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WO1998022527A1 - Composition de resine epoxyde appropriee au moulage en feuille - Google Patents

Composition de resine epoxyde appropriee au moulage en feuille Download PDF

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Publication number
WO1998022527A1
WO1998022527A1 PCT/EP1997/006507 EP9706507W WO9822527A1 WO 1998022527 A1 WO1998022527 A1 WO 1998022527A1 EP 9706507 W EP9706507 W EP 9706507W WO 9822527 A1 WO9822527 A1 WO 9822527A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy
composition
optionally
composition according
thickening agent
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.)
Ceased
Application number
PCT/EP1997/006507
Other languages
English (en)
Inventor
Seetha Maha Lakshmi Coleman-Kammula
Geert Florizoone
Isabelle Anette Marie Madeleine Tiberghien
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.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of WO1998022527A1 publication Critical patent/WO1998022527A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/40—Macromolecules 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/40—Macromolecules 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the invention relates to an epoxy resin composition suitable for use in the Sheet Moulding Compound (SMC) moulding process.
  • the composition can be made by mixing the ingredients, where after the composition thickens during storing for a number of days.
  • the thickened product thus obtained may be cured under subsequently- imposed curing conditions.
  • Sheet Moulding Compound (SMC) moulding has over the last years gained wide acceptance, especially in the automotive industry (bumpers, boot lids etc.) and further in the electrical industry (castings, low voltage applications etc.) .
  • the most commonly used resins in this technique are unsaturated polyester resins.
  • a reactive monomer is used to cross-link the resin.
  • a vinylmonomer is used as monomer and in particular styrene monomer is used.
  • a vinylmonomer (e.g. styrene) solution of the unsaturated carboxyl-terminated polyester is mixed with a peroxide (or other initiator) , a thickening agent such as magnesium oxide, and a filler such as calcium carbonate or clay.
  • This liquid mixture is then mixed with e.g. chopped fibre or fibreglass between two sheets of (polyethylene) film, and air bubbles are removed by squeeze rolls.
  • the viscosity increases from an initial value of usually between 0.01 and 100 Pa . s to a value usually in the range of 30.000 to 150.000 Pa.s.
  • the increase in viscosity is caused by reaction of the carboxyl end groups of the polyester with the thickening agent.
  • polyester based SMC compositions use is made of styrene as a reactive diluent. As styrene may leak from the aged/thickened sheet, it might impose a health risk, as styrene nowadays is considered to be a relatively hazardous compound. The exposure to styrene problem may be overcome by installing extractors, which is, however, an expensive solution. Further, government regulations are expected to come into force to reduce the use of styrene.
  • compositions comprise one or more liquid epoxy compounds, one or more acidic thickening compounds which react with a part of the epoxy groups at relatively low temperature resulting in a thickened composition, a latent curing agent which reacts with the remaining epoxy groups at relatively high temperature, resulting in a full cure of the composition, and optionally one or more catalyst for the reaction between the epoxy groups and the acidic thickening agent and/or the reaction between the epoxy groups and the curing agent, fillers and reinforcing fibres.
  • reactive diluents comprising an epoxy group may be present.
  • additives may be added as releasing agents, pigments, flame retardants, low profile additives etc.
  • the curing agent involved should be latent at room temperature for a period of at least 7 days and should only become active at temperatures of 80 °C and higher.
  • compositions of the present invention show better mechanical and thermal properties and an improved chemical resistance, especially against basic chemicals and acid chemicals, when compared with the traditional polyester based SMC compositions. It is furthermore observed that the compositions according to the present invention show viscosity properties closely corresponding to the conventional SMC compositions, as initial and final viscosity and time-viscosity profile, while also the curing rate is more or less comparable.
  • compositions according to the present invention show initial viscosities of the total composition in the range of from 30 to 100 Pa.s, final viscosities of the total composition in the range of from 30,000 to 150,000 and a time-viscosity profile during thickening, characterized by the beforementioned viscosity increase within a period from 1 hour to 80 hours.
  • initial viscosities of the total composition in the range of from 30 to 100 Pa.s
  • final viscosities of the total composition in the range of from 30,000 to 150,000
  • a time-viscosity profile during thickening characterized by the beforementioned viscosity increase within a period from 1 hour to 80 hours.
  • the present invention relates to a composition
  • a composition comprising (1) a liquid epoxy compound comprising on average more than one epoxy group per molecule, (2) a thickening agent comprising on average more than one carboxylic acid group per molecule or the anhydride thereof, which thickening agent effectively thickens the composition at ambient conditions, (3) optionally a catalyst for the reaction between the epoxy compound and the thickening agent, (4) a curing agent which effectively cures the epoxy compounds at elevated temperature, (5) optionally a catalyst for the reaction between the epoxy compounds and the curing agent, (6) optionally reinforcement fibres and (7) optionally a filler compound.
  • the present invention preferably relates to compositions free of vinylmonomer, and in particular styrene, and free of solvent.
  • At ambient conditions is meant that a reaction takes place at temperatures in the range of from 10 to 50 °C and under atmospheric pressure.
  • the epoxy resins used as starting material in the present invention generally have an average of more than one, suitably at least 1.5, preferably at least 1.7, reactive 1,2-epoxy groups per molecule.
  • These epoxy compounds generally have an average of up to 6, preferably up to 4, more preferably up to 2.5, reactive 1,2-epoxy groups per molecule.
  • These epoxy compounds can be monomeric or polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heteroaromatic and may be substituted, if desired, with other substituents in addition to the epoxy groups, e.g. hydroxyl groups, alkoxyl groups or halogen atoms, especially bromine atoms.
  • Suitable epoxy compounds are the reaction products of polyphenols and epihalohydrins, polyalcohols and epihalo- hydrins, amines and epihalohydrins, sulphur containing compounds and epihalohydrins, polycarboxylic acids and epihalohydrins or mixtures thereof.
  • Preferred epoxy compounds are the reaction products of polyphenols and epihalohydrins, of polyalcohols and epihalohydrins, polycarboxylic acids and epihalohydrins or mixtures thereof, the reaction products of polyphenols and epihalohydrins especially preferred.
  • Illustrative examples of epoxy compounds are described in for instance The Handbook of Epoxy Resins by H. Lee and K. Neville, McGraw-Hill, New York (1967), Epoxy Resins, Chemistry and Technology, edited by CA. May, Marcel Dekker (1988) and Chemistry and Technology of Epoxy Resins, edited by B. Ellis, Blackie Academic & Professional (1993) .
  • Epoxy compounds of particular interest in the practice of the present invention include diglycidyl ethers of bisphenol compounds, particularly those compounds represented by general formula I,
  • each A independently is a divalent hydrocarbon group having 1 to 8 carbon atoms, preferably methylene or isopropylidene, -C(0) ⁇ , -0-, -S- , -S-S-, -S(O)-, -S(0)2- or a covalent bond
  • each X independently is hydrogen, an alkyl group having 1 to 4 carbon atoms, preferably methyl, or halogen, preferably chlorine or bromine
  • n has an average value of 0 to 12, preferably 0 to 2. More preferably A is isopropylene, X is hydrogen or bromine, especially hydrogen, and n is up to 0.2.
  • the average epoxy equivalent weight is from 140 to 3000 and preferably from 170 up to 950, more preferably from 180 to 450
  • epoxy compounds are those derived from bisphenol A and bisphenol F type epoxy compounds and preferably bisphenol A type epoxy compounds, having an average epoxy equivalent weight of from 160 to 200. They are commercially available from Shell Chemicals Europe under the trade names EPIKOTE 826, 828, 862 and 806.
  • epoxy compounds derived from brominated. bisphenol A compounds can be used and more in particular those which have an epoxy equivalent of from 200 to 800.
  • Further useful epoxy compounds are epoxy novolac resins.
  • the epoxy novolac resins can be obtained by reacting, preferably in the presence of a basic catalyst, e.g. sodium or potassium hydroxide, an epihalohydrin, e.g.
  • epichlorohydrin with the resinous condensate of an aldehyde, e.g. formaldehyde, and either a monohydric phenol, e.g. phenol itself, or a polyhydric phenol. Further details concerning the nature and preparation of these epoxy novolacs resins can be obtained in Handbook of Epoxy Resins and the other references mentioned above.
  • the above-mentioned epoxy compounds are obtainable by means known for the preparation of epoxy resins from a compound containing hydroxyl groups by reacting such compounds with an epihalohydrin in the presence of a suitable catalyst and reacting the resultant intermediate halohydrin ether with a basic acting substance such as an alkali metal hydroxide. It has to be observed that many of the usual epoxy compounds to be used for the production of the modified resins of this invention will be commercially available.
  • the thickening agents used as starting material in the present invention generally have on average two or more carboxyl groups per molecule and more in particular from 2 to 6 on average .
  • the thickening agent can be monomeric or polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heteroaromatic and may be substituted, if desired, with other substituents in addition to the carboxyl groups, e.g. hydroxyl groups, alkoxyl groups, alkyl groups and in particular those having from 1 to 4 carbon atoms, or halogen atoms, especially bromine atoms.
  • thickening agents can be used wherein a part of the total present carboxyl groups have been transformed into anhydride groups.
  • the thickening agent is a saturated or unsaturated aliphatic or cycloaliphatic dicarboxylic acid, optionally substituted by one or more alkyl groups, especially Cl-4 alkyl groups, more especially methyl groups, or the corresponding anhydride.
  • the aliphatic or cycloaliphatic part suitably comprises 4 to 9 carbon atoms, preferably 5 to 7 carbon atoms.
  • Examples are hexahydrophthalic acid, tetrahydrophthalic acid, dihydro- phthalic acid, methyl hexahydrophthalic acid, methyl tetrahydrophthalic acid, methyl endomethylene tetrahydrophthalic acid or the corresponding anhydrides.
  • the anhydrides are used.
  • Another type of suitable thickening agents are the dicarboxylic reaction products of the above described anhydrides and aliphatic dialcohols. Suitable dialcohols comprising between two and eight carbon atoms, optionally substituted by one or more Cl-4, especially methyl groups, can be used.
  • the thickening agent is a liquid at ambient temperature, or is a low melting compound, e.g. melting below 50 °C, especially below 30 °C.
  • the amount of thickening agent to be used will be less then the stoichiometric amount with respect to the epoxy groups. Suitably up to 0.75 equivalents of carboxylic groups with respect to epoxy groups will be used, especially less then 0.50 equivalents. Preferably the amount is between 0.05 and 0.25, more preferably about 0.15 equivalent.
  • the amount of thickening agent should always result in an effective thickening of the composition, i.e. the composition should be converted in a mouldable composition in a practical period of time.
  • a suitable conversion period is between 1 and 40 days, more suitably between 2 and 30 days, preferably between 3 and 20 days. Especially a period between 10 and 15 days is used.
  • the thickening of the composition is suitably carried out at temperatures between 0 °C and 60 °C, more suitably between 10 °C and 50 °C, especially between 15 °C and 40 °C, preferably between 20 °C and 30 °C. It will be appreciated that when the thickening agent has been consumed, no further increase in viscosity will occur due to the reaction between the thickening agent and the epoxy compound.
  • the viscosity of the mouldable composition is suitably between 20,000 and 300,000 Pa.s, more suitably between 25,000 and 250,000 Pa.s. Preferably the viscosity is between 30,000 and 200,000, more preferably between 50,000 and 150,000.
  • the latent curing agent to be used in the compositions of the present invention may be each suitable curing agent to cure epoxy resins at elevated temperature, i.e. a temperature above 80 °C, suitably above 120 °C. Curing agents which reacts at lower temperature will result in products which have an insufficiently long shelf live.
  • the shelf live of the thickened composition should be at least 10 days, suitably at least 20 days, preferably at least 30 days, more preferably at least two months. Very attractive are shelf lives of three months or more, e.g. up to a year.
  • Suitable curing agents are polyamine, polyamide, polyamidoamine and polyaminoadduct, a polycarboxylic acid or anhydride thereof or a polyphenolic compound.
  • Suitable examples include primary and secondary aliphatic polyamines, modified imidazoles, carboxylic acids and anhydrides thereof, phenolic hydroxyl-containing compounds, guanidines, biguanidines, polyamides, Mannich bases, ketimines, oxazolines and combinations thereof.
  • Particularly suitable curing agents include, for example, ethylene diamine, diethylenetri- amine, triethylenetetramine, dicyandiamide, modified imidazoles, diaminocyclohexane, adipic acid, phosphoric acid or combinations thereof.
  • Many of the suitable curing agents are commercially available.
  • the curing agents are employed in an amount which will effectively cure the composition containing the modified epoxy resin. These amounts will depend upon the particular epoxy resin and the curing agent employed. Suitable amounts are from 0.4 to 1.2, suitably from 0.6 to 1.1, more suitably from 0.8 to 1.0, most suitably about 1 equivalent of curing agent per epoxide equivalent (remained after thickening) for those curing agents which cure by reacting with the epoxy group of the epoxy resin.
  • the Handbook of Epoxy Resins and the other two references mentioned above contain various discussions concerning the curing of epoxy resins as well as a compilation of suitable curing agents.
  • Curing is suitably performed at temperatures between 90 and 250 °C, especially between 120 and 200 °C. Curing times depend on curing agent and temperature, but should be such that substantially all (i.e. more than 95 percent, preferably more than 98 percent) reactive groups have reacted. Usually the curing time is between 1 and 120 minutes, suitably between 2 and 60 minutes, preferably between 3 and 30 minutes, more preferably between 4 and 20 minutes.
  • a catalyst may be used for the thickening of the composition.
  • accelerators such as ureas, tertiary amines, imidazoles, phosphenes, octoates, and boron trifluorides are known in the literature. In this respect reference is also made to the three general references mentioned above.
  • the preferred accelerators are imidazoles, for example 1-methyl imida- zole, 2-ethyl imidazole, 2-methyl-4-ethyl imidazole and isopropyl imidazole. Because of its availability and performance characteristics, 2-methyl imidazole is the preferred accelerator.
  • the accelerator will be present in the composition in an amount effective to increase the cure rate and/or lower the cure temperature of the composition, generally in an amount from 0.01 to 7, preferably from 0.05 to 3 weight percent, based on the weight of the composition.
  • thermosettable compositions of the present invention can be blended with other materials such as (reactive) diluents, pigments, dyes, flow modifiers, thickeners, anti-foamers, fire retarding or suppressing agents and combinations thereof.
  • additives are added in functionally amounts, e.g. the pigments and/or dyes are added in quantities which will provide the composition with the desired colour.
  • the amount of additives is from 0 to 50 percent by weight, especially 2 to 20 percent, based upon the combined weight of the epoxy resin and the curing agent.
  • the composition usually will contain reinforcement fibres such chopped fibres, woven- or non woven mats etc.
  • the fibres are suitable made from glass or mineral wool, but may also be nylon fibres, aramide fibres, carbon fibres etc.
  • fillers may be applied in the compositions of the present application.
  • Suitable fillers are aluminium oxide, silica, modified montmorillonites, calcium carbonate and clay.
  • SMC compositions according to the present invention were prepared, comprising the ingredients as listed in the following Table 1, which also contains the respective relevant physical properties of the cured compositions .
  • SMC compositions Two SMC compositions were prepared. One of them, derived from an epoxy resin is to be regarded as a typical representative of the compositions according to the present invention (Ex. 3), and the other, derived from a polyester resin, as a typical representative of the usual prior art compositions (Co p. Ex. a) .
  • composition ingredients and the relevant properties have been listed in Tables 2 and 3.

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

Abstract

Cette invention porte sur une composition qui comprend 1) un composé époxy liquide contenant en moyenne plus d'un groupe époxy par molécule, 2) un agent épaississant contenant en moyenne plus d'un groupe acide carboxylique par molécule ou l'anhydride dudit groupe, ledit agent épaississant épaississant efficacement la composition dans des conditions ambiantes, 3) éventuellement un catalyseur pour faire réagir le composé époxy avec l'agent épaississant, 4) un agent de traitement latent qui cuit efficacement les composés époxy à des températures élevées, 5) éventuellement un catalyseur pour faire réagir les composés époxy avec l'agent de traitement, 6) éventuellement des fibres de renforcement et 7) éventuellement un composé de charge.
PCT/EP1997/006507 1996-11-18 1997-11-17 Composition de resine epoxyde appropriee au moulage en feuille Ceased WO1998022527A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP96203221.5 1996-11-18
EP96203221 1996-11-18

Publications (1)

Publication Number Publication Date
WO1998022527A1 true WO1998022527A1 (fr) 1998-05-28

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WO (1) WO1998022527A1 (fr)
ZA (1) ZA9710293B (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103497287A (zh) * 2013-09-09 2014-01-08 华东理工大学华昌聚合物有限公司 一种smc/bmc用环氧乙烯基酯树脂的合成工艺
EP2803687A1 (fr) 2013-05-13 2014-11-19 Basf Se Composition de résine époxide pour produits fibre-matrice semi-finis
WO2016182077A1 (fr) * 2015-05-13 2016-11-17 三菱レイヨン株式会社 Mélange à mouler en feuille et matériau composite renforcé par des fibres
EP3178863A1 (fr) 2015-12-11 2017-06-14 Evonik Degussa GmbH Compositions de résine epoxydes destinées à la fabrication de composites stables en stock
WO2018077836A1 (fr) 2016-10-28 2018-05-03 Basf Se Composition de résine époxy à durcissement rapide pour produits semi-finis à matrice fibreuse
CN110536914A (zh) * 2017-04-12 2019-12-03 三菱化学株式会社 片状模塑料及纤维增强复合材料
WO2023054575A1 (fr) 2021-09-29 2023-04-06 三菱ケミカル株式会社 Procédé de production de préimprégné et préimprégné
EP4180477A1 (fr) 2021-11-15 2023-05-17 Evonik Operations GmbH Composites de résine époxy destinés à la fabrication de composites stables au stockage

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995021738A1 (fr) * 1994-02-14 1995-08-17 Thiokol Corporation Formules de resine a matrice adaptee par des methodes chimiorheologiques, contenant des agents de polymerisation anhydrides
WO1995022437A1 (fr) * 1994-02-18 1995-08-24 Thiokol Corporation Formules de resines matricielles contenant des durcisseurs anhydres et des tensioactifs

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995021738A1 (fr) * 1994-02-14 1995-08-17 Thiokol Corporation Formules de resine a matrice adaptee par des methodes chimiorheologiques, contenant des agents de polymerisation anhydrides
WO1995022437A1 (fr) * 1994-02-18 1995-08-24 Thiokol Corporation Formules de resines matricielles contenant des durcisseurs anhydres et des tensioactifs

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US10017614B2 (en) 2013-05-13 2018-07-10 Reichhold As Epoxy-resin composition for fiber-matrix semifinished products
EP2803687A1 (fr) 2013-05-13 2014-11-19 Basf Se Composition de résine époxide pour produits fibre-matrice semi-finis
WO2014184012A1 (fr) 2013-05-13 2014-11-20 Basf Se Composition de résine époxy pour produits semi-finis fibres-matrice
KR20160006752A (ko) * 2013-05-13 2016-01-19 바스프 에스이 섬유-매트릭스 반마감 생성물용 에폭시드 수지 조성물
CN105377939A (zh) * 2013-05-13 2016-03-02 巴斯夫欧洲公司 用于纤维基质半成品的环氧树脂组合物
JP2016517910A (ja) * 2013-05-13 2016-06-20 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 繊維マトリックス半製品のためのエポキシ樹脂組成物
CN111647255A (zh) * 2013-05-13 2020-09-11 赖克霍德股份有限公司 用于纤维基质半成品的环氧树脂组合物
KR102205915B1 (ko) * 2013-05-13 2021-01-21 레이크홀드 에이에스 섬유-매트릭스 반마감 생성물용 에폭시드 수지 조성물
TWI686420B (zh) * 2013-05-13 2020-03-01 挪威商瑞奇豪德公司 用於纖維基質半成品的環氧樹脂組成物
CN103497287A (zh) * 2013-09-09 2014-01-08 华东理工大学华昌聚合物有限公司 一种smc/bmc用环氧乙烯基酯树脂的合成工艺
WO2016182077A1 (fr) * 2015-05-13 2016-11-17 三菱レイヨン株式会社 Mélange à mouler en feuille et matériau composite renforcé par des fibres
US10494475B2 (en) 2015-05-13 2019-12-03 Mitsubishi Chemical Corporation Sheet-molding compound and fiber-reinforced composite material
JPWO2016182077A1 (ja) * 2015-05-13 2017-05-25 三菱ケミカル株式会社 シートモールディングコンパウンド及び繊維強化複合材料
EP3178863A1 (fr) 2015-12-11 2017-06-14 Evonik Degussa GmbH Compositions de résine epoxydes destinées à la fabrication de composites stables en stock
WO2018077836A1 (fr) 2016-10-28 2018-05-03 Basf Se Composition de résine époxy à durcissement rapide pour produits semi-finis à matrice fibreuse
CN110536914A (zh) * 2017-04-12 2019-12-03 三菱化学株式会社 片状模塑料及纤维增强复合材料
EP3611210A4 (fr) * 2017-04-12 2020-05-06 Mitsubishi Chemical Corporation Composé de moulage en feuille et matériau composite renforcé par des fibres
JP2022179548A (ja) * 2017-04-12 2022-12-02 三菱ケミカル株式会社 シートモールディングコンパウンド、および繊維強化複合材料
CN110536914B (zh) * 2017-04-12 2023-03-14 三菱化学株式会社 片状模塑料及纤维增强复合材料
JP2024097920A (ja) * 2017-04-12 2024-07-19 三菱ケミカル株式会社 シートモールディングコンパウンド、および繊維強化複合材料
US12275838B2 (en) 2017-04-12 2025-04-15 Mitsubishi Chemical Corporation Sheet molding compound and fiber-reinforced composite material
JP7726332B2 (ja) 2017-04-12 2025-08-20 三菱ケミカル株式会社 シートモールディングコンパウンド、および繊維強化複合材料
WO2023054575A1 (fr) 2021-09-29 2023-04-06 三菱ケミカル株式会社 Procédé de production de préimprégné et préimprégné
EP4180477A1 (fr) 2021-11-15 2023-05-17 Evonik Operations GmbH Composites de résine époxy destinés à la fabrication de composites stables au stockage
WO2023083782A1 (fr) 2021-11-15 2023-05-19 Evonik Operations Gmbh Compositions de résine époxy pour la production de composites stables au stockage

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ZA9710293B (en) 1998-06-10

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