TW201105501A - Release process paper and process for producing same - Google Patents

Release process paper and process for producing same Download PDF

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Publication number
TW201105501A
TW201105501A TW099109658A TW99109658A TW201105501A TW 201105501 A TW201105501 A TW 201105501A TW 099109658 A TW099109658 A TW 099109658A TW 99109658 A TW99109658 A TW 99109658A TW 201105501 A TW201105501 A TW 201105501A
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Taiwan
Prior art keywords
ionizing radiation
release paper
layer
meth
paper
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TW099109658A
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Chinese (zh)
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TWI494216B (en
Inventor
Kyoko Kogo
Noriyuki Shiina
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Dainippon Printing Co Ltd
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Publication of TW201105501A publication Critical patent/TW201105501A/en
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Publication of TWI494216B publication Critical patent/TWI494216B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • B32B5/147—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces by treatment of the layer
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/001—Release paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Paper (AREA)

Abstract

To provide process release paper having a shaping face in which surface glossiness is 60 or higher in 60[deg.] reflection and excellent in heat resistance and a releasing property. The process release paper is characterized in that a paper base material, an ionization radiation curable resin layer and a thermocurable silicone layer are laminated in this order. The process release paper is suitable for manufacturing synthetic leather and a melamine decorative board having the surface glossiness of 60 or higher in 60[deg.] reflection because the paper is excellent in the heat resistance and the releasing property.

Description

201105501 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種工程剝離紙，更詳而言之，其係賦 型面之表面光澤度於60。反射爲60以上，可適宜使用於耐 熱性、耐溶劑性優，高光澤之合成皮革或三聚氰胺化妝板 之製造。 【先前技術】 以往，就合成皮革而言，已廣泛使用以氯化乙烯系樹 脂或聚胺基甲酸酯樹脂作爲主原料者。如此之合成皮革係 常使用離型紙而製造。例如，爲製造聚胺基甲酸酯皮，於 離型紙上塗佈糊狀之聚胺基甲酸酯樹脂，乾燥、固化後貼 合基布而從離型紙剝離。若於離型紙形成與天然皮革同樣 之花紋或其他之凹凸，可對所得到之合成皮革表面賦予良 好的花紋。依同樣之原理，於離型紙上塗佈糊狀之聚胺基 甲酸酯樹脂，乾燥、固化後，形成氯化乙烯發泡層而與基 布貼合，亦可從離型紙剝離。又，製造氯化乙烯皮之方法 ，係於離型紙上塗佈氯化乙烯溶膠，加熱、凝膠化之後， 形成氯化乙烯發泡層而與基布貼合，亦可從離型紙剝離。 可使用於如此之合成皮革的製造之離型紙，一般，於 紙基材塗佈由樹脂所構成之剝離層而調製。離型紙係轉印 其表面花紋而於合成皮革上形成表面花紋者，必須具有適 於賦型之表面狀態。其中，得到斑紋（mura)比較少之樹脂 表面層的方法，已揭示使由聚丙烯與聚乙烯所構成之樹脂 -5- 201105501 組成物、與聚丙烯均聚物共押出於基材上之層合方法（特 開平5-82806號公報）》層合聚丙稀之層合物因以可層合 之溫度押出，押出斑紋嚴重，但爲改善此，若混合低密度 聚乙烯，相溶性差，故產生光澤斑紋或表面粗糙。因此， 其特徵在於：使具有特定之熔融流動率的聚丙烯與特定_ 造之聚乙烯所構成的樹脂組成物、與特定之熔融流動率的 聚丙烯均聚物共押出於基材上，改良表面狀態者。若依上 述之特開平5-82806號公報，使前述樹脂組成物與聚丙烯 均聚物共押出而以前述樹脂組成物作爲基材側，因使用特 定之樹脂組成物，可解決押出斑紋，因使用聚丙烯均聚物 ，產生耐熱性及光澤斑紋或表面粗糙均無之優異的表面狀 態。在實施例中係評估押出斑紋等之層合性以及表面狀態 ，得到表面光澤及平滑性優異之層合物。 又，製造於表面貼合布作爲基材之聚胺基甲酸酯系合 成皮革，於離型紙塗佈及乾燥聚胺基甲酸酯樹脂，然後， 爲貼合前述布基材，於聚胺基甲酸酯層上使用含有以異氰 酸酯基作爲官能基之成分的第1液、與由多元醇所構成之 第2液所構成之聚胺基甲酸酯系2液型接著劑。此2液型接 著劑係黏著力強，於沙發等之家具類或鞋等之使用期間很 長者或使用頻繁者常被使用，但在上述步驟中具有高反應 性之異氰酸酯基移動至離型紙，有時損害工程用離型紙之 剝離性，生產性會降低。對於如此之聚胺基甲酸酯系2液 型接著劑亦容易剝離，且耐熱性優之離型紙，有由紙與電 離輻射線硬化膜所構成之附壓紋的剝離紙（特開2005- 201105501 1 8 6 5 1 6號公報）。在上述特開2 0 0 5 - 1 8 6 5 1 6號公報中係就 前述硬化膜而言，使用如下者：異氰酸酯化合物、與具 有（甲基）丙烯醯基且可與異氰酸酯化合物反應之（甲基 )丙烯酸化合物、不具有（甲基）丙烯醯基且可與異氰酸 酯基反應之化合物的反應生成物，使含有軟化點爲40 °C以 上之電離輻射線硬化性組成物的電離輻射線硬化性組成物 藉電離輻射線硬化者。在實施例中係設有塡縫層的紙基材 塗佈上述電離輻射線硬化性組成物2次而形成電離輻射線 硬化膜，製造壓紋賦型性、耐熱性及反覆剝離性優之附壓 紋的剝離紙。 又，就賦型被形成物者而言，有使用於三聚氰胺等之 熱硬化性樹脂化妝板的沖壓加工之賦型片。如此之賦型片 ，已提出一種賦型片，其係於基材薄膜（PET薄膜）形成 底塗層，於此底塗層上形成由電離輻射線硬化性樹脂層所 構成的賦型面，於前述基材薄膜之另一面設有阻止由三次 元交聯硬化樹脂所構成的滲出成分之塗佈層（特開平07- 2 76 5 69號公報）。此賦型片係熱硬化性樹脂化妝板的沖壓 加工一般以加熱溫度100〜150°C、壓力5〜lOOKg/cm2、加熱 加壓時間5〜30分鐘的高溫高壓條件進行，故在以PET等作 爲基材薄膜之賦型片中，係PET中之寡聚物或可塑劑等之 流動性的低分子成分會滲出，污染沖壓之金屬板，且無法 再利用賦型片，有鑑於此者。在上述公報中係已提出藉由 使賦型片爲上述之構成，俾層合阻止滲出成分之塗佈層， 故可避免因滲出造成之污染。 201105501 專利文獻1 :特開平5- 828 06號公報 專利文獻2 :特開2 0 0 5 - 1 8 6 5 1 6號公報 專利文獻3 :特開平07-276 5 69號公報 【發明內容】 發明之揭示 發明欲解決之課題 使用離型紙所製造之合成皮革係除其表面消光之消光 型外，平滑性優且具光澤之光亮型亦符合用途或需要者之 喜好所製造。尤其，具有高光澤表面之合成皮革或三聚氰 胺化妝板，期望需要者之嗜好高且可安定而製造。 但，層合記載於上述特開平5 -82806號公報之聚丙烯 的層合物，因使用熱塑性之聚丙烯，耐熱性不充分，反覆 使用次數受限制》 又，記載於上述特開2005- 1 865 1 6號公報之離型紙， 因具有電離輻射線硬化膜，機械強度優異，但層合2層電 離輻射線硬化性組成物而形成電離輻射線硬化膜者。電離 輻射線硬化性組成物係極昂貴，但若降低使用量，樹脂層 變薄’故很難形成所希望之賦型面。因此，若可使用廉價 之化合物而製造工程離型紙，很有利。尤其，離型紙係製 造時經過捲取步驟，故宜黏著性少，耐溶劑性優。 又’工程離型紙係亦可使用於對三聚氰胺化妝板等之 表面賦型時。具體上’使包裝紙、含浸三聚氰胺樹脂之紙 管紙、含浸三聚氰胺樹脂之化妝板、含浸三聚氰胺樹脂之 -8- 201105501 外層紙依序重疊，於前述外層紙上層合工程離型紙 溫、高壓條件進行沖壓加工而製造三聚氰胺化妝板 ，必須離型紙亦耐熱性、耐壓性優，但記載於上述 07-2765 69號公報之賦型片就可抑制滲出而言，雖 但因基材薄膜爲PET，有時依PET之熔融溫度而設 溫度或壓力之限定。 工程離型紙係必須可從被賦型物容易剝離。在 三聚氰胺化妝板之製造中，係藉由沖壓加工，從前 紙及含浸三聚氰胺樹脂的化妝紙滲出之三聚氰胺樹 而形成三聚氰胺樹脂層，故工程離型紙必須具有對 氰胺樹脂性之優異的剝離性。尤其，賦型面爲高光 爲確保高度的剝離性，期望對於三聚氰胺樹脂等之 性優之工程離型紙。 本發明係有鑑於上述之各種問題者，目的在於 種離型紙，其係可在合成皮革製造步驟中使用2液 劑，亦可反覆製造由氯化乙烯皮等融點高的樹脂組 構成之合成皮革，且耐熱性、機械性強度及賦型性 〇 又，本發明之目的在於提供一種工程剝離紙， 可使用於對受高溫、高壓條件負荷之三聚氰胺化妝 表面形成高光澤的賦型面時，於耐熱性、機械強度 性優異者。 用以解決課題之手段 而以高 。因此 特開平 優異， 定加熱 前述之 述外層 脂硬化 於三聚 澤時， 耐藥品 提供一 型接著 成物所 優異者 其係亦 板等的 、剝離 -9- 201105501 本發明人等係詳細硏究工程剝離紙之構成的結果’發 現：使含（甲基）丙烯醯基之丙烯酸系共聚物所構成的電 離輻射線硬化性組成物藉由電離輻射線硬化而成之電離輻 射線硬化樹脂層於耐溶劑性優，爲不沾黏，該含（甲基） 丙烯醯基之丙烯酸系共聚物可廉價地製造，故可廉價且簡 單地製造耐溶劑性、賦型性、離型性優之工程剝離紙；進 一步’若於紙基材層合由聚烯烴系樹脂等之熱塑性樹脂所 構成的層作爲中間層，與紙基材之接著性優，同時因其熱 塑性，高光澤之賦型性優，適宜作爲光亮型之剝離紙；於 電離輻射線硬化樹脂上層合熱硬化聚矽氧層，即使使用聚 胺基甲酸酯系2液接著劑等之反應性強的接著劑時，或可 確保三聚氰胺化妝板之製造時亦優的剝離性；如此之工程 剝離紙係極可適宜使用來作爲對合成皮革或三聚氰胺化妝 板的表面賦型高光澤表面時之賦型片。終完成本發明。 亦即本發明係提供一種工程剝離紙，其特徵在於：依 序層合紙基材、電離輻射線硬化樹脂層、與熱硬化聚矽氧 層’且賦型面之表面光澤度於60°反射爲60以上。 又本發明係提供一種合成皮革用工程剝離紙，其係可 使用於合成皮革之製造。 又本發明係提供一種三聚氰胺化妝板用工程剝離紙， 其係可使用於三聚氰胺化妝板之製造。 本發明係提供一種上述工程剝離紙之製造方法，其特 徵在於：於表面光澤度在60°反射爲60以上的紙基材上層 合熱塑性樹脂，然後，於前述熱塑性樹脂進行表面處理， -10- 201105501 形成表面處理層，於前述表面處理層上層合電離輻射線硬 化性組成物及熱硬化性聚矽氧組成物而得到層合物，對此 層合物進行表面光澤度於60°反射爲60以上之賦型處理， 繼而，對前述經賦型處理之層合物進行電離輻射線硬化處 理。 本發明係提供一種上述工程剝離紙之製造方法，其特 徵在於：於表面光澤度於75°反射爲90以上之鏡面銅版紙 之鏡面銅版層上層合電離輻射線硬化性組成物及熱硬化性 聚矽氧組成物，繼而，對前述層合物進行電離輻射線硬化 處理。 發明之效果 本發明之工程剝離紙係因具有表面光澤度在60°反射 爲60以上之賦型面，故可適宜使用於高光澤之合成皮革或 三聚氰胺化妝板之製造。 本發明之工程剝離紙係因具有由含（甲基）丙烯醯基 之丙烯酸系共聚物所構成之電離輻射線硬化樹脂層，故耐 溶劑性、賦型性、離型性優異，可爲複數次之再使用，有 經濟性。 又，工程剝離紙之賦型層因以熱塑性樹脂層與電離輻 射線硬化樹脂層所構成，可確保層之厚度，可形成優異之 高光澤。 進一步，若依本發明之工程剝離紙，具有對2液聚胺 基甲酸酯或氯化乙烯安定之反覆剝離性能，可減少靜電放 -11 - 201105501 電所造成之剝離不良。 用以實施發明之最佳形態 本發明之第一係工程剝離紙，其特徵在於：依序層合 紙基材、電離輻射線硬化樹脂層'與熱硬化聚矽氧層’且 賦型面之表面光澤度於60°反射爲60以上。亦可於前述紙 基材與電離輻射線硬化樹脂層之間形成中間層。參照表示 本發明之較佳態樣的一例之圖1，同時並詳細說明本發明 (1 )工程剝離紙 本發明之工程剝離紙係如圖1所示般，依序層合熱硬 化聚矽氧層（10)、電離輻射線硬化樹脂層（20)、熱塑性樹 脂層（3 0)與紙基材（4〇)，藉使熱硬化聚矽氧層（10)接觸 於被賦型物，可賦型成特定形狀。如圖2(a)所示般，前 述紙基材（40)與電離輻射線硬化樹脂層（20)之間形成中間 層（3 0 )。中間層（3 0 )係不僅由單層所構成之情形，亦 可爲由複數之層所構成的多層構造，於多層構造係亦可具 有進行熱塑性樹脂層或塡縫層之表面處理所形成之表面處 理層’藉由表面處理層之形成，可提昇與電離輻射線硬化 樹脂層（20)之接觸性。具體上，如圖2(b)所示般，本 發明之工程剝離紙係於前述紙基材（4 0 )、與電離輻射線 硬化樹脂層（20 )之間具有由熱塑性樹脂層所構成之中間 層（3 0 )時，以2層以上構成熱塑性樹脂層，例如，由聚 丙烯系樹脂所構成之第一聚烯烴系樹脂層（30A”）與由聚 -12- 201105501 丙烯系樹脂與聚乙烯系樹脂之組成物所構成之第二聚烯烴 系樹脂層（30A’），可於紙基材（40 )上層合第二聚烯烴 系樹脂層（30A’），可形成於其上依序層合第一聚烯烴系 樹脂層（30A”）、電暈處理等之表面處理層（33)、電離 輻射線硬化樹脂層（20 )、熱硬化聚矽氧（1 〇 )之構成。 藉此，可提昇紙基材（40 )與熱塑性樹脂層（3 0 )之接著 性。 又，雖未圖示，但構成本發明之工程剝離紙的電離輻 射線硬化樹脂層（20 )亦可爲單層，但亦可爲2層以上之 多層。例如，可於電離輻射線硬化樹脂層層合含有無機顏 料之電離輻射線硬化樹脂層（20A )與不含有無機顔料之 電離輻射線硬化樹脂層（20B )。使電離輻射線硬化樹脂 層（20A )層合於紙基材，然後，層合電離輻射線硬化樹 脂層（20B )，不設有中間層（30 )，亦可確保塡縫效果 〇 本發明之工程剝離紙係其特徵在於：賦型面之表面光 澤度於60°反射爲60以上。又，在本說明書中，表面光澤 度係依JIS P8142所規定之60度、或以75度鏡面光澤度的 測定方法所測得者。 (2 )紙基材 在本發明所使用之紙基材係必須具有至少具有可承受 層合電離輻射線硬化樹脂層（20 )及熱硬化聚矽氧層（1 0 )之工程的強度，於合成皮革之塗佈、形成時或三聚氰胺 -13- 201105501 化妝板的表面賦型表面光澤度於60°反射爲60以上之光澤 時的離型紙之耐熱性、耐藥品性等之性質。除牛皮紙、上 質紙、單面光牛皮紙、純白.蠟紙、半透明紙（glassine paper)、杯原紙等之非塗佈紙外，亦可使用不使用天然紙 漿之合成紙等。爲了合成皮革或三聚氰胺化妝板之加工適 性，就耐久性、耐熱性優而言，宜使用由天然紙漿所構成 之紙。 在本發明中，使用來作爲基材層之紙，係秤量 15〜300g/m2、宜爲100〜180g/m2。若爲此範圍，高光澤之 賦型容易。又，紙係宜爲中性紙。含有硫酸鋁等之酸性紙 ，若於合成皮革或三聚氰胺化妝板之製造步驟反覆使用， 有時會產生熱劣化，因此，於初期很難再使用。若爲中性 紙，可防止如此之熱劣化。 又，在本發明所使用之紙係亦可使用中性松香或烷基 烯酮（Ketene)二聚體、烯基琥珀酸酐作爲上漿劑，亦可使 用陽離子性之聚丙烯醯胺或陽離子性澱粉等作爲定影劑。 又，因上述理由最宜不使用硫酸鋁，但亦可使用硫酸鋁而 以pH 6〜9的中性區域進行抄紙。其他，依需要而除了上述 之上漿劑之外，定影劑之外，亦可適當含有製紙用各種塡 料、良率提昇劑、乾燥紙力增強劑、濕潤紙力增強劑、結 合劑、分散劑、凝集劑、可塑劑、接著劑。 進一步，在本發明所使用之紙基材係例如亦可使用一 般之微塗佈印刷用紙、塗佈印刷用紙、樹脂塗佈紙、加工 原紙、剝離原紙、雙面塗佈剝離原紙等之預先形成後述之 -14- 201105501 塡縫層或樹脂層的市售品。 又，在本發明中係亦可使用表面光澤度在75°反射爲 90以上之鏡面轉印至前述塗佈面所得到之鏡面銅版紙等作 爲紙基材。 (3 )電離輻射線硬化樹脂層 在本發明所使用之電離輻射線硬化樹脂層係使由含有 (甲基）丙烯醯基之丙烯酸系共聚物（I)所構成的電離輻 射線硬化性組成物、或（甲基）丙烯酸酯 35~80質量份、縮 水甘油基（甲基）丙烯酸酯2 0〜6 0質量份、其他之（甲基）丙烯 酸酯0〜3 0質量份所構成之共聚物，與（甲基）丙烯酸10〜30 質量份反應而成之含有（甲基）丙烯醯基之丙烯酸系共聚物 (II )所構成之電離輻射線硬化性組成物藉電離輻射線硬 化而成者，該含有（甲基）丙烯醯基之丙烯酸系共聚物（I )係重量平均分子量（Mw)爲5 000〜200000，更佳係 15000〜100000，尤宜爲15000〜70000。又，含有（甲基）丙 烯醯基之丙烯酸系共聚物（I)之分散比（Mw/Mn )爲 1.0〜5.0 ’更佳係1.5〜4.0，尤佳係1.9~3.5，玻璃轉移點溫 度（Tg)爲40〜150°C，更佳係65〜12(TC，尤佳係65〜90°C 。又’在本發明中，重量平均分子量及數目平均分子量係 依凝膠滲透色層分析（GPC)法以聚苯乙烯換算所求得之値 。工程剝離紙係製造合成皮革或三聚氰胺化妝板時，必須 電離輻射線硬化樹脂層與極薄層之熱硬化聚矽氧層一起形 成賦型面，一般賦型係以溫度40〜15 0°C實施。若依本發明 -15- 201105501 ，可知由上述含有（甲基）丙烯醢基之丙烯酸系共聚物所構 成之電離輻射線硬化性組成物係耐溶劑性優，於熱硬化聚 矽氧層與電離輻射線硬化樹脂層形成表面光澤度在60°C反 射爲60以上之賦型面時，未過度軟化而賦型性優，而且， 電離輻射線硬化樹脂層形成時爲未沾黏，故原材之捲取很 容易，操作性極優。 如此之含有（甲基）丙烯醯基之丙烯酸系共聚物（1)係例 如（甲基.）丙烯酸酯系單體單元（A)與含有環氧基之（甲基）丙 烯酸酯系單體單元（B)的含有環氧基的共聚物（C)，與（甲 基）丙烯酸反應而得到。 在本發明中（甲基）丙烯酸酯系單體單元（A)，係有甲 基丙烯酸甲酯、丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁 酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸羥乙酯、 甲基丙烯酸羥乙酯、二環戊基丙烯酸酯、二環戊基甲基丙 烯酸酯、2 -(二環戊基氧）乙基丙烯酸酯、2 -(二環戊基 氧）乙基甲基丙烯酸酯、2 -(二環戊基氧）乙基-2’-(丙烯 醯基氧）乙基醚、2 -(二環戊基氧）乙基氧）乙基-2’-(甲 基丙烯醯基氧）乙基醚、2-{2-(二環戊基氧）乙基氧} - 1-{2，-(丙烯醯基氧）乙基氧}乙烷、2-{2-(二環戊基氧）乙基 氧} - 1- {2’-(甲基丙烯醯基氧）乙基氧}乙烷、二環戊烯 基丙烯酸酯、二環戊烯基甲基丙烯酸酯、2 -(二環戊烯基 氧）乙基丙烯酸酯、2 -(二環戊烯基氧）乙基甲基丙烯酸酯 、2 -(二環戊烯基氧）乙基-2’-(丙烯醯基氧）乙基醚、 2 -(二環戊烯基氧）乙基-2’-(甲基丙烯醯基氧）乙基醚、 -16- 201105501 2-{2-(二環戊基氧）乙基氧）-{2’_ (丙嫌醯基氧）乙基氧 }乙烷、2 - {2-(二環戊烯基氧）乙基氧} - 1- {2’-(甲基丙 烯醯基氧）乙基氧}乙烷、二羥甲基-三環癸烷二丙烯酸酯 、二羥甲基-三環癸烷二甲基丙烯酸酯、異冰片基丙烯酸 酯、異冰片基甲基丙烯酸酯、環己基丙烯酸酯、環己基甲 基丙烯酸酯等。此等之中’可適宜使用甲基丙烯酸甲酯、 丙烯酸甲酯、異冰片基甲基丙烯酸酯、異冰片基丙烯酸酯 等。 又，含有環氧基的（甲基）丙烯酸酯系單體單元（B)係 有縮水甘油基甲基丙烯酸酯、甲基縮水甘油基甲基丙烯酸 酯、3,4 -環氧基環己基甲基甲基丙烯酸酯、3,4 -環氧基 環己基甲基丙烯酸酯、氮丙啶基（甲基）丙烯酸酯等。 上述（甲基）丙烯酸酯系單體單元（A)與含有環氧基的（ 甲基）丙烯酸酯系單體單元（B)之調配比係於單體單元之合 計質量中使上述含有環氧基的（甲基）丙烯酸酯系單體單元 (B)調配成5〜95質量％。若低於5質量％，無法確保充分的 雙鍵當量，而有時損及含有（甲基）丙烯醯基之丙烯酸系共 聚物（I )之硬化後的耐溶劑性、耐擦過性。另外，若超過 95質量％ ’產生Tg太低所造成之未硬化膜的觸感，有時損 及賦型性。 又’在本發明所使用之電離輻射線硬化性組成物係亦 可由（甲基）丙烯酸酯35〜80質量份、縮水甘油基（甲基）丙烯 酸酯20〜60質量份、其他之（甲基）丙烯酸酯〇〜3〇質量份所 構成之共聚物，與（甲基）丙烯酸1〇〜30質量份反應而成之 -17- 201105501 含有（甲基）丙烯醯基之丙烯酸系共聚物（π)。（甲基）丙烯 酸酯及其他之（甲基）丙烯酸酯係相當於上述（甲基）丙烯酸 酯系單體單元（A)，縮水甘油基（甲基）丙烯酸酯係相當於 含有環氧基之（甲基）丙烯酸酯系單體單元（B)。因此’其 他之（甲基）丙烯酸酯係可從上述（甲基）丙烯酸酯系單體單 元（A)之中適當選擇。 反應係使上述單體單元在自由基起始劑之存在下共聚 合所得到。自由基起始劑係無特別限制，但可使2,2’ -偶 氮雙（2,4 -二甲基戊腈）、2,2’ -偶氮雙異丁腈、2,2’ -偶 氮雙（2 -甲基丁腈）、1，1’ -偶氮雙-(環己烷-1 -甲腈） 、偶氮雙甲基丁腈、2,2’-偶氮雙- (4 -甲氧基-2,4-二甲基 戊腈）、2,2’ -偶氮雙異丁腈、2,2’ -偶氮雙異酪酸二甲酯 等之偶氮化合物；過氧化氫；月桂基過氧化物、2,4 -二 氯苯甲醯基過氧化物、第三丁基過氧化三甲基乙酸酯、 3,5，5 -三甲基己醯基過氧化物、辛醯基過氧化物、癸醯 基過氧化物、月桂醯基過氧化物、琥珀酸過氧化物、乙醯 基過氧化物、第三丁基過氧化-2 -乙基己酸酯、間甲苯 醯基過氧化物、苯甲醯基過氧化物、第三丁基過氧化馬來 酸、第三丁基過氧化月桂酸酯、第三丁基過氧化-3，5,5 -三甲基己酸酯、環己酮過氧化物、第三丁基過氧 化異丙基碳酸酯、2,5 -二甲基-2,5 -二（苯甲醯基過氧化 )己烷、2，2 -雙（第三丁基過氧化）辛烷、第三丁基過氧化 乙酸酯、2,2-雙（第三丁基過氧化）丁烷、第三丁基過氧化 苯甲酸酯、正丁基-4,4-雙（第三丁基過氧化）戊酸酯、 -18- 201105501 二-第三丁基-二過氧化異酞酸酯、甲乙酮過氧化物、二 枯基過氧化物、2,5 -二甲基（第三丁基過氧化）己烷、第三 丁基枯基過氧化物等之過氧化物；過硫酸鉀、過硫酸銨、 氯酸鈉等之過氧化物、或此等過氧化物與還原劑之組合所 得到之氧化還原系起始劑等一般自由基起始劑符合聚合方 法而適當選擇。上述聚合起始劑之使用量係依其種類或聚 合條件而異，但相對於上述單體100質量份一般爲0.1〜10 質量份》 聚合溫度依聚合起始劑之種類而定，但一般爲40〜180 °C，宜爲50~150°C，更宜爲60〜130°C。又，反應壓可爲大 氣壓，亦可爲加壓條件，一般爲0.1 5~0.5 MPa»又，聚合 時間爲3 ~ 1 5小時。 使如上述之單體單元（a)、單體單元（B)藉溶液聚合進 行聚合。可使用於溶液聚合之溶劑係可使用正己烷、庚烷 、辛烷等之脂肪族烴化合物；環己烷、甲基環己烷、乙基 環己烷等之脂環式烴化合物；苯、甲苯、二甲苯、異丙苯 等之芳香族烴化合物；四氫呋喃、二正丁基醚、乙二醇二 甲基醚、乙二醇二乙基醚等之醚化合物等的有機溶劑、甲 醇、乙醇等之醇類、丙酮、甲基異丁基酮等之酮類、乙基 苯、甲乙酮、酸酸丁酯等之公知的溶劑。其中，宜使用甲 乙酮、甲醇、甲苯、乙基苯、醋酸丁酯等。如此之溶劑亦 可使用1種，亦可使用2種以上。 反應溶劑中之單體濃度宜爲10〜80質量％。單體濃度 小於1 〇質量％，有時無法得到充分的反應速度，若高於80 -19- 201105501 質量％，恐於反應中產生凝膠化物。 爲得到充分的反應速度，本反應宜使用觸媒而實施。 觸媒係可使用三苯基磷、三丁基磷等之磷類、三乙基胺、 二甲基苯甲基胺等之胺類、二甲基硫醚、二苯基硫醚等之 硫醚類等，但，從反應速度之面宜爲磷類，尤宜爲三苯基 磷。 此等觸媒之量相對於含有環氧基之（甲基）丙烯酸酯系 單體單元（B)，一般爲0.1〜10質量％。觸媒量相對於含有環 氧基之（甲基）丙烯酸酯系單體單元（B)，少於0.1質量％時 ，有時無法得到充分的反應速度，加入多於1 〇質量％，恐 對所生成之樹脂的各物性造成不良影嚮。 爲防止反應中之凝膠化物的生成，可舉例如氫醌、氫 醌單甲基醚、酚噻嗪、4 -羥基-2,2,6,6 -四甲基六氫吡 啶-N -氧、4 -乙醯基胺基-2,2,6,6 -四甲基六氫吡啶-N -氧、4 -苯甲醯基氧-2，2,6,6 -四甲基六氫吡啶-N-氧、4 -氧代-2,2,6,6 -四甲基六氫吡啶-n -氧、 2,2，6,6 -四甲基六氫卩比D定-N -氧等之N -氧自由基系化 合物；氫醌 '氫醌單甲基醚、2,6 -二-第三丁 - 4-甲基 酚' 2,2’-亞甲基雙（4-乙基-6 -第三丁基酚）、2,6-二 第三丁基-N，N -二甲基胺基-對甲酚、2,4 -二甲基-6 -第三丁基酚、4 -第三丁基兒萘酚' 4,4’ -硫-雙（3 -甲基-6-第三丁基酚）、4,4’-亞丁基-雙（3 -甲基- 6-第三丁基酚）等之酚系化合物；酚噻嗪、N，N’-二苯基-對 苯二胺、苯基-々-萘基胺、N，N’ -二-冷-萘基-對苯 -20- 201105501 二胺、N -苯基- Ν’ -異丙基-對苯二胺等之胺化合物； 1，4 -二羥基-2,2,6,6 -四甲基六氫吡啶、4 -二羥基-2，2,6，6 -四甲基六氫吡啶等之羥基胺系化合物；二苯甲酮 、2,5 - _•弟二丁氨醒等之醒系化合物；氯化第~鐵、二 甲基二硫胺基甲酸銅等之銅化合物等。此等係可分別單獨 或混合2種以上而使用。此等之聚合抑制劑的量相對於反 應液全體宜爲1〜lOOOOppm。 然後，若所得到之共聚物（C)與（甲基）丙烯酸反應， 可得到含有（甲基）丙烯醯基之丙烯酸系共聚物（I )、（π) 。藉以（甲基）丙烯酸更佳係以丙烯酸改性，可於含有（甲 基）丙烯醯基之丙烯酸系共聚物導入雙鍵。在本發明所使 用之含有（甲基）丙烯醯基之丙烯酸系共聚物（I )係成爲電 離輻射線硬化樹脂層者，爲藉硬化而確保耐溶劑性、耐熱 性等，雙鍵當量宜爲0.5〜4.5meq/g，更宜爲0.5〜4.0meg/g ，尤宜爲0.7〜3.6meq/g。因此，（甲基）丙烯酸係雙鍵當量 成爲上述範圍，可與共聚物（C)反應。 共聚物（C)與（甲基）丙烯酸之反應係宜在溶液中，3級 胺觸媒、4級銨鹽觸媒、3級磷觸媒、4級磷鹽觸媒、有機 錫化合物觸媒的存在下進行。具體上係可使用三苯基磷、 三丁基磷等之磷類、三乙基胺、二甲基苯甲基胺等之胺類 、二甲基硫醚、二苯基硫醚等之硫醚類等。 上述反應時間、反應溫度係依所選擇之溶劑或反應壓 力等而異，但壓力爲大氣壓~0.2]\〇&，一般溫度爲50~160 °C，反應時間爲3~50小時。 -21 - 201105501 本發明之電離輻射線硬化性組成物係重量平均分子量 (Mw)爲5000〜200000，分散比（Mw/Mn)爲1.0〜5.0，玻璃轉 移點溫度（Tg)含有40〜150 °C之含有（甲基）丙烯醯基之丙烯 酸系共聚物（I )。若含有（甲基）丙烯醯基之丙烯酸系共聚 物（I)之Tg低於40°C，形成表面光澤度在60°C反射爲60以 上之賦型面時，進行溶融，賦型性變成不良，或，未硬化 之膜產生沾黏，有時損及薄片之捲取。另外，若超過150 °C，形成上述表面光澤度在60°C反射爲60以上之賦型面時 ，必須施加極端的高溫，又，有時損及硬化後之可撓性。 又，本發明規定之Tg的測定，係以後述之實施例記載的方 法進行測定者。又，若超過1 5 0 °C，有時很難賦型。又， 由（甲基）丙烯酸酯35〜80質量份、縮水甘油基（甲基）丙烯酸 酯20〜60質量份、其他之（甲基）丙烯酸酯〇〜30質量份所構 成之共聚物，與（甲基）丙烯酸10〜3 0質量份反應而成之含 有（甲基）丙烯醯基之丙烯酸系共聚物（Π )係重量平均分子 量（Mw)或Tg無限制，但成型爲工程剝離紙宜玻璃轉移溫 度爲40~150°C ，更宜爲65〜120°C。Tg係與重量平均分子 量（Mw)或雙鍵當量相關，故爲滿足上述玻璃轉移溫度， 只要含有雙鍵且調製重量平均分子量（Mw)即可。宜爲 5000〜200000，更宜爲 1 5000〜1 00000，尤宜爲 1 5000~70000 。若低於5 000，有時耐溶劑性或強靭性差，另外，若超過 2〇0000 ’樹脂黏度變高，有時很難處理。又，玻璃轉移點 溫度（Tg)爲40〜150°C，更宜爲65〜120°c，尤宜爲65〜90°c 。若爲此範圍，使含有（甲基）丙烯醯基之丙烯酸系共聚物 -22- 201105501 (π )硬化後’耐溶劑性、耐擦過性優，且無未硬化膜之沾 黏感，賦型性優。 本發明所使用之電離輻射線硬化性組成物係亦可爲只 由上述含有（甲基）丙烯醯基之丙烯酸系共聚物（I )' (Π) 所構成者。所謂組成物係調配2種以上之物質者，但從含 有（甲基）丙烯醯基之丙烯酸系共聚物（I )之分散比明顯可 知，含有相異之分子量的含有（甲基）丙烯醯基之丙烯酸系 共聚物，故在本案中只由含有（甲基）丙烯醯基之丙烯酸系 共聚物所構成時亦稱爲電離輻射線硬化性組成物。另外， 在本發明所使用之電離輻射線硬化性組成物中係進一步亦 可調配無機顏料、光聚合起始劑、其他。藉由無機顏料之 調配，可對工程剝離紙賦予消光感。如此之無機顏料可例 示滑石、高嶺土、氧化矽、碳酸鈣、硫酸鋇、氧化鈦、氧 化鋅等。無機顏料宜於電離輻射線硬化樹脂層調配成爲 0.5〜50質量％，更宜爲1~10質量％。電離輻射線硬化樹脂 層以2層以上之多層所構成時，在各層中之無機顏料的調 配量成爲上述範圍。 可調配於電離輻射線硬化性組成物之光聚合起始劑係 有2,2 -二甲氧基-2苯基乙醯苯、苯偶因乙基醚、乙醯苯 、二乙氧基乙醯苯、苯甲基二甲基縮酮、2 -羥基-2-甲 基丙醯苯、2 -甲基-1- [4-(甲基硫）苯基]-2-嗎啉基丙 烷-1、1-羥基環己基苯基酮、二苯甲酮、對氯二苯甲酮 、希米勒酮、N，N -二甲基胺基安息香酸異戊酯、2 -氯 硫雜蒽酮、2，4-二乙基硫雜蒽酮等。光聚合起始劑之調 -23- 201105501 配量相對於含有（甲基）丙烯醯基之丙烯酸系共聚物100質 量份爲1〜10質量份。 進一步，爲改質含有（甲基）丙烯醯基之丙烯酸系共聚 物之硬化特性，亦可於電離輻射線硬化性組成物中在無損 其特性之範圍含有其他之樹脂、聚矽氧化合物、反應性單 體、其他之光硬化性聚化物等作爲任意成分。 其他之樹脂係有甲基丙烯酸樹脂、氯化聚丙烯、環氧 樹脂、聚胺基甲酸酯樹脂、聚酯樹脂、聚乙烯醇、聚乙烯 基乙縮醛等，反應性單體有甲基（甲基）丙烯酸酯、乙基（ 甲基）丙烯酸酯、丙基（甲基）丙烯酸酯、丁基（甲基）丙烯酸 酯、乙基己基（甲基）丙烯酸酯、硬脂基（甲基）丙烯酸酯、 月桂基（甲基）丙烯酸酯 '十三碳基（甲基）丙烯酸酯、三羥 甲基丙烷三丙烯酸酯、三（丙烯醯氧基乙基）三聚異氰酸酯 、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯等。 光硬化性聚合物有多官能（甲基）丙烯酸酯寡聚物。調 配量係相對於該含有（甲基）丙烯醯基之丙烯酸系共聚物 100質量份爲30質量份以下，更宜爲10質量份以下。多官 能（甲基）丙烯酸酯寡聚物係於1分子中具有2個以上之（甲 基）丙烯醯基者’例如有三環癸烷二羥甲基二丙烯酸醋、 雙酚F之環氧乙烷改性二丙烯酸酯、雙酚a之環氧乙院改 性二丙烯酸酯、三聚異氰酸酯之環氧乙烷改性二丙稀酸酯 、聚丙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯 '三經甲基 丙烷三丙烯酸酯、三羥甲基丙烷之環氧丙烷改性三丙稀酸 醋、三經甲基丙烷之環氧乙烷改性三丙烯酸酯、季戊四醇 -24- 201105501 三丙烯酸酯、季戊四醇四丙烯酸酯、雙三羥甲基丙烷四丙 烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯 、胺基甲酸酯丙烯酸酯等。此等係亦可組合2種以上而調 配。 此電離輻射線硬化性組成物係亦可相對於含有（甲基） 丙烯醯基之丙烯酸系共聚物100質量份而以10-1000質量份 之溶劑稀釋而塗佈。若溶劑之稀釋賦予適於塗佈之黏度、 例如在25 °C中1 〇~3 000mPa ·秒之黏度，同時於乾燥此之 步驟中，可移動至聚矽氧化合物之適當表面。 溶劑係可使用例如甲苯、二甲苯等之芳香族烴系溶劑 、甲乙酮、甲基異丁基酮、環己酮等之酮系溶劑、醋酸乙 酯、醋酸丁酯、醋酸異丁酯等之酯系溶劑、二乙二醇乙基 醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇單甲基醚、3-甲基-3-甲氧基丁基乙酸酯、乙基-3-乙氧基丙酸酯等 之甘醇醚酯系溶劑、四氫呋喃、二噁烷等之醚系溶劑、 N-甲基吡咯烷酮等之非質子性極性溶等。 塗佈方式係可使用直接凹版塗佈、逆式凹版塗佈、凹 平版塗佈、微凹版塗佈、直接輥塗佈、逆式輥塗佈、簾式 塗佈、刮刀塗佈、氣刀塗佈、桿塗佈、模縫塗佈、噴塗等 公知之方法，於熱塑性膜上塗佈後，以溫度90~ 13 0°C乾燥 及加熱，以乾燥爐蒸發溶劑而使電離輻射線硬化性組成物 熱硬化。此溫度係高於電離輻射線硬化性組成物之軟化點 ，且低於電離輻射線硬化性組成物溶融之溫度的範圍。 電離輻射線硬化樹脂層之厚度宜爲1~50μιη，更宜爲 -25- 201105501 3〜2 0μηι。若薄於Ιμηι，微細之賦型性的轉印變差，另外， 若超過5 0 μ m，有時樹脂之硬化性變差。如前述般，電離 輻射線硬化樹脂層以2層以上之多層所構成時，使全層之 厚度爲上述範圍。 又，上述熱硬化之電離輻射線硬化性組成物係形成表 面光澤度在60°反射爲60以上之賦型面後，從熱硬化聚矽 氧層側照射紫外線或電子束俾可使之電離輻射線硬化。紫 外線之光源可使用低壓水銀燈、中壓水銀燈、高壓水銀燈 、金屬鹵素燈、氙燈、鎢絲燈等。電子束之照射方式可使 用掃描方式、簾束方式、大光斑（broad beam)方式等，電 子束之加速電壓以50〜3 00kV爲適宜。 (4 )熱硬化聚矽氧層 本發明所使用之熱硬化聚矽氧層係使含有烯基之有機 聚矽氧烷、有機氫聚矽氧烷及鈾系硬化觸媒所構成之熱硬 化性聚矽氧組成物進行熱硬化所形成者。 含有烯基之有機聚矽氧烷之一例可舉例如下述之化合 物。 [化1] X-R1—和 0+和0廿如0 L·[—严七—201105501 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an engineering release paper, and more specifically, the surface gloss of the shaped surface is 60. The reflection is 60 or more, and it can be suitably used for the manufacture of synthetic leather or melamine cosmetic board which is excellent in heat resistance and solvent resistance and high gloss. [Prior Art] Conventionally, in the case of synthetic leather, a vinyl chloride resin or a polyurethane resin has been widely used as a main raw material. Such synthetic leathers are often manufactured using release paper. For example, in order to produce a polyurethane skin, a paste-like polyurethane resin is applied onto a release paper, dried, cured, and then bonded to a base fabric to be peeled off from the release paper. If the release paper forms the same pattern or other irregularities as the natural leather, a good pattern can be imparted to the surface of the resulting synthetic leather. According to the same principle, a paste-like polyurethane resin is applied onto a release paper, dried and solidified to form a vinyl chloride foam layer to be bonded to the base fabric, and may be peeled off from the release paper. Further, in the method for producing a vinyl chloride skin, a vinyl chloride sol is applied onto a release paper, and after heating and gelation, a vinyl chloride foam layer is formed to adhere to the base fabric, and the release paper may be peeled off from the release paper. The release paper which can be used for the production of such synthetic leather is generally prepared by applying a release layer composed of a resin to a paper substrate. The release paper is transferred to its surface pattern to form a surface pattern on the synthetic leather, and must have a surface state suitable for shaping. Among them, a method of obtaining a resin surface layer having a relatively small number of mura has revealed that a composition of a resin composed of polypropylene and polyethylene-5-201105501 and a homopolymer of polypropylene are co-bindered on a substrate. The method of the method of laminating polypropylene laminates is carried out by laminating at a temperature at which lamination is possible, and the speckle is severe, but in order to improve this, if low-density polyethylene is mixed, compatibility is poor, so Produces glossy markings or rough surfaces. Therefore, it is characterized in that a resin composition composed of a specific melt flow rate of polypropylene and a specific polyethylene is co-bindered with a specific melt flow rate polypropylene homopolymer on a substrate, and is improved. Surface state. According to the above-mentioned Japanese Patent Publication No. Hei 5-82806, the resin composition and the polypropylene homopolymer are co-extruded, and the resin composition is used as the substrate side, and the specific resin composition can be used to solve the embossing. The use of a polypropylene homopolymer produces an excellent surface state in which heat resistance and gloss streaks or surface roughness are not obtained. In the examples, the laminates of the embossing and the like and the surface state were evaluated to obtain a laminate excellent in surface gloss and smoothness. Moreover, the polyurethane-based synthetic leather produced by using a surface-bonding cloth as a base material is coated and dried with a polyurethane resin on a release paper, and then bonded to the above-mentioned cloth substrate in a polyamine. A polyurethane-based 2-liquid type adhesive comprising a first liquid containing a component having an isocyanate group as a functional group and a second liquid composed of a polyhydric alcohol is used for the urethane layer. The two-component type adhesive is strong in adhesion, and is often used in furniture or shoes such as sofas, which are often used or used frequently, but the isocyanate group having high reactivity in the above steps is moved to the release paper. Sometimes the peeling property of the release paper for engineering is impaired, and the productivity is lowered. Such a polyurethane-based 2-liquid type adhesive is also easily peeled off, and the heat-resistant release paper has an embossed release paper composed of paper and an ionizing radiation cured film (Special Edition 2005- 201105501 1 8 6 5 1 6 bulletin). In the above-mentioned Japanese Patent Publication No. 2000-186, the use of the above-mentioned cured film is as follows: an isocyanate compound having a (meth)acryl oxime group and reacting with an isocyanate compound ( a reaction product of a methyl methacrylate compound, a compound having no (meth) acrylonitrile group and reacting with an isocyanate group, and an ionizing radiation hardening composition containing an ionizing radiation curable composition having a softening point of 40 ° C or more The sexual composition is hardened by ionizing radiation. In the embodiment, the paper substrate provided with the quilting layer is coated with the ionizing radiation curable composition twice to form an ionizing radiation curing film, and the embossing property, heat resistance and removability are excellent. Embossed release paper. Further, in the case of forming a molded article, there is a forming sheet for press working of a thermosetting resin cosmetic board such as melamine. In such a shaped sheet, a shaped sheet has been proposed which is formed on a base film (PET film) to form an undercoat layer on which a forming surface composed of an ionizing radiation curable resin layer is formed. On the other surface of the base film, a coating layer for preventing an oozing component composed of a three-dimensional cross-linking resin is provided (Japanese Laid-Open Patent Publication No. Hei 07-276576). The press processing of the molded sheet thermosetting resin cosmetic board is generally carried out under the conditions of high temperature and high pressure at a heating temperature of 100 to 150 ° C, a pressure of 5 to 10 OKg/cm 2 , and a heating and pressing time of 5 to 30 minutes, so that PET is used. In the shaped sheet of the base film, the low molecular component of the fluidity such as the oligomer or the plasticizer in the PET oozes out, contaminates the pressed metal plate, and the shaped sheet cannot be reused. In the above publication, it has been proposed to prevent the contamination due to bleeding by laminating the coating layer which prevents the bleed out component by forming the shaped sheet as described above. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention The synthetic leather produced by the release paper is manufactured in addition to the matte finish of the surface matte finish, and the smoothness and the glossy finish are also manufactured according to the use or preference of the user. In particular, a synthetic leather or a melamine cosmetic board having a high gloss surface is desired to be manufactured with high hobby and stability. However, the laminate of the polypropylene disclosed in Japanese Laid-Open Patent Publication No. Hei 5-82806 is not limited in heat resistance due to the use of thermoplastic polypropylene, and the number of times of repeated use is limited. Further, it is described in the above-mentioned JP-A-2005- 1 The release paper of the 865-16 publication has an ionizing radiation curing film and is excellent in mechanical strength. However, two layers of ionizing radiation curable composition are laminated to form an ionizing radiation cured film. The ionizing radiation hardening composition is extremely expensive, but if the amount of use is lowered, the resin layer becomes thin, so that it is difficult to form a desired molding surface. Therefore, it is advantageous if an engineering release paper can be produced using an inexpensive compound. In particular, since the release paper is subjected to the winding step during the production, it is preferable to have less adhesiveness and excellent solvent resistance. Further, the engineering release paper system can also be used when forming a surface on a melamine cosmetic board or the like. Specifically, the packaging paper, the paper tube paper impregnated with melamine resin, the cosmetic board impregnated with melamine resin, and the outer layer paper impregnated with melamine resin are sequentially superposed on each other, and the temperature and high pressure conditions of the release paper on the outer layer paper are carried out. In the production of a melamine cosmetic board by press working, the release paper is also excellent in heat resistance and pressure resistance. However, the molded sheet described in the above-mentioned Japanese Patent Publication No. 07-2765 69 can suppress bleeding, but the base film is PET. Sometimes the temperature or pressure is limited by the melting temperature of PET. The engineered release paper system must be easily peelable from the shaped article. In the manufacture of a melamine cosmetic board, a melamine resin layer is formed from a melamine tree exfoliated from a front paper and a cosmetic paper impregnated with melamine resin by press working, so that the engineered release paper must have excellent peelability to cyanamide resin. In particular, the shaped surface is high-gloss. In order to ensure high peelability, an engineered release paper excellent in properties such as melamine resin is desired. The present invention has been made in view of the above various problems, and an object is to provide a release paper which can be used in the synthetic leather manufacturing step by using a two-liquid preparation, or can be repeatedly produced by a resin group having a high melting point such as vinyl chloride skin. Leather, heat resistance, mechanical strength and formability, and an object of the present invention is to provide an engineering release paper which can be used for forming a high gloss profile on a melamine cosmetic surface subjected to high temperature and high pressure conditions. Excellent in heat resistance and mechanical strength. The means to solve the problem is high. Therefore, it is excellent in special-opening, and when the above-mentioned outer layer of the above-mentioned fat is hardened in the trimer, the product is excellent in the type of the one which is excellent in the product, and the peeling is performed on the plate. -9-201105501 The inventors are in detail. As a result of the constitution of the engineered release paper, it was found that the ionizing radiation curable composition composed of the (meth)acrylonitrile-based acrylic copolymer was ionized by the ionizing radiation hardening resin layer. The solvent-resistant property is excellent, and the (meth)acrylonitrile-based acrylic copolymer can be produced at low cost, so that it is possible to inexpensively and easily manufacture an excellent solvent resistance, formability, and release property. Further, if a paper substrate is laminated with a layer composed of a thermoplastic resin such as a polyolefin resin as an intermediate layer, it has excellent adhesion to a paper substrate, and at the same time, it is excellent in thermoplasticity and high gloss. It is suitable as a bright type of release paper; the thermosetting polysiloxane layer is laminated on the ionizing radiation curing resin, and even when a highly reactive adhesive such as a polyurethane adhesive is used, Preferably also ensure that the manufacturing time or the melamine decorative laminate peelable; release paper so Engineering Department electrode can be suitably used as the shaping surface of the sheet when shaping a synthetic leather or a melamine decorative board high gloss surface pair. The invention is finally completed. That is, the present invention provides an engineering release paper characterized by sequentially laminating a paper substrate, an ionizing radiation hardening resin layer, and a thermosetting polysilicon layer, and the surface gloss of the shaped surface is reflected at 60°. It is 60 or more. Further, the present invention provides an engineered release paper for synthetic leather which can be used in the manufacture of synthetic leather. Further, the present invention provides an engineering release paper for a melamine cosmetic board which can be used for the manufacture of a melamine cosmetic board. The present invention provides a method for producing the above-mentioned engineered release paper, which comprises laminating a thermoplastic resin on a paper substrate having a surface gloss of 60° or more and reflecting 60 or more, and then subjecting the thermoplastic resin to surface treatment, -10- 201105501 A surface treatment layer is formed, and an ionizing radiation curable composition and a thermosetting polyfluorene oxide composition are laminated on the surface treatment layer to obtain a laminate, and the surface gloss of the laminate is 60° at 60°. The above-described forming treatment, and then the above-mentioned shaped treatment of the laminate is subjected to ionizing radiation hardening treatment. The present invention provides a method for producing the above-mentioned engineering release paper, characterized in that an ionizing radiation hardening composition and a thermosetting polyposition are laminated on a mirror-coated copper plate layer of a mirror coated paper having a surface gloss of 75 or more and reflecting at 90 or more. The oxygen composition is then subjected to ionizing radiation hardening treatment to the aforementioned laminate. EFFECTS OF THE INVENTION The engineered release paper of the present invention is suitably used for the production of high gloss synthetic leather or melamine cosmetic panels because it has a surface having a surface gloss of 60° or more. Since the engineered release paper of the present invention has an ionizing radiation-curable resin layer composed of an (meth)acrylonitrile-based acrylic copolymer, it is excellent in solvent resistance, formability, and release property, and can be plural It is economical to use it again. Further, since the forming layer of the engineered release paper is composed of a thermoplastic resin layer and an ionizing radiation-curable resin layer, the thickness of the layer can be ensured, and excellent high gloss can be formed. Further, according to the engineering release paper of the present invention, the peeling property against the two-liquid polyurethane or the vinyl chloride stability can reduce the peeling failure caused by the electrostatic discharge -11 - 201105501. BEST MODE FOR CARRYING OUT THE INVENTION The first type of engineering release paper of the present invention is characterized by sequentially laminating a paper substrate, an ionizing radiation curing resin layer 'and a thermally hardened polysiloxane layer' and a shaped surface The surface gloss is 60 or more at 60°. An intermediate layer may also be formed between the aforementioned paper substrate and the ionizing radiation hardening resin layer. Referring to Fig. 1 showing an example of a preferred embodiment of the present invention, the present invention (1) Engineering Release Paper The engineering release paper of the present invention is sequentially laminated as shown in Fig. The layer (10), the ionizing radiation curing resin layer (20), the thermoplastic resin layer (30) and the paper substrate (4〇), by contacting the thermally hardened polysilicon layer (10) with the shaped object, Shaped into a specific shape. As shown in Fig. 2(a), an intermediate layer (30) is formed between the paper substrate (40) and the ionizing radiation-curable resin layer (20). The intermediate layer (30) may be formed of a single layer or a multilayer structure composed of a plurality of layers, and the multilayer structure may have a surface treatment of a thermoplastic resin layer or a quilting layer. The surface treatment layer 'is improved in contact with the ionizing radiation-curable resin layer (20) by the formation of the surface treatment layer. Specifically, as shown in FIG. 2(b), the engineered release paper of the present invention has a thermoplastic resin layer between the paper substrate (40) and the ionizing radiation-curable resin layer (20). In the case of the intermediate layer (30), the thermoplastic resin layer is composed of two or more layers, for example, the first polyolefin-based resin layer (30A" composed of a polypropylene-based resin and the poly--12-201105501 propylene-based resin and poly A second polyolefin-based resin layer (30A') composed of a composition of a vinyl resin, a second polyolefin-based resin layer (30A') may be laminated on the paper substrate (40), and may be formed thereon The surface of the first polyolefin-based resin layer (30A"), the surface treatment layer (33) such as corona treatment, the ionizing radiation-curable resin layer (20), and the thermosetting polysiloxane (1 〇) are laminated. Thereby, the adhesion of the paper substrate (40) to the thermoplastic resin layer (30) can be improved. Further, although not shown, the ionizing radiation-curable resin layer (20) constituting the engineered release paper of the present invention may be a single layer, but may be a plurality of layers of two or more layers. For example, the ionizing radiation-curable resin layer (20A) containing an inorganic pigment and the ionizing radiation-curable resin layer (20B) containing no inorganic pigment may be laminated on the ionizing radiation-curable resin layer. The ionizing radiation-curable resin layer (20A) is laminated on the paper substrate, and then the ionizing radiation-curable resin layer (20B) is laminated, and the intermediate layer (30) is not provided, and the quilting effect can be ensured. The engineered release paper is characterized in that the surface gloss of the shaped surface is 60 or more at 60°. Further, in the present specification, the surface gloss is measured in accordance with the method of measuring 60 degrees as specified in JIS P8142 or the specular gloss of 75 degrees. (2) Paper substrate The paper substrate used in the present invention must have at least the strength to withstand the engineering of the laminated ionizing radiation hardening resin layer (20) and the thermally hardened polysilicon layer (10). Coating of synthetic leather, formation or melamine-13-201105501 The surface-formed surface gloss of a cosmetic board is such that the gloss of 60° or more is 60° or more, and the properties of the release paper are such as heat resistance and chemical resistance. In addition to kraft paper, high quality paper, single-sided light kraft paper, pure white. As the non-coated paper such as stencil paper, glassine paper, or cup base paper, synthetic paper which does not use natural pulp or the like can be used. In order to optimize the processing suitability of leather or melamine cosmetic board, it is preferable to use paper made of natural pulp in terms of durability and heat resistance. In the present invention, the paper used as the substrate layer is weighed in an amount of 15 to 300 g/m2, preferably 100 to 180 g/m2. For this range, high gloss is easy to shape. Also, the paper system should be neutral paper. Acid paper containing aluminum sulfate or the like may be thermally degraded in the initial stage if it is used repeatedly in the production steps of synthetic leather or melamine cosmetic board. If it is a neutral paper, it can prevent such thermal deterioration. Further, in the paper system used in the present invention, neutral rosin, alkylene ketone (Ketene) dimer, alkenyl succinic anhydride may be used as the sizing agent, and cationic polypropylene decylamine or cationic may also be used. Starch or the like acts as a fixing agent. Further, for the above reasons, aluminum sulfate is preferably not used, but aluminum sulfate may be used to carry out papermaking in a neutral region having a pH of 6 to 9. In addition to the above-mentioned slurry, the fixing agent may optionally contain various kinds of materials for papermaking, a yield improving agent, a drying paper strength enhancer, a moist paper strength enhancer, a binder, and dispersion. Agent, aggregating agent, plasticizer, adhesive. Further, in the paper substrate used in the present invention, for example, a general micro-coated printing paper, a coated printing paper, a resin coated paper, a processed base paper, a release base paper, a double-coated base paper, or the like may be used in advance. 14-201105501 hereinafter referred to as a quilted layer or a resin layer. Further, in the present invention, a mirror-finished paper obtained by transferring a mirror surface having a surface gloss of 90 or more to 90 or more to the coated surface may be used as a paper substrate. (3) Ionizing radiation-curable resin layer The ionizing radiation-curable resin layer used in the present invention is an ionizing radiation-curable composition composed of an (meth)acrylonitrile-based acrylic copolymer (I). Or a copolymer of 35 to 80 parts by mass of (meth) acrylate, 20 to 60 parts by mass of glycidyl (meth) acrylate, and 0 to 30 parts by mass of other (meth) acrylate. The ionizing radiation-curable composition composed of the (meth)acryl-based acrylic copolymer (II) reacted with 10 to 30 parts by mass of (meth)acrylic acid is hardened by ionizing radiation. The (meth)acrylonitrile-containing acrylic copolymer (I) has a weight average molecular weight (Mw) of from 5,000 to 200,000, more preferably from 15,000 to 100,000, particularly preferably from 15,000 to 70,000. Further, the dispersion ratio (Mw/Mn) of the (meth)acrylonitrile-containing acrylic copolymer (I) is 1. 0~5. 0 ’ better system 1. 5~4. 0, especially good 1. 9~3. 5, glass transition point temperature (Tg) is 40~150 ° C, more preferably 65~12 (TC, especially good 65~90 ° C. Also 'in the present invention, weight average molecular weight and number average molecular weight The gel permeation chromatography (GPC) method is obtained by polystyrene conversion. When the synthetic release paper is used to make synthetic leather or melamine cosmetic board, it is necessary to ionize the radiation hardening resin layer and the extremely thin layer of the thermosetting polycondensation. The oxygen layer is formed together with a shaped surface, and the general type is carried out at a temperature of 40 to 15 ° C. According to the invention, -15-201105501, it is known that the (meth)acryloyl group-containing acrylic copolymer is composed of the above. The ionizing radiation hardening composition is excellent in solvent resistance, and when the surface of the thermosetting polysilicon layer and the ionizing radiation curing resin layer is formed to have a surface gloss of 60° C. and is 60 or more, the surface is not excessively softened. The type is excellent, and the ionizing radiation hardening resin layer is not sticky when formed, so that the coiling of the raw material is easy and the workability is excellent. Such an acrylic copolymer containing (meth)acrylonitrile group (1) ) for example (methyl. The epoxy group-containing monomer unit (A) and the epoxy group-containing (meth)acrylate monomer unit (B)-containing epoxy group-containing copolymer (C) are reacted with (meth)acrylic acid to obtain . In the present invention, the (meth) acrylate monomer unit (A) is methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate or isobutyl methacrylate. Ester, hydroxyethyl acrylate, hydroxyethyl methacrylate, dicyclopentyl acrylate, dicyclopentyl methacrylate, 2-(dicyclopentyloxy)ethyl acrylate, 2-(dicyclopentyl) Ethyl oxy)ethyl methacrylate, 2-(dicyclopentyloxy)ethyl-2'-(acrylenyloxy)ethyl ether, 2-(dicyclopentyloxy)ethyloxy)ethyl -2'-(methacryloyloxy)ethyl ether, 2-{2-(dicyclopentyloxy)ethyloxy} - 1-{2,-(propylene decyloxy)ethyloxy}B Alkane, 2-{2-(dicyclopentyloxy)ethyloxy} - 1 {2'-(methacryloyloxy)ethyloxy}ethane, dicyclopentenyl acrylate, bicyclo Pentenyl methacrylate, 2-(dicyclopentenyloxy)ethyl acrylate, 2-(dicyclopentenyloxy)ethyl methacrylate, 2-(dicyclopentenyloxy) Ethyl-2'-(acrylenyloxy)ethyl ether, 2-(dicyclopentenyloxy)ethyl-2 -(methacryloyloxy)ethyl ether, -16- 201105501 2-{2-(dicyclopentyloxy)ethyloxy)-{2'_(propyl decyloxy)ethyloxy}B Alkane, 2 - {2-(dicyclopentenyloxy)ethyloxy} - 1 {2'-(methacryloyloxy)ethyloxy}ethane, dimethylol-tricyclodecane Diacrylate, dimethylol-tricyclodecane dimethacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, and the like. Among these, methyl methacrylate, methyl acrylate, isobornyl methacrylate, isobornyl acrylate, and the like can be suitably used. Further, the epoxy group-containing (meth) acrylate monomer unit (B) is glycidyl methacrylate, methyl glycidyl methacrylate, and 3,4-epoxycyclohexyl A methacrylate, a 3,4-epoxycyclohexyl methacrylate, an aziridine (meth) acrylate or the like. The compounding ratio of the (meth) acrylate monomer unit (A) to the epoxy group-containing (meth) acrylate monomer unit (B) is based on the total mass of the monomer units to cause the above-mentioned epoxy The (meth) acrylate monomer unit (B) is blended in an amount of 5 to 95% by mass. When the amount is less than 5% by mass, a sufficient double bond equivalent cannot be ensured, and the solvent resistance and scratch resistance after curing of the (meth)acryl fluorenyl group-containing acrylic copolymer (I) may be impaired. On the other hand, when it exceeds 95% by mass, the touch of the uncured film caused by the Tg is too low, and the formability is sometimes impaired. Further, the ionizing radiation curable composition used in the present invention may be 35 to 80 parts by mass of (meth) acrylate, 20 to 60 parts by mass of glycidyl (meth) acrylate, and the like (methyl). a copolymer composed of acrylate 〇3 〇 parts by mass and reacted with 1 to 30 parts by mass of (meth)acrylic acid -17-201105501 Acrylic copolymer containing (meth)acryl fluorenyl group (π ). The (meth) acrylate and other (meth) acrylates correspond to the above (meth) acrylate monomer unit (A), and the glycidyl (meth) acrylate type corresponds to an epoxy group. (Meth)acrylate monomer unit (B). Therefore, the other (meth) acrylate type can be appropriately selected from the above (meth) acrylate type monomer unit (A). The reaction system is obtained by copolymerizing the above monomer units in the presence of a radical initiator. The radical initiator is not particularly limited, but can be 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'- Azobis(2-methylbutyronitrile), 1,1'-azobis-(cyclohexane-1 -carbonitrile), azobismethylbutyronitrile, 2,2'-azobis- ( Azo compound such as 4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyric acid dimethyl ester; peroxidation Hydrogen; lauryl peroxide, 2,4-dichlorobenzhydryl peroxide, tert-butylperoxytrimethyl acetate, 3,5,5-trimethylhexyl peroxide , octyl sulfoxide, sulfhydryl peroxide, lauryl peroxide, succinic peroxide, ethoxylated peroxide, tert-butylperoxy-2-ethylhexanoate, m-toluene Mercapto peroxide, benzhydryl peroxide, tert-butylperoxymaleic acid, tert-butylperoxylaurate, tert-butylperoxy-3,5,5-trimethyl Caproic acid ester, cyclohexanone peroxide, tert-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-di(benzoyl) Peroxide) hexane, 2,2-bis(t-butylperoxy)octane, tert-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, third Butyl peroxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, -18- 201105501 di-t-butyl-diperoxyisonate, methyl ethyl ketone a peroxide such as peroxide, dicumyl peroxide, 2,5-dimethyl (t-butylperoxy)hexane, or a third butyl cumyl peroxide; potassium persulfate or persulfate A general radical initiator such as a peroxide such as ammonium or sodium chlorate or a redox initiator obtained by a combination of such a peroxide and a reducing agent is appropriately selected in accordance with a polymerization method. The amount of the above polymerization initiator to be used varies depending on the kind or polymerization conditions, but is generally 0% by mass based on 100 parts by mass of the above monomers. 1 to 10 parts by mass The polymerization temperature depends on the type of the polymerization initiator, but is usually 40 to 180 ° C, preferably 50 to 150 ° C, more preferably 60 to 130 ° C. Further, the reaction pressure may be atmospheric pressure or a pressurized condition, and is generally 0. 1 5~0. 5 MPa» Again, the polymerization time is 3 ~ 15 hours. The monomer unit (a) and the monomer unit (B) as described above are polymerized by solution polymerization. The solvent used for the solution polymerization may be an aliphatic hydrocarbon compound such as n-hexane, heptane or octane; an alicyclic hydrocarbon compound such as cyclohexane, methylcyclohexane or ethylcyclohexane; benzene; An aromatic hydrocarbon compound such as toluene, xylene or cumene; an organic solvent such as an ether compound such as tetrahydrofuran, di-n-butyl ether, ethylene glycol dimethyl ether or ethylene glycol diethyl ether; methanol or ethanol A known solvent such as a ketone such as an alcohol, acetone or methyl isobutyl ketone, ethyl benzene, methyl ethyl ketone or butyl acrylate. Among them, methyl ethyl ketone, methanol, toluene, ethylbenzene, butyl acetate, and the like are preferably used. One type of the solvent may be used, or two or more types may be used. The monomer concentration in the reaction solvent is preferably from 10 to 80% by mass. When the monomer concentration is less than 1% by mass, a sufficient reaction rate may not be obtained. If it is higher than 80 -19 to 201105501% by mass, gelation may occur in the reaction. In order to obtain a sufficient reaction rate, the reaction is preferably carried out using a catalyst. The catalyst may be a phosphorus such as triphenylphosphine or tributylphosphine, an amine such as triethylamine or dimethylbenzylamine, or a sulfur such as dimethyl sulfide or diphenyl sulfide. Ethers and the like, but the surface of the reaction rate is preferably phosphorus, and particularly preferably triphenylphosphine. The amount of such a catalyst is generally 0% with respect to the (meth) acrylate monomer unit (B) containing an epoxy group. 1 to 10% by mass. The amount of the catalyst is less than 0 with respect to the (meth) acrylate monomer unit (B) containing an epoxy group. When the amount is 1% by mass, a sufficient reaction rate may not be obtained, and more than 1% by mass may be added, which may cause adverse effects on the physical properties of the produced resin. In order to prevent the formation of a gel in the reaction, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-N-oxygen 4-Ethylamino-2,2,6,6-tetramethylhexahydropyridine-N-oxygen, 4-benzylideneoxy-2,2,6,6-tetramethylhexahydropyridine -N-oxygen, 4-oxo-2,2,6,6-tetramethylhexahydropyridine-n-oxygen, 2,2,6,6-tetramethylhexahydroindole ratio D-N-oxygen N-oxyl radical compound; hydroquinone 'hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol' 2,2'-methylenebis(4-ethyl -6 -t-butylphenol), 2,6-di-t-butyl-N,N-dimethylamino-p-cresol, 2,4-dimethyl-6-tert-butylphenol, 4 - tert-butyl naphthol' 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-) a phenolic compound such as a third butyl phenol); phenothiazine, N,N'-diphenyl-p-phenylenediamine, phenyl-indole-naphthylamine, N,N'-di-col-naphthyl -P-Benzene-20- 201105501 Amine, N-phenyl- Ν'-isopropyl-p-phenylenediamine and other amine compounds; 1,4 -dihydroxy-2,2,6,6-tetramethyl-6 Hydrogen pyridyl a hydroxylamine compound such as 4-dihydroxy-2,2,6,6-tetramethylhexahydropyridine; a wake-up compound such as benzophenone or 2,5-?•dibutylammine; chlorine A copper compound such as iron, copper or dimethyldithiocarbamate is used. These may be used alone or in combination of two or more. The amount of the polymerization inhibitor is preferably from 1 to 100 ppm based on the total amount of the reaction liquid. Then, when the obtained copolymer (C) is reacted with (meth)acrylic acid, the (meth)acrylonitrile-containing acrylic copolymers (I) and (π) can be obtained. Further, (meth)acrylic acid is preferably modified with acrylic acid, and a double bond can be introduced into the acrylic copolymer containing a (meth)acrylonitrile group. The (meth)acrylonitrile-containing acrylic copolymer (I) used in the present invention is an ionizing radiation-curable resin layer, and is required to have solvent resistance and heat resistance by hardening, and the double bond equivalent is preferably 0. 5~4. 5meq/g, more preferably 0. 5~4. 0meg/g, especially 0. 7~3. 6meq/g. Therefore, the (meth)acrylic double bond equivalent is in the above range and can be reacted with the copolymer (C). The reaction of the copolymer (C) with (meth)acrylic acid is preferably in solution, a tertiary amine catalyst, a 4-grade ammonium salt catalyst, a tertiary phosphorus catalyst, a 4-stage phosphorus salt catalyst, an organotin compound catalyst. In the presence of. Specifically, a phosphorus such as triphenylphosphine or tributylphosphine, an amine such as triethylamine or dimethylbenzylamine, or a sulfur such as dimethyl sulfide or diphenyl sulfide can be used. Ethers, etc. The above reaction time and reaction temperature vary depending on the selected solvent or reaction pressure, but the pressure is atmospheric pressure ~0. 2] \ 〇 &, the general temperature is 50 ~ 160 ° C, the reaction time is 3 ~ 50 hours. -21 - 201105501 The ionizing radiation curable composition of the present invention has a weight average molecular weight (Mw) of 5,000 to 200,000 and a dispersion ratio (Mw/Mn) of 1. 0~5. 0. The glass transition point temperature (Tg) contains a (meth)acrylonitrile-based acrylic copolymer (I) at 40 to 150 °C. When the Tg of the (meth)acrylonitrile-based acrylic copolymer (I) is less than 40 ° C, when the surface glossiness is reflected at 60 ° C to 60 or more, the surface is melted, and the formability is changed. Poor, or, the uncured film is sticky, sometimes damaging the sheet. Further, when the surface glossiness is more than 150 ° C and the surface glossiness is 60 ° C or more, the extreme high temperature must be applied, and the flexibility after curing may be impaired. Further, the measurement of Tg prescribed by the present invention is carried out by the method described in the examples described later. Moreover, if it exceeds 150 ° C, it may be difficult to form. Further, a copolymer composed of 35 to 80 parts by mass of (meth) acrylate, 20 to 60 parts by mass of glycidyl (meth) acrylate, and ( to 30 parts by mass of other (meth) acrylate, and The (meth)acryloyl group-containing acrylic copolymer (Π) having a weight average molecular weight (Mw) or Tg is not limited, but is formed into an engineering release paper, which is obtained by reacting 10 to 30 parts by mass of (meth)acrylic acid. The glass transition temperature is 40 to 150 ° C, more preferably 65 to 120 ° C. Since the Tg system is related to the weight average molecular weight (Mw) or the double bond equivalent, it is sufficient to satisfy the above glass transition temperature as long as it contains a double bond and prepares a weight average molecular weight (Mw). It should be 5000~200000, more preferably 1 5000~1 00000, especially 1 5000~70000. If it is less than 5,000, the solvent resistance or the toughness may be inferior, and if the viscosity of the resin exceeds 20,000 Å, the viscosity may become high, which may be difficult to handle. Further, the glass transition point temperature (Tg) is 40 to 150 ° C, more preferably 65 to 120 ° C, and particularly preferably 65 to 90 ° C. For this range, the (meth)acrylonitrile-containing acrylic copolymer-22-201105501 (π) is cured, and has excellent solvent resistance and scratch resistance, and has no stickiness of the uncured film. Excellent. The ionizing radiation curable composition used in the present invention may be composed only of the above (meth)acrylonitrile-containing acrylic copolymer (I)' (Π). The composition is a mixture of two or more substances. However, it is apparent from the dispersion ratio of the (meth)acryloyl group-containing acrylic copolymer (I) that the (meth)acrylonitrile group containing a different molecular weight is contained. The acrylic copolymer is also referred to as an ionizing radiation curable composition when it is composed only of an acrylic copolymer containing a (meth)acrylonitrile group. Further, in the ionizing radiation curable composition used in the present invention, an inorganic pigment, a photopolymerization initiator, or the like may be further blended. By blending inorganic pigments, it is possible to impart a matting feel to the engineered release paper. Such inorganic pigments may, for example, be talc, kaolin, cerium oxide, calcium carbonate, barium sulfate, titanium oxide, zinc oxide or the like. The inorganic pigment is preferably formulated in an ionizing radiation hardening resin layer to become 0. 5 to 50% by mass, more preferably 1 to 10% by mass. When the ionizing radiation-curable resin layer is composed of two or more layers, the amount of the inorganic pigment in each layer is in the above range. The photopolymerization initiator which can be formulated as an ionizing radiation hardening composition is 2,2-dimethoxy-2-phenylethyl benzene, benzoin ethyl ether, ethyl benzene, diethoxy B Toluene, benzyldimethylketal, 2-hydroxy-2-methylpropionylbenzene, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane- 1, 1-hydroxycyclohexyl phenyl ketone, benzophenone, p-chlorobenzophenone, cimelone, N,N-dimethylamino benzoic acid isoamyl ester, 2-chlorothiazepine , 2,4-diethylthiaxanthone, and the like. Adjustment of Photopolymerization Starter -23-201105501 The amount is 1 to 10 parts by mass based on 100 parts by mass of the acrylic copolymer containing (meth)acryl fluorenyl group. Further, in order to modify the hardening property of the (meth)acrylonitrile-containing acrylic copolymer, other resins, polyoxynitrides, and reactions may be contained in the ionizing radiation curable composition insofar as the properties are not impaired. A monomer or other photocurable polymer is used as an optional component. Other resins are methacrylic resin, chlorinated polypropylene, epoxy resin, polyurethane resin, polyester resin, polyvinyl alcohol, polyvinyl acetal, etc., and the reactive monomer has methyl group. (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethyl hexyl (meth) acrylate, stearyl (methyl) Acrylate, lauryl (meth) acrylate 'tridecyl (meth) acrylate, trimethylolpropane triacrylate, tris(propylene methoxyethyl) trimeric isocyanate, pentaerythritol tetraacrylate , dipentaerythritol hexaacrylate, and the like. The photocurable polymer is a polyfunctional (meth) acrylate oligomer. The amount is 30 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the (meth)acryl fluorenyl group-containing acrylic copolymer. The polyfunctional (meth) acrylate oligomer is a compound having two or more (meth) acrylonitrile groups in one molecule, for example, an epoxy having a tricyclodecane dimethylol diacrylate vinegar or a bisphenol F. Ethane modified diacrylate, bisphenol a, epoxy epoxide modified diacrylate, trimeric isocyanate, ethylene oxide modified diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate Ester's trimethylpropane triacrylate, trimethylolpropane propylene oxide modified tripropylene vinegar, trimethyl propylene oxide ethylene oxide modified triacrylate, pentaerythritol-24-201105501 Acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, urethane acrylate, and the like. These may be combined in combination of two or more. The ionizing radiation curable composition may be applied by diluting with 10 to 1000 parts by mass of a solvent based on 100 parts by mass of the (meth)acrylonitrile-based acrylic copolymer. If the dilution of the solvent imparts a viscosity suitable for coating, for example, a viscosity of from 1 〇 to 3 000 mPa·s at 25 ° C, and in the drying step, it can be moved to the appropriate surface of the polysiloxane. As the solvent, for example, an aromatic hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or an ester of ethyl acetate, butyl acetate or isobutyl acetate may be used. Solvent, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, 3-methyl-3-methoxybutyl acetate, ethyl-3-B A glycol ether ester solvent such as oxypropionate, an ether solvent such as tetrahydrofuran or dioxane, or an aprotic polar solution such as N-methylpyrrolidone. The coating method can use direct gravure coating, reverse gravure coating, gravure coating, micro gravure coating, direct roll coating, reverse roll coating, curtain coating, blade coating, air knife coating. A well-known method such as cloth coating, rod coating, die coating, and spraying is applied to a thermoplastic film, dried and heated at a temperature of 90 to 130 ° C, and the solvent is evaporated in a drying furnace to form an ionizing radiation hardening composition. The material is hardened by heat. This temperature is higher than the softening point of the ionizing radiation curable composition and lower than the temperature at which the ionizing radiation curable composition melts. The thickness of the ionizing radiation hardening resin layer is preferably from 1 to 50 μm, more preferably from -25 to 201105501 3 to 2 0 μη. When it is thinner than Ιμηι, the transfer of the fine formability is deteriorated, and when it exceeds 50 μm, the hardenability of the resin may be deteriorated. As described above, when the ionizing radiation-curable resin layer is composed of two or more layers, the thickness of the entire layer is in the above range. Further, the above-mentioned thermally hardened ionizing radiation curable composition is formed by forming a surface having a surface gloss of 60° or more, and then irradiating ultraviolet rays or electron beams from the side of the thermally hardened polysiloxane layer to ionize the radiation. Line hardening. The source of the ultraviolet light can be a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, or the like. The electron beam irradiation method may be a scanning method, a curtain beam method, a broad beam method, or the like, and the acceleration voltage of the electron beam is preferably 50 to 300 kV. (4) Thermosetting polyfluorene oxide layer The thermosetting polyfluorinated layer used in the present invention is a thermosetting property composed of an alkenyl group-containing organopolyoxane, an organic hydrogen polyoxyalkylene, and a uranium-based hardening catalyst. The polyoxonium composition is formed by thermal hardening. An example of the alkenyl group-containing organopolyoxane may, for example, be the following compound. [Chemical 1] X-R1—and 0+ and 0廿such as 0 L·[—strict seven—

R R R2-Z R R (上述式中，R主要爲甲基，但爲其他之烷基或苯基等之 芳基或其等之組合，1 + m + n爲1以上之整數，各矽氧烷單 元亦可隨機配置。X、Y及Z之中至少一個於乙烯基、烯丙 -26- 201105501 基（-CH2-CH = CH2 )基或（甲基）丙烯醯基等爲加成聚合 性基，R1〜R3爲單鍵或烯基。） 上述之含有烯基的有機聚矽氧烷之分子量並無特別限 定，但一般適宜爲3500〜2 0000的範圍。此等之含有烯基的 有機聚矽氧烷係可從市場取得，可於本發明容易地使用。 本發明所使用之有機氫聚矽氧烷係在上述通式中-R1-X、-R2-Z、及-R3-Y之中至少一個爲氫原子者，對於其他 之取代基、矽氧烷單元的排列、分子量等與前述通式同樣 。此等之含有烯基的有機聚矽氧烷係可從市場取得，可於 本發明容易地使用。 含有烯基的有機聚矽氧烷與有機氫聚矽氧烷之使用比 率係以兩者具有之反應性基的莫耳比來決定，前者與後者 之比爲4: 1〜1: 4，尤宜爲1: 1〜1: 3之範圍，若超出此範 圍’就離型性之降低、塗膜強度之降低、未反應之反應性 基所造成的保存性之劣化等而言無法得到滿足之性能。 在本發明中係進一步使用鉑系硬化觸媒。觸媒係前述 含有烯基的有機聚矽氧烷與有機氫聚矽氧烷每100質量份 約5〜2 00質量份左右爲較佳之使用量。 由上述含有烯基的有機聚矽氧烷與有機氫聚矽氧烷及 鉑系硬化觸媒所構成之熱硬化性聚矽氧組成物係即使在常 溫下亦進行反應，在塗佈液中之反應的進行成爲離型性降 低之原因，又，於塗佈液之保存性或處理性產生問題。在 本發明中爲解決如此之問題，在常溫下對於熱硬化性聚矽 氧組成物具有反應抑制效果，於加熱處理時亦可使用解決 -27- 201105501 其抑制效果之反應抑制劑。具體上，在本發明所使用之反 應抑制劑就溶劑之溶液的狀態，抑制上述硬化觸媒對熱硬 化性聚矽氧組成物的作用，所加熱之狀態或溶劑揮發之狀 態，亦即，加熱或乾燥狀態中係非抑制上述硬化觸媒之作 用，而爲可促進之材料。如此之硬化抑制劑可舉例如乙炔 醇之甲矽烷基化物等。此等之反應抑制劑可從市場取得而 使用》如此之反應抑制劑係前述熱硬化性聚矽氧組成物每 100質量份宜以約5〜100質量份之比率使用。 如此之熱硬化性聚矽氧組成物係亦可使用市售品，例 如，可於由含有烯基的有機聚矽氧烷與有機氫聚矽氧烷之 混合物所構成的加成聚合型聚矽氧材料之主劑（信越化學 工業股份公司製、KS-3 603 )混合由鈾系硬化觸媒所構成 之硬化劑（信越化學工業股份公司製、CAT-PL-50T )而 調製。 上述熱硬化性聚矽氧組成物係在常溫下爲固體狀態， 但於加工時藉加熱變化成液體狀態之材料。本發明之熱硬 化性聚矽氧組成物係固定表面光澤度在60°反射爲60以上 之賦型面，同時爲得到強度等充分的皮膜物性，必須爲硬 化性。 本發明之熱硬化性聚砂氧層的形成方法本身係可與前 述熱硬化性聚矽氧組成物之塗佈、乾燥加熱、熟成等染料 受容層的形成同樣，所形成之前述熱硬化聚砂氧層的厚度 宜爲0.01~20μιη之範圍。 -28- 201105501 (5 )熱塑性樹脂層 在本發明中亦可於電離輻射線硬化樹脂層之間形成中 間層。中間層係爲確保耐熱性、賦型性、剝離性、耐溶劑 性、塡縫效果所配設者，爲熱塑性樹脂層或塡縫層。 在本發明中構成熱塑性樹脂層之熱塑性樹脂係可依照 被賦型物之種類或製造條件而適當選擇。丙烯酸系樹脂外 ，可例示如聚乙烯、聚丙烯、聚甲基戊烯等之聚烯烴系樹 脂、其他、聚矽氧系樹脂、含胺基醇酸之醇酸系樹脂等。 其中，宜使用聚丙烯系樹脂。因耐熱性優異。在本發明所 使用之聚丙烯系樹脂係只要無損作爲工程剝離紙之耐熱性 ’不限於丙烯單獨聚合物，而以丙烯作爲主體，亦可爲此 丙烯與例如乙烯、丁烯、戊烯、己烯、辛烯、4-聚甲基戊 嫌-1等的α -嫌烴之共聚物。 又，經過氯化乙烯系樹脂等超過溫度180 °C之熱處理 工程而製造合成皮革，或以高溫/高壓條件所製造之三聚 氰胺化妝板等的製造時，宜使用聚甲基戊烯系樹脂。例如 ’從氯化乙烯系樹脂製造合成皮革時，有時使氯化乙烯系 樹脂發泡而層合，此時之乾燥溫度成爲18 0〜2 10 °C。因此 ’要求對於如此之高溫的耐熱性，可適宜使用融點更高之 聚甲基戊烯系樹脂。在本發明所使用之聚甲基戊烯系樹脂 係以4-甲基-1 -戊烯作爲主成分之TPX等的聚合物，4-甲 基-1-戊烯之單獨聚合物外，亦可爲4-甲基-1-戊烯與其他 之α -烯烴，例如乙烯、丙烯、1-丁烯、1-己烯、1-辛烯、 1-癸烯、1-十四碳烯、1-十八碳烯等的碳數2〜20之α -烯烴 -29- 201105501 的聚合物。可適宜使用例如使4·甲基-卜戊烯以97〜98質量 %，使α -烯烴以2~3質量％之範圍含有的4-甲基-1·戊烯作 爲主體的共聚物’以微分掃描型熱量計（DSC法）所測定 的融點爲23 6〜2 3 8 °C ’依據ASTM D 1 23 8而荷重=2.16kg、 溫度=260 °C之條件所測定的熔融流動率（MFR )爲 16 0〜200 g/10分之範圍的樹脂等。對於在以氯化乙烯系樹 脂作爲合成皮革製造原料時之製造步驟的熱處理溫度或三 聚氰胺化妝板之製造中的加溫條件，耐熱性優且對此等賦 予表面光澤度在60°反射爲60以上之光澤後的剝離亦容易 〇 在本發明中，熱塑性樹脂層（3 0 )係不限定於單層， 而如前述之圖2(b)所示般，亦可爲如下之多層即含有選 自由聚丙烯系樹脂及聚甲基戊烯系樹脂之第一聚烯烴系樹 脂層（3 0A”）、與由構成前述第1聚烯烴系樹脂層之樹脂 與聚乙烯系樹脂的組成物所構成之第二聚烯烴系樹脂層（ 30A’）。又，多層係不限定於2層，而亦可爲3層或其以上 〇 構成第二聚烯烴系樹脂之構成前述第一聚烯烴系樹脂 層之樹脂與聚乙烯系樹脂的組成物中，聚乙烯系樹脂之調 配量爲5〜80質量％，更宜爲10〜50質量％。聚乙烯係較聚丙 烯系樹脂或聚甲基戊烯系樹脂等融點更低，但若爲上述範 圍’可使第一聚烯烴系樹脂層（30 A”）與紙基材（40 )適 當接著’且可確保承受合成皮革之製造或三聚氰胺化妝板 之製造的耐熱性。 -30- 201105501 此時，所使用之聚乙烯系樹脂並無特別限制，亦可爲 低密度聚乙烯、中密度聚乙烯、高密度聚乙嫌之任一者。 但’因依密度而融點相異’故較佳係融點爲3 ，更 宜爲1 1 0〜1 2 0 °C者。若爲此範圍’可確保作爲工程剝離紙 之耐熱性。 上述熱塑性樹脂層係可使前述聚烯烴系樹脂或組成物 樹脂以輥塗佈、凹版塗佈、押出塗佈、刮刀塗佈、繞線棒 塗佈、浸漬塗佈等層合於紙基材來調製。 熱塑性樹脂（30A )之厚度宜爲3〜4〇μηι，更宜爲 5〜2 0μηι。若薄於3μιη’有時合成皮革或三聚氰胺化妝板製 造後的剝離性會降低，另外，若超過4 0 μ m，有時離型紙 之捲曲變大》 又，熱塑性樹脂層（3 0 A )爲多層時，例如含有第— 聚烯烴系樹脂層（30A”）與第二聚烯烴系樹脂層（30A， )等時，亦可於共押出等層合於紙基材上。 在本發明中，亦可爲熱塑性樹脂層（30A)具有表面 處理層（33)者。藉由如此之表面處理而可提昇與電離輻 射線硬化樹脂層之密著性。如此之表面處理係火焰處理、 電暈放電處理、臭氧處理、使用氧氣或氮氣等之低溫電漿 處理 '輝光放電處理、使用化學藥品等而處理之氧化處理 、其他等之前處理等。又，預先任意地塗佈底塗劑、下塗 劑、錨定塗佈劑、接著劑、或、蒸鍍錨定塗佈劑等，亦可 進行表面處理。又，前述塗佈劑係可使用例如聚酯系樹脂 、聚醯胺系樹脂、聚胺基甲酸酯系樹脂、環氧系樹脂、酚 -31 - 201105501 系樹脂、（甲基）丙烯酸系樹脂、聚醋酸乙烯酯系樹脂、 聚乙烯或聚丙烯等之聚烯烴系樹脂或其共聚物乃至改性樹 脂、纖維素系樹脂、其他等作爲載劑之主成分的樹脂組成 物。 在如此之表面處理中，尤其適宜進行電暈處理或電漿 處理。若進行電暈處理，一般剝離強度會提高，故例如使 用所得到之工程剝離紙而製造聚胺基甲酸酯合成皮革時， 有時工程剝離紙會破裂，但在本發明中係藉由特定組成之 電離輻射線硬化性組成物而構成電離輻射線硬化樹脂層， 故未提昇剝離強度且可確保反覆剝離性。 (6 )塡縫層 可形成塡縫層作爲本發明之中間層。塡縫層係例如可 使用相對於具有造膜性之樹脂而含有無機顏料0.5〜50質量 %者。 具有造膜性之樹脂係可適宜使用聚乙烯醇、丙稀酸樹 脂、苯乙烯丙烯酸樹脂、纖維素衍生物、聚酯樹脂、聚胺 基甲酸酯樹脂、三聚氰胺樹脂、醇酸樹脂、胺基醇酸樹脂 、聚氯化乙烯樹脂、聚偏氯乙烯樹脂 '合成乳膠、天然橡 膠、聚丁 一嫌、本乙稀-丁 —嫌系聚合物 '丙燃睛-丁二嫌 系聚合物、甲基丙烯酸甲酯-丁二烯系聚合物、2_乙燃基 吡啶-苯乙烯·丁二烯系聚合物、聚氯丁二烯、聚異戊二燃 、聚苯乙烯、聚胺基甲酸酯、丙烯酸酯系聚合物、聚醋酸 乙烯酯、醋酸乙烯酯共聚物、醋酸乙烯酯-乙燃系共聚物 -32- 201105501 、两烯酸酯-苯乙烯系聚合物、聚乙烯、氯化乙烯系聚合 物、偏氯乙烯系聚合物、含有環氧基的樹脂等。此等係混 合2種以上而使用。 無機顏料係具有滑石、高嶺土、氧化矽、碳酸鈣、硫 酸鋇' 氧化鈦、氧化鋅等，對於具有前述造膜性之樹脂， 調配0.5〜70質量％。若低於〇.5質量％，有時降低塡縫效果 ’另外，若超過70質量％，有時阻礙賦型性》此塡縫層宜 爲0.5〜2 0 g/m2，即充分。塡縫材料之塗佈可以與前述之熱 塑性樹脂層相同的方法進行。塡縫材料之塗佈係相對於固 形分100質量份一般以10〜1000質量份之溶劑進行稀釋而塗 佈。藉溶劑之稀釋可於塗佈賦予適當的黏度例如在25它中 爲10〜3000mPa.秒之黏度。 (7 )工程剝離紙之製造方法 本發明之工程剝離紙係於紙基材上藉電離輻射線使電 離輻射線硬化樹脂層及熱硬化聚矽氧層所層合的層合物硬 化者，若爲於表面形成表面光澤度於60°反射爲60以上之 賦型面者即可，未限制於其製造方法。 例如於表面光澤度於75°反射爲90以上之鏡面銅版紙 的鏡面銅版層上層合電離輻射線硬化性組成物及熱硬'化性 聚矽氧組成物，然後，可對前述層合物進行電離輻射線硬 化處理並製造（參照圖3 )。鏡面銅版紙的鏡面銅版層係 具有在75°反射爲90以上之表面光澤度，若於此鏡面銅版 層上層合電離輻射線硬化性組成物及熱硬化性聚矽氧組成 -33- 201105501 物而捲取，依存於前述鏡面銅版層的表面光澤度，而可製 造賦型面具有於60°反射爲60以上之表面光澤度的工程剝 離紙。 又，於特定之紙基材上層合電離輻射線硬化性組成物 層及熱硬化性聚矽氧組成物層而得到層合物，於此層合物 上形成表面光澤度於60°反射爲60以上的賦型面，然後， 可進行電離輻射線硬化處理並製造。此時，層合物進一步 層合熱塑性樹脂層作爲中間層時，係宜於紙基材層合熱塑 性樹脂層，然後對熱塑性樹脂層進行表面處理，於前述表 面處理層上層合電離輻射線硬化性樹脂組成物層及熱硬化 性聚矽氧組成物層而得到層合物。例如，前述層合物爲如 圖2(b)所示之紙基材（40)、第二聚烯烴系樹脂層（ 30A’）、第一聚烯烴系樹脂層（30A”）、第一聚烯烴系 樹脂層（3 0 A”）上之表面處理層（3 3 )、電離輻射線硬化 樹脂層（20)、及熱硬化聚矽氧層（10)所構成時，如圖 4所示般，於押出機A(70)饋入構成第二聚烯烴系樹脂 層之樹脂組成物（2)、於押出機B ( 70’）饋入構成第一聚 烯烴系樹脂層之樹脂（1)，介由T模頭（75 )而使此等共 押出於紙基材（40 )上而以支撐輥（60 )與冷卻輥（50 ) 進行層合及接著。然後，於第一聚烯烴系樹脂層（30A”） 上進行例如電暈處理等，形成表面處理層（33)。又，押 出機A ( 70 )或押出機B ( 70’）之加熱溫度係只要依照所 使用之樹脂的融點或熔融流動率、所調配之消光劑的種類 或調配量等而適當選擇即可。然後，於紙基材或上述表面 -34- 201105501 處理層上塗佈電離輻射線硬化性組成物，乾燥及熱硬化而 使電離輻射線性組成物膜熱硬化。然後，於所熱硬化之電 離輻射線性組成物膜上塗佈熱硬化性聚矽氧組成物，進行 加熱乾燥而形成熱硬化聚矽氧膜。藉此可製造賦型加工前 層合物。然後，於此賦型加工前層合物進行表面光澤度於 6〇°反射爲60以上之賦型處理，可形成特定之高光澤面， 作爲工程剝離紙。例如，使具有表面光澤度於60°反射爲 60以上之賦型面之賦型輥與接受此賦型輥的表面光澤度於 60°反射爲60以上之面的紙輥或金屬輥對向而具備之賦型 加工機，或使前述賦型輥與具有此賦型輥的表面光澤度於 60°反射爲60以上之表面的金屬輥對向而具備的賦型加工 機上，使上述賦型加工前層合物流動，藉被加熱之賦型輥 而施加壓力，可於賦型加工前層合物形成表面光澤度於 60°反射爲60以上之賦型面。又，亦可不使用賦型輥而使 用平賦型板而以平沖壓形成表面光澤度於60°反射爲60以 上之賦型面。 在本發明中電離輻射線硬化處理係從熱硬化聚矽氧膜 側照射紫外線或電子束，使熱硬化電離輻射線性組成物膜 硬化，形成電離輻射線硬化樹脂層。紫外線之光源係可使 用低壓水銀燈、中壓水銀燈、高壓水銀燈、金屬鹵素燈、 氙燈、鎢絲燈等。電子束之照射方式可使用掃描方式、簾 束方式、大光斑方式等，電子束之加速電壓以50〜3 00kV 爲適宜。 又，本發明之工程剝離紙的前述賦型前的厚度宜爲 -35- 201105501 30~500μΓη’ 更宜爲 100~300μηι。若厚度低於 30μιη 性會降低，在製造步驟捲取時變成易斷裂等之生產 性會降低。另外’若超過5 00μηι，有時工程剝離紙 捲取變大，加工性降低。 (8)合成皮革之製造方法 可使用本發明之合成皮革用工程剝離紙，與使 之剝離紙同樣做法而製造合成皮革。 首先，於工程剝離紙之熱硬化聚矽氧層上塗佈 革用之樹脂組成物。塗佈於熱硬化聚矽氧層上之樹 係形成於上述工程剝離紙之賦型面的表面光澤度； 射爲60以上之光澤面被形成，故對應於此之高光澤 前述樹脂組成物。其後，再貼合基布（例如，織布 布等），乾燥樹脂層，冷卻後，使剝離紙剝離，俾 合成皮革。於上述之合成皮革用的樹脂組成物係可 胺基甲酸酯、聚氯化乙烯等之樹脂。使用聚胺基甲 ，宜使樹脂組成物之固形分爲20〜50質量％。又， 氯化乙烯時，宜使用與酞酸二辛酯、酞酸二月桂酯 塑劑、發泡劑' 安定劑等混合並分散之樹脂組成物 脂組成物之塗佈方法可舉例如刮刀塗佈、輥塗佈、 佈等之以往公知的塗佈方法。使用如此之本發明的 離紙之合成皮革的製造中，係在高溫下進行之氯化 皮革製造時，亦可防止紙基材與熱塑性樹脂層之間 ’耐熱性優，且藉機械強度高之電離輻射線硬化樹 ，賦型 性適合 之寬幅 用習知 合成皮 脂層， 主60。反 轉印至 、不織 可得到 使用聚 酸酯時 使用聚 等之可 。此樹 凹版塗 工程剝 乙烯系 的剝離 脂層的 -36- 201105501 存在及剝離性優之熱硬化聚矽氧層的存在，可反覆安定生 產。 (9 )三聚氰胺化妝板之製造 使用本發明之三聚氰胺化妝板用工程剝離紙，與習知 之賦型薄片同樣做法而製造三聚氰胺化妝板。 首先，如圖5所示般，於支撐紙（310)上，重疊4片 含浸有三聚氰胺樹脂的紙芯用紙（3 20 )，於其上依序重 疊含浸三聚氰胺樹脂之化妝紙（3 3 0 )、含浸三聚氰胺樹 脂之外覆層紙（3 40 )。於前述外覆層紙（340 )上重疊本 發明之工程剝離紙（1 00 )以使具有表面光澤度於60°反 射爲60以上之賦型面的熱硬化聚矽氧面（10 )接觸於前述 外覆層紙（340 )。再挾於2片之鏡面加工金屬板（400A 、400B )之間，以沖壓，溫度常溫〜180 °C 、壓力 70〜120kg/cm2、加熱時間10分鐘〜2小時之條件，進行加熱 加壓而調製層合板。又，加熱加壓條件係亦可以相異之溫 度、壓力的沖壓進行複數次。即使任一者，藉由沖壓加工 ，於前述層合板之表面係三聚氰胺樹脂會從外覆層紙（ 3 40 )及含浸三聚氰胺樹脂之化妝紙（3 3 0 )滲出，再硬化 而形成三聚氰胺樹脂層。於此三聚氰胺樹脂層的表面，係 藉由工程剝離紙（100)，形成表面光澤度於60°反射爲 60以上之光澤的賦型面。於沖壓加工後，冷卻至室溫後， 從沖壓機取出，若剝離工程剝離紙（1 00 )，可得到於表 面具有前述光澤之賦型面之三聚氰胺化妝板（ 300 )。又 -37- 201105501 ，三聚氰胺化妝板（100 )係層合前述層合板之材料2~20 段，亦可進行多段沖壓而製造。例如，如圖6所示般，對 抗前述層合板之材料而2段重疊以進行沖壓來製造。在本 發明中，亦可適宜使用如此之多段沖壓。 又，就三聚氰胺化妝板之製造方法，有使用合板或硬 質板取代上述紙芯用紙，可以10〜40 Kg/cm2之低壓調製之 低壓三聚氰胺化妝板，亦可適宜使用如此之低壓三聚氰胺 化妝板。 如此之本發明的工程剝離紙係因耐熱性、耐溶劑性、 剝離性優異，故即使在三聚氰胺化妝板之製造條件的高溫 下，可防止紙基材與熱塑性樹脂層之間的剝離，且藉機械 強度高之電離輻射線硬化樹脂層的存在及剝離性優之熱硬 化聚矽氧層的存在，可反覆安定生產。 【實施方式】 實施例 其次，表示具體之實施例而更詳細地說明本發明。 (合成例1 ) 於具備攪拌機、滴下漏斗、回流冷卻器、氮氣導入管 及溫度計之玻璃燒瓶中，置入作爲單體之甲II丙烯酸甲酯 3 〇g、縮水甘油基甲基丙烯酸酯70g、與作爲溶劑之甲乙酮 9〇g而加熱至80°C後，再使作爲聚合起始劑之2,2’-偶氮雙 (2,4-二甲基戊腈）1.08溶解於甲乙酮128之溶液中，花3 -38- 201105501 小時滴下，進—步，以80 °c聚合3小時’得到具有環氧基 之共聚物A 1的甲乙酮溶液（固形分5 0 . 1 % )。繼而，直接 保持80 °C，一邊吹入乾燥空氣’一邊加入氫醌單甲基醚 0.05g、三苯基磷l.〇g、丙烯酸25g、甲乙酮25g，直接反 應35小時，得到含有（甲基）丙烯醯基之丙烯酸系共聚物之 甲乙酮溶液（固形分 50·6%、Mn=11000、Mw = 2l000)。 該共聚物之玻璃轉移溫度爲62 °C，雙鍵量爲3.6。將結果 表示於下述表1中。 (合成例2~13) 除變更成下述之表1及表2所示的原料以外，其餘係與 合成例1同樣地進行聚合及反應，得到含有（甲基）丙烯醯 基之丙烯酸系共聚物之甲乙酮溶液（固形分50.8% )。將 該共聚物之重量平均分子量、數目平均分子量、玻璃轉移 溫度、雙鍵量表示於表1、表2中。又，僅合成例，將2,2’-偶氮雙（2,4-二甲基戊腈）之使用量變更成2.6g，而改變 重量平均分子量。 又，表中之簡稱爲以下。 IBX :異冰片基甲基丙烯酸酯、 MMA :甲基丙烯酸甲酯、 BMA : 丁基甲基丙烯酸酯、 IBMA :異丁基甲基丙烯酸酯、 GMA :縮水甘油基甲基丙烯酸酯、 AA ： 丙烯酸、 -39- 201105501 Μη :數目平均分子量、 Mw :重量平均分子量、 (測定條件） 測定條件如以下般。 (1)含有（甲基）丙烯醯基之丙烯酸系共聚物之重量平均 分子量（Mw )係以如下之條件測定。 (i)管柱：「TSK-GEL MULTIPORE HXL-Mx4」（ Tosoh公司製） (ii )管柱溫度：40°C (iii )溶離液：四氫呋喃（THF )RR R2-Z RR (In the above formula, R is mainly a methyl group, but is an alkyl group such as another alkyl group or a phenyl group, or a combination thereof, and 1 + m + n is an integer of 1 or more, and each decane is used. The unit may also be randomly arranged. At least one of X, Y and Z is an addition polymerization group based on a vinyl group, an allylic group 26-201105501 group (-CH2-CH=CH2) group or a (meth) acrylonitrile group. R1 to R3 are a single bond or an alkenyl group.) The molecular weight of the above-mentioned alkenyl group-containing organopolyoxane is not particularly limited, but is generally preferably in the range of 3,500 to 20,000. These alkenyl group-containing organic polyoxyalkylenes are commercially available and can be easily used in the present invention. The organohydrogen polyoxyalkylene used in the present invention is one in which at least one of -R1-X, -R2-Z, and -R3-Y is a hydrogen atom in the above formula, and for other substituents, decane. The arrangement of the units, the molecular weight, and the like are the same as those of the above formula. These alkenyl group-containing organopolyoxyalkylenes are commercially available and can be easily used in the present invention. The ratio of the use of the alkenyl group-containing organopolyoxane to the organohydrogenpolyoxane is determined by the molar ratio of the reactive groups of the two, and the ratio of the former to the latter is 4:1 to 1:4. It is preferably in the range of 1:1 to 1:3. If it exceeds this range, the reduction in release property, the decrease in coating strength, and the deterioration of preservability due to unreacted reactive groups cannot be satisfied. performance. In the present invention, a platinum-based hardening catalyst is further used. The catalyst is preferably used in an amount of about 5 to 200 parts by mass per 100 parts by mass of the organic polyoxyalkylene group having an alkenyl group and the organic hydrogen polyoxyalkylene. The thermosetting polyfluorene oxide composition comprising the alkenyl group-containing organopolyoxane and the organohydrogenpolysiloxane and the platinum-based curing catalyst is reacted at a normal temperature, and is in a coating liquid. The progress of the reaction is a cause of a decrease in release property, and a problem arises in the preservability or handleability of the coating liquid. In order to solve such a problem, the present invention has a reaction suppressing effect on the thermosetting polyphosphonium composition at normal temperature, and a reaction inhibitor which solves the inhibitory effect of -27-201105501 can also be used in the heat treatment. Specifically, in the state of the solution of the solvent used in the present invention, the action of the curing catalyst on the thermosetting polyfluorene composition is suppressed, and the state of heating or the state in which the solvent is volatilized, that is, heating In the dry state, it does not inhibit the action of the above-mentioned hardening catalyst, but is a material that can be promoted. Such a hardening inhibitor may, for example, be a mercaptoalkylate of ethynyl alcohol or the like. Such a reaction inhibitor can be obtained from the market. The reaction inhibitor is such that the thermosetting polyphosphonium composition is preferably used in a ratio of about 5 to 100 parts by mass per 100 parts by mass. A commercially available product may be used as the thermosetting polyoxyl composition, for example, an addition polymerization type polycondensate composed of a mixture of an alkenyl group-containing organopolyoxane and an organic hydrogen polyoxyalkylene. The main agent of the oxygen material (manufactured by Shin-Etsu Chemical Co., Ltd., KS-3 603) was prepared by mixing a hardener (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) composed of a uranium-based hardening catalyst. The thermosetting polyphosphonium composition is a material which is in a solid state at normal temperature but which changes to a liquid state by heating during processing. The heat-hardening polyxanthene composition of the present invention has a surface gloss of 60° or more, and is required to have a coating surface of 60 or more. In order to obtain sufficient film properties such as strength, it is required to be hard. The method for forming the thermosetting polysilicic oxide layer of the present invention itself can be formed in the same manner as the formation of the dye-receiving layer such as coating, drying, heating, and aging of the thermosetting polyfluorene oxide composition. The thickness of the oxygen layer is preferably in the range of 0.01 to 20 μm. -28-201105501 (5) Thermoplastic Resin Layer In the present invention, an intermediate layer may be formed between the ionizing radiation-curable resin layers. The intermediate layer is a thermoplastic resin layer or a quilted layer in order to ensure heat resistance, formability, peelability, solvent resistance, and quilting effect. The thermoplastic resin constituting the thermoplastic resin layer in the present invention can be appropriately selected depending on the type of the shaped material or the production conditions. Examples of the acrylic resin include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, and other polyoxonated resins and alkyd-based alkyd resins. Among them, a polypropylene resin is preferably used. Excellent in heat resistance. The polypropylene-based resin used in the present invention is not limited to the heat resistance of the engineered release paper, and is not limited to the propylene single polymer, but is mainly composed of propylene, and may be, for example, propylene and ethylene, butene, pentene, and hexene. a copolymer of an alpha, a stimulating hydrocarbon such as an alkene, an octene or a 4-polymethylpentane-1. Further, when a synthetic leather is produced by a heat treatment process at a temperature of 180 °C or higher, such as a chlorinated vinyl resin, or a melamine cosmetic board produced under high temperature/high pressure conditions, a polymethylpentene resin is preferably used. For example, when synthetic leather is produced from a vinyl chloride resin, the vinyl chloride resin may be foamed and laminated, and the drying temperature at this time may be 18 0 to 2 10 °C. Therefore, it is required to use a polymethylpentene-based resin having a higher melting point for such high-temperature heat resistance. The polymethylpentene-based resin used in the present invention is a polymer such as TPX having 4-methyl-1-pentene as a main component, and a separate polymer of 4-methyl-1-pentene. It may be 4-methyl-1-pentene and other α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, A polymer of 1-octadecene or the like having a carbon number of 2 to 20 α-olefin-29-201105501. For example, a copolymer in which 4-methyl-p-pentene is contained in an amount of from 97 to 98% by mass and 4-methyl-1.pentene contained in the range of from 2 to 3% by mass of the α-olefin is used is preferably used. The melting point measured by the differential scanning calorimeter (DSC method) is 23 6 to 2 3 8 ° C. The melt flow rate measured according to ASTM D 1 23 8 and the load = 2.16 kg, temperature = 260 ° C ( MFR) is a resin in the range of 16 0 to 200 g/10 minutes. The heat treatment temperature in the production step of the production step of the chlorinated vinyl resin as the raw material for the synthetic leather or the heating condition in the production of the melamine cosmetic sheet is excellent in heat resistance, and the surface gloss is 60 or more at 60°. The peeling after the gloss is also easy to be used in the present invention, and the thermoplastic resin layer (30) is not limited to a single layer, and as shown in the above-mentioned FIG. 2(b), the following layers may be selected from a first polyolefin-based resin layer (30A) of a polypropylene resin and a polymethylpentene resin, and a composition of a resin and a polyethylene resin constituting the first polyolefin-based resin layer. Further, the second polyolefin-based resin layer (30A') is not limited to two layers, and may be three or more layers of a second polyolefin-based resin constituting the first polyolefin-based resin layer. In the composition of the resin and the polyethylene resin, the blending amount of the polyethylene resin is 5 to 80% by mass, more preferably 10 to 50% by mass. Polyethylene is a polypropylene resin or a polymethylpentene resin. The melting point is lower, but if it is Range 'make a first polyolefin resin layer (30 A ") and the paper base material (40) then appropriate' and can ensure heat resistance for producing melamine decorative plate or manufacturing of synthetic leather. -30- 201105501 In this case, the polyethylene resin to be used is not particularly limited, and may be any of low density polyethylene, medium density polyethylene, and high density polyethylene. However, because the melting point is different depending on the density, the preferred melting point is 3, and it is preferably 1 1 0 to 1 2 0 °C. If it is this range, the heat resistance of the paper as the engineering release can be ensured. In the thermoplastic resin layer, the polyolefin resin or the composition resin may be laminated on a paper substrate by roll coating, gravure coating, extrusion coating, blade coating, wire bar coating, dip coating, or the like. modulation. The thickness of the thermoplastic resin (30A) is preferably 3 to 4 〇 μηι, more preferably 5 to 2 0 μη. If it is thinner than 3 μm, the peeling property of the synthetic leather or the melamine cosmetic sheet may be lowered, and if it exceeds 40 μm, the curl of the release paper may become large. Further, the thermoplastic resin layer (30 A) is When the multilayer layer contains, for example, the first polyolefin-based resin layer (30A) and the second polyolefin-based resin layer (30A), it may be laminated on the paper substrate by co-extrusion or the like. The thermoplastic resin layer (30A) may also have a surface treatment layer (33). By such surface treatment, the adhesion to the ionizing radiation hardening resin layer can be improved. Such surface treatment is flame treatment, corona discharge. Treatment, ozone treatment, low-temperature plasma treatment using oxygen or nitrogen, etc. 'Glow discharge treatment, oxidation treatment using chemical treatment, etc., and other pretreatments, etc. Further, the primer, the undercoating agent, and the undercoating agent are applied in advance. The anchor coating agent, the adhesive agent, or the vapor deposition anchor coating agent, etc. may be subjected to a surface treatment. Further, for the coating agent, for example, a polyester resin, a polyamide resin, or a polyamine group may be used. Formate resin , epoxy resin, phenol-31 - 201105501 resin, (meth)acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene or polypropylene or copolymer thereof, or modified resin, fiber A resin composition which is a main component of a carrier resin, such as a resin, etc. In such surface treatment, corona treatment or plasma treatment is particularly suitable. If corona treatment is performed, the peel strength is generally improved, so for example, When the obtained engineering release paper is used to produce a polyurethane synthetic leather, the engineered release paper may be broken, but in the present invention, the ionizing radiation hardening is constituted by a specific composition of the ionizing radiation hardening composition. The resin layer does not improve the peel strength and can ensure the releasability. (6) The quilting layer can form a quilting layer as the intermediate layer of the present invention. The quilting layer can be used, for example, with respect to the resin having film forming properties. The inorganic pigment may be used in an amount of 0.5 to 50% by mass. The resin having a film forming property may suitably be a polyvinyl alcohol, an acrylic resin, a styrene acrylic resin, a cellulose derivative, or a poly Resin, polyurethane resin, melamine resin, alkyd resin, amino alkyd resin, polyvinyl chloride resin, polyvinylidene chloride resin 'synthetic latex, natural rubber, polybutylene, Benthene- D--supply polymer 'acrylic eye-butyl dimethacrylate polymer, methyl methacrylate-butadiene polymer, 2_ephthyl pyridyl-styrene-butadiene polymer, polychlorinated Butadiene, polyisoprene, polystyrene, polyurethane, acrylate polymer, polyvinyl acetate, vinyl acetate copolymer, vinyl acetate-ethane combustion copolymer-32- 201105501, a dienoate-styrene-based polymer, a polyethylene, a vinyl chloride polymer, a vinylidene chloride-based polymer, an epoxy group-containing resin, etc. These two or more are used in combination. The talc, kaolin, cerium oxide, calcium carbonate, barium sulfate 'titanium oxide, zinc oxide, etc. are blended, and the resin having the film forming property described above is formulated in an amount of 0.5 to 70% by mass. When the amount is less than 5% by mass, the quilting effect may be lowered. When the amount exceeds 70% by mass, the formability may be inhibited. The quilting layer is preferably 0.5 to 20 g/m2, that is, sufficient. The application of the quilting material can be carried out in the same manner as the above-mentioned thermoplastic resin layer. The coating of the quilting material is usually diluted with 10 to 1000 parts by mass of the solvent based on 100 parts by mass of the solid content. The dilution by solvent can impart a suitable viscosity to the coating, for example, at 25, which is a viscosity of 10 to 3000 mPa. (7) Method for producing engineered release paper The engineered release paper of the present invention is obtained by hardening a laminate of an ionizing radiation-curable resin layer and a thermosetting polysiloxane layer by ionizing radiation on a paper substrate. In order to form a surface having a surface gloss of 60° or more and a reflection of 60 or more on the surface, it is not limited to the production method. For example, an ionizing radiation hardening composition and a thermosetting polycrystalline oxygen composition are laminated on a mirror copper plate layer of a mirror coated paper having a surface gloss of 75° or more and reflecting at 90° or more, and then the laminate can be subjected to the above laminate. The ionizing radiation is hardened and manufactured (see Fig. 3). The mirror-coated copper layer of the mirror coated paper has a surface gloss of 90 or more at 75°, and if the mirror-coated copper layer is laminated with an ionizing radiation hardening composition and a thermosetting polyoxygen composition - 33-201105501 Winding, depending on the surface gloss of the mirror-finished layer, can produce an engineered release paper having a surface gloss of 60 or more at 60°. Further, a layered ionizing radiation curable composition layer and a thermosetting polyfluorene oxide layer are laminated on a specific paper substrate to obtain a laminate having a surface gloss of 60° on the laminate. The above-mentioned shaped surface can then be subjected to ionizing radiation hardening treatment and manufactured. In this case, when the laminate further laminates the thermoplastic resin layer as the intermediate layer, it is preferred to laminate the thermoplastic resin layer on the paper substrate, and then subject the thermoplastic resin layer to a surface treatment to laminate the ionizing radiation hardenability on the surface treatment layer. The resin composition layer and the thermosetting polyfluorene oxide composition layer were obtained to obtain a laminate. For example, the laminate is a paper substrate (40), a second polyolefin resin layer (30A'), a first polyolefin resin layer (30A"), and a first polymerization as shown in Fig. 2(b). When the surface treatment layer (3 3 ) on the olefin-based resin layer (30 A), the ionizing radiation-curable resin layer (20), and the thermosetting polysiloxane layer (10) are formed, as shown in FIG. The extruder A (70) feeds the resin composition (2) constituting the second polyolefin-based resin layer, and the extruder B (70') feeds the resin (1) constituting the first polyolefin-based resin layer. These co-presses are placed on the paper substrate (40) via a T-die (75) and laminated with a support roll (60) and a chill roll (50). Then, for example, corona treatment or the like is performed on the first polyolefin-based resin layer (30A") to form a surface-treated layer (33). Further, the heating temperature system of the extruder A (70) or the extruder B (70') is used. It suffices to appropriately select according to the melting point or melt flow rate of the resin to be used, the type or amount of the matting agent to be blended, etc. Then, the ionization is applied to the paper substrate or the above-mentioned surface-34-201105501 treated layer. The radiation curable composition is dried and thermally hardened to thermally cure the linear composition film of ionizing radiation. Then, the thermosetting polyphosphonium composition is coated on the thermally hardened linear composition film of ionizing radiation, and dried by heating. The thermosetting polyfluorene oxide film is formed, whereby the pre-processed laminate can be produced. Then, the pre-formed laminate is subjected to a forming treatment of a surface gloss of 6 〇° to 60 or more. Forming a specific high-gloss surface as an engineered release paper. For example, a profiled roll having a profiled surface having a surface gloss of 60° or more reflected to 60 or more and a surface glossiness of 60° for receiving the profiled roll are 60 Above A forming machine provided by a roll or a metal roll, or a forming machine having the forming roll facing the metal roll having a surface gloss of 60° or more and having a surface gloss of 60° or more On the machine, the laminate before the forming process is allowed to flow, and the pressure is applied by the heated forming roller, so that the laminate can form a surface having a surface gloss of 60° or more and 60 or more before the forming process. Further, it is also possible to form a forming surface having a surface gloss of 60° and a reflection of 60 or more by flat pressing without using a forming roll. In the present invention, the ionizing radiation hardening treatment is performed from a thermally hardened polyoxygenated oxygen. The film side is irradiated with ultraviolet rays or electron beams to harden the linear composition film of the thermosetting ionizing radiation to form an ionizing radiation hardening resin layer. The ultraviolet light source can use a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, and tungsten. For the irradiation of the electron beam, a scanning method, a curtain beam method, a large spot method, or the like can be used, and an acceleration voltage of the electron beam is preferably 50 to 300 kV. Further, the engineering release paper of the present invention is suitable. The thickness before the shaping is preferably -35-201105501 30~500μΓη' is preferably 100~300μηι. If the thickness is less than 30μηη, the productivity will be lowered, and the productivity will become easy to break during the winding of the manufacturing step. When it exceeds 500 rpm, the process paper roll may become large, and workability may fall. (8) The manufacturing method of synthetic leather can use the engineering peeling paper of synthetic leather of this invention, and manufacture of synthetic leather like the peeling paper. First, the resin composition for the leather is coated on the thermosetting polysilicon layer of the engineering release paper. The tree coated on the thermosetting polysiloxane layer is formed on the surface gloss of the forming surface of the above engineering release paper. Degree; a glossy surface having an injection of 60 or more is formed, so the high-gloss resin composition corresponding thereto is used. Thereafter, the base fabric (e.g., woven fabric, etc.) is further bonded, and the resin layer is dried. After cooling, the release paper is peeled off, and the leather is synthetically synthesized. The resin composition for synthetic leather described above may be a resin such as urethane or polyvinyl chloride. When the polyamino group is used, the solid content of the resin composition is preferably 20 to 50% by mass. Further, in the case of ethylene chloride, a coating method of a resin composition which is mixed and dispersed with dioctyl phthalate, dilauroyl phthalate plastic, a foaming agent, a stabilizer, or the like is preferably used, for example, a doctor blade coating method. A conventionally known coating method such as cloth, roll coating, or cloth. In the production of the synthetic leather of the paper-off paper of the present invention, when the chlorinated leather is produced at a high temperature, the paper substrate and the thermoplastic resin layer can be prevented from being excellent in heat resistance and high in mechanical strength. Ionizing radiation hardening tree, suitable for the wide range of synthetic synthetic sebum layer, the main 60. Reverse transfer to and non-woven can be achieved by using polyacrylates. The tree is gravure coated and stripped of the vinyl-based peeling grease layer -36- 201105501 The presence and exfoliation of the thermosetting polysulfonate layer can be stabilized and produced. (9) Manufacture of a melamine cosmetic board A melamine cosmetic board was produced in the same manner as a conventional shaped sheet using the engineering release paper for a melamine cosmetic board of the present invention. First, as shown in FIG. 5, four sheets of paper core paper (3 20 ) impregnated with melamine resin are superposed on the support paper (310), and the cosmetic paper impregnated with melamine resin is sequentially superposed thereon (3 3 0 ) , coated with melamine resin coated paper (3 40 ). The engineering release paper (100) of the present invention is superposed on the outer cover paper (340) to contact the thermosetting polyxanthene surface (10) having a surface having a surface gloss of 60° or more to 60 or more. The outer cover paper (340). Then, it is placed between two mirror-finished metal plates (400A, 400B), and is heated and pressurized by pressing, temperature normal temperature ~180 °C, pressure 70~120kg/cm2, heating time 10 minutes~2 hours. Modulate the laminate. Further, the heating and pressurizing conditions may be performed plural times in different temperatures and pressures. Even if it is a stamping process, the melamine resin on the surface of the laminate is exuded from the outer cover paper (3 40 ) and the cosmetic paper impregnated with melamine resin (3 3 0 ), and then hardened to form a melamine resin layer. . On the surface of the melamine resin layer, an engineered release paper (100) is used to form a molding surface having a gloss of 60 or more on the surface gloss of 60°. After the press working, after cooling to room temperature, it is taken out from the press, and if the release paper (100) is peeled off, a melamine cosmetic board (300) having the above-mentioned gloss forming surface can be obtained. -37- 201105501, the melamine cosmetic board (100) is laminated with 2 to 20 sections of the above-mentioned laminate, and can also be manufactured by multi-stage stamping. For example, as shown in Fig. 6, a material which is resistant to the above-mentioned laminate is overlapped in two stages for pressing. In the present invention, such a plurality of sections of stamping can also be suitably used. Further, as for the method for producing a melamine cosmetic board, there is a low pressure melamine cosmetic board which can be used at a low pressure of 10 to 40 Kg/cm2 by using a plywood or a hard board instead of the above paper core paper, and such a low pressure melamine cosmetic board can also be suitably used. Since the engineered release paper of the present invention is excellent in heat resistance, solvent resistance, and releasability, peeling between the paper base material and the thermoplastic resin layer can be prevented even at a high temperature in the production conditions of the melamine cosmetic board. The presence of an ionizing radiation hardening resin layer having a high mechanical strength and the presence of a heat-hardenable polysiloxane layer excellent in releasability can be stably produced. [Embodiment] Embodiments Next, the present invention will be described in more detail with reference to specific examples. (Synthesis Example 1) In a glass flask equipped with a stirrer, a dropping funnel, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, a methyl methacrylate 3 〇g and a glycidyl methacrylate 70 g as a monomer were placed. After heating to 80 ° C with 9 〇g of methyl ethyl ketone as a solvent, a solution of 2,2'-azobis(2,4-dimethylvaleronitrile) 1.08 as a polymerization initiator was dissolved in methyl ethyl ketone 128 In the flower, 3 - 38 - 201105501 hours, the polymerization was carried out at 80 ° C for 3 hours to obtain a methyl ethyl ketone solution (solid content 50.1 %) of the copolymer A 1 having an epoxy group. Then, while directly maintaining the temperature of 80 ° C, 0.05 g of hydroquinone monomethyl ether, 35 g of triphenylphosphine, 25 g of acrylic acid, and 25 g of methyl ethyl ketone were added while blowing dry air, and the reaction was carried out for 35 hours to obtain a methyl group. A methyl ethyl ketone solution of an acrylic copolymer based on an acrylonitrile group (solid content: 50.6%, Mn = 11,000, Mw = 21,000). The copolymer had a glass transition temperature of 62 ° C and a double bond amount of 3.6. The results are shown in Table 1 below. (Synthesis Examples 2 to 13) Polymerization and reaction were carried out in the same manner as in Synthesis Example 1 except that the materials shown in Tables 1 and 2 below were changed to obtain an acrylic copolymer containing (meth)acrylonitrile group. A solution of methyl ethyl ketone (solids 50.8%). The weight average molecular weight, the number average molecular weight, the glass transition temperature, and the double bond amount of the copolymer are shown in Tables 1 and 2. Further, in the synthesis example only, the amount of 2,2'-azobis(2,4-dimethylvaleronitrile) used was changed to 2.6 g, and the weight average molecular weight was changed. Also, the abbreviation in the table is as follows. IBX: isobornyl methacrylate, MMA: methyl methacrylate, BMA: butyl methacrylate, IBMA: isobutyl methacrylate, GMA: glycidyl methacrylate, AA: acrylic acid, -39- 201105501 Μη : number average molecular weight, Mw : weight average molecular weight, (measurement conditions) The measurement conditions are as follows. (1) The weight average molecular weight (Mw) of the (meth)acrylonitrile-containing acrylic copolymer was measured under the following conditions. (i) Column: "TSK-GEL MULTIPORE HXL-Mx4" (manufactured by Tosoh Corporation) (ii) Column temperature: 40 ° C (iii) Dissolution: tetrahydrofuran (THF)

(W)檢測器：RI (v) 檢測器溫度：4(TC、 (vi) 標準溫度：聚苯乙烯 (2 )雙鍵當量：從組成比算出。 (3 ) Tg係依據下述式而算出樹脂之設計Tg (玻璃轉移溫 度）。又，以Tg|、Tg2、…所示之單一聚合物的玻璃轉移 溫度係採用聚合物手冊記載的値。 [數1] 1 / T g = ( w 1 / T g 1 + W 2 / T g 2 + W 3 / T g 3 + …+ W n / T g η + ) (式中’ 1、2…n係表示構成之單體種類，Tgn: n單體單 -40 - 201105501 —聚合物之玻璃轉移溫度（Κ ) 、wn :構成中之n單體單 元的重量比、Tg :玻璃轉移溫度（κ )。） (合成例1 4 ) 添加由含有烯基之有機聚矽氧烷與有機氫聚矽氧烷之 混合物所構成的加成聚合型聚矽氧材料之主劑（信越化學 工業股份公司製、KS-B 603 ) 1 〇〇質量份與由鈾系硬化觸 媒所構成之硬化劑（信越化學工業股份公司製、CAT-PL-50T) 0.1質量份、作爲稀釋溶劑之甲苯以使固形分濃度成 爲1 0質量％ ’而調製熱硬化性聚矽氧組成物。 (實驗例1 ) 對於合成例1之含有（甲基）丙烯醯基之丙烯酸系共聚 物100質量份添加光聚合起始劑（Ciba Specialty Chemicals公司製，Irgacu re 184) 3質量份、作爲稀釋劑 之甲乙酮，以使固形分濃度成爲30質量％，製作電離輻射 線硬化性組成物。 於成爲基材之紙上係鏡面銅版紙（鏡面銅版層 10〜40μιη、754反射之光澤度爲90以上）的鏡面銅版層之上 ，以凹版塗佈器塗佈上述電離輻射線硬化性組成物4g/m2 ，繼而，塗佈於合成例1 4所調製之熱硬化聚矽氧電離輻射 線硬化性組成物，以使乾燥時之塗佈量成爲〇. 1 g/m2，以 1 2(TC加熱1小時，蒸發乾燥、熱硬化而形成熱硬化聚矽氧 膜。 -41 - 201105501 繼而’使用輸出120W/cm之高壓水銀燈，進行600 mj/cm2之紫外線照射，使前述電離輻射線硬化性組成物膜 硬化’得到工程剝離紙。此工程剝離紙之重覆剝離性表示 於表5中。此工程剝離紙之賦型面的表面光澤度係於60°反 射爲60以上。 又，重覆剝離性係調製表3所示之組成的酯系聚胺基 甲酸酯樹脂組成物，於實驗例得到之剝離紙以刮刀塗佈器 塗佈成乾燥厚度20μπι，以16(TC熱風乾燥1分鐘而形成聚 胺基甲酸酯表皮層，於聚胺基甲酸酯表皮層上使作爲接著 劑之表4所示的二液硬化型聚酯系聚胺基甲酸酯接著劑以 刮刀塗佈器塗佈，以使乾燥厚度成爲4 0μπι，再貼合基布 ，使此貼合物以l2〇°C熱風乾燥5分鐘，進一步，在40°C下 熟成24小時而使接著劑反應固化後，使剝離紙與聚胺基甲 酸酯表皮層之剝離強度（15mm寬）以剝離速度3 00mm/分 、剝離角度90°測定之方法進行評估。 (實驗例 2〜10 ) 除使用合成例2〜9、及合成例13之含有（甲基）丙烯醯 基之丙烯酸系共聚物取代合成例1之含有（甲基）丙烯醯基 之丙烯酸系共聚物以外，其餘係與實驗例丨同樣操作而 製作工程剝離紙，與實驗例1同樣做法而測定對於反覆使 用之剝離性。結果表示於下述表5中。 (比較例1 ) -42 - 201105501 除使用使含有聚矽氧之醇酸樹脂三聚氰胺硬化者取代 合成例1之含有（甲基）丙烯醯基之丙烯酸系共聚物以外， 其餘係與實驗例1同樣操作而製作工程剝離紙，與實驗例1 同樣做法而測定對於反覆使用之剝離性。結果表示於表5 中〇 (實驗例1 1 ) 於實驗例1得到之工程剝離紙的賦型面，就靜電處理 而言進行電暈處理（7kw )。然後，從所得到之工程剝離 紙製作3個試驗片，對3檢體評估剝離強度，有關其中之一 檢體測定對於進一步反覆使用之剝離性。使3檢體之剝離 強度表示於下述表6中。又，剝離強度係調製下述表3所示 之組成的酯系聚胺基甲酸酯樹脂組成物，於實驗例1 1得到 之工程剝離紙以刮刀塗佈器塗佈成乾燥厚度20 μηι，以1 20 °C熱風乾燥1分鐘而形成聚胺基甲酸酯表皮層，於聚胺基 甲酸酯表皮層上使作爲接著劑層之表4所示的二液硬化型 聚酯系聚胺基甲酸酯接著劑以刮刀塗佈器塗佈，以使乾燥 厚度成爲40μηι，再貼合基布，使此貼合物以120°C熱風乾 燥5分鐘，進一步，在40°C下熟成24小時而使接著劑反應 固化後，使剝離紙與聚胺基甲酸酯表皮層之剝離強度（ 15mm寬）以剝離速度3 00mm/分、剝離角度90°測定之方法 進行評估。 (比較例2 ) -43- 201105501 於比較例1得到之工程剝離紙的賦型面，I 同樣做法進行電暈處理，從所得到之工程剝離 體，與實驗例1 1同樣做法評估剝離強度。使結: 述表6中。 I實驗例1 1 紙製作2檢 艮表示於下 -44- 201105501 f--li】 合成例7 1 〇 1 ΙΟ 39000 18000 1 2.2 oo CO 合成例6 〇 1 S ΙΑ CM 36000 16000 | 2.3 00 〇0 CO 丨合成例5 1 δ 1 路 3ΘΟΟΟ 16000 cn CQ 00 c4 合成例4 1 窝 〇 S Μ 33000 15000 2.2 c〇 合成例3 1 δ 1 ΙΛ CM 29000 13000 eg ci s 2.8 合成例2 1 1 |22.5 1 23000 120⑽ σ» CD 丨合成例1 1 1 1 21000 11000 1.9 I 丨3-6 讀 IBUA I % 1 Mw/Mn 1 Tg(TC) 雙鍵當量(meq/e). 樹脂組成 分子量 -45- 201105501 【s cn i <n U3 1〇 1 [ 1 17.5 1 42000 1 18000 2.3 122 ! 2.0 丨合成例12 1 1 另 40000 18000 CNJ N ιΛ CO CO s <ίπ 1 S 1 12.5 38000 16000 寸 Ud 卜 U5 合成例10 S 1 1 〇 LO 62000 23000 |2.7 r- 〇· 丨合成例9 〇 1 1 1 S 27000 13000 2.1 Wl to 3.6 合成例8 〇 ? 1 1 S 18000 9000 2.0 2.8 1 ΙΒΧ 1 蠢 1 ΙΒΜ& S 5 Μ lUv/Mn TgCC) | 雙鍵當量(raeq/g) 樹脂組成 分子量 -46- 201105501 [表3] 酯系聚胺基甲酸酯樹脂組成物 酯系聚胺基甲酸_ (大□本油墨化學工業(株)社製、CRISVON NB-637N) 100質量份 顔料 (大日本油墨化學工業(株)社製、DAILAC TV-COLOR) 15質量份 甲乙酮 . 20筧量份 二甲基甲醯胺.. 10 質Ϊ# [表4] 聚酯系聚胺基甲酸酯接著劑 主劑:二液硬化型酯系聚胺基甲酸酯樹月旨 (大日本油墨化學工業(株)社製、CRISVON4070) 100質量份 #匕劑:二液硬化型胺基甲酸酯樹脂用硬化劑 (大日本油墨化學工業(株)社製、CRISVONNX) 15質量份 促進劑:二液硬化型胺基甲酸酯樹脂用硬化促進劑 (大日本油墨化學工業(株)社製、CRISVON ACCEL HM) 20質量份 溶劑:甲乙酮 10質量份 [表5] 反覆剝離性 反覆使用所產生之剝離性f 1 化(gf/15mm 寬） 第1次 第2次 第3次 第依 第5次 實驗例1 合成例1 3 7 3 3 34 3 1 2 7 實驗例2 合成例2 44 54 4 9 3 5 4 6 實驗例3 合成例3 40 4 3 4 3 2 7 3 6 實驗例4 合成例4 2 9 2 8 38 3 3 2 9 實驗例5 合成例5 2 9 3 8 33 3 5 3 4 實驗例6 合成例6 5 3 2 9 4 1 30 3 0 實驗例7 合成例7 3 3 3 0 3 2 32 3 4 實驗例8 合成例8 3 1 3 S 39 3 5 3 7 實驗例9 合成例9 30 3 3 3 3 3 7 3 3 實驗例10 合成例13 3 1 3 1 2 6 24 2 4 實驗例11 5 6 6 7 7 8 8 1 10 0 [表6] 剝離性 1楡體 2檢i豎 3檢匿 比較例2 256 破裂 — 3 3 5 3 4 7 -47 - 201105501 (實驗例 1 2 ) 使用實驗例1得到之工程剝離紙，如圖5所示般’於支 撐紙（310 )(中性紙：坪量130g/m2)之上’重疊4片含浸 有三聚氰胺樹脂的紙芯用紙（3 20 )，於其上依序重疊含 浸三聚氰胺樹脂之化妝紙（3 3 0 )、含浸三聚氰胺樹脂之 外覆層紙（340 )，然後於其上重疊上述工程剝離紙（1 〇〇 )以使具有表面光澤度於60°反射爲60以上之賦型面的熱 硬化聚矽氧面（10)接觸於外覆層紙（340)。再挾於2片 之鏡面加工金屬板（400A、400B )之間，以l〇〇kg/cm2之 壓力從常溫花5分鐘昇溫至1 5 0 °C，以1 5 0 °C花7分鐘’從 150 °C花7分鐘降溫至常溫150 °C。藉由沖壓加工’從外覆 層紙（340 )及含浸三聚氰胺樹脂之化妝紙（3 30)滲出之 三聚氰胺樹脂會硬化而形成三聚氰胺樹脂層’於此三聚氰 胺樹脂層形成以工程剝離紙（100 )所得到之表面光澤度 於60°反射爲60以上之高光澤表面。 (結果） 合成例12之含有（甲基）丙烯醯基之丙烯酸系共聚物係 Tg爲3 5 °C，產生溫度之軟化’無法製造工程剝離紙。 如實驗例7、8所示般’合成例7與合成例8之含有（甲 基）丙烯醯基之丙烯酸系共聚物係組成、Tg、雙鍵當量相 同，但重量平均分子量及數目平均分子量相異者。即使使 重量平均分子量從39000降低至18000時’如實驗例7、實 驗例8所示般，可同時有效地使用來作爲工程剝離紙。 -48- 201105501 從上述表5之結果，實驗例1〜1 0之剝離紙即使以反覆 使用之剝離試驗進行5次，任一者剝離強度均爲54gf/l 5mm 寬以下且安定，可有效地使用來作爲剝離紙。尤其，如實 驗例10所示般，即使Tg爲122 °C之特定的含有（甲基）丙烯 醯基之丙烯酸系共聚物，即使以反覆使用之剝離試驗進行 5次，可有效地使用來作爲剝離紙。另外，比較例1係就重 覆剝離性剝離強度會上昇》 從上述表6之結果，若比較比較例2所示之習知品與實 驗例1 1之工程剝離紙，在比較例2中係1檢體爲2 6 5 g f/1 5 mm 寬，第2檢體爲所謂破裂之結果，但在實驗例1 1中3檢體分 別爲 33gf/15mm寬、53 gf/15mm 寬、47 gf/15mm寬。比較 例2與實驗例1 1係爲觀察靜電氣之影響，於工程剝離紙之 賦型面進行電暈處理者，但在比較例2中藉電暈處理而剝 離強度增加亦即剝離性降低，藉此而工程剝離紙會破裂， 但在實驗例1 1中所示之本案發明的工程剝離紙係即使進行 電暈處理，剝離強度亦無變化。此事係顯示本發明之工程 剝離紙即使有靜電，亦可維持高的剝離性。而且，如表5 所示般，可知能重覆剝離。 如實驗例1 2所示般，本發明之工程剝離紙係於三聚氰 胺化妝板之製造等負荷高溫高壓條件之製造步驟，亦可對 三聚氰胺化妝板之表面充分地形成壓紋。 【圖式簡單說明】 圖1係說明層合紙基材、電離輻射線硬化樹脂層、與 -49- 201105501 熱硬化聚矽氧層之本發明的工程剝離紙之層合構成圖。 圖2 (a)係說明於紙基材與電離輻射線硬化樹脂層之間 進一步形成塡縫層的工程剝離紙之層合構成圖，圖2 ( b ) 係塡縫層爲熱塑性樹脂層，且具有第一聚烯烴系樹脂層（ 30’）與第二聚烯烴系樹脂層（30”）與表面處理層（33)之 本發明的工程剝離紙之層合構成圖。 圖3係表示本發明之工程剝離紙的製造步驟圖。 圖4係表示製造於本發明所使用之賦型前層合物的步 驟之一部分圖。 圖5係說明三聚氰胺化妝板之製造步驟的圖。 圖6係以多段沖壓說明三聚氰胺化妝板之製造步驟的 圖。 【主要元件符號說明】 1 :聚丙烯系樹脂 2 :聚丙烯系樹脂與聚乙烯系樹脂之組成物樹脂 10:熱硬化聚矽氧層 20 :電離輻射線硬化樹脂層 30 :塡縫層 3 0A’ ：第一聚烯烴系樹脂層 30A” ：第二聚烯烴系樹脂層 33 :表面處理層 40 :紙基材 100 :工程剝離紙 -50- 201105501 3 00 ··三聚氰胺化妝板 400A、400B :鏡面加工金屬板 -51(W) Detector: RI (v) Detector temperature: 4 (TC, (vi) Standard temperature: polystyrene (2) double bond equivalent: calculated from the composition ratio. (3) Tg is calculated according to the following formula Resin design Tg (glass transition temperature). Further, the glass transition temperature of a single polymer represented by Tg|, Tg2, ... is based on the enthalpy described in the polymer manual. [1] 1 / T g = ( w 1 / T g 1 + W 2 / T g 2 + W 3 / T g 3 + ... + W n / T g η + ) (wherein, 1, 2...n represent the monomer species of the composition, Tgn: n single体单-40 - 201105501 - Glass transition temperature of polymer (Κ), wn: weight ratio of n monomer units in the composition, Tg: glass transition temperature (κ). (Synthesis Example 1 4 ) Addition of alkene A main component of an addition polymerization type polyoxonium material composed of a mixture of an organic polyoxane and an organic hydrogen polyoxyalkylene (manufactured by Shin-Etsu Chemical Co., Ltd., KS-B 603) 0.1 parts by mass of a hardening agent composed of a uranium-based hardening catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T), and toluene as a diluent solvent to make the solid content concentration 10% by mass Further, a thermosetting polyfluorene composition was prepared. (Experimental Example 1) A photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to 100 parts by mass of the (meth)acrylonyl group-containing acrylic copolymer of Synthesis Example 1. Irgacu re 184) 3 parts by mass of methyl ethyl ketone as a diluent to prepare an ionizing radiation curable composition so that the solid content concentration is 30% by mass. On the paper to be a substrate, mirror-coated coated paper (mirror copper plate layer 10 to 40 μm) And the above-mentioned ionizing radiation curable composition 4 g/m2 was applied onto the mirror-coated copper plate layer having a gloss of 754 and a gloss of 90 or more, and then coated with the heat hardening prepared by the synthesis example 14. The polyfluorene ionizing radiation hardening composition was set so that the coating amount at the time of drying became 1. 1 g/m2, and the thermosetting polyfluorene oxide film was formed by heating at 12 °C for 1 hour, evaporative drying, and heat curing. -41 - 201105501 Then, using a high-pressure mercury lamp outputting 120 W/cm, ultraviolet irradiation of 600 mj/cm2 was performed to harden the ionizing radiation curable composition film to obtain an engineering release paper. The exfoliation is shown in Table 5. The surface gloss of the surface of the engineered release paper was 60 or more at 60°. Further, the removability was an ester-based polyamine group having the composition shown in Table 3. The ester resin composition, the release paper obtained in the experimental example was applied as a dry thickness of 20 μm by a knife coater, and dried at 16 (TC hot air for 1 minute to form a polyurethane skin layer on the polyaminocarboxylic acid. On the ester skin layer, the two-liquid-curing polyester-based polyurethane adhesive agent shown in Table 4 as an adhesive was applied by a knife coater so that the dry thickness became 40 μm and the base fabric was attached. The laminate was dried by hot air at 1 ° C for 5 minutes, and further, after being cured at 40 ° C for 24 hours to cure the adhesive, the peel strength of the release paper and the polyurethane skin layer was adjusted ( 15 mm width) was evaluated by a method of measuring a peeling speed of 300 mm/min and a peeling angle of 90°. (Experimental Examples 2 to 10) The acrylic copolymer containing (meth)acryl fluorenyl group of Synthesis Example 1 was replaced by the acrylic copolymer containing the (meth)acryl fluorenyl group of Synthesis Examples 2 to 9 and Synthesis Example 13. In the same manner as in the experimental example, except for the above, an engineering release paper was produced, and the peeling property for repeated use was measured in the same manner as in Experimental Example 1. The results are shown in Table 5 below. (Comparative Example 1) -42 - 201105501 The same procedure as in Experimental Example 1 was carried out except that the methacrylic acid-containing melamine-containing acrylonitrile-containing acrylic copolymer was replaced with the methacrylic acid-containing methacrylate-containing acrylic copolymer. The engineered release paper was produced by the operation, and the peeling property for repeated use was measured in the same manner as in Experimental Example 1. The results are shown in Table 5 (Experimental Example 1 1). The molding surface of the engineering release paper obtained in Experimental Example 1 was subjected to corona treatment (7 kw) for electrostatic treatment. Then, three test pieces were prepared from the obtained engineering release paper, and the peel strength was evaluated for the three samples, and one of the samples was measured for removability for further repeated use. The peel strength of the three samples was shown in Table 6 below. Further, the peel strength was prepared by preparing an ester-based polyurethane resin composition having the composition shown in Table 3 below, and the engineering release paper obtained in Experimental Example 1 was applied by a knife coater to a dry thickness of 20 μm. It was dried by hot air at 1 20 ° C for 1 minute to form a polyurethane skin layer, and the two-liquid-curing polyester-based polyamine shown in Table 4 as an adhesive layer was formed on the polyurethane skin layer. The urethane adhesive was applied by a knife coater so that the dry thickness became 40 μm, and the base fabric was attached, and the laminate was dried by hot air at 120 ° C for 5 minutes, and further, cooked at 40 ° C. After the adhesive reaction was cured in an hour, the peel strength (15 mm width) of the release paper and the polyurethane skin layer was evaluated by a peeling speed of 300 mm/min and a peeling angle of 90°. (Comparative Example 2) -43-201105501 The forming surface of the engineering release paper obtained in Comparative Example 1 was subjected to corona treatment in the same manner, and the peel strength was evaluated in the same manner as in Experimental Example 1 from the obtained engineering release body. Make a knot: described in Table 6. I Experimental Example 1 1 Paper production 2 inspection is shown in the following -44-201105501 f--li Synthesis Example 7 1 〇1 ΙΟ 39000 18000 1 2.2 oo CO Synthesis Example 6 〇1 S ΙΑ CM 36000 16000 | 2.3 00 〇0 CO 丨 Synthesis Example 5 1 δ 1 way 3 ΘΟΟΟ 16000 cn CQ 00 c4 Synthesis Example 4 1 Nest 〇 S Μ 33000 15000 2.2 c〇 Synthesis Example 3 1 δ 1 ΙΛ CM 29000 13000 eg ci s 2.8 Synthesis Example 2 1 1 | 22.5 1 23000 120(10) σ» CD 丨 Synthesis Example 1 1 1 1 21000 11000 1.9 I 丨3-6 Read IBUA I % 1 Mw/Mn 1 Tg(TC) Double bond equivalent (meq/e). Resin composition molecular weight -45- 201105501 s cn i <n U3 1〇1 [ 1 17.5 1 42000 1 18000 2.3 122 ! 2.0 丨Synthesis Example 12 1 1 Another 40000 18000 CNJ N ιΛ CO CO s <ίπ 1 S 1 12.5 38000 16000 inch Ud Bu U5 Synthesis Example 10 S 1 1 〇LO 62000 23000 |2.7 r- 〇·丨 Synthesis Example 9 〇1 1 1 S 27000 13000 2.1 Wl to 3.6 Synthesis Example 8 〇? 1 1 S 18000 9000 2.0 2.8 1 ΙΒΧ 1 Stupid 1 ΙΒΜ& S 5 Μ lUv/Mn TgCC) | Double bond equivalent (raeq/g) Resin composition molecular weight -46- 201105501 [Table 3] Ester-based polyurethane Fat composition ester-based polyaminocarboxylic acid _ (CRISVON NB-637N, manufactured by Otsuka Ink Chemical Industry Co., Ltd.) 100 parts by mass of pigment (DAILAC TV-COLOR, manufactured by Dainippon Ink and Chemicals Co., Ltd.) 15 Part by mass of methyl ethyl ketone. 20 parts by weight of dimethylformamide. 10 Ϊ# [Table 4] Polyester polyurethane adhesive base agent: two-liquid hardening ester polyurethane月 旨 ( 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 : : : : : : : : : : : : : : : : : : : : : : : : : : : : C C C C C 15 parts by mass of accelerator: a hardening accelerator for a two-liquid-hardening urethane resin (CRISVON ACCEL HM, manufactured by Dainippon Ink and Chemicals Co., Ltd.) 20 parts by mass of solvent: methyl ethyl ketone 10 parts by mass [Table 5] The peeling property f 1 (gf/15 mm width) generated by the repeated peeling repetitive use The first, second, third, fifth, fifth experimental example 1 Synthesis Example 1 3 7 3 3 34 3 1 2 7 Experimental Example 2 Synthesis Example 2 44 54 4 9 3 5 4 6 Experimental Example 3 Synthesis Example 3 40 4 3 4 3 2 7 3 6 Experimental Example 4 Synthesis Example 4 2 9 2 8 38 3 3 2 9 Experimental Example 5 Synthesis Example 5 2 9 3 8 33 3 5 3 4 Experimental Example 6 Synthesis Example 6 5 3 2 9 4 1 30 3 0 Experimental Example 7 Synthesis Example 7 3 3 3 0 3 2 32 3 4 Experimental Example 8 Synthesis Example 8 3 1 3 S 39 3 5 3 7 Experimental Example 9 Synthesis Example 9 30 3 3 3 3 3 7 3 3 Experimental Example 10 Synthesis Example 13 3 1 3 1 2 6 24 2 4 Experimental Example 11 5 6 6 7 7 8 8 1 10 0 [Table 6] Peelability 1 楡 2 detection i vertical 3 inspection Comparative Example 2 256 rupture — 3 3 5 3 4 7 -47 - 201105501 (Experimental Example 1 2 ) The engineering release paper obtained in Experimental Example 1, such as As shown in Fig. 5, 'over the support paper (310) (neutral paper: 130 g/m2), four sheets of paper core paper (3 20 ) impregnated with melamine resin were superimposed thereon, and the impregnated melamine was sequentially superposed thereon. a cosmetic paper (3 3 0 ) of resin, a coated paper (340) impregnated with melamine resin, and then the above-mentioned engineering release paper (1 〇〇) is superposed thereon so that the surface glossiness is reflected at 60° to 60 or more. The thermosetting polyxanium surface (10) of the shaped surface is in contact with the outer cover paper (340). Between the two mirror-finished metal plates (400A, 400B), the temperature is raised from normal temperature for 5 minutes to 150 °C at a pressure of l〇〇kg/cm2, and spent 7 minutes at 150 °C. Cool down from 150 °C for 7 minutes to 150 °C. The melamine resin oozing out from the outer cover paper (340) and the cosmetic paper (3 30) impregnated with melamine resin is hardened by press working to form a melamine resin layer. The melamine resin layer is formed on the detached paper (100). The resulting surface gloss is reflected at 60° to a high gloss surface of 60 or more. (Result) The (meth)acrylonitrile-containing acrylic copolymer of Synthesis Example 12 had a Tg of 35 ° C and was softened by temperature. As shown in Experimental Examples 7 and 8, the acrylic copolymer containing the (meth)acrylonitrile group of Synthesis Example 7 and Synthesis Example 8 has the same Tg and double bond equivalent weight, but the weight average molecular weight and the number average molecular weight phase. Different. Even when the weight average molecular weight was lowered from 39000 to 18,000', as shown in Experimental Example 7 and Experimental Example 8, it can be effectively used at the same time as an engineering release paper. -48-201105501 From the results of Table 5 above, the release papers of Experimental Examples 1 to 10 were subjected to peeling test for repeated use five times, and any peeling strength was 54 gf/l 5 mm or less and stable, which was effective. Used as a release paper. In particular, as shown in Experimental Example 10, even if the specific (meth)acrylonitrile-containing acrylic copolymer having a Tg of 122 ° C was used five times in a peeling test for repeated use, it can be effectively used as Strip the paper. Further, in Comparative Example 1, the peeling peel strength was increased. From the results of the above Table 6, when the conventional product shown in Comparative Example 2 and the engineering release paper of Experimental Example 1 were compared, in Comparative Example 2, the test was performed. The body was 2 6 5 gf / 1 5 mm wide, and the second specimen was the result of so-called rupture, but in the experimental example 1 1 the specimens were 33 gf / 15 mm wide, 53 gf / 15 mm wide, 47 gf / 15 mm wide, respectively. . In Comparative Example 2 and Experimental Example 1 1 , the effect of the electrostatic gas was observed, and the surface of the engineered release paper was subjected to corona treatment. However, in Comparative Example 2, the peel strength was increased by the corona treatment, that is, the peeling property was lowered. As a result, the engineered release paper was broken, but the peeling strength of the engineered release paper of the present invention shown in Experimental Example 1 was not changed even if corona treatment was performed. This shows that the engineered release paper of the present invention maintains high peelability even when static electricity is present. Further, as shown in Table 5, it was found that the peeling could be repeated. As shown in Experimental Example 1, the engineered release paper of the present invention can be sufficiently embossed on the surface of a melamine cosmetic board by a manufacturing step of a high temperature and high pressure condition such as production of a melamine cosmetic board. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a laminated structure of a laminated paper substrate, an ionizing radiation curing resin layer, and an engineering release paper of the present invention in a thermosetting polyoxygenated layer of -49-201105501. 2(a) is a view showing a laminated structure of an engineering release paper in which a quilting layer is further formed between a paper substrate and an ionizing radiation-curable resin layer, and FIG. 2(b) is a thermoplastic resin layer, and A laminated structure of the engineered release paper of the present invention having the first polyolefin-based resin layer (30') and the second polyolefin-based resin layer (30") and the surface-treated layer (33). Fig. 3 shows the present invention. Figure 4 is a partial view showing the steps of manufacturing the pre-formed laminate used in the present invention. Figure 5 is a view showing the steps of manufacturing the melamine cosmetic board. Stamping instructions for the manufacturing steps of the melamine cosmetic board. [Explanation of main component symbols] 1: Polypropylene resin 2: Composition of polypropylene resin and polyethylene resin Resin 10: Thermosetting polyfluorinated layer 20: Ionizing radiation Line hardening resin layer 30: quilting layer 30A': first polyolefin-based resin layer 30A": second polyolefin-based resin layer 33: surface treatment layer 40: paper substrate 100: engineering release paper-50 - 201105501 3 00 ··Melamine makeup board 400 A, 400B: Mirror-finished metal plate -51

Claims (1)

201105501 七、申請專利範圍： 1 . 一種工程剝離紙，其特徵在於：依序層合紙基材、 電離輻射線硬化樹脂層、與熱硬化聚矽氧層’且賦型面之 表面光澤度於60°反射爲60以上。 2.如申請專利範圍第1項之工程剝離紙，其中前述電 離輻射線硬化樹脂層係由重量平均分子量（Mw )爲 5,000 〜200,000、分散比（Mw/Mn)爲 1.0~5.0、且玻璃轉 移點溫度（Tg)爲40~150°C之含有（甲基）丙烯醯基的丙 烯酸系共聚物（I )所構成的電離輻射線硬化性組成物藉 由電離輻射線硬化者。 3 .如申請專利範圍第2項之工程剝離紙，其中前述含 有（甲基）丙烯醯基的丙烯酸系共聚物（I)係含有（甲 基）丙烯酸酯系單體單元（A)與含有環氧基的（甲基）丙 烯酸酯系單體單元（B)之含有環氧基的共聚物（C)， 與（甲基）丙烯酸反應而成之共聚物。 4 ·如申請專利範圍第3項之工程剝離紙，其中前述丙 烯酸系共聚物係雙鍵當量爲0.5〜4.5meq/g。 5 .如申請專利範圍第1項之工程剝離紙，其中前述電 離輻射線硬化樹脂層係 由（甲基）丙烯酸酯35〜80質量份、縮水甘油基（甲基 )丙烯酸酯20〜60質量份、其他之（甲基）丙烯酸酯〇〜30質量 份所構成的共聚物，與（甲基）丙烯酸10〜3 0質量份反應而 成之含有（甲基）丙烯醯基的丙烯酸系共聚物（Π)所構 成的電離輻射線硬化性組成物藉由電離輻射線硬化者。 -52- 201105501 6 ·如申請專利範圍第1〜5項中任一項之工程剝離紙， 其中前述電離輻射線硬化樹脂層係以0.5-50質量％之範圍 含有無機顏料者。 7 .如申請專利範圍第1 ~6項中任—項之工程剝離紙， 其中於前述紙基材與電離輻射線硬化樹脂層之間形成中間 層。 8·如申請專利範圍第7項之工程剝離紙，其中前述中 間層係由熱塑性樹脂所構成。 9·如申請專利範圍第1〜8項中任一項之工程剝離紙， 其中前述熱硬化聚矽氧層係由含有烯基之有機聚矽氧烷、 有機氫聚矽氧烷及鉑系硬化觸媒所構成之熱硬化性聚矽氧 組成物進行熱硬化所形成。 1 〇 .如申請專利範圍第1〜9項中任一項之工程剝離紙， 其係可使用於合成皮革之製造。 1 1 ·如申請專利範圍第1〜9項中任一項之工程剝離紙， 其係可使用於三聚氰胺化妝板之製造。 12.~種申請專利範圍第1〜9項中任一項之工程剝離紙 的製造方法，其特徵在於·· 於表面光澤度於60。反射爲60 以上的紙基材上層合熱塑性樹脂，然後，於前述熱塑性樹 脂進行表面處理，形成表面處理層，於前述表面處理層上 層合電離輻射線硬化性組成物及熱硬化性聚矽氧組成物而 得到層合物，對此層合物進行表面光澤度於60。反射爲60 以上之賦型處理，繼而，對前述經賦型處理之層合物進行 電離輻射線硬化處理。 -53- 201105501 13.—種申請專利範圍第1〜9項中任一項之工程剝離紙 的製造方法，其特徵在於：於表面光澤度於75°反射爲90 以上之澆鑄塗佈紙之澆鑄塗佈層上層合電離輻射線硬化性 組成物及熱硬化性聚矽氧組成物，繼而，對前述層合物進 行電離輻射線硬化處理。 -54-201105501 VII. Patent application scope: 1. An engineering release paper characterized in that the paper substrate, the ionizing radiation hardening resin layer and the thermosetting polysilicon layer are sequentially laminated and the surface gloss of the shaped surface is The 60° reflection is 60 or more. 2. The engineering release paper according to claim 1, wherein the ionizing radiation hardening resin layer has a weight average molecular weight (Mw) of 5,000 to 200,000, a dispersion ratio (Mw/Mn) of 1.0 to 5.0, and glass transfer. An ionizing radiation curable composition composed of an acrylic copolymer (I) containing a (meth)acryl fluorenyl group having a temperature (Tg) of 40 to 150 ° C is hardened by ionizing radiation. 3. The engineered release paper according to claim 2, wherein the (meth)acryloyl group-containing acrylic copolymer (I) contains a (meth)acrylate monomer unit (A) and a ring containing The epoxy group-containing copolymer (C) of the (meth)acrylate monomer unit (B) of the oxy group is a copolymer obtained by reacting with (meth)acrylic acid. 4. The engineered release paper according to claim 3, wherein the acrylic acid copolymer has a double bond equivalent of 0.5 to 4.5 meq/g. 5. The engineered release paper according to claim 1, wherein the ionizing radiation-curable resin layer is 35 to 80 parts by mass of (meth) acrylate and 20 to 60 parts by mass of glycidyl (meth) acrylate. And a (meth)acryloyl group-containing acrylic copolymer obtained by reacting another copolymer of (meth)acrylate 〇 30 parts by mass with 10 to 30 parts by mass of (meth)acrylic acid ( The ionizing radiation curable composition composed of Π) is hardened by ionizing radiation. The engineering release paper of any one of Claims 1 to 5, wherein the ionizing radiation-curable resin layer contains an inorganic pigment in a range of 0.5 to 50% by mass. 7. The engineered release paper according to any one of claims 1 to 6, wherein an intermediate layer is formed between the paper substrate and the ionizing radiation hardening resin layer. 8. The engineered release paper of claim 7, wherein the intermediate layer is composed of a thermoplastic resin. 9. The engineered release paper according to any one of claims 1 to 8, wherein the thermosetting polysiloxane layer is an organopolysiloxane containing an alkenyl group, an organohydrogenpolyoxyalkylene, and a platinum-based hardening layer. The thermosetting polyphosphonium composition composed of a catalyst is formed by thermal hardening. 1 . The engineered release paper according to any one of claims 1 to 9, which can be used for the manufacture of synthetic leather. 1 1 . The engineered release paper according to any one of claims 1 to 9, which can be used for the manufacture of a melamine cosmetic board. The method for producing an engineered release paper according to any one of claims 1 to 9, which is characterized in that the surface glossiness is 60. The thermoplastic resin is laminated on a paper substrate having a reflection of 60 or more, and then the surface of the thermoplastic resin is surface-treated to form a surface-treated layer, and the surface-treated layer is laminated with an ionizing radiation curable composition and a thermosetting polyfluorene oxide. A laminate was obtained to give a surface gloss of 60 to the laminate. The reflection is a forming treatment of 60 or more, and then the laminate subjected to the above-described shaping treatment is subjected to ionizing radiation hardening treatment. The method for producing a engineered release paper according to any one of the preceding claims, wherein the casting of coated casting paper having a surface gloss of 75° or more is 90 or more. The ionizing radiation curable composition and the thermosetting polyfluorene oxide composition are laminated on the coating layer, and then the laminate is subjected to ionizing radiation hardening treatment. -54-
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