TW201103745A - Thermal transfer sheet cover film - Google Patents

Abstract

The present invention relates to a cover film for thermal transfer sheet which comprises plastic film as the substrate. A heat-resistance layer and a slipping layer are coated subsequently on the backside of the substrate. The purpose of the present invention incorporates a polymer-inorganic composite layer on the frontside of the substrate as protective layer. This composite layer has high transparent, high glossy and anti-scrubbing characteristics. Furthermore, a polymer-inorganic composite layer according to the present invention is formed by a general coating method and its layer thickness according to the present invention is in the range of 0.1 μ m to 10 μ m.

Description

201103745 invention is formed by a general coating method and its layer thickness according to the present invention is in the range of 0.1 μιη to 10 μιη. 四、指定代表圖： (一) 本案指定代表圖為：第（1 )圖。 (二) 本代表圖之元件符號簡單說明： 1基材 2接著層 3抗熱滑層 4染料層 4Y黃色染料層 4M洋紅色染料層 4C靛藍色染料層 5接著層 6保護層 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式201103745] is represented by a general coating method and its layer thickness according to the present invention is in the range of 0.1 μιη to 10 μιη. 4. The designated representative figure: (1) The representative representative figure of the case is: (1). (b) The symbol of the representative figure is briefly described as follows: 1 substrate 2 followed by layer 3 anti-heat sliding layer 4 dye layer 4Y yellow dye layer 4M magenta dye layer 4C 靛 blue dye layer 5 followed by layer 6 protective layer 5. When there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention.

RR

六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種熱轉印型色帶之保護膜 201103745 【先前技術】 昇華里熱轉£卩$錄方法是利用昇華型熱轉印列表機在加熱頭提供 攝氏約200度的高溫’將色帶上的三種原色的染料依照次序昇華轉印 到圖像接收薄片的染料接受層上。昇華型色帶的三原色通常為黃色 (Yellow)、洋紅色(Magenta)、觳藍色(Cyan)’當色帶上三種原色的染料 依照次序昇轉印麵像接收料·材上後，通倾會進行一道程 序是將-層透明的保護轉印到全彩套色關像上使圖像具有抗6. Description of the Invention: [Technical Field] The present invention relates to a protective film for a thermal transfer type ribbon 201103745 [Prior Art] The sublimation heat transfer method is a sublimation type thermal transfer list machine The heating head is supplied with a high temperature of about 200 degrees Celsius'. The dyes of the three primary colors on the ribbon are sublimed in order to be transferred onto the dye receiving layer of the image receiving sheet. The three primary colors of the sublimation ribbon are usually yellow, magenta, and cyan. When the dyes of the three primary colors on the ribbon are lifted in the order of the transfer surface, the material is poured. A process is performed to transfer the transparent protection of the layer to the full color set to make the image resistant.

到、财磨、抗紫外光及抗氡化等功能，讓圖像可以長久保存。因此， 昇華型熱轉印記錄方法所得到關像具有相#多實f的優點，例如色 彩銳利、圖案牢靠度高、影像清晰、色彩鮮盤、色域寬廣、穩定性高、 立體感強以及環保等優點。 前案提到熱轉印型色帶之保護膜材料設計有：美國專利_，斯 提到保護層包含光固化型氨醋修飾的壓克力樹脂之;美國專利 6’737，152提縣護層有多層結構形成的夾層，包含至少—層壓克力樹 脂和-層聚_脂；_專利6,352,767卿_包含軸不可溶的 有誠分的細微粒子；美國專利6,346,316提到保護層包含脂環族聚酷 樹脂，含妓應«外歧收賴絲力單體的絲物；美國專利 6,946,423提到可熱轉印保護層含有蠛，離型層包含水溶性高分子·美 國專利_彻提咖層具編澤，在加叙編測所測的 的光澤度不應低於60%。 綜上所述’昇華鶴轉印記錄方法之圖像接㈣片 色透明、高光澤及耐到、耐磨的設計，方 具有無 且不致影觸像轉㈣片表面並 且不U像色澤，另—方面發明人基於學理的根據：有餐無機^ 201103745 合材料(Organic· inorganic composite material)可明顯增加原本有機化合 物的耐到性’於是設計用溶勝-凝朦法(Sol-gel process)使高分子材料與 無機化合物反應’形成尚分子-無機複合材料(p〇lymer_inorganje composite material) ’此材料具有好的離型特性，在不使用離型層的請 況下可以從塑膠膜完全剝離，並藉由接著層的辅助順利轉印至圖片 上，經實驗證實對圖像的保護具有實質的幫助，因此本項發明的保護 膜設計提供了簡易又有效的方法。 【發明内容】 • 本發明乃有關一種用於熱轉印型色帶之保護膜。 本發明之目的在保護圖像接收薄片影像的完整性。 為達此目的，依本發明熱轉印型色帶之保護膜係於該圖像接收薄 片上轉印一種高分子與無機化合物所製備之有機無機混成複合材料做 為保護膜’該保護膜厚度為0.1微米至10微米。 圖示之簡單說明： 1 基材 2 抗熱層 3 滑層 4 染料層 4Y 黃色染料層 4M洋紅色染料層 4C 靛藍色染料層 5 接著層 6 保護層 圖1乃依本發明一種熱轉印型色帶之保護膜之切面輪廓圖。 以下將詳述本發明： 圖1是依本發明、熱轉印型色帶之保護膜"（以下稱為、保護膜"） 之剖面圖。在此圖中，1表示基材，2表示抗熱層，3表示滑層，4表The functions of arrival, fiscal grinding, anti-ultraviolet light and anti-smashing make images last long. Therefore, the image obtained by the sublimation type thermal transfer recording method has the advantages of many colors, such as sharp color, high pattern reliability, clear image, fresh color, wide color gamut, high stability, strong stereoscopic effect, and Environmental protection and other advantages. The former case mentioned that the protective film material of the thermal transfer type ribbon has the following design: US Patent _, the protective layer contains the photocurable vinegar modified acrylic resin; the US patent 6'737, 152 The interlayer having a multi-layered structure comprising at least a laminated resin and a layer of poly-lipid; _ Patent 6,352,767 _ contains fine particles which are insoluble in the shaft; and US Pat. No. 6,346,316 discloses that the protective layer comprises an alicyclic ring. Polyurethane resin, which contains 丝 « _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The layers are braided, and the gloss measured in the Canadian test shall not be less than 60%. In summary, the image of the sublimation crane transfer recording method (four) is transparent, high-gloss and resistant to wear and wear, and has no and no image-like surface (four) surface and no U-color, and - Aspects of the inventors based on the theory: there is a meal inorganic ^ 201103745 composite material (Organic · inorganic composite material can significantly increase the resistance of the original organic compound ' so the design uses the Sol-gel process (Sol-gel process) Polymer material reacts with inorganic compound to form 'p〇lymer_inorganje composite material' This material has good release characteristics and can be completely peeled off from the plastic film without using the release layer. The protective film design of the present invention provides a simple and effective method by the fact that the adhesion of the adhesive layer is smoothly transferred to the image and it is confirmed by experiments that the protection of the image is substantially helpful. SUMMARY OF THE INVENTION The present invention relates to a protective film for a thermal transfer type ribbon. It is an object of the present invention to protect the integrity of an image receiving sheet image. In order to achieve the object, the protective film of the thermal transfer type ribbon according to the present invention is an organic-inorganic hybrid composite material prepared by transferring a polymer and an inorganic compound onto the image receiving sheet as a protective film. It is from 0.1 micron to 10 microns. Brief description of the illustration: 1 substrate 2 heat resistant layer 3 sliding layer 4 dye layer 4Y yellow dye layer 4M magenta dye layer 4C indigo dye layer 5 followed by layer 6 protective layer Figure 1 is a thermal transfer color according to the present invention The profile of the cut surface of the protective film. The present invention will be described in detail below. Fig. 1 is a cross-sectional view showing a protective film of a thermal transfer type ribbon (hereinafter referred to as "protective film") according to the present invention. In this figure, 1 indicates the substrate, 2 indicates the heat resistant layer, 3 indicates the slip layer, and 4 tables.

201103745 示染料層(4Y:黃色逛姐思 、色細層’ 4Μ:洋紅色染料層，4 C ··款藍色染料層）， 5表示接著層’6表示保護層。 基材1可採用的塑膠薄膜，如聚_脂、聚對苯二甲酸乙二醋、 纖維素樹脂、料__，厚雜縣3.30微米。 接著層所用之接著劑5材料可採用水性或有機溶劑型接著劑，如 、克力樹减相、聚氨峨蹄賴、魏細旨接著劑、聚醋樹脂 接著劑等。 將保護層6利用刮刀式塗佈法、淋幕式塗佈法狹縫式塗佈法、 模唇式塗佈法、逗點滾塗式塗佈法(咖_丨丨桿式塗佈法(bar _ng) ' E7版錢佈法(g__ating)#枝賴㈣職^之表面 上’經過烘箱烘烤將麵除錢，再將接著劑s壯述之塗佈方式塗 佈於保護層6上並經過烘箱烘烤將溶赚去。同理抗歸2及滑層 3用相同加工方式塗佈於塑膠膜1的另一面。 本發明所使用的保護層5,其材料設計為高分子與無機化合物之複 合材料，複合過程是透過溶膠-凝膠法製備，所使用的高分子材料可採 用含醇官能基的化合物’如聚乙烯醇、聚乙烯醇縮丁酸、醇基纖維素、 聚乙二醇等。無機化合物可採用石夕炫氧化合物，包含四烧氧化合物及 二烷氧基二烷化合物。四烷氧化合物結構如通式I，二烷氧基二烷化合 物結構如通式II所示： 201103745 尺3〇—Si——〇r3 - - - (II ) R2 其中Ri、R2、R3為烷基，通常為直鏈型烷基如甲基、乙基。通式I可 採用四曱氧基矽烷或四乙氧基矽烷。通式II可採用二甲氧基二曱基矽 烷或二乙氧基二曱基矽烷。 【實施方式】 本發明的較佳方法示於圖一，依照本方法所製備之熱轉印型色帶 之保護膜，於黃色、洋紅色、靛藍色染料昇華熱轉印形成圖像後，經 過熱轉印覆蓋於圖像接收薄片上，保護圖像的完整。 兹以實施例及對照例說明，例中所有份數均以重量計算。 實跑例：製備熱轉印刑色帶之保讜膜6 本發明之保護層塗料實施程序是先將含醇官能基的樹脂(如聚乙 烯醇、聚乙烯醇縮丁醛、醇基纖維素、聚乙二醇等)攪拌溶解在溶劑當 中，再將所要複合的無機化合物的前驅物加入溶液令並持續穩定的攪 拌，此無機化合物的前驅物結構如通式I及Η所闡明的化合物，可採 用矽烷氧化合物，包含四烷氧化合物(四甲氧基矽烷或四乙氧基矽烷) 及一烧氧基一燒化合物(二甲氧基二甲基石夕院或二乙氧基二甲基石夕 烷）。以下是以實際的例子來說明本發明。201103745 shows the dye layer (4Y: yellow shopper, color layer] 4Μ: magenta dye layer, 4 C · blue dye layer), and 5 indicates the adhesion layer '6 indicates a protective layer. The plastic film of the substrate 1 can be used, such as poly-lipid, polyethylene terephthalate, cellulose resin, material __, 3.30 micron in Houza County. The material of the adhesive 5 used in the subsequent layer may be an aqueous or organic solvent type adhesive such as kelly phase depletion, polyaluminum hydrazone, a fine adhesive, a polyester resin, and the like. The protective layer 6 is applied by a doctor blade coating method, a curtain coating method, a slit coating method, a lip coating method, and a comma-roll coating method (a coffee-claw coating method). Bar _ng) 'E7 version of the money cloth method (g__ating) #枝赖(四) job ^ on the surface 'after baking the oven to remove the money, and then apply the coating method of the adhesive s in the protective layer 6 and After oven baking, it will be dissolved. The same anti-return 2 and the sliding layer 3 are applied to the other side of the plastic film 1 by the same processing method. The protective layer 5 used in the present invention is designed as a polymer and an inorganic compound. The composite material is prepared by a sol-gel method, and the polymer material used may be an alcohol functional group-containing compound such as polyvinyl alcohol, polyvinyl butyric acid, alcohol-based cellulose, polyethylene. Alcohol, etc. The inorganic compound may be a compound of a sulphur oxide containing a tetrasodium alkoxide compound and a dialkoxy dioxane compound. The structure of the tetraalkoxy compound is as shown in the formula I, and the structure of the dialkoxydioxane compound is as shown in the formula II. Show: 201103745 尺3〇—Si—〇r3 - - - (II) R2 where Ri, R2, and R3 are alkyl groups, usually A linear alkyl group such as a methyl group or an ethyl group. A tetramethoxy decane or a tetraethoxy decane may be used in the formula I. The general formula II may be a dimethoxy decyl decane or a diethoxy fluorenyl group. [Description] The preferred method of the present invention is shown in FIG. 1. The protective film of the thermal transfer type ribbon prepared according to the method is formed after the yellow, magenta, and indigo dye sublimation thermal transfer forms an image. Covering the image receiving sheet with thermal transfer to protect the integrity of the image. All examples are given by weight in the examples and comparative examples. Example: Preparation of thermal transfer ribbon The protective layer coating method of the present invention is to first dissolve an alcohol functional group-containing resin (such as polyvinyl alcohol, polyvinyl butyral, alcohol-based cellulose, polyethylene glycol, etc.) in a solvent. Then, the precursor of the inorganic compound to be compounded is added to the solution and the stirring is continued stably. The precursor structure of the inorganic compound is as shown in the formula I and the compound of the formula, and the decane oxygen compound may be used, including the tetraalkoxy compound ( Tetramethoxydecane or tetraethoxy Silane), and a group having a burn burn compound (Dimethoxy or dimethyl cornerstone Tokyo Institute alkyl diethoxy dimethyl cornerstone evening). The following is a practical example of the present invention will be described.

製備保護層塗料6A 將2伤聚已稀醇縮丁路（型號：B10TX ’長春化學）溶解於38份 201103745 的乙醇，持續穩定的麟並加入2.4份的四乙氧基石夕烧，之後緩緩加入 鹽酸並將紐值膽到Μ之間’鱗整個齡溶鱗顧拌並加熱 至迴流狀態’最後在迴流狀態維持約2小睥卽+ Λ士电 ζ』旰即π成本案之保護層塗料 範例之一。 製備保護層塗料6Β 將10份聚乙烯醇（Polyvinyl alcohol，MW=14〇〇，曰本处〇^公司） • 溶解於100份的去離子水及50份的乙醇，持續穩定的授拌並加入12份的 四乙氧基矽烷，之後緩緩加入鹽酸並將酸鹼值調整到3_4之間，再將整個混 合溶液維持攪拌並加熱至迴流狀態，最後在迴流狀態維持約2小時即完成 本案之保護層塗料範例之一。Preparation of protective layer coating 6A Dissolve 2 smear and dilute alcohol condensate (model: B10TX 'Changchun Chemical) in 38 parts of 201103745 of ethanol, continue to stabilize the lining and add 2.4 parts of tetraethoxy zebra, then slowly Add hydrochloric acid and add the value of the broth to the Μ ' 鳞 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个 整个One of the examples. Preparation of protective coating 6 Β 10 parts of polyvinyl alcohol (MW = 14 〇〇, 曰 〇 公司 company) • Dissolved in 100 parts of deionized water and 50 parts of ethanol, continuous stable mixing and adding 12 parts of tetraethoxy decane, then slowly add hydrochloric acid and adjust the pH to between 3 and 4. The whole mixed solution is stirred and heated to reflux, and finally maintained in reflux for about 2 hours. One of the examples of protective coatings.

製備普氙染料層涂料4V 將5.5份黃色染料(Macrolex Yellow 6G，德國Bayer公司）、4.5份 • 聚乙浠醇縮丁搭(Polyvinyl butyral resin ; Eslec BX-1，日本 SekisuiPreparation of Pu'er dye layer coating 4V 5.5 parts of yellow dye (Macrolex Yellow 6G, Bayer, Germany), 4.5 parts • Polyvinyl butyral resin; Eslec BX-1, Japan Sekisui

Chemical公司）；加入到90份混合溶劑(等重量比例之甲苯與甲基乙基 酮）’持續穩定的攪拌8小時後得到混合均勻之黃色染料層塗料。Chemical company); added to 90 parts of a mixed solvent (equal weight ratio of toluene and methyl ethyl ketone)' continued stable stirring for 8 hours to obtain a uniformly mixed yellow dye layer coating.

盤備洋紅夂染料層塗料4M 將2.6份紅色染料(MS Red G，日本Mitsui Toatsu公司）、1·4份紫 色染料(Macrolex Red Violet R，德國Bayer公司）、4份聚乙烯醇縮丁醛 (Polyvinyl butyral resin ; Eslec BX-1 ’ 日本 Sekisui Chemical 公司）；加 入到90份混合溶劑(40份甲苯、40份甲基乙基酮、10份異丙醇），持 201103745 續穩定的攪拌8小時後得到混合均勻之洋紅色染料層塗料。Plated magenta dye layer coating 4M 2.6 parts of red dye (MS Red G, Mitsui Toatsu, Japan), 1.4 parts of purple dye (Macrolex Red Violet R, Bayer, Germany), 4 parts of polyvinyl butyral ( Polyvinyl butyral resin ; Eslec BX-1 'Sekisui Chemical Co., Japan); added to 90 parts of mixed solvent (40 parts of toluene, 40 parts of methyl ethyl ketone, 10 parts of isopropyl alcohol), with stable stirring for 8 hours after 201103745 A uniformly mixed magenta dye layer coating is obtained.

塑備靛兹色染料層塗料4C 將4份鼓藍色染料(Kayaset Blue 714，日本Nippon Kayaku公司）、 4.3 份聚乙稀醇縮丁搭(Polyvinyl butyral resin; Eslec BX-.l，日本 Sekisui Chemical公司）；加入到90份混合溶劑(4〇份甲笨、40份甲基乙基酮、 10份異丙醇），持續穩定的攪拌8小時後得到混合均勻之靛籃色染料層 塗料。 製備抗熱層塗料2 將 4.5 份聚乙稀醇縮丁搭(Polyvinyl butyral resin ; Eslec BX-1，日 本 Sekisui Chemical 公司）、1，6-己二異氰酸醋（Hexamethylene Diisocyanate，沂慶貿易股份有限公司）；加入到90份混合溶劑(45份f 苯、45份曱基乙基酮），持續穩定的攪拌4小時後得到混合均勻之抗熱 層塗料。 製備滑層涂斜3 將 1 份矽油(X-22-343，日本 Shinetsu Kagaku Kogyo K.K.公司）、3 份聚 乙烯醇縮丁醛(Polyvinyl butyral resin ; Eslec KS-5，日本 Sekisui Chemical 公 司）；加入到96份混合溶劑(48份甲苯、48份甲基乙基酮），持續穩定的攪 拌4小時後得到混合均勻之接受層塗料。 將本發明所製備的高分子與無機化合物之複合材料做熱轉印型色帶保 護膜之保縣與未添加錢化合物之純高分子保護層經鱗印後進行錯筆 201103745 硬度測試比較，結果顯示聚乙烯醇縮丁醛（型號：B10TX，長春化學）與 聚乙烯醇（Polyvinyl alcoho卜MW=1,400，曰本Showa公司）之硬度均為 2H，而本發明之高分子與無機化合物之複合材料6A之熱轉印型色帶保護 膜硬度為3H，本發明之保護層材料6B處理之熱轉印型色帶保護膜硬度為 6H。從實驗結果可以發現：（1)本發明所製備的高分子與無機化合物之複合 材料做熱轉印型色帶保護膜硬度明顯地增加；（2)聚乙烯醇與四乙氧基矽烷 % 所形成的高分子-無機化合物比聚乙烯醇縮丁醛與四乙氧基矽烷所形成的高 刀子、無機化合物具有較佳的硬度與抗刮能力^ 【圖式簡單說明】 圖1係本發明熱轉印型色帶之保護膜示意圖。 【主要元件符號說明】Plastic 靛 dye color layer coating 4C 4 parts of drum blue dye (Kayaset Blue 714, Nippon Kayaku, Japan), 4.3 parts of polyvinyl butyral resin; Eslec BX-.l, Sekisui Chemical, Japan Company); added to 90 parts of mixed solvent (4 parts of methyl ketone, 40 parts of methyl ethyl ketone, 10 parts of isopropyl alcohol), and continued stable stirring for 8 hours to obtain a uniformly mixed enamel dye layer coating. Preparation of heat-resistant layer coating 2 4.5 parts of Polyvinyl butyral resin; Eslec BX-1, Japan Sekisui Chemical Co., Ltd., Hexamethylene Diisocyanate, Zhaoqing Trading Co., Ltd. Co., Ltd.); added to 90 parts of mixed solvent (45 parts of f benzene, 45 parts of mercaptoethyl ketone), and continued to stir for 4 hours to obtain a uniform heat-resistant layer coating. Preparation of slip layer coating oblique 3 1 part of eucalyptus oil (X-22-343, Japan Shinetsu Kagaku Kogyo KK company), 3 parts of polyvinyl butyral (Polyvinyl butyral resin; Eslec KS-5, Japan Sekisui Chemical Company); To 96 parts of a mixed solvent (48 parts of toluene, 48 parts of methyl ethyl ketone), stirring was continued for 4 hours to obtain a uniformly mixed receiving layer coating. The composite material of the polymer and the inorganic compound prepared by the invention is used as a thermal transfer type ribbon protective film of Baoxian County and the pure polymer protective layer of the unadded money compound is scaled and then subjected to the wrong pen 201103745 hardness test, and the result is compared. It is shown that polyvinyl butyral (model: B10TX, Changchun Chemical) and polyvinyl alcohol (Polyvinyl alcoho MW = 1,400, 曰本Showa) have a hardness of 2H, and the composite of the polymer and the inorganic compound of the present invention The thermal transfer type protective film of 6A has a hardness of 3H, and the thermal transfer type protective film of the protective layer material 6B of the present invention has a hardness of 6H. From the experimental results, it can be found that: (1) the composite material of the polymer and the inorganic compound prepared by the invention has a significantly increased hardness of the thermal transfer type protective film; (2) polyvinyl alcohol and tetraethoxy decane% The formed polymer-inorganic compound has better hardness and scratch resistance than the high knife and inorganic compound formed by polyvinyl butyral and tetraethoxydecane. [Simplified illustration] FIG. 1 is a heat of the present invention. Schematic diagram of the protective film of the transfer type ribbon. [Main component symbol description]

1基材 2抗熱層 3滑層 4染料層 4Y黃色染料層4Μ洋紅色染料層 4C靛藍色染料層5接著層 6保護層1 substrate 2 heat resistant layer 3 slip layer 4 dye layer 4Y yellow dye layer 4 Μ magenta dye layer 4C 靛 blue dye layer 5 subsequent layer 6 protective layer

Claims (1)

201103745 七、申請專利範圍： 1· -種_印型色帶之保護膜，其包括： 一基材，用明印傳輸並承載所塗佈材料； 著曰係辅助保護層熱轉印順利接著於圖像接收薄片： 一保護層，將保護層轉印到全彩套色的圖像上，使圖像具有抗到、耐 磨等功％*’讓®像可域久保存。此保護層是塗佈—高分子·無機化合 Φ 物複合材料。 2·如申請專利範圍第1項所述之色帶，並包含： 一百色染料層，係承載昇華轉印所需用的黃色染料； 一洋紅色染料層，係承載昇華轉印所需用的洋紅色染料； 一靛藍色染料層，係承載昇華轉印所需用的靛藍色染料； 一抗熱層，係、提升基材_溫性’防止基材因受熱產生皺摺的現象； 滑層，係提升基材的滑度，使列印過程順利進行； • 3,如申請專利範圍第1項所述之保護層，其中高分子韻複合材料是使 用溶膠-凝膠法所製備。 (如申請專利範圍第i項所述之保護層，是藉由泛用塗佈方式所形成之 0·1微米至10微米厚度的薄獏材料。 5.如申請專概圍第i項所述之保護層，其中高分子·無機化合物複合材 料所提到的高分子材料是指含醇官能基的化合物。 6·如申請專利範圍第5項所述之含醇官化合物是指乙烯醇、聚乙騎 縮丁醛'醇基纖維素、與聚乙二醇。 201103745 7·如申請專利範圍第1項所述之保護層，其♦古 、〒阿刀子-無機化合物複合材 料所提到的無機化合物是指矽烷氧化合物。 &如申料利細第7 _叙魏減合物是細綠化合物與二炫 氧基'一院化合物。 9. 如申請專利範圍第8項所述之四烧氧化合物是指四曱氧基石夕烧與四乙 氧基矽烷。 10. 如申請專利範圍第8項所述之二烷氧基二烷化合物是指二甲氧基二甲 基矽烷與二乙氧基二甲基矽烷。 11·如申請專利範圍第1項所述之熱轉印型色帶之保護膜，其中之保護層的 塗佈方式是指線棒塗佈、刮刀塗佈、風刀塗佈、狭缝塗佈、逗點滾塗佈、 模唇塗佈、桿式塗佈與凹版塗佈。201103745 VII. Patent application scope: 1. The protective film of the _print ribbon, which comprises: a substrate, which is transported and carried by the imprint; the thermal transfer of the auxiliary protective layer is followed by Image receiving sheet: A protective layer that transfers the protective layer to the full-color image, so that the image has anti-wear, wear-resistance, etc.*. This protective layer is a coating-polymer/inorganic compound Φ composite. 2. The ribbon as described in claim 1, and comprising: a one-color dye layer for carrying a yellow dye for sublimation transfer; a magenta dye layer for carrying sublimation transfer a magenta dye; a blue dye layer that carries the indigo dye required for sublimation transfer; a heat resistant layer that lifts the substrate _temperature' prevents the substrate from wrinkling due to heat; The layer is to improve the smoothness of the substrate, so that the printing process can be carried out smoothly; • 3, as claimed in claim 1, wherein the polymer rhyme composite material is prepared by a sol-gel method. (The protective layer described in item i of the patent application is a thin tantalum material having a thickness of from 0.1 μm to 10 μm formed by a general coating method. 5. As described in the application item i) The protective layer, wherein the polymer material mentioned in the polymer/inorganic compound composite refers to a compound having an alcohol functional group. 6. The alcohol-containing compound as described in claim 5 refers to vinyl alcohol and poly. B riding butanalol alcohol-based cellulose, and polyethylene glycol. 201103745 7 · The protective layer mentioned in the first paragraph of the patent application, the inorganic mentioned in the ♦ ancient, 〒 knife-inorganic compound composite The compound refers to a decane oxygen compound. &<><><>><>> Oxygen compound means tetradecyl oxysulfan and tetraethoxy decane. 10. The dialkoxydialkyl compound as described in claim 8 refers to dimethoxy dimethyl decane and diethoxy Dimethyl decane. 11. Thermal transfer as described in claim 1 The protective film of the ribbon, wherein the coating method of the protective layer refers to wire bar coating, blade coating, air knife coating, slit coating, comma roll coating, lip coating, rod coating Coated with gravure.