M269189 八、新型說明： 【新型所屬之技術領域】 本新型是有關於一種積層結構（laminating structure)， 特別是關於一種具有一貼合積層單元（bonding laminate unit) 之積層結構，該貼合積層單元包含一含有苯乙烯_丁二烯-苯 乙稀（styrene-butadiene-styrene，於下文中簡稱為「SBS」） 嵌段共聚物（block copolymer)之基質層以及一含有聚胺基甲 酸酯（polyurethane，於下文中簡稱為「PU」）之表面層。 【先前技術】 由於動物保育之觀念的日益成熟，致使動物皮革原料 之取得與使用受到更多的限制，因此，已有許多藉由層合 一或多層聚合物層在一底布層（base fabric layer)上來製造人 造皮革之研究，且所製得之人造皮革可廣泛應用於鞋類、 傢倶、汽車之内裝物件、箱、袋及成衣等產品。 習知用於製造人造皮革之聚合物層的原料之一為聚氣 乙烯（polyvinyl chloride，於下文中簡稱為「PVC」）。由 PVC所製成之聚合物層不僅具備防水功能，並可強化及穩 固該底布層之結構，同時提供良好的表面觸感與屈曲手感 (flexion feel)。然而，近年來發現使用PVC原料會產生戴奥 辛（dioxin)、重金屬及鄰苯二曱酸鹽（Phthalates)等污染物， 對環境會造成嚴重的傷害，因此，PVC已逐漸被禁止使用 。所以，業界亦積極尋求符合環保之其他材料。 另一習知的材料為濕式PU(Wet PU)，但其成本高於 PVC，因此，目前亦嘗試使用苯乙烯系（styrenic)嵌段共聚物 M269189 與pu之一組合，不過，此一組合又會因為苯乙烯類聚合物· 與PU之相容性不佳，無法良好地接合在一起，而容易產生 剝離或分層情形。 為了改善本乙細類聚合物與PU之相容性，於審杳中 (pending)之中華民國新型專利申請案第932〇6516號，本創 作人曾提及一種具有一背膠積層（backing laminate)i複合織 物°亥月膠積層包含下列二層結構：一施加至該織物層之 黏合層、一施加至該黏合層之中間層，以及一施加至該中 間層之表面改質層，其中，該黏合層具有一黏合組成物， 該黏合組成物包含一與一丙烯酸酯（acrylate)單體接枝之 SBS肷段共聚物，以及摻混有已接枝之該SBS嵌段共聚物 之pu’該中間層具有-含有一 SBS嵌段共聚物及—溶劑之 組成物。於本創作人之前案中，該背膠積層係用來提供一 足以給予該複合織物良好手觸感性質之厚度。 由上述可知，對於一成本低廉、表面不易剝離及性質 良好之積層材料，仍存在一需求。 該審查中之中華民國新型專利申請案第932〇6516號的 整體内容被併入本案，以供做為參考資料。 【新型内容】 本新型之一目的在於提供一種貼合積層單元，該貼合 積層單元係藉由結合一含有pu系樹脂之表面層及一含有 SBS嵌段共聚物之基質層而製得，且該含有sbs嵌段共聚 物之基質層可有效提昇該貼合積層單元之屈曲手感性質及 降低製造成本。 ' M269189 ί新型之另—目的在於提供—種具有-接著層之貼合 積層早兀，該接著層係由一包括一與一單體接枝之皿嵌 段共聚物之接著組成物所構成，且用以接合-含有PU之表 面層與一含有SBS嵌段共聚物之基質層。 本新型之又另-目的在於提供—種具有_含叩系樹脂 之表面層之貼合積層單元，該含pu系樹脂之表面層具有一 外視面’且該外視面可依據最終產品的需要㈣製成不同 的花紋及圖案。 本新型之再另-目的在於提供一種具有一貼合積層單 元之積層結構’該制結構藉由結合—織物層、—織物接 著層與一貼合積層單元而製成。 依據本新型之一方面，一貼合積層單元包含一由一 系樹脂所構成且具有一外視面及一内接面之表面層、一設 置於該表面層之内接面上且由—接著組成物所構成之接^ 層：以及-設置於該接著層上且由一基質組成物所構成之 基質層。該接著組成物包括—與—單體接枝之sbs嵌段共 聚物，以及該基質組成物含有一 SBS嵌段共聚物。 依據本新型之另一方面，一具有上述貼合積層單元之 積層結構包含一織物層、一設置該織物層上之貼合積層單 元，以及一設置於該織物層與該貼合積層單元之間的織物 接著層。該接著層及該織物接著層分別由—接著組成物所 構成。 上述之接著組成物是由一 SBS嵌段共聚物與一單體進 行反應來製備，以改善該SBS嵌段共聚物對於pu之相容性 M269189 ’並有效接合該含有SBS嵌段共聚物之基質層與該含有ρυ· 之表面層。 【實施方式】 有關本新型之前述及其他技術内容、特點與功效，在 以下配合參考圖式之較佳實施例的詳細說明中，將可清楚 的呈現。 如圖1所示，本新型首先提供一種貼合積層單元1 ,包 含··一表面層11、一接著層12以及一基質層13。 該表面層11是由一 PU系樹脂所構成，且具有一外視 面111及一相反於該外視面1Π之内接面112。當將該貼合 積層單元與其他材料（例如：織物、木材等）結合而製成一產 品時，該表面層11之外視面11丨即形成該產品之外觀，且 可依據產品的需求，壓製成不同的花紋及圖案。 在製造该表面層時’亦可依據習知技術及產品需求， 加入其他添加劑，例如：增加表面光滑度及提昇耐刮性 (anti-scratch)之平滑劑（smoothing agent)或讓表面呈現霧面 效果之消光劑（matting agent)等。但需注意的是，若平滑劑 添加過量時，反而會讓表面層丨丨產生黏滯感，並影響接著 效果；以及若消光劑添加過量時，會致使表面層u之耐刮 效果不佳。 该接著層12是設置於該表面層11之内接面丨12上，且 由一接著組成物所構成，該接著組成物包括一與一單體接 枝之SBS嵌段共聚物。 較佳地，在該接著組成物中，與SBS嵌段共聚物接枝 M269189 之單體係為一選自於由下列所構成之族群的化合物：丙烯. 酸（acrylic acid)單體、丙浠酸酉旨系（aerylie)單體、甲基丙烯 酸（methacrylic acid)單體、甲基丙烯酸酷系（methacrylic)單 體、川頁丁稀二酸酐（maleic anhydride)以及此等之一組合。 適合與SBS嵌段共聚物接枝之丙烯酸酯系單體的例子 包含：丙烯酸甲酯（methyl acrylate，MA)、丙烯酸乙酯 (ethyl acrylate，EA)、丙浠酸丁酯（butyl acrylate，BA)、丙 稀酸乙基己酯（2-ethylhexyl acrylate，2-EHA)、丙稀酸經基 乙酯（2-hydroxyethyl acrylate，2-HEA)等。適合與 SBS 後段 共聚物接枝之甲基丙烯酸酯系單體的例子包含：甲基丙烯 酸乙酯（ethyl methacrylate，EMA)、甲基丙浠酸環氧丙酯 (glycidyl methacrylate，GMA)、甲基丙稀酸異丁酯（isobutyl methacrylate ，IBMA)、曱基丙烯酸十二 S旨（lauryl methacrylate ，LMA)、甲基丙烯酸正 丁酉旨（n-butyl methacrylate，NBMA)、甲基丙浠酸十 八酉旨（stearyl methacrylate，SMA)、甲基丙浠酸乙基己酉旨（2-ethylhexyl methacrylate，2-EHMA)、曱基丙烯酸經基丙酷（2-hydroxypropyl methacrylate，2-HPMA)，以及甲基丙浠酸二 甲基胺基乙醋（dimethylaminoethyl methacrylate，DMAEMA) 等。 更佳地，在該接著組成物中，與SBS嵌段共聚物接枝 之單體係為一選自於由下列所構成之族群的化合物：丙烯 酸、曱基丙烯酸、曱基丙烯酸羥基乙酯、順丁烯二酸酐以 及此等之一組合。而在本新型之具體例中，該與SBS嵌段 M269189 共聚物接枝之單體為丙烯酸單體。 此外，SBS嵌段共聚物與上述單體的比例可依照產品 的而求進行調整，且依據反應的需要，可於接枝反應中加 =適當的觸媒’而在本新型之具體例中，所使用之觸媒為. 過乳化苯甲醯(benz〇yl per〇xide，Bp〇)。而適合用於上述接 枝反應之溶劑的例子為··甲苯㈨比⑶匀、乙酸丁酯 acetate)以及環己烷（cycl〇hexane)等。在本新型之具體例中 ，用於上述接枝反應之溶劑為甲苯。而所製得之接著組成. 物可利用加入一溶劑來調整黏度，較佳之黏度範圍為 _ 500〜3〇,〇〇〇 cps。 該基質層13是相背於該表面層u而設置在該接著層 12上，且由一含有一 SBS嵌段共聚物之基質組成物所構成 。亥基貝層13為該貼合積層1之最内層，且該基質層13 之非與。亥接者層12接合之面是用來與其他材料結合。 較佳地，除了 SBS嵌段共聚物之外，該用以構成基質 層13之基質組成物更含有一塑化劑；更佳地，該基質組成 物中之塑化劑為石蠟油（Paraffin 〇U)或環烷油（naphthenic · 0l1)。塑化劑之添加量會決定產品的硬度及抗張強度（tensile r strength) ’故塑化劑的添加量可依據產品的品質需求進行調 整’且亦須配合各種規格之SBS進行變化。但需注意的是 右塑化劑添加過置時’可能會產生移R(migrati〇n)現象。 在該基質組成物中，SBS嵌段共聚物的規格可依據產 品之製程與物性的需求而做不同的選擇及變化。需注意的 疋產的抗張強度與撕裂強度（tearing strength)及車縫強 10 M269189 度（seam strength)有關，而產品的硬度及反撥彈性（reb〇und) 則會決定產品的屈曲手感，其中，產品的抗張強度隨著 SBS嵌段共聚物的分子量而改變，產品的硬度則由該基質 組成物中之苯乙烯與丁二烯的比例及塑化劑的含量而決定 ，以及產品的反撥彈性則依據該基質組成物中之苯乙烯與 丁 一炸的比例而決定。 為了減輕該基質層13之重量及調整產品的屈曲手感， 選擇性地，該基質組成物更含有一發泡劑（bl〇wing agent)。 於該基質組成物中，可選用各種市售之發泡劑，且可依據 習知技術及產品需求，額外添加其他有助於氣泡成長之添 加劑，例如碳酸鈣（Cac03)或滑石粉（takum powder)等之填 充劑（filling agent)。 再者，如圖2所示，本新型另提供一種具有上述貼合 積層單元1之積層結構，包含：一織物層2、一設置於該織 物層2上之貼合積層單元丨，以及一設置於該織物層2與該 貼合積層單元1之間的織物接著層3。該積層結構中之貼合 積層單元1的各層組成如前文所述，且該織物接著層2亦 由上述之接著組成物所構成，因此，將不再多加贅述。 <製備例> 用以形成積層結構之各層組成物的製備 1 ·用於構成該表面層11之漿料是將1 〇〇份重量計之pu、 0〜5份重量計之色料、〇」〜！份重量計之平滑劑以及 1〜5份重量計之消光劑進行調配混合而製得。 2.用於構成該接著層12及該織物接著層3之接著組成物 是將15份重量計之SBS嵌段共聚物與15份重量計之 M269189 丙細®文予以混合，並於69.6份重量計之甲苯、〇2 p 量計之過氧化苯甲醯以及0·2份重量計之抗氧化劑二在 下進行接枝反應而製得。上述接枝反應之溫度為 反應時間約為4〜5小時。 3·用於構成該基質層13之基質組成物是將1〇〇份重量呀 之SBS肷段共聚物、35份重量計之塑化劑（石壤油或環 烷油）、2.4份之發泡劑、3〜12份重量計之填充劑、^ 份重量計之色料以及〇·4份重量計之抗氧化劑予以調配 混合，並於125〜135°C之溫度進行反應而製得。 <實施例> 利用壓延加工（calendering)製程或淋膜加工（mm coating)製程，將上述製備例中之基質組成物塗佈於一聚乙 烯膜上，以於該聚乙烯膜上形成一基質層13,其中，壓延 加工製程所使用之裝置如圖3所示，淋膜加工製程所使用 之裝置如圖4所示，以及該聚乙烯膜之作用在於防止該基 質層13自身形成捲曲膠著狀。 於圖3中，壓延加工製程所使用之裝置包含一底材捲 繞輥輪（base material take-up r〇ller)3l、一 入料口（h〇pper)32 、一螺桿壓出機（eXtriuier)33、倒L型壓延輥輪組（reverse [ calendering r〇llers)34、壓紋輪（embossing r〇Uer)35、橡膠輪 (mbber roller)36、冷卻輪組（cooling r〇Uers)37 以及半製品 捲取輥輪38，元件編號39則表示一塗佈材料。 於圖4中，淋膜加工製程所使用之裝置包含一底材捲 繞輥輪41、一入料口 42、一螺桿壓出機43、一 τ型模（τ_ 12 M269189 心)44、一橡膠輪45、一壓紋輪邨、一冷卻輪組47车 製品捲取幸昆輪48，元件編號49則表示一塗佈材料。牛 接著利用刀式塗佈（knife c〇ating)製程或親輪塗 7ting)製程’將上述製備例中之接著組成物塗佈於上述基 質層13上’同時將該聚乙烯膜移除，以於該基質層η : 形成：接著層12。最後’同樣地利用刀式塗佈製‘或链輪 坌佈製私，將上述用以構成表面層之聚料塗佈於該接著只 12上」以於該接著層12上形成一表面層u，並製得—貼： 積層單7G 1。其中’輥輪塗佈製程所使用之裝置如圖5所示 ，刀式塗佈製程所使用之裝置如圖6所示。 不 於圖5中，輥輪塗佈製程所使用之裝置包含一底材捲 繞輥輪51、一順向紋路輥輪（forward r〇ller)52、—逆向紋路 棍輪（reVerse roller)53、一烘箱54、一聚乙婦膜捲取概輪w 以及一半製品捲取輥輪58，元件編號59則表示—塗佈材料 〇 於圖6中’刀式塗佈製程所使用之裝置包含—底材捲 繞心輪61、一支撐平板62、一到刀（knife)63、-供箱64、 。一聚乙稀膜捲取輥輪65以及—半製品捲取輕輪料，元件編 號69則表示一塗佈材料。 然後利用刀式塗佈製程，將上述製備例中之接著組成 物塗佈於-織物層2上，以於該織物層2上形成—織物接 著層3❿製得一接合織物，再利用一貼合製程〜 process)，如圖7所示，將上述之貼合積層單元ι捲繞於一 底材捲取輥輪71上，並將該含有織物層2及織物接著層3 13 M269189 之接合織物捲繞於一捲取輥輪72上，以將該貼合積層單元 1與上述接合織物進行接合，而獲得一積層結構。 於圖7中，該貼合製程所使用之裝置包含一底材捲取 輥輪71、一捲取輥輪72、一預熱輪組73、一烘箱％、一 軟質橡膠輪75、一壓紋輪76以及一成品捲取輪78。 選擇性地，除了上述之製程外，本新型之積層結構可 運用習知方法進行製造。值得一提地，該積層結構之貼合 積層單元之表面層可首先塗佈於一具有花紋之離型紙 (release paper)上，再依序塗佈一接著層及一基質層，最後 再與塗佈有一織物接著層之織物層結合，即可製得一具 有一形成有花紋圖案之表面之積層結構。 綜上所述，本新型提供一種貼合積層單元，該貼合積 層單元包含一含有PU系樹脂之表面層、一含有一與一單體 接枝之SBS嵌段共聚物之接著層以及一含有SBS嵌段共聚 物之基負&。该表面層具有一外視面及一内接面，該外視 面可進製成不同花紋及圖案。纟新型亦提供一種積 層結構，該積層結構包含上述貼合積層單元、一織物接著 層以及一織物層。 准以上所述者，僅為本新型之較佳實施例而已，當不 能以此限定本新型實施之範圍，即大凡依本新型申請專利 範圍及新型說明内容所作之簡單的等效變化與修飾，皆仍 屬本新型專利涵蓋之範圍内。 【圖式簡單說明】 圖1是一示意圖，顯示一依據本新型之一具體例之貼 14 M269189 合積層單元； 圖2是一示意圖，顯示一依據本新型之一具體例之積 層結構； 圖3是一示意圖，說明一用於製造本新型之積層結構 之裝置； 圖4是一示意圖，說明一用於製造本新型之積層結構 之另一裝置； 圖5是一示意圖，說明一用於製造本新型之積層結構 之又另一裝置； 圖6是一示意圖，說明一用於製造本新型之積層結構 之又另一裝置；及 圖7是一示意圖，說明一用於製造本新型之積層結構 之又另一裝置。 M269189 【主要元件符號說明】 1....... •…貼合積層單元 11 ····· •…基質層 111… •…外視面 112… •…内接面 12 •… •…接著層 13 •…· 7....... •…純梭装© z....... j 31 ••… •…底材捲繞輥輪 32 ··..· •…入料口 33 "… …·螺桿壓出機 34 ····· •…倒L型壓延輥輪組 35 · _.· …·壓紋輪 36 ·.··· …·橡膠輪 37 •…· •…冷卻輪組 38 ••… •…半製品捲取輥輪 39 ••… •…塗佈材料 41 ····· •…底材捲繞輥輪 42 ••… …·入料口 43 ····. •…螺桿壓出機 44 •…· ••••T型模 45 "… •…橡膠輪 46 *·.·· •…壓紋輪 47 •…· •…冷卻輪組 48 ·.··. •…半製品捲取輥輪 49 ••… •…塗佈材料 51 _··.· •…底材捲繞輥輪 52 ··..· •…順向紋路輥輪 53 ••… —逆向紋路報輪 54 *··.. …·烘箱 55 •.… •…聚乙稀膜捲取輥輪 58 ….· …·半製品捲取輥輪 59…· •塗佈材料 61 …*· •…底材捲繞輥輪 62 •…· •…支撐平板 63 ••… •…刮刀 64 ···.. •…烘箱 65 ··.·. …·聚乙烯膜捲取輥輪 68 •，… •…半製品捲取輥輪 69 ••… •…塗佈材料 71 ··..· •…底材捲繞輥輪 72 ·.·.· •…捲取輥輪 73 ••… …··預熱輪組 74 ·.··· …·烘箱 75 ••… •…軟質橡膠輪 76 ··..· •…壓紋輪 16 M269189 78 成品捲取輪 17M269189 8. Description of the new model: [Technical field to which the new model belongs] The new model relates to a laminating structure, and more particularly to a laminating structure having a bonding laminate unit. It includes a matrix layer containing a styrene-butadiene-styrene (hereinafter referred to as "SBS") block copolymer, and a polyurethane ( polyurethane, hereinafter simply referred to as "PU"). [Previous technology] As the concept of animal conservation has become more and more mature, the access to and use of animal leather materials has been more restricted. Therefore, there have been many base fabric layers by laminating one or more polymer layers on a base fabric layer. layer) to study the manufacture of artificial leather, and the manufactured artificial leather can be widely used in footwear, furniture, automotive interiors, boxes, bags and garments. One of the conventional materials used to make the polymer layer of artificial leather is polyvinyl chloride (hereinafter simply referred to as "PVC"). The polymer layer made of PVC not only has the waterproof function, but also strengthens and stabilizes the structure of the base fabric layer, while providing a good surface touch and flexion feel. However, in recent years, it has been found that the use of PVC raw materials will produce pollutants such as dioxin, heavy metals, and phthalates, and will cause serious harm to the environment. Therefore, PVC has been gradually banned. Therefore, the industry is also actively seeking other materials that are environmentally friendly. Another conventional material is wet PU (Wet PU), but its cost is higher than PVC. Therefore, a combination of styrenic block copolymer M269189 and pu is also currently being tried. However, this combination In addition, because the styrenic polymer has poor compatibility with PU, it cannot be well bonded together, which may cause peeling or delamination. In order to improve the compatibility of this class B polymer with PU, in the pending new patent application of the Republic of China No. 932006516, the author mentioned a method with a backing laminate ) i composite fabric ° Hayue glue layer includes the following two-layer structure: an adhesive layer applied to the fabric layer, an intermediate layer applied to the adhesive layer, and a surface modification layer applied to the intermediate layer, wherein, The adhesive layer has an adhesive composition, which includes an SBS segment copolymer grafted with an acrylate monomer, and a pu 'blended with the grafted SBS block copolymer. The intermediate layer has a composition containing an SBS block copolymer and a solvent. In the author's previous case, the adhesive backing layer was used to provide a thickness sufficient to give the composite fabric good hand feel properties. From the above, it is known that there is still a need for a laminated material with low cost, difficult surface peeling and good properties. The entire contents of the Republic of China New Patent Application No. 9320806516 under review are incorporated into this case for reference. [New content] One of the objects of the present invention is to provide a laminated build-up unit, which is produced by combining a surface layer containing a pu-based resin and a matrix layer containing an SBS block copolymer, and The matrix layer containing the sbs block copolymer can effectively improve the buckling feel property of the laminated unit and reduce the manufacturing cost. 'M269189 A new type—the purpose is to provide—a laminating laminate with a bonding layer consisting of a bonding composition comprising a plate-block copolymer grafted with a monomer, And used to join-a surface layer containing PU and a matrix layer containing SBS block copolymer. Another new purpose of the new model is to provide a lamination and lamination unit having a surface layer containing 叩 series resin, the surface layer containing pu series resin has an external view ', and the external view can be based on the final product. Need to make different patterns and patterns. Yet another object of the present invention is to provide a laminated structure having a laminated laminated unit ', which is made by combining a -fabric layer, -fabric adhesion layer, and a laminated laminated unit. According to one aspect of the present invention, a laminating and laminating unit includes a surface layer composed of a series of resin and having an external viewing surface and an inward surface, an inward surface provided on the surface layer, and- The bonding layer composed of the composition: and-a matrix layer provided on the bonding layer and composed of a matrix composition. The adhering composition includes an -to-monomer grafted sbs block copolymer, and the matrix composition contains an SBS block copolymer. According to another aspect of the present invention, a laminated structure having the above-mentioned laminated laminated unit includes a fabric layer, a laminated laminated unit provided on the textile layer, and a laminated layer provided between the textile layer and the laminated laminated unit. Layer of fabric. The adhesive layer and the fabric adhesive layer are each composed of an adhesive composition. The above-mentioned adhesive composition is prepared by reacting an SBS block copolymer with a monomer to improve the compatibility of the SBS block copolymer with pu M269189 'and effectively join the matrix containing the SBS block copolymer. Layer and the surface layer containing ρυ ·. [Embodiment] The foregoing and other technical contents, features, and effects of the present invention will be clearly presented in the following detailed description of the preferred embodiment with reference to the drawings. As shown in FIG. 1, the present invention first provides a laminated unit 1 including a surface layer 11, an adhesive layer 12, and a matrix layer 13. The surface layer 11 is made of a PU-based resin, and has an outer view surface 111 and an inner contact surface 112 opposite to the outer view surface 1Π. When the laminated layer unit is combined with other materials (for example, fabric, wood, etc.) to make a product, the outer surface 11 of the surface layer 11 forms the appearance of the product, and can be based on the product's requirements. Compressed into different patterns and patterns. In the manufacture of the surface layer, it is also possible to add other additives, such as a smoothing agent to increase surface smoothness and anti-scratch, or to make the surface appear matte, according to the known technology and product requirements. Effect of matting agent. However, it should be noted that if the smoothing agent is added in excess, it will make the surface layer sticky and affect the subsequent effect; and if the matting agent is added in excess, the scratch resistance of the surface layer u will be poor. The adhesive layer 12 is disposed on the inner surface 12 of the surface layer 11 and is composed of an adhesive composition, which includes an SBS block copolymer grafted with a monomer. Preferably, in the adhesive composition, the single system grafted with the SBS block copolymer M269189 is a compound selected from the group consisting of: acrylic acid monomers, acrylic acid Aerylie monomer, methacrylic acid monomer, methacrylic monomer, maleic anhydride, and one of these combinations. Examples of acrylate monomers suitable for grafting with SBS block copolymers include: methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA) , 2-ethylhexyl acrylate (2-EHA), 2-hydroxyethyl acrylate (2-HEA), etc. Examples of methacrylate monomers suitable for grafting with SBS back-end copolymers include: ethyl methacrylate (EMA), glycidyl methacrylate (GMA), methyl Isobutyl methacrylate (IBMA), lauryl methacrylate (LMA), n-butyl methacrylate (NBMA), octadecyl methylpropionate Stearyl methacrylate (SMA), 2-ethylhexyl methacrylate (2-EHMA), 2-hydroxypropyl methacrylate (2-HPMA), and methyl Dimethylaminoethyl methacrylate (DMAEMA), etc. More preferably, in the bonding composition, the single system grafted with the SBS block copolymer is a compound selected from the group consisting of acrylic acid, fluorenyl acrylic acid, hydroxyethyl acrylate, Maleic anhydride and one of these combinations. In the specific example of the present invention, the monomer grafted with the SBS block M269189 copolymer is an acrylic monomer. In addition, the ratio of the SBS block copolymer to the above monomers can be adjusted according to the requirements of the product, and according to the needs of the reaction, the = appropriate catalyst can be added to the grafting reaction. In the specific example of the new model, The catalyst used was benzyl peroxide (Bpo). Examples of suitable solvents for the above-mentioned grafting reaction include: toluene tocopherol ratio CU, butyl acetate, and cyclohexane. In a specific example of the present invention, the solvent used for the above-mentioned graft reaction is toluene. And the prepared adhesive composition can be adjusted by adding a solvent, and the preferred viscosity range is _ 500 ~ 30.0 cps. The matrix layer 13 is disposed on the adhesion layer 12 opposite to the surface layer u, and is composed of a matrix composition containing an SBS block copolymer. The helical shell layer 13 is the innermost layer of the laminating layer 1, and the matrix layer 13 is not the same. The joining surface of the helical connector layer 12 is used for bonding with other materials. Preferably, in addition to the SBS block copolymer, the matrix composition used to form the matrix layer 13 further contains a plasticizer; more preferably, the plasticizer in the matrix composition is paraffin oil (Paraffin). U) or naphthenic oil (naphthenic · 01l). The amount of plasticizer added will determine the hardness and tensile strength of the product ‘so the amount of plasticizer added can be adjusted according to the quality requirements of the product’ and it must be changed in accordance with various specifications of SBS. However, it should be noted that when the right plasticizer is added too far, R (migration) may occur. In the matrix composition, the specifications of the SBS block copolymer can be selected and changed differently according to the production process and physical properties of the product. It should be noted that the tensile strength of the product is related to the tearing strength and seam strength of 10 M269189, and the hardness and rebundance of the product will determine the flexing feel of the product. Among them, the tensile strength of the product changes with the molecular weight of the SBS block copolymer, and the hardness of the product is determined by the ratio of styrene to butadiene in the matrix composition and the content of plasticizer, as well as the Reverse elasticity is determined based on the ratio of styrene to dichloromethane in the matrix composition. In order to reduce the weight of the matrix layer 13 and adjust the flexing feel of the product, optionally, the matrix composition further contains a blowing agent. In the matrix composition, various commercially available foaming agents can be selected, and other additives that can help bubble growth, such as calcium carbonate (Cac03) or talc powder (takum powder), can be additionally added according to the conventional technology and product requirements. ) And other filling agents. Furthermore, as shown in FIG. 2, the present invention further provides a laminated structure having the above-mentioned laminated laminated unit 1, including: a fabric layer 2, a laminated laminated unit provided on the textile layer 2, and an arrangement A fabric bonding layer 3 is formed between the fabric layer 2 and the laminated unit 1. The composition of the layers of the laminated laminated unit 1 in the laminated structure is as described above, and the fabric adhesive layer 2 is also composed of the adhesive composition described above, so it will not be described in detail. < Preparation example > Preparation of each layer composition for forming a laminated structure 1 · The slurry used to form the surface layer 11 is made of 100 parts by weight of pu, 0 to 5 parts by weight of colorant, 〇 "~! The smoothing agent in parts by weight and the matting agent in 1 to 5 parts by weight are prepared by mixing and mixing. 2. The adhesive composition used to form the adhesive layer 12 and the fabric adhesive layer 3 is a mixture of 15 parts by weight of SBS block copolymer and 15 parts by weight of M269189 acrylic®, and 69.6 parts by weight It was prepared by carrying out a graft reaction with toluene, benzophenone peroxide in an amount of 0.2 p, and antioxidant 2 in an amount of 0.2 parts by weight. The temperature of the above grafting reaction is about 4 to 5 hours. 3. The matrix composition used to form the matrix layer 13 is composed of 100 parts by weight of an SBS segment copolymer, 35 parts by weight of a plasticizer (stone earth oil or naphthenic oil), and 2.4 parts of hair. A foaming agent, 3 to 12 parts by weight of a filler, ^ parts by weight of a colorant, and 0.4 parts by weight of an antioxidant are formulated and mixed, and are prepared by reacting at a temperature of 125 to 135 ° C. < Example > The calendering process or the mm coating process was used to coat the matrix composition in the above-mentioned preparation example on a polyethylene film to form a polyethylene film on the polyethylene film. The substrate layer 13, wherein the device used in the calendering process is shown in FIG. 3, the device used in the laminating process is shown in FIG. 4, and the role of the polyethylene film is to prevent the substrate layer 13 from forming curls and glues shape. In FIG. 3, the device used in the calendering process includes a base material take-up roller 31, a material inlet 32, and a screw extruder (eXtriuier). ) 33. Inverted L-shaped calendering rollers (reverse [calendering r〇llers) 34, embossing rollers (embossing r〇Uer) 35, rubber wheels (mbber roller) 36, cooling wheels (cooling r〇Uers) 37 and The semi-finished product take-up roller 38, and the component number 39 indicates a coating material. In Figure 4, the equipment used in the coating process includes a substrate winding roller 41, a feed inlet 42, a screw extruder 43, a τ mold (τ_ 12 M269189 core) 44, and a rubber Wheel 45, an embossed wheel village, a cooling wheel group 47 car products take Xingkun wheel 48, and the component number 49 represents a coating material. The cattle then used a knife coating process or a round-coating process to apply the adhesive composition in the above-mentioned preparation example to the substrate layer 13 at the same time, while removing the polyethylene film to On this matrix layer η: formed: followed by layer 12. Finally, the same method is used for “knife coating” or sprocket cloth to make the above-mentioned polymer for forming the surface layer, and then coating the adhesive layer 12 to form a surface layer u on the adhesive layer 12. And made-posted: Multilayer single 7G 1. The device used in the 'roller coating process' is shown in FIG. 5, and the device used in the knife coating process is shown in FIG. As shown in FIG. 5, the device used in the roller coating process includes a substrate winding roller 51, a forward grain roller 52, a reVerse roller 53, An oven 54, a polyethylene film take-up roller w and half of the product take-up roller 58, the component number 59 indicates-coating material. In Figure 6, the device used in the 'knife coating process includes-bottom The material winding core wheel 61, a support plate 62, a knife 63, a supply box 64, and the like. A polyethylene film take-up roller 65 and a semi-finished product take up a light material, and the component number 69 indicates a coating material. Then, using the knife coating process, the adhesive composition in the above-mentioned preparation example is coated on the fabric layer 2 to form on the fabric layer 2-the fabric bonding layer 3 is used to prepare a bonding fabric, and then a bonding is used. Process ~ process), as shown in FIG. 7, the above-mentioned laminating and laminating unit ι is wound on a substrate winding roller 71, and the bonded fabric roll including the fabric layer 2 and the fabric adhesive layer 3 13 M269189 It is wound on a take-up roller 72 to join the laminated and laminated unit 1 with the above-mentioned joining fabric to obtain a laminated structure. In FIG. 7, the device used in the laminating process includes a substrate take-up roller 71, a take-up roller 72, a preheating wheel set 73, an oven%, a soft rubber wheel 75, and an embossing. Wheel 76 and a finished product take-up wheel 78. Alternatively, in addition to the above-mentioned processes, the novel laminated structure can be manufactured by conventional methods. It is worth mentioning that the surface layer of the laminated lamination unit of the laminated structure can be coated on a release paper with a pattern first, followed by a subsequent layer and a substrate layer, and finally with the coating The fabric is combined with a fabric layer followed by a fabric layer to obtain a laminated structure having a surface on which a pattern is formed. To sum up, the present invention provides a laminated build-up unit, which comprises a surface layer containing a PU-based resin, an adhesive layer containing an SBS block copolymer grafted with a monomer, and a SBS block copolymer base &. The surface layer has an outer view surface and an inner connection surface, and the outer view surface can be made into different patterns and patterns. Xuanxin also provides a laminated structure including the above-mentioned laminated laminated unit, a fabric adhesive layer, and a fabric layer. The above-mentioned ones are only the preferred embodiments of the present invention. When the scope of implementation of the present invention cannot be limited in this way, that is, the simple equivalent changes and modifications made according to the scope of the patent application and the description of the new model, All are still covered by the new patent. [Brief description of the drawings] FIG. 1 is a schematic diagram showing a sticker 14 M269189 laminated unit according to a specific example of the present invention; FIG. 2 is a schematic diagram showing a laminated structure according to a specific example of the present invention; FIG. 3 Is a schematic diagram illustrating a device for manufacturing the novel laminated structure; FIG. 4 is a schematic diagram illustrating another device for manufacturing the novel laminated structure; FIG. 5 is a schematic diagram illustrating a device for manufacturing the novel structure Fig. 6 is a schematic diagram illustrating another apparatus for manufacturing the novel laminated structure; and Fig. 7 is a schematic diagram illustrating a apparatus for manufacturing the novel laminated structure. Yet another device. M269189 [Description of main component symbols] 1 .... •… laminated laminated unit 11 ······… matrix layer 111… •… outside view 112… •… inner face 12 •… •… Next layer 13 •… · 7 ....... •… pure shuttle © z ....... j 31 ••… •… substrate winding roller 32 ······… Feed 33 " ...… Screw Extruder 34 ······· Inverted L-shaped Calender Roller Set 35 · _ ··… · Embossing Wheel 36 ······· Rubber Wheel 37 •… · •… Cooling wheel set 38 ••… •… Semi-product winding roller 39 ••… •… Coating material 41 ······… Substrate winding roller 42 ••…… Feeding port 43 ··· .. •… Screw extruder 44 •… · •••• T-die 45 "… •… Rubber wheel 46 * ·. ·· •… Embossing wheel 47 •… · •… Cooling wheel Group 48 ····. ··························· of coating material 51 ········… Wheel 53 ••… —Reverse Grain Reporting Wheel 54 * ·· ..… · Oven 55 •.… •… Polyethylene Take-up roll 58… ..… · Semi-finished take-up roll 59… • Coating material 61… * · •… Substrate take-up roll 62 62…… Support plate 63 •… 64 ······· Oven 65 ········· Polyethylene film take-up roll 68 68 ····················· Coating material 71 ··· Substrate winding roller 72 ·························· Preheating wheel set 74 ······· Oven 75 ••… • ... 76 ·· .. ··… Embossing wheel 16 M269189 78 Finished take-up wheel 17