201002518 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種具有優異的硬度、耐磨性及密著性 之 '活性能量線硬化性塗膜之積層體的製造方法，及以該方 法製造之積層體。 【先前技術】 爲了使紙、木材、塑膠、金屬、玻璃等基材的表面， 賦有硬度、耐擦傷性、耐摩擦性、耐藥品性等的各種性能 以保護表面，故進行被覆。 做爲塗布劑者主要是使用活性能量線硬化性組成物。 這是因爲它具有比使用熱塑性樹脂或熱硬化性樹脂的情況 更優異的表面耐擦傷性、耐磨擦性。 於各種基材或基材上直接塗布活性能量線硬化組成物 而形成圖案層時，由於活性能量線硬化性組成物硬化時的 體積收縮等，而降低層間的密著性且產生密著不良。 爲了解決前述密著不良的問題，有設置底漆層至被稱 作固定層之中間層，以取得在層間的密著提高的方法情 浣。雖然這些使用熱硬化樹脂與熱塑性樹脂等做爲底漆、 固定，但爲了硬度、耐擦傷性、耐摩擦性、耐藥品性等的 物性，因此不使用該等做爲最外層。 在裝飾片的領域中，已知以熱乾燥而變爲非黏著，使 用熱或電子束來完全硬化固定劑。然而，因爲只有熱硬化 型或電子束硬化型固定劑時硬度或耐擦傷性不夠充分’故 有例如全面設置含有消光劑的電子硬化型樹脂構成的頂塗 層。然而，適合的固定劑之組成不是特定的。（參照專利文 201002518 獻1)。 相同領域中，已知做爲第一保護層者以水性乳化樹脂 爲主成分之活性能量線硬化型水性樹脂組成物，及做爲第 二保護層者以不包含水性乳化樹脂之活性能量線硬化型水 性樹脂組成物所構成之表面強化修飾紙。雖然第一保護層 爲活性能量線硬化性組成物，但使用水性乳化系的情況， 做爲最外層之可使用的硬度並不夠充分，因此設置第二保 護層來提高表面硬度及耐久性（參照專利文獻2)。 此外，例如已知使用中間層用熱乾燥型電離放射線硬 化樹脂。該等樹脂爲含有電離放射線反應性雙鍵的水性乳 液或含有電子放射線反應性雙鍵的水溶性或溶劑可溶性樹 脂等，樹脂的Tg爲40°C以上、較佳爲60°C以上。即使中 間層爲活性能量線硬化性組成物，但因爲有水性乳化系， 故並無做爲最外層之可使用的硬度，因此設置頂塗層使表 面硬度提高（參照專利文獻3)。 做爲轉印構成用頂塗劑的使用例子，已知在形成丙烯 酸系的電離放射線硬化型樹脂保護層後，在電子線照射前 形成圖案層之轉印片。然而，爲了顯現電子照射前的非黏 著性，相對於電離放射線必須爲非交聯型的熱塑性丙烯酸 樹脂，但不能得到充分的硬度（參照專利文獻4)。 做爲轉印構成用頂塗劑的使用例子，此外，已知在形 成胺基甲酸酯系的硬化型樹脂保護層後，照射紫外線使塗 膜硬化後，形成從紫外線吸收劑層至接著劑層的方式（參照 專利文獻5)。 然而，具有活性能量線硬化性塗膜之積層體不能獲得 201002518 完全滿足表面硬度、耐擦傷性及密著性。 【專利文獻1】特開平8-28 1 896號公報 【專利文獻2】特開平9-290487號公報 【專利文獻3】特開平10-1 1 9226號公報 【專利文獻4】特開平7- 3 1 499 5號公報 【專利文獻5】特開200 8 -6 70 8號公報 【發明内容】 本發明的課題係提供具有優異的硬度、耐磨性及密著: 性的塗膜之積層體的製造方法，及以該製造方法所製得白勺 積層體。 爲了使塗膜的硬化性充分顯現，且得到在進行重複g 布時的層間密著性，而藉由在活性能量線硬化性組成物巾 含有非黏著型的胺基甲酸酯樹脂來達成上述的課題而完$ 本發明。即，第一，本發明係提供一種積層體之製造方法， 其特徵在於依序具有下列步驟：（1)在基材上塗布含有（a) 在主骨架具有胺基甲酸酯鍵、（b)軟化點爲40-150°C、（c) 重量平均分子量爲5,000- 1，〇〇〇,〇〇〇、且（d)可溶於有機溶劑 中的活性能量線硬化性樹脂之活性能量線硬化性組成物之 步驟；（2)非伴隨活性能量線照射之乾燥步驟；（3)全面或部 分重複塗布含有從熱塑性組成物、熱硬化性組成物及活性 能量線硬化性組成物所組成之群組中選出之1種以上的組 成物之步驟；（4)照射活性能量線之硬化步驟。 此外’第二，本發明係提供以前述製造方法所得到的 積層體。 由本發明的製造方法所製造的積層體係用來做爲具有 201002518 底塗層功能之裝飾片構造，其係前述（i)在基材上含有（a) 在主骨架具有胺基甲酸酯鍵、（b)軟化點爲40-l5〇°C、（c) 重量平均分子量爲5,000-1，〇〇〇,〇〇〇、且（d)可溶於有機溶劑 中的活性能量線硬化性樹脂之活性能量線硬化性組成物的 硬化層，具有做爲基底之充分的硬度且確保上層的密著 性。又，即使使用做爲上塗層功能之轉印片也具有充分密 著性，特別地，因爲構成相同硬化層之表面而確保更佳的 表面硬度、耐擦傷性。 【實施方式】 本發明係提供一種積層體之製造方法，其特徵在於依 序具有下列步驟：（1)在基材上塗布含有（a)在主骨架具有 胺基甲酸酯鍵、（b)軟化點爲40_150°C、（c)重量平均分子 量爲5，000 - 1，000 ,〇〇〇、且（d)可溶於有機溶劑中的活性能 量線硬化性樹脂之活性能量線硬化性組成物（以下，含有非 黏著型胺基甲酸酯樹脂之活性能量線硬化組成物）之步 驟；（2 )非伴隨活性能量線照射之乾燥步驟；（3 )塗布含有 從熱塑性組成物、熱硬化性組成物及活性能量線硬化性組 成物所組成之群組中選出之1種以上的組成物之步驟；（4 ) 照射活性能量線之硬化步驟。 做爲以本發明的製造方法所製得的積層體之構造，其 係可例舉例如轉印片構造、裝飾片構造。 轉印片構造的情況，於經脫模處理的PET原板等上藉 由下述步驟：（1)塗布含有上述非黏著型胺基甲酸酯樹脂之 活性能量線硬化組成物以做爲頂塗層之步驟；（2 )非伴隨活 性能量線照射之乾燥步驟；（3)塗布含有至少一種以上選自 201002518 由熱塑性組成物、熱硬化性組成物及活性能量線硬化性組 成物所組成之組成物以做爲固定層之步驟；此外，非伴隨 活性能量線照射之乾燥步驟，並塗布接著層之步驟而構成 轉印片，使用該轉印片，並藉由（4 )轉印與成形步驟；（5 ) 照射活性能量線之硬化步驟，而形成成型物。 裝飾片構造的情況，於薄紙、塑膠片等的原板上藉由 下述步驟：（1)塗布含有前述非黏著型胺基甲酸酯樹脂之活 性能量線硬化性組成物以做爲固定層的步驟；（2 )非伴隨活 性能量線照射之乾燥步驟；（3 )塗布含有活性能量線的組成 物以做爲頂塗層之步驟；（4 )經由照射活性能量線之硬化步 驟，而形成裝飾片。 轉印片構造的情況和裝飾片構造的情況下，含有前述 非黏著型胺基甲酸酯樹脂之活性能量線硬化組成物，在塗 布後、以熱、風等乾燥塗膜，使溶劑成分蒸發，而形成非 黏著的塗膜。因此，不需要使用活性能量線來硬化同層， 而可於其上塗布下一步驟的層。這是特別地以凹版印刷方 式來塗布的情況，其對於在每一塗覆單元不設置活性能量 線照射裝置，而可以重複塗覆等的理由爲有利的。又，所 謂的非黏著係指經由手指接觸塗膜的表面沒有感覺黏手的 程度之乾燥而言。 本發明使用的活性能量線硬化性組成物爲含有非黏著 型胺基甲酸酯樹脂之活性能量線硬化性組成物。非黏著型 胺基甲酸酯樹脂之軟化點爲40 - 1 50 °C、重量平均分子量爲 5，000 - 1，〇〇〇，000、胺基甲酸酯樹脂可溶於有機溶劑中。軟 化點較佳爲60°C〜150°C、更佳爲70°C~150°C。重量平均分 201002518 子量較佳爲10, 〇〇〇〜600,000，更佳爲50,〇〇〇〜600,000。做 爲有機溶劑可使用甲醇、乙醇、異丙醇、丁醇等的醇系溶 劑，丙酮、甲基乙基酮、甲基異丁基酮等的酮系溶劑，乙 酸乙酯、乙酸丁酯等的酯系溶劑，甲塞路蘇、乙塞路蘇等 的醚系溶劑，甲苯、己烷、環己烷等的烴基系溶劑，四氫 呋喃等有機溶劑及其混合溶劑，在考慮熱塑性有機化合物 的溶解之情況較佳爲酮系溶劑或酯系溶劑。 使用於本發明的製造方法，如上所述而得知含有非黏 著型胺基甲酸酯樹脂之活性能量線硬化性組成物，在不偏 離本發明的目的之範圍內，爲了賦予各種功能可以添加活 性能量線硬化型單體、丙烯酸胺基甲酸酯、聚酯丙烯酸酯、 丙烯酸環氧酯等的活性能量線硬化性低聚物、丙烯酸丙烯 醯酯等的活性能量線硬化型聚合物、著色劑、體質顏料、 聚矽氧、潤滑劑、可塑劑、消泡劑、氧化防止劑、紫外線 吸收劑、光安定劑、耦合劑、界面活性劑、有機溶劑及螯 合劑、無機塡料、有機塡料等的添加劑。 本發明的製造方法中，做爲塗膜形成用組成物的塗布 方法’例如套版印刷、膠版印刷、輕塗、凹版塗布、棒材 塗漆機等。 於本發明的製造方法中所用的含非黏著性胺基甲酸酯 樹脂之活性能量線硬化性組成物、及在下一步驟之活性能 量線硬化性組成物係照射電子束、紫外線、或r射線等的電 離放射線等來硬化。以紫外線來硬化的情況，使用具備高 壓水銀燈、激分子燈（e x c i m e r 1 a m p)、金屬鹵化物水銀燈 之已知的紫外線照射裝置。硬化時的紫外線照射量較佳爲 201002518 30~1500roJ/cra2。照射量小於30mJ/cm2時不完全硬化、超過 1 5 OOraJ/cm2時塗膜變黃、經由熱可能產生基材的損傷等。 以電子束而硬化的情況，可以使用已知的電子束照射 裝置。硬化時的電子束照射量較佳爲10〜10 OkGy。照射量 小於10 kGy時不能完全硬化，超過100 kGy可能產生塗膜、 基材的損傷等。 照射紫外線而硬化的情況，按所需要，相對於1 00質 量份的活性能量線硬化性化合物而言，經由紫外線的照射 產生自由基等之光（聚合）起始劑較佳添加爲0.1至20質量 份左右。 做爲自由基產生型的光（聚合）起始劑者可列舉例如二 苯乙二酮、二苯甲酮、米其勒酮、2 -氯氧硫灿嘎、2,4 -二 乙基氧硫卩山唱等的除去氫型態，及苯偶姻乙醚、二乙氧基 苯乙酮、苄基甲基縮酮、羥環己基苯基酮、2-羥基-2甲基 苯基酮等的光開裂型態。可使用其中之單獨或組合複數種。 於轉印片構造，固定層的形成係可列舉例如丙烯酸樹 脂、聚酯樹脂、胺基甲酸酯樹脂、環氧樹脂、三聚氫胺樹 脂，其中使用單獨或複數的物的組合來完成。又，可使用 其中之混合各種活性能量線硬化型組成物及各種聚異氰酸 酯等。 於裝飾片構造中，頂塗層的形成係例如可使用各種活 性能量線硬化型組成物等。 其次，所例舉的實施例係用來具體說明本發明。又， 本說明書未預先特別限定時，份及％係以質量爲基準。表1 中例舉轉印片構造的例子。表1顯示實施例及比較例的塗 -10- 201002518 膜組成物的評價結果。 [表1][Technical Field] The present invention relates to a method for producing a laminate of an active energy ray-curable coating film having excellent hardness, wear resistance and adhesion, and a method therefor Manufacturing of laminates. [Prior Art] In order to protect the surface by imparting various properties such as hardness, scratch resistance, abrasion resistance, and chemical resistance to the surface of a substrate such as paper, wood, plastic, metal, or glass, it is coated. As the coating agent, an active energy ray hardening composition is mainly used. This is because it has superior surface scratch resistance and abrasion resistance than in the case of using a thermoplastic resin or a thermosetting resin. When the active energy ray-hardening composition is directly applied to various substrates or substrates to form a pattern layer, the volume of the active energy ray-curable composition is reduced during shrinkage, and the adhesion between the layers is lowered to cause adhesion defects. In order to solve the above problem of poor adhesion, there is a case where a primer layer is provided to an intermediate layer called a fixed layer to obtain an adhesion between layers. Although these thermosetting resins and thermoplastic resins are used as a primer and are fixed, they are not used as the outermost layer for physical properties such as hardness, scratch resistance, abrasion resistance, and chemical resistance. In the field of decorative sheets, it is known to become non-adhesive by heat drying, and heat or electron beams are used to completely harden the fixing agent. However, since only the thermosetting type or the electron beam hardening type fixing agent is insufficient in hardness or scratch resistance, for example, a top coat layer composed of an electronic hardening type resin containing a matting agent is provided in total. However, the composition of a suitable fixative is not specific. (Refer to Patent Document 201002518 for 1). In the same field, an active energy ray-curable aqueous resin composition containing an aqueous emulsion resin as a first protective layer and an active energy ray hardening without an aqueous emulsified resin as a second protective layer are known. A surface-reinforced paper composed of a water-based resin composition. Although the first protective layer is an active energy ray-curable composition, in the case of using an aqueous emulsified system, the hardness which can be used as the outermost layer is not sufficient, so a second protective layer is provided to improve surface hardness and durability (refer to Patent Document 2). Further, for example, it is known to use an intermediate layer to harden the resin with a thermally dry type ionizing radiation. These resins are aqueous emulsions containing ionizing radiation-reactive double bonds or water-soluble or solvent-soluble resins containing electron-radioactive double bonds, and the resin has a Tg of 40 ° C or higher, preferably 60 ° C or higher. Even if the intermediate layer is an active energy ray-curable composition, since it has an aqueous emulsification system, it does not have the hardness which can be used as the outermost layer. Therefore, the top coat layer is provided to improve the surface hardness (see Patent Document 3). As an example of use of the top coating agent for transfer printing, a transfer sheet in which a pattern layer is formed before electron beam irradiation after forming an acrylic acid-based ionizing radiation-curable resin protective layer is known. However, in order to exhibit non-adhesiveness before electron irradiation, it is necessary to be a non-crosslinked thermoplastic acryl resin with respect to ionizing radiation, but sufficient hardness cannot be obtained (see Patent Document 4). As an example of use of a top coat agent for transfer formation, it is known that after forming a urethane-based curable resin protective layer, ultraviolet rays are applied to cure the coating film to form an ultraviolet absorber layer to an adhesive. The method of the layer (refer to Patent Document 5). However, a laminate having an active energy ray-curable coating film cannot obtain 201002518, which fully satisfies surface hardness, scratch resistance, and adhesion. [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-290487 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei No. Hei. [Patent Document 5] [Patent Document 5] JP-A No. 200 8 -6 70 8 SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate having a coating film having excellent hardness, wear resistance, and adhesion: a manufacturing method, and a laminate obtained by the manufacturing method. In order to sufficiently exhibit the curability of the coating film and to obtain the interlayer adhesion when repeating the g-cloth, the above-mentioned active energy ray-curable composition towel contains a non-adhesive urethane resin to achieve the above. The subject matter is completed by the present invention. That is, first, the present invention provides a method for producing a laminate, which is characterized by the following steps: (1) coating on a substrate containing (a) having a urethane bond in the main skeleton, (b) a softening point of 40-150 ° C, (c) an active energy ray of an active energy ray-curable resin having a weight average molecular weight of 5,000 - 1, 〇〇〇, 〇〇〇, and (d) soluble in an organic solvent a step of a hardening composition; (2) a drying step without irradiation with an active energy ray; (3) a full or partial repeated coating comprising a thermoplastic composition, a thermosetting composition, and an active energy ray-curable composition. a step of selecting one or more compositions in the group; (4) a hardening step of irradiating the active energy rays. Further, 'second', the present invention provides a laminate obtained by the aforementioned production method. The laminate system produced by the production method of the present invention is used as a decorative sheet structure having a 201002518 undercoat function, which is (i) contains (a) a urethane bond in the main skeleton on the substrate, (b) a softening point of 40-l5 〇 ° C, (c) an active energy ray-curable resin having a weight average molecular weight of 5,000-1, lanthanum, cerium, and (d) soluble in an organic solvent The hardened layer of the active energy ray-curable composition has sufficient hardness as a base and ensures adhesion of the upper layer. Further, even if a transfer sheet having a function as an overcoat layer is used, it has sufficient adhesion, and in particular, it is possible to ensure better surface hardness and scratch resistance by constituting the surface of the same hardened layer. [Embodiment] The present invention provides a method for producing a laminate, which is characterized by the following steps: (1) coating on a substrate containing (a) having a urethane bond in the main skeleton, (b) The active energy ray hardening composition of the active energy ray-curable resin which has a softening point of 40-150 ° C, (c) a weight average molecular weight of 5,000 - 1,000 , 〇〇〇, and (d) soluble in an organic solvent (hereinafter, a step of containing an active energy ray-hardening composition of a non-adhesive urethane resin); (2) a drying step without irradiation with an active energy ray; (3) coating containing a thermoplastic composition, and thermosetting a step of selecting one or more components selected from the group consisting of a sexual composition and an active energy ray-curable composition; and (4) a step of curing the active energy ray. The structure of the laminate obtained by the production method of the present invention may, for example, be a transfer sheet structure or a decorative sheet structure. In the case of the transfer sheet structure, the demolded PET original sheet or the like is subjected to the following steps: (1) coating an active energy ray hardening composition containing the above non-adhesive urethane resin as a top coat. a step of layering; (2) a drying step without irradiation with active energy rays; (3) coating comprising at least one component selected from the group consisting of thermoplastic composition, thermosetting composition and active energy ray hardening composition selected from 201002518 The step of using the material as a fixed layer; further, the drying step without the irradiation of the active energy ray, and the step of applying the subsequent layer to form a transfer sheet, using the transfer sheet, and by (4) transfer and forming steps (5) A hardening step of irradiating the active energy ray to form a shaped body. In the case of the decorative sheet structure, the original sheet of a thin paper, a plastic sheet or the like is subjected to the following steps: (1) applying an active energy ray-curable composition containing the aforementioned non-adhesive urethane resin as a fixed layer. a step; (2) a drying step that is not accompanied by active energy ray irradiation; (3) a step of applying a composition containing active energy rays as a top coat; (4) forming a decoration by a hardening step of irradiating an active energy ray sheet. In the case of the transfer sheet structure and the decorative sheet structure, the active energy ray-curing composition containing the non-adhesive urethane resin is dried, and after drying, the coating film is dried by heat or air to evaporate the solvent component. And form a non-adhesive coating film. Therefore, it is not necessary to use an active energy ray to harden the same layer, and the layer of the next step can be coated thereon. This is particularly the case where it is applied by gravure printing, which is advantageous for the case where the active energy ray irradiation device is not provided for each coating unit, and coating or the like can be repeated. Further, the term "non-adhesive" means that the surface of the coating film which is in contact with the finger is not dry to the extent that it is sticky. The active energy ray-curable composition used in the present invention is an active energy ray-curable composition containing a non-adhesive urethane resin. The non-adhesive urethane resin has a softening point of 40 - 1 50 ° C and a weight average molecular weight of 5,000 - 1, 〇〇〇, 000, and the urethane resin is soluble in an organic solvent. The softening point is preferably from 60 ° C to 150 ° C, more preferably from 70 ° C to 150 ° C. The weight average score 201002518 is preferably 10, 〇〇〇~600,000, more preferably 50, 〇〇〇~600,000. As the organic solvent, an alcohol solvent such as methanol, ethanol, isopropanol or butanol, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, ethyl acetate or butyl acetate may be used. An ester solvent, an ether solvent such as methacetin or ethixos, a hydrocarbon solvent such as toluene, hexane or cyclohexane; an organic solvent such as tetrahydrofuran or a mixed solvent thereof, in consideration of dissolution of a thermoplastic organic compound; The case is preferably a ketone solvent or an ester solvent. As described above, the active energy ray-curable composition containing a non-adhesive urethane resin can be added as described above in order to impart various functions without departing from the object of the present invention. Active energy ray-curable oligomer such as active energy ray-curable monomer, urethane urethane, polyester acrylate, or epoxy acrylate, active energy ray-curable polymer such as acryl acrylate, and coloring Agents, extender pigments, polyfluorene oxides, lubricants, plasticizers, defoamers, oxidation inhibitors, UV absorbers, light stabilizers, coupling agents, surfactants, organic solvents and chelating agents, inorganic materials, organic germanium Additives such as materials. In the production method of the present invention, it is used as a coating method for a composition for forming a coating film, for example, a stencil printing, an offset printing, a light coating, a gravure coating, a bar coater, or the like. The active energy ray-curable composition containing the non-adhesive urethane resin used in the production method of the present invention, and the active energy ray-curable composition in the next step are irradiated with an electron beam, ultraviolet rays, or r-rays. Ionizing radiation, etc. to harden. In the case of curing by ultraviolet rays, a known ultraviolet irradiation device including a high pressure mercury lamp, an excimer lamp (e x c i m e r 1 a m p), or a metal halide mercury lamp is used. The amount of ultraviolet rays upon hardening is preferably 201002518 30 to 1500 roJ/cra2. When the irradiation amount is less than 30 mJ/cm2, the coating film is not completely cured, and when the irradiation amount is more than 1,500 ÅJ/cm2, the coating film becomes yellow, and damage of the substrate may occur due to heat. In the case of hardening with an electron beam, a known electron beam irradiation device can be used. The electron beam irradiation amount at the time of hardening is preferably 10 to 10 OkGy. When the irradiation amount is less than 10 kGy, it cannot be completely cured. If it exceeds 100 kGy, damage to the coating film or the substrate may occur. In the case of curing with ultraviolet rays, it is preferable to add a light (polymerization) initiator which generates radicals or the like via ultraviolet irradiation to 0.1 to 20 parts by mass of the active energy ray-curable compound as needed. The mass is around. As the photopolymerization initiator of the radical generation type, for example, diphenylethylenedione, benzophenone, mischrone, 2-chlorooxosulfan, 2,4-diethyloxy The hydrogen-removing form of thiopurine sing, etc., and benzoin ethyl ether, diethoxyacetophenone, benzyl methyl ketal, hydroxycyclohexyl phenyl ketone, 2-hydroxy-2 methyl phenyl ketone, etc. Light cracking pattern. A plurality of them may be used alone or in combination. In the transfer sheet construction, the formation of the pinned layer may, for example, be an acrylic resin, a polyester resin, a urethane resin, an epoxy resin or a melamine resin, which is carried out using a combination of individual or plural substances. Further, various active energy ray-curable compositions, various polyisocyanates, and the like can be used. In the construction of the decorative sheet, the top coat layer can be formed, for example, by using various kinds of active wire-hardening type compositions and the like. Second, the exemplified embodiments are intended to specifically illustrate the invention. Further, in the case where the present specification is not particularly limited in advance, the parts and % are based on the mass. An example of the structure of the transfer sheet is exemplified in Table 1. Table 1 shows the evaluation results of the film compositions of the coatings of Examples and Comparative Examples -10-201002518. [Table 1]
實施例1 實施例2 比較例1 比較例2 原板（脫膜處理之PET) 1層 Art resin AH-51M40 65 65 — — 紫外光UV1700B — — 15 40 DIANAL BR85 — — 25 一 IRGACURE184 3 3 3 2 甲基乙基酮 32 32 57 58 塗布量 5 g/m2 5 g/m2 5 g/m2 5 g/m2 UV照射 te te j \ w te j\\\ 有 非黏著性 有 有 有 有（UV後） 耐阻隔性 〇 〇 △ 〇 彎曲性 〇 〇 〇 X 2層 ACRYDICA-814 60 50 60 60 Art resin AH-51M40 — 10 — 一 Desmodur L75 10 10 10 10 乙酸乙酯 30 30 30 30 塗布量 2 g/m2 2 g/m2 2 g/m2 2 g/m2 UV照射 M /\s\ 姐 y \ W Μ y\\\ 3層 Paraloid B-72 20 20 20 20 甲基乙基酮 80 80 80 80 塗布量 2 g/m2 2 g/m2 2 g/m2 2 g/m2 成形(對ABS板的熱轉印） 轉印後的UV照射 有 有 有 姐 耐拋光性 〇 〇 X 〇 密著性 〇 〇 〇 X 表2中，例舉裝飾片構造的例子。表2顯示實施例3 及比較例3、4塗膜組成物及評價結果。 -11 - 201002518 [表2]Example 1 Example 2 Comparative Example 1 Comparative Example 2 Original plate (PET for release film treatment) 1 layer Art resin AH-51M40 65 65 — UV light UV1700B — — 15 40 DIANAL BR85 — — 25 A IRGACURE184 3 3 3 2 A Base ethyl ketone 32 32 57 58 Coating amount 5 g/m2 5 g/m2 5 g/m2 5 g/m2 UV irradiation te te j \ w te j\\\ There are non-adhesive properties (after UV) Barrier resistance 〇〇 〇 〇 bendability 〇〇〇 X 2 layer ACRYDICA-814 60 50 60 60 Art resin AH-51M40 — 10 — One Desmodur L75 10 10 10 10 Ethyl acetate 30 30 30 30 Coating amount 2 g/m2 2 g/m2 2 g/m2 2 g/m2 UV irradiation M /\s\ sister y \ W Μ y\\\ 3 layers Paraloid B-72 20 20 20 20 methyl ethyl ketone 80 80 80 80 coating amount 2 g/m2 2 g/m2 2 g/m2 2 g/m2 Forming (thermal transfer to ABS board) UV irradiation after transfer has a polishing resistance 〇〇X 〇Adhesiveness 〇〇〇X In 2, an example of a decorative sheet structure is exemplified. Table 2 shows the composition of the coating film of Example 3 and Comparative Examples 3 and 4 and the evaluation results. -11 - 201002518 [Table 2]
實施例3 比較例3 比較例4 原板（薄紙） 1層 Art resin AH-51M40 62 — — 紫外光UV1700B — 15 40 DIANAL BR85 — 25 — AROWIX M402 3 — — SYLOID 7000 3 3 3 IRGACURE184 3 3 2 甲基乙基酮 29 57 58 塗布量(全部塗覆） 2g/m1 2 3 4 5 2g/m2 2 g/m2 UV照射 Μ y\\\ Μ 有 非黏著性 有 有 有（UV後） 2層 紫外光UV1700B 40 40 40 IRGACURE184 2 2 2 甲基乙基酮 58 58 58 塗布量(部分塗覆） 8g/m2 8g/m2 8 g/m2 UV照射 有 有 有 成形( 貼合MDF板） MEK硏磨 〇 x憮第2層之部分) 〇 耐拋光性 〇 X憮第2層之部分） 〇 密著性 〇 〇 X 表1及表2的原料如下。 -12- 1Example 3 Comparative Example 3 Comparative Example 4 Original plate (thin paper) 1 layer Art resin AH-51M40 62 — UV light UV1700B — 15 40 DIANAL BR85 — 25 — AROWIX M402 3 — — SYLOID 7000 3 3 3 IRGACURE184 3 3 2 Methyl Ethyl ketone 29 57 58 Coating amount (all coating) 2g/m1 2 3 4 5 2g/m2 2 g/m2 UV irradiation Μ y\\\ Μ Non-adhesive (UV) 2 layers of UV light UV1700B 40 40 40 IRGACURE184 2 2 2 Methyl ethyl ketone 58 58 58 Coating amount (partial coating) 8g/m2 8g/m2 8 g/m2 UV irradiation is formed (fitted with MDF board) MEK 硏 〇怃 Part 2 of the )) 〇 抛光 抛光 怃 怃 X怃 part of the second layer) 〇 Closeness 〇〇 X The raw materials of Table 1 and Table 2 are as follows. -12- 1
Art resin AH-51M40根上工業股份有限公司製非黏 著型丙烯酸胺基甲酯。 2 紫外光UV 1 7 00B 日本合成化學股份有限公司（液 狀）丙烯酸胺基甲酸酯。 3 DIANAL BR85 三菱麗陽股份有限公司製丙烯酸酯 樹脂（T g 約 1 0 0 °C )。 4 AROWIXM- 402東亞合成股份有限公司製二新戊四醇六 丙烯酸酯。 5 ACRYDIC A-814 D I C股份有限公司製丙烯酸多醇。 201002518 住友拜耳胺基甲酸酯股份有限 (6 ) Desraodur L- 7 5 公司聚異氰酸酯。 (7) Paraloid B-72 ROHM & HAAS 製丙烯酸樹脂（Tg 約 40〇C )。 (8) IRGACURE184 汽巴精化股份有限公司製光聚 合起始劑。 (9) SYL0ID 7000 格電斯有限公司製氧化矽（平均 粒徑約5 μ m )。 樣品形成條件如下。 用棒材塗漆機將原板全面塗覆第1層，於100 °C約60 秒乾燥而使溶劑揮發。第2層在第1層的上面，實施例i、 2、比較例1、2以全面塗覆的情況，實施例3、比較例4、 5以部分塗覆的情況，於1 〇〇°C約60秒乾燥使溶劑揮發。 於表1及表2所記載的硬化條件使塗膜完全硬化。硬化條 件爲照射UV : 1燈120W/cm高壓水銀燈1路徑（path) 10m/ 分°進行熱硬化的情況爲在60°C靜置3天。 (評價方法） 非黏著性 於1 〇 〇 °C，約6 0秒的熱乾燥後，以手指接觸 來評價。 耐阻隔性 於塗覆物上設置PET薄膜（東洋紡績（股）製 5101、25pm)，100g/cm2、4(TC 放置 24 小時， 評估PET薄膜內的轉移狀態。 彎曲性 將塗覆物彎曲1 80，評估塗膜的破裂狀態。 MEK硏磨 將脫脂棉泡在MEK中’評估於塗覆物表面進 行100次雙面硏磨時的塗膜狀態。 -13- 201002518 實施例1、2中，塗布第1層，以熱風來乾燥，任意塗 膜的表面沒有膨黏的（非黏著），可以平滑地塗布做爲固定 層的第2層。又塗布第3層的接著劑轉印後以紫外線照射 而乾燥’顯示優異固定層的密著性、表面的耐拋光性等特 性。 實施例3，上塗層（第2層）與固定層（第1層）呈現良 好的密著性，相對於MEK硏磨及耐拋光性，其擁有良好的 耐溶劑性且顯示良好的表面硬度。 [產業利用性] 本發發明的積層體的製造方法適用具有優異的硬度、 耐溶劑性、耐摩擦性及密著性的塗膜之轉印片、裝飾片等 積層體的製造方法。 【圖式簡單說明】 Μ 〇 【主要元件符號說明】 Μ 〇 yiw -14-Art resin AH-51M40 Non-adhesive aminomethyl acrylate manufactured by Gensei Industrial Co., Ltd. 2 Ultraviolet UV 1 7 00B Synthetic Chemical Co., Ltd. (liquid) urethane acrylate. 3 DIANAL BR85 acrylate resin (T g approx. 100 °C) manufactured by Mitsubishi Rayon Co., Ltd. 4 AROWIXM-402 East Asia Synthetic Co., Ltd. produces dipentaerythritol hexaacrylate. 5 ACRYDIC A-814 D I C Co., Ltd. made acrylic acid polyol. 201002518 Sumitomo Bayer Carbamate Co., Ltd. (6) Desraodur L- 7 5 Polyisocyanate. (7) Paraloid B-72 ROHM & HAAS acrylic resin (Tg approx. 40〇C). (8) IRGACURE184 Ciba Specialty Chemicals Co., Ltd. Photopolymerization starter. (9) SYL0ID 7000 yttrium oxide yttrium oxide (average particle size of about 5 μ m). The sample formation conditions are as follows. The original layer was completely coated with the first layer by a bar coater and dried at 100 ° C for about 60 seconds to evaporate the solvent. The second layer is on the top of the first layer, the examples i, 2, and the comparative examples 1 and 2 are applied in a full-scale manner, and the case of the embodiment 3 and the comparative examples 4 and 5 is partially coated at 1 〇〇 ° C. Drying for about 60 seconds allowed the solvent to evaporate. The coating film was completely cured under the curing conditions described in Tables 1 and 2. The hardening condition is irradiation with UV: 1 lamp 120 W/cm high pressure mercury lamp 1 path 10 m/min. The case of thermal hardening is to stand at 60 ° C for 3 days. (Evaluation method) Non-adhesiveness After heat drying at about 1 〇 C ° C for about 60 seconds, it was evaluated by finger contact. Barrier resistance The PET film (5101, 25 pm, manufactured by Toyobo Co., Ltd.) was placed on the coating, and 100 g/cm2, 4 (TC was placed for 24 hours to evaluate the transfer state in the PET film. Bending to bend the coating 1 80. Evaluation of the rupture state of the coating film MEK honing was carried out in MEK to evaluate the state of the coating film when the surface of the coating was subjected to 100 times of double-sided honing. -13- 201002518 In Examples 1, 2, coating The first layer is dried by hot air, and the surface of any coating film is not swelled (non-adhesive), and can be smoothly applied as the second layer of the fixed layer. The third layer of the adhesive is applied and transferred to ultraviolet light. The drying 'shows excellent adhesion of the anchor layer and surface polishing resistance. In Example 3, the top coat (the second layer) and the fixed layer (the first layer) exhibit good adhesion to the MEK. Honing and polishing resistance, which has good solvent resistance and exhibits good surface hardness. [Industrial Applicability] The method for producing a laminate of the present invention has excellent hardness, solvent resistance, abrasion resistance and density. Transfer film and decorative film The method of manufacturing a laminate.] [Brief Description of the drawings The main element symbol square Μ DESCRIPTION Μ square yiw -14-