CN111344338A - 预浸料、纤维强化复合材料及成形体 - Google Patents

预浸料、纤维强化复合材料及成形体 Download PDF

Info

Publication number
CN111344338A
CN111344338A CN201880070028.9A CN201880070028A CN111344338A CN 111344338 A CN111344338 A CN 111344338A CN 201880070028 A CN201880070028 A CN 201880070028A CN 111344338 A CN111344338 A CN 111344338A
Authority
CN
China
Prior art keywords
mass
fiber
reinforced composite
composite material
prepreg
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201880070028.9A
Other languages
English (en)
Other versions
CN111344338B (zh
Inventor
南昌树
松本隆之
古俣步
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
JXTG Nippon Oil and Energy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JXTG Nippon Oil and Energy Corp filed Critical JXTG Nippon Oil and Energy Corp
Publication of CN111344338A publication Critical patent/CN111344338A/zh
Application granted granted Critical
Publication of CN111344338B publication Critical patent/CN111344338B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50Amines
    • C08G59/504Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/04Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/38Layered products comprising a layer of synthetic resin comprising epoxy resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/22Layered 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
    • B32B5/24Layered 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
    • B32B5/26Layered 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066Flame-proofing or flame-retarding additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34922Melamine; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34924Triazines containing cyanurate groups; Tautomers thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/033 layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/044 layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/055 or more layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/20All layers being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02Synthetic macromolecular fibres
    • B32B2262/0246Acrylic resin fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
    • B32B2262/106Carbon fibres, e.g. graphite fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02Synthetic macromolecular particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00Condition, form or state of the layers or laminate
    • B32B2305/07Parts immersed or impregnated in a matrix
    • B32B2305/076Prepregs
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00Condition, form or state of the layers or laminate
    • B32B2305/72Cured, e.g. vulcanised, cross-linked
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • B32B2307/3065Flame resistant or retardant, fire resistant or retardant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51Elastic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558Impact strength, toughness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/732Dimensional properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2363/00Epoxy resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00Vehicles
    • B32B2605/08Cars
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00Vehicles
    • B32B2605/18Aircraft
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • C08G59/24Di-epoxy compounds carbocyclic
    • C08G59/245Di-epoxy compounds carbocyclic aromatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50Amines
    • C08G59/5046Amines heterocyclic
    • C08G59/5053Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/508Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
    • C08G59/5086Triazines; Melamines; Guanamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/04Epoxynovolacs
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/902High modulus filament or fiber
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/92Fire or heat protection feature
    • Y10S428/921Fire or flameproofing
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31511Of epoxy ether

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

本发明的预浸料包含:碳纤维;和,树脂组合物,其含有具有联苯结构的环氧树脂、固化剂以及氰脲酸三聚氰胺。

Description

预浸料、纤维强化复合材料及成形体
技术领域
本发明涉及预浸料、纤维强化复合材料及成形体。
背景技术
包含碳纤维与基质树脂的纤维强化复合材料轻量且具有优异的强度,故而可在各种用途中使用。
这种纤维强化复合材料有时要求阻燃性,一直以来,已知有配混卤素系阻燃剂或磷系阻燃剂、使得纤维强化复合材料阻燃化的方法。例如,专利文献1中记载了在用于形成基质树脂的环氧树脂组合物中配混磷化合物而获得具有优异的阻燃性的纤维强化复合材料的方法。
现有技术文献
专利文献
专利文献1:国际公开第2005/082982号
发明内容
发明要解决的问题
然而,在使用卤素系阻燃剂及磷系阻燃剂时,存在燃烧时产生有毒气体、废弃时的环境负荷的课题。
另外,近年来,研究在电气/电子仪器的壳体中使用纤维强化复合材料,就壳体的薄壁化/仪器的重量减轻的观点而言,要求厚度薄的纤维强化复合材料。并且,在以往的方法中,难以提供即使厚度薄也可确保充分的阻燃性、且不含卤素及磷的纤维强化复合材料。
因此,本发明的目的在于,提供即使不使用卤素系阻燃剂及磷系阻燃剂也可形成兼具薄度与阻燃性的纤维强化复合材料的预浸料。本发明的目的还在于,提供使用上述预浸料形成的纤维强化复合材料及包含其的成形体。
用于解决问题的方案
本发明的一个方式涉及一种预浸料,其包含:碳纤维;和,树脂组合物,其含有具有联苯结构的环氧树脂、固化剂及氰脲酸三聚氰胺。根据上述预浸料,可在不使用卤素系阻燃剂及磷系阻燃剂的情况下,形成兼具薄度与阻燃性的纤维强化复合材料。
在一个方式中,上述氰脲酸三聚氰胺的含量以树脂组合物的总量基准计可以为20~40质量%。
在一个方式中,上述树脂组合物中的氯原子的含量可以为1质量%以下。
在一个方式中,上述树脂组合物中的磷原子的含量可以为0.1质量%以下。
本发明的另一方式涉及一种纤维强化复合材料,其为将多个预浸料层叠并固化而的纤维强化复合材料,上述预浸料中的至少一个为上述的预浸料。
一个方式的纤维强化复合材料的层叠方向的厚度可以为1.5mm以下。
一个方式的纤维强化复合材料的基于UL94燃烧试验的阻燃性评价可以为V-0或V-1。
本发明的另一个方式涉及一种成形体,其包含上述纤维强化复合材料。
发明的效果
根据本发明,提供:即使不使用卤素系阻燃剂及磷系阻燃剂,也可形成兼具薄度与阻燃性的纤维强化复合材料的预浸料。另外,根据本发明,提供:使用上述预浸料而形成的纤维强化复合材料及包含其的成形体。
具体实施方式
以下,对本发明的适宜的实施方式进行说明。
(预浸料)
本实施方式的预浸料包含:碳纤维;和,树脂组合物,其含有具有联苯结构的环氧树脂、固化剂及氰脲酸三聚氰胺。根据上述预浸料,可在不使用卤素系阻燃剂及磷系阻燃剂的情况下,形成兼具薄度与阻燃性的纤维强化复合材料。
碳纤维并没有特别限定,可没有特别限制地使用能够用于纤维强化复合材料的碳纤维。作为碳纤维,根据原料的不同,存在聚丙烯腈(PAN)系碳纤维及沥青系碳纤维。沥青系碳纤维具有拉伸弹性高的特性,另一方面,PAN系碳纤维具有拉伸强度高的特性。本实施方式的碳纤维可为PAN系碳纤维,也可为沥青系碳纤维,但就可获得耐变形性更优异的碳纤维强化复合材料的观点而言,更优选沥青系碳纤维。
本实施方式的预浸料优选包含拉伸模量为150GPa以上的碳纤维。另外,碳纤维的拉伸模量更优选为200GPa以上,进一步优选为450GPa以上,更进一步优选为600GPa以上。使用多种预浸料时,优选预浸料中所含的碳纤维的大部分(例如为70质量%以上、优选为80质量%以上)具有上述适宜的拉伸模量。需要说明的是,本说明书中,碳纤维的拉伸模量是指依据JIS R7601(1986)所测定的线料拉伸模量。
本实施方式的预浸料中,每单位面积的碳纤维量例如也可以为30g/m2以上,优选为50g/m2以上,更优选为70g/m2以上。通过设为上述碳纤维量,可于将纤维强化复合材料成形时,减少用于获得特定的厚度的层叠片数,可使作业简便。另外,每单位面积的碳纤维量例如可以为3000g/m2以下,优选为2000g/m2以下,更优选为1000g/m2以下。由此,可抑制孔隙的产生,容易获得均匀的纤维强化复合材料。
关于预浸料中的碳纤维的含量,以预浸料的总量基准计,例如可以为20质量%以上,优选为30质量%以上,更优选为40质量%以上。由此,纤维强化复合材料的强度进一步改善。另外,关于预浸料中的碳纤维的含量,以预浸料的总量基准计,例如可为90质量%以下,优选为85质量%以下,更优选为80质量%以下。由此,可抑制孔隙的产生,容易获得均匀的纤维强化复合材料。
树脂组合物含有具有联苯结构的环氧树脂、固化剂及氰脲酸三聚氰胺。通过树脂组合物的固化,形成纤维强化复合材料中的基质树脂。
具有联苯结构的环氧树脂(以下,根据情况也称为“环氧树脂(A)”)为具有联苯结构和两个以上环氧基的化合物。
联苯结构表示两个苯环以单键进行共价键而成的结构。环氧树脂(A)中的联苯结构也可于苯环上具有取代基。作为该取代基,例如可列举出:烷基、芳基、芳烷基、羟基、烷氧基等。
环氧树脂(A)的环氧当量并没有特别限定,例如可以为150以上,优选为200以上,更优选为250以上。另外,环氧树脂(A)的环氧当量例如可以为1000以下,优选为700以下,更优选为400以下。
作为环氧树脂(A),例如可列举出:下述式(A-1)所表示的环氧树脂。
Figure BDA0002468876660000041
式中,n表示1以上的整数,优选为1~30,更优选为1~10。
作为环氧树脂(A),也可以使用市售品,例如可适宜地使用NC-3000、NC-3000H、NC-3100(以上为日本化药制造,商品名)等。
关于树脂组合物中的环氧树脂(A)的含量,以树脂组合物的总量基准计,例如可以为15质量%以上,优选为20质量%以上,更优选为25质量%以上。由此,纤维强化复合材料的耐热性、韧性进一步改善。另外,关于环氧树脂(A)的含量,以树脂组合物的总量基准计,例如可为45质量%以下,优选为40质量%以下,更优选为35质量%以下。由此,可将树脂组合物保持为适当的粘度,可使作业简便。
树脂组合物可以进一步含有环氧树脂(A)以外的其他环氧树脂(以下,根据情况也称为“环氧树脂(B)”)。环氧树脂(B)可以称为具有两个以上的环氧基且不具有联苯结构的化合物。
作为环氧树脂(B),只要为可与环氧树脂(A)一同固化的环氧树脂,则并没有特别限定。环氧树脂(B)可为了调整树脂组合物的粘度、改善组成成分的固化性等而配混。
作为环氧树脂(B),例如可列举出:双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、间苯二酚型环氧树脂、具有萘骨架的环氧树脂等。
环氧树脂(A)的含量相对于环氧树脂(A)及环氧树脂(B)的合计量例如可以为20质量%以上,优选为25质量%以上,更优选为30质量%以上。由此,纤维强化复合材料的耐热性进一步改善。
环氧树脂(A)的含量相对于环氧树脂(A)及环氧树脂(B)的合计量的上限并没有特别限定,例如可以为40质量%以下,也可以为35质量%以下。
关于环氧树脂(A)及环氧树脂(B)的合计量,以树脂组合物的总量基准计,例如可以为50质量%以上,优选为55质量%以上,更优选为60质量%以上。由此,作为纤维强化复合材料容易获得更适宜的机械物性。另外,关于环氧树脂(A)及环氧树脂(B)的合计量,以树脂组合物的总量基准计,例如可以为80质量%以下,优选为75质量%以下,更优选为70质量%以下。由此,可以将其他树脂、固化剂、固化促进剂等添加物以树脂组合物的构成材料的形式充分添加,实现各种物性的改善。
固化剂只要为能够使环氧树脂(A)(根据情况为环氧树脂(A)及环氧树脂(B))固化的固化剂即可。作为固化剂,例如可列举出:胺系固化剂、酸酐系固化剂、酚系固化剂等,这些中,优选为胺系固化剂,其中,更优选为双氰胺及二氨基二苯砜。
固化剂的含量并没有特别限定,以树脂组合物的总量基准计,例如可以为0.1质量%以上,优选为0.5质量%以上,更优选为1质量%以上。另外,固化剂的含量以树脂组合物的总量基准计例如可以为10质量%以下,优选为8质量%以下,更优选为6质量%以下。
关于氰脲酸三聚氰胺的含量,以树脂组合物的总量基准计,例如可以为15质量%以上,优选为20质量%以上,更优选为25质量%以上。由此,纤维强化复合材料的耐热性进一步改善。另外,关于氰脲酸三聚氰胺的含量,以树脂组合物的总量基准计,例如可以为50质量%以下,优选为45质量%以下,更优选为40质量%以下。由此,可将树脂组合物保持为适当的粘度,作业性改善。
氰脲酸三聚氰胺的含量C2与环氧树脂(A)的含量C1的比(C2/C1)(质量比)例如可以为0.5以上,优选为1.0以上。另外,上述比(C2/C1)例如可以为3.0以下,优选为2.0以下。若为这种比(C2/C1),则有纤维强化复合材料的厚度薄的情况下的阻燃性会进一步改善的倾向。
关于环氧树脂(A)的含量C1与氰脲酸三聚氰胺的含量C2的合计量(C1+C2),以树脂组合物的总量基准计,例如可以为30质量%以上,优选为35质量%以上,更优选为40质量%以上。另外,关于上述合计量(C1+C2),以树脂组合物的总量基准计,例如可以为80质量%以下,优选为75质量%以下,更优选为70质量%以下。若为这种合计量(C1+C2),则有纤维强化复合材料的厚度薄的情况下的阻燃性会进一步改善的倾向。
树脂组合物也可以进一步含有固化促进剂。作为与双氰胺组合而使用的固化促进剂,例如可列举出:3-苯基-1,1-二甲基脲、3-(4-氯苯基)-1,1-二甲基脲、3-(3,4-二氯苯基)-1,1-二甲基脲(DCMU)等,这些中,优选为3-(3,4-二氯苯基)-1,1-二甲基脲(DCMU)。
固化促进剂的含量并没有特别限定,以树脂组合物的总量基准计,例如可以为0.1质量%以上,优选为0.5质量%以上,更优选为1质量%以上。另外,关于固化促进剂的含量,以树脂组合物的总量基准计,例如可以为10质量%以下,优选为8质量%以下,更优选为6质量%以下。
树脂组合物也可以进一步含有上述以外的其他成分。作为其他成分,例如可列举出无机微粒、有机微粒等。关于这种其他成分的含量,分别以树脂组合物的总量基准计,例如可以为50质量%以下,优选为40质量%以下,更优选为30质量%以下。另外,上述其他成分的含量例如可以为0质量%以上,也可为10质量%以上。
树脂组合物的50℃下的粘度优选为10Pa·s以上,更优选为50Pa·s以上。由此,可充分抑制树脂组合物的滴落等,有预浸料的制造变得更容易的倾向。另外,树脂组合物于50℃下的粘度优选为20000Pa·s以下,更优选为10000Pa·s以下。由此,树脂组合物的粘性及铺覆性变得更适宜。
树脂组合物中的氯原子的含量例如可以为1质量%以下,优选为0.5质量%以下,更优选为0.1质量%以下,也可为检测极限以下。根据上述树脂组合物,可基于上述的构成而确保充分的阻燃性并抑制燃烧时的含氯气体的产生。
树脂组合物中的磷原子的含量例如可以为0.1质量%以下,优选为0.01%质量以下,更优选为0.001质量%以下,也可以为检测极限以下。磷系化合物与树脂的相容性低的情况较多,有难以制作均质的预浸料的情况。针对该问题,本实施方式中,基于上述构成,可确保充分的阻燃性并容易地获得均质的预浸料。另外,也可基于减少磷原子的含量而充分确保环境安全性。
树脂组合物的固化后的玻璃化转变温度(Tg)优选为120℃以上,更优选为150℃以上。根据上述树脂组合物,可获得耐热性更优异的纤维强化复合材料。
本实施方式的预浸料的制造方法并没有特别限定。例如,预浸料可基于如下方式制造:准备将碳纤维在一方向并纱而成的碳纤维束,在该碳纤维束中含浸树脂组合物,从而制造。作为含浸树脂组合物的方法,例如可列举出:
使树脂组合物溶解于溶剂中进行低粘度化并含浸的湿式法;直接含浸基于加热而低粘度化的树脂组合物的热熔法(干式法)等。
可将本实施方式的预浸料层叠并固化而获得纤维强化复合材料。以如此的方式所获得的纤维强化复合材料可兼具薄度与阻燃性。
(纤维强化复合材料)
本实施方式的纤维强化复合材料是将多个预浸料进行层叠并固化而成者,多个预浸料中的至少一个为上述实施方式的预浸料。本实施方式中,多个预浸料中,可使半数以上为上述实施方式的预浸料,也可使全部为上述实施方式的预浸料。关于经层叠并固化的多个预浸料,其各自的构成可以相同、也可以不同。
纤维强化复合材料的形状并没有特别限定,例如可以为板状。
纤维强化复合材料的厚度(层叠方向的厚度)并没有特别限定,就兼具薄度与阻燃性的观点而言,优选为1.5mm以下,更优选为1.0mm以下。另外,纤维强化复合材料的厚度的下限并没有特别限定,例如可以为0.2mm以上,也可以为0.4mm以上。
预浸料的层叠片数并没有特别限定,例如可以为2~16片,优选为4~8片。
纤维强化复合材料的基于UL94燃烧试验的阻燃性评价优选为V-0或V-1,更优选为V-0。这种纤维强化复合材料可以说阻燃性尤其优异。
纤维强化复合材料的制造方法并没有特别限定。例如,可通过层叠多个预浸料并进行热固化而制造。热固化的条件并没有特别限定,只要为使预浸料的树脂组合物固化的条件即可。该制造方法中,例如也可以于热固化时将预浸料的层叠体变化为特定的形状,从而获得成形为特定的形状的纤维强化复合材料。
热固化时的加热温度例如可以为100~150℃,也可以为110~140℃。另外,热固化时的加热时间例如可以为10分钟~3小时,也可以为20分钟~2小时。
也可以于热固化时赋予压力,加压条件例如可以为0.1~0.9MPa。
本实施方式的纤维强化复合材料例如可适宜地用于电子/电气仪器的壳体等要求薄度及阻燃性这两种特性的用途。另外,本实施方式的纤维强化复合材料也可适宜地用于飞机、汽车等的构造材料、高尔夫杆身、钓竿等运动用品、土木材料等用途。
以上,已对本发明的优选的实施方式进行了说明,但本发明并不限定于上述实施方式。
实施例
以下,利用实施例更具体地说明本发明,但本发明并不限定于实施例。
(实施例A-1)
将具有联苯结构的环氧树脂(NC-3000,日本化药公司制造)40质量份、双酚A型环氧树脂(YD-128,新日铁住金化学公司制造)14质量份、苯酚酚醛清漆型环氧树脂(YDPN-638,新日铁住金化学公司制造)20质量份、氰脲酸三聚氰胺(MC-6000,日产化学公司制造)40质量份、双氰胺(DICY)4质量份及3-(3,4-二氯苯基)-1,1-二甲基脲(DCMU)3质量份进行混合,从而获得树脂组合物A-1。所获得的树脂组合物A-1于30℃下的粘度为60100Pa·s。另外,于140℃下固化2小时后的树脂固化物的玻璃化转变温度为155℃,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
继而,准备XN-80(Nippon Graphite Fiber Co.,Ltd.制造,拉伸模量为780GPa)作为碳纤维,并在该碳纤维中含浸树脂组合物A-1。由此,获得每单位面积的碳纤维的量为125g/m2、树脂含有率为32%的预浸料(预浸料A-1)。
(实施例A-2)
将具有联苯结构的环氧树脂、双酚A型环氧树脂及苯酚酚醛清漆型环氧树脂的配混量分别变更为35质量份、19质量份及13质量份,除此以外,以与实施例A-1相同的方式获得树脂组合物A-2。所获得的树脂组合物A-2于30℃下的粘度为22100Pa·s。另外,于140℃下固化2小时后的树脂组合物的玻璃化转变温度为151℃,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
继而,使用树脂组合物A-2代替树脂组合物A-1,除此以外,以与实施例A-1相同的方式进行预浸料的制作,获得每单位面积的碳纤维的量为125g/m2、树脂含有率为32%的预浸料(预浸料A-2)。
(实施例A-3)
将具有联苯结构的环氧树脂、双酚A型环氧树脂及苯酚酚醛清漆型环氧树脂的配混量分别变更为30质量份、14质量份及23质量份,进而混合苯氧基树脂(YP-70,新日铁住金化学公司制造)5质量份,除此以外,以与实施例A-1相同的方式获得树脂组合物A-3。所获得的树脂组合物A-3于30℃下的粘度为113000Pa·s。另外,于140℃下固化2小时后的玻璃化转变温度为153℃,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
继而,使用树脂组合物A-3代替树脂组合物A-1,除此以外,以与实施例A-1相同的方式进行预浸料的制作,获得每单位面积的碳纤维的量为125g/m2、树脂含有率为32%的预浸料(预浸料A-3)。
(实施例A-4)
将具有联苯结构的环氧树脂、双酚A型环氧树脂及苯酚酚醛清漆型环氧树脂的配混量分别变更为30质量份、32质量份及0质量份,进而混合苯氧基树脂(YP-70,新日铁住金化学公司制造)10质量份,除此以外,以与实施例A-1相同的方式获得树脂组合物A-4。所获得的树脂组合物A-4于30℃下的粘度为35000Pa·s。另外,于140℃下固化2小时后的树脂组合物的玻璃化转变温度为128℃,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
继而,使用树脂组合物A-4代替树脂组合物A-1,除此以外,以与实施例A-1相同的方式进行预浸料的制作,获得每单位面积的碳纤维的量为125g/m2、树脂含有率为32%的预浸料(预浸料A-4)。
(实施例A-5)
使用T700S(Toray公司制造,拉伸模量230GPa)作为碳纤维,除此以外,以与实施例A-2相同的方式进行预浸料的制作,获得每单位面积的碳纤维的量为200g/m2、树脂含有率为32%的预浸料(预浸料A-5)。
(比较例X-1)
将双酚A型环氧树脂(YD-128,新日铁住金化学公司制造)37质量份、双酚A型环氧树脂(YD-11,新日铁住金化学公司制造)33质量份、苯酚酚醛清漆型环氧树脂(YDPN-638,新日铁住金化学公司制造)30质量份、苯氧基树脂(YP-70,新日铁住金化学公司制造)15质量份、双氰胺(DICY)4质量份及3-(3,4-二氯苯基)-1,1-二甲基脲(DCMU)3质量份进行混合,获得树脂组合物X-1。所获得的树脂组合物X-1于30℃下的粘度为24100Pa·s。另外,于140℃下固化2小时后的树脂固化物的玻璃化转变温度为131℃,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-not。
继而,准备作为碳纤维的XN-80(Nippon Graphite Fiber Co.,Ltd.制造,拉伸模量为780GPa),在该碳纤维中含浸树脂组合物X-1。由此,获得每单位面积的碳纤维的量为125g/m2、树脂含有率为32%的预浸料(预浸料X-1)。
(比较例X-2)
将YD-11的配混量变更为13质量份,进而混合氰脲酸三聚氰胺(MC-6000,日产化学公司制造)20质量份,除此以外,以与比较例X-1相同的方式获得树脂组合物X-2。所获得的树脂组合物X-2于30℃下的粘度为10600Pa·s。另外,于140℃下固化2小时后的树脂固化物的玻璃化转变温度为128℃,进行与UL94燃烧试验相同的阻燃性评价,结果相当于V-2。
(比较例X-3)
将YP-70及MC-6000的配混量分别变更为5质量份及0质量份,进而混合具有联苯结构的环氧树脂(NC-3000,日本化药公司制造)30质量份,除此以外,以与比较例X-2相同的方式获得树脂组合物X-3。所获得的树脂组合物X-3于30℃下的粘度为16600Pa·s。另外,于140℃下固化2小时后的树脂固化物的玻璃化转变温度为134℃,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-not。
(实施例B-1)
层叠4片预浸料A-1,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度0.57mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
(实施例B-2)
层叠4片预浸料A-2,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度0.43mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
(实施例B-3)
层叠4片预浸料A-3,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度0.57mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
(实施例B-4)
层叠4片预浸料A-4,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度0.57mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-1。
(实施例B-5)
层叠4片预浸料A-5,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度0.85mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
(实施例B-6)
层叠10片预浸料A-2,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度1.1mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
(实施例B-7)
层叠3片预浸料A-5,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度0.67mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-1。
(实施例B-8)
按照A-2/A-2/A-5/A-2/A-2的顺序将预浸料A-2及预浸料A-5层叠5片,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度0.65mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-0。
(比较例Y-1)
层叠16片预浸料X-1,在高压釜中以压力0.6MPa、140℃×2小时的条件进行固化,获得厚度2.4mm的纤维强化复合材料板。针对所获得的纤维强化复合材料板,进行与UL94燃烧试验同等的阻燃性评价,结果相当于V-not。
产业上的可利用性
本发明的预浸料即使不使用卤素系阻燃剂及磷系阻燃剂,也可形成兼具薄度与阻燃性的纤维强化复合材料。因此,本发明的预浸料可优选用于电气、电子仪器的壳体等用途。

Claims (8)

1.一种预浸料,其包含:
碳纤维;和
树脂组合物,含有具有联苯结构的环氧树脂、固化剂以及氰脲酸三聚氰胺。
2.根据权利要求1所述的预浸料,其中,所述氰脲酸三聚氰胺的含量以树脂组合物的总量基准计为20~40质量%。
3.根据权利要求1或2所述的预浸料,其中,所述树脂组合物中的氯原子的含量为1质量%以下。
4.根据权利要求1至3中任一项所述的预浸料,其中,所述树脂组合物中的磷原子的含量为0.1质量%以下。
5.一种纤维强化复合材料,其为将多个预浸料层叠并固化而成的纤维强化复合材料,
所述预浸料中的至少一个为权利要求1至4中任一项所述的预浸料。
6.根据权利要求5所述的纤维强化复合材料,其层叠方向的厚度为1.5mm以下。
7.根据权利要求5所述的纤维强化复合材料,其基于UL94燃烧试验的阻燃性评价为V-0或V-1。
8.一种成形体,其包含权利要求5至7中任一项所述的纤维强化复合材料。
CN201880070028.9A 2017-11-14 2018-11-13 预浸料、纤维强化复合材料及成形体 Active CN111344338B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017219064A JP6896591B2 (ja) 2017-11-14 2017-11-14 プリプレグ、繊維強化複合材料及び成形体
JP2017-219064 2017-11-14
PCT/JP2018/042008 WO2019098201A1 (ja) 2017-11-14 2018-11-13 プリプレグ、繊維強化複合材料及び成形体

Publications (2)

Publication Number Publication Date
CN111344338A true CN111344338A (zh) 2020-06-26
CN111344338B CN111344338B (zh) 2022-08-23

Family

ID=66539562

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880070028.9A Active CN111344338B (zh) 2017-11-14 2018-11-13 预浸料、纤维强化复合材料及成形体

Country Status (6)

Country Link
US (1) US11319406B2 (zh)
JP (1) JP6896591B2 (zh)
KR (1) KR102684013B1 (zh)
CN (1) CN111344338B (zh)
TW (1) TWI789455B (zh)
WO (1) WO2019098201A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117425687A (zh) * 2021-06-08 2024-01-19 日铁化学材料株式会社 单向增强纤维预浸料、使用该预浸料的纤维增强塑料片、纤维增强塑料的制造方法以及纤维增强塑料

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381506A (zh) * 2008-09-26 2009-03-11 广东生益科技股份有限公司 无卤无磷阻燃环氧树脂组合物以及用其制作的粘结片与覆铜箔层压板
JP2010275374A (ja) * 2009-05-26 2010-12-09 Panasonic Electric Works Co Ltd フレキシブルプリント配線板用樹脂組成物、樹脂フィルム、プリプレグ、樹脂付き金属箔、フレキシブルプリント配線板
JP2010275375A (ja) * 2009-05-26 2010-12-09 Panasonic Electric Works Co Ltd プリント配線板用エポキシ樹脂組成物、樹脂フィルム、プリプレグ、樹脂付き金属箔、フレキシブルプリント配線板

Family Cites Families (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3836409A1 (de) * 1988-10-26 1990-05-03 Ferrozell Sachs & Co Gmbh Prepregs fuer selbstverloeschende verbundwerkstoffe und verfahren zu deren herstellung
US5037869A (en) * 1990-06-08 1991-08-06 Monsanto Company Process for preparing flame retardant polyamide molding resins containing melamine cyanurate
JPH07331033A (ja) * 1994-06-15 1995-12-19 Sumitomo Bakelite Co Ltd 強靭で難燃性良好なエポキシ樹脂組成物
JPH08301982A (ja) * 1995-05-09 1996-11-19 Toray Ind Inc 繊維強化複合材料用エポキシ樹脂組成物、プリプレグおよびコンポジット
JPH1135795A (ja) * 1997-07-14 1999-02-09 Hitachi Chem Co Ltd エポキシ樹脂組成物、エポキシ樹脂プリプレグ及びエポキシ樹脂積層板
JPH11140277A (ja) * 1997-11-10 1999-05-25 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及びこれを用いた半導体装置
JP4029456B2 (ja) * 1998-01-29 2008-01-09 日立化成工業株式会社 難燃性非ハロゲンエポキシ樹脂組成物、それを用いたプリプレグ及び電気配線板用積層板
WO2000039188A1 (fr) * 1998-12-25 2000-07-06 Mitsubishi Rayon Co., Ltd. Composition de resine epoxyde, preimpregne, et rouleau a base de resine renforcee avec des fibres de renforcement
US6440567B1 (en) * 2000-03-31 2002-08-27 Isola Laminate Systems Corp. Halogen free flame retardant adhesive resin coated composite
JP2001302823A (ja) * 2000-04-24 2001-10-31 Nippon Mitsubishi Oil Corp 繊維強化複合材料用樹脂組成物、プリプレグおよび繊維強化複合材料
JP4478294B2 (ja) * 2000-06-02 2010-06-09 ポリプラスチックス株式会社 難燃性樹脂組成物
JP2002003702A (ja) * 2000-06-21 2002-01-09 Matsushita Electric Works Ltd エポキシ樹脂組成物、絶縁フィルム、樹脂付き金属箔及び多層プリント配線板
CN100345679C (zh) * 2000-12-12 2007-10-31 C核心技术公司 带有传导约束芯的轻重量电路板
US6998434B2 (en) * 2001-02-05 2006-02-14 Toray Industries, Inc. Carbon fiber reinforced resin composition, molding compounds and molded products therefrom
JP2003238657A (ja) * 2002-02-14 2003-08-27 Toray Ind Inc エポキシ樹脂組成物、樹脂硬化物、プリプレグおよび繊維強化複合材料
WO2003082976A1 (en) * 2002-03-28 2003-10-09 Sumitomo Bakelite Company Limited Thermosetting resin composition and epoxy resin molding material using the composition and semiconductor device
JP4400060B2 (ja) * 2003-02-17 2010-01-20 日立化成工業株式会社 絶縁樹脂組成物及びその使用
US20040166241A1 (en) * 2003-02-20 2004-08-26 Henkel Loctite Corporation Molding compositions containing quaternary organophosphonium salts
US6936646B2 (en) * 2003-04-30 2005-08-30 Henkel Corporation Flame-retardant molding compositions
WO2005082982A1 (ja) 2004-02-27 2005-09-09 Toray Industries, Inc. 炭素繊維強化複合材料用エポキシ樹脂組成物、プリプレグ、一体化成形品、繊維強化複合材料板、および電気・電子機器用筐体
JP2006124434A (ja) * 2004-10-26 2006-05-18 Matsushita Electric Works Ltd エポキシ樹脂無機複合シート及び成形品
US7718741B2 (en) * 2005-03-18 2010-05-18 Dainippon Ink And Chemicals, Inc. Epoxy resin composition and cured article thereof, novel epoxy resin and production method thereof, and novel phenol resin
JP2006265458A (ja) * 2005-03-25 2006-10-05 Yokohama Rubber Co Ltd:The プリプレグ用樹脂組成物およびプリプレグ
JP2006291094A (ja) * 2005-04-13 2006-10-26 Yokohama Rubber Co Ltd:The 繊維強化複合材料用エポキシ樹脂組成物
CA2615104C (en) * 2005-07-13 2010-12-21 Mitsubishi Rayon Co., Ltd. Prepreg
ATE496971T1 (de) * 2005-11-16 2011-02-15 Basf Se Flammwidrige prepregs und laminate für leiterplatten
JP2007224162A (ja) * 2006-02-23 2007-09-06 Matsushita Electric Works Ltd 難燃性樹脂組成物、プリプレグ、樹脂シート、成形品
US8138245B2 (en) * 2006-04-04 2012-03-20 Dsm Ip Assets B.V. Halogen free flame retardant polyester composition
JP2007291227A (ja) * 2006-04-25 2007-11-08 Toto Kasei Co Ltd 難燃性炭素繊維強化複合材料
WO2008020594A1 (fr) * 2006-08-17 2008-02-21 Nipponkayaku Kabushikikaisha Résine époxy liquide modifiée, composition de résine époxy contenant celle-ci et produit cuit dérivé
US7687722B2 (en) * 2006-10-03 2010-03-30 Endicott Interconnect Technologies, Inc. Halogen-free circuitized substrate with reduced thermal expansion, method of making same, multilayered substrate structure utilizing same, and information handling system utilizing same
KR100847003B1 (ko) * 2006-11-21 2008-07-17 대덕전자 주식회사 인쇄 회로 기판을 위한 탄소 섬유 보강재
CA2735996A1 (en) * 2008-09-29 2010-04-01 Toray Industries, Inc. Epoxy resin composition, prepreg and fiber-reinforced composite material
EP2343327B1 (en) * 2008-10-22 2013-07-24 DIC Corporation Curable resin composition and cured product thereof, printed circuit board, and epoxy resin and method for producing same
TWI486372B (zh) * 2008-11-28 2015-06-01 Ajinomoto Kk Resin composition
JP5228853B2 (ja) * 2008-12-01 2013-07-03 東レ株式会社 エポキシ樹脂組成物、繊維強化複合材料およびそれらの製造方法
EP2412741B1 (en) * 2009-03-25 2019-10-23 Toray Industries, Inc. Epoxy resin composition, prepreg, carbon fiber reinforced composite material, and housing for electronic or electrical component
CN101597421A (zh) * 2009-07-09 2009-12-09 江苏兴华胶带股份有限公司 无卤无磷阻燃环氧树脂组成物及其制造方法
GB2472423B (en) * 2009-08-05 2012-01-11 Gurit Uk Ltd Fire-retardant composite materials
TWI400297B (zh) * 2010-02-02 2013-07-01 Nanya Plastics Corp 印刷電路板用高導熱、無鹵難燃樹脂組成物及其預浸漬體及塗層物
TW201204548A (en) * 2010-02-05 2012-02-01 Sumitomo Bakelite Co Prepreg, laminate, printed wiring board, and semiconductor device
EP2557121B1 (en) * 2010-04-08 2020-03-04 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg and laminate
CN101851480A (zh) * 2010-05-11 2010-10-06 华烁科技股份有限公司 一种用于挠性覆铜板的无卤无磷阻燃合成树脂胶粘剂
CN103189418B (zh) * 2010-08-06 2015-08-12 日立化成株式会社 相容性树脂的制造方法、热固化性树脂组合物、预浸料及层叠板
US20120095132A1 (en) * 2010-10-19 2012-04-19 Chung-Hao Chang Halogen- and phosphorus-free thermosetting resin composition
WO2012165423A1 (ja) * 2011-05-31 2012-12-06 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ及び積層板
TWI513747B (zh) * 2011-06-13 2015-12-21 Nanya Plastics Corp A high frequency copper foil substrate and the composite material used
CN102276959B (zh) * 2011-06-22 2012-11-21 天津市凯华绝缘材料有限公司 一种非卤非磷化阻燃型环氧树脂组合物及其制备方法
CN102875968B (zh) * 2011-07-11 2016-05-11 滁州格美特科技有限公司 一种阻燃增强型环氧塑料板材及其制备方法
CN102276961A (zh) * 2011-07-22 2011-12-14 苏州生益科技有限公司 无卤无磷环氧树脂组合物及使用其制作的半固化片及层压板
CN102504532B (zh) * 2011-10-18 2013-09-18 广东生益科技股份有限公司 无卤低介电树脂组合物及使用其制作的预浸料与覆铜箔层压板
US9005761B2 (en) * 2011-12-22 2015-04-14 Elite Material Co., Ltd. Halogen-free resin composition and its application for copper clad laminate and printed circuit board
KR101188025B1 (ko) * 2012-02-20 2012-10-08 조연호 일방향 탄소섬유 프리프레그 직물을 이용한 복합재료 및 그를 이용한 동박적층판
KR101767690B1 (ko) * 2012-03-07 2017-08-11 심천 워트 어드밴스드 머티리얼즈 주식회사 열경화성 수지 제조용 조성물 및 그의 경화물, 상기 경화물을 포함하는 프리프레그, 및 상기 프리프레그를 채용한 금속박 적층판과 프린트 배선판
JP5919048B2 (ja) * 2012-03-15 2016-05-18 デンカ株式会社 エポキシ樹脂組成物、エポキシ樹脂シート、金属ベース回路基板
CN104271671B (zh) * 2012-03-29 2016-11-09 三菱瓦斯化学株式会社 树脂组合物、预浸料、树脂片和覆金属箔层叠板
US9190045B2 (en) * 2012-06-20 2015-11-17 Hyundai Motor Company Noise-absorbent fabric for vehicle and method for manufacturing the same
CN103540101B (zh) * 2012-07-17 2016-01-20 台光电子材料(昆山)有限公司 无卤素树脂组合物及应用其的铜箔基板及印刷电路板
TWI601755B (zh) * 2012-09-26 2017-10-11 Dainippon Ink & Chemicals Epoxy resin, curable resin composition, cured product thereof, and printed circuit board
KR101428426B1 (ko) * 2013-12-19 2014-08-07 현대자동차주식회사 내열성 및 성형성이 개선된 흡차음재 및 이의 제조방법
JP6536565B2 (ja) * 2014-03-06 2019-07-03 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、樹脂シート、金属箔張積層板及びプリント配線板
CN104974520B (zh) 2014-04-02 2017-11-03 广东生益科技股份有限公司 一种无卤树脂组合物及其用途
CN103881309B (zh) * 2014-04-11 2017-05-24 广东生益科技股份有限公司 一种无卤无磷阻燃树脂组合物
US20170158807A1 (en) * 2014-07-02 2017-06-08 Dic Corporation Epoxy resin composition for electronic material, cured product thereof and electronic member
JP6428153B2 (ja) * 2014-10-27 2018-11-28 味の素株式会社 樹脂組成物
US20170313043A1 (en) * 2014-10-27 2017-11-02 Zeon Corporation Curable epoxy composition and film, laminated film, prepreg, laminate, cured article, and composite article obtained using same
CN104448702B (zh) * 2014-11-11 2017-05-24 广东生益科技股份有限公司 一种无卤树脂组合物及用其制作的预浸料与层压板
CN104371273B (zh) * 2014-11-11 2017-05-24 广东生益科技股份有限公司 一种无卤树脂组合物及用其制作的预浸料与层压板
CN105778413B (zh) * 2014-12-26 2018-11-27 广东生益科技股份有限公司 一种无卤环氧树脂组合物以及使用它的预浸料和层压板
CN104610704A (zh) * 2015-01-28 2015-05-13 清远市普塞呋磷化学有限公司 一种无卤阻燃酸酐固化环氧树脂组合物
WO2016121356A1 (ja) * 2015-01-30 2016-08-04 パナソニックIpマネジメント株式会社 封止用エポキシ樹脂組成物、硬化物、及び半導体装置
CN106977879A (zh) * 2017-03-29 2017-07-25 江苏恒神股份有限公司 一种液体成型无卤低毒高阻燃性能碳纤维复合材料的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381506A (zh) * 2008-09-26 2009-03-11 广东生益科技股份有限公司 无卤无磷阻燃环氧树脂组合物以及用其制作的粘结片与覆铜箔层压板
JP2010275374A (ja) * 2009-05-26 2010-12-09 Panasonic Electric Works Co Ltd フレキシブルプリント配線板用樹脂組成物、樹脂フィルム、プリプレグ、樹脂付き金属箔、フレキシブルプリント配線板
JP2010275375A (ja) * 2009-05-26 2010-12-09 Panasonic Electric Works Co Ltd プリント配線板用エポキシ樹脂組成物、樹脂フィルム、プリプレグ、樹脂付き金属箔、フレキシブルプリント配線板

Also Published As

Publication number Publication date
US11319406B2 (en) 2022-05-03
KR20200078474A (ko) 2020-07-01
KR102684013B1 (ko) 2024-07-12
JP6896591B2 (ja) 2021-06-30
WO2019098201A1 (ja) 2019-05-23
TW201922876A (zh) 2019-06-16
TWI789455B (zh) 2023-01-11
JP2019089931A (ja) 2019-06-13
US20200339739A1 (en) 2020-10-29
CN111344338B (zh) 2022-08-23

Similar Documents

Publication Publication Date Title
JP5454138B2 (ja) エポキシ樹脂組成物、繊維強化複合材料、およびその製造方法
KR101190102B1 (ko) 일체화 성형품, 섬유강화 복합재료판, 및 전기/전자기기용 케이싱
JP6007914B2 (ja) 真空成形用プリプレグ、繊維強化複合材料およびその製造方法
WO2016199857A1 (ja) エポキシ樹脂組成物、成形品、プリプレグ、繊維強化複合材料および構造体
WO2013046452A1 (ja) 繊維強化樹脂複合材及びその製造方法
TW201041929A (en) Epoxy resin composition, prepreg, carbon fiber-reinforced composite material and electronic-electric component casings
US20200040146A1 (en) Method for preparing benzoxazine-containing resin composition, and prepreg and laminate made therefrom
TW200916513A (en) Composite material
JPS60260621A (ja) 成形材料用樹脂組成物
CN111344338B (zh) 预浸料、纤维强化复合材料及成形体
JP2011148938A (ja) エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
JP2007302746A (ja) リン含有変性エポキシ樹脂、難燃性マトリックス樹脂組成物、プリプレグ及び複合材料
JP5223781B2 (ja) 樹脂組成物、プリプレグ及び積層板
JP2017218573A (ja) エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
JP6913399B2 (ja) 熱硬化性樹脂組成物、繊維強化樹脂複合材料及びその製造方法
CN112262174A (zh) 环氧树脂配制物
JP2006077202A (ja) 難燃性プリプレグ
WO2022154041A1 (ja) 積層体、その製造方法およびプリプレグ
WO2021153644A1 (ja) エポキシ樹脂組成物、樹脂硬化物、プリプレグおよび繊維強化複合材料
JP2021183380A (ja) プリプレグ及び不燃材料
JP2024046878A (ja) エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
JP2023127055A (ja) 積層体
JP2020049681A (ja) 複合材及びプリプレグ積層体
JPS63265917A (ja) 成形材料用樹脂組成物

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP01 Change in the name or title of a patent holder

Address after: Tokyo, Japan

Patentee after: Yinnengshi Co.,Ltd.

Address before: Tokyo, Japan

Patentee before: JXTG Energy Corp.

CP01 Change in the name or title of a patent holder