TWI362425B - Process for preparing a composite material - Google Patents

Process for preparing a composite material Download PDF

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Publication number
TWI362425B
TWI362425B TW93113724A TW93113724A TWI362425B TW I362425 B TWI362425 B TW I362425B TW 93113724 A TW93113724 A TW 93113724A TW 93113724 A TW93113724 A TW 93113724A TW I362425 B TWI362425 B TW I362425B
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TW
Taiwan
Prior art keywords
substrate
layer
deposition step
vapor deposition
temperature
Prior art date
Application number
TW93113724A
Other languages
English (en)
Other versions
TW200502421A (en
Inventor
Shahab Jahromi
Original Assignee
Dsm Ip Assets Bv
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Filing date
Publication date
Application filed by Dsm Ip Assets Bv filed Critical Dsm Ip Assets Bv
Publication of TW200502421A publication Critical patent/TW200502421A/zh
Application granted granted Critical
Publication of TWI362425B publication Critical patent/TWI362425B/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
    • B05D3/044—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
    • B05D3/044—Pretreatment
    • B05D3/0446—Pretreatment of a polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
    • B05D3/0453—After-treatment
    • B05D3/046—Curing or evaporating the solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/062—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/062—Pretreatment
    • B05D3/063—Pretreatment of polymeric substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B05D3/144—Pretreatment of polymeric substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/145—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31605—Next to free metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Wrappers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

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1362425 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於製造複合材料的方法，該複合材料包含 基材和該基材上的層’該方法包含氣相沈積步驟，其中在 壓力低於1000 Pa時’將含三嗪化合物的複合物沈積在該 基材上，藉以形成該層。 【先前技術】 由WO 99/66097可得知此等方法。在WO 99/66097 中，以含三嗪的層主要作爲阻障層，減少例如基材的氧穿 透率（OTR)。WO 99/66097提到各種適合的三嗪化合物， 如三聚氰胺。 此習知方法的缺點係阻障性質不一定夠。 【發明內容】 本發明的目的在於減少上述的缺點。 本發明的目的可以基材溫度在-1 5 與+ I 2 5。(：之間的 氣相沈積步驟達成。 本發明的優點係可製得具改良性質，特別是與阻障有 關的性質，的複合材料。令人驚訝的是選擇較高的基材溫 .度將可導致具改良阻障性質的複合材料，而—般在工業上 基材溫度係-2〇°C或更低。 【實施方式】 •4- (2) 1362425 根據本發明的方法製造的複合材料包含基 係作爲該層的承載體之材料；就是該層施於其 該基材基本上可由均相材料組成，或其本身可 料或複合材料。該基材可包含各種層。該基材 平坦的’或可具有複雜的三維形狀。適當基材 薄膜等彈性包裝材、小刷子 '瓶子或預先成形 硬式包裝材。較佳地，該基材包含聚合材料、 、金屬、金屬化合物、金屬氧化物、陶瓷或其 物的實施例係熱塑性化合物及熱固性化合物。 物的實施例係聚乙烯（PE)、聚丙烯（PP)及聚對 二醋（PET)。此等熱塑性化合物經常以薄膜的 無論就其本來的樣子或經配向的形式；此配向 向的’例如雙軸定向聚丙烯膜（B0PP)。較佳 係本身係包括含鋁、氧化鋁、鋁和氧化鋁，或 相沈積層之複合材料，藉以將根據本發明的層 層或含矽層表面。 根據本發明的複合材料包含該基材上的層 沈積步驟將此層施於基材上。氣相沈積本身係 爲係習知’所以氣相沈積步驟經常在減壓時， 壓力的壓力時’進行。根據本發明的方法中， ]00 0 Pa。在氣相沈積步驟中.，化合物係沈積 藉以恐成該層。該化合物根據本發明包含三嗪 則上可選甩任何三嗪化合物；較佳地，該三嗪 二聚氰胺、蜜白胺、蜜勒胺、蜜弄、以可聚合 :材。該基材 上的物體。 爲非均相材 基本上可爲 的實施例係 的包裝盒等 紙、硬紙板 組合。聚合 熱塑性化合 苯二甲酸乙 形式使用， 可爲雙軸定 地，該基材 氧化矽的氣 施於該含鋁 p藉由氣相 屬習知。因 即低於大氣 壓力爲低於 在基材上， 化合物。原 化合物包含 基團官能化 (3) (3)1362425 的三聚氰胺、三聚氰胺鹽類或其混合物。更佳地，該三嗪 化合物包含三聚氰胺；最佳地，該三嗪化合物基本上由三 聚氰胺所組成。 氣相沈積步驟在基材上生成的層厚度取決於其預期用 途，因此可以在寬廣的範圍內變化。較佳地，層厚度小於 100微米，更佳地小於10微米，又更佳地小於1微米； 最小厚度最好至少2 nm，更佳地至少10 nm。 在氣相沈積步驟期間，基材的溫度在-1 5 °C與+ 1 25 °C 之間。本文中將基材的溫度定義爲未經氣相沈積的基材部 分之溫度。例如，若對控溫塗布滾筒上導引的薄膜進行氣 相沈積步驟，基材的溫度就是塗布滾筒所控制的溫度，就 是與塗布滾筒直接接觸的膜表面部分的溫度。在此情況之 下’並有鑑於欲沈積的化合物經常都有遠高於125 °C的溫 度，如習知一般都會發生基材被沈積的那一側的溫度高於 未經沈積那一側的溫度。 與基材溫度係-20 °C或更低的氣相沈積步驟相比，發 現當基材溫度上升到-1 5 °C及以上時，複合材料的阻障性 質可獲得改善。另一方面，爲了維持可以接受的沈積速度 和確保基材保持完整無缺，即不變形、熔融或劣解，通常 基材的溫度需要維持在+] 25 °C以下，或視該基材之特定性 質之要求儘可能遠低於+] 2 5 °C，同時維持在-1 5。(：以上。 較佳地’在氣相沈積步驟期間，基材的溫度爲-5 °C、〇 t： 或 +5°C或以上；更佳地’該溫度爲+]〇t、+]5t或+20 °C或以上。經發現當基材的溫度遠高於_ I 5。(：時，可發現 -6- (4) (4)1362425 阻障性質提高得又更快。如上所示，基於基材安定性及/ 或速度的經濟價値的理由，可能有用或必須確使氣相沈積 步驟期間的基材溫度維持在+125 °C以下，較佳地在+90 °C 以下，更佳地在+60°C或+50°C以下，特別是在+40°C以下 ，且最佳地在+30°C或以下。 可確使基材具有定義溫度的方法係習知者。有一種此 類可確使基材具有定義溫度的方法可應用於以下的實施例 中：基材有至少一區域、平面或側邊未經氣相沈積任何層 ;然後使該區域.、平面或側邊與冷卻表面或加熱表面接觸 ，使溫度達到所需的水準並保持在該水準。至於實施例， 已知有時候該基材係薄膜且以氣相沈積步驟充當連續方法 中的半連續部分進行，藉以使該層沈積在膜之一側上，該 薄膜可透過控溫滾筒導引，也就是習知的塗布滾筒，以此 方式使膜之另一側-不準備沈積任何層·在氣相沈積步驟之 前及/或期間及/或之後與該控溫滾筒接觸。 根據本發明的氣相沈積步驟在]〇〇〇 Pa或更低的壓力 下進行。如習知氣相沈積步驟可在次大氣壓的壓力下進行 ’例如在該1000 Pa或在〗〇〇 Pa或10 Pa或更低等的壓力 時。在WO 99/66097的實施例中，甚至將壓力降到5x10·3. P a和1 X ] 0·2 Pa之間。令人驚訝地發現複合材料的性質， 例如阻障性質，可再進一步降低氣相沈積步驟進行時的壓 力而獲得又更進一步的改善，較佳降至4χ】(Γ3 pa或以下 。更佳地，氣相沈積步驟可在2X1(T3 Pa或以下.，或〗X I 0·3 Pa或以下的壓力時進行；特別是氣相沈積步驟可在 (5) (5)1362425 5X1(T4 Pa或以下，或lx〗(Γ4 Pa或以下的壓力時進行；更 具體而言，氣相沈積步驟可在5x1 O·5 Pa或以下，或1χ 1〇_5 Pa或以下的壓力時進行；最佳地，氣相沈積步驟可 在5xl〇·6 Pa或甚至lx〗〇·6 pa或以下的壓力時進行。目前 ，咸認爲壓力低於lxl(T1()Pa將導致無法如所示般更進〜 步提高其助益。 在根據本發明的方法之替代具體例中，氣相沈積步驟 的壓力降至4x1 0·3 Pa或更低時對於最後得到的複合材料 的·例如：阻障性質-的效應係此方法可部份地或甚至完全 地取代在氣相沈積步驟時將基材溫度調整至-1 5 t與+ 1 2 5 °C之間的方法之有益效應。在此替代性具體例中，可藉此 將基材溫度降至-1 5 °C以下、· 2 0。〇、· 4 0.。(3或甚至6 0 °C或 以下。 一般而言該層包括含三嗪化合物的粒子。其中該化合 物呈現結晶態及未經聚合形態並經由邊界分離的粒子係普 通熟於此藝之士所習知的一般結晶性化合物。.若該層基本 上由包含三嗉化合物的粒子所構成，將可達到該層賦予該 性質的最佳效應’特別是關於阻障性質。若該層完全地或 幾乎完全地由含三嗉化合物的細粒所構成，最好整個層基 本上都由三嗪化合物所組成》 在層中的粒子尺寸’在此定義爲在粒子內平行於基材 表面（即由最上層所觀察到）的最大尺寸。頃發現在第二 層含二D秦的粒于平均尺寸可能與測定阻障性質等重要特徵 時第二層的厚度一樣重要，或甚至更重要。在不受理論說 -8- (6) 1362425 明的限制下，咸認爲最佳的阻障性質可將重點放在粒子間 的邊界數量和尺寸而非沈積層的厚度而達到’這與熟於此 藝之士可能預期的結果相反。咸認爲粒子間的邊界在賦予 複合材料以阻障性質方面係相對較纖維的點；因此’若平 均粒子尺寸變得太小，有許多邊界的阻障性質就不太會發 揮作用。另一方面，若平均粒子尺寸變得太大，咸認爲其 本身的邊界面積不成比例地變得更大，於是阻障性質同樣 也會受損。平均粒子尺寸較佳爲至少1 〇 nm，更佳爲至少 5 0 n m >又更佳爲100 nm，最佳爲至少200 nm。平均粒子 ' 尺寸較佳至多2000 nm，更佳至多1000 nm，又更佳至多 ' 600 nm，最佳至多 400 nm。在本發明內文中，平均尺寸 表示數量平均。在較佳的具體例中，因爲該層基本上係由 三嗪化合物所組成，所以於粒子內的三嗪晶體結構並無明 顯地中斷。 根據本明的方法中，氣相沈積步驟最好以能使含三嗪 化合物的粒子之平均尺寸介.於10 nm與2000 nm之間的方 式進行。頃發現氣相沈積粒子的平均尺寸取決於此粒子長 在其上的表面上方之成核數目：成核點數目越大，平均粒 子尺寸就越小。所以沈積粒子的平均尺寸可藉由調整氣相 &積步驟中會影響粒子成長的成核點數目的加工條件而加 以改變。根據本發明可發現成核數目會隨著沈積溫度，即 含三嗪化合物被加熱的溫度，和基材溫度之間的差異增加 而增加。較佳地，該溫度差介於1 5 0 °C與3 7 0。(：之間，但 另一方面又與根據本發明的基材之溫度範圍有關。同.樣地 -9 - (7) (7)1362425 ，發現若氣相沈積步驟在提高的壓力下進行時，成核點數 目就會減少。較佳地，氣相沈積步驟的壓力介於10·6 Pa 與1(T2 Pa之間。再者，要注意基材的本質對於會形成的 成核數目也有影響。因此熟於此藝之士可運用以上所提供 關於溫度差與壓力的參數之教旨，經由實驗決定氣相沈積 步驟的最佳加工條件爲何以達到以上提供介於較佳範圍內 的平均粒子尺寸。 在氣相沈積步驟之前或期間，又更進一步地使該基材 歷經進一步的加工步驟將有助於增進根據本發明的方法得 到的複合材料之性質》在氣相沈積步驟期間或之後，又更 進一步地使該基材歷經進一步的加工步驟也有助於增進根 據本發明的方法得到的複合材料之性質。此進一步加工的 步驟之實施例係：交聯步驟，其中使該層中的三嗪化合物 與其本身或另一化合物發生反應，無論該化合物與該三嗪 化合物一起用於該層內或者分開地但與該層接觸；電漿處 理；電暈處理；施加紫外線；施加電子束。此進一步的加 工步驟可助於增進該層的特.定標的性質，例如附著力、耐 淫性或耐刮性》而更進一步的加工步驟可以改變粒子的尺 寸和層的結構。 較佳地’在氣相沈積步驟之前或期間以電漿、電暈、 紫外線照射、電子束或反應性氣體處理該基材。反應性氣 體係可與三嗉化合物及/或產生反應的氣體。該反應可能 立即發生’或隨後發生。該反應可不經輔助就會發生，或 藉助於溫度或照射處理等輔助裝置而發生。.反應性氣體較 -10- (8) (8)1362425 佳包含水及/或甲醛。在較佳的具體例中，該基材係包括 含鋁層的複合材料，而含三嗪化合物的層就沈積在含鋁的 層之上，且反應性氣體包含水蒸氣。由於水蒸氣與鋁的化 學反應，會使化合物形成於含鋁的層表面上，該含鋁的層 會增進含三嗪的層對基材的附著力。 較佳地，在氣相沈積期間或之後，以電漿、電暈、 UV照射 '電子束或反應性氣體處理該複合材料。該反應 性氣體較佳包含水及/或甲醛。 根據本發明的具體例中，將第二層加至該複合材料之 含三嗪化合物的氣相沈積層（在此具體例中稱之爲第一層 )上面。第二層可氣相沈積於第一層上，但也可以其他任 何習知的方式施加，例如經由疊層法。該第二層可含任何 化合物’取決於複合材料的功能及/或所需的性質。例如 :熱塑性或熱固性聚合化合物、與第一層的化合物相同或 不同的三嗪化合物 '鋁等金屬化合物、氧化鋁等金屬氧化 物。第二層本身可爲複合材料。 就氣相.沈積的技術而言，過去用於產生第一層，再就 三嗪化合物的特性而言，發現該第一層可作爲內層。本文 的內層表示可壓平或整平任何出現在基材表面的表面粗糙 不平中之至少一部分，使得第二層可施於更加平滑的表面 (即較少的表面粗糙不平）；這樣的優點係可降低損及第二 層的風險。再者，發現若以第一層的整平功能爲主要功能 且充當阻障層的功能較不重要時，在氣相沈積步驟期間的 S材溫度範圍就可介於比以上提供者更爲寬廣的範圍內， -11 - (9) (9)1362425 由此較佳爲-60°C與+125°C之間，更佳爲-"。(：與+“芄之 間。 本發明更進一步係關於複合材料，其可藉由上述根據 本發明的方法獲得。該複合材料可用於任何應用中，特別 是需要低〇TR等阻障性質的應用中，例如對氧敏感的製 品或如食品等會腐敗的製品的包裝。 本發明將藉由實施例及比較實驗的方式加以說明^ 實施例1 以雙軸定向聚丙烯（Β Ο P P)組成的薄膜之形態將三聚氛 胺組成的層氣相沈積在基材上。在1 0 p a或約1 .X 1 .〇 ·4大 氣壓的壓力時進行氣相沈積步驟。基材溫度係+2〇 °C。.使 三聚氰胺由坩堝蒸發；該坩堝中的三聚氰胺係維持在31〇 °C的溫度。使三聚氰胺沈積在基材上。該基材以每秒7公 尺的速度沿著坩堝導引；此係極高的速度，反映出工業上 實行的條件。最後得到的複合材料具有47 cm3/m2.bar.day 的氧穿透率（〇TR)。 比較實驗1 以實施例】之相同方式製備複合材料，但基材的溫度 係-2 0°C而非+20°C。對沒有任何層沈積的基材（B0PP)進行 測量時，◦丁R 係由 i600 降至]20 cm3 /m2.bar.day。 由實施例及比較實驗可輕易地見到儘管與未經處理的 基材相比’習知的方祛已經可使OTR有利降低，而可增 -12- (10) 1362425 進阻障性質，但根據本發明的方法可使OTR更進一步降 低，即進一步增進阻障性質。 -13 -

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1362425
件3Α·:第〇93丨丨3724號申請專利範:¾.修正本 拾、申請專利範園 ••V -- - 民國10 ί‘月1._7曰,修正
1. —種製造複合材料的方法，該複合材料包含基材 和該基材上的層’其中該基材包含含有鋁或氧化鋁或氧化 矽的氣相沈積層，該方法包含氣相沈積步驟，其中在壓力 低於1000 Pa時’將含三嗪化合物的化合物沈積在該基材 上’藉以形成該層’其中在該氣相沈積步驟期間，該基材 的溫度在-15°C與+50 °C之間及其中該三嗪化合物包含三聚 氰胺、蜜白胺、蜜勒胺、蜜弄（melon)或其混合物。 2. 如申請專利範圍第1項之方法，其中在該氣相沈 積步驟期間，該基材的溫度介於〇°C與+50 °C之間。 3 ·如申請專利範圍第1項之方法，其中該氣相沈積 步驟在壓力低於5xl(T3 Pa時進行。 4. 如申請專利範圍第1項之方法，其中該三嗪化合 物包含三聚氰胺。 5. 如申請專利範圍第1項之方法，其中該基材在氣 相沈積步驟之前，先以電漿、電暈、UV照射或電子束加 以處理。 6. 如申請專利範圍第1項之方法，其中該基材在氣 相沈積步驟之前，先以反應性氣體加以處理。 7-如申請專利範圍第6項之方法，其中該反應性氣 體包含水及/或甲醛。 8.如申請專利範圍第1項之方法，其中，在該三嗪 1362425 -— —— 化合物之該氣相沈積步驟之後，另一層係加至其上。 9.如申請專利範圍第8項之方法，其中該另一層係 » 經由疊層法加上的。 * 10·如申請專利範圍第8項之方法’其中該另一層包 含熱塑性化合物。 11.如申請專利範圍第1項之方法，其中該基材包含 聚合薄膜。 φ 12·如申請專利範圍第11項之方法，其中該基材包 含雙軸定向聚丙烯膜0 1 3 ' 種複α材料，其係藉由如申請專利範圍第1至 12項中任一項之方法製得。 1 4·如申請專利範圍第丨3項之複合材料，其係用於 包裝方面。 15·如申請專利範圍第14項之複合材料，其係用於 食品包裝。 -2 -
TW93113724A 2003-05-15 2004-05-14 Process for preparing a composite material TWI362425B (en)

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