TWI252858B - High speed method of making microporous film products - Google Patents

High speed method of making microporous film products Download PDF

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TWI252858B
TWI252858B TW094108528A TW94108528A TWI252858B TW I252858 B TWI252858 B TW I252858B TW 094108528 A TW094108528 A TW 094108528A TW 94108528 A TW94108528 A TW 94108528A TW I252858 B TWI252858 B TW I252858B
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Taiwan
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film
weight
microporous
stretching
roller
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TW094108528A
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TW200530301A (en
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Pai-Chuan Wu
Leopoldo V Cancio
Girish K Sharma
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Clopay Plastic Prod Co
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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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • 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
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0625—LLDPE, i.e. linear low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • 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
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Description

1252858 九、發明說明： 【發明所屬之技術領域】 微孔薄膜產物的製法已知有一段時間。例如Uu之美國專 利第3,832,267號教示含有分散非晶形聚合物相之聚稀煙薄 膜於拉伸或定向前炼體壓紋，而改良薄膜之氣體及水氣透 過性。根據Liu之，267號專利案，具有分散非晶形聚丙稀相 之結晶形聚丙浠薄膜於雙軸牵伸（拉伸）之前首先壓紋生產 具有較尚滲透性之定向無孔膜。分散不定形相用於提供微 孔隙來提升其他方面皆為無孔性薄膜之滲透性俾便改良水 氣透過性（MVT)。壓紋膜較佳循序壓紋及牵伸。 1976年Schwarz公開一篇報告敘述聚合物攙合物及組合 物生產 Μ 孔基質（Eckhard C.A· Schwartz (Biax-Fiberfilm)，’’ 新穎原纖化薄膜結構，其製造及用途”，紙張合成會議 (TAPPI)，1976年33_39頁）。根據該報告，二或多種不相容 性聚合物薄膜，此處一種聚合物形成連續相及第二種聚合 物形成非連續相，當拉伸時將相分離藉此於聚合物母質形 成空隙並增高薄膜之孔隙度。可結晶化聚合物之連續薄膜 母質也以無機填充劑如黏土、二氧化鈦、碳酸鈣等填充而 於拉伸聚合物基質提供微孔隙度。 多篇其他專利案及公告案揭示微孔熱塑性薄膜產物的製 造現象。例如歐洲專利141 592揭示使用聚烯烴特別含分散 聚苯乙烯相之乙烯-乙酸乙烯酯（EVA)，其當拉伸時可生產 工隙薄膜其可改良薄膜之水氣滲透性。EP，592專利案也揭 示以厚區及薄區壓紋EVA薄膜接著拉伸而首先獲得具有空 100319.doc 1252858 隙之薄膜，該薄膜當進一步拉伸時可生產網狀產物之循序 步驟。美國專利第4,452,845及4,596,738號揭示拉伸熱塑性 薄膜’此處分散相為聚乙稀填充以碳酸詞於拉伸時獲得顯 微空隙。稱後美國專利第4,777,073 ; 4,814,124及4,921，653 揭示前述稍早公開文獻之相同方法，涉及首先壓紋含填充 劑之聚烯烴薄膜然後拉伸該薄膜而獲得微孔產物。 參照美國專利第4,705,812及4,705,813號，微孔膜係由線 性低密度聚乙烯（LLDPE)及低密度聚乙烯（LDPE)與硫酸鋇 作為無機填充劑之攙合物生產，平均粒徑〇1 _7微米。也已 知使用熱塑性橡膠例如克來敦（Kraton)改性LLDPE及LDPE 攙合物。其他專利案例如美國專利第4,582,871號揭示使用 熱塑性苯乙稀嵌段三聚物生產微孔膜與其他不相容聚合物 如苯乙烯。業界多種其他概略教示可參考美國專利第 4,472,328及4,921，652號之揭示内容。 有關未拉伸非織基料之擠塑層合包括美國專利第 2,714,571 ; 3,058,868 ; 4,522,203 ; 4,614,679 ; 4,692,368 ; 4,753,840及5,035,941號。前述，863及，368專利案揭示於加壓 辕夾頭層合未拉伸非織纖維基料前拉伸擠塑聚合物薄膜。 f203及’941專利案係針對於加壓輥夾頭共同擠塑多層聚合 物膜與未拉伸非織基料。，84〇專利案揭示與薄膜擠塑層合劑 預先形成非織聚合物纖維材料俾改良非織纖維與薄膜間的 黏合。特別’840專利案揭示習知壓紋擠塑來於非織基層形成 被化區及非密化區隨後擠塑層合俾利用密化纖維區改良非 織纖維基料與薄膜間的黏合。，941專利案也教示未拉伸非織 100319.doc 1252858 基料其祕塑層合至單層聚合物薄膜其對於由纖維基質平 面概略垂直伸展的纖維引起的針孔敏感，如此此專利案揭 示使用乡4共同擠塑薄膜層纟防止針孔問題。此外，黏合 疏鬆非織纖維至聚合物膜方法揭示於美國專利3,622,422; 4,379，197及 4,725,473。 也已知使用交織輥拉伸非織纖維基料來降低基重，此領 域之專利案範例例如美國專利第 ’664專利案揭示使用一對指狀交又輥增加交差方向⑺或 機器方向（MD)拉伸之非織纖維基料俾增強並軟化非織基料 之方法。’664專利案也揭示替代具體例，其中非織纖維基料 係於交織拉伸之前層合至熱塑性薄膜。 曾經努力製造可呼吸之非織複合障壁纖物，其不透液體 但可透過水氣。美國專利第5,4〇9,761號為專利業界之製法 之一例。根據該’761號專利案，非織複合織物係經由超音波 黏合微孔熱塑性薄膜至非織纖維熱塑性材料層製造。此等 及其他可呼吸之非織與熱塑性材料層合物之製法傾向於設 计Φ貝的製造技術及/或昂貴原料。 雖然業界積極努力開發可呼吸微孔薄膜及層合物俾提供 空氣及水氣滲透性但具液體障壁性質，仍有待進一步改 良。特別希望改良於高速生產機器上生產微孔膜產物及層 合物。也極為希望生產微孔膜產物而無非期望的針孔以及 不含牽伸共振。過去嘗試提高生產速度結果導致薄膜斷裂 或具有非一致性質的薄膜產物。 【先前技術】 100319.doc 1252858
本發明之高速方法涉及熔體攙混一 漢之高速方法。微孔薄 。微孔膜與非織基質之 種組合物包含 ⑷約35%至約45%重量比線性㈣度聚乙稀， (b) 約3%至約10%重量比低密度聚乙烯， (c) 約40%至約55%番吾屮难舱忽坫士丸丨丄、，
-乙烯-丁烯·苯乙烯及其攙合物。 熔體攙混組合物經擠塑較佳通過開縫槽擠塑至輥夹頭， 輥附有氣刀而以至少約55〇 fpm至約12〇〇 fpm之速度形成薄 膜而無牽伸共振。曾經達成至少約75〇fpm至約12〇〇印瓜或 以上之速度而無牵伸共振。使用空氣刀輔助去除牵伸共振 為已知，例如參考美國專利第4,626,574號。隨後較高拉伸 力以高速沿大致均勻跨越薄膜線施加於薄膜且貫穿其深度 而提供微孔膜。如此該專利案提供附有均勻規袼之非織基 材之微孔膜之層合物之高速製法。可防止過去會造成薄膜 產物規格或厚度不規則之牵伸共振問題可避免，即使達約 75〇-1200 fpm之線性速度仍可防止。 於成分約略範圍内之LLDPE及LDPE之攙合物可生產薄 膜，而當使用規定量之碳酸鈣平衡時不會斷裂或生成針 孔。特別LLDPE之存在量為約35%至約45%重量比俾便提供 足量母質來載運碳酸鈣填充劑粒子，藉此致使薄膜被處理 100319.doc 1252858 及拉伸而無針孔及斷裂。數量約3%至約i〇%重量比之LDpE 也可生產不含針孔之薄膜且可做高速生產而無牽伸共振。 聚合物母質以約4 0 %至約5 5 %重量比平均粒徑約！微米之碳 酸鈣粒子平衡而獲得足夠MVT於約1〇〇〇克/平方米/日至 4〇〇〇克/平方米/曰之範圍。此外，熔體攙混組合物需要三嵌 段聚合物含量為約2%至約6%重量比俾輔助高速生產時拉 伸而無斷裂。遞增拉伸力於線上於周圍條件下或於升溫下 以約550 fpm至約uoo fpm或以上之速度沿著大致均勻跨越 薄膜線外加於形成的薄膜且貫穿其深度而提供微孔膜。 本發明方法也涉及於擠塑過程層合微孔可成形熱塑性薄 膜至非織纖維基料。擠塑層合係於與非織纖維基料連同可 微孔成形熱塑性擠塑物引進輥夾頭之相等高速進行。纖維 基料與擠塑物間之壓縮力控制成可黏合基料一面至薄膜而 形成層合物。然後層合物沿大致均勻跨越層合物之線且於 方向貝穿其深度之線遞增拉伸而使薄膜變成微孔。層合 物可，交又方向及機器方向二方向拉伸而提供可輸送水氣 及空氣之仿可呼吸布之液體障壁。 優點及目的參照後文詳細說明將顯 本發明之其他利益、優點及目的參 然易明。 【發明内容】
上生產微孔膜及其 A.该方法使用材料 ’斗之層合產物。該方法之另一目的係生產具 均勻孔隙度且不會斷裂之微孔薄膜產物。 100319.doc 10 1252858 如過去之發展，此等及其他目的於本發明之較佳形式可 經由首先熔體攙混一種組合物達成，該組合物包含 (a) 約35%至約45%重量比線性低密度聚乙稀， (b) 約3%至約10%重量比低密度聚乙稀， (c) 約40%至約55%重量比碳酸鈣填充劑粒子，及 ⑷約2%至約6%重量比苯乙烯三嵌段共聚物選自包括苯 乙烯-丁二烯-苯乙烯’苯乙烯-異戊間二烯_苯乙烯及苯乙烯 -乙烯-丁稀-苯乙烯及其攙合物， 擠塑熔體攙混組合物至輥夾頭而以至少約55〇印⑺至約 1200 fpm之速度形成薄膜不含牵伸共振，及 沿大致均句跨越薄膜以及遍佈其深度之線以該速度施加 遞增拉伸力至該薄膜而提供微孔膜。 較佳形式中，熔體攙混組合物主要包含約重量比 LLDPE 、力4/。重里比LDPE ’約44%重量比碳酸鈣填充劑粒 子具有平均粒徑約1微米’及約3%重量比三嵌段聚合物特 別苯乙稀-丁 一烯·苯乙稀。若有所需，微孔薄膜產物之挺度 〖生夤可藉包括同岔度聚乙烯約〇_5%重量比及重量比 一氧化鈦拴制。典型添加加工助劑如氟碳聚合物添加量為 _·1%至約〇·2%，例如卜丙烯、U，鄉^ 氟乙烯之/、聚物。二肷段聚合物也可攙混油、Μ、抗氧化 劑及安定劑。抗氧化劑包括肆(亞甲基(3,5_二·第三丁基_4_ Κ氫桂皮δ〇)甲燒（商品名為伊嘉諾（_丽口〇1〇)及參 (2’4 一第一丁基笨基）亞磷酸酯（商品名為伊嘉福 ㈣心）168)總量5_4_啊(每百萬份之廢數）。 100319.doc 1252858 壓紋膜及扁平膜可根據本發明原理生產。於壓紋膜之 例，輥之夾頭包含金屬壓紋膜及橡皮筋輥。輥間壓縮力形 成預定厚度約0.5至約10密耳之壓紋膜。也發現具有拋光錯 表面之輥可形成平坦膜。無論薄膜為壓紋膜或平坦膜，當 以高速遞減拉伸時，產生微孔薄膜產物具有高水氣透過率 (MVTR)於約1000至4〇〇〇克/平方米/日之可接受範圍。發現 平坦膜比較壓紋膜更均勻遞減拉伸。該方法係於周圍溫度 φ 或至溫或於升高溫度進行。如前述，微孔膜層合物可以非 織纖維基料獲得。 非織纖維基料包含聚乙烯、聚丙烯、聚g旨類、嫘營、纖 維素、尼龍纖維及此等纖維之混紡物。對非織纖維基料曾 提出夕個疋義。纖維通常為短纖或連續長纖。非織物通常 分作紡黏、梳毛、炫吹等。纖維或長纖可為雙成份俾輔助 黏合。例如可使用具有不同聚合物如聚乙烯（pE)及聚丙烯 (PP)之鞘與中心之纖維；或可使用叩與pp纖維混合物。此 • 處使用’’非織纖維基料，，於其俗名定義表示概略平坦結構其 相對平坦、撓性且多孔，由短纖或連續長纖組成。至於非 織物之進一步說明可參考”非織纖物底劑及參考抽樣器"作 者E· A. Vaughn ’非織纖物協會第3版丨992年。 車乂佳幵y式中，祕孔層合物使用規格或厚度約〇 Μ至1 〇密 薄膜，隨用途而定薄膜厚度可改變，最佳於拋棄式用 :厚約0.25至2密耳。層合薄片之非織纖維基料通常具有重 曰為克/平方碼至75克/平方碼，較佳約2〇至約刊克/平方 複。物或層合物於交叉方向（CD)遞增拉伸形成CD拉伸 100319.doc -12- 1252858 複合物。此外CD拉伸可藉著於機器方向（MD)拉伸而形成於 CD及MD兩方向拉伸之複合物。如前述，微孔膜或層合物 可用於多種不同用途例如嬰兒尿片、嬰兒訓練褲、衛生棉 及衣物等需要水氣及空氣透過性以及流體障壁性質等用 途。 B · k孔膜及層合物之拉伸器 多種不同拉伸器及技術可用於拉伸非織纖維基料及可微 孔成形膜之薄膜或層合物。此等短纖之非織梳毛纖維基料 或非織紡黏纖維基料之層合物可以拉伸器及下述技術拉 伸0 1·對角線對咬拉伸器 對左及右螺旋齒輪狀元件於平
可作動而指示對咬輥之齒之接合深度。 對角線對咬拉伸器係由一 行軸上組成。軸設置於二機 承上，而上鱼A孫/ffr你击士
驅動裝置典型用於驅動靜態對咬輥。 若上對咬輥為了通 100319.doc 1252858 過機器或安全緣故解除接合，則較佳使用上與下對咬輥間 ^無齒隙齒輪配置俾便確保當再度接合時一根對咬輥的齒 17、、、τ吊落入另一根對咬輕之齒間而避免可能損害對咬齒的 齒頂間的實體接觸。若對咬輥保持穩定接合，則上對咬輥 典型無需被驅動。驅動可藉由驅動對咬輥通過拉伸材料 成。
對咬輥相當類似細節距螺旋齒輪。較佳具體例中輥直徑 5^935对’螺旋角45度，正常節距〇1()㈣，直徑節距％，加 壓角14%度，基本上為長齒頂齒輪。如此產生又窄又深的 齒側錄其允許齒旁有約〇·_忖對咬接合及約㈣5对餘隙 供材料厚度。此並非設計用於傳遞旋轉扭矩，於正常對咬 拉伸作業中也未作金屬-金屬接觸。 2·交又方向對咬拉伸器 交又方向對咬拉伸設備同對角線對咬拉伸器，差異在於 對咬輥之深度及其他下述次要領域。因交叉方向對咬元件 可有大的接合深度，故要緊地設備合併可使兩根對咬輕轴 於頂轴升降時保持平行的裝置。需要如此俾確保對咬輥之 =常=一根對咬輥之齒間且防止對咬齒間實體接觸 了此&成的損傷。此種平行動作可由齒條及齒輪配置達 成，其中固定齒條附著至各側框架緊鄰可垂直滑動件。主 =㈣框架及於軸承於垂直滑動件作動。_齒輪駐在^ 車各鈿且作動接合齒條產生預定的平行運動。 交又方向對咬拉伸器的驅動必須作動上及下對&胃曰 對咬拉伸具相對高摩擦係數之材料時除外。驅動^為： 100319.doc 14 1252858 二隙原、因為小s機器方向之未對正或驅動滑脫不成問 題。其理由由交叉方向對咬元件之說明將顯然易明。 又又方向對咬兀件係、由實心材料機製而成，最佳說明為 兩種不同直捏圓盤之交替堆疊場。較佳具體例中，對咬圓 盤直4 6 f厚0.031时，邊緣有完整半徑。隔開對咬圓盤 之間㈣圓盤直徑為51/2忖及厚〇._时。兩根此種構造之 ‘可對叹至〇.23W，於各邊留TGG19忖之餘隙供材料使 用。如同對角線對咬拉伸器，此交又方向對 有0.100吋節距。 3·機器方向對咬拉伸器 機器方向對咬拉伸設備同對角線對咬拉伸n，但對咬輥 的設計除外。機器方向對咬輥緊密類似 較佳具體例中輥直徑為5.9 棘齒輪 A々々π η " 即距〇· 100吋，3ο個直徑方 :即Ζ度壓力角，基本上為-長齒頂齒輪。於此等輥 ^-次通料，㈣偏㈣.㈣料得更㈣及更大餘隙。 使用約0.090吋接合此項配 、’ 餘隙。 置於材科厚度该邊具有0.010时 4·遞增拉伸技術 產;:二::二Γ:向或機器方向對咬拉伸器可用於生 形成：夢月…、可微孔成形膜之遞減拉伸膜或層合物而 Φ成本發明之微孔薄膜 ^ 炫訪長纖之非織纖維基料盘可:::伸作業可用於短纖或 層合物。本發明之獨特方面之孔成形熱塑性薄膜之挤塑 物層合物可遞增拉伸獲得極Ά矛’纺黏長纖之非織纖維織 °為柔軟的層合物纖維外觀其類 J00319.doc 1252858 =布料。非織纖維騎與可微孔成形狀層合物例如使用 又又方向及/或機器方向對咬拉#器遞減拉#，—次通過拉 伸器附有輥接合深度為約G._m12w，速度為^別 pm至、、、ij 12GG fpm或以上。此種遞減或對咬拉伸結果獲得具 有絕佳呼錢及液輯壁性質之層合物，而又^供=黏 合強度及仿軟布質地。
下列實例舉例說明本發明之微孔膜及層合物之製法。銲 於此等實例及其進一步詳細說明，業界人士顯然易知可未 惊離本發明之範圍做出多種變化。 【實施方式】 實例1-5 具有下表1報告組成的LLDPE與LDPE之攙合物經擠塑 形成薄膜，然後薄膜遞增拉伸獲得微孔膜。 表1 配方（以重昼' 計） 1 2 3 4~' 5 CJ ac 〇3 LLDPE 44.2 441- 44.2 4479 44.2 41.9 44,2 41.9 44.2 41.9 LDPE 1.5 3.7 3.7 3.7 10.2 1—0.2 10.2 T〇T2 10.2 螺杯 RPM A 33 45 57 75 B 33 45 57 64~~'^ 75 暴重（克/平方 米） 45 45 45 45 45 規格（密耳） 2 2Γ 2 2 — 2 直線速度（fpm) 550 700 900 1000 『200~ 氣刀（cfm/忖） 5:25 ^25 5-25 5-25 『25 基料穩定性 規格控制不 良帶有牽伸 共振 良好基料穩定性不含牽个 *共振 其他成份包括2.5%重量比苯乙烯-丁二烯-笨乙烯（SBS) 100319.doc -16- 1252858 三礙段共聚物，殼牌公司克來敦（Kraton)2122X，其為 SBS<5 0%重量比+礦油<3〇%重量比，EVA共聚物<15%重量 比’聚苯乙烯<10%重量比，烴樹脂<1〇%重量比，抗氧化 劑/安定劑<1%重量比及水合非晶形矽氧<1%重量比。 1-5配方採用圖i圖解顯示的擠塑裝置擠塑成為薄膜。如 所不裝置可有及無層合用於薄膜擠塑。於薄膜擠塑之例， 實例1-5配方由擠塑機丨進給通過開縫模2形成擠塑產物6， 擠塑產物進給至附有氣刀3之橡皮輥5與金屬輥4之夾頭。實 施擠塑層合時纖維材料9基料由輥13連續輸入其也引進橡 皮輥5與金屬輥4之夾頭。實例^中，熱塑性薄膜生產用於 隨後遞增拉伸而形成微孔膜。如表丨所示超過約55〇印历至 1200 fpm速度，製造厚約2密耳之聚乙烯膜6其於輥7捲離。 氣刀3長度約120吋及開口約〇·〇35吋_〇〇6〇吋，空氣吹送通 過開口以約5 cfm/吋至25 cfm/吋牴住擠塑產物6。夾頭及氣 刀之壓縮力控制為製造薄膜不形成針孔且於實例2·5之例 • 不含牵伸共振。當LDPE以1.5%重量比含量含括於組合物 時，於550 fpm線性速度出現牵伸共振。但當LDpEw3 7% 重量比含括於配方，LLDPE含量為441_44·9%重量比時可以 大55〇fpms 1200 fpm之高速生產薄膜而無牽伸共振。擠塑 產物A及B由進料區段至螺桿梢端之溶體溫度維持於約 400-430°F，模温為約450T而擠塑約2密耳（45克/平方米）之 前驅物膜。 圖3為線圖驗證實例丨_5之直線速度。實例丨僅含15%重量 比LDPE’獲得薄膜規格㈣不良帶有㈣共振，即使使用 100319.doc 1252858 氣刀3亦如此 但當LDPE增加至約3·7%重量比時可獲得絕 佳基料穩定性而無牽伸共振，即使直線速度升高至約12⑽ fpm亦如此。以圖解顯示於圖3。 圖4為線圖驗證於不同溫度及拉伸輥接合條件下由實例 2-5遞增拉伸前驅物膜所得壓紋膜及平扫膜_ 一肤一 #之水蒸氣
透過性質。如圖1示意顯示，於周圍溫度輸入薄膜12通過控 溫輥20及21隨後通過交叉方向及機器方向增量拉伸親（ι〇 及11及10,及11，），可控制溫度及接合深度。顯然如圖4所示 平坦膜之MVTR超過壓紋膜之MVTR。簡言之，達成約12〇〇_ 2400克/平方米/日之壓紋膜MVTR，而達成約19〇〇_32〇〇克/ 平方米/日之平坦膜MVTR。出乎意外的亦如圖5所示，微孔 膜之MVTR也可於拉伸期間藉基料溫度控制。圖5顯示於交 叉方向拉伸前加熱至不同溫度之薄膜可獲得不同MVTRs。 圖5報告資料以為深0·065吋之交叉方向輥接合及深〇 〇4〇忖 之機器方向輥接合資料，此處輥2 1之溫度維持於周圍溫 度。壓紋膜係使用金屬壓紋輥製造，具有矩形凹刻交叉方 向及機器方向線，每吋約165-300線。此圖樣例如揭示於美 國專利第4,376,147號，併述於此以供參考。此種顯微圖樣 獲得無光澤之薄膜但肉眼無法分辨。 鑑於前文說明顯然易知業界人士了解採用本發明之原理 依據材料及條件而定可做多種變化。 【圖式簡單說明】 參照附圖將更了解本發明，附圖中： 圖1為用於製造本發明之微孔層合物之線上擠塑層合與 100319.doc -18 - 1252858 遞增拉伸裝置之示意圖。 圖2為沿圖1線2-2所取之剖面圖示例說明以圖解形式示 例說明對咬輥。 μ 圖3為線圖驗證實例1-5之線性速度。 圖4為線圖驗證壓紋微孔膜及平坦微孔膜之水蒸氣透過 性質。 圖5為線圖驗證水蒸氣透過速率可藉加熱前驅物膜調整。 【主要元件符號說明】
1 代表擠塑機 2 代表開縫模 3 代表氣刀 4 代表金屬輥 5 代表橡皮輥 6 代表聚乙烯膜 7 代表幸昆 9 代表纖維材料輸入網 10 代表拉伸親 10f 代表拉伸輥 11 代表拉伸輥 11， 代表拉伸輥 12 代表輸入薄膜 13 代表輥 20 代表控溫輥 21 代表控溫輥 100319.doc • 19-

Claims (1)

1252858 十、申請專利範圍： 1. 一種具有高水氣透過率（MVTR)之遞增拉伸性無壓紋 膜，其包含一含有粒子分散相之熱塑性聚合物膜，該膜 具有自0.25至2密耳（mils)之厚度，且膜中具有遞增拉伸區 域，以賦予該膜一根據ASTM E 96E方法測得之大於1900 克/米2/天之MVTR之微孔性。 2. 根據申請專利範圍第1項之膜，其具有根據ASTM E 96E 方法測得之自1900至3200克/米2/天之MVTR。
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EP1078013A1 (en) 2001-02-28
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