TW201843035A - 三維成形品 - Google Patents

三維成形品 Download PDF

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Publication number
TW201843035A
TW201843035A TW107109288A TW107109288A TW201843035A TW 201843035 A TW201843035 A TW 201843035A TW 107109288 A TW107109288 A TW 107109288A TW 107109288 A TW107109288 A TW 107109288A TW 201843035 A TW201843035 A TW 201843035A
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TW
Taiwan
Prior art keywords
article
fabric
fibers
acrylic
article according
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TW107109288A
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English (en)
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TWI818905B (zh
Inventor
穆瑞特 歐茲曼
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荷蘭商帝斯曼知識產權資產管理有限公司
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Publication of TW201843035A publication Critical patent/TW201843035A/zh
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H1/00—Personal protection gear
    • F41H1/04—Protection helmets
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/083—Combinations of continuous fibres or fibrous profiled structures oriented in one direction and reinforcements forming a two dimensional structure, e.g. mats
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/20—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres
    • B29C70/205—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres the structure being shaped to form a three-dimensional configuration
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/22—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
    • B29C70/222—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure the structure being shaped to form a three dimensional configuration
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B5/024—Woven fabric
    • 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
    • B32B5/026—Knitted fabric
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    • 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
    • B32B5/08—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 the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different 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
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B32B5/262—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a woven fabric layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0478—Fibre- or fabric-reinforced layers in combination with plastics layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
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    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0485—Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers
    • 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
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12—Thermoplastic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/48—Wearing apparel
    • B29L2031/4807—Headwear
    • B29L2031/4814—Hats
    • B29L2031/4821—Helmets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • F41H1/00—Personal protection gear
    • F41H1/04—Protection helmets
    • F41H1/08—Protection helmets of plastics; Plastic head-shields

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Abstract

本發明有關具有外部和內部表面的三維成形品，該外表面包含至少一種拉張強度至少為1.5GPa之聚乙烯纖維織物（100），該織物以一基於丙烯酸之熱塑性材料浸透。三維成形品可進一步包含具有單向排列纖維的單層。三維成形品具有一改進表面外觀，因此僅需微少或不需後處理且對塗層和塗料有良好的附著力。

Description

三維成形品
發明領域 本發明涉及具有外、內表面的三維成形品。本發明進一步涉及用於製造三維成形品的方法，以及一具有聚丙烯基熱塑性材料外表面的聚乙烯纖維織物用於製造三維成形品，較佳用於製造三維形狀抗衝擊製品，更佳用於製造三維形狀防彈製品的用途。
發明背景 WO2007107359描述一由單向聚乙烯纖維和聚氨基甲酸酯基體材料組成的三維成形品，該三維成形品藉由一方法製成，依此方法一控制構件被應用來降低產品中的變異性。
儘管習知技術的三維成形品具有低變異性，但仍尋求進一步的改進，特別是在表面外觀方面。
發明概要 本發明的一目的是提供具有改進表面外觀的三維成形品。
該目的通過具有外表面（'1'）和內表面（'2'）的三維成形品來實現，該外表面包含至少一種織物（'100'），該織物包含拉張強度為至少1.5Gpa的聚乙烯纖維，該織物以基於丙烯酸之熱塑性材料浸透。
依據本發明的三維成形品具有一改進的表面外觀。依據本發明的三維成形品的另一個優點是塗佈層和塗料的改進黏合性。這增加了被塗佈之三維成形品的耐久性，並因而較不容易發生塗佈層或塗料從製品剝落或磨損。
較佳實施例之詳細說明 依據本發明的三維成形品具有外表面（1）和內表面（2），一般在至少2個方向上具有曲率，且可以是例如，拱頂，圓頂，半圓頂，頭盔和頂篷。
本發明中使用的至少一種織物（100）是具有例如平紋，方平，緞紋和四經破斜紋組織的一梭織物，但其亦可為針織網眼織物，或者是以多種傳統技術中的任一種形成織物的網眼織物。例如，這種纖維網眼織物也可以是毛氈。
用於本發明的至少一種織物（100）包含具有至少1.5GPa，較佳為至少2.5Gpa之拉張強度的聚乙烯纖維。更佳地，織物中的纖維具有至少3.5GPa的強度，這導致更好的結構剛性。尤更佳地織物中的纖維具有至少4GPa的強度以獲得具有更佳衝擊性能的產品，且最合意為至少4.5GPa，產生具有非常好的防彈性能的三維成形品。
用於本發明的聚乙烯纖維可以合適地基於線性聚乙烯（PE）。線性聚乙烯在本文中理解為意指每100個C原子具有少於1個側鏈，且較佳每300個C原子具有少於1個側鏈的聚乙烯；一側鏈或支鏈通常含有至多10個C原子。線性聚乙烯可以進一步含有至多5mol％的一種或多種可與其共聚的其它烯烴，諸如丙烯，丁烯，戊烯，4-甲基戊烯，辛烯。較佳地，線型聚乙烯是具有至少4dl/g，更佳為至少8dl/g之特性黏度（IV，如在135℃下對十氫化萘的溶液測定）的超高分子量聚乙烯。
由諸如在GB 2042414 A或WO 01/73173中描述的凝膠紡絲程序製備的由聚乙烯長絲組成的高性能聚乙烯（HPPE）纖維較佳使用於織物或單層中。凝膠紡絲程序主要由以下步驟組成：製備具有高特性黏度的一線型聚乙烯溶液，在高於溶解溫度的溫度下將溶液紡成長絲，將長絲冷卻至凝膠化溫度以下，以致發生膠凝，並在去除溶劑之前、期間或之後拉伸長絲。此一拉伸導致已延伸纖維具有至少1.5GPa的強度。如果這些聚乙烯纖維高度延伸，它們的強度至少為3.0GPa。
使用於本發明的至少一種織物（100）以一基於丙烯酸的熱塑性材料浸透。在一特別實施方案中，基於丙烯酸之熱塑性材料丙烯酸樹脂或丙烯酸聚合物具有至少25℃的玻璃轉變溫度Tg。基於丙烯酸樹脂的熱塑性材料本身在本技術領域中是公知的。本發明中使用之丙烯酸樹脂的Tg較佳為至少25℃，更佳為至少35℃，尤更佳者為至少45℃，最合意為至少55℃。通常，聚合物的Tg將在25至120℃的範圍內，更通常在30至90℃的範圍內。在一個特殊的實施方案中，使用在本發明中的熱塑性丙烯酸樹脂具有一在25℃和53℃之間的Tg，並以含水分散體形式施用。
Tg為至少25℃的熱塑性丙烯酸樹脂較佳包含包含一丙烯酸聚合物，該丙烯酸聚合物包含甲基丙烯酸甲酯，丙烯酸乙酯及/或丙烯酸丁酯。丙烯酸聚合物可基於包含0-10重量％，較佳0.1-8重量％，更佳0.5-7重量％，尤更佳0.5-6重量％，最合意係0.5-4重量％之前驅物的一酸根，且進一步可基於0-30重量％之間，較佳0-20重量％之間，更佳0-15重量％之間，尤更佳0-10重量％之間，且最合意係在1-10重量％之間的量的-OH官能單體。丙烯酸聚合物的數平均分子量通常為至少1000克/莫耳，更通常為至少2,000克/莫耳。上限通常不超過2,000,000克/莫耳。數平均分子量一般在5,000克/莫耳和800,000克/莫耳之間，較佳在10,000克/莫耳和500,000克/莫耳之間，更佳在100,000克/莫耳和500,000克/莫耳之間。在另一個實施方案中，丙烯酸聚合物的重量平均分子量通常為至少10000克/莫耳，更通常至少20,000克/莫耳。上限通常不超過4,000,000克/莫耳。重量平均分子量一般在15,000克/莫耳和2,500,000克/莫耳之間，較佳在20,000克/莫耳和2,000,000克/莫耳之間，更佳在50,000克/莫耳和1,500,000克/莫耳之間。
丙烯酸聚合物或用於浸透織物（100）的丙烯酸聚合物可以是包含20-600nm，更佳30-400nm，最合意為50-300nm之聚合物粒度的乳液。該乳液一般具有2-11，較佳3-10，更佳4-9之一pH。固體含量一般為10-60重量％，較佳20-55重量％，最合意為30-50重量％。所提及的丙烯酸聚合物在下文中更詳細地描述。該丙烯酸樹脂或丙烯酸聚合物包括乙烯基聚合物，且較佳包含（甲基）丙烯酸酯以及可選地也包含（甲基）丙烯酸聚合物，包括甲基丙烯酸甲酯，丙烯酸乙酯及/或丙烯酸丁酯，及苯乙烯-（甲基）丙烯酸酯或苯乙烯-（甲基）丙烯酸聚合物。
乙烯基聚合物在本文中通常是指衍生自加成聚合（通常藉自由基方法）的至少一種烯屬不飽和單體的聚合物。因此，在此乙烯基單體是指能夠進行自由基聚合的烯屬不飽和單體。乙烯基聚合物較佳由0-10重量％之至少一種含有酸官能基的乙烯基單體（單體（i））與90-100重量％之不包含在（i）中的另一乙烯基單體（單體（ii））所形成。這種乙烯基單體（ⅱ）的實例包括共軛二烯，可選地取代二烯；苯乙烯和取代苯乙烯；烯烴諸如乙烯或丙烯；鹵乙烯；乙烯酯類諸如乙酸乙烯酯，丙酸乙烯酯，月桂酸乙烯酯和新癸酸的乙烯基酯，諸如VeoVaTM 9和VeoVaTM 10（VeoVa是殼牌公司的商標）；雜環乙烯基化合物，單烯屬不飽和二羧酸的二烷基酯（諸如順丁烯二酸二正丁酯和反丁烯二酸二正丁酯；乙烯基醚；且特別是下式的丙烯酸和甲基丙烯酸之酯： CH2 =CR1 CO2 R2 其中 R1 是H或甲基以及 R2 是可選地取代的1至20個碳原子，較佳1至8個碳原子的烷基或5至12個環碳原子的環烷基。
此種單體的進一步特定實例包括烷基酯和（氯）烷基酯諸如a-氯丙烯酸甲酯，a-氯丙烯酸正丙酯，a-氯丙烯酸正丁酯，β-丙烯酸氯乙酯，β-丙烯酸氯丁酯，（甲基）丙烯酸甲酯，（甲基）丙烯酸乙酯，（甲基）丙烯酸丙酯（所有異構體），（甲基）丙烯酸丁酯（所有異構體），（甲基）丙烯酸異冰片酯，（甲基）丙烯酸環己酯，（甲基）丙烯酸2-乙基己酯，（甲基）丙烯酸辛酯，（甲基）丙烯酸月桂酯，（甲基）丙烯酸三氟乙酯，順丁烯二酸二乙酯，反丁烯二酸二乙酯；乙烯基酯諸如乙酸烯丙酯，氯乙酸烯丙酯，乙酸甲基烯丙酯，乙酸乙烯酯，乙酸異丙烯酯；乙烯基鹵化物諸如氯乙烯，偏二氯乙烯，氯丙烯，1,2-二氯丙烯-2，甲基烯丙氯和三氯乙烯；腈諸如丙烯腈和甲基丙烯腈；乙烯基芳基諸如苯乙烯，a-甲基苯乙烯，鄰甲基苯乙烯，間甲基苯乙烯，對甲基苯乙烯，五氯苯乙烯，鄰氯苯乙烯，間氯苯乙烯，對氯苯乙烯和對氰基苯乙烯；共軛二烯或氯二烯諸如丁二烯和氯丁二烯；以及乙烯基取代的雜環亞胺諸如2-乙烯基吡啶和乙烯基咔唑。其他亦可用於形成乙烯基聚合物的乙烯基單體為帶有一官能基（且以上未曾提及）的乙烯基單體。這些可以包括例如羥基官能單體諸如丙烯酸羥乙酯（HEA）和甲基丙烯酸羥乙酯（HEMA），以及烯屬不飽和醯胺諸如丙烯醯胺和甲基丙烯醯胺。併入作為（iii）之一部分的此種官能單體的量以形成該乙烯基聚合物之全部單體組合物為基礎係0至20重量％，較佳0至7重量％，更佳0至2重量％。然而，在大多數情況下不使用這種官能單體。其它也可用於形成乙烯基聚合物的乙烯基單體為帶有可交聯基團（且以上未曾提及）者。可交聯基團在與交聯劑結合時或藉由彼此反應而賦予交聯性。帶有可交聯基團的乙烯基單體包括例如烯丙基，環氧丙基或乙醯乙醯氧基酯，乙醯乙醯氧基醯胺，酮和醛官能乙烯基單體，含酮醯胺諸如二丙酮丙烯醯胺，及矽烷官能（甲基）丙烯酸單體。較佳之帶有可交聯基團的乙烯基單體為甲基丙烯酸乙醯乙醯氧基乙酯（AAEM），二丙酮丙烯醯胺（DAAM）和矽烷官能（甲基）丙烯酸單體，且最合意為DAAM。特別合意的乙烯基單體（ii）選自甲基丙烯酸甲酯，丙烯酸正丁酯，甲基丙烯酸正丁酯，丙烯酸乙酯，甲基丙烯酸乙酯，丙烯酸2-乙基己酯，苯乙烯和丙烯腈中的一或多者。
含有一酸官能基的乙烯基單體（i）較佳為一烯屬不飽和單羧酸或二羧酸，其例子包括丙烯酸，甲基丙烯酸，丙烯酸2-羧乙酯，反丁烯二酸，順丁烯二酸，伊康酸和二羧酸之單取代的C1-C20烷基酯。單羧酸是較佳的，且用於（i）的特別合意之單體是甲基丙烯酸和丙烯酸中的一或兩者。
乙烯基聚合物可以藉由本技術領域已知的任何自由基聚合方法製備，諸如乳液聚合或懸浮聚合。乳液聚合是較佳的。聚合物可以使用本技術領域已知的各種聚合方法製備，諸如批次，序列和梯度聚合，也通常稱為動力進料聚合。如果需要，可以使用預先形成或原位形成的種子。
單體組合物聚合形成乙烯基聚合物通常需要使用產生自由基的起始劑引發聚合反應。合適的產生自由基的起始劑包括無機過氧化物諸如K，Na或過硫酸銨，過氧化氫或過碳酸鹽；有機過氧化物，諸如醯基過氧化物，包括例如過氧化苯甲醯，烷基氫過氧化物諸如叔丁基氫過氧化物和異丙苯氫過氧化物；二烷基過氧化物諸如二叔丁基過氧化物；過氧酯諸如過苯甲酸叔丁酯等；也可以使用混合物。EDTA（EDTA：四醋酸乙二胺）也可以用作氧化還原起始劑系統的一部分。可以使用表面活性劑以幫助聚合單體和得到的乙烯基聚合物A在水中的分散或乳化。合適的表面活性劑包括但不限於習知的陰離子，陽離子及/或非離子表面活性劑及其混合物，諸如二烷基磺基丁二酸鹽的Na，K和NH4鹽，硫酸化油的Na，K和NH4鹽，烷基磺酸的Na，K和NH4鹽，Na，K和NH4烷基硫酸鹽，磺酸的鹼金屬鹽；脂肪醇，乙氧基化脂肪酸及/或脂肪醯胺，以及脂肪酸的Na，K和NH4鹽諸如硬脂酸鈉和油酸鈉。其它陰離子表面活性劑包括與磺酸基連接的烷基或（烷基）芳基，硫酸半酯基團（依次連接到聚乙二醇醚基團），膦酸基團，磷酸類似物和磷酸酯或羧酸基團。陽離子表面活性劑包括與季銨鹽基團連接的烷基或（烷基）芳基。非離子表面活性劑包括聚乙二醇醚化合物且較佳為聚氧化乙烯化合物。藉由在聚合過程中使用一鏈轉移劑（CTA）諸如3-巰基丙酸或正月桂基硫醇，可以降低乙烯基聚合物的分子量Mw。使用特定Co螯合物催化劑作為CTA的催化鏈轉移聚合也可用來降低Mw。
本發明中基於丙烯酸之熱塑性材料是一基於丙烯酸樹脂或丙烯酸聚合物的熱塑性基體材料，其較佳具有至少25℃的玻璃轉變溫度。基體材料的備選實施方式可包含基於玻璃轉變溫度為至少25℃的丙烯酸樹脂或丙烯酸聚合物的熱固性同等物。
依據本發明的三維成形品經證明具有改善的表面外觀。以此一方式製品可被塗覆而需要施加較少的底漆或表面加工，或者甚至在塗覆塗層之前不需要處理表面以平整瑕疵和褶皺。
在上述織物（100）中，基於丙烯酸之熱塑性材料以至多70重量％，較佳至多60重量％，更佳地至多50重量％之量存在。該織物包含至少10％，較佳至少15重量％，更佳地至少20重量％之基於丙烯酸的熱塑性材料。通常，該基於丙烯酸的熱塑性材料以10-60重量％，較佳20-50重量％，更佳30-40重量％的量存在於織物中。
織物（100）的重量通常在100克/平方公尺至400克/平方公尺，較佳150克/平方公尺至300克/平方公尺的範圍內變化。
依據本發明的三維製品可以包含兩層或更多層織物（100）。這兩層或更多層（100）可被互相直接連接，或者可被交替而連接到其他基於纖維的片材。合適的三維成形品可以由數層織物（100）組成，藉此使這種製品的總重量為100-500克/平方公尺。除了織物層（100）之外，依據本發明的製品可包含其他基於纖維之片材或層。這樣的層可以包含編織、單向或非編織纖維層。這樣的層可適當地基於包括聚烯烴纖維，超高分子質量聚乙烯纖維，超高分子質量聚丙烯纖維，聚芳醯胺纖維，超高分子質量聚乙烯醇纖維，來自液晶聚合物的纖維或其混合物的纖維。合適的聚烯烴特別是乙烯和丙烯的均聚物和共聚物，其亦可含有少量的一或多種其他聚合物，特別是其它的烯烴-1-聚合物。較佳地，纖維網眼織物包括超高分子質量聚乙烯纖維。
在一個較佳的實施方案中，該製品進一步包含至少一個，較佳至少2個具有單向排列的超高分子質量聚乙烯纖維的層。以下將具有嵌入一塑膠基體材料中的單向排列纖維之層稱為單層。塑膠基體材料一詞是指將纖維保持在一起且較佳地完全或至少部分地包封纖維的材料。這種單層（本技術領域中具有通常知識者也稱為預浸體）且獲得這種單層的方法在例如揭露於EP 191306和WO 95/00318 A1中。單層可以藉由使多個纖維共平面且在一個平面上平行的方式定向來獲得，例如藉由將多個纖維或紗自一纖維捲筒框架拉過一斬刀，且在定向前、 定向期間或定向後以一習知方式用塑膠基體材料浸透纖維。在此一程序中，可以使用先前已經用塑膠基體材料以外的聚合物塗佈的纖維，以便例如在處理過程中保護纖維或者為了獲得纖維在該單層之塑膠上的更佳黏附。較佳使用未塗佈的纖維。可以在將纖維塗覆或接觸塑膠基體材料之前將纖維進行處理。此一處理包括電漿或電暈處理。
單層的重量通常從20克/平方公尺至200克/平方公尺，較佳30克/平方公尺至100克/平方公尺，較佳40克/平方公尺至75克/平方公尺變化。
通常堆疊單層，使得在疊層中兩個相繼的單層中的纖維的方向通常相差一角度α。雖然可以在廣大範圍內選擇角度α，但角度α較佳在45至135度之間，更佳在65至115度之間，且最合意在80至100度之間。在後者的較佳範圍內，特別較佳的角度α約為90度。堆疊的單層通常可商購，具有例如2,4或6個單層，且在本技術領域中被稱為正交層(cross ply)。
在正交層中，纖維網眼織物佔據了片材總體積的不同比例。然而，較佳地，纖維網眼織物包含至少約50體積％的複合材料，更佳約70體積％，且最合意為至少約75體積％，其中基體可選地佔據剩餘體積。
纖維一詞不僅包含單絲，且尤其亦包含複絲紗或平帶。平帶的寬度較佳在2毫米和100毫米之間，更佳在5毫米和60毫米之間，最合意在10毫米和40毫米之間。平帶的厚度較佳在10微米和200微米之間，更佳在25微米和100微米之間。平帶可以由一種材料的單一構件組成，但亦可包含單向定向的纖維及可選的基體材料。帶亦可經由凝膠紡絲程序製造，但也可以藉由一固相程序獲得，藉此將聚合物粉末壓實並拉伸以獲得具有所需強度之帶。
使用在可選單層中的纖維可以與織物（100）中的纖維相同，或者從物理或化學觀點係為不同並具有至少1.5GPa，較佳至少2.5GPa的強度。更合意者單層中使用的纖維具有至少3.5GPa的強度，此導致高衝擊性質和具有增加剛性的最終產品的良好組合。尤更佳者，本發明網眼織物中使用的纖維具有至少4Gpa，且最合意至少4.5GPa的強度以獲得具有良好防彈性能的產品。
以塑膠基體材料浸透單向排列的纖維可以例如藉由將一或多層塑膠膜施加到纖維平面的頂部，底部或兩側，然後將它們與纖維一起通過加熱壓力輥來達成。然而，較佳地，纖維在一個平面內以平行方式定向後，塗佈一定量的含有單層塑膠基體材料的液體物質。這樣做的優點是達成更迅速且更佳地浸透纖維。液體物質可以是例如塑膠的溶液，分散體或熔體。如果在製造單層中使用塑膠基體材料的溶液或分散體，則該方法也包含蒸發溶劑或分散劑，較佳地隨以在升高的溫度下壓縮。如此的溫度和壓力很容易由常規實驗來確定，且通常在70℃和纖維的熔化溫度之間，較佳在75-135℃之間，及在1-100巴之間，較佳在5-80巴之間，更佳在10和60巴之間。
為了製造單層，較佳地使用熱塑性基體材料的水分散體，依此在應用於HPPE纖維之後至少部分，較佳至少90重量％，更佳至少99重量％的水被蒸發。
本發明的一個特殊實施方案涉及三維成形品，其包含浸透有一Tg至少25℃的熱塑性丙烯酸樹脂的至少一HPPE纖維織物（100），該製品進一步包含至少兩個單向排列的HPPE纖維與一基體的單層。較佳地織物中的HPPE纖維或單向排列纖維是強度至少為3.5GPa的聚乙烯纖維。在一特定的實施方式中，聚氨基甲酸酯或聚醚氨基甲酸酯是基於脂族二異氰酸鹽，因為這進一步改善了產品性能，包括其顏色穩定性。這些用於單向排列纖維的塑膠基體材料的100％模數至少為3MPa。較佳地100％模數至少為5MPa。100％模數通常低於500MPa。
在另一個較佳的實施方案中，用於單向排列纖維的合適選替基體材料是Kraton® ，由一水分散體施加。Kraton® 聚合物包含100％模數為1.4MPa的苯乙烯-異戊二烯-苯乙烯（SIS）三嵌段共聚物組合物。
另一個較佳的實施方案有關於用於浸透織物（100）的合適材料，其以一乙烯及/或丙烯之官能化均聚物或共聚物，也被提及為聚乙烯，聚丙烯或其共聚物的含水懸浮液施加。其可包含各種形式的聚乙烯，乙烯-丙烯共聚物，其他具有諸如以下共聚單體的乙烯共聚物：1-丁烯，異丁烯以及與含雜原子的單體如丙烯酸，甲基丙烯酸，乙酸乙烯酯，順丁烯二酸酐，丙烯酸乙酯，丙烯酸甲酯；一般為α-烯烴和環烯均聚物和共聚物，或其摻合物。較佳其為一乙烯或丙烯的共聚物，可含有一種或多種具有2至12個碳原子的烯烴作為共聚單體，特別是乙烯，丙烯，異丁烯，1-丁烯，1-己烯，4-甲基-1-戊烯， 1-辛烯，丙烯酸，甲基丙烯酸和乙酸乙烯酯。在聚合物樹脂中不存在共聚單體的情況下，可以使用種類繁多的聚乙烯或聚丙烯，其中有線性低密度聚乙烯（LLDPE），極低密度聚乙烯（VLDPE），低密度聚乙烯（LDPE），等規聚丙烯，無規聚丙烯，間規聚丙烯或其摻合物。官能化意指聚合物是經由共聚或接枝被官能化。接枝涉聚合物主鏈主要以包含雜原子的烯屬不飽和單體化學改性，而官能共聚物涉及乙烯或丙烯與烯屬不飽和單體的共聚合反應。較佳地烯屬不飽和單體包含氧及/或氮原子。最合意之烯屬不飽和單體包含產生醯化聚合物的羧酸基團或其衍生物，特別是在乙醯化聚乙烯或聚丙烯中。較佳地，羧酸反應物選自丙烯酸，甲基丙烯酸，桂皮酸，巴豆酸和順丁烯二酸，反丁烯二酸及伊康酸反應物所組成之群組。該官能化聚合物通常包含1-10重量％的羧酸反應物或更多。這種官能化在樹脂中的存在可實質上增強樹脂的分散性及/或使為此一目的而存在的進一步添加劑諸如表面活性劑得以減少。
本發明進一步涉及一種製造具有外表面和內表面的三維成形品的方法，包含以下步驟： （a）提供至少一種抗拉強度至少為1.5GPa的聚乙烯纖維織物，該織物以基於丙烯的酸熱塑性材料浸透，藉此至少一織物形成該製品的外層，以及 （b）將來自（a）的產物與至少一個可選的單向排列纖維之單層堆疊 （c）提供一用於成形三維製品的模具， （d）可選地以一脫模劑塗覆模具表面 （e）將步驟（b）的疊層放置在模具中，接著 （f）在一90至145℃間的溫度下，較佳在一100至135℃間的溫度下，在一1至35MPa間的壓力下，於一2至60分鐘間的期間內壓縮疊層，接著 （g）冷卻至80℃以下的溫度，且將如此獲得的製品由模具中脫離
經證明使用一具有聚乙烯纖維和一基於丙烯之酸熱塑性材料為外表面的織物用於製造三維成形品是非常有益的。不僅可以使模製產品表面光滑且可使塗料附著力更好。
進一步經證明脫模劑對產品的表面外觀是有利的。另一選擇是一經塗覆模具用於製造依據本發明的三維製品。
受益於本發明的合適三維成形品包括拱頂，圓頂，半圓頂，帽子，施工頭盔，運動頭盔，摩托車頭盔，防彈頭盔和頂篷。
在圖式中，圖1表示具有外（1）和內（2）表面的三維成形品之橫截面圖，外表面包含至少一包含聚乙烯纖維的織物（100）。 測試程序
丙烯酸熱塑性材料的聚合物數平均分子量係藉由依據DIN 55672之凝膠滲透層析術在40℃下，以四氫呋喃作為溶劑而被測定，作為包裝材料且使用聚苯乙烯Mp 160-10,000,000（聚合物標準服務（PSS）DIN檢定的苯乙烯/二乙烯苯為標準品。
實例中之聚合物的玻璃轉變溫度使用以℃表示的值，該值係用微差掃描熱量法DSC（10℃/分鐘）實驗確定，採微分曲線的峰值為Tg。
基體材料的模數依據ISO 527測定。100％模數是在長度為100毫米（夾子之間的自由長度）和寬度為24毫米的膜條上測定。100％模數是在0％和100％之應變之間測量的正割模數。
拉張強度（或強度）按照ASTM D885M中之規定對複絲紗定義及測定，在25℃下使用標稱隔距長度為500毫米的纖維，50％/分鐘之十字頭速度測量。在測得的應力-應變曲線的基礎上，將模數確定為介於0.3和1％應變之間的梯度。為計算模數和強度，測得之張力除以由稱重10公尺纖維測定之織度，Gpa值採取0.97克/立方公分之密度來計算。
聚乙烯的特性黏度（IV）依據ASTM D1601，在135℃的十氫萘中測定，溶解時間為16小時，以2克/公升溶液之量的DBPC作為抗氧化劑，在不同濃度下測得的黏度外推至零濃度； 使用依據ISO 2409的'Gitterschnitt'測試進行黏合 測試。試樣以1毫米的刮擦距離以規則圖樣刮擦，依此刮擦必須在塗層中而非在基材中。將一3M黏合帶（ScotchTM ）施用在刮擦圖樣上並隨後拉下。良好的附著力意味塗層不會脫落。不良附著性會導致塗層與基材分離。
分離量以目視定量。
本發明現在將藉由下述比較實驗和實例進一步闡明，但不受限於此。實例
材料：織物 ：具有3.5GPa強度的Dyneema® UHMWPE纖維和30重量％的Neocryl® （甲基丙烯酸甲酯-丙烯酸共聚物）的平紋織物；片材的總重量為245克/平方公尺CF ：聚乙烯纖維在一個方向上和碳纖維在相對方向上的平織結構，具有31重量％的聚乙烯；一個片材的總重量為235克/平方公尺UD ：一由Dyneema® UHMWPE纖維交叉合股單層之層所組合之片材，強度為3.5GPa，18重量％基於一聚醚二醇和一脂族二異氰酸鹽的聚氨基甲酸酯樹脂；該片材的總重量為145克/平方公尺 比較實驗A：
一頭盔係藉由堆疊43片UD並在175巴的壓力和130℃的溫度下於25分鐘期間內在模具內將其模壓，接著在壓力下冷卻到至少80℃後由模具中脫離而被製造。在將疊層放入模具之前，以一脫模劑噴灑模具。
在切削頭盔邊緣殘片之後，由於一些在外表面上的細絲從切邊脫層而出現一些表面缺陷。此外由於模製程序而在外表面層中出現一些褶皺。頭盔用標準綠色塗料塗覆，且目視檢查表面外觀。可以看出表面缺陷不能由塗料減輕，缺陷在外表面仍然可見。
塗料附著力經由Gitterschnitt進行測試，且由於塗料剝落而被證明不佳。 比較實驗B：
一頭盔與比較實驗A相同地製造，42片UD和一個CF外層被模壓。
頭盔的外表面沒有褶皺發生；然而，由於在頭盔的更垂直部分中的高剪力，CF中碳纖維發生纖維斷裂。施加塗料後由於在CF外層中仍然可見的斷裂纖維，頭盔的表面外觀有缺陷。
經由Gitterschnitt的塗料附著力被證明良好，無塗料剝落發生。 例1：
一頭盔與比較實驗A相同地製造，42片UD和一個外織物層被模壓。
模壓後頭盔的外表面層無褶皺；未發生纖維斷裂且表面光滑。塗漆後表面外觀光滑無缺陷。
經由Gitterschnitt的塗料附著力證明為良好，無塗料剝落。
如實例1所例舉的，只有依據本發明的製品在施加塗料之前和之後表現出良好的表面外觀以及良好的塗料黏附性。
1‧‧‧外表面
2‧‧‧內表面
100‧‧‧織物
圖1係一具有外表面和內表面的三維成形品之橫截面圖

Claims (15)

  1. 一種具有外表面和內表面的三維成形品，該外表面包含抗拉強度為至少1.5GPa的至少一個聚乙烯纖維織物，該織物係以一基於丙烯酸的熱塑性材料浸透。
  2. 依據請求項1的製品，其中該基於丙烯酸的熱塑性材料具有至少25℃的玻璃轉變溫度。
  3. 依據請求項1或2的製品，其中該基於丙烯酸的熱塑性材料之量在4與35重量％之間。
  4. 依據請求項1-3的製品，其中該纖維是UHMWPE纖維。
  5. 依據請求項1-4的製品，其中該織物是一平紋織物(plain woven fabric)。
  6. 依據請求項1-5的製品，進一步包含至少一個單向纖維的單層。
  7. 依據請求項1-6的製品，進一步包含至少兩層單向排齊的聚乙烯纖維。
  8. 依據請求項1-7的製品，其中該具有單向排齊之纖維的單層包含一基體材料，該基體材料具有一至少3MPa的100％模數。
  9. 依據請求項8的製品，其中該基體材料是一熱塑性聚氨基甲酸酯。
  10. 依據請求項1-9的製品，其中該製品具有每平方公尺75及1250克間的面積重量。
  11. 依據請求項1-10的製品，其中該製品具有每平方公尺125及1000克間的面積重量。
  12. 依據前述請求項中任一項的製品，其中該製品是一頭盔。
  13. 依據前述請求項中任一項的製品，其中該製品是雷達天線罩。
  14. 一種用以製造一具有外表面和內表面的三維成形品的方法，包含以下步驟： （a）提供具有抗拉強度至少為1.5GPa的至少一個聚乙烯纖維織物，該織物係以一基於丙烯酸之熱塑性材料浸透，藉此至少一個織物形成該製品的該外層，以及 （b）將來自（a）的產物與至少一個可選的單向排齊纖維之單層堆疊 （c）提供一用於成形該三維物品的模具， （d）可選地以一脫模劑塗覆該模具表面 （e）將步驟（b）的疊層放置在該模具中，接著 （f）於90至135℃間的溫度下，在1與35MPa間的壓力下，在2至60分鐘之期間內壓縮該疊層，接著 （g）冷卻至一80℃以下的溫度，且使所獲製品脫離該模具。
  15. 一種以具有基於聚丙烯之熱塑性材料作為外表面的聚乙烯纖維的織物用於製造包括雷達天線罩、頭盔之三維成形品的用途。
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