters. In many specific embodiments, the aromatic, polyethylenic knife group is isophthalate and / or para-ester. One or both of these molecular clusters may exist. In a specific embodiment, the isophthalate and the terephthalate are present at a molar ratio in the range of about 0.20 to 5 · 0:!, And in another specific embodiment, the isophthalate It exists in a molar ratio with terephthalates in the range of about 025 to 01. When the molar ratio of the isophthalate to the terephthalate is greater than about 4.0: 1, the number of successive oligomers may be formed in some specific embodiments. When the Mo # ratio of the isophthalate to the terephthalate is less than about 0.25: 1, the number of insoluble polymers will be formed in some other specific embodiments. In some specific embodiments, the 9811.doc 200538281 isoearthate and parathionate ratio is about 0.40 to 2.5: 4, and in the specific embodiment, It is about G.67 ^ 5 ·· 丨. In the example of the solid body, the aromatic block in the copolymerization-carbonic acid 1 is not included in the anhydride block of at least two monomer units that can be connected to the polymer chain. In this article, the term “without anhydride bond” means that the copolymer is heated at a temperature of about 28 ° C (29 ° F to 29 ° C), which is carbonic acid, which takes 5 minutes in one instance. Small reduction in molecular weight of the copolyestercarbonate

' 〇而在其匕具體實施例中，則減少5%。 在該共聚®旨碳酸S旨之碳酸㈣段中，式（I)之R2各獨立為 衍生自二絲化合物之有機錢。就大部份而該，該聚合 物中至少約6G% R2基團總數為芳香族有機基團，且其差額 為脂肪族基團、脂環系、基團、或芳香族基團。適合之R2基 團包括（但不限於）間_伸苯基、對_伸苯基、4,4，-雙伸苯基、 4,4’-雙（3,5-二甲基）伸苯基、2,2_雙（心伸苯基）丙烧及類似基 團，例如，該等相當於美國專利第4,217,438號中之名稱或 化學式（通有或特定）所揭示之經二羥基取代之芳香烴。在本 發明某些具體實施例中，二羥基化合物包括6_羥基_b(4，羥 苯基）-1，3,3-三甲基茚滿、4,4，_(3,3,5•三甲基環亞己基）雙 酚；1，1-雙（4-羥基-3-甲基苯基）環己烷；2,2-雙（4-羥苯基） 丙烷（通稱為雙酚-八）；4,4-雙（4-羥苯基）庚烷；2,2-雙（4-羥 基-3,5-二甲基苯基）丙烷；2,2_雙（‘羥基-3-甲基苯基）丙 烷；2,2-雙（4-羥基-3-乙基苯基）丙烷；2,2-雙（4-羥基-3-異丙 基苯基）丙烷；2,4f-二羥基二苯基甲烷；雙（2_羥苯基）甲烷； 雙（4-羥苯基）f烷；雙（4-羥基-5-硝基苯基）甲烷；雙（4-羥基- 98811.doc -10 - 200538281 2,6-二甲基-3-甲氧基苯基）甲烷；1,1-雙（4-羥苯基）乙烷；1，卜 雙（4-羥基-2-氯苯基）乙烷；2,2-雙（3-苯基-4-羥苯基）丙烷； 雙（4-羥苯基）環己基甲烷；2,2-雙（4-羥苯基）-1-苯基丙烷； 3,5,3’，5’_四氣_4,4_二羥苯基丙烷；2,4,-二羥笨基颯；2,6- 二羥基萘；氫醌、間苯二酚；經〇：1-3烷基取代之間苯二酚。 在一項特別具體實施例中，該二羥基化合物包括雙酚A。 適合之二羥基化合物亦包括該等含茚滿結構單元之二經 基化合物’例如，由式（II)代表之化合物，該化合物為3-(4-經苯基）·1，1，3-三甲基茚滿-5-醇，及由式（III)代表之化合 物’該化合物為1-(4-羥苯基）-1，3,3-三曱基茚滿-5-醇：'〇 In its specific embodiment, it is reduced by 5%. In the fluorene carbonate segment of the Copolymer® Carbonate S, each R2 of formula (I) is independently an organic coin derived from a difilament compound. For the most part, at least about 6G% of the total number of R2 groups in the polymer are aromatic organic groups, and the difference is an aliphatic group, an alicyclic system, a group, or an aromatic group. Suitable R2 groups include (but are not limited to) m-phenylene, p-phenylene, 4,4, -bis-phenylene, 4,4'-bis (3,5-dimethyl) phenylene Radicals, 2,2-bis (tetraphenyl) propane, and similar groups, for example, these are equivalent to the dihydroxyl-substituted compounds disclosed in the name or chemical formula (general or specific) of US Patent No. 4,217,438. Aromatic hydrocarbons. In certain embodiments of the present invention, the dihydroxy compound includes 6-hydroxy_b (4, hydroxyphenyl) -1,3,3-trimethylindane, 4,4, _ (3,3,5 • Trimethylcyclohexylene) bisphenol; 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane; 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol -8); 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 2,2-bis ('hydroxy- 3-methylphenyl) propane; 2,2-bis (4-hydroxy-3-ethylphenyl) propane; 2,2-bis (4-hydroxy-3-isopropylphenyl) propane; 2 ,, 4f-dihydroxydiphenylmethane; bis (2-hydroxyphenyl) methane; bis (4-hydroxyphenyl) f-alkane; bis (4-hydroxy-5-nitrophenyl) methane; bis (4-hydroxy -98811.doc -10-200538281 2,6-dimethyl-3-methoxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,4-bis (4-hydroxy- 2-chlorophenyl) ethane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; bis (4-hydroxyphenyl) cyclohexylmethane; 2,2-bis (4-hydroxybenzene) ) -1-phenylpropane; 3,5,3 ', 5'_tetrakis-4,4_dihydroxyphenylpropane; 2,4, -dihydroxybenzidine; 2,6-bis Hydroxynaphthalene; Hydroquinone, Resorcinol; Resorcinol substituted with 0: 1-3 alkyl. In a particularly specific embodiment, the dihydroxy compound includes bisphenol A. Suitable dihydroxy compounds also include those dimer compounds containing indan structural units, for example, a compound represented by formula (II), which is 3- (4-transphenyl) · 1,1,3- Trimethylindan-5-ol, and a compound represented by the formula (III) 'This compound is 1- (4-hydroxyphenyl) -1,3,3-trifluorenylindan-5-ol:

(Hi) 適合之經二羥基取代之芳香烴包括具有式（IV)之 2,2,2’，2’-四氫_1，1、螺雙[111_茚]二醇： 98811.doc -11 - 200538281(Hi) Suitable dihydroxy-substituted aromatic hydrocarbons include 2,2,2 ', 2'-tetrahydro_1,1, spirobis [111_indene] diol having formula (IV): 98811.doc- 11-200538281

其中R3各獨立選自單價烴基及_基；R4、R5、R6、及R7 各獨立為(：1-6烧基；R8及R9各獨立為Η或Cl_6烷基；且η各獨 立選自值自0至3之正整數。在一項特別具體實施例中，該 φ 2,2,2·，2’-四氫-1，1’-螺雙 ΠΗ_ 茚]二醇為 2,2,2，，2，-四氫_ 3,3,3’，3’_四甲基_1，1’_螺雙[11^茚]_6,6，_二醇（有時候稱為 ，，SBI，，）。 如本發明各具體實施例中所使用，該名詞”烷基"係意指 含碳與氫原子，及視需要尚含有，例如，選自元素週期表 第15、16及17族之原子之直鏈烷基、分支鏈烷基、芳烷基、 環烷基、雙環烷基、三環烷基及多環烷基。烷基可呈飽和 性或不飽和性，且可包含，例如，乙烯基及烯丙基。該名 • 詞”烧基"亦包括烷氧化物基團之烷基部份。在各種具體實 施例中，正烧基及分支鏈烧基為該等含有自i至約32個碳原 子之烧基，且包括非限制性說明實例··視需要經一或多種 選自Ci-C32烧基、CVCh環烧基或芳基之基團取代之Ci_C32 烷基；及視需要經一或多種選自Cl_c32烷基之基團取代之 5環烷基。一些特別的說明實例包括甲基、乙基、正一 丙基、異丙基、正-丁基、第二-丁基、第三_ 丁基、戊基、 新戊基、己基、庚基、辛基、壬基、癸基、十一烷基及十 98811.doc •12- 200538281 非限制性說明實例包括 烷基。環烷基及雙環烷基Wherein R3 is each independently selected from a monovalent hydrocarbon group and _ group; R4, R5, R6, and R7 are each independently (: 1-6 alkyl groups; R8 and R9 are each independently fluorene or Cl_6 alkyl group; and each η is independently selected from a value A positive integer from 0 to 3. In a particularly specific embodiment, the φ 2,2,2 ·, 2'-tetrahydro-1,1'-spirobiΠΗ_indene] diol is 2,2,2 ,, 2, -tetrahydro_ 3,3,3 ', 3'_tetramethyl_1,1'_spirobis [11 ^ indene] _6,6, _diol (sometimes called, SBI, As used in the specific embodiments of the present invention, the term "alkyl" means containing carbon and hydrogen atoms, and if necessary, for example, selected from Groups 15, 16 and 17 of the Periodic Table of Elements Atoms are straight-chain alkyl, branched-chain alkyl, aralkyl, cycloalkyl, bicycloalkyl, tricycloalkyl, and polycyclic alkyl. The alkyl group may be saturated or unsaturated, and may include, For example, vinyl and allyl. The name "alkyl" also includes the alkyl portion of the alkoxide group. In various embodiments, n-alkyl and branched alkyl are those containing Carbyl from i to about 32 carbon atoms, and includes non-limiting illustrative examples · If necessary, Ci_C32 alkyl substituted with one or more groups selected from Ci-C32 alkyl, CVCh ring alkyl or aryl groups; and 5 if substituted with one or more groups selected from Cl_c32 alkyl groups Cycloalkyl. Some specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, tert-butyl, pentyl, neopentyl, hexyl , Heptyl, octyl, nonyl, decyl, undecyl, and ten98811.doc • 12- 200538281 Non-limiting illustrative examples include alkyl. Cycloalkyl and bicycloalkyl

環丁基、環戊基、環己基、曱基環己基、環庚基、雙環庚 基及金剛烷基。在各種具體實施例中，芳烧基為令等八有 自7至約14個碳原子之芳烷基；這些包括（但不限於）：苄 苯基丁基、苯基丙基、及苯基乙基。在各種具體實施例^ 用於本發明各具體實施例中之芳基為該等含自6至Μ個環 碳原子之經取代或未經取代之芳基或雜芳基。這些芳美2 -些非限定說明實例包括視需要經一或多種選自:心 基、Cs-cu環烷基或芳基之基團取代之C6_Cis芳基。芳基2 一些特別說明實例包括經取代或未經取代之苯基、^苯 基、甲苯基及萘基。雜芳基包括該等含有自約3至約1〇個環 碳原子之雜芳基，且包括(但不限於)三畊基、嘧啶基、吡啶 基、呋喃基、噻唑啉基、喹啉基。 在-些具體實施例中，R2各為芳香族有機基團，且在特 別具體實施例中，其係為式（V)基團： (V) Α1 —γ—a: 其中v與v各為單環二價芳基，且γ為橋基，其中一或 兩個碳原子可分隔Al及Α2。就Υ而言，式⑽之該等自由 價化學鍵通常在Α^Α2之間位或對位處。其中❻有式⑺ 之化σ物為雙盼’且為簡潔起見，該名詞"雙朌"有時候在 文中係用以表示該經二經基取代之芳香烴；㈣，應該瞭 解若必要亦可使用此種類型之非雙酚化合物。 甘在式（V)巾，言，Al及Α2代表未絲狀伸苯基或 』取代之衍生物’其說明性取代基（―或多種）為烧基、稀 98811 .doc -13- 200538281 基、及齒素（特別為漠）。在許多具體實施例中，…及"代 表未經取代之伸苯基ϋΑ2可皆為對·伸苯基，但是其可 皆為鄰-伸苯基或間_伸苯基、或其中之一為鄰-或間-伸苯 基，而另一個為對-伸苯基。 橋基Υ為-種其中一或兩個原子可以將^從八2中分離出 之基團。在-項特別具體實施例中，—原子可以將^從八2 分離出。此種基團之實例為_C = 〇、_〇_、_s…_s〇 -或-S〇2_、Cyclobutyl, cyclopentyl, cyclohexyl, fluorenylcyclohexyl, cycloheptyl, bicycloheptyl and adamantyl. In various embodiments, the aralkyl group is an aralkyl group having 7 to about 14 carbon atoms; these include (but are not limited to): benzylphenylbutyl, phenylpropyl, and phenyl Ethyl. The aryl groups used in the various embodiments of the present invention are those substituted or unsubstituted aryl or heteroaryl groups containing from 6 to M ring carbon atoms. These Fangmei 2-some non-limiting illustrative examples include a C6_Cis aryl group optionally substituted with one or more groups selected from the group consisting of: cardiac, Cs-cucycloalkyl, or aryl. Aryl 2 Some specific examples include substituted or unsubstituted phenyl, phenyl, tolyl and naphthyl. Heteroaryl includes such heteroaryl groups containing from about 3 to about 10 ring carbon atoms, and includes, but is not limited to, trisyl, pyrimidinyl, pyridyl, furyl, thiazolinyl, quinolinyl . In some specific embodiments, R2 is each an aromatic organic group, and in a specific embodiment, it is a group of formula (V): (V) A1 —γ-a: where v and v are each A monocyclic divalent aryl group, and γ is a bridge group, in which one or two carbon atoms can separate Al and A2. As far as Υ is concerned, these free valence chemical bonds of formula 通常 are usually in the position of or opposite to A ^ A2. Among them, ❻ has the formula ⑺ σ is double hope 'and for the sake of brevity, the term " double 朌 " is sometimes used in the text to represent the aromatic hydrocarbon substituted by a dibasic radical; ㈣, we should understand that Non-bisphenol compounds of this type can also be used if necessary. Gan said in formula (V), that Al and A2 represent non-filament phenylene or "substituted derivative". The illustrative substituents (-or more) are alkynyl, dilute 98811.doc -13-200538281 , And dentin (especially desert). In many specific embodiments, ... and " represents unsubstituted phenylene ϋA2 may be p-phenylene, but they may all be o-phenylene or m-phenylene, or one of them Is ortho- or meta-phenylene, and the other is para-phenylene. The bridging group Υ is a group in which one or two atoms can separate ^ from 8-2. In a particularly specific embodiment, an atom may separate ^ from 8-2. Examples of such groups are _C = 〇, _〇_, _s ..._ s〇-or -S〇2_,

亞甲基、環己基亞甲基、2-[2.2.1]-雙環庚基亞甲基、伸2乙 基、異亞丙基、新亞戊基、環亞己基、環亞十五烧基、環 亞十二院基、及亞金㈣基。在某些具體實施例中，該等 基團為偕·伸烧基。然:而，其亦包括不飽和基團。基於本發 明目的之有效性及特別適合性、特別的雙㈣2,2.雙 苯基）丙烷（下文稱為雙酚A4BPA)，其中γ為異亞丙基且 A1及A2各為對-伸苯基。 根據任何未經反應之L3-二羥基苯分子團是否存在於如 下述之反應混合物内，該碳酸酯嵌段中之R2可以由衍生自 1，3-二羥基苯分子團之基團組成或至少部份包含該基團。因 此在本發明一項具體實施例中，該共聚酯碳酸酯包含具 有R2基團之碳酸醋嵌段，該R2基團係衍生自與該聚芳化物 甘人#又中之至少一個1，3 ·二經基苯分子團相同之二經基化合 物。在另一項具體實施例中，該共聚酯碳酸酯包含具有R2 基團（其係衍生自與該芳化物嵌段中之任何丨，3_二羥基苯分 子團不同之一髮基化合物）之碳酸酯嵌段。在又另一項具體 實施例中，該共聚酯碳酸酯包含具有R2基團群之混合物之 98811.doc -14- 200538281Methylene, cyclohexylene methylene, 2- [2.2.1] -bicycloheptyl methylene, 2ethyl, isopropylidene, neopentylene, cyclohexylene, cyclopentadecenyl , Central Asian Twelve Yuan Foundation, and Yakinji. In certain embodiments, these groups are fluorene. However: it also includes unsaturated groups. For the purpose and effectiveness of the present invention, special bisfluorene 2,2.bisphenyl) propane (hereinafter referred to as bisphenol A4BPA), where γ is isopropylidene and A1 and A2 are each p-extendylbenzene base. Depending on whether any unreacted L3-dihydroxybenzene molecular groups are present in the reaction mixture as described below, R2 in the carbonate block may consist of groups derived from 1,3-dihydroxybenzene molecular groups or at least A part contains this group. Therefore, in a specific embodiment of the present invention, the copolyestercarbonate includes a carbonate block having an R2 group, the R2 group is derived from at least one of the polyarylates, Ganren # 1, 3. Dimorphic compounds with the same diacylbenzene group. In another specific embodiment, the copolyestercarbonate contains an R2 group (derived from a hairpin compound that is different from any of the 3,2-dihydroxybenzene molecular groups in the aryl block) Carbonate blocks. In yet another specific embodiment, the copolyestercarbonate comprises a mixture of R811 groups 98811.doc -14- 200538281

碳酸酉旨嵌段’該r2基團群之混合物係衍生自二經化合物， 其至少一種與該聚芳化物嵌段中之任何二羥基苯分子 團相同，且其至少-種與該分子團不同。當衍生自二經基 化合物^基團群之混合物存在時，則與存在於聚芳化物 後段中之二經基化合物相同之二録化合物對該等與存在 於聚芳化嵌段中之二經基化合物不同之二經基化合物的莫 耳比，通常為約i : 999至999: i。在某些特別具體實施例 中，該共聚s旨碳酸a旨包含具有r2基團群之混合物之碳酸醋 欣段，該R2基團群之混合物係衍生自未經取代之間苯二 酚，經取代之間苯二酚、及雙酚八中之至少兩種。 本發明包括二嵌段、三嵌段、及多嵌段共聚酯碳酸酯。 在含芳化物鏈員之嵌段與含有機碳酸酯鏈員之嵌段間的化 學鏈合物，通常包括芳化物分子團之二酚殘基與有機碳酸The carbonic acid carbonate block 'the mixture of r2 groups is derived from a dimer compound, at least one of which is the same as any dihydroxybenzene molecular group in the polyarylate block, and at least one of which is different from the molecular group . When a mixture derived from a diradical compound is present, the same compound as the diradical compound present in the rear section of the polyarylate compound is the same as the diradical compound present in the polyarylate block. The molar ratio of the base compound is different from that of the base compound, and is usually about i: 999 to 999: i. In some specific embodiments, the copolymerization of carbonic acid and carbonic acid includes a carbonic acid ester segment having a mixture of r2 groups. The mixture of R2 groups is derived from unsubstituted resorcinol. Substitute at least two of resorcinol and bisphenol eight. The present invention includes diblock, triblock, and multiblock copolyestercarbonates. A chemical link between a block containing an aromatic chain member and a block containing an organic carbonate chain member, typically including diphenol residues of the aromatic compound and organic carbonic acid

酯分子團之（=0)-〇-分子團間的碳酸酯鏈合物，但是亦可包 含其它鍵合物種類，例如，酯及/或酸酐，在該等嵌段間之 一般碳酸酯鍵合物如式（VI)所示，其甲Rl&p如前文定義：(= 0) -0-carbonate chains between ester groups, but can also contain other bond types, such as esters and / or anhydrides, and general carbonate bonds between these blocks The compound is shown in formula (VI), and its R1 & p is as defined above:

在一項具體實施例中，該共聚酯碳酸酯實質上由在芳化 物嵌段與有機碳酸酯嵌段間具有碳酸酯鍵合物之二嵌段共 聚物組成。在另一項具體實施例中，該共聚酯碳酸酯實質 上由在芳化物叙段與有機碳酸酯末端嵌段間具有碳酸酯鍵 合物之三嵌段碳酸酯-酯_碳酸酯共聚物組成，一般而言，係 98811.doc -15- 200538281 自含有至少一個（且通常為兩個）經基末端部位之含n一 羥基苯芳化物之寡聚物（下文有時候稱為羥基末端性聚酉旨 中間物）’製備該在芳化物嵌段與有機碳酸酯嵌段間具有至 少一種碳酸酯鍵合物之共聚酯碳酸酯。In a specific embodiment, the copolyestercarbonate consists essentially of a diblock copolymer having a carbonate bond between an aromatic block and an organic carbonate block. In another specific embodiment, the copolyestercarbonate is essentially a triblock carbonate-ester-carbonate copolymer having a carbonate bond between an aromatic compound segment and an organic carbonate terminal block. The composition, generally speaking, is 98811.doc -15- 200538281 self-contained oligomers containing n-hydroxybenzene aromatic compounds containing at least one (and usually two) via the base terminal site (hereinafter sometimes referred to as hydroxyl terminal Polyimide intermediate) 'to prepare the copolyestercarbonate having at least one carbonate bond between the arylate block and the organic carbonate block.

在另一項具體實施例中，該共聚酯碳酸酯包含藉由如式 (VII)所示之碳酸酯鍵合物所聯結之芳化物：In another specific embodiment, the copolyestercarbonate comprises an aromatic compound linked by a carbonate bond as shown in formula (VII):

其中R、P、及η如上文定義，且該芳化物結構單元如式 (I)所述。可以於貫質上無與該經基末端性聚酯中間物不同 之任何二羥基化合物之情況下，自羥基末端性聚酯中間物 與碳酸酯先質之反應產生該含式（VII)之共聚酯碳酸酯。在 其它具體貫施例中，該共聚酯碳酸酯可包含具有，例如， 如文中所述之不同結構單元與不同結構之共聚酯碳酸酯群 的混合物。Wherein R, P, and η are as defined above, and the aryl structural unit is as described in formula (I). The reaction of the hydroxyl-terminated polyester intermediate with the carbonate precursor can produce the compound containing formula (VII) without any dihydroxy compound different from the radical-terminated polyester intermediate. Polyester carbonate. In other specific embodiments, the copolyestercarbonate may comprise a mixture having, for example, different structural units and copolyestercarbonate groups of different structures as described herein.

在適用於本發明之該等共聚醋碳酸酯，該等嵌段之分佈 可以使共聚物具有所要之芳化物嵌段對碳酸酯嵌段的重量 比例。在一項具體實施例中，該共聚酯碳酸酯含有約5至約 99重量％芳化物嵌段；在另一項具體實施例中含有約⑼至 約98重量％芳化物嵌段；在另一項具體實施例中，含有約 40至約98重量％芳化物嵌段；在另一項具體實施例中，含 有約60至約98重量％芳化物嵌段；在另一項具體實施例 中，含有約80至約96重量％芳化物嵌段；及在又另一項具 98811.doc -16- 200538281 體實施例t，含有約85至約95重量％芳化物嵌段。 該共聚酯碳酸酯薄膜可包含其它組，例如，本行已知之 添加劑，其包括（但不限於）安定劑、色彩安定劑、熱安定劑、 光安定劑、辅助性uv遮蔽劑、辅助性1；¥吸收劑、阻燃劑、 抗滴落劑、助流劑、增塑劑、醋交換抑制劑、抗靜電劑、 脫模劑、及著色劑’例如’金屬片、玻璃片及玻璃珠、陶 究顆粒、其它聚合物顆料、染料及顏料，其它可是有機物、 無機物或有機金屬物。在—項特別具體實施射，含共聚 酯碳酸酯之層實質上呈透明性。 該塗層之厚度足以保護各該下面之層、避免風蝕，特別 為避免UM射之作用，如敎所知，該塗層之厚度足以保 持任何含著色劑之層的光澤及色彩安定性。在一項具體實 施例中’ β亥塗層之厚度在約2至2,500微米範圍内，在另一 項具體實施例中，在約1()至25()微米範圍内，而在另一項具 體實施例中，則在約5(Μ75微米範圍内。 右必要，可以在該塗層上包含覆蓋層來提供，例如，抗 磨耗!·生或抗刮痕性。在一項特別具體實施例中’係提供聚 石夕氧覆蓋層在含共聚酯碳酸酯之塗層上。 、發月之夕層物件包括含具有碳酸酯結構單元之聚合物 的=層°在-項具體實施例中，該第二層之聚合物包含 種均聚碳酸醋。可加工成為薄膜或薄片之任何聚碳 2白適合。在各項具體實施例中’適合之聚碳酸醋包含 自單體之結構單元之聚合物，該等單體係選自由 等上述用於s亥欲段共聚酿碳酸醋之碳酸醋嵌段之化 98811.doc -17- 200538281 合物所組成的群組。在特別具體實施 ,A 於肀，聚碳酸酉旨簿腔: 包含雙酚Λ均-或共聚碳酸酯。在 專膜 ,^ 項特別具體實施例 中，聚碳酸酯薄膜包含雙酚Α均聚碳酸萨。 ^ 例中，聚碳酸酯薄膜包含至少一種第' /、匕具體貫施 〆禋弟—聚碳酸酯與至少一 種其它聚合物樹脂之摻合物，其實例 包括（但不限於）在結構 早凡或为子董或运兩項參數上與該第_聚碳酸醋不同之第 二聚碳酸醋；或聚醋；或加成聚合物，例如，丙烯腈-丁二 婦-苯乙婦共聚物或丙婦腈.苯乙烤_丙缚酸共聚物。 該第二層可包含其它組份，例如，本行已知之添加劑， 其包括（但不限於）安定劑、色彩安定劑、熱安定劑、光安定 劑、UV遮蔽劑、uv吸收劑、阻燃劑、抗滴落劑、助流劑、 增塑劑、醋交換抑制劑、抗靜電劑、脫模劑、填料、及著 色劑’例如’金屬[玻璃片及玻璃珠、陶瓷顆粒、其它 聚合物顆粒、染料及顏料，該著色财以有機物、無機物 或有機金屬物。在一項特別具體實施例中，第二層尚包含 至少一種著色劑。在另一項特別具體實施例中，第二層兼 含雙酚A聚碳酸醋及至少一種選自由染料、顏料、玻璃片、 及金屬片所組成之群組之著色劑。在—項㈣具體實施例 中，金屬片包括鋁片。在另一項特別具體實施例中，金屬 片包括大小為約20-70微米之紹片。著色劑之其它實例包括 (但不限於）Solvent Yell〇w 93、Solvent Yell〇w 163、solventIn the copolyacetate carbonates suitable for use in the present invention, the distribution of the blocks may allow the copolymer to have the desired weight ratio of arylate block to carbonate block. In a specific embodiment, the copolyestercarbonate contains about 5 to about 99% by weight of arylate blocks; in another specific embodiment contains about ⑼ to about 98% by weight of arylate blocks; in another In a specific embodiment, it contains about 40 to about 98% by weight of arylate blocks; in another specific embodiment, it contains about 60 to about 98% by weight of arylate blocks; in another specific embodiment Containing about 80 to about 96% by weight of arylate blocks; and in yet another embodiment 98988.doc -16-200538281 embodiment t, containing about 85 to about 95% by weight of arylate blocks. The copolyestercarbonate film may include other groups, for example, additives known to the bank, including, but not limited to, stabilizers, color stabilizers, heat stabilizers, light stabilizers, auxiliary UV shielding agents, auxiliary properties 1; ¥ absorbent, flame retardant, anti-dripping agent, glidant, plasticizer, vinegar exchange inhibitor, antistatic agent, release agent, and coloring agent 'such as' metal sheet, glass sheet and glass beads , Ceramic particles, other polymer particles, dyes and pigments, others can be organic, inorganic or organic metal. In the above-mentioned embodiment, the copolyester carbonate-containing layer is substantially transparent. The thickness of the coating is sufficient to protect the underlying layers and to avoid wind erosion, especially to avoid the effects of UM radiation. As known, the thickness of the coating is sufficient to maintain the gloss and color stability of any colorant-containing layer. In one embodiment, the thickness of the β-sea coating is in the range of about 2 to 2,500 microns, in another embodiment, in the range of about 1 () to 25 () microns, and in another In a specific embodiment, it is in the range of about 5 μm. Right, if necessary, a cover layer may be provided on the coating to provide, for example, abrasion resistance or scratch resistance. In a particularly specific embodiment Zhong 'is to provide a polysilicone oxygen coating on a coating containing a copolyestercarbonate. The article of the moonlight evening layer includes a layer containing a polymer having a carbonate structural unit. In the specific embodiment The polymer of the second layer contains a kind of homopolycarbonate. Any polycarbonate that can be processed into a film or sheet is suitable. In various embodiments, the 'suitable polycarbonate contains a structural unit from a monomer. Polymers, these single systems are selected from the group consisting of the above-mentioned compounds of the carbonate block used for the copolymerization of carbonated vinegar in the above-mentioned stage. Yu Li, Polycarbonate: Includes bisphenol Λ homo- or copolycarbonate. In particular embodiments of the film, the polycarbonate film includes bisphenol A homopolycarbonate. ^ In the example, the polycarbonate film includes at least one kind of polycarbonate and polycarbonate. Blends of at least one other polymer resin, examples of which include (but are not limited to) a second polycarbonate that differs from the first polycarbonate in two parameters: its structure is early or it is a subsidiary of the company; or Vinegar; or an addition polymer, such as an acrylonitrile-butadiene-acetophenone copolymer or a propionitrile. Acetophenone-propionic acid copolymer. This second layer may contain other components, such as Known additives, including (but not limited to) stabilizers, color stabilizers, heat stabilizers, light stabilizers, UV shielding agents, UV absorbers, flame retardants, anti-dripping agents, glidants, plasticizers Agents, vinegar exchange inhibitors, antistatic agents, release agents, fillers, and coloring agents such as' metal [glass flakes and glass beads, ceramic particles, other polymer particles, dyes and pigments, the coloring property is organic, inorganic Or organometallics. In a particular embodiment The second layer still contains at least one coloring agent. In another specific embodiment, the second layer contains bisphenol A polycarbonate and at least one selected from the group consisting of dyes, pigments, glass flakes, and metal flakes. Group of coloring agents. In the specific embodiment of the item, the metal sheet includes an aluminum sheet. In another particular embodiment, the metal sheet includes a sheet having a size of about 20-70 microns. Other examples of the colorant Including (but not limited to) Solvent Yell〇w 93, Solvent Yell〇w 163, solvent

Yellow 114/Disperse Yellow 54、Solvent Violet 36、SolventYellow 114 / Disperse Yellow 54, Solvent Violet 36, Solvent

Violet 13 ^ Solvent Red 195 ^ Solvent Red 179 ^ Solvent Red 135 ^ Solvent Orange 60 ^ Sovlent Green 3 ^ Solvent Blue 97 ^ 98811.doc -18- 200538281Violet 13 ^ Solvent Red 195 ^ Solvent Red 179 ^ Solvent Red 135 ^ Solvent Orange 60 ^ Sovlent Green 3 ^ Solvent Blue 97 ^ 98811.doc -18- 200538281

Solvent Blue 104、Solvent Blue 101、Macrolex Yellow E2R、 Disperse Yellow 201、Disperse Red 60、Diaresin Red K、 Colorplast Red LB、Pigment Yellow 183、Pigment Yellow 138、Pigment Yellow 110、Pigment Violet 29、Pigment Red 209、Pigment Red 202、Pigment Red 178、Pigment Red 149、 Pigment Red 122、Pigment Orange 68、Pigment Green 7、 Pigment Green 36、Pigment Blue 60、Pigment Blue 15:4、 Pigment Blue 15:3、Pigment Yellow 53、Pigment Yellow 184、Pigment Yellow 119、Pigment White 6、Pigment Red 101、Pigment Green 50、Pigment Green 17、Pigment Brown 24、Pigment Blue 29、Pigment Blue 28、Pigment Black 7、 翻酸鉛、鉻酸錯、硫化錦、績基>6西化鑛、及硫化編。增量 及強化填料之實例包括（但不限於）矽石、矽酸鹽、沸石、二 氧化鈦、石粉、玻璃纖維或玻璃珠、碳纖維、石墨、碳酸 鈣、滑石、雲母、鋅鋇白、氧化鋅、矽酸锆、氧化鐵、矽 蕩土、碳酸妈、氧化鎮、氧化鉻、氧化結、氧化紹、碎石 英、煅土、滑石、高嶺土、石棉、纖維素、木粉、軟木、 棉及合成織物纖維、特別為強化纖維，例如，玻璃纖維、 碳纖維、及金屬纖維。 在一項具體實施例中，該第二層之厚度在約2至2,500微 米範圍内，在另一項具體實施例中，在約10至1，〇〇〇微米範 圍内，且在另一項具體實施例中，在約50至600微米範圍 内。一黏著層可視需要存在於該含共聚酯碳酸酯塗層與該 含碳酸酯結構單元第二層之間。在各項具體實施例中，該 98811.doc -19- 200538281 視^要選用之勒rg 7 —· 3 G 3，該等本技藝已知可以使含碳酸 0日結構單兀之命人 一 * 口物之表面或層得到黏著性的化合物。在 二具體實施例中，該視需要選用之黏著層具透明性，且 =一項具體實施例中，該視需要選用之黏著層之顏色與 該第二層相同。Solvent Blue 104, Solvent Blue 101, Macrolex Yellow E2R, Disperse Yellow 201, Disperse Red 60, Diaresin Red K, Colorplast Red LB, Pigment Yellow 183, Pigment Yellow 138, Pigment Yellow 110, Pigment Violet 29, Pigment Red 209, Pigment Red 202, Pigment Red 178, Pigment Red 149, Pigment Red 122, Pigment Orange 68, Pigment Green 7, Pigment Green 36, Pigment Blue 60, Pigment Blue 15: 4, Pigment Blue 15: 3, Pigment Yellow 53, Pigment Yellow 184, Pigment Yellow 119, Pigment White 6, Pigment Red 101, Pigment Green 50, Pigment Green 17, Pigment Brown 24, Pigment Blue 29, Pigment Blue 28, Pigment Black 7, Lead Tartrate, Chromic Acid, Sulfur, Sulfur, Baseline > 6 Western chemical ore, and sulfur knitting. Examples of extender and reinforcing fillers include, but are not limited to, silica, silicate, zeolite, titanium dioxide, stone powder, glass fiber or glass beads, carbon fiber, graphite, calcium carbonate, talc, mica, zinc barium white, zinc oxide, Zirconium silicate, iron oxide, siliceous earth, carbon dioxide, oxidized town, chromium oxide, oxidized oxide, sintered oxide, crushed quartz, calcined earth, talc, kaolin, asbestos, cellulose, wood flour, cork, cotton and synthetic Textile fibers, especially reinforcing fibers, such as glass fibers, carbon fibers, and metal fibers. In a specific embodiment, the thickness of the second layer is in a range of about 2 to 2,500 microns, in another specific embodiment, in a range of about 10 to 1,000 microns, and in another In a specific embodiment, it is in the range of about 50 to 600 microns. An adhesive layer may be present between the copolyester-containing carbonate coating and the second layer of the carbonate-containing structural unit as required. In various specific embodiments, the 98811.doc -19- 200538281 depends on the choice of Le rg 7 — · 3 G 3, which is known in the art to make the 0-day structure containing carbonic acid a fatal person Adhesive compounds are obtained on the surface or layer of the mouthpiece. In the two specific embodiments, the optional adhesive layer is transparent, and in one embodiment, the color of the optional adhesive layer is the same as that of the second layer.

本發明多層物件φ夕、奋人I — 之適曰基片包含至少一種含聚丙烯結 單X之來0物。在本文中，該名詞”聚丙稀"係指含衍生 自丙稀之結構單元之聚合物，且其包括均聚丙稀及含衍生 自丙稀之結構單元之共聚物。在某些具體實施例中，該聚 丙烯可以是具有至少約70重量％、或至少約80重量％、或至 少約90重$ %衍生自丙稀之聚合反應之結構單元的共聚 物0 含聚丙烯之基片可包括官能化或非官能化聚丙烯、或官 能化與非官能化聚合物之混合物。適合之含聚丙烯基片之 說明實例包括丙烯之無規、接枝、及嵌段共聚物，其進一 v3至冋約30重里％衍生自CyCw α烯烴（其包括芳香族 α烯烴）之結構單元。在一項特別具體實施例中，適合之α 烯烴為乙烯。在其它具體實施例中，適合之基片包括，藉 由聚丙烯均聚物或含聚丙烯共聚物與至少一種選自由乙烯 基羧酸或酸酐、丙烯酸、甲基丙烯酸、順丁烯二酸、及衣 康酸、衣康酸酐、反丁稀二酸、蘋果酸、及順丁烯二酸與 反丁烯二酸及一元醇之單酯類所組成之群組的極性官能基 化劑’進行之反應所形成之酸-或酸酐·官能基化聚丙稀均聚 物或共聚物。應瞭解在某些具體實施例中，酸及酸野官能 98811.doc -20- 200538281 性皆可同時存在於含聚丙烯基片上。在又其它具體實施例 中’適合之基片包括藉由，例如，經酸官能基化（且特別為 經酸酐官能基化）之聚丙烯與含至少一個第一或第二胺基 之官能基化劑的反應所形成之經胺官能基化聚丙烯。其說 月貫例包括（2、伸烧基一胺；乙二胺、丙二胺、丁二胺、 己私：，來氧化伸烧基一 fe , N -烧基（2、伸烧基二胺； Ν-烷基α、ω乙二胺；Ν-己基乙二胺；雙胺基烷基）芳 族化合物；對-伸二甲苯基二胺及間_伸二甲苯基二胺。在某 些具體實施例中，如根據ASTM D790於23°C下測定，較佳 聚丙烯之彎曲模數為每。C平方吋至少約ι〇〇,〇〇〇碎（689百萬 帕）。在其它具體實施例中，當根DI 238於216公 斤及200°C下測定時，聚丙烯之熔流指數為每1〇分鐘約〇1 至約50克，較佳為每1〇分鐘約i至約3〇克。含聚丙烯之基片 尚包合上述均聚物與共聚物之摻合物。在其它具體實施例 中，含聚丙烯之基片包含上述均聚物及共聚物與至少一種 熱塑性材料之摻合物。適合之熱塑性材料之說明實例包括 (但不限於）聚伸苯基醚、聚醯胺、聚酯、聚醚醯亞胺、聚乙 烯及聚苯乙烯。在一項特別具體實施例中，含聚丙烯之基 板包含聚丙烯均聚物或共聚物與聚（2,心二甲基·丨，4_伸苯基 醚）之混合物。在另一項說明具體實施例中，適合之含聚丙 烯基片為熱塑性聚烯烴，亦稱為”TP〇，，。 在其中含聚丙烯基片為均聚丙烯之具體實施例中，該均 聚丙烯之結晶物含量通常為至少約2〇%，較佳為至少約 30〇/。。在另一項具體實施例中，均聚丙烯基片之結晶性含 98811.doc 21 200538281 量為小於約90%或小於約80%。 對於該含聚丙烯基片層之厚度並無特別限制，其限制條 件為可以將含該基片之多層物件加工成最終所要型式。在 一項具體實施例中，該含聚丙烯之基片層之厚度在約2至 12,5〇〇微米範圍内，在另一項具體實施例中，在約5至1〇,〇⑼ 锨米範圍内，在另一項具體實施例中，在約1〇至6,〇〇〇微米 範圍内，在另一項具體實施例中，在約1〇至2,5〇〇微米範圍 内，在另一項具體實施例中，在約1〇至1，〇〇〇微米範圍内， • 在另一項具體實施例中，在約1〇至6〇〇微米範圍内，在另一 項具體實施例中，在約10至375微米範圍内，在另一項具體 實施例中，在約20至300微米範圍内，在另一項具體實施例 中，在約20至250微米範圍内，且在另一項具體實施例中， 在約25至175微米範圍内。 含聚丙烯之基片層可額外含有本行已知之添加劑，其包 括（仁不限於）著色劑、顏料、染料、抗衝擊改質劑、安定劑、 φ & I安定劑、熱安定劑、光安定劑、UV遮蔽劑、UV吸收劑、 阻燃劑、抗滴落劑、填料、助流劑、增塑劑、醋安定換抑 制脅丨抗靜電劑、及脫模劑。在本發明一項具體實施例中， 含聚丙稀之基片亦可合併至少一種填料及/或著色劑。增量 及增化劑、與著色劑之實例包括發石1酸鹽、漭石、二 氧化鈦、石粉、玻璃纖維或玻璃珠、碳纖維、碳黑、石墨、 碳酸鈣、滑石、雲母、鋅鋇白、氧化鋅、矽酸锆、氧化鐵、 石夕:桌土、碳酸鈣、氧化鎂、氧化鉻、氧化锆、氧化鋁、碎 石英仏土、滑石、兩嶺土、石棉、纖維素、木粉、軟木、 98811.doc •22- 200538281 棉及α成織物纖維、特別為強化填料，例如，玻璃纖維、 碳纖維、及金屬纖維、與著色劑，例如，金屬片、玻璃片. μ璃m顆粒、其它聚合物顆粒、染料及顏料，該. 者色劑可以是有機物、無機物或有機金屬物。 本發明之多層物件包含至少一種含經胺官能基化之聚丙 烯與聚胺基曱酸醋之反應產物的黏著層。在本發明某些且 體實施例中’該黏著層可視需要包含未經胺官能基化之第 聚丙稀纟#特別具體實施例中，該第二聚丙婦包含 適於作為基片層之任何聚丙稀。在另一項特別具體實施例 中’該第二聚丙稀包含與存在於基片層之聚丙烯相同之聚 丙烯。 在本文中，該經胺官能基化之聚㈣係指經胺官能基化 之聚丙締均聚物或共聚物、或其混合物。經胺官能基化之 聚丙烯可衍生自（但不限於）適於作為上述基板層之任何聚 丙烯。可藉由任何已知製法製備經胺官能基化聚丙烯，且 其可包括第一經胺官能基化聚丙烯、第二經胺官能基化聚 丙稀或第一及第二經胺官能基化聚丙稀。在一項具體實 施例中，可藉由⑴帶有至少一種胺反應性基團之聚丙烯（有 時候在下文稱為胺反應性聚丙烯）及（Η)帶有至少兩種胺基 (其可皆為第一胺、或可皆為第二胺、或其中之一可為第一 胺，而另一個為第二胺）之胺化合物的反應以製備適合之經 ♦ 胺s能基化聚丙烯。雖然本發明並不受限於任何操作理 · 淪，咸信在該胺化合物上僅有一種統計學上高比例之胺與 π有胺反應性基團之聚丙烯反應，因此可製備帶有游離態 988il.doc -23- 200538281 胺基之官能基化聚丙熵。黑女 娜帶有胺反應性基團之聚丙稀實例 包含该專帶有至少一籍；H & &於 禋、自由酸、酯、及酸酐所組成之群 組之官能基的聚丙烯。在特別具體實施例中，帶有胺反應 性基團之聚丙烯實例，可衍生自熔態或固態法中之聚丙稀 與乙烯基叛酸或酸酐、丙稀、甲基丙烯酸、順丁稀二酸、 順丁稀二酸肝、衣康酸、衣康酸酐、反丁稀二酸、蘋果酸 或順丁：二酸及反丁烯二酸與一元醇之反應。應瞭解在某 些具體實施例中，gt及酸酐官能性可同時皆存在於帶有胺 反應性基團之聚丙4上 '經胺官能化聚丙烯之製法實例係 示於Q-W.Lu等人，Macromolecular Symposia，Volume 198, ΡΡ· 221-232(2003)中。 在各項具體實施例中，適用之聚胺基甲酸酯包含本技藝 已知可以使含碳酸酯結構單元之聚合物之表面或層具有黏 著性的熱塑性聚胺基甲酸酯。熱塑性聚胺基甲酸酯通常包 各衍生自多元醇鏈（其係藉由衍生自至少一種有機二異氰 酸醋及至少一種視需要選用之鏈增長劑之硬斷片而連接在 起）之結構單元。該等多元醇鏈通常被稱為軟斷片，其可 以產生低溫徺性及室溫彈性。一般而言，該軟斷片之濃度 愈南’該聚胺基甲酸酯之模數、抗拉強度、及硬度愈低、 而伸長率會增加。 在某些具體實施例中，供熱塑性聚胺基甲酸酯之多元醇 包括（但不限於）至少一種選自由聚醚多元醇、聚酯多元醇及 其混合物所組成之群組之多元醇。在一些特別具體實施例 中’熱塑性聚胺基曱酸酯包含衍生自實質上直鏈之聚醚多 98811.doc -24- 200538281 :醇或聚醋多元醇及鏈增長劑(其係選自由c2-Cl。二酵所組 紅之群組）之結構早凡。（^‘二醇鏈增長劑之說明實例包 括（但不限於）乙二醇、〗，弘丙二 > 哔 I4· 丁一醇、1，5-戊二醇、 1，6 -己一醇、新戊二醇、I〆 — 衣己一甲醇；氫醌雙_(羥乙基） 醚；環己二醇（1，4_、1 3_、及1 汉丨，2_異構物）、異亞丙基雙（環 己醇），一乙二醇、三乙二醇、_ _ ^ 一丙一知、聚乙二醇；乙醇The multi-layered article of the present invention, Xi Xingren I—is suitable for the substrate including at least one kind of polypropylene-containing single X. In this context, the term "polypropylene" refers to polymers containing structural units derived from acrylic, and it includes homopolypropylene and copolymers containing structural units derived from polypropylene. In certain embodiments The polypropylene may be a copolymer having at least about 70% by weight, or at least about 80% by weight, or at least about 90% by weight of a polymer unit derived from a propylene polymerization reaction. The polypropylene-containing substrate may include Functionalized or non-functionalized polypropylene, or a mixture of functionalized and non-functionalized polymers. Illustrative examples of suitable polypropylene-containing substrates include random, grafted, and block copolymers of propylene, which range from v3 to冋 About 30% by weight of structural units derived from CyCw alpha olefins (including aromatic alpha olefins). In a particular embodiment, a suitable alpha olefin is ethylene. In other embodiments, suitable substrates include With polypropylene homopolymer or polypropylene-containing copolymer and at least one selected from the group consisting of vinyl carboxylic acid or anhydride, acrylic acid, methacrylic acid, maleic acid, and itaconic acid, itaconic anhydride, transbutylene Diacid, Acid- or acid anhydride-functionalized polypropylene formed by the reaction of a polar functionalizing agent 'in the group consisting of fruit acid, maleic acid and fumaric acid and monoesters of monoalcohols Homopolymers or copolymers. It should be understood that in some embodiments, both acid and acid wild functions may be present on a polypropylene-containing substrate at the same time. In other embodiments, it is suitable The substrate includes, for example, an amine formed by the reaction of an acid-functionalized (and particularly an anhydride-functionalized) polypropylene with a functionalizing agent containing at least one first or second amine group. Functionalized polypropylene. Its examples include (2, ethylene-based amine; ethylene diamine, propylene diamine, butylenediamine, hexane: to oxidize ethylene-based, N-alkyl ( 2. Dialkylene diamine; N-alkylα, ω ethylenediamine; N-hexylethylenediamine; bisaminoalkyl) aromatic compounds; p-xylylenediamine and m-xylylenediamine In certain embodiments, the flexural modulus of polypropylene is preferably per C as determined at 23 ° C according to ASTM D790. The square inch is at least about 500,000,000,000 (689 million Pa). In other specific examples, when the root DI 238 is measured at 216 kg and 200 ° C, the melt flow index of polypropylene is 1 per 1 About 0.1 to about 50 grams per minute, preferably about 1 to about 30 grams per 10 minutes. The polypropylene-containing substrate still contains the blend of the above homopolymers and copolymers. In other specific implementations In the example, the polypropylene-containing substrate includes a blend of the above homopolymers and copolymers with at least one thermoplastic material. Illustrative examples of suitable thermoplastic materials include, but are not limited to, polyphenylene ether, polyamide, Polyester, polyether, imine, polyethylene, and polystyrene. In a particularly specific embodiment, the polypropylene-containing substrate comprises a polypropylene homopolymer or copolymer and poly (2, xin dimethyl · 丨, 4-phenylene ether). In another illustrative embodiment, a suitable polypropylene-containing substrate is a thermoplastic polyolefin, also known as "TP0,". In a specific embodiment where the polypropylene-containing substrate is a homopolypropylene, the The crystalline content of polypropylene is usually at least about 20%, preferably at least about 30%. In another embodiment, the crystallinity of the homopolypropylene substrate is 98811.doc 21 200538281 in an amount of less than About 90% or less than about 80%. There is no particular limitation on the thickness of the polypropylene-containing substrate layer, and the limitation is that the multilayer object containing the substrate can be processed into the final desired type. In a specific embodiment The thickness of the polypropylene-containing substrate layer is in a range of about 2 to 12,500 microns, in another specific embodiment, in a range of about 5 to 10,000,000 μm, in another In a specific embodiment, in a range of about 10 to 6,000 microns, in another specific embodiment, in a range of about 10 to 2,500 microns, in another specific embodiment In the range of about 10 to 1,000 microns, in another specific embodiment, in the range of about 1 In the range of 600 to 600 microns, in another specific embodiment, in the range of about 10 to 375 microns, in another specific embodiment, in the range of about 20 to 300 microns, in another specific implementation For example, in the range of about 20 to 250 micrometers, and in another specific embodiment, in the range of about 25 to 175 micrometers. The polypropylene-containing substrate layer may additionally contain additives known to the bank, including ( Kernel is not limited to) colorants, pigments, dyes, impact modifiers, stabilizers, φ & I stabilizers, heat stabilizers, light stabilizers, UV shielding agents, UV absorbers, flame retardants, anti-drip Agents, fillers, glidants, plasticizers, vinegar stabilizers, antistatic agents, and mold release agents. In a specific embodiment of the present invention, a polypropylene-containing substrate may also incorporate at least one filler and / Or colorants. Examples of extenders and enhancers, and colorants include fluorite 1 acid salt, vermiculite, titanium dioxide, stone powder, glass fiber or glass beads, carbon fiber, carbon black, graphite, calcium carbonate, talc, mica , Zinc barium white, zinc oxide, zirconium silicate, iron oxide, stone Evening: table soil, calcium carbonate, magnesium oxide, chromium oxide, zirconia, alumina, crushed quartz vermiculite, talc, amphibian, asbestos, cellulose, wood flour, softwood, 98811.doc • 22- 200538281 cotton and Alpha fabric fibers, especially reinforcing fillers, such as glass fibers, carbon fibers, and metal fibers, and colorants, such as metal flakes, glass flakes. μ glass particles, other polymer particles, dyes and pigments, the The toner may be organic, inorganic, or organometallic. The multilayered article of the present invention includes at least one adhesive layer containing the reaction product of an amine-functionalized polypropylene and a polyacetate. In some aspects of the present invention, In the embodiment, the adhesive layer may optionally include a second polypropylene that is not amine functionalized. In a specific embodiment, the second polypropylene includes any polypropylene suitable as a substrate layer. In another particular embodiment, 'the second polypropylene contains the same polypropylene as the polypropylene present in the substrate layer. Herein, the amine-functionalized polyfluorene means an amine-functionalized polypropylene homopolymer or copolymer, or a mixture thereof. The amine-functionalized polypropylene may be derived from, but not limited to, any polypropylene suitable for use as the substrate layer described above. The amine-functionalized polypropylene may be prepared by any known method, and it may include a first amine-functionalized polypropylene, a second amine-functionalized polypropylene, or a first and a second amine-functionalized polypropylene. Polypropylene. In a specific embodiment, polypropylene with at least one amine-reactive group (sometimes referred to as amine-reactive polypropylene) and (ii) with at least two amine groups (which May be the first amine, or may be both the second amine, or one of them may be the first amine and the other is the second amine) to react with an amine compound to prepare a suitable polymer Acrylic. Although the present invention is not limited to any operation theory, only one statistically high proportion of amines on the amine compound reacts with polypropylene with amine-reactive groups, so it can be prepared with a free state. 988il.doc -23- 200538281 Amine functionalized polypropylene entropy. Examples of polypropylene with black amine-reactive groups include polypropylene that has at least one functional group consisting of H & H, free acids, esters, and anhydrides. In particular embodiments, examples of polypropylenes with amine-reactive groups can be derived from polypropylene and vinyl acid or anhydride, acrylic, methacrylic, and cis-butane diamine in the melt or solid state method. Acid, maleic acid liver, itaconic acid, itaconic anhydride, fumaric acid, malic acid or maleic acid: the reaction of diacid and fumaric acid with monohydric alcohol. It should be understood that in certain embodiments, both gt and anhydride functionality may be present on polypropylene 4 with amine-reactive groups. Examples of the method for preparing amine-functionalized polypropylene are shown in QW. Lu et al., Macromolecular Symposia, Volume 198, PP 221-232 (2003). In various embodiments, suitable polyurethanes include thermoplastic polyurethanes known in the art to impart adhesion to the surface or layer of polymers containing carbonate structural units. Thermoplastic polyurethanes typically contain a structure derived from a polyol chain (attached by a hard segment derived from at least one organic diisocyanate and at least one optional chain extender) unit. These polyol chains are often referred to as soft fragments, which can produce low temperature flexibility and room temperature elasticity. Generally speaking, the lower the concentration of the soft segment, the lower the modulus, tensile strength, and hardness of the polyurethane, and the elongation will increase. In certain embodiments, the polyol for the thermoplastic polyurethane includes, but is not limited to, at least one polyol selected from the group consisting of polyether polyols, polyester polyols, and mixtures thereof. In some particular embodiments, the 'thermoplastic polyamino acid esters comprise polyethers derived from substantially linear chains 98811.doc -24-200538281: alcohols or polyester polyols and chain extenders (which are selected from the group consisting of c2 -Cl. The red group of the two yeasts) has an early structure. (^ 'Illustrative examples of diol chain extenders include (but are not limited to) ethylene glycol, propylene glycol, acetone, acetone, acetone, acetone, etc.] Bet I4 · butanediol, 1,5-pentanediol, 1,6-hexanediol , Neopentyl glycol, I〆—Isohexane-methanol; hydroquinone bis_ (hydroxyethyl) ether; cyclohexanediol (1,4_, 1 3_, and 1 han, 2_ isomers), iso Propylene bis (cyclohexanol), monoethylene glycol, triethylene glycol, _ ^ propylene dizhi, polyethylene glycol; ethanol

胺、Ν·甲基二乙醇胺、及諸如此類；及上述任-種之混合 物。在其它特別具體實施财，熱塑性聚胺基f酸醋包含， 衍生自聚乙二醇、聚氧化丙二醇、聚氧化四己二醇、及四 氫咬鳴與環氧乙炫及/或環氧丙烧之共聚物的其卜種之 結構單元。適合之㈣多元醇之數量平均分子量通常為至 少400,較佳為至少125〇,且更佳為至少2，_，但是小於 2〇,〇〇〇，較佳小於1〇,000，且更佳小於8，_。 在又其它特別具體實施例中，熱塑性聚胺基甲酸酯包含 衍生自聚酯多元醇之結構單元，該聚酯多元醇係衍生自己 一酸及至少一種選自由C2_C1()二醇所組成之群組之二醇，其 說明實例包括上文列舉之二醇。熱塑性聚胺基甲酸酯亦可 包含衍生自其它聚酯多元醇之結構單元，該等聚酯多元醇 係衍生自使用，例如，乙二醇、乙醇胺及諸如此類冬起始 劑使η-己内酯進行之聚合反應，且其係藉由多羧酸（例如， 酜酸、對酞酸、琥珀酸、戊二酸、己二酸、壬二酸及類似 酸）與多羥醇（例如，乙二醇、丁二醇、環己烷二甲醇及諸如 此類）之酯化反應而製成。 用以製備熱塑性聚胺基曱酸酯之一般二異氰酸酯包括 98811.doc -25- 200538281 (但不限於）MDI(亞甲基二苯基二異氰酸_)，其包括其4,4,_Amines, N.methyldiethanolamine, and the like; and mixtures of any of the foregoing. In other specific implementations, the thermoplastic polyamino acid vinegar contains, derived from polyethylene glycol, polypropylene oxide, polytetrahexylene glycol, and tetrahydrobiting and ethylene oxide and / or propylene oxide The structural unit of the fired copolymer. The number average molecular weight of suitable fluorene polyols is usually at least 400, preferably at least 125, and more preferably at least 2, but less than 20,000, preferably less than 10,000, and more preferably Less than 8, _. In still other specific embodiments, the thermoplastic polyurethane comprises a structural unit derived from a polyester polyol which is derived from a monoacid and at least one selected from the group consisting of C2_C1 () diol Groups of diols, illustrative examples of which include the diols listed above. Thermoplastic polyurethanes may also contain structural units derived from other polyester polyols which are derived from use, for example, ethylene glycol, ethanolamine, and the like winter initiators such that Polymerization of esters by polycarboxylic acids (eg, osmic acid, terephthalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and similar acids) and polyhydric alcohols (eg, ethyl Glycol, butanediol, cyclohexanedimethanol and the like). Common diisocyanates used to make thermoplastic polyurethanes include 98811.doc -25- 200538281 (but not limited to) MDI (methylene diphenyl diisocyanate), which includes its 4,4, _

一異構物、2,4’-異構物及其混合物；六亞甲基二異氰酸酯、 異佛爾酮（iS〇Ph〇rone)二異氰酸酯、亞甲基雙（環己基共氰酸 酯）及其4,4’-異構物、2,4，-異構物及其混合物、及其所有幾 何異構物（其包括反式/反式、順式/反式 '順式/順式及其混 合物）、環伸己基二異氰酸酯、及其丨，2_異構物、u_異構物、 及1，4-異構物、卜甲基_2,5_環己基二異氰酸醋、丨_甲基_2,4_ 環伸己基二異氰酸醋、i•曱基_2,6環伸己基二異氰酸醋及 4,4’-異亞丙基雙（環己基異氰酸酯）、間_及對-伸苯基二異氰 酸醋、氣伸苯基二異氰酸醋、α，α，_伸二甲苯基二異氰酸醋、 2,4-及2’6-甲苯二異氰酸酯及後兩種異構物之混合物、甲苯 胺二異氰酸酯、1，5-萘二異氰酸酯、4,4ι_二異氰酸基二環己 基物、及其所有幾何異構物與混合物及諸如此類。亦包括Monoisomers, 2,4'-isomers and mixtures thereof; hexamethylene diisocyanate, isophorone (isophorone) diisocyanate, methylenebis (cyclohexyl cocyanate) And its 4,4'-isomers, 2,4, -isomers and mixtures thereof, and all geometric isomers thereof (which includes trans / trans, cis / trans' cis / cis And mixtures thereof), cyclohexyl diisocyanate, and its 2-isomers, u-isomers, and 1,4-isomers, methyl-2,5-cyclohexyl diisocyanate,丨 _methyl_2,4_ cyclohexyl diisocyanate, i • fluorenyl_2,6 cyclohexyl diisocyanate and 4,4'-isopropylidenebis (cyclohexyl isocyanate), M- and p-phenylene diisocyanate, p-phenylene diisocyanate, α, α, _xylylene diisocyanate, 2,4- and 2'6-toluene diisocyanate And mixtures of the latter two isomers, toluidine diisocyanate, 1,5-naphthalene diisocyanate, 4,4-m-diisocyanatodicyclohexyl, and all their geometric isomers and mixtures and the like. Also include

MDI之經改質型。在某些具體實施例中，適合之熱塑性聚 胺基甲酸酯包含該等硬度在介於約6〇。蕭氏(sh〇re)A與約 75。蕭氏D(其係藉由ASTM D224〇4IS〇 868測知）間之範圍 内的熱塑性聚基甲酸酯。在其它具體實施例中，如藉由 ASTM D-1238測知，適合之熱塑性聚胺基甲酸酯之熔流指 數為每10分鐘約4至100克，較佳為1〇至9〇克。該熱塑性聚 胺基甲酸酿可視需要包含至少一種填料，例如，結晶狀矽 石或石英、或碳黑。 可以於緊密混合之條件下，化合含經胺官能基化之聚丙 烯之/½合物及聚胺基甲酸酯以製備，該含經胺官能基化聚 丙烯與聚胺基甲酸酯之反應產物的黏著層。在一項特別具 98811.doc -26- 200538281 體實施例中，可以以熔態法（例如，使用擠製機、捏揉裝置、 輥磨機、高黏度混合裝置及諸如此類）化合含經胺官能基化 來丙稀之混合物及聚胺基曱酸酯。在一項特別具體實施例 中，可以以單一步驟擠製法化合該含經胺官能基化聚丙烯 ^混合物及聚胺基曱酸_，其係藉由將胺反應性聚丙烯及 胺化合物饋入擠製機之進料口孔以製備該擠製機前部份之 經胺官能基化聚丙烯，繼而，視需要進行去揮發作用，然 後將聚胺基甲酸酯饋入下游進料口。在本發明某些具體實 _ 施例中，可以在該經胺基官能基化聚丙婦與聚胺基甲酸酉旨 化合後，例如，該視需要選用之去揮發步驟後，添加視需 要選用之胺中止劑。適合之胺中止劑在本技藝中係為吾人 所熟知；其說明實例包括（但不限於）環氧基物、酸酐、酸、 嘮唑啉及異氰酸酯。 雖然本發明不受限於任何操作理論，咸信經胺官能基化 聚丙烯上之游離態胺基可以與胺基甲酸酯鍵合物或異氰酸 Φ 根端基（其係得自，例如，聚胺基甲酸酯之降解反應）反應， 以形成可作為聚丙烯及聚胺基甲酸酯之相容劑之聚丙烯_ 聚胺基甲酸酯共聚物。因此，在本發明另一項具體實施例 中，该黏著層包含聚丙烯_聚胺基甲酸酯共聚物。然後，該 共聚物之聚丙烯部份可以與含聚丙烯之基板相容，因此可 以使該等多層物件組份之間得到適合黏著性。經胺官能基 化聚丙烯與聚胺基甲酸酯之相容性摻合物之製法實例係示 於 Q._W.Lu 等人’ Macromolecular Symposia, volume 198, ρρ·221-232(2003)中。 98SU.doc -27- 200538281 该黏著層亦可視需要包含未經反應之胺官能基化聚丙 烯，或聚胺基甲酸酯或兩者。在本發明另一項具體實施例 中’該黏著層包含已相容之聚丙烯_聚胺基甲酸酯摻合物， 可藉由經胺官能基化聚丙烯與聚胺基甲酸酯之反應產物提 供該相容作用。未經胺官能基化之第二聚丙烯亦可視需要 存在於黏著層中。可以在該經胺官能基化聚丙烯與聚胺基 甲酸酯之緊密混合前、期間或後，藉由緊密混合步驟，使 該第二聚丙烯與經胺官能基化聚丙烯及聚胺基f酸酯化 合。在一項具體實施例中，可以將未經胺官能基化之第二 聚丙烯與胺反應性聚丙烯一起饋入該進料口、或與聚胺基 甲酸酯一起饋入下游進料口、或同時饋入該進料口及下游 進料孔。 在一項具體實施例中，該聚胺基甲酸酯對 聚丙稀之重量/重量比在介於約5:95與約98:2間:^ 内。在此範圍β，以黏著層之重量為基準計，該黏著層中 之聚胺基甲酸酯比例大於約2〇重量％、較佳大於約％重量 %’且更佳大於約40重量％。在此範圍内，以黏著層之總重 為基準計’該聚胺基甲酸S旨之含量亦較佳通f小於或等於 約90重量。/0’更佳小於或等於約85重量％，且最佳小於或等 於約80重量％。 當存在該未經胺官能基化之視需要選用之第二聚丙烯 時’黏著層中之各種聚合物樹月旨可以以任何所要重量比存 在，其限制條件為可得到該第二層與基板層間之適當黏著 性。以黏著劑之重量為基準計’在某些具體實施例中，該 98811.doc -28- 200538281 視需要選用之聚丙稀之含量可以在介於約5重量％與約8〇 重量％間之範圍内；在其它具體實施例中，係介於約5重量 %與約45重量％間之範圍内；在其它具體實施例中，係介於 約10重量％與約30重量％間之範圍内。 用於夕層物件中之该含經胺官能基化聚丙烯與聚胺基甲 酸酯之反應產物的黏著層，可以呈薄膜或薄片型式。在各 種具體實施例中，該黏著層之厚度可以在介於約8微米與約 2500微米間之範圍内，·在其它具體實施例中，係介於約25 籲微米與約2_微米間之範圍内；在其它具體實施例中，係 介於約50微米與約15〇〇微米間之範圍内；在其它具體實施 例中，係介於約1〇〇微米與約13〇〇微米間之範圍内；且在又 其它具體實施例中，係介於約5〇〇微米與約胸微米間之範 圍内。在-些其它具體實施例中，黏著層厚度可以在介於 約10微米與約650微米間之範圍内；在其它具體實施例中， 係介於約25微米與約400微米間之範圍内；且在又其它具體 實施例中’係、介於約5〇微米與約260微米間之範圍内。 在本發明之某些具體實施例中，該多層物件可包括⑴第 一黏著層，其包含經胺官能基化聚丙烯與聚胺基甲酸酉旨之 反應產物、及（ii)視需要選用之至少一層第二黏著層，其包 含熱塑性聚胺基曱酸醋，該視需要選用之黏著層係與該第 二層及第一黏著層互相接觸。該視需要選用之第二黏著層 之熱塑性聚胺基甲酸醋可以是，本技藝已知可以使含碳酸 醋結構單元之聚合物之表面或層具有黏著性的任何熱塑性 聚胺基甲酸醋。在-項特別具體實施例中，該視需要選用 98811.doc -29- 200538281 之第二黏著層之熱塑性聚胺基甲酸酯與該第一黏著層所使 用之熱塑性聚胺基甲酸酯相同。 在另一項具體實施例中，本發明係提供製備含文中所述 該等層組份之多層物件之方法。在某些具體實施例中，係 使孩含肷丨又共聚酯碳酸酯之塗層、及含碳酸酯結構單元之 聚合物的第二層，形成含至少兩層之含共聚酯碳酸酯/碳酸 酯之聚合物組件。可藉由已知方法，例如，藉由這兩種材 質之薄膜或薄片之多重擠出成形以製備此種組件。在其它 具體實施例中’可藉由層合法、或溶劑或熔態塗布法以製 備此種組件。在一項特別具體實施例中，係在熔方法中， 她用忒塗層至第二層上。適合之適用方法包括製備塗層之 個別薄片，繼而施用至第二層，或同時製備這兩層。因此， 可以使用下述方法，例如，模製法、壓縮成形法、熱成形 法、夕重射出成形法、多重擠出成形法、重疊模製法、多 擊式射出成形法、片狀成形法及先將該塗層薄膜配置在第 二層之表面上，然後通常在射出成形裝置中結這兩層（例 如，模内裝飾法）。彳以於本行已知條件下進行這些操作。 含塗層及第二層之組件可包括該等層之合併厚度。在某 些具體實施例中，此種組件之厚度在介於約ig微米與約 2500微米間之範圍内；在其它具體實施例中，係介於物 微米與約1_微米間之範圍内；在其它具體實施例中，係 介於約10微米與約500微米間之範圍内；且在又其它具體實 施例中，係介於約10微米與約250微米間之範圍内。貫 可藉由本技藝已知之方法，合併含塗層、第二層、黏著 98811.doc 200538281 層及基板之各該層以形成該多層物件。在一項具體實施例 中可藉由已知方法，合併含共聚酯碳酸酯/碳酸酯之聚合 物組件及個別黏著層與基板層以形成該多層物件。已知方 法包括（但不限於）層合法及壓縮成形法。或者，可以於製備 該組件之方法（例如，多重擠出成形法）後或期間，於該含共 聚酯碳酸酯/碳酸酯之聚合物組件附近形成該黏著層，並使 其成為該薄膜組件之不可缺部份，接著可以使用已知方法 (例如，藉由使用熱及壓力等之方法）直接在該基板層附近形 成。或者，可以在黏著層附近形成該第二層，其係藉由， 例如，一起直接共擠製各該層，繼而使用已知方法（其包括 層合法及壓縮成形法，但不限於此）形成具有共聚酯碳酸酯 塗層之組件。接著可以使用已知方法，在基板層附近直接 形成该組件。可視需要在模製前，使該含共聚酯碳酸酯/碳 酸酯之聚合物組件經熱成形，得到該物件之大概形狀。在 各種具體實施例中，可藉由已知方法（其包括層合法及壓縮 成形法，但不限於此）進行於一層附近形成另一層之步驟。 亦可施用含該塗層、第二層、及黏著層之結構至基板層， 其係藉由將該含塗層、第二層、及黏著層之結構裝入射出 成形機内，並將該基板射出在該結構之後。藉由該方法， 可進行模内裝飾及諸如此類。在一項具體實施例中，該基 板層之兩侧可接受其它各層，而在另一項具體實施例中， 其它各層僅施用至該基板層之一側。 一般而言，含本發明各層組份之該多層物件之特徵為除 耐候性外尚具有該基片層之一般有用性質，例如，改良初 98811.doc -31 - 200538281 光澤性、改良初色彩、改良抗紫外線㈣性及光澤維持性、 改良衝擊強度、及在其最終應用之抗有機溶劑性。根據，’ 例如’塗層/基板組合等之因素，該多層物件可具有回收· f生因此可利用再製原料作為進一步製備本發明物件之基 片。3亥多層物件通常幾乎無内熱應力，該内熱應力有時候 係自各層間之CTE失配所誘發。該多層物件亦可具有優異 環境安定性，例如，熱及水解安定性。在本發明具體實施 例中4夕層物件之9G度抗撕強度大於未使用黏結層或僅 使用熱塑性聚胺基甲酸醋所組成之黏結層所製成之類似多 層物件。在其它具體實施例中，該多層物件之9〇度抗撕強 度為每米至少7GG牛頓。在又其它具體實施例中，該多層物 件之90度抗撕強度為每米至少1750牛頓。 在一些特定具體實施例甲，可藉由一種選自以下方法所 、’且成之群組之方法製備該多層物件，該等方法⑴包括以下 步驟·⑷製備具有塗層與第二層之組件’及⑻合併該組件 與個別黏著層及基片層；該方法（ii)包括以下步驟··（a)製備 具有塗層與第二層之組件，⑻在基板層附近形成黏著層， 及（e)合併該組件及黏著層/基片層組合；及該方法⑴丨）包括 以下步驟：⑷製備具有塗層、第二層、及#著層之組件， 及（b)在基片層附近形成該組件。 可以製成之含本發明各層組份之多層物件包括供〇Vad . 應用之物件；供飛機、汽車、貨車、軍用交通工具（其包括 . 汽車、飛機、及水運交通工具）、小型摩托車、及摩托車等 之外部及内部組件，其包括儀表板、後圍側板、車門檻板、 98811.doc -32- 200538281 直立面板、水平面板、裝飾物、支柱、中間立柱、擋泥板、 車門、活動車頂、行李艙蓋、發動 保險横、飾帶、護樹、鏡框、支柱縫飾、=A modified version of MDI. In certain embodiments, suitable thermoplastic polyurethanes include such hardnesses between about 60. Shore A and about 75. Shaw D (as measured by ASTM D224040 ISO 868) is a thermoplastic polyurethane. In other specific embodiments, as measured by ASTM D-1238, the melt flow index of suitable thermoplastic polyurethanes is about 4 to 100 grams, preferably 10 to 90 grams, every 10 minutes. The thermoplastic polyurethane may optionally contain at least one filler, for example, crystalline silica or quartz, or carbon black. It can be prepared by combining the amine-functionalized polypropylene compound and polyurethane under intimately mixed conditions. The amine-functionalized polypropylene and polyurethane-containing Adhesive layer of reaction product. In a particular embodiment of 98811.doc -26- 200538281, the amine function can be combined in a molten state (for example, using an extruder, a kneading device, a roll mill, a high viscosity mixing device, and the like). It is a mixture of acrylamide and polyurethane. In a particular embodiment, the amine-functionalized polypropylene-containing mixture and the polyaminoacetic acid can be combined in a single-step extrusion method by feeding an amine-reactive polypropylene and an amine compound into the mixture. The feed hole of the extruder is used to prepare the amine-functionalized polypropylene in the front part of the extruder. Then, if necessary, devolatization is performed, and then the polyurethane is fed into the downstream feed inlet. In some specific embodiments of the present invention, after the amino-functionalized polypropylene is compounded with polyurethane, for example, after the devolatization step is used as needed, it can be added as needed. Amine stopping agent. Suitable amine termination agents are well known in the art; illustrative examples include, but are not limited to, epoxy, anhydride, acid, oxazoline, and isocyanate. Although the present invention is not limited to any theory of operation, the free amine group on the amine-functionalized polypropylene may be bonded to a urethane bond or an isocyanate Φ end group (which is derived from, for example, , Degradation reaction of polyurethane) reaction to form a polypropylene_polyurethane copolymer which can be used as a compatibilizer of polypropylene and polyurethane. Therefore, in another specific embodiment of the present invention, the adhesive layer comprises a polypropylene-polyurethane copolymer. Then, the polypropylene portion of the copolymer can be compatible with a substrate containing polypropylene, so that suitable adhesion can be obtained between the components of the multilayer object. An example of a method for preparing an amine-functionalized polypropylene-compatible polyurethane blend is shown in Q._W. Lu et al. 'Macromolecular Symposia, volume 198, ρρ 221-223 (2003) . 98SU.doc -27- 200538281 The adhesive layer may optionally contain unreacted amine-functionalized polypropylene, or polyurethane or both. In another embodiment of the present invention, 'the adhesive layer comprises a compatible polypropylene-polyurethane blend, which can be modified by amine-functionalized polypropylene and polyurethane. The reaction product provides this compatibility. A second polypropylene that is not amine-functionalized may also be present in the adhesive layer as required. Before, during or after the intimate mixing of the amine-functionalized polypropylene and polyurethane, the second polypropylene and the amine-functionalized polypropylene and polyamine can be made by the intimate mixing step. f. Ester compound. In a specific embodiment, a second polypropylene that is not amine-functionalized can be fed into the feed port together with an amine-reactive polypropylene or a downstream feed port together with a polyurethane. , Or both the feed inlet and the downstream feed hole. In a specific embodiment, the weight / weight ratio of the polyurethane to polypropylene is between about 5:95 and about 98: 2. In this range β, based on the weight of the adhesive layer, the proportion of polyurethane in the adhesive layer is greater than about 20% by weight, preferably greater than about %% by weight 'and more preferably greater than about 40% by weight. Within this range, based on the total weight of the adhesive layer, the content of the polyurethane S is preferably less than or equal to about 90 weight. / 0 'is more preferably less than or equal to about 85% by weight, and most preferably less than or equal to about 80% by weight. When the second polypropylene, which is optionally selected without amine functionalization, is present, the various polymer trees in the 'adhesive layer' can exist in any desired weight ratio, and the limitation is that the second layer and the substrate can be obtained Proper adhesion between layers. Based on the weight of the adhesive 'In certain embodiments, the content of the 98811.doc -28- 200538281 optionally used polypropylene can be in a range between about 5% by weight and about 80% by weight In other embodiments, the range is between about 5% by weight and about 45% by weight; in other embodiments, the range is between about 10% by weight and about 30% by weight. The adhesive layer containing the reaction product of the amine-functionalized polypropylene and polyurethane used in the layer object may be in the form of a film or a sheet. In various embodiments, the thickness of the adhesive layer may be between about 8 microns and about 2500 microns. In other embodiments, the thickness is between about 25 microns and about 2 microns. In other embodiments, the range is between about 50 microns and about 15,000 microns. In other embodiments, the range is between about 100 microns and about 13,000 microns. Within a range; and in still other embodiments, the range is between about 500 microns and about breast microns. In some other specific embodiments, the thickness of the adhesive layer may be in a range between about 10 microns and about 650 microns; in other specific embodiments, it is in a range between about 25 microns and about 400 microns; And in still other embodiments, the range is between about 50 microns and about 260 microns. In some specific embodiments of the present invention, the multi-layered article may include a first adhesion layer, which includes a reaction product of amine-functionalized polypropylene and polyurethane, and (ii) optionally selected At least one second adhesive layer, which contains thermoplastic polyurethane, and the optional adhesive layer is in contact with the second layer and the first adhesive layer as needed. The thermoplastic polyurethane used as the second adhesive layer optionally may be any thermoplastic polyurethane known in the art to make the surface or layer of the polymer containing the carbonate structural unit adhesive. In the particular embodiment, the thermoplastic polyurethane used in the second adhesive layer of 98811.doc -29-200538281 is selected as needed, and the thermoplastic polyurethane used in the first adhesive layer is the same. . In another specific embodiment, the present invention provides a method for preparing a multilayer article containing the layer components described herein. In some embodiments, the coating containing a copolyester carbonate and a second layer of a polymer containing carbonate structural units are formed to form a copolyester carbonate containing at least two layers / Carbonate polymer components. Such components can be made by known methods, for example, by multiple extrusion of films or sheets of these two materials. In other embodiments, such a component can be prepared by lamination, or solvent or melt coating. In a particularly specific embodiment, in the melting process, she coats the second layer with rhenium. A suitable suitable method includes preparing individual sheets of the coating and then applying to a second layer, or both. Therefore, the following methods can be used, for example, a molding method, a compression molding method, a thermoforming method, a re-injection molding method, a multiple extrusion molding method, an overlap molding method, a multi-shot injection molding method, a sheet molding method, and The coating film is disposed on the surface of the second layer, and then the two layers are usually bonded in an injection molding apparatus (for example, in-mold decoration method). Do these operations under known conditions in the bank. Components that include a coating and a second layer may include the combined thickness of these layers. In some specific embodiments, the thickness of such a component is in a range between about ig microns and about 2500 microns; in other specific embodiments, it is in a range between physical microns and about 1-micron; In other embodiments, the range is between about 10 microns and about 500 microns; and in still other embodiments, the range is between about 10 microns and about 250 microns. Through the methods known in the art, each layer including the coating layer, the second layer, the adhesive layer 98811.doc 200538281, and the substrate can be combined to form the multilayer object. In a specific embodiment, a polymer component containing a copolyestercarbonate / carbonate, and an individual adhesive layer and a substrate layer may be combined to form the multilayer object by a known method. Known methods include, but are not limited to, lamination and compression molding. Alternatively, the adhesive layer may be formed near the copolyestercarbonate / carbonate-containing polymer component after the method of preparing the component (for example, a multi-extrusion molding method) and become the thin-film component. Indispensable parts can then be formed directly near the substrate layer using known methods (for example, by using methods such as heat and pressure). Alternatively, the second layer may be formed near the adhesive layer, for example, by directly co-extruding each of the layers together, and then using a known method (which includes layer method and compression molding method, but is not limited thereto) Components with a copolyestercarbonate coating. The assembly can then be formed directly near the substrate layer using known methods. If necessary, before molding, the copolyestercarbonate / carbonate-containing polymer component is thermoformed to obtain the approximate shape of the object. In various embodiments, the step of forming another layer in the vicinity of one layer may be performed by known methods (including but not limited to layer lamination and compression molding). The structure containing the coating layer, the second layer, and the adhesive layer can also be applied to the substrate layer. The structure containing the coating layer, the second layer, and the adhesive layer is charged into the forming machine, and the substrate is Projected behind the structure. With this method, in-mold decoration and the like can be performed. In one embodiment, the other sides of the substrate layer can accept other layers, while in another embodiment, the other layers are applied to only one side of the substrate layer. Generally speaking, the multi-layer object containing the components of the present invention is characterized by having the general useful properties of the substrate layer in addition to weather resistance, such as improved glossiness, improved glossiness, improved initial color, Improved UV resistance and gloss retention, improved impact strength, and resistance to organic solvents in its final application. According to factors such as 'coating / substrate combination', the multi-layered article may have a recycling material, and thus a reprocessed material may be used as a substrate for further preparing the article of the present invention. Multi-layered articles are usually almost free of internal thermal stress, which is sometimes induced by CTE mismatches between layers. The multilayer article may also have excellent environmental stability, such as thermal and hydrolytic stability. In the specific embodiment of the present invention, the 9G-layer tear resistance of the four-layer object is greater than that of a similar multi-layer object made without using an adhesive layer or using only an adhesive layer composed of thermoplastic polyurethane. In other specific embodiments, the 90 degree tear resistance of the multilayer article is at least 7GG Newton per meter. In still other embodiments, the multilayer item has a 90 degree tear resistance of at least 1750 Newtons per meter. In some specific embodiments A, the multilayer object can be prepared by a method selected from the group consisting of the following methods, which include the following steps: ⑷ preparing a component having a coating and a second layer 'And ⑻ merge the component with individual adhesive layers and substrate layers; the method (ii) includes the following steps ... (a) preparing a component with a coating and a second layer, ⑻ forming an adhesive layer near the substrate layer, and ( e) merging the component and the adhesive layer / substrate layer combination; and the method ⑴ 丨) includes the following steps: ⑷ preparing a component having a coating layer, a second layer, and a substrate layer, and (b) near the substrate layer Form this component. Multi-layered articles containing various layers of the present invention that can be made include articles for 0Vad. Applications; for airplanes, cars, trucks, military vehicles (including cars, aircraft, and water vehicles), scooters, And motorcycle and other external and internal components, including dashboards, rear side panels, sill panels, 98811.doc -32- 200538281 upright panels, horizontal panels, decorative objects, pillars, center pillars, fenders, doors, Moving roof, luggage compartment cover, launching insurance cross, ribbon, tree guard, picture frame, pillar sewing, =

嵌條、車輪護蓋、前顯示器罩、門把手、擾流板、窗框、 頭燈迷框、頭燈、尾燈、尾燈罩、尾燈迷框、牌照板外殼、 車頂架、及腳踏板；供戶外交通工具及裝置之機殼、護罩、 儀表板&零件，風力渴輪翼及外殼；供電氣及電信裝置 之口蔓罩，戶外傢倶，飛機元件；船隻及船用設備，其包括 裝飾物、護罩、及外殼；舷外馬達外殼；測深計外殼、個 化上航行器’水上摩托車；水池；水療設備；熱浴桶； 皆梯覆蓋物；建築及結構應用，例如，上釉、屋頂、 由戶、地板、裝飾窗戶陳設或處理；供圖畫、油畫、海報、 及類似展示項目之已處理玻璃遮蓋物；光學透鏡；眼鏡； 橋用眼鏡，可植入式眼鏡；護牆板，及門；廚柜棱面； 經保護之平面藝術作品；戶外及室内標訪；供自動振員機 (ATM)之外罩、外殼、儀表板、及零件；供草坪及園藝拖拉 機剪草機、及工具（其包括草坪及園藝工具）之外罩、外殼、 儀表板及零件，窗飾、門部’·運動設備及玩具；供雪車 之外=、外殼、儀表板、及零件；休旅車儀表板及元件，· 遊樂場叹槪’鞋帶’·自塑膠-木材組合物製成之物件；高爾 '矿己A用事業坑覆蓋物；電腦外殼；桌上型電腦 外殼，手提式電腦外殼；膝上型電腦，掌握型電腦外殼； 監視器外殼；列印機外殼；鍵盤；傳真機（FAX machine)外 设’影印機外殼；電話外殼；電話座盤；行動電話外殼； 98811.doc -33- 200538281 無線電發報機外殼；無線電接收機外殼；燈飾；照明設備； 反射器；網路介面裝置外殼；變壓器外殼；冷氣機外殼； 供大眾運輸工具之包材或座塾材料；供火車、地下鐵、或 ，包材或座塾材料；計量器外殼；天線外殼；供人造 術星接收益之包材；覆膜頭盍及個人保護設備；覆膜合成 或天然織物；覆膜膠卷及相片；覆膜上漆物件；覆膜染色 物件，覆膜螢光物件；覆膜發泡體物件；及類似應用。本 發明進-步涵蓋對該等物件之額外製備操作法，例如，模 I内裝飾法、在油漆烘箱内烘乾、層合法及/或熱成形法，但 不限於此。 不需要進一步詳$，咸信熟悉本技藝者可藉由使用文中 之說明，完全利用本發明。以下實例係用以提供額外指導 、、α熟悉本技藝者來實踐本發明。所提供該等實例係僅用以 f示助成本申請案之教示之說明。因此，如附加申請專利 範圍中所疋義，這些實例無論如何並無意限制本發明。 —將試樣切成2.54厘米（cm)寬細條，並使用9〇度撕剝試驗以 母分鐘2·54厘米之十字頭分離速度，#用In_n測試裝置 (Modei 4505)測試黏著力之抗撕剝性。此種黏著性試驗^法 為熟悉本技藝者所熟知，且概述在，例如，美國專利第 3,965,057號中。本試驗程序中之測試裝置係由一系列可動 式輥或支架所組成，其可以使該試驗試樣以恆定9〇度角沿 著其全部未切割長度被撕剝。該裝置係由一系列^個^^ 厘米（其係幾何性附著於兩個側支架及基座上）所組成。可調 整這兩個下輥以致使該裝置可調整不同厚度之試驗試樣。 98811.doc -34 - 200538281 使用適合之頂夾器以固定該塑膠層。該試驗試樣之長為 15·2厘米’寬為2·54厘米。已確定—部份該試驗試樣仍維持 未黏結。各黏著性試樣測試至少3種試驗試樣。在實際測試 程序中，將該爽具附著於測試機之可動式機頭上，其附著 位置可以使該經撕剝塑膠層於試驗期間，與該試驗試樣形 成90度角。將該試驗試樣定位於夾具内，並將該未固定的 表面牢固夾緊。然後將該夾具釘在測試機之上機頭。該試 驗試樣上並沒有負荷物，接著將稱重裝置平衡至零。準備 自動記錄至少10.2厘米之撕剝距離之撕剝負載對該機頭之 位置。可忽略前2.54厘米之撕剝距離，自自動記錄曲線得 到撕剝塑膠層所需之負載。然後計算抗撕強度，其公式如 下： ?_剝離負載(牛頓） "試樣之寬度(米） 在下述實例中，該共聚酯碳酸酯-聚碳酸酯薄膜組件包含 共聚醋碳酸酯薄膜層及聚碳酸酯薄膜層。該共聚酯碳酸醋 薄膜包含具有衍生自間苯二酚、異酞酸、及對酞酸之丙婦 酸結構單元，及衍生自雙酚Α之碳酸酯結構單元的共聚酯碳 酸酯。該聚碳酸酯薄膜包含雙酚A聚碳酸酯。可藉由共擠製 0.254毫米厚之透明共聚酯碳酸酯薄膜及〇·5毫米厚之著色 聚碳酸酯層以製備該共聚酯碳酸酯-聚碳酸酯薄膜組件。衍 生自聚丙烯與順丁烯二酸酐，且包含約0.55重量％酸酐結構 單元之順丁烯二酸化聚丙稀，（Fusabond MZ-109D，下文稱 為PP-MA)，係得自Dupont。熱塑性聚胺基甲酸酯（Avalon 70AE ;下文稱為τρυ)及含有約90°/。聚丙烯結構單元之聚丙 98811.doc -35 - 200538281 烯無規共聚物（13M11級，下文稱為PP)，皆得自Huntsman。 含N-己基乙二胺（其係為一種第一-第二二胺）之二胺類係得 自Aldrich。一基板材料為含聚丙烯結構單元之ESCORENE PP8224樹脂，且其係得自ExxonMobil。 實例1 製備含經接枝胺基團之官能基化聚丙烯。以1 : 1莫MA對 二胺1 : 1之莫耳比製備PP-MA及N-己基乙二胺之混合物。 於180°C及40 rpm下在L/D = 25之16毫米共旋轉交纏雙軸螺 旋擠製機上擠製該混合物。使該熔體經由2毫米直徑圓模擠 製，在室溫水浴中經冷卻，並製粒。所得到之官能基化聚 丙烯在下文稱為PP-F1。 實例2 製備相容性TPU/PP摻合物。於200°C及70 rpm下，在雙軸 螺旋擠製機上擠製TPU、PP及實例1之官能基化聚丙烯 (PP-F1)之摻合物（其重量比為70/25/5)。該螺旋構型包含兩 個捏揉組件。該熔體係藉由2毫米直徑圓模擠製，在室溫水 浴中經冷卻，並製粒。得到相容性TPU/PP摻合物。 實例3 藉由壓縮成形法製備含⑴共聚酯碳酸酯-聚碳酸酯薄膜 組件、（ii)實例2之相容性TPU/PP摻合物及（iii)含ESCORENE 聚丙烯基板之多層物件。將5克（g)實例2之相容性TPU/PP摻 合物試樣壓製成〇· 18毫米（mm)厚之薄膜，然後切成大小為 6.4厘米（cm)x 12.7厘米之試樣。將含ESCORENE聚丙烯基片 射出以形成3.2毫米厚板。將ESCORENE板基片放在壓縮成 98811.doc -36- 200538281 形壓機内之3,2毫米厚TEFLON框（6.4厘米χ12·7厘米開口） 中，並將TPU/PP摻合物薄膜放在該基片上，並將共聚酯碳 酸酯-聚碳酸酯薄膜組件放在TPU/PP摻合物薄膜上，且聚碳 酸酯侧鄰接於該TPU/PP摻合物薄膜。於i7(TC上在該經加熱 壓板之間，將該組件預加熱5分鐘，然後使其接受2.76百萬 帕壓力，費時3分鐘。接著開啟該壓機，並移除經模製部份。 經發現’該共聚酯碳酸酯-聚碳酸酯薄膜組件對該基片之黏 著力很優異。90度抗撕強度為每米3748牛頓（N/m)。該抗撕 失效模式為界面黏結層/共聚酯碳酸酯-聚碳酸酯薄膜組 件、界面黏結層/基片、及内聚性基片失效之組合。 比較實例1 為比較目的，於與實例2相同之加工條件下，藉由擠製法 製備不含官能基化聚丙烯之非相容性Tpu/pp摻合物（其重 量比為70/30)。藉由壓縮成形法製備含⑴共聚酯碳酸酯_聚 碳酸酯薄膜組件、（ii)非相容性TPLNpp掺合物及（出）含 ESCORENE聚丙婦基片之多層物件。將5克τρυ/ρρ摻合物試 樣壓製成0.18毫米厚之薄膜，並切成大小為6·4厘米χι2·7厘 米之試樣。使用實例3所述之相同方法製備具有該等層組份 之多層物件。經發現，该共聚酯碳酸酯_聚碳酸酯薄膜組件 對该ESCORENE基片之黏著力很差。經發現，9〇度抗撕強 度小於525 N/m。 比較實例2 為比較目的，於如實例2之相同加工條件下，藉由擠製法 製備非相容性TPU/PP/PP-MA摻合物（其重量比為7〇/25/5)。 988il.doc -37- 200538281 藉由壓縮成形製備含⑴共聚酯碳酸酯-聚碳酸酯薄膜組 件、（u)TPU/PP/PP-MA摻合物及（出）含ESCORENE聚丙烯基 片之多層物件。將5克TPU/PP/PP-MA試樣壓製成〇·ΐ8毫米 厚之薄膜，並切成大小為6.4厘米xl2.7厘米之薄板。使用實 例3所述之相同方法製備具有該等層組份之多層物件。經發 現，该共聚酯碳酸酯-聚碳酸酯薄膜組件對該ESC〇RENE基 片之黏著力很差。經發現，90度抗撕強度小於525 N/m。 比較實例3 為比較目的，藉由壓縮成形法製備含⑴共聚酯碳酸酯· 聚碳酸酯薄臈組件、（ii)TPU及含esc〇rene聚丙烯基 片之多層物件。將5克TPU試樣壓製成0·18毫米厚之薄膜， 成大】為6·4厘米xl2.7厘米之薄板。使用實例3所述之 才Π方法裝備具有该等層組份之多層物件。經發現，丁？口 與基片間之黏著性很差。該物件會於τρυ與基片間之接觸 面處脫層，且其9〇度抗撕強度小於350 N/m。 雖然在一般具體實施例中已說明並描述本發明，但是本 發明並無意受限於其所示之細節，因為無論如何只要不違 本發月之精神，可以有各種修飾及代用物。因此，藉由 僅使用例订實驗法，熟悉本技藝者可想出文中所揭示之本 發明其它修飾及同等物，且如以下中請專利範圍所定義， 咸^所有該等修飾及同等物皆在本發明之精神及範圍内。 =中列舉之所有專利、專利申請案及已公佈論文係以引用 的方式併入本文中。 988ll.doc -38-Panels, wheel covers, front display covers, door handles, spoilers, window frames, headlight fans, headlights, taillights, taillight covers, fanlight fans, license plate housings, roof racks, and foot pedals ; Enclosures, shrouds, instrument panels & parts for outdoor vehicles and installations, wind thirsty wings and shells; mouthpieces for power supply and telecommunications devices, outdoor furniture, aircraft components; ships and marine equipment, Includes decorations, shrouds, and shells; outboard motor shells; depth sounder shells, personalised aircraft 'water scooters; pools; spa equipment; hot tubs; ladder ladder covers; architectural and structural applications, such as, Glazing, roof, home, floor, decorative window furnishing or treatment; processed glass coverings for pictures, paintings, posters, and similar display items; optical lenses; glasses; bridge glasses, implantable glasses; Wall panels and doors; Kitchen cabinet facets; Protected graphic art works; Outdoor and indoor bidding; ATM covers, enclosures, instrument panels, and parts; for lawn and garden tractor mowing machine And tools (including lawn and garden tools) covers, shells, dashboards and parts, window decorations, door parts, sports equipment and toys; snowmobiles, shells, dashboards, and parts; recreational vehicles Dashboards and components, · Playground sighs 'laces' · Objects made from plastic-wood composition; Gore's mine cover for business pits; computer cases; desktop computer cases, portable computers Shell; laptop computer, master computer shell; monitor shell; printer shell; keyboard; fax machine (FAX machine) peripherals' copier shell; phone shell; phone holder; mobile phone shell; 98811.doc -33- 200538281 Radio transmitter housing; Radio receiver housing; Lighting; Lighting equipment; Reflector; Network interface device housing; Transformer housing; Air conditioner housing; Package or seat material for public transportation; For trains, Underground railway, or, packaging materials or housing materials; meter housings; antenna housings; packaging materials for artificial satellites to receive benefits; film heads and personal protective equipment; film synthetic or natural weaving Laminated films and photographs; Laminated painted objects; Laminated dyed objects, Laminated fluorescent objects; Laminated foam objects; and similar applications. The present invention further covers additional preparation operations for such objects, such as mold I interior decoration method, drying in a paint oven, lamination method and / or thermoforming method, but is not limited thereto. No further details are required. Those skilled in the art can fully utilize the present invention by using the instructions in the text. The following examples are provided to provide additional guidance for those skilled in the art to practice the invention. These examples are provided for illustration purposes only. Therefore, these examples are not intended to limit the invention in any way, as defined in the scope of the additional patent application. — Cut the sample into thin strips of 2.54 centimeters (cm) wide, and use a 90 degree peel test at a crosshead separation speed of 2.54 cm in female minutes. # Test the adhesion resistance with the In_n test device (Modei 4505) Exfoliative. Such an adhesion test method is well known to those skilled in the art and is summarized in, for example, U.S. Patent No. 3,965,057. The test device in this test procedure consists of a series of movable rollers or stands that allow the test specimen to be peeled at a constant 90 degree angle along its entire uncut length. The device is composed of a series of ^^ cm (which is geometrically attached to two side supports and a base). The two lower rolls can be adjusted so that the device can adjust test specimens of different thicknesses. 98811.doc -34-200538281 Use a suitable top clamp to secure the plastic layer. The length of this test sample was 15.2 cm 'and the width was 2.54 cm. Determined—Some of the test specimens remain unbonded. Each adhesive sample is tested with at least 3 test samples. In the actual test procedure, the fixture is attached to the movable head of the testing machine at a position where the peeled plastic layer can form a 90-degree angle with the test specimen during the test. The test specimen is positioned in a jig, and the unfixed surface is firmly clamped. The fixture is then nailed to the head of the tester. There is no load on the test specimen and the weighing device is then equilibrated to zero. Preparation Automatically record the position of the peel load on the nose with a peel distance of at least 10.2 cm. The first 2.54 cm of peeling distance can be ignored, and the load required to peel the plastic layer can be obtained from the automatic recording curve. Then calculate the tear strength, the formula is as follows:? _Peel load (Newton) " Width of the sample (meters) In the following example, the copolyestercarbonate-polycarbonate film module contains a copolyestercarbonate film layer And polycarbonate film layer. The copolyestercarbonate film includes a copolyestercarbonate having a structural unit derived from resorcinol, isophthalic acid, and terephthalic acid, and a carbonate structural unit derived from bisphenol A. The polycarbonate film contains bisphenol A polycarbonate. The copolyestercarbonate-polycarbonate film module can be prepared by co-extrusion of a 0.254mm thick transparent copolyestercarbonate film and a 0.5mm thick colored polycarbonate layer. A maleated polyacrylic acid (Fusabond MZ-109D, hereinafter referred to as PP-MA) derived from polypropylene and maleic anhydride and containing about 0.55% by weight of anhydride structural units, is obtained from Dupont. Thermoplastic polyurethane (Avalon 70AE; hereinafter referred to as τρυ) and contains about 90 ° /. Polypropylene structural units of polypropylene 98811.doc -35-200538281 olefin random copolymers (grade 13M11, hereinafter referred to as PP) are all available from Huntsman. Diamines containing N-hexylethylenediamine, which is a first-second diamine, were obtained from Aldrich. A substrate material is an ESCORENE PP8224 resin containing polypropylene structural units, and it is obtained from ExxonMobil. Example 1 Preparation of functionalized polypropylene containing grafted amine groups. A mixture of PP-MA and N-hexylethylenediamine was prepared at a molar ratio of 1: 1 MoMA to diamine 1: 1. The mixture was extruded at a temperature of 180 ° C and 40 rpm on a 16 mm co-rotating twin-screw extruder with L / D = 25. The melt was extruded through a 2 mm diameter circular die, cooled in a room temperature water bath, and pelletized. The obtained functionalized polypropylene is hereinafter referred to as PP-F1. Example 2 A compatible TPU / PP blend was prepared. Blend of TPU, PP and the functionalized polypropylene (PP-F1) of Example 1 at 200 ° C and 70 rpm on a biaxial screw extruder (the weight ratio is 70/25/5 ). The spiral configuration includes two kneading components. The melt system was extruded through a 2 mm diameter circular die, cooled in a room temperature water bath, and pelletized. A compatible TPU / PP blend was obtained. Example 3 A fluorene-containing copolyestercarbonate-polycarbonate film module was prepared by compression molding, (ii) the compatible TPU / PP blend of Example 2 and (iii) a multilayer article containing an ESCORENE polypropylene substrate. A 5 g (g) sample of the compatible TPU / PP blend of Example 2 was pressed into a film having a thickness of 18 mm (mm), and then cut into a sample having a size of 6.4 cm (cm) x 12.7 cm. An ESCORENE-containing polypropylene substrate was shot to form a 3.2 mm thick plate. The ESCORENE board substrate was placed in a 3,2 mm thick TEFLON frame (6.4 cm x 12.7 cm opening) compressed into a press of 98811.doc -36- 200538281, and the TPU / PP blend film was placed in On this substrate, a copolyestercarbonate-polycarbonate film module is placed on the TPU / PP blend film, and the polycarbonate side is adjacent to the TPU / PP blend film. Between the heated platens on the i7 (TC), the assembly was preheated for 5 minutes, and then subjected to a pressure of 2.76 million Pascals, which took 3 minutes. Then the press was turned on, and the molded part was removed. It was found that the copolyestercarbonate-polycarbonate film module has excellent adhesion to the substrate. The 90 degree tear strength is 3748 Newtons per meter (N / m). The tear failure mode is the interface adhesion layer / Copolyestercarbonate-polycarbonate film module, interfacial adhesive layer / substrate, and cohesive substrate failure. Comparative Example 1 For comparison purposes, under the same processing conditions as in Example 2, by extrusion A non-compatible Tpu / pp blend (with a weight ratio of 70/30) containing no functionalized polypropylene is prepared by a manufacturing method. A fluorene-containing copolyestercarbonate_polycarbonate film module is prepared by a compression molding method, (Ii) Non-compatible TPLNpp blend and (export) multilayer articles containing ESCORENE polypropylene substrates. 5 g τρυ / ρρ blend samples were pressed into 0.18 mm thick films and cut into a size of 6 4 cm x 2 · 7 cm sample. The same method as described in Example 3 was used to prepare the samples with these layers. Multi-layer object of component. The copolyestercarbonate_polycarbonate film module was found to have poor adhesion to the ESCORENE substrate. The 90 degree tear strength was found to be less than 525 N / m. Comparative Example 2 For comparison purposes, an incompatible TPU / PP / PP-MA blend (with a weight ratio of 70/25/5) was prepared by extrusion under the same processing conditions as in Example 2. 988il.doc- 37- 200538281 Preparation of fluorene-containing copolyestercarbonate-polycarbonate film modules, (u) TPU / PP / PP-MA blends and (export) multi-layer articles containing ESCORENE polypropylene substrates by compression molding. A 5 g TPU / PP / PP-MA sample was pressed into a 0.8 mm thick film and cut into a sheet of size 6.4 cm x 2.7 cm. The components with these layers were prepared using the same method described in Example 3. Multi-layer object. The copolyestercarbonate-polycarbonate film module was found to have poor adhesion to the ESCORENE substrate. The 90-degree tear strength was found to be less than 525 N / m. Comparative Example 3 is For comparison purposes, a fluorene-containing copolyestercarbonate · polycarbonate thin fluorene component was prepared by compression molding, (ii) TPU and escorene. A multi-layer object of an acrylic substrate. A 5 g TPU sample was pressed into a thin film of 0 · 18 mm thick, which was a thin plate of 6.4 cm x 12.7 cm. The method described in Example 3 is equipped with the Multi-layered objects of equal layer composition. It was found that the adhesion between Dingkou and the substrate was very poor. The object would delaminate at the interface between τρυ and the substrate, and its 90-degree tear strength was less than 350. N / m. Although the invention has been illustrated and described in general specific embodiments, the invention is not intended to be limited to the details shown, because in any case as long as it does not violate the spirit of the present month, there can be various modifications and substitutions Thing. Therefore, by using only examples of experimental methods, those skilled in the art can come up with other modifications and equivalents of the present invention disclosed in the text, and as defined in the following patent scope, all such modifications and equivalents are Within the spirit and scope of the present invention. All patents, patent applications, and published papers listed in = are incorporated herein by reference. 988ll.doc -38-

Claims (1)

200538281 、申請專利範固： 1. -種多層物件’其包含⑴一塗層，其包括含衍生自至少 ’3螽基笨及至少一芳香族二羧酸之結構單元之嵌 段共聚醋碳酸醋，丨）一箆—s (11)第一層，其包括含有碳酸酯結構 单凡之聚合物，㈣一基片層，其包含聚丙稀，及㈣至 少-黏者層，其包含經胺官能化之聚丙烯及聚胺基甲酸 醋之反應產物；其中該塗層係與該第二層互相接觸，且 3亥黏者層係與該第二層及該基片層互相接觸。 2· t請求：1 一之物件’其中該塗層包含至少-選自由未經取 代之間本一盼、2 -甲美簡焚-八 T基間本一酚、及其混合物所組成之群 組之1，3-二羥基笨。 3.:請求項2之物件’其中該以·二羥基苯為未經取代之間 苯二紛。 I I::::之：件’其中該芳香族二羧酸係選自由異醜 二主t ^、奈_2,6_二羧酸、及其混合物所組成之群組。 酸之混合物。其+以㈣二㈣為異㈣與對駄 6· 之物件」其中經異耿酸衍生之結構單元對經對 :何之結構單元的比率為約0.25至4.0 : 1。 ㈣^ 5之物件’其中經異醜酸衍生之結構單元對經對 \ 之結構單元的比率為約0.40至2.5 : 1。 8. =項1之物件’其中該共聚醋碳酸醋包含約1〇至約99 垔重/。之芳化物嵌段。 9. 如請求項1之物件，其中該共聚醋侧包含約6。至約％ 98811.doc 200538281 重里〇/〇之芳化物嵌段。 10 ·如請求1 + I 只11物件，其中該共聚酯碳酸酯之碳酸酯部份包 含衍生自雙酚A之結構單元。 11 ·如吻求項1之物件，其中該第二層包含雙酚A聚碳酸酯。 12·=明求項1之物件，其中該第二層尚包含至少一選自由染 ； 顏料、金屬片、及玻璃片所組成之群組之著色劑。 13·如凊求項1之物件，其中該基片層包含至少-均聚丙烯或 含何生自丙烯之結構單元之共聚物、或其摻合物。 月求員13之物件’其中該基片層包含一含至少約7〇重 置％衍生自丙烯之結構單元之共聚物。 15·如請求項13之物件，其中該基片層包含一含至少約重 量％衍生自丙烯之結構單元之共聚物。 1 6·如凊求項丨之物件，其中該經胺官能基化之聚丙烯係衍生 自帶有至少一胺反應性基團之聚丙烯及帶有至少兩種胺 基團之胺化合物的反應。 17·如請求項16之物件，其中該胺反應性基團包含酸酐。 18·如租求項16之物件，其中該胺化合物具有兩胺基團，其 皆為第一胺基，或其中之一為第一胺基，而另一為第二 胺基。 19. 如請求項1之物件，其中該聚胺基甲酸酯為含衍生自至少 一多元醇、至少一有機二異氰酸酯及至少一視需要選用 之鏈增長劑之結構單元的熱塑性聚胺基甲酸酯。 20. 如請求項19之物件，其中該聚胺基甲酸酯之硬度在介於 約60度Shore A與約75度Shore D間之範圍内。 98811.doc 200538281 21.如請求項19之物件，其中如藉由ASTM_1238測定該聚胺 基甲酸酯之溶流率為每1〇分鐘約4至1〇〇克。 22·如請求項1之物件，其中該聚胺基甲酸酯對經胺官能基化 聚丙烯之比率在介於約5: 95與約98 : 2間之範圍内。 23,如請求項1之物件，其中該黏著層尚包含至少一未經胺官 能基化之第二聚丙烯。 24·如明求項23之物件’其中該第二聚丙稀與用於該基片層 之聚丙稀相同。 • 25·如清求項23之物件，其中以該黏著層之重量為基準計， X第聚丙烯之存在量在介於約5重量％與約80重量。/〇間 之範圍内。 士睛求項1之物件’其中該多層物件之9〇度撕剝力為每米 至少700牛頓。 旁长員26之物件’其中該多層物件之9〇度撕剝力為每 米至少1750牛頓。 ❿28· Γ睛求項1之物件，其中各層之厚度為：塗層約2至2,500 ' =第層約2至2,50〇微米；及黏著層約8至2,5〇〇微米。 29^ 1求項1之物件，其係為〇vad裝置；供飛機、汽車、 貨車軍用交通工具、軍用汽車、軍用飛機、軍用水運 通具+型摩托車、摩托車之外部或内部組件，其 括儀表板、後圍側板、車門檻板、直立面板、水平面 板、裝飾物、；^ ^ , 彳、中間立柱、播泥板、車門、活動車 :、7李艙蓋、發動機罩、保護罩、車頂、保險槓、飾 '濩栅、鏡框、支柱縫飾、覆蓋層、車身側嵌條、車 98811.doc 200538281 輪遵蓋、# +如 …、裔罩、門把手、擾流板、窗框、頭燈迷 框、頭燈、 〜 、 燈、尾燈罩、尾燈迷框、牌照板外殼、車 後矣*s腳墙板，供戶外交通卫具及裝置之機殼、護罩、 置：、或零件；風力渦輪翼或外殼；供電氣或電信裝 丨外傢俱’飛機元件；船隻或船用設備之外 =部組件，其包括裝飾物、護罩、或外殼；般外馬 測深5十外殼、個人水上航行器；水上摩托車；200538281, applied for patent Fangu: 1.-a multi-layered object 'comprising a coating, comprising a block copolymer vinegar carbonate carbonate containing a structural unit derived from at least' 3 fluorene and at least one aromatic dicarboxylic acid (1) — 箆 (11) The first layer, which includes a polymer containing a carbonate structure, a substrate layer, which contains polypropylene, and an at least-adhesive layer, which contains an amine function Reaction product of modified polypropylene and polyurethane; wherein the coating is in contact with the second layer, and the adhesive layer is in contact with the second layer and the substrate layer. 2 · t request: 1 of the object 'wherein the coating comprises at least-selected from the group consisting of unsubstituted benzylamine, 2-metaquinol-octatylbenzophenol, and mixtures thereof Group 1,3-dihydroxybenzyl. 3 .: The article of claim 2 ′, wherein the dihydroxybenzene is unsubstituted benzenediphenyl. I I :::: 之: 件 'wherein the aromatic dicarboxylic acid is selected from the group consisting of isouglyl main t ^, naphthalene-2,6-dicarboxylic acid, and mixtures thereof. Mixture of acids. Its + the object with ㈣ ㈣ as a ㈣ and 駄 6 ″ “wherein the ratio of the structural unit derived from iso-glyceric acid to the structural unit of the ratio of pairs to: is about 0.25 to 4.0: 1.物件 ^ 5 的 物 ’wherein the ratio of the structural unit derived from isougic acid to the structural unit of warp to \ is about 0.40 to 2.5: 1. 8. = Article of Item 1 ', wherein the copolymerized vinegar carbonate comprises about 10 to about 99 t / w. Of the aromatic block. 9. The article as claimed in claim 1, wherein the copolyester side contains about 6. To about 98811.doc 200538281 arylate block of 0/0. 10 · As requested 1 + I only 11 articles, wherein the carbonate portion of the copolyestercarbonate contains a structural unit derived from bisphenol A. 11-The article of claim 1, wherein the second layer comprises bisphenol A polycarbonate. 12 · = The object of Mingqiu item 1, wherein the second layer further comprises at least one coloring agent selected from the group consisting of dye; pigment, metal sheet, and glass sheet. 13. The article of claim 1, wherein the substrate layer comprises at least-homopolypropylene or a copolymer containing a structural unit derived from propylene, or a blend thereof. Article of the Month Seeker 13 'wherein the substrate layer comprises a copolymer containing at least about 70% by weight of a structural unit derived from propylene. 15. The article of claim 13, wherein the substrate layer comprises a copolymer containing at least about weight percent of a structural unit derived from propylene. 16. The article according to claim 1, wherein the amine-functionalized polypropylene is a reaction derived from a polypropylene having at least one amine-reactive group and an amine compound having at least two amine groups . 17. The article of claim 16, wherein the amine-reactive group comprises an acid anhydride. 18. The article of claim 16, wherein the amine compound has two amine groups, each of which is a first amine group, or one of which is a first amine group, and the other is a second amine group. 19. The article of claim 1, wherein the polyurethane is a thermoplastic polyurethane containing structural units derived from at least one polyol, at least one organic diisocyanate, and at least one optional chain extender Formate. 20. The article of claim 19, wherein the hardness of the polyurethane is in a range between about 60 degrees Shore A and about 75 degrees Shore D. 98811.doc 200538281 21. The article of claim 19, wherein the polyurethane has a solution flow rate of about 4 to 100 grams per 10 minutes, as determined by ASTM_1238. 22. The article of claim 1, wherein the ratio of the polyurethane to the amine-functionalized polypropylene is in a range between about 5:95 and about 98: 2. 23. The article of claim 1, wherein the adhesive layer further comprises at least one second polypropylene which is not functionalized with an amine. 24. The article of item 23 of claim 23, wherein the second polypropylene is the same as the polypropylene used for the substrate layer. • 25. The article according to item 23 of Qing, wherein the X-th polypropylene is present in an amount between about 5% by weight and about 80% by weight based on the weight of the adhesive layer. / 〇 之间。 Within the range. The object of ShiJin item 1, wherein the 90 degree peel force of the multilayer object is at least 700 Newtons per meter. The article of the layman 26 'wherein the 90 degree peel force of the multilayer article is at least 1750 Newtons per meter. ❿28 · The object of item 1 in which the thickness of each layer is: the coating layer is about 2 to 2,500 '= the second layer is about 2 to 2,500 microns; and the adhesive layer is about 8 to 2,500 microns. 29 ^ 1 The item of claim 1, which is an ovad device; for aircraft, cars, trucks, military vehicles, military cars, military aircraft, military water transport equipment + motorcycles, external or internal components of motorcycles, which Including dashboard, rear side panels, sill panels, upright panels, horizontal panels, decorative objects, ^ ^, 彳, middle pillars, mud boards, doors, movable vehicles: 7 Li hatch, engine cover, protective cover , Roof, bumper, trim, grille, picture frame, pillar stitching, overlay, body side molding, car 98811.doc 200538281 wheel compliance cover, # + such as ..., hood, door handle, spoiler, Window frame, headlight fan frame, headlight, ~, lamp, tail light cover, tail light fan frame, license plate shell, rear sill * s foot wall panel, housing, cover, housing for outdoor traffic guards and devices :, Or parts; wind turbine wings or enclosures; power supply gas or telecommunications equipment; exterior furniture; aircraft components; external components of ships or marine equipment, including decorative objects, shrouds, or shells; general sounding 50 Shell, personal watercraft; jetski ; 水池，水療設備；熱浴桶；階梯；階梯覆蓋物；建築或 結構應用’其包括，上轴、屋頂、窗戶、地板、裝都窗 戶陳设或處理；供圖晝、油畫、海報、或類似展示項目 之已處理麵遮蓋物；光學透鏡；眼鏡；紅用眼鏡； 可植入式眼鏡；護牆板或門；廚柜檯面；經保護之平面 藝術作。π ’戶夕卜或室内標誌；供自動櫃員機(A，)之外 罩、外般、儀表板、或零件；供草坪或園藝拖拉機、剪 儀表板、或零件；窗飾或門飾；運動設備或玩具；供雪 車之外軍、外殼、儀表板、或零件；休旅車儀表板或元 件；遊樂場設施；鞋帶；自塑膠·木材組合物製成之物件； 高爾夫球場標記；公用事業坑覆蓋物；電腦外殼；桌上 型電腦外殼；手提式電腦外殼；膝上型電腦；掌握型電 腦外般；監視n外殼；π印機外殼；鍵盤；傳真機（fax machine)外般；影印機外殼；電話外般；電話座盤；行動 電話外殼；無線電發報機外殼；無線電接收機外殼；燈 飾；照明設備；反射器；網路介面裝置外殼；變壓器外 草機、或I具’其包括草坪或園藝卫具之外罩、外般、 988 Π,doc 200538281 殼；冷氣機外殼；供大料輸工具之包材或座塾材料； i、火車地下鐵、或公車之包材或座塾材料；計量器外 殼；天線外殼；供人造衛星接收器之包材；覆臈頭盘或 個人保護ax備，覆膜合成或天然、織物；覆膜膠卷或相片； 覆膜上漆物件；覆膜染色物件；覆膜螢光物件；或覆膜 發泡體物件。 ' 3〇· -種多層物件，其包含⑴一塗層，其包括含有衍生自未 經取代之間苯二酚、異酞酸及對酞酸之混合物、及雙酚A 之釔構單元之嵌段共聚酯碳酸酯；（丨丨）一第二層，其包括 可視需要含有至少一著色劑之雙酚A聚碳酸酯；〇⑴一基 片層，其係選自由均聚丙烯及含至少約7〇重量％衍生自丙 烯之結構單元之共聚物所組成的群組；及（iv)—黏著層， 其包含經胺官能基化聚丙烯與聚胺基甲酸酯之反應產 物； 其中該塗層與該第二層互相接觸，而該黏著層與該第 二層及該基片層互相接觸；且其中該多層物件之9〇度抗 撕強度為每米至少700牛頓。 31· —種薄膜組件’其包含⑴一塗層，其包括含有衍生自至 少一種1，3-二羥基苯及至少一芳香族二羧酸之結構單元 之嵌段共聚酯碳酸酯、（Π)—第二層，其包括含碳酸酯結 構單元之聚合物、及（iii)一黏著層，其包含經胺官能基化 聚丙烯與聚胺基甲酸酯之反應產物。 32_如請求項3 1之薄膜組件，其中該塗層包括含衍生自未經 取代之間苯二酚、異酞酸與對酞酸之混合物、及雙酚A之 9881l.doc 200538281 結構單元的嵌段共聚酯碳酸酯；且該第二層包含可視需 要含有至少一著色劑之雙酚A聚碳酸酯。 3 3. —種製備多層物件之方法 其包括含衍生自至少一 1,3-二羥基苯及至少一芳香族二 幾酸之結構皁元之嵌段共聚g旨碳酸酯、（丨丨）一第二層，其 包括含石反酸酯結構單元之聚合物、（iii) 一基片層，其包含 聚丙烯、及（IV)至少一黏著層，其包含經胺官能基化聚丙 烯與聚胺基甲酸酯之反應產物，其中該塗層係與該第二層 互相接觸，且該黏著層係與該第二層及該基片層互相接觸； 該方法係選自由以下方法所組成之群組：方法⑴包括 以下步驟⑷製備具有塗層與第三層之預組件，及⑻合併 該預組件及個別黏著層與基片層；方法（ii)包括以^步 驟：⑷製備具有塗層與第二層之預組件，⑻在該基片層 附近形成黏著層，及⑷合併該預組件與黏著層/基片層二 合；及方法（iii)包含以下步驟：⑷製備具有塗層、第二層 及黏著層之預組件，及⑻在該基片層附近形成該預組件。 34.=了之方法，其中該塗層與第二層之組件係藉由 共擠製法而形成。 3 5 ·如請求項3 3之方法，且φ焱益山a A ，、中係藉由層合法或壓縮 在該黏著層附近形成該組件。 法 36.如請求項33之方法’其中該塗層 取代之門贫_ ^ 選自由未經 :戈之間本一紛、2_甲基間苯二齡、及其 群組之1，3-二羥基苯。 且成之 37·如請求項33之方法， 、μ， 一勉基苯為未經取代之間 98811.doc 200538281 苯二酚。 38. 如請求項33之方法，其中該芳香族二幾酸係選自由異賦 酸、對駄酸、萘_2,6-二緩酸、及其混合物所組成之群組。 39. 如請求項38之方法，苴φ钤忿关# ^ 香族一幾酸為異S太酸與對 酞酸之混合物。 一、 々月长貝39之方法，其中該經異酞酸衍生之結構單元 經對耿酸衍生之結構單元的比率為約〇25至4〇:卜’Pools, spa equipment; hot tubs; steps; step coverings; architectural or structural applications' which include, decoration or treatment of upper shafts, roofs, windows, floors, windows, etc .; photo courtesy, paintings, posters or similar Optic lenses; glasses; red glasses; implantable glasses; wall panels or doors; kitchen counter tops; protected graphic art works. π 'Hou Xibu or indoor signs; for covers, exteriors, dashboards, or parts of ATMs (A,); for lawn or garden tractors, cutting dashboards, or parts; window or door trims; sports equipment or Toys; army, housing, dashboard, or parts for snowmobiles; recreational vehicle dashboards or components; playground equipment; shoelaces; articles made from plastic and wood compositions; golf course markings; utility pits Covers; computer casings; desktop computer casings; portable computer casings; laptop computers; master-type computer exteriors; surveillance n casings; π printer casings; keyboards; fax machines (fax machines) outside; photocopiers Housing; phone-like; phone holder; mobile phone housing; radio transmitter housing; radio receiver housing; lighting; lighting equipment; reflectors; network interface device housing; transformer lawnmower, or equipment including lawns Or horticultural protective cover, 988 Π, doc 200538281 shell; air conditioner shell; packing material or seat material for large-scale transportation tools; i. Train subway, or bus Materials or housing materials; meter housings; antenna housings; packaging materials for satellite receivers; cladding head plates or personal protection ax equipment, synthetic or natural fabrics; film or photographs; film coating Objects; coated dyed objects; coated fluorescent objects; or coated foam objects. '30. A multi-layered article comprising a monolayer coating comprising an embedded yttrium unit containing a mixture of unsubstituted resorcinol, isophthalic acid and terephthalic acid, and bisphenol A Segment copolyestercarbonate; (丨 丨) a second layer comprising a bisphenol A polycarbonate containing at least one colorant as needed; a substrate layer selected from homopolypropylene and containing at least one A group of about 70% by weight of a copolymer derived from a structural unit derived from propylene; and (iv) an adhesive layer comprising a reaction product of an amine-functionalized polypropylene and a polyurethane; wherein the The coating layer is in contact with the second layer, and the adhesive layer is in contact with the second layer and the substrate layer; and the 90-degree tear strength of the multilayer object is at least 700 Newtons per meter. 31 · —A kind of thin film module comprising a coating layer comprising a block copolyester carbonate containing structural units derived from at least one 1,3-dihydroxybenzene and at least one aromatic dicarboxylic acid, (Π ) —A second layer comprising a polymer containing carbonate structural units, and (iii) an adhesive layer comprising a reaction product of an amine-functionalized polypropylene and a polyurethane. 32_ The thin-film module of claim 31, wherein the coating includes a structural unit comprising 9881l.doc 200538281 derived from unsubstituted resorcinol, a mixture of isophthalic acid and terephthalic acid, and bisphenol A. A block copolyester carbonate; and the second layer comprises a bisphenol A polycarbonate optionally containing at least one colorant. 3 3. —A method for preparing a multilayer article, which comprises a block copolymer of a structural copolymer containing structural saponin derived from at least one 1,3-dihydroxybenzene and at least one aromatic diquinic acid, (丨 丨)- The second layer includes a polymer containing a stone invert ester structural unit, (iii) a substrate layer including polypropylene, and (IV) at least one adhesive layer including amine-functionalized polypropylene and a polymer The reaction product of a urethane, wherein the coating layer is in contact with the second layer, and the adhesive layer is in contact with the second layer and the substrate layer; the method is selected from the group consisting of Group: Method ⑴ includes the following steps: preparing a pre-assembly with a coating and a third layer, and ⑻ combining the pre-assembly and individual adhesive layers and substrate layers; method (ii) includes the following steps: ⑷ preparing a coating with And the second layer of the pre-assembly, (i) forming an adhesive layer near the substrate layer, and (ii) merging the pre-assembly with the adhesive layer / substrate layer to combine; and method (iii) includes the following steps: (i) preparing a coating, Pre-assembly of the second layer and adhesive layer, and The pre-assembly is formed near the layer. 34. = method, wherein the coating and the second layer of components are formed by coextrusion. 3 5 · According to the method of claim 3 3, and φ 焱 Yishan a A,, the system is formed by the layer law or compression near the adhesive layer. Method 36. The method according to claim 33, wherein the coating is replaced by a gated ^ ^ selected from the group consisting of non-tributary, dimethyl isophthalate, 2-methyl isophthalene, and groups of 1, 3- Dihydroxybenzene. And the result 37. As in the method of claim 33,, μ, monomethylbenzene is unsubstituted between 98811.doc 200538281. 38. The method as claimed in claim 33, wherein the aromatic diisocyanic acid is selected from the group consisting of isobaric acid, p-ortho-acid, naphthalene-2,6-diabituric acid, and mixtures thereof. 39. As in the method of claim 38, 苴 φ 钤 忿 关 # ^ fragrant mono-acid is a mixture of iso-S-toluic acid and terephthalic acid. I. The method of 々 月 长 贝 39, wherein the ratio of the structural unit derived from isophthalic acid to the structural unit derived from genoic acid is about 025 to 40: 41. 如請求項39之方法，其中該經異酞酸衍生之結構單元對 、至對醜西夂衍生之結構單元❾t匕率為約0.40至2.5 : 1。 42. 如”月求項33之方法，其中該共聚醋碳酸醋包含約1〇至約 99重量％之芳化物嵌段。 43. 如請求項33之方法，其中該共聚醋碳酸醋包含約6〇至約 98重量％之芳化物嵌段。 44·如μ求項33之方法，其中該共聚酯碳酸酯之碳酸酯部份 包含衍生自雙酚Α之結構單元。 45·如明求項33之方法，其中該第二層包含雙酚a聚碳酸酯。 46·如明求項33之方法，其中該第二層尚包含至少一選自由 染料 '顏料、金屬片、及玻璃片所組成之群組之著色劑。 47.如請求項33之方法，其中該基片層包含至少一均聚丙烯 二竹生自丙稀之結構早元之共聚物、或其推合物。 48·如請求項47之方法，其中該基片層包含一含至少約70重 置％竹生自丙烯之結構單元之共聚物。 49·如叫求項47之方法，其中該基片層包含一含至少約90重 篁〇/°街生自丙烯之結構單元之共聚物。 98811.doc 200538281 5〇·如請求項33之方法，其中該經胺官能基化之聚丙埽係衍 生自帶有至少一胺反應性基團之聚丙烯與帶有至少兩 基團之胺化合物的反應。 5 1 ·如請求項5〇之方法，其中該胺反應性基團包含酸軒。 52·如請求項50之方法，其中該胺化合物具有兩胺基團，其 皆為第二胺基、或其中之一為第一胺基，而另一為第一 胺基。 53·如請求項33之方法，其中該聚胺基甲酸酯為熱塑性聚胺 基甲酸酯，其含有衍生自至少一多元醇、至少一有機一 異氰酸酯及至少一視需要選用之鏈增長劑之結構單元。 54·如味求項53之方法，其中該聚胺基甲酸酯之硬度在介於 約6〇。Sh〇re Α與約75。Shore D間之範圍内。 55·如叫求項53之方法，其中如藉由ASTM D_1238測定該聚 月女基甲酸酷之熔流率為每1〇分鐘約4至1〇〇克。 56·如％求項33之方法，其中該聚胺基甲酸酯對經胺官能基 化聚丙烯之比率在介於約5 : 95與約98 : 2間之範圍内。 57· $明求項33之方法，其中該黏著層尚包含至少一未經月安 官能基化之第二聚丙烯。 长員57之方法，其中該第二聚丙烯與用於該基片層 中之聚丙烯相同。 9 5 9 ·如請求項5 7 、之方去，其中以該黏著層之重量為基準計， ^〜一聚丙烯之存在量在介於約5重量％與約80重量％間 6〇·如請求項33之方法 其中該多層物件之90度撕剝力為每 9881 l.doc 200538281 米至少700牛頓。 61·如請求項60之方法，其中該多層物件之9〇度撕剝力為每 米至少1750牛頓。 62·如請求項33之方法，其中各層之厚度為：塗層約2至2,5〇〇 微米；第二層約2至2,500微米；及黏著層約8至2,500微米。 63· —種製備多層物件之方法，該多層物件包含⑴一塗層， 其包括含衍生自未經取代之間苯二酚、異酞酸與對酞 酸、及雙酚A之結構單元的嵌段共聚酯碳酸酯；（丨丨）第二 層，其包含可視需要含有至少一著色劑之雙酚A聚碳酸 酯’·（出）一基片層，其係選自由均聚丙烯及含至少約7〇 重量。/Q衍生自丙烯之結構單元之共聚物所組成之群組；及 (iv)—黏著層，其包含經胺官能基化聚丙烯與聚胺基甲酸 醋之反應產物， 其中a亥塗層與该第二層互相接觸，而該黏著層與該第 二層及該基片層互相接觸；且其中該多層物件之9〇度撕 剝力為每米至少700牛頓； 該方法係選自由以下方法所組成之群組，方法⑴包括 以下步驟（a)製備具有塗層與第二層之組件，及卬）合併該 組件及個別黏著層與基片層；方法⑼包括以下㈣：⑷ 製備具有，塗層與第二層之組件，⑻在該基片層附近形成 黏著層’及（C)合併該組件與黏著層/基片層组合；及方法 (iii)包含以下步驟：（a)製備具有塗層、第二層、及黏著層 之組件，及（b)在該基片層附近形成該組件。 98811.doc 200538281 七、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明: 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無）41. The method of claim 39, wherein the isophthalic acid-derived structural unit pair, to the structural unit derived from cyperazole, has a ratio of about 0.40 to 2.5: 1. 42. The method according to item 33, wherein the copolyacetic acid carbonate comprises about 10 to about 99% by weight of aryl compound blocks. 43. The method according to item 33, wherein the copolyacetic acid carbonate contains about 6 0 to about 98% by weight of the aryl block. 44. The method of [mu] seeking item 33, wherein the carbonate portion of the copolyestercarbonate comprises a structural unit derived from bisphenol A. 45. Such a term The method of 33, wherein the second layer comprises bisphenol a polycarbonate. 46. The method of item 33, wherein the second layer further comprises at least one selected from the group consisting of dyes, pigments, metal flakes, and glass flakes. 47. The method according to claim 33, wherein the substrate layer comprises at least one homopolypropylene dibamboo-derived precopolymer or its inferred structure. 48. If requested The method of item 47, wherein the substrate layer comprises a copolymer containing at least about 70% by weight of a structural unit derived from propylene. 49. The method of claim 47, wherein the substrate layer includes a substrate containing at least about 90 Copolymers with a weight of 0 / ° from the structural unit of propylene. 98811.doc 200538281 5 The method according to claim 33, wherein the amine-functional polypropylene is derived from the reaction of a polypropylene having at least one amine-reactive group and an amine compound having at least two groups. 5 1 The method of claim 50, wherein the amine-reactive group comprises acid. 52. The method of claim 50, wherein the amine compound has two amine groups, each of which is a second amine group, or one of them is The first amine group and the other is the first amine group. 53. The method of claim 33, wherein the polyurethane is a thermoplastic polyurethane which contains a derivative derived from at least one polyol, Structural unit of at least one organic monoisocyanate and at least one optional chain extender. 54. The method according to item 53, wherein the hardness of the polyurethane is between about 60. Shore A Within a range between about 75. Shore D. 55. If called by the method of item 53, wherein the melt flow rate of the poly-methylene carboxylic acid is about 4 to 100 per 10 minutes, as measured by ASTM D_1238. 56. The method of claim 33, wherein the polyurethane is amine-functionalized polypropylene The ratio is in a range between about 5:95 and about 98: 2. 57. The method of claim 33, wherein the adhesive layer still contains at least one second polypropylene that is not functionalized with moonlight. The method of the senior member 57, wherein the second polypropylene is the same as the polypropylene used in the substrate layer. 9 5 9 · If the request item 5 7 is used, the weight is based on the weight of the adhesive layer, ^ ~ A polypropylene is present in an amount between about 5% by weight and about 80% by weight. 60. The method of claim 33, wherein the 90 degree peel force of the multilayer object is at least 700 per 9881 l.doc 200538281 meters Newton. 61. The method of claim 60, wherein the 90 degree peel force of the multilayer article is at least 1750 Newtons per meter. 62. The method of claim 33, wherein the thickness of each layer is: the coating layer is about 2 to 2,500 microns; the second layer is about 2 to 2,500 microns; and the adhesive layer is about 8 to 2,500 microns. 63 · —A method for preparing a multi-layered article, the multi-layered article includes a first coating, which includes embedded units containing structural units derived from unsubstituted resorcinol, isophthalic acid and terephthalic acid, and bisphenol A Segment copolyestercarbonate; (丨 丨) a second layer comprising a bisphenol A polycarbonate '· (out) a substrate layer containing at least one colorant as required, which is selected from the group consisting of homopolypropylene and containing At least about 70 weight. / Q is a group of copolymers derived from structural units of propylene; and (iv) an adhesive layer containing the reaction product of amine-functionalized polypropylene and polyurethane, wherein the a The second layer is in contact with each other, and the adhesive layer is in contact with the second layer and the substrate layer; and the 90-degree peel force of the multilayer object is at least 700 Newtons per meter; the method is selected from the following methods: The group consisting of method ⑴ includes the following steps (a) preparing a component having a coating and a second layer, and ii) merging the component and individual adhesive layers and substrate layers; method ⑼ includes the following ㈣: ⑷ preparing, The component of the coating layer and the second layer, (i) forming an adhesive layer near the substrate layer 'and (C) combining the component with the adhesive layer / substrate layer combination; and method (iii) includes the following steps: (a) preparing The component of the coating, the second layer, and the adhesive layer, and (b) forming the component near the substrate layer. 98811.doc 200538281 VII. Designated representative map: (1) The designated representative map of this case is: (none) (II) The component symbols of this representative map are simply explained: 8. If there is a chemical formula in this case, please disclose the one that can best show the characteristics of the invention. Chemical formula: (none) 98811.doc98811.doc