TW200808672A - Sizing composition for glass fibers, sized fiber glass products, and composites - Google Patents
Sizing composition for glass fibers, sized fiber glass products, and composites Download PDFInfo
- Publication number
- TW200808672A TW200808672A TW96121361A TW96121361A TW200808672A TW 200808672 A TW200808672 A TW 200808672A TW 96121361 A TW96121361 A TW 96121361A TW 96121361 A TW96121361 A TW 96121361A TW 200808672 A TW200808672 A TW 200808672A
- Authority
- TW
- Taiwan
- Prior art keywords
- composition
- sizing composition
- weight
- glass fiber
- sizing
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Medicinal Chemistry (AREA)
- Wood Science & Technology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
200808672 九·、發明說明： 【發明所屬之技術領域】 本發明係關於玻璃纖維上漿組合物、經上漿之玻璃纖雄 產品及經至少部分地塗覆有上漿組合物之玻璃纖維加強的 材料。 【先前技術】 對諸如玻璃纖維之玻璃型表面存在多種化學處理以有助 於其加工性能及應用。在玻璃長絲或纖維形成之後及束紫 之前，可用塗料組合物或上漿組合物來處理該等玻璃長絲 或纖維，將該組合物施加至至少一部分個別長絲表面上以 保護其免於磨損且有助於加工。如本文中所用，術語"上 漿組合物”、"上漿"、"黏合劑組合物，，、，,黏合劑”或"上喂" 係指在形成後塗佈於長絲上的塗料組合物。上聚組合物ζ 在後續加工步驟，諸如纖維在經過接觸點之加工㈣中提 供保護，諸如在以下過程中：將纖維及束纏繞在成妒卷t (f〇rming package)上’乾燥水基或溶劑基上毁組合物以: 除水或溶劑，將紗線自—個卷筒缠繞至線輛上，傳 以使其置於通常用作織物中經紗之極大卷筒上，在濕潤條 件或乾燥條件中短切，粗纺成更大捆束或束組 強 之退繞或其他後續過程。 强 另外，當上毅組合物置於在纖維加強型塑料生 聚合物基質之纖維上時，該等組合物可起到雙重作" 該等應用巾m合物可提供㈣且 ㈣在 質聚合物或樹脂之間提^^B & w , 卜了在纖維與基 之_相容性。玻璃纖維 121823.doc 200808672 織織物、席子、粗紗及短切束之形式與諸如熱固性及熱塑 性，脂之樹脂-起用於加強應用。在該等應用中，可能需 要最大化纖維表面與聚合樹脂之間的相容性。 由玻璃、纖維加強之樹脂之一實例為聚g盘胺樹月旨。過去， 4有聚胺基甲_作為主要組份之上漿組合物已被用於塗 • 1用於聚醯胺加強應用中之玻填纖維。聚胺基曱酸醋顯示 出兵聚胺及其他樹脂的良好相容性，而導致複合物具有 • 所要結構性f。然而，雖然聚胺基甲酸酷可提供與某些樹 脂之優良相容性，但是使用聚胺基甲酸醋作為玻璃纖維上 漿組合物的主要組份在有些情況下儘管具有優良相容性但 卻可能並不需要。 希望提供包含降低量或極少量聚胺基甲酸酯之上漿組合 物，該等上漿組合物顯示出可與具有聚胺基甲酸酯作為主 要組份之上漿組合物相比較的物理及化學性質。另外，希 .王提供包含經塗覆有上漿組合物之玻璃纖維加強的聚合樹 _ 月旨之複合材料，該等上漿組合物包含降低量或極少量聚胺 基甲酸酯，該等複合材料展現出可與包含塗覆有具有聚胺 基甲酸酯作為主要組份之上漿組合物之玻璃纖維的複合材 料相比較的物理及機械性質。 【發明内容】 本發明之某些實施例係關於水性上漿組合物及至少部分 地塗覆有水性上漿組合物之玻璃纖維。在某些實施例中， 亦提供包括玻璃纖維加強盤聚合樹脂之複合材料。在某些 實施例中，本發明之上漿組合物可包含降低量之聚胺基甲 121823.doc 200808672 酸醋’同時該等組合物顯示出可與具有聚胺基曱酸酯作為 主要組份之上漿組合物相比較的物理及化學性質。 在某些貫施例中，上漿組合物包含以總固體計大於約6 5 重量％上漿組合物之量的至少一種聚乙烯醇及以總固體計 大於約5重量％之量的至少一種偶合劑。在另一實施例 中’聚乙烯醇可以總固體計大於約7〇重量％上漿組合物之200808672 IX. Description of the Invention: Technical Field of the Invention The present invention relates to a glass fiber sizing composition, a sized glass fiber male product, and a glass fiber reinforced at least partially coated with a sizing composition. material. [Prior Art] There are various chemical treatments for glass-type surfaces such as glass fibers to aid in their processing properties and applications. The glass filaments or fibers may be treated with a coating composition or sizing composition after glass filaments or fibers are formed and before the bundle is applied, and the composition is applied to at least a portion of the individual filament surfaces to protect them from Wear and help with processing. As used herein, the terms "sizing composition", "sizing", "gluing agent composition,,,,,,,,," A coating composition on a filament. The up-polymerizing composition ζ provides protection in subsequent processing steps, such as processing of the fibers through the contact point (4), such as in the following process: winding the fibers and bundles onto a t〇rming package 'dry water base Or solvent-based destruction of the composition to: in addition to water or solvent, the yarn is wound from a reel onto the line, passed to the extreme reel normally used as warp in the fabric, in wet conditions Or short-cut in dry conditions, roving into larger bundles or bundles of strong unwinding or other subsequent processes. In addition, when the composition is placed on the fiber of the fiber-reinforced plastic raw polymer matrix, the composition can serve as a double "the application of the composition can provide (four) and (d) in the polymer Or the resin between the ^ ^ B & w, the compatibility of the fiber and the base. Glass Fiber 121823.doc 200808672 The form of woven fabrics, mats, rovings and chopped strands, and resins such as thermosetting and thermoplastics, are used to enhance applications. In such applications, it may be desirable to maximize the compatibility between the fiber surface and the polymeric resin. An example of a resin reinforced by glass or fiber is a polyg-amine. In the past, 4 polyaminosyl-based as a primary component slurry composition has been used for coating glass filler fibers for use in polyamine-reinforced applications. The polyamine phthalic acid vinegar shows good compatibility with the polyamine and other resins, resulting in a composite having the desired structure f. However, although polyurethanes provide excellent compatibility with certain resins, the use of polyurethane as a major component of glass fiber sizing compositions, in some cases, despite excellent compatibility, May not be needed. It is desirable to provide a slurry composition comprising a reduced or minimal amount of polyurethane which exhibits physics comparable to a slurry composition having a polyurethane as the primary component. And chemical properties. In addition, the king provides a composite material comprising a glass fiber reinforced polymer tree reinforced with a sizing composition, the sizing composition comprising a reduced amount or a very small amount of a polyurethane, such The composite exhibits physical and mechanical properties comparable to composites comprising glass fibers coated with a polyurethane as a primary component. SUMMARY OF THE INVENTION Certain embodiments of the present invention relate to aqueous sizing compositions and glass fibers that are at least partially coated with an aqueous sizing composition. In certain embodiments, a composite material comprising a glass fiber reinforced disc polymeric resin is also provided. In certain embodiments, the syrup composition of the present invention may comprise a reduced amount of polyaminol 121823.doc 200808672 vinegar' while the compositions are shown to have a polyamine phthalate as the primary component The physical and chemical properties of the slurry composition compared. In certain embodiments, the sizing composition comprises at least one polyvinyl alcohol in an amount greater than about 65% by weight sizing composition by total solids and at least one in an amount greater than about 5% by weight based on total solids. Coupling agent. In another embodiment, the polyvinyl alcohol may be greater than about 7% by weight of the sizing composition, based on the total solids.
里存在。在另一實施例中，聚乙烯醇可以總固體計大於約 80重量％上漿組合物之量存在。在另一實施例中，聚乙烯 醇可以總固體計大於約90重量％上漿組合物之量存在。 在其他實施例中，上漿組合物可包含以總固體計大於約 50重1 %上漿組合物之量的至少一種聚乙烯醇、至少一種 聚胺基甲酸酯及至少一種偶合劑。在某些實施例中，聚乙 烯醇可以總固體計大於約6〇重量.％上漿組合物之量存在。 在某些實施例中，聚胺基甲酸酯可以總固體計多達約3〇重 量％上漿組合物之量存在。在某些實施例中，偶合劑可以 ~固脰at大於約5重量％上漿組合物之量存在。 根據某些實施例，上漿組合物可進一步包含包括異氰酸 酯、酸酐及丙烯酸酯之其他組份。在一實施例中，上漿組 合物可包含以總固體計大於約4〇重量％上漿組合物之量的 至少-種聚乙烯醇、至少一種偶合劑及至少一種選自由聚 胺基甲酸酯、封端純難、丙烯岐、酸酐及其组合组 成之群的其他組份。在某些實施例中，至少-種其他組份 Μ選自由聚胺基甲酸醋、封端異’氰酸酯、丙稀酸酸 肝及其組合組成之群的複數種組份。在某些實施例中，偶 121823.doc 200808672 合劑可以總固體計大於約5重量％ ±漿組合物之量存在。 在某些實施例中，至少—種其他組份可以總固體計大於約 40重量％上漿組合物之量存在。 本發明之其他實施例係關於至少部分地塗覆有本發明之 上漿組合物的玻璃纖維。至少部分地塗覆有本發明之上聚 組合物之玻璃纖維可聚集成束。在某些實施例中，玻璃纖 維束可包含至少部分地塗覆有上漿組合物之至少一根玻璃Exist. In another embodiment, the polyvinyl alcohol may be present in an amount greater than about 80% by weight of the sizing composition based on total solids. In another embodiment, the polyvinyl alcohol can be present in an amount greater than about 90% by weight of the sizing composition on a total solids basis. In other embodiments, the sizing composition can comprise at least one polyvinyl alcohol, at least one polyurethane, and at least one coupling agent in an amount greater than about 50 weight percent of the sizing composition, based on total solids. In certain embodiments, the polyvinyl alcohol can be present in an amount greater than about 6 Torr.% by weight of the total sizing composition. In certain embodiments, the polyurethane may be present in an amount of up to about 3% by weight of the total sizing composition of the sizing composition. In certain embodiments, the coupling agent can be present in an amount greater than about 5% by weight of the sizing composition. According to certain embodiments, the sizing composition may further comprise other components including isocyanates, anhydrides, and acrylates. In one embodiment, the sizing composition may comprise at least one polyvinyl alcohol, at least one coupling agent, and at least one selected from the group consisting of polyaminocarboxylic acids in an amount greater than about 4% by weight of the sizing composition based on total solids. Other components of the group consisting of esters, terminally blocked, propylene oxime, anhydrides, and combinations thereof. In certain embodiments, at least one of the other components is selected from the group consisting of polyurethane curd, blocked iso-cyanate, acetoacid liver, and combinations thereof. In certain embodiments, the couple 121823.doc 200808672 mixture may be present in an amount greater than about 5% by weight of the total solids of the slurry composition. In certain embodiments, at least one of the other components may be present in an amount greater than about 40% by weight of the total sizing composition. Other embodiments of the invention pertain to glass fibers that are at least partially coated with the sizing composition of the present invention. The glass fibers at least partially coated with the above-described polymeric composition of the present invention can be gathered into a bundle. In certain embodiments, the glass fiber bundle can comprise at least one glass that is at least partially coated with a sizing composition
纖維，該上漿組合物包含以總固體計大於約㈣量％上聚 組合物之量的至少—ίφ ψ 7 ^ ^ 種I乙烯醇、至少一種聚胺基甲酸酯 及至少一種偶合劑。 本發明另外可提供經玻璃纖維加強之聚合樹脂，其中根 :康本發明之實施例’玻璃纖維至少部分地塗覆有上漿組合 :。聚合樹脂可包含熱塑性樹脂及熱固性樹脂。在某些實 轭例中，聚合樹脂可包含聚醯胺樹脂。 在其他實施例中’本發明提供產生纖維加強型聚合複合 :::方法、。在一實施例中’ 一種產生纖維加強型聚合複 :將之方法包含：提供複數根至少部分地塗覆有本發明 :組合物之殘餘物的麵纖維、將複數根玻璃纖維併 a 口樹脂内且使聚合樹脂成型為複合物。 在隨後的本發明 等及其他實施例。 【實施方式】 之只施方式中更詳盡地描述本發明之此 為達成本說明書，之 書中的表示成份數量 的，除非另外規定，否則用於說明 反應條件等等之所有數目在各狀況 121823.doc 200808672 下皆應理解為經術語"約”修飾。因此，除非相反地指出， ^則以下„兄明書中所闡述之數字參數皆為近似值，其可視 。又法待由本發明所獲得之所要特性而變化。絲毫不願試圖 限制等效於申請專利範圍之範缚之學說的應用，各數字史 數應至少«所報導之有效數字^由普通捨人技術來解 釋0 、儘管闡述本㈣之廣大料之數字㈣及參數設定為近 <值i_特疋只例中所述之數值仍盡可能準讀地報導。然 而：任何數值固有地含有某些誤差，該等誤差由可見於： 自測試量測中之標準差引起。 應進—步注意，用於本說明書中之單數形式"-”及”該” :非明顯地且明確地限於一個對象，否則包括複數個對 之,月之某些貫施例係關於具有降低量的聚胺基甲酸酉旨 組合物。在某些實施例中’當該等上聚組合物至少 /、Tv致破璃纖維顯示出可 .生曾。土甘一， 切之上漿組合物相比較的 來^十 例中，上裝組合物可用於塗覆用於加強 I Sr树月曰中之玻璃纖維。 本發明之實施例通常在其用於破璃 之複合材料之生產、裝配及應用中上下^包含玻璃纖維 讲羽， 卜文中論述。然而， 元、白此項技術者應瞭解本發明 中。 於其他紡織材料之加工 在某些實施例中，本發明之上衆組合物包^總⑽計 121823.doc 10- 200808672 大於約6 5重量％上毁組合物之量的至少一種聚乙烯醇及以 總固體計大於約5重量％之量的至少一種偶合劑。在另一 實施例中，聚乙烯醇可以總固體計大於約70重量％上漿組 合物之夏存在。在另一實施例中，聚乙烯醇可以總固體計 大於约80重量％上漿組合物之量存在。在另一實施例中， 聚乙烯醇可以總固體計大於約9Ό重量％上漿紐合物之量存 在。 根據本發明之某些實施例，上漿組合物包含以總固體計 大於約50重量％上漿組合物之量的至少一種聚乙烤醇、至 少一種聚胺基曱酸酯及至少一種偶合劑。在某些實施例 中，聚乙烯醇以總固體計大於約60重量❶/。之量存在。在某 些實施例中，聚胺基甲酸酯可以總固體計多達約3〇重量％ 上漿組合物之量存在。在某些實施例中，偶合劑可以總固 體计大於約5重量％上漿組合物之量存在。 根據本發明之某些實施例，上漿組合物可進一步包含其 他組份，包括異氰酸酯、酸酐及丙烯酸酯。在一實施例 中，上漿組合物可包含以總固體計大於約4〇重量％上漿組 合物之量的至少一種聚乙烯醇、至少一赛 一種偶合劑及至少一The fiber, the sizing composition comprising at least -4 mega gram of vinyl alcohol, at least one polyurethane, and at least one coupling agent in an amount greater than about (four) percent by weight of the total composition. The invention further provides a glass fiber reinforced polymeric resin wherein the glass of the embodiment of the invention is at least partially coated with a sizing combination: The polymeric resin may comprise a thermoplastic resin and a thermosetting resin. In some embodiments, the polymeric resin may comprise a polyamide resin. In other embodiments, the invention provides for the production of fiber reinforced polymeric composite ::: methods. In one embodiment, a method of producing a fiber-reinforced polymeric composite comprises: providing a plurality of facing fibers at least partially coated with a residue of the present invention: a plurality of glass fibers and a resin And the polymer resin is molded into a composite. The invention and the like are described in the following. [Embodiment] The present invention is described in more detail in order to achieve the number of components in the book, and unless otherwise specified, all the numbers used to explain the reaction conditions and the like are in each state 121823. .doc 200808672 should be understood to be modified by the term "about." Therefore, unless stated to the contrary, ^ the numerical parameters set forth in the following „brothers are approximate and visible. It is also subject to the desired characteristics obtained by the present invention. In no way attempt to limit the application of the doctrine equivalent to the scope of the patent application scope, the numerical history should be at least «the effective number reported ^ is interpreted by the ordinary technology, 0, although the number of the material of this (four) is explained (4) and the parameter is set to near <value i_Specially, the value stated in the example is still reported as far as possible. However: any numerical value inherently contains certain errors which are caused by the standard deviation in the self-test measurement. It should be noted that the singular forms "-" and "the" in this specification are not explicitly and explicitly limited to one object, and otherwise include a plurality of pairs, some of the monthly embodiments are A reduced amount of a polyurethane composition. In some embodiments, 'when such agglomerated composition is at least /, Tv-induced glass fiber exhibits a good life. In the ten cases, the top-loading composition can be used to coat the glass fibers used to strengthen the I Sr tree. The embodiments of the present invention are generally used in the production and assembly of composite materials for glass breaking. And the application of the upper and lower ^ contains glass fiber feathers, discussed in Bu Wenzhong. However, the skilled person should understand the invention. Processing of other textile materials In some embodiments, the above composition of the present invention Package total (10) 121823.doc 10-200808672 greater than about 5% by weight of the composition of the at least one polyvinyl alcohol and at least one coupling agent in an amount greater than about 5% by weight based on total solids. In the examples, the polyvinyl alcohol may be based on the total solids. It is present in the summer of about 70% by weight of the sizing composition. In another embodiment, the polyvinyl alcohol may be present in an amount greater than about 80% by weight of the sizing composition on a total solids. In another embodiment, polyvinyl alcohol The amount of sizing broth may be greater than about 9% by weight total solids. According to some embodiments of the invention, the sizing composition comprises at least one of greater than about 50% by weight sizing composition by total solids. Polyvinyl alcohol, at least one polyamino phthalate, and at least one coupling agent. In certain embodiments, the polyvinyl alcohol is present in an amount greater than about 60 weight percent based on total solids. In certain embodiments The polyurethane may be present in an amount of up to about 3% by weight of the total sizing composition of the sizing composition. In certain embodiments, the coupling agent may be greater than about 5% by weight of the sizing composition by total solids. In accordance with certain embodiments of the present invention, the sizing composition may further comprise other components, including isocyanates, anhydrides, and acrylates. In one embodiment, the sizing composition may comprise greater than about 4 Torr based on total solids. Weight% sizing combination The amount of at least one polyvinyl alcohol, at least one coupling agent and at least one kind of a game
之量存在。在某些實施例中.，至少一 、約5重量％上漿組合物 一種其他組份可以總固 121823.doc 200808672 體計大於約4〇重量％上衆組合物之量存在。在其他實施例 中，至少一種其他組份可以總固體計大於約5〇重量％上漿 組合物之量存在。在另一實施例中，至少一種其他組份; 以總固體計大於或等於約6〇重量％上漿組合物之量存在。 現在轉向可包括在本發明之上裝組合物之多個里實子施例中 的組份，本發明之上漿組合物包含聚乙烯醇。The amount exists. In certain embodiments, at least one, about 5% by weight sizing composition, one other component may be present in an amount greater than about 4% by weight of the total composition. In other embodiments, at least one other component may be present in an amount greater than about 5% by weight of the total sizing composition. In another embodiment, at least one other component; is present in an amount greater than or equal to about 6% by weight of the sizing composition, based on total solids. Turning now to the components which may be included in the plurality of embodiments of the composition of the present invention, the syrup composition of the present invention comprises polyvinyl alcohol.
適用於本發明之上襞組合物中的聚乙烯醇可藉由水解或 皂化方法付生自聚乙酸乙婦醋。可得到 醇且常常根據水解度及黏度來分級。聚乙締醇供2 = 基=水解度來表徵其以烯醇產品，且術語”水解度”本文 中意欲具有一般熟習此項技術者所瞭解之相同含義。 j本中請案中，可根據水解度來表徵聚乙稀醇。在某些 只她例中，用於本發明之上漿組合物中之聚乙烯醇可超過 8〇%被水解。在其他實施例中，》乙稀醇可超過85%被水 解在其他只施例中，聚乙烯醇可超過98〇/。被水解。 、根據本备明之某些實施例，上聚組合物中之聚乙稀醇組 :可包含具有特定平均水解度之聚乙稀醇。在其他實施例 曰丄聚乙稀醇組份包含具有不同平均水解度之聚乙稀醇之 ::物。舉例而言’在一實施例中，上漿組合物中的聚乙 2組t可包含超過抓被水解之聚乙婦醇與超過9爾 之I乙稀醇的混合物。本發明之實施例涵蓋以任何組 5存在之本文中所述聚乙_混合物。 限之上聚組合物實施例中之市售聚乙稀醇的非 只歹1 可包括購自 Celanese C〇rporation 的 CElv〇L® 121823.doc 12 200808672 系列聚乙烯醇。可用於本發明之上漿組合物之多個實施例 中的CELVOL⑧系列聚乙烯醇的若干實例於表1中提供。 表Ι-CELVOL㊣系列聚乙烯醇 ’ 聚乙烯醇~~一 mPa(4%/20°C) 888S8898.98. 7 0 4 0 0 i 43.5.4. CELVOL® 205 CELVOL® 203 CELVOL® 502 CELVOL® 305 CELVOL ⑧ 103 可用於本發明之上漿組合物之多個實施例中的市售聚乙 烯醇的其他非限制性實例包含購自Kuraray Specialties Europe的MO WIOL®系歹聚乙烯醇。可用於本發明之上漿 組合物之多個實施例中的MOWIOL⑧系列聚乙烯醇的若干 實例於表2中提供。 表2-MO WIOL®系列聚乙烯醇 聚乙烯醇 水解％ 黏度 mPa(4%/20°C) MOWIOL ⑧ 4-88 87.7 4.0 MOWIOL㊣ 3-83 82.6 3.0 MOWIOL⑧ 3-98 98.4 3.5 本發明之上漿組合物之實施例可包含不同量的聚乙烯 醇。本發明之上漿組合物中的聚乙烯醇量可視若干因素而 定，該等因素諸如（但不限於）與待加強樹脂之相容性、玻 璃纖維之絨毛及飛花及束完整性、與上漿組合物之其他組 份的相容性及上漿組合物之有效黏度。聚乙烯醇可顯示出 優良的成膜性質且可向玻璃谶維提供優良之束完整性。此 外，聚乙烯醇，之極性可促進與包括聚醯胺之各種熱塑性樹 脂之相容性。 121823.doc -13- 200808672 在某些實施例中，聚乙烯醇可以總固體計大於5〇重量。/。 上聚組合物之量存在。在某些實施例中，$乙烯醇可以妙 固體計大於8〇重量％上聚組合物之量存在。在其他實施: 中，聚乙稀醇可以總固體計大於90重量％上聚組合物之量 存在。根據本發明之不同實施例，存在於上漿組合物中^ 聚乙烯醇量於表3中提供。 表3-上漿組合物中聚乙烯醇量之範圍The polyvinyl alcohol suitable for use in the top composition of the present invention can be derived from polyacetate ethyl vinegar by a hydrolysis or saponification method. Alcohols are available and are often graded according to the degree of hydrolysis and viscosity. Polyethylhydrin is characterized by a degree of hydrolysis of 2 = base = degree of hydrolysis, and the term "degree of hydrolysis" is intended to have the same meaning as understood by those of ordinary skill in the art. In the case of the present application, the polyethylene glycol can be characterized according to the degree of hydrolysis. In some of her cases, the polyvinyl alcohol used in the sizing composition of the present invention may be hydrolyzed in excess of 8 % by weight. In other embodiments, "Ethyl alcohol can be more than 85% hydrolyzed in other applications, and polyvinyl alcohol can exceed 98". Being hydrolyzed. According to certain embodiments of the present disclosure, the polyethylene glycol group in the superpolymer composition may comprise a polyethylene glycol having a specific average degree of hydrolysis. In other embodiments, the polyethylene glycol component comprises a polyethylene glycol having a different average degree of hydrolysis. By way of example, in one embodiment, the polyethylene-2 group t in the sizing composition can comprise a mixture of more than the sequestered hydrolyzed polyethylol and more than 9 liters of ethylene glycol. Embodiments of the invention encompass the polyethylenic mixtures described herein in the presence of any of the groups 5. The non-only oxime 1 of the commercially available polyethylene glycol in the above embodiment of the polymeric composition may include the CElv® L® 121823.doc 12 200808672 series of polyvinyl alcohol available from Celanese C〇rporation. Several examples of CELVOL 8 series polyvinyl alcohols that can be used in various embodiments of the sizing compositions of the present invention are provided in Table 1. Table - CELVOL series of polyvinyl alcohol 'polyvinyl alcohol ~ ~ one mPa (4% / 20 ° C) 888S8898.98. 7 0 4 0 0 i 43.5.4. CELVOL® 205 CELVOL® 203 CELVOL® 502 CELVOL® 305 CELVOL 8 103 Other non-limiting examples of commercially available polyvinyl alcohols that can be used in various embodiments of the sizing compositions of the present invention include MO WIOL® 歹 polyvinyl alcohol available from Kuraray Specialties Europe. Several examples of MOWIOL 8 series polyvinyl alcohols that can be used in various embodiments of the top syrup compositions of the present invention are provided in Table 2. Table 2 - MO WIOL® series polyvinyl alcohol polyvinyl alcohol hydrolysis % viscosity mPa (4% / 20 ° C) MOWIOL 8 4-88 87.7 4.0 MOWIOL positive 3-83 82.6 3.0 MOWIOL8 3-98 98.4 3.5 The pulp of the invention Embodiments of the composition can include varying amounts of polyvinyl alcohol. The amount of polyvinyl alcohol in the syrup composition of the present invention may depend on a number of factors such as, but not limited to, compatibility with the resin to be reinforced, vitreous of the glass fibers, and fly and bundle integrity, and The compatibility of the other components of the syrup composition and the effective viscosity of the sizing composition. Polyvinyl alcohol exhibits excellent film-forming properties and provides excellent bundle integrity to the glass. In addition, the polarity of polyvinyl alcohol promotes compatibility with various thermoplastic resins including polyamidamine. 121823.doc -13- 200808672 In certain embodiments, the polyvinyl alcohol can be greater than 5 ounces by weight based on total solids. /. The amount of the upper polymerization composition is present. In certain embodiments, the amount of ethylene vinyl alcohol present in the solids is greater than 8% by weight of the agglomerating composition. In other embodiments: the polyethylene glycol can be present in an amount greater than 90% by weight of the total composition of the superpolymer composition. According to various embodiments of the invention, the amount of polyvinyl alcohol present in the sizing composition is provided in Table 3. Table 3 - Scope of the amount of polyvinyl alcohol in the sizing composition
>65 65-70 70-80 >80 80-85 85-90 >90 90-95 95-100 ；- 1 量’重量％* 以總固體計 本發明之上漿組合物之某些實施例可包含至少—種偶合 劑。在某些實施例中，本發明之上栽組合物可包含複數: 偶合劑。適用於本發明中之偶合劑可包含可操作用於與玻 璃纖維表面反應或以其他方式被吸引，但不一定係藉由 (例如)凡得瓦爾力(Van der Waals)、偶極，極或其他分子 間相互作用而結合至玻璃表面的—或多個官能基。在玻璃 纖維與樹脂接觸之實施例中…或多種偶合劑可與樹月旨相 互作用以促進樹脂與玻璃纖維的黏著。儘管偶合劑與樹脂 之間的相互作用通常是化學反應，但根據本發明之實施例 121823.doc •14- 200808672 的偶合劑與樹月旨之間之相互作用可包含多種化學反應、靜 電相互作用或其他有吸引力的分子間相互作用。 包含複數種偶合劑之本發明之上漿組合物的實施例可提 7塗覆有上漿組合物的玻璃纖維.，該等上漿組合物可用於 乡種方法及應用卜舉例而言.，複數種偶合劑可促進與多 ， tt樹脂系統及/或其他基質（諸如各種聚酿胺樹脂及基幻之 有利的相互作用。 • 根據本發明之實施例，偶合射包含有機㈣。用於本 發明之某些實施例中的有機石夕烧可包含胺基官能石夕烧。舉 例而言，胺基官能石夕焼可用於至少部分地塗覆用於加強聚 醯胺樹月旨之玻璃纖維。可用於本發明之某些實施例中的胺 基官能矽烷之兩個實例為胺基烷基_三烷氧基矽烷及二胺 基石夕烧。用於本發明之上漿組合物之某些實施例中的胺基 烧基-三烧氧基砍烧的非限制性實例包含胺基丙基三甲氧 基石夕烧及γ-胺基丙基三乙氧基石夕炫。市售丫_胺基丙基三乙 藝 氧基石夕烧包含來自DeGussa AG (Duseld〇rf，^国㈣之 dyNASYLAN AME0及來自 〇si Speciames …邮。㈣， N.Y)之A-1100。可用於上漿組合物之某些實施例中的二胺 基矽烷之非限制性實例包括Ν_β(胺基丁基）γ_胺基丙基甲基 三甲氧基矽烷（DYNASYLAN 11 89)、Ν_β(胺基乙基）γ_胺基 丙基三曱氧基矽烷及Ν-β(胺基乙基）γ_胺基丙基三甲氧基矽 烷（DYNASYLAN DAMO) 〇 本發明之上漿組合物.中的'偶合劑之量及類型可視多個因 素而定，該等因素諸如（但不限於）偶合劑對於特定樹脂的 121823.doc 15 200808672 親和性及偶合劑與上漿組合物之其他組份的相容性。表4 提供可用於本發明之上漿組合物之各個實施例中的偶合劑 量的例示性範圍。 表4 -上漿組合物中偶合劑量之範圍 _____1 - ^ ~ 5-10 _ <15 __ *以總固體計 在某些實施例中，本發明之上漿組合物可包含至少一種 聚胺基甲酸酯。聚胺基甲酸酯通常藉由多官能異氰酸酯與 醇之反應經由形成胺基甲酸酯鍵而合成。用於本發明之實 施例中的聚胺基曱酸酯可由脂族、環脂族或芳族多官能異 氰酸酯產生。舉例而言，由脂族異氰酸酯所產生之聚胺基 甲酸酯在某些實施例中可顯示出所要顏色特徵。在某些.實 施例中，聚胺基甲酸酯可以水性分散液形式引入本發明之 上漿組合物内。 在某些實施例中，聚胺基甲酸酯組份包含單一聚胺基曱 酸酯種類。在其他實施例中，本發明之上漿組合物之聚胺 基甲酸酯組份可包含聚胺基甲酸酯的混合物。本發明之某 些實施例涵蓋以任何組合存在之本文中所述聚胺基曱酸SI 混合物。 用於本發明之上漿組合物中的聚胺基曱酸酯之非限制性 實例包含 WITCOBOND⑧ 60X、WITCOBOND® W-213、 WITCOBOND® 234 、 WITCOBOND ⑧ W-290H 及 121823.doc -16- 200808672 WITCOBOND® W-296 (購自 Crompton Corporation->65 65-70 70-80 > 80 80-85 85-90 > 90 90-95 95-100 ;- 1 Amount '% by weight* Certain implementations of the syrup composition of the present invention based on total solids Examples may include at least one coupling agent. In certain embodiments, the top compositions of the present invention may comprise a plurality of: coupling agents. Coupling agents suitable for use in the present invention may comprise operable to react with or otherwise be attracted to the surface of the glass fiber, but not necessarily by, for example, Van der Waals, dipole, or Other intermolecular interactions that bind to the glass surface - or multiple functional groups. In the examples where the glass fibers are in contact with the resin, or a plurality of coupling agents may interact with the tree to promote adhesion of the resin to the glass fibers. Although the interaction between the coupling agent and the resin is generally a chemical reaction, the interaction between the coupling agent according to the embodiment 121823.doc •14-200808672 and the tree can include various chemical reactions and electrostatic interactions. Or other attractive intermolecular interactions. An embodiment of the syrup composition of the present invention comprising a plurality of coupling agents can provide a glass fiber coated with a sizing composition. The sizing compositions can be used in rural methods and applications. A plurality of coupling agents can promote advantageous interactions with multiple, tt resin systems and/or other substrates such as various polyamine resins and genomics. • According to an embodiment of the invention, the coupling comprises organic (IV). The organoceramics in certain embodiments of the invention may comprise an amine functional stone. For example, the amine functional cerium can be used to at least partially coat the glass fibers used to strengthen the polyamine tree. Two examples of amino-functional decane useful in certain embodiments of the invention are aminoalkyl-trialkoxydecanes and diamine-based smolderings. Certain of the syrup compositions useful in the present invention. Non-limiting examples of the amine-alkyl-oxyalkyloxy chopping in the examples include aminopropyltrimethoxy-zetan and gamma-aminopropyltriethoxy-xanthine. Commercially available oxime-amino groups Propyl triethyl ethoxylate is contained from DeGussa AG (Duseld〇 Rf, ^ country (d) dyNASYLAN AME0 and from 〇si Speciames ... (A), NY) A-1100. Non-limiting examples of diamino decane useful in certain embodiments of the sizing composition include Ν_β ( Aminobutyl) γ-aminopropylmethyltrimethoxydecane (DYNASYLAN 11 89), Ν_β(aminoethyl)γ-aminopropyltrimethoxy decane and Ν-β (aminoethyl) γ_Aminopropyltrimethoxydecane (DYNASYLAN DAMO) The amount and type of 'coupling agent' in the syrup composition of the present invention may depend on a number of factors such as, but not limited to, The compatibility of the mixture with the specific resin for 121823.doc 15 200808672 and the compatibility of the coupling agent with the other components of the sizing composition. Table 4 provides coupling doses that can be used in various embodiments of the sizing composition of the present invention. Illustrative range. Table 4 - Range of coupling doses in the sizing composition _____1 - ^ ~ 5-10 _ <15 __ * In terms of total solids, in certain embodiments, the syrup composition of the present invention may comprise At least one polyurethane. Polyurethanes are typically made from polyfunctional isocyanates and alcohols. It should be synthesized via the formation of a urethane linkage. Polyaminophthalic acid esters useful in embodiments of the invention may be derived from aliphatic, cycloaliphatic or aromatic polyfunctional isocyanates. For example, from aliphatic isocyanates The resulting polyurethane may exhibit desirable color characteristics in certain embodiments. In certain embodiments, the polyurethane may be incorporated into the top composition of the present invention in the form of an aqueous dispersion. In certain embodiments, the polyurethane component comprises a single polyamino phthalate species. In other embodiments, the polyurethane component of the syrup composition of the present invention can comprise a mixture of polyurethanes. Some embodiments of the invention encompass the polyamine citric acid SI mixtures described herein in any combination. Non-limiting examples of polyaminophthalic acid esters useful in the slurry compositions of the present invention include WITCOBOND8 60X, WITCOBOND® W-213, WITCOBOND® 234, WITCOBOND 8 W-290H and 121823.doc -16- 200808672 WITCOBOND ® W-296 (available from Crompton Corporation-
Unn*oyal Chemical)。用於本發明之上裝.組合物中的聚胺基 甲酸S旨之其他非限制性實例包括BAYbqnd⑧PU-130、 BAYBOND® PU-4GGS及 BAYBOND® XP-7G55 (購自 BayerUnn*oyal Chemical). Other non-limiting examples of polyaminocarboxylic acid S used in the topcoat compositions of the present invention include BAYbqnd8PU-130, BAYBOND® PU-4GGS, and BAYBOND® XP-7G55 (available from Bayer).
Material Science) ° 聚胺基甲酸酯先前已用作上漿組合物中之成膜劑，該等 上漿組合物用於至少部分地塗覆用於諸如加強聚醯胺樹脂 φ. 之加強應用之玻璃纖維。在該等上漿組合物中，聚胺基曱 酸酯通常為除水以外以最大量存在的組份。本發明之某些 貫施例係關於聚胺基甲酸酯並不代表主要組份（例如，諸 如聚乙烯醇之另一組份以較大量存在）之上漿組合物。在 某些實施例中，聚胺基甲酸酯代表次要組份（例如，不是 上漿組合物中之最大非水組份）。因為聚胺基甲酸酯可能 是昂貴的，所以使用較廉價之組份以用於減少特定應甩的 上漿組合物中之所需聚胺基甲酸酯量可能是合乎需要的。 _ 因此，在包含聚胺基曱酸酯之上漿組合物之實施例中， 可使用不同量之聚胺基甲酸酯。可用於本發明之上漿組合 物之某些實施例中的聚胺基甲酸酯的量可視多種因素而 - $ ’該等因素包括但不限於與上漿組合物中其他組份之相 .繼聚胺基甲酸酉旨之成本，以使上讓玻璃纖維為一種商 業可行之產品。在某些實施例中，聚胺基甲酸醋可以總固 體計多達約30重量％上衆組合物之量存在。表$表示可用 於包含聚胺基甲酸酉旨之本發明之上蒙組合物之不同實施例 中的基甲酸|旨量的例示性範圍。 121823.doc 17 200808672 表5-上漿組合物中聚胺基甲酸酯量之範圍Material Science) ° Polyurethanes have previously been used as film formers in sizing compositions for at least partial coating for reinforcement applications such as reinforced polyamide resin φ. Glass fiber. In such sizing compositions, the polyamino phthalate is typically the component present in maximum amount other than water. Some embodiments of the present invention relate to polyurethane compositions which do not represent a major component (e.g., such that another component of polyvinyl alcohol is present in greater amounts). In certain embodiments, the polyurethane represents a minor component (e.g., not the largest non-aqueous component of the sizing composition). Because polyurethanes can be expensive, it may be desirable to use less expensive components for reducing the amount of polyurethane required in a particular sizing composition. Thus, in embodiments comprising a polyamine phthalate oversize composition, different amounts of polyurethane can be used. The amount of polyurethane that can be used in certain embodiments of the syrup compositions of the present invention can be varied depending on a number of factors - including, but not limited to, the other components of the sizing composition. Following the cost of urethane, the glass fiber is a commercially viable product. In certain embodiments, the polyurethane urethane may be present in an amount of up to about 30% by weight of the total composition of the total solids. Table $ represents an exemplary range of carboxylic acid used in various embodiments of the above-described top composition of the present invention comprising a polyurethane. 121823.doc 17 200808672 Table 5 - Scope of the amount of polyurethane in the sizing composition
以總固體計 在某t 5轭例t，本發明之上漿組合物可進一步包含諸 如封端異氰酉夂®曰之異氰酸酯。如本文中所用，冑語"封端 異氰fee S日係“如下任何異氰酸酯，其中異氰酸_基已盘 ，合物反應以便所得封端異氰伽在饥下對於活性氫穩 定’且在上漿組合物中所存在之任何成膜劑起反應之溫度 以下的溫度下盥活w与 /、 虱反應。在某些實施例中，可聯合使 用兩種或兩種以上異氰酸酯。 ° 在心有機異氰酸酯之製備中，可使用任何適合之有機 聚異乳酸_。可在（諸如但不限於）上漿組合物乾 擠出期間，藉由臂里皇純 ^ I，、亂酸酯與上漿組合物中成膜劑形成交 聯的犯力、稭由聚異氰酸酯與聚醯胺樹脂相互作用的能力 及/或藉由聚異氰酸酿.與上I组合物之其他 的能力來確定谪人夕女Μ ^ 口 機聚異氰酸酯。適合之有機聚異氰 S欠i曰之非限制性實彳I发 酸醋、四亞甲基二里：合物’諸如三亞甲基二異氰 A a _ 土 /、氘酸酯、六亞甲基二異氰酸酯及亞丁 ί^ΓδΙ或酮二異氰賴1PD〜環伸烧基化 =一嗓M 己燒二異氰酸酷·；芳族化合物，諸如對 ;脂芳族化合物’諸如4,4:二伸苯基曱 121823.doc -18- 200808672 烷二異氰酸醋、2,4-甲苯二異氰酸g旨或2,6_甲苯二異氰酸 酉旨或其混合物。適合之高碳聚異氰酸_之非限制性實例包 ^諸如三苯m，4，，4"_三異氰酸§旨及2,4,6_三異氣酸醋甲 苯之三異氰酸醋。實踐本發明時可使用的有機聚異氯酸醋 之其他實例包括縮二脲類型之有機聚異氰酸酯，及用於二 聚或三聚反應產生四員、五員或六員環之有機聚異氰酸 酉旨。六員環中’可能提及衍生自多種二異氰酸酉旨單獨、多 種二異氰酸I旨與其他異氰酸酯（例如單異氰酸酯、二昱氰 酸醋或聚異氰酸酉旨）-起或與二氧化碳一起進行同質4 或異質三聚作用之異三聚氰酸環。在該後者狀況下，來自 異二聚氰酸環之氮被氧替代。 =^封端劑可藉由防止封端異氰酸㈣反應直至到達 ρρ ,. . ^ , 了為適合之封端劑的化合物之非 限制性貝例包括（但不限於） 甲基乙基酮肟、丙明肟及 因Μ 、諸如…酿胺之内醯胺類及吼唾類。 因為相對於經醇封端之聚異氰酸顆而言二 類及吡唑類封端之聚異氰酸铲 ' i胺 反應，所以可能需要使曰内更低溫度下解除封端且 在實施例中，封端显、仏胺類及D比咕類。 叫打Chemical之… 包含以NAJ_1058形式來自 乳液。 8 '已内釀胺封端之脂族聚異氛酸酉旨水性 上漿組合物中的封端異氰 等因素諸如（但不限於u+ * 了視右干因素而疋，該 相容性、用於上襞組合二==組合物之其他組份的 物甲之任何成膜劑之類型及數量及 121823.doc -19- 200808672 上漿組合物的右*私& 里㈣… 舉例而言’上漿組合物中之封端 異亂酸酯量的下限 玎鳊 度之有效量來確〜1 維持加㈣熱塑性樹脂強 ,^0a 疋表6表示可用於包含封端異氰酸酯之 本發明之上漿組合物 ^ y k ^ 物之不同貫施例中的封端異氰酸酯量的 例示性範圚。 ^ 表6-上漿組合物中封端異氛酸醋量之範圍The syrup composition of the present invention may further comprise, for example, a blocked isocyanide® oxime isocyanate in a t 5 yoke t. As used herein, the slang "blocking isocyanide feel S Japanese "is any isocyanate in which the isocyanate has been reacted so that the resulting blocked isocyanide is stable to active hydrogen in the hunger" Any of the film formers present in the sizing composition will react with the hydrazine at temperatures below the temperature at which the reaction is carried out. In certain embodiments, two or more isocyanates may be used in combination. In the preparation of the organic isocyanate, any suitable organic polyisolactic acid can be used. It can be used, for example, but not limited to, during the dry extrusion of the sizing composition, by means of the arm, and the sizing and sizing. The film forming agent in the composition forms a cross-linking force, the ability of the straw to interact with the polyisocyanate and the polyamide resin, and/or the ability to be brewed by polyisocyanic acid and the other components of the above I composition to determine the deafness夕女Μ ^ Mouth machine polyisocyanate. Suitable for organic polyisocyanate S 曰 i曰 non-restrictive 彳 I acid vinegar, tetramethylene di ali: compound 'such as trimethylene diisocyan A A _ soil /, phthalate, hexamethylene diisocyanate and butyl Γ δ Or keto diisocyanide 1PD~cycloalkylation = one 嗓M hexane diisocyanate; aromatic compound, such as a pair; a fatty aromatic compound such as 4,4: diphenyl phenyl 121823. Doc -18- 200808672 Alkyl diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate or a mixture thereof. Suitable for high carbon polyisocyanate A limiting example includes triisoisocyanate such as triphenyl m,4,,4"_triisocyanate § and 2,4,6-triiso-gas oleate toluene. Organic which can be used in the practice of the present invention Other examples of polyisochloric acid vinegars include biuret type organic polyisocyanates, and organic polyisocyanates for dimerization or trimerization to produce four, five or six member rings. 'It may be mentioned that a variety of diisocyanates derived from a variety of diisocyanates are intended to be combined with other isocyanates (for example monoisocyanates, diisocyanate or polyisocyanates) or with carbon dioxide. Homogeneous 4 or heterotrimeric heterocyanuric acid ring. In this latter condition, the nitrogen from the iso-di-cyanate ring is replaced by oxygen. Stopping the isocyanate (iv) reaction until reaching ρρ, . . . , a non-limiting example of a compound that is a suitable blocking agent includes, but is not limited to, methyl ethyl ketone oxime, cumming oxime, and ruthenium For example, the amines and terpenoids of the amines are because the two types of pyridinium-terminated polyisocyanate 'i amine react with respect to the alcohol-terminated polyisocyanate. It may be desirable to deblock the lower temperature in the crucible and in the examples, the end caps, the guanamines and the D oxime class. Called Chemical... Contains the form of the emulsion in the form of NAJ_1058. The end of the aliphatic polyiso-acidic acid in the aqueous sizing composition of the blocked isocyanide and other factors such as (but not limited to u + * has the right to dry factors and 疋, the compatibility, for the upper sputum combination two = = type and amount of any film former of the other components of the composition and 121823.doc -19- 200808672 sizing composition of the right * private & (4) ... For example, in the sizing composition The effective amount of the lower limit of the amount of blocked isocyanate is determined to be ~1. The addition of (four) thermoplastic resin is strong, ^0a 疋 Table 6 indicates that Comprising a sizing composition of the present invention diisocyanate blocked isocyanate ^ y k ^ Fan Hui exemplary blocked isocyanate was consistent amounts of different embodiments of the. ^ Table 6 - Scope of the amount of blocked isocyanate in the sizing composition
以總固體計 本^明之上漿組合物之某些實施例可進一步包含至少一 種們α Θ1潤滑劑可用於減少玻璃纖維之間的長絲間磨 相，且減少加工期間玻璃纖維與接觸點之間的磨損。潤滑 鈉可包έ與上漿組合物之其他組份相容的任何陽離子、陰 離子或非離子玻璃纖維潤滑劑或其混合物。用於本發明之 上聚組合物中的潤滑劑之非限制性實例可包括脂肪酸與聚 乙烯亞胺之縮合物及經醯胺取代之聚乙烯亞胺。在某些實 施例中’本發明之上漿組合物可包含：包含部分醯胺化之 聚乙烯亞胺之第一潤滑劑，諸如購自Henkel Corporation (Kankakee，111.)或 Congis Corporation (Cincinnati Ohio)之 EMERY® 6717及包含羧酸與氧化乙烯之共聚物的第二潤 滑劑’诸如購自 Akzo Nobel (Netherlands)之 DAPRAL® GE202。在某些實(施例中，上漿組·合物可包含此等潤滑劑 121823.doc -20- 200808672 中之任一者。 包括在上漿紐人^ 1 H。物中的潤滑劑量可视一％ 定，該等因素諸如G A夕種因素而 足以促、隹姻、“ 不限於）足以減少長絲間磨損之量、 疋乂促進製造择竹由 入私^ 作中破璃纖維的加工性能之量及盥上 合物之其他組份相容之量。在某些實施例中，本^二 水組2物中的潤滑劑量可以總固體計小於㈣重量％Some embodiments of the slurry composition of the present invention may further comprise at least one α Θ 1 lubricant which can be used to reduce the interfiber filament phase between the glass fibers and to reduce the glass fibers and the contact points during processing. Between wear and tear. Lubricating Sodium may be any cationic, anionic or nonionic glass fiber lubricant or mixture thereof that is compatible with the other components of the sizing composition. Non-limiting examples of the lubricant used in the above polypolymer composition of the present invention may include a condensate of a fatty acid and a polyethyleneimine and a polyethyleneimine substituted with a decylamine. In certain embodiments, the syrup composition of the present invention may comprise: a first lubricant comprising a partially amided polyethyleneimine, such as from Henkel Corporation (Kankakee, 111.) or Congis Corporation (Cincinnati Ohio). EMERY® 6717 and a second lubricant comprising a copolymer of a carboxylic acid and ethylene oxide such as DAPRAL® GE202 available from Akzo Nobel (Netherlands). In some embodiments, the sizing composition may comprise any of these lubricants 121823.doc -20- 200808672. The amount of lubricant included in the sizing newcomer 1 H may be Depending on the factors, such factors as GA factors can be sufficient to promote, marry, "not limited" enough to reduce the amount of wear between the filaments, and promote the processing of glass fibers from the manufacturing process. The amount of performance and the amount of other components of the ruthenium complex are compatible. In certain embodiments, the amount of lubricant in the dimethylidene group 2 may be less than (four) weight percent based on total solids.
=貫施例中’潤滑劑可以總固體計多達約5重量％之量 在某些實施例中’本發明之上漿組合物可進一步包含諸 如酸酐、丙烯酸酯或其組合之其他組份。 v 如本文中所用之_可包含酸酐之單體、募聚及多聚形 式以及其水解及中和形式。舉例而言，在—實施例中，酸 昕可包含以單體形式存在之順丁稀：_或衣康酸肝 (itaconic anhydride)。在其他實施例中，酸酐可包含且有 -或多個酸酐部分之寡聚物及聚合物。在該等實施射， 酸肝部分可併人寡聚物及聚.合物之主鏈中，或另外可為偶 合至主鏈之取代基。在某些實施例中，順丁烯二酸肝及/ 或衣康酸酐可與一或多個其他單體共聚合，產生酸酐寡聚 物或聚合物。在某些實施例中，酸酐可包含來自Lindau Chemicals, Inc·之 MALDENE 286及來自 Zeeland Chemicais Inc之 ZEMAC E400。 如本文中所用之丙烯酸酯可包含包括丙烯酸之丙烯酸酯 的單體，、寡聚及多聚形式以及其中和形式。舉例而言，在 一實施例中，丙烯酸酯·可包含曱基丙烯酸酯及曱基丙烯酸 121823.doc -21 · 200808672 甲酉曰單體在其他實施例中，丙稀酸_可包含具有__或少 個丙烯酸部分之寡聚物及聚合物。在該等實施例中，丙： n刀可併人寡聚物或聚合物之主鏈中，或另外可為偶合 至主鏈之取代基。 酸酐及丙烯酸醋通常可改良纖維加強型熱塑性樹脂之抗 水解性。纟某些實施例中，酸酐、丙烯酸酯 總固體計多達約75重量％上漿組合物之量存在 上浆組合物中。在其他實施例中，酸酐、丙烯_或其、= ::二：體計大於約4°重量%上漿組合物之量存在於本 :1衆組合物中。在另-實施例中，酸肝、丙稀酸醋 5八組合可以總固體計大於約50重量％上漿組合物之旦疒 在於本發明之上浆組合物中。在另—實施例中，酸軒里 烯酸酯或其組合可以總固體計大於或等於約崎量 組合物之量存在於本發明之上漿組合物中。 本發明亦提供包含至少部分地塗覆有本發明之上漿组人 物的玻璃纖維之玻璃纖維束。本發明之實施例涵蓋包二 至少部分地塗覆有本發明之上襞組合物的破璃纖維 玻璃纖維束。根據本發明之實施例，用於至少部分地冷 覆玻璃纖維的上浆組合物可包含任何組合及任何量之與2 文中所述一致的上漿組合物組份。 一 、在某些實施例中’本發明之玻璃纖維束包含至少一根至 夕^ 7刀地塗覆有上漿組合物之玻璃纖維，該上漿組合物勺 含以總固顧大於物重量％上漿組合物之量的至少 聚乙稀醇及以總固體計大於約5重量％上漿組合物之量的 121823.doc -22- 200808672 至少 '一種偶合劑。 在某些實施例中，本發明之玻璃纖維束可包人 一 至少部分地塗覆有上漿組合物之玻璃纖維，該上漿組合物 包含以總固體計大於約50重量％上漿組合物之量2至=一 種聚乙烯醇、至少一種聚胺基甲酸，旨及至少—種偶合劑。 待上漿之玻璃纖維類型可由多個因素來確定，諸二伸 不限於)上漿玻璃纖維之預定最終用途。在某些 中，玻壤纖維可為任何類型，只要破璃纖維與熱塑性或熱 樹脂相容。在一實施例中，玻璃纖維可用於加強聚醯 月女樹脂，產生纖維加強型熱塑性複 ,,.^ 初適用於加強熱塑 十或熱固性樹脂之玻璃纖維包括短切型纖維及諸如連％ 紗之長纖維。用來加強熱塑性樹脂之短切型破填纖维：長 ==徑可由多個因素來確p該等因素諸如（但不限… 备玻璃纖維與熱塑性樹脂熔融捏合時容易處㈣、玻_ 及玻璃纖維分散能力。在某些實施例中，玻 度可為大於—。在其他實施例中，玻璃纖維 声可人 在其他貫細例中，破璃纖維之長 •^〇"M3.175mm(l/8^^12.7mm(1/24k^〇 H =實施例中，玻璃纖維之平均直徑可為大於8㈣。 〜貫施财’麵纖維之平均直徑可為小於25叫。 用::發明中之玻璃纖維之非限制性實例可包括由可 t=組合物所製備的玻璃'纖維，該等可纖維化玻璃 ”咖“ &破場”、”A_玻璃”、"C_玻璃，'、，，s-玻璃”、 玻璃，，（耐腐純玻璃）及其不含氟‘及/或蝴之衍生 121823.doc -23- 200808672 物。玻璃纖維之典型調配物揭示於K. Lowenstein，Tk Manufacturing Technology Manufacturing Technology of (^〇77".仙<9似 G/au mers (第 3版，1993)中。 本發明亦提供玻璃纖維加強型樹脂組合物及產生玻璃纖 、准加強型树知組合物之方法。根據本發明之實施例，用於 至少部分地塗覆用於樹脂加強應用的玻璃纖維的上漿組合 物可包含任何組合及任何量之與本文中所述一致的上漿組 合物組份。 根據本發明之實施例，經玻璃纖維加強之樹脂組合物可 包含熱塑性樹脂及/或熱固性樹脂。熱塑性材料之非限制 性貫例包含聚稀烴、聚縮酸、聚酿胺、聚壤酸酯、聚苯乙 烯、苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯苯乙烯（ABS) 共？κ物、聚氣乙烯、聚對苯二曱酸乙二醇酉旨、聚對苯二甲 酸丁 一醇醋及熱塑性樹脂之摻和物。 本發明之玻璃纖維之某些實施例可尤其適於加強聚醯胺 樹脂。在某些實施例中，經玻璃纖維加強之聚醯胺樹脂可 包含耐綸6、耐綸6:6、耐綸6:12、耐綸4:6、耐綸6:10、耐 綸12、聚醯胺6T(聚六亞甲基對苯二甲醯胺）、聚醯胺61(聚 /、亞甲基間苯一曱酿胺）或其混合物。可基於樹脂之機械 特徵、耐熱性、玻璃轉移溫度、成形性及模塑外觀來選擇 特定聚酸胺樹脂。 聚舊胺熱塑性樹脂可經脂肪酸金屬鹽潤滑，諸如具有9 個或9個以上碳原子之脂肪酸的鈉，鋰、鈣、鎂、鋅或鋁 鹽，忒等月曰肪酸諸如癸酸、月桂酸、肉豆蔻酸、軟脂酸、 121823.doc -24- 200808672 更月曰酉夂、一十一烷酸、蠟酸、褐煤酸、蜂花酸、油酸及芥 次另外可如合使用兩種或兩種以上脂肪酸金屬鹽。 方酉夂至屬孤可用於減少擠壓機中熱塑性聚醯胺樹脂及上 聚破璃纖維之熔融捏合期間的扭力、可用於改良樹脂之脫 模特徵或用於改良射出成形期間樹脂之熔融流。在一實施 ’中使用硬月日^^來潤滑經上漿玻璃纖維加強之聚醯胺 樹脂。如結合本發明之上漿組合物所述之已内醯胺封端異 氰酸酷可改良硬脂酸鈣潤滑之聚醯胺樹脂的強度。 在某些貫施如j巾，纖維加強型樹脂組合4匆包含聚酿胺樹 月曰及至少部分地塗覆有本發明之上漿組合物之殘餘物的玻 璃纖維。在某些實施例中，上漿組合物包含聚乙烯醇及偶 。劑，其中聚乙烯醇以總固體計大於約5〇重量％上漿組合 物之里存在。在其他實施例中，聚乙烯醇可以總固體計大 於約90重量％上漿組合物之量存在。在某些實施例中，上 漿組合物亦可包含聚胺基甲酸酯。 在某些實施例中，產生纖維加強型樹脂組合物之方法包 s ·提供至少部分地塗覆有本發明之上漿組合物之殘餘物 的複數根玻璃纖維、將複數根玻璃纖維併入樹脂内且使樹 脂成形為複合物。在某些實施例中，上漿組合物包含聚乙 烯醇及偶合劑，其中聚乙烯醇以總固體計大於約5〇重量％ 上漿組合物之量存在。在某些實施例中，1乙烯醇以總固 體計大於90重量_%上漿組合物之量存在。根據本發明之實 知例，在產生纖維加強型樹脂組合物之方法中用小立 、 、主夕部 么地塗覆玻璃纖雄的上漿組合物可包含任何組合及任何旦 121823.doc -25- 200808672 之與本文：所述-致的上漿組合物組份。 可使用熟習此項技 組份來製備本發明之將的任何適合方法’藉由添加 依序添加，或-可=物。舉例而言，組份可相互 物。 ，、了預稀釋於載劑中然後組合形成上漿組合 上裝組合物可藉由孰 於玻璃输雜 “、、白此項技★者已知之適合方法施加 滾筒二但不限於)使破璃纖維與諸如 方式。可：：益之靜態或動態施料器接觸或噴霧或其他 漿玻璃纖唯' 施料方式、待上漿玻璃纖維之特徵及上 水坂增纖維的預定用会 泛範 ^ °物中之非揮發性組分的總濃度。 在某二貫施例中，上將έ入 之轤维出刑π 水，，且5物可在熟習此項技術者已知 =成型#作期間’以單一步驟施加至 些貫施例中，在上喈細人舲 长呆 著乾燥纖維以移除載劑:“續破璃纖維之後，接 在某些非限制性實施例中，上漿組合物可為多部分上漿 組合物，以致於以複數個步驟將上 由 維上。與彳y 口物知加於玻璃纖 勺入A 在一非限制性實施例中，上漿組合物可 :::部分上漿組合物，而該上漿組合物以兩步法施加。 组=7二一實例中’第一部分上聚組合物可包含錢 及潤）月别組份’其在諸如纖維形成期間的第一步驟中 施加。第二部分上聚組合物可包含聚乙歸醇組份、可為植 合物部分之任何聚胺基曱酸酿及/或另外之砂燒組份，且 可在开> 成玻璃纖維束之後於第二步驟中施加。 121823. doc -26- 200808672 在某些實施例中玻璃纖維束可切短。玻璃纖維束在某些 實施例中可在乾燥之前切短或在其他實施例中可在乾燥之 後切短。使用熟習此項技術者已知之技術可切短連續纖維 玻璃束，該等技術包括但不限於直接切短法及遠程切短 法。The lubricant may be present in an amount of up to about 5% by weight based on total solids. In certain embodiments, the top composition of the present invention may further comprise other components such as anhydrides, acrylates or combinations thereof. v As used herein, may include monomers, polycondensation and multimerization forms of anhydrides, as well as hydrolyzed and neutralized forms thereof. For example, in an embodiment, the guanidine may comprise cis-butane in the form of a monomer: _ or itaconic anhydride. In other embodiments, the anhydride may comprise oligomers and polymers having - or more anhydride moieties. In such a reaction, the acid liver portion may be in the main chain of the human oligomer and the polymer, or may additionally be a substituent coupled to the main chain. In certain embodiments, the maleic acid liver and/or itaconic anhydride can be copolymerized with one or more other monomers to produce an anhydride oligomer or polymer. In certain embodiments, the anhydride may comprise MALDENE 286 from Lindau Chemicals, Inc. and ZEMAC E400 from Zeeland Chemicais Inc. The acrylate as used herein may comprise monomers comprising acrylates of acrylic acid, oligomeric and polymeric forms, and neutralized forms. For example, in one embodiment, the acrylate may comprise a methacrylate and a methacrylic acid 121823.doc -21 · 200808672 a formazan monomer. In other embodiments, the acrylic acid _ may comprise __ Or a small amount of oligomers and polymers of acrylic acid. In such embodiments, the C: n-knife can be in the backbone of the oligomer or polymer, or alternatively can be a substituent coupled to the backbone. The acid anhydride and acrylic vinegar generally improve the hydrolysis resistance of the fiber-reinforced thermoplastic resin. In certain embodiments, the anhydride, acrylate total solids are present in the sizing composition in an amount up to about 75% by weight of the sizing composition. In other embodiments, the amount of the sizing composition greater than about 4% by weight of the anhydride, propylene or its =: 2:2 is present in the present invention. In another embodiment, the combination of sour liver and acetoacetate 5 can be greater than about 50% by weight of the total solids of the sizing composition in the top composition of the present invention. In another embodiment, the acid decyl acrylate or combination thereof may be present in the top slurry composition of the present invention in an amount greater than or equal to the amount of the total solids of the composition. The present invention also provides a glass fiber bundle comprising glass fibers at least partially coated with the above-described pulp group of the present invention. Embodiments of the present invention contemplate a bundle of glass fiberglass fibers that are at least partially coated with the top composition of the present invention. In accordance with an embodiment of the present invention, the sizing composition for at least partially cooling the glass fibers can comprise any combination and any amount of the sizing composition component consistent with that described in 2. 1. In certain embodiments, 'the glass fiber bundle of the present invention comprises at least one glass fiber coated with a sizing composition up to 7 knives, the sizing composition scoop containing a total weight greater than the weight of the material % sizing composition of at least a polyethylene glycol and an amount of greater than about 5% by weight total sizing composition of 121823.doc -22-200808672 at least one coupling agent. In certain embodiments, the glass fiber bundles of the present invention can comprise a glass fiber at least partially coated with a sizing composition, the sizing composition comprising greater than about 50% by weight sizing composition by total solids An amount of 2 to = a polyvinyl alcohol, at least one polyaminocarboxylic acid, and at least one coupling agent. The type of fiberglass to be sized can be determined by a number of factors, not limited to the intended end use of the sizing fiberglass. In some cases, the glass fiber may be of any type as long as the glass fiber is compatible with the thermoplastic or thermoplastic resin. In one embodiment, the glass fiber can be used to reinforce the polyether resin, to produce a fiber-reinforced thermoplastic composite, and the glass fiber that is initially suitable for reinforcing thermoplastic ten or thermosetting resins includes chopped fibers and such as % yarn. Long fiber. Short-cut type break-through fiber used to reinforce thermoplastic resin: length == diameter can be determined by a number of factors such as (but not limited to... glass fiber and thermoplastic resin are easy to melt and knead (4), glass _ and Glass fiber dispersing ability. In some embodiments, the glassyness may be greater than -. In other embodiments, the glass fiber sound can be in other fine examples, the length of the glass fiber is ^^〇"M3.175mm (l/8^^12.7mm (1/24k^〇H = in the embodiment, the average diameter of the glass fiber can be greater than 8 (four). The average diameter of the fiber can be less than 25. Non-limiting examples of glass fibers in the process may include glass 'fibers made from t = composition, such fiberizable glass "cafe" & breaking, "A_glass", "C_glass , ',,, s-glass, glass, (corrosion-resistant pure glass) and its non-fluorine- and/or butterfly derivative 121823.doc -23- 200808672. Typical formulations of glass fiber are disclosed in K. Lowenstein, Tk Manufacturing Technology Manufacturing Technology of (^〇77".仙<9like G/au mers (3rd) Edition, 1993). The present invention also provides a glass fiber reinforced resin composition and a method of producing a glass fiber, quasi-reinforced novel composition. According to an embodiment of the present invention, for at least partially coating for resin reinforcement The sizing composition of the applied glass fibers may comprise any combination and any amount of sizing composition components consistent with those described herein. According to an embodiment of the invention, the glass fiber reinforced resin composition may comprise a thermoplastic resin. And/or thermosetting resins. Non-limiting examples of thermoplastic materials include polydihydrocarbons, polyacids, polyamines, polytropics, polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene. A blend of styrene (ABS), gamma, polyethylene, polyethylene terephthalate, polybutylene terephthalate, and a thermoplastic resin. Some embodiments may be particularly suitable for reinforcing a polyamide resin. In certain embodiments, the glass fiber reinforced polyamide resin may comprise nylon 6, nylon 6: 6, nylon 6: 12, nylon 4 :6, nylon 6:10, nylon 12, poly 6T (polyhexamethylene terephthalamide), polyamine 61 (poly/methylene meta-phenylene amide) or a mixture thereof based on mechanical properties of the resin, heat resistance, glass transition temperature , formability and molding appearance to select a specific polyamine resin. Poly-old amine thermoplastic resin can be lubricated with fatty acid metal salts, such as sodium with 9 or more carbon atoms of fatty acids, lithium, calcium, magnesium, zinc or Aluminium salt, barium and other fatty acids such as citric acid, lauric acid, myristic acid, palmitic acid, 121823.doc -24- 200808672 erythraea, undecanoic acid, wax acid, montanic acid, bee In the case of flower acid, oleic acid and mustard, two or more fatty acid metal salts may be used in combination. The bismuth can be used to reduce the torsion during melt-kneading of the thermoplastic polyamide resin and the upper glass fiber in the extruder, to improve the release characteristics of the resin, or to improve the melt flow of the resin during injection molding. . The sizing glass fiber reinforced polyamide resin is lubricated in an embodiment using a hard moon day ^^. The strength of the calcium sulphate-lubricated polyamine resin can be improved by the combination of the guanamine-terminated isocyanate described in connection with the syrup composition of the present invention. In some applications, such as a j-fiber, the fiber-reinforced resin combination 4 comprises a glass fiber of a polyamine tree and a glass fiber at least partially coated with the residue of the slurry composition of the present invention. In certain embodiments, the sizing composition comprises polyvinyl alcohol and even. An agent wherein polyvinyl alcohol is present in the sizing composition in an amount greater than about 5% by weight based on total solids. In other embodiments, the polyvinyl alcohol may be present in an amount greater than about 90% by weight of the sizing composition on a total solids basis. In certain embodiments, the sizing composition may also comprise a polyurethane. In certain embodiments, a method of producing a fiber-reinforced resin composition comprises: providing a plurality of glass fibers at least partially coated with a residue of the slurry composition of the present invention, and incorporating a plurality of glass fibers into the resin The resin is formed into a composite. In certain embodiments, the sizing composition comprises a polyvinyl alcohol and a coupling agent, wherein the polyvinyl alcohol is present in an amount greater than about 5% by weight of the sizing composition based on total solids. In certain embodiments, the vinyl alcohol is present in an amount greater than 90% by weight of the total sizing composition. According to a practical example of the present invention, the sizing composition for coating the glass fiber male in the method of producing the fiber-reinforced resin composition may comprise any combination and any one of the 121823.doc - 25-200808672 and herein: the resulting sizing composition component. Any suitable method of the invention may be used to prepare the present invention by the addition of sequential additions, or - can be used. For example, components can be inter-objective. , pre-dilution in the carrier and then combined to form a sizing combination top-loading composition can be applied to the glass by means of a suitable method known to those skilled in the art of glass, but not limited to Fibers and other methods such as: can be: static or dynamic feeder contact or spray or other pulp glass fiber only 'application mode, the characteristics of the fiber to be sizing and the predetermined use of the water 坂 fiber will be general ^ The total concentration of non-volatile components in the °. In a second embodiment, the upper part of the έ 出 出 出 出 出 water, and 5 things can be known to those skilled in the art = molding # During the period 'applied to a number of applications in a single step, the dry fiber is left in the upper layer to remove the carrier: "after the glass fiber is continued, in some non-limiting examples, sizing The composition can be a multi-part sizing composition such that it is topped up in a number of steps. The sizing composition can be applied to a glass fiber in a non-limiting embodiment. The sizing composition can be applied to a ::: partial sizing composition, and the sizing composition is applied in a two-step process. In the group = 7 two-in-one example, the 'first partial agglomerating composition may comprise money and moisture." the monthly component 'which is applied during the first step, such as during fiber formation. The second portion of the top polymerizable composition may comprise a polyglycol group, any polyamine ruthenic acid which may be a portion of the plant, and/or another calcined component, and may be in a glass fiber bundle. It is then applied in the second step. 121823. doc -26- 200808672 In some embodiments the bundle of glass fibers can be shortened. The glass fiber bundle may be chopped short before drying in some embodiments or may be chopped after drying in other embodiments. Continuous fiberglass bundles can be cut using techniques known to those skilled in the art, including but not limited to direct chopping and remote chopping.
如上所述，短切玻璃纖維之長度可視多個因素而定，該 等因素諸如（但不限於）短切玻璃纖雄將用於加強之熱塑性 樹脂類塑及玻璃纖維加強型熱塑性樹脂物品之預定用途。 如上所述，在上漿短切纖維用於加強聚醯胺樹脂之實施例 中，長度可能會具有1 mm之下限。此外，用於加強聚醯胺 樹脂之上聚短切纖維可能會具有5 0 mm之長度上限。 纖維上的上毁組合物之量可以"燒失量”或"L〇i”之形式 量測。如本文中所用，術語，，燒失量”或”L〇I”意謂玻璃纖 維上所存在的乾燥上漿組合物之重量百分數，其藉由方程 式1測定： L〇I—l〇〇x[(W乾燥-W裸）/W乾燥] (方程式1) 其中W㈣為在22CTF(約10VG)下烘箱中乾燥6〇分鐘之後的 纖維重量加塗層重量，且w裸為玻璃纖維在烘箱中115〇卞 (約621。〇下加熱20分鐘且在乾燥器中冷卻至室溫之後的裸 玻璃纖維重量。 根據某些實施例，塗霜右太恭0日 u胳 土设有本發明之上漿組合物的玻璃纖 維可具有在約0.1至以重量％範圍内之燒失量。 σ用短刀♦連績束或其混合物，以熟習此項技術者 已知之任何適合成形方法將上聚玻璃纖維併入熱塑性樹脂. 121823.doc -27- 200808672 内。上漿短切纖維束可在乾燥粉末混合物中與熱塑性樹脂 混合。混合物可經壓縮或射出成形產生玻璃纖雄加強型熱 塑性樹脂物品。玻璃纖維加強型熱塑性樹脂可用於諸如射 出成形、擠製成形、吹製成形或加壓成形之成形方法。 現將藉由以下非限制性實例來說明本發明之一實施例。 實例1 根據表7中所闡述的配方來製備本發明之上漿組合物之 一非限制性實例。 表7-實例1之上漿組合物配方 組份 量(kg) 總固體重量％ 石夕烷丨 0.805 10.0 聚乙烯醇“ 3.4 67.7 聚胺基曱酸酯 2.275 20.4 潤滑劑iv 0.06525 1.3 潤滑劑v 0.0352 0.7 乙酸vi 0.292 0.0 總固體5%，pH 4.25As noted above, the length of the chopped glass fibers can be determined by a number of factors such as, but not limited to, the chopped glass fiber will be used to reinforce the thermoplastic resin-like and glass fiber reinforced thermoplastic resin articles. use. As described above, in the embodiment in which the sized chopped fibers are used to reinforce the polyamide resin, the length may have a lower limit of 1 mm. In addition, the polycoke fibers used to reinforce the polyamide resin may have an upper length limit of 50 mm. The amount of the destructive composition on the fiber can be measured in the form of "loss of ignition" or "L〇i". As used herein, the term "burning loss" or "L〇I" means the weight percent of the dry sizing composition present on the glass fibers, as determined by Equation 1: L〇I—l〇〇x [(W dry-W bare) / W dry] (Equation 1) where W (four) is the fiber weight plus coating weight after drying in an oven at 22 CTF (about 10 VG) for 6 minutes, and w bare glass fiber in the oven 115 〇卞 (about 621. The bare glass fiber weight after heating under the arm for 20 minutes and cooling to room temperature in a desiccator. According to some embodiments, the cream is right on the 0th. The glass fibers of the pulp composition may have a loss on ignition in the range of from about 0.1 to about 9% by weight. σ. Use a short knife ♦ a bundle or a mixture thereof to assemble the glass fiber by any suitable forming method known to those skilled in the art. Incorporating thermoplastic resin. 121823.doc -27- 200808672. The sizing chopped fiber bundle can be mixed with a thermoplastic resin in a dry powder mixture. The mixture can be compressed or injection molded to produce a glass fiber reinforced thermoplastic resin article. Reinforced thermoplastic resin For forming methods such as injection molding, extrusion molding, blow molding or pressure forming. One embodiment of the invention will now be illustrated by the following non-limiting examples. Example 1 According to the formulation set forth in Table 7 A non-limiting example of the preparation of the syrup composition of the present invention is shown in Table 7. - Example 1 Top Slurry Composition Formulation Amount (kg) Total Solids Weight % Astragalus 丨0.805 10.0 Polyvinyl Alcohol "3.467.7 Polyamine Phthalate 2.275 20.4 Lubricant iv 0.06525 1.3 Lubricant v 0.0352 0.7 Acetic acid vi 0.292 0.0 Total solids 5%, pH 4.25
1來自 DeGussa AG.之 DYNASYLAN AMEO1 from DeGussa AG. DYNASYLAN AMEO
2來自 Kuraray Specialties GmbH之 MOWIOL 3-852 from Kuraray Specialties GmbH MOWIOL 3-85
3來自 Bayer Material Science AG之BAYBOND RSC3497 4來自 Congis Corporation之 EMERY 6717L 5DAPRAL GE202 Akzo Nobel 680%來自 Chemphora Chemie Partner之乙酸 表7中所列之組份量表示可用於製備100 kg上漿組合物 之量。可藉由調節所示之量，來製備其他量之上漿組合物。 實例1之上漿組合物之製備·. 121823.doc -28 - 200808672 表7中所提供之上漿組合物通常根據下述程序來製備 用於在組份添加至主混合槽之前製備個別組份 製備上漿組合物的技術員（techniti⑽）而變化。 之水量可視 以下所述之 水量可足以製備表7中之上漿組合物 加水以使得上漿組合物稀釋至所要最終體積 可在程序結束時添 25°C下將20 kg水添加至主混合槽中。將〇 2675 kg乙酸3 BAYBOND RSC3497 from Bayer Material Science AG 4 EMERY 6717L from Congis Corporation 5DAPRAL GE202 Akzo Nobel 680% acetic acid from Chemphora Chemie Partner The amount of the components listed in Table 7 represents the amount that can be used to prepare a 100 kg sizing composition. Other amounts of the above slurry composition can be prepared by adjusting the amounts indicated. Preparation of the slurry composition of Example 1. 121823.doc -28 - 200808672 The slurry composition provided in Table 7 is generally prepared according to the following procedure for preparing individual components before the components are added to the main mixing tank. The technician (techniti (10)) who prepared the sizing composition varied. The amount of water may be sufficient to prepare the above slurry composition in Table 7 by adding water to allow the sizing composition to be diluted to the desired final volume. 20 kg of water may be added to the main mixing tank at 25 ° C at the end of the procedure. in. Will 〇 2675 kg acetic acid
及〇·，kg㈣添加至主混合槽中之水中，且使所得混合 物攪拌10幺釦。在70 C下將i kg水添加至副混合槽中。將 0.0245 kg乙酸及0·06525 kg潤滑劑添加至副混合槽中之水 中。將所得潤滑劑溶液攪拌15分鐘且隨後添加至主混合槽 中在70 C下將1 kg水添加至副混合槽中。將〇 〇352 ^另 -潤滑劑添加至副混合槽中之水中。將所得潤滑劑溶液攪 拌10分鐘且隨後添加至主混合槽中。將規定量聚胺基甲酸 酯添加至主混合槽中，且攪拌所得溶液。 1在70°C下將15 kg水添加至乳液槽中。將規定量聚乙烯 醇添加至乳液槽中。將所得混合物擾拌6()分鐘且接著添加 至主混合槽十。在添加聚乙烯醇之後，攪拌主混合槽中之 所得混合物且又添加水以使得混合物達到其最終體積。上 漿組合物具有表7中所指定之重量百分數固體及pH值。 可由本發明展現之所要特徵包括(但不限於)供應包含聚 乙烯醇作為主要組份之用於加強.聚合材料的上漿組合物； 供應包含聚胺基甲酸酯作為次要組份之用於加強聚合材料 的上漿組合物；供應可至少部分地塗覆用於加強聚醯胺材 料之玻璃纖維之包含.聚乙稀.醇作為主要組份的上“人 121823.doc -29- 200808672 物’供應可至少部分地塗覆用於加強聚醯胺材料之玻璃纖 、准之匕έ t胺基甲酸酯作為次要組份的上漿組合物；等 等。 描述實現本發明不同目的 解此等實施例僅說明本發明 神及範疇的情況下，多種修 者而言易顯而易見的。 本發明之不同實施例。應瞭 原理。在不悖離本發明 及其改進對於熟習此項技術 121823.doc -30 -And 〇·, kg (d) was added to the water in the main mixing tank, and the resulting mixture was stirred for 10 幺. I kg of water was added to the secondary mixing tank at 70 C. Add 0.0245 kg of acetic acid and 0·06525 kg of lubricant to the water in the secondary mixing tank. The resulting lubricant solution was stirred for 15 minutes and then added to the main mixing tank to add 1 kg of water to the secondary mixing tank at 70 C. Add 〇 352 ^ another - lubricant to the water in the secondary mixing tank. The resulting lubricant solution was stirred for 10 minutes and then added to the main mixing tank. A prescribed amount of polyurethane was added to the main mixing tank, and the resulting solution was stirred. 1 Add 15 kg of water to the emulsion tank at 70 °C. A specified amount of polyvinyl alcohol is added to the emulsion tank. The resulting mixture was scrambled for 6 () minutes and then added to the main mixing tank 10. After the addition of the polyvinyl alcohol, the resulting mixture in the main mixing tank was stirred and water was added again to bring the mixture to its final volume. The sizing composition has the weight percent solids and pH values specified in Table 7. The desired features that can be exhibited by the present invention include, but are not limited to, the supply of a sizing composition for reinforcing a polymeric material comprising polyvinyl alcohol as a major component; the supply of a polyurethane containing a minor component as a secondary component a sizing composition for reinforcing a polymeric material; supplying a glass fiber which is at least partially coated for reinforcing a polyamide material. Polyethylene. Alcohol as a main component of the above "person 121823.doc -29- 200808672 The 'supply can be at least partially coated with a sizing composition for reinforcing the glass fiber of the polyamide material, the quasi-t-carbamate as a secondary component; etc. Describe the different purposes of the present invention. The embodiments are merely illustrative of the invention and the scope of the invention is readily apparent to those skilled in the art. The various embodiments of the invention are in accordance with the principles of the invention. 121823.doc -30 -
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/452,024 US20070286999A1 (en) | 2006-06-13 | 2006-06-13 | Sizing composition for glass fibers, sized fiber glass products, and composites |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW200808672A true TW200808672A (en) | 2008-02-16 |
Family
ID=38822344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW96121361A TW200808672A (en) | 2006-06-13 | 2007-06-13 | Sizing composition for glass fibers, sized fiber glass products, and composites |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20070286999A1 (en) |
| TW (1) | TW200808672A (en) |
| WO (1) | WO2007146278A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110685087A (en) * | 2019-11-22 | 2020-01-14 | 上海曙雀贸易有限公司 | Coating film-forming glass fiber yarn and preparation method and application thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070154697A1 (en) * | 2005-12-30 | 2007-07-05 | Cossement Marc R | Two-part sizing composition for reinforcement fibers |
| WO2010029387A1 (en) * | 2008-09-11 | 2010-03-18 | Idris Kaynak | A method for production of a nano-reinforced material |
| US8686068B2 (en) * | 2008-10-17 | 2014-04-01 | Zeon Corporation | Polymerizable composition, cross-linkable shaped article, cross-linked shaped article, and cross-linked shaped article composite |
| EP2559673B1 (en) * | 2011-08-19 | 2018-10-03 | Johns Manville | Sizing composition for fibers and sized fibers |
| CN106458737A (en) * | 2014-04-04 | 2017-02-22 | Ppg工业俄亥俄公司 | Sizing compositions for wet and dry filament winding |
| CN105273365B (en) * | 2014-06-30 | 2019-03-26 | 康廷南拓结构塑料有限公司 | Sheet molding compounds comprising surface modified glass filler |
| EP3665213A2 (en) * | 2017-08-07 | 2020-06-17 | Zoltek Corporation | Polyvinyl alcohol-sized fillers for reinforcing plastics |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185138A (en) * | 1978-12-20 | 1980-01-22 | Ppg Industries, Inc. | Size composition and method of producing same to render glass fiber having improved dispersibility in aqueous solutions |
| US4455343A (en) * | 1980-12-29 | 1984-06-19 | Ppg Industries, Inc. | Aqueous treating composition for glass fiber strands used to produce mats for thermoplastics |
| DE3107008A1 (en) * | 1981-02-25 | 1982-09-09 | Hoechst Ag, 6000 Frankfurt | SIZING AGENT FOR SYNTHESIS FIBERS |
| US4338233A (en) * | 1981-06-15 | 1982-07-06 | Ppg Industries, Inc. | Aqueous sizing composition and sized glass fibers and method |
| US4845140A (en) * | 1986-07-07 | 1989-07-04 | Air Products And Chemicals, Inc. | Waxless polyvinyl alcohol size composition |
| US5024890A (en) * | 1987-03-12 | 1991-06-18 | Owens-Corning Fiberglass Corporation | Size composition for impregnating filament strands and glass fibers coated therein |
| KR950004062B1 (en) * | 1990-04-05 | 1995-04-25 | 피피지 인더스트리즈, 인코포레이티드 | Chemical composition to produce water soluble curable films on fibrous surfaces and said treated fibers |
| DE69025330T2 (en) * | 1990-07-06 | 1996-09-05 | Ube Nitto Kasei Co | FIBER REINFORCED POLYAMIDE RESIN COMPOSITION AND PRODUCTION THEREOF |
| US5262469A (en) * | 1991-12-13 | 1993-11-16 | Shimadzu Corporation | Oxynitride glass fiber for composite products, and glass fiber-reinforced products |
| US5300696A (en) * | 1992-12-29 | 1994-04-05 | Uop | C4 rejection for etherification and isomerization process |
| EP0990727A1 (en) * | 1998-10-02 | 2000-04-05 | Johns Manville International Inc. | Polycarboxy/polyol fiberglass binder |
| US6955844B2 (en) * | 2002-05-24 | 2005-10-18 | Innovative Construction And Building Materials | Construction materials containing surface modified fibers |
| US7144600B2 (en) * | 2003-02-18 | 2006-12-05 | Milliken & Company | Wax-free lubricant for use in sizing yarns, methods using same and fabrics produced therefrom |
| US6884838B2 (en) * | 2003-02-20 | 2005-04-26 | Johns Manville International, Inc. | Water repellant fiberglass binder |
| US6884849B2 (en) * | 2003-02-21 | 2005-04-26 | Owens-Corning Fiberglas Technology, Inc. | Poly alcohol-based binder composition |
-
2006
- 2006-06-13 US US11/452,024 patent/US20070286999A1/en not_active Abandoned
-
2007
- 2007-06-12 WO PCT/US2007/013764 patent/WO2007146278A2/en active Application Filing
- 2007-06-13 TW TW96121361A patent/TW200808672A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110685087A (en) * | 2019-11-22 | 2020-01-14 | 上海曙雀贸易有限公司 | Coating film-forming glass fiber yarn and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007146278A3 (en) | 2008-03-20 |
| US20070286999A1 (en) | 2007-12-13 |
| WO2007146278A2 (en) | 2007-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW200808672A (en) | Sizing composition for glass fibers, sized fiber glass products, and composites | |
| TWI384004B (en) | Sizing composition and glass fiber reinforced thermoplastic resin | |
| CN101558020B (en) | Sizing compositions and glass fiber reinforced thermoplastic composites | |
| TWI619780B (en) | Two part sizing composition for coating glass fibres and composite reinforced with such glass fibres | |
| US6005026A (en) | Sizing composition for glass fibers for reinforcement of engineered thermoplastic materials | |
| US20110281487A1 (en) | Gas barrier molded article and method for producing the same | |
| EP0991603B1 (en) | High solubility size composition for fibers | |
| JP5222243B2 (en) | Reinforcing fiber sizing agents, synthetic fiber strands and fiber reinforced composites | |
| TW201034992A (en) | Fiber reinforced polymeric composites and methods of making the same | |
| TW574160B (en) | System for preparing glass fiber pellets having low discoloration | |
| TW201307493A (en) | Sizing composition for charges used in thermoplastic polymeric material reinforcement, reinforced polymeric materials and method of manufacture | |
| JP2016034897A (en) | Glass fiber sizing agent and glass fiber-reinforced thermoplastic resin composition | |
| TW472080B (en) | Sizing composition for glass yarns, process using this composition and products resulting therefrom | |
| CA2831141C (en) | Fiber glass strands and reinforced products comprising the same | |
| JP2011231414A (en) | Sizing agent for reinforcing fiber, synthetic fiber strand, and fiber reinforced composite material | |
| JP4989790B2 (en) | Reinforcing fiber sizing agents, synthetic fiber strands and fiber reinforced composites | |
| KR101999900B1 (en) | Sizing composition and glass fiber using the same | |
| MXPA01012813A (en) | Nylon 6-silicone blends. | |
| JPH0463095B2 (en) | ||
| JP4013516B2 (en) | Glass fiber chopped strands bundled by a glass fiber sizing agent containing magnesium chloride | |
| US11718934B2 (en) | Manufacture of composite dispersion based resin-infused random fiber mat | |
| JP2003073150A (en) | Binder for glass fiber, containing polyamide resin |