WO2017114416A1 - Composite honeycomb sandwich board and method for preparing the same - Google Patents

Composite honeycomb sandwich board and method for preparing the same Download PDF

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Publication number
WO2017114416A1
WO2017114416A1 PCT/CN2016/112651 CN2016112651W WO2017114416A1 WO 2017114416 A1 WO2017114416 A1 WO 2017114416A1 CN 2016112651 W CN2016112651 W CN 2016112651W WO 2017114416 A1 WO2017114416 A1 WO 2017114416A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
honeycomb sandwich
sandwich board
composite honeycomb
coupling agent
Prior art date
Application number
PCT/CN2016/112651
Other languages
French (fr)
Inventor
Wei Zhou
Yongliang SUN
Fulan TANG
Original Assignee
Byd Company Limited
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 Byd Company Limited filed Critical Byd Company Limited
Publication of WO2017114416A1 publication Critical patent/WO2017114416A1/en

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    • B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
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Definitions

  • the present disclosure relates to a composite material in a sandwich structure, specifically to a composite honeycomb sandwich board and a method for preparing the same.
  • honeycomb sandwich board with structure characteristics of light weight, high specificstrength and stiffness and function characteristics such as sound and heat insulationhas been widely used in the engineering field, such as aerospace, ships, high-speed trains, wind turbine blades, civil construction.
  • the honeycomb sandwich board is commonly constitutedbyplacing a corelayer (ina honeycomb structure) between two outer layers (which may be made of a metal material or a resin composite material) .
  • the two outer layers provide strength in tension (e.g., most bending moment) for the core layer, while the core layer mainly resists to shearing force and guaranteesreliable connection with the twoouter layers.
  • it is generally to process thetwoouter layers and the core layerseparatelyat first, which are then subjected to combination by means of jointingwith an adhesive directly.
  • the existingadhesive usually a solvent adhesive
  • a solvent adhesive has disadvantages such as being unfriendly to environment, low bonding strength, and delamination tendency between the two outer layers (e.g., made of aluminum or resin composite material) and the core layer (in a honeycomb structure) .
  • An object of the present disclosure is to provide a composite honeycomb sandwich board and a method for preparing the composite honeycomb sandwich board, so as to improve bondingstrengthbetween a core layerin a honeycomb structureandan outer layer made of an epoxy resin reinforcing material, thereby being friendly to environment.
  • a composite honeycomb sandwich board including: a core layer, in a honeycomb structure, having upper and lower surfaces, and made of aluminum; and an outer layer, combined at at least one of the upper and lower surfaces and made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition;
  • the epoxy resin composition includes an epoxy resin, a latent curing agent, an accelerator, a coupling agent, and optionally a toughening agent and a filler; and the coupling agent includes an amido-containing silane coupling agent.
  • the present disclosure provides in embodimentsa method for preparing the composite honeycomb sandwich board mentioned above.
  • the method includes: providing an outer layer made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition, and the epoxy resin compositionincludes an epoxy resin, a latent curing agent, an accelerator, a coupling agent, optionally a toughening agent and a filler; providing a core layer, in a honeycomb structure and made of aluminum; and placing the outer layer at at least one of upper and lower surfaces of the core layer followed by heat pressing treatment, so as to obtain the composite honeycomb sandwich board.
  • the composite honeycomb sandwich board according to embodiments of the present disclosure has the following advantages.
  • the outer layer made oftheepoxy resin reinforcing material is combined at at least one of upper and lower surfaces of the core layerin the honeycomb structure by means of curing the epoxy resin reinforcing material through the heating press treatment, resulting in no need to use the solventadhesive, thereby being friendly to environment.
  • the amino-containing silane coupling agent is added to the resin composition, such that the outer layer outer layer is combined with the core layer with a relative stable structure during curing the epoxy resin reinforcing material, thereby improving the bonding strength between the outer layer and the core layer, and avoiding occurrence of delamination for the composite honeycomb sandwich board.
  • a composite honeycomb sandwich board including: a core layer, in a honeycomb structure, having upper and lower surfaces, and made of aluminum; and an outer layer, combined at at least one of the upper and lower surfaces and made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition;
  • the epoxy resin composition includes an epoxy resin, a latent curing agent, an accelerator, a coupling agent, and optionally a toughening agent and a filler; and the coupling agent includes an amido-containing silane coupling agent.
  • the outer layer made of the epoxy resin reinforcing material is combined at at least one of upper and lower surfaces of the core layerin the honeycomb structure by means of curing the epoxy resin reinforcing material through the heating press treatment, resulting in no need to use a solventadhesive, thereby being friendly to environment.
  • the amino-containing silane coupling agent is added to the resin composition, such that the outer layer outer layer is combined with the core layer with a relative stable structure during curing the epoxy resin reinforcing material, thereby improving the bonding strength between the outer layer and the core layer, and avoiding occurrence of delamination for the composite honeycomb sandwich board.
  • the coupling agent includes but not limited to one or more of ⁇ -amigrammagenopropyltriethoxysilane (i.e., H 2 N (CH 2 ) 3 Si (OC 2 H 5 ) 3 , for example GradesA-1100 andKH-550) , ⁇ -aminopropyltrimethoxysilane (i.e., H 2 N (CH 2 ) 3 Si (OCH 3 ) 3 , for example Grade A-1110) , N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane (NH 2 (CH 2 ) 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 , for example Grades A-1120 andKBM-603) , N- ⁇ (aminoethyl) - ⁇ -aminopropyl methyl dimethoxysilane (NH 2 (CH 2 ) 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 , for example Grades A-11
  • the coupling agent includes the amino-containingsilane coupling agent.
  • the amino-containingsilane coupling agent contains at least two amino groups, thereby further enhancingthe bonding strength between the core layer and the outer layer.
  • the amino-containingsilane coupling agent withat least two amino groups includes but not limited to one or more of N- (6-aminohexyl) aminomethyltriethoxysilane (for example GradeSIA0592.6 purchased from Gelest Company) , N- (2-N-benzyl aminoethyl) -3-aminopropyl trimethoxysilane (for example Grade SIB0956.0 purchased from Gelest Company) , diethylenetriaminepropyl trimethoxysilane (for example Grade SIA0400.0 purchased from Gelest Company) , bis [3-trimethoxysilyl) propyl] ethylenediamine and N-3- [amino isopropyl (polyoxy isopropyl) ] aminopropyltrimethoxysilane.
  • N- (6-aminohexyl) aminomethyltriethoxysilane for example GradeSIA0592.6 purchased from Gelest Company
  • the coupling agentfurther includesanepoxy-containingsilane coupling agent.
  • the amino-containingsilane coupling agent and the epoxy-containingsilane coupling agent are used in combination, thereby further enhancingthe bonding strength between the core layerand the outer layer.
  • a weight ratio of the epoxy-containingsilane coupling agent to the amino-containingsilane coupling agent ranges from 0.5: 1 to 2: 1.
  • the epoxy-containingsilane coupling agent is selected from one or more of 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane (A-1861 purchased from Momentive Company) , 2- (3, 4-epoxy cyclohexane) ethyltrimethoxysilane, (3-epoxypropoxy propyl) trimethoxysilane, (3-epoxypropoxy propyl) triethoxysilane (KH560 purchased from Shenzhen YouYueChangHao Co., Ltd.
  • the epoxy-containingsilane coupling agent further includes one or more of A-187 and A-186 purchased from Momentive Company, as well as Z-6041 andZ-6042 purchased from Dow Corning Company. In still other embodiments of present disclosure, the epoxy-containingsilane coupling agentcontains two epoxy groups.
  • the coupling agentfurther includes the coupling auxiliary agent.
  • the coupling auxiliary agent is selected from one or more of (C 2 H 5 O) 3 Si-CH 2 CH 2 -Si- (C 2 H 5 O) 3 , (C 2 H 5 O) 3 Si-CH 2 RCH 2 -Si- (C 2 H 5 O) 3 and (CH 3 O) 3 Si-CH 2 RCH 2 -Si- (CH 3 O) 3 , in whichR is a reactive organic group (for example selected from one or a moreof -NH-, -CH 2 -, -CHOH, -CH (O) CH-, -COO-and -CHCOOH) and/or a non-reactive organic group (for example selected from one or more of -CH 2 -, -CH 2 CH 2 -and -CH 2 CH 2 CH 2 -) .
  • R is a reactive organic group (for example selected from one or a moreof -NH-, -CH 2 -, -CHOH, -CH (O) CH-, -COO
  • the amino-containingsilane coupling agent and/or the epoxy-containingsilane coupling agent are/is used in the silane coupling agent, in combination with thecoupling auxiliary agent, such that the bonding strength between the core layerand the outer layers are further enhanced.
  • aweight ratio of the coupling auxiliary agent to the amino-containingsilane coupling agent ranges from 0.1: 1 to 0.5: 1.
  • the coupling auxiliary agent includes but not limit to one or more of (CH 3 O) 3 Si-CH 2 CH 2 -Si- (CH 3 O) 3 , (CH 3 O) 3 Si-CH 2 NHCH 2 -Si- (CH 3 O) 3 , (CH 3 O) 3 Si-CH 2 -CH (O) CH-CH 2 -Si- (CH 3 O) 3 .
  • (CH 3 O) 3 Si-CH 2 CH 2 -Si- (CH 3 O) 3 may be Grade 1817 purchased from Gelest Company.
  • the epoxy resin composition includes 35wt%to 90wt%of the epoxy resin (e.g, a hot-melt type) , 1wt%to 10wt%of the latent curing agent, 0.1wt%to 5wt%of the silane coupling agent, 0wt%to 40wt%of the toughening agent, 0.5wt%to 20wt%of the accelerator, and 0wt%to 60wt%of the fillers.
  • the epoxy resin composition e.g, a hot-melt type
  • the epoxy resin composition in other embodiments of present disclosure, based on the total weight of the epoxy resin composition, the epoxy resin compositionincludes 35wt%to 90wt%of the epoxy resin, 3wt%to 8wt%of the latent curing agent, 0.3wt%to 3wt%of the silane coupling agent, 3wt%to 15wt%of the toughening agent, 0.5wt%to 5wt%of the accelerator, and 0wt%to 60wt%of the fillers, in which the epoxy resin composition does not include a solvent.
  • the epoxy resin is capable of impregnatinginto the reinforcing materialafter hot meltedby heating.
  • the epoxy resin includes but not limited to one of more of bisphenol A epoxy resin, bisphenolF epoxy resin, phenolic epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenolF epoxy resin, cycloaliphatic epoxy resin, o-cresol epoxy resin, triglycidylisocyanurate, bisphenolfluorenyl epoxy resin, adamantaneepoxy resin and hydantoin epoxy resins.
  • the epoxy resin used in embodiments of the present disclosure may be a commercially available product, including but not limit to, epoxy resin purchased from TaiWanNanYa Epoxy Resin Co., Ltd, such as NPEL-127, NPEL-127E, NPEL-127H, NPEL-128, NPEL-128E, NPEL-128G, NPEL-128R, NPEL-128S, NPEL-134, NPEL-136, NPEL-134, NPEL-231, NPEF-164X, NPEF-170, NPEF-175, NPEF-176, NPEF-185, NPEF-187, NPEF-198, NPPN-631, NPPN-638, andNPPN-638S; epoxy resinpurchased from Nantong XingChenSynthetic Material Co., Ltd, such as0161, 0161L, 0161E, 0164, 0164E, 0164EA, 0164D, 0164C, 0174, 0174E, 0176E, 01
  • the epoxy resin in some embodiments of present disclosure, includes bisphenolA epoxy resin and phenolic epoxy resin. In some embodiments of present disclosure, based on the total weight of the epoxy resin, the epoxy resinincludes 60wt%to 85wt%of the bisphenolA epoxy resin and 15wt%to 40wt%of the phenolic epoxy resin.
  • the bisphenolA epoxy resin and the phenolic epoxy resin are used in combination, such thatthe bonding strength between the core layer and the outer layers are enhanced, while the outer layer is provided with improved heat resistance, therebyimprovingheat resistance forthe composite honeycomb sandwich board.
  • the bisphenolA epoxy resin is of an epoxide value of 0.3 to 0.6
  • the phenolic epoxy resin is of an epoxide value of 0.4 to 0.7.
  • the bisphenolA epoxy resin and the phenolic epoxy resin eachcan be a commercially available product.
  • the bisphenolA epoxy resin may be, for example, purchased from NanYa Epoxy Resin Co., Ltd, such asNPEL-127, NPEL-128, NPEL-134, NPEL-136 andNPEL-231; or purchased from LanXing Chemical New Materials Co., Ltd, such as840L, 840, 850S, 850A, 850D, 860L and860.
  • the phenolic epoxy resin maybe: for example, purchased from NanYa Epoxy Resin Co., Ltd, such asNPPN-631, NPPN-638 andNPPN-638S; or purchased from Dow Chemical Company, such asD. E. N. 438 orD. E. N. 439.
  • the latent curing agent is one or more of dicyandiamide, an imidazolium compound and organic hydrazine.
  • the imidazolium compound includes but not limited to one or more of an imidazole derivative such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole.
  • the organic hydrazine includes but not limited to a hydrazine compound such as adipodihydrazide and sebacicdihydrazide.
  • the latent curing agent can be a commercially available product, including but not limited to the dicyandiamidepurchased from Air Products and Chemicals, Inc; the imidazolium compound purchased from Shikoku Chemicals Corporation, such as2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ and2P4MHZ; and adipodihydrazide (organic hydrazide) purchased from Shandong Xiya Chemical Industry Co., Ltd.
  • the accelerator in the case that the latent curing agent is dicyandiamide, can be one or more of phenyldimethylurea, 2, 4-toluene bisdimethylurea, 4, 4 -methylene bisphenyl dimethylurea and alicyclicbiuret.
  • the accelerator can bea commercially available product purchased from German Evonik Degussa Company, suchUR300, UR500 andUR700.
  • the accelerator in the case that the latent curing agent is organic hydrazine, can be one or more of phenyldimethylurea, 2, 4-toluene bisdimethylurea, 4, 4 -methylene bisphenyl dimethylurea and alicyclicbiuret.
  • the toughening agent is one or more of polyurethane modified epoxy resin (with 5wt%to 30wt%of polyurethane, and an epoxy value of0.4 to 0.6) , carboxyl terminated nitrile rubber modified epoxy resin (with 5wt%to 40wt%of carboxyl terminated nitrile rubber, and an epoxy valueof0.2 to 0.3) , silicone modified epoxy resin (with 10wt%to 40wt%of silicone, and with an epoxy valueof 0.05 to 0.15) and dimer acid modified epoxy resin (with 20 wt%to 40wt%of dimer acid, and an epoxy value of 0.15 to 0.35) .
  • the toughening agent ispolyurethane modified epoxy resin and/or dimer acid modified epoxy resin.
  • the toughening agent can be a commercially available product, for example, polyurethane modified epoxy resin HypoxUA10 purchased from American CVC Corporation or polyurethane modified epoxy resin 102D-1 purchased from HengChuangInsulating Materials Co. Ltd; for another example, carboxyl terminated nitrile rubber modified epoxy resin 1340 purchased from ShenZhenJiaDiDa Chemical Co. Ltd; for still another example, silicone modified epoxy resin Si1200 purchased from Mitsubishi Corporation; andfor a further example, dimer acid modified epoxy resin DA323 purchased from American CVC Corporation.
  • polyurethane modified epoxy resin HypoxUA10 purchased from American CVC Corporation or polyurethane modified epoxy resin 102D-1 purchased from HengChuangInsulating Materials Co. Ltd
  • carboxyl terminated nitrile rubber modified epoxy resin 1340 purchased from ShenZhenJiaDiDa Chemical Co. Ltd
  • silicone modified epoxy resin Si1200 purchased from Mitsubishi Corporation
  • dimer acid modified epoxy resin DA323 purchased from American CVC Corporation.
  • the filler is of an average particle size D50below 30 microns, for example below 25 microns.
  • the filler can be an inorganicor organicfiller.
  • the inorganic filler includes but not limited to one or more of barium sulfate, barium titanate, silicon oxide, quartz, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum, alumina, aluminum hydroxide, mica and kaolin.
  • the organic filler includes but not limited to polyimide (PI) and polytetrafluoro ethylene (PTFE) both in a form of powders. Accordingly, the outer layer is provided with improved characteristics such as good adhesion and high hardness.
  • the epoxy resin compositionfurther includes viscosity increasing filler. In some embodiments of present disclosure, based on the total weight of the epoxy resin composition, the epoxy resin composition includes 1wt%to 15wt%of the viscosity increasing filler. In some embodiments of present disclosure, the viscosity increasingfilleris one or more of aluminum, alumina, mica and kaolin.
  • the epoxy resin compositionfurther includes an adjuvant according to requirements to manufacturing or applying the composite honeycomb sandwich board.
  • the adjuvant includes but not limited to one or more of a pigment, an antifoaming agent, a dispersant and a retardant.
  • the epoxy resin composition based on the total weight of the epoxy resin composition, includes 0wt%to 0.5wt%of the pigment, 0wt%to 0.8wt%of the antifoaming agent, 0wt%to 0.5wt%of the dispersant, 0wt%to 30wt%of theretardant.
  • the pigment is one or more of phthalocyanine green, phthalocyanineblue, carbon black, ultramarine, lithopone, permanent violet, permanent yellow and titanium pigment.
  • the pigment can be a commercially available product, e.g., atitanium pigmentpurchased from American Dupont Corporation, such as R-706, R-900, R-902, R-931, R-960, R-102, R-103, R-104, R-105 andR-350; atitanium pigment purchased from Japanese ISHIHARA SANGYO KAISHA, LTD, such asR-930, CR-60-2, R-200, R-600, R-980, CR-50, CR-50-2, CR-58, CR-58-2, CR-93, CR-80, CR-80, CR -95 and CR-97; a pigment purchased from BASF Company, such as BASF L6480 blue, BASF L3980 red, Green L8730, BlueK
  • the antifoaming agent can be organosilicone and/or acrylics.
  • the antifoaming agent can be a commercially available product, e.g., an antifoaming agentKS-66 purchased from Japanese Shin-Etsu Company; an antifoaming agent purchased fromGermany TEGO Corporation, such asFoamexN, Foamex815N, Foamex825, Foamex840 and Foamex842; anantifoaming agent purchased from Elementis Specialties Company, such asDEUCHEM3200, DEUCHEM3500, DEUCHEM5300, DEUCHEM5400, DEUCHEM5600, DEUCHEM6500, DEUCHEM6800 and DEUCHEM6600; andan acrylicsantifoaming agentpurchased from German BYK Corporation, such asBYK-051, BYK-052, BYK-053 and BYK-057.
  • the dispersant can be one or more of the following: a dispersant purchased from German BYK Corporation, such asANTI-TERRA-U, ANTI-TERRA-U80, ANTI-TERRA-U100, DISPERBYK-101, DISPERBYK-130, BYK-220S, LACTIMON, LACTIMON-WS, BYK-W 966, DISPERBYK, BYK-154, BYK-9076, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-102, DISPERBYK-111, DISPERBYK-180, DISPERBYK-106, DISPERBYK-187, DISPERBYK-181, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-115, DISPERBYK-160,
  • a dispersant purchased
  • the retardant includes, in addition to thefiller mentioned above, and one or more of hypophosphite, zinc borate, zinc molybdate, zinc oxide, antimonic oxide, magnesium hydroxide, aluminum hydroxide, microsilica and nanoscalemontmorillonoid.
  • the epoxy resin reinforcing material includes 40wt%to 60wt%of the epoxy resin composition.
  • the epoxy resin composition is of a grammage of 400 g/m 2 to 2000g/m 2 .
  • the reinforcing material includes but not limited to fiberglass cloth.
  • the core layer is of a thickness of 2 mm to 9mm, and in a honeycomb structure which is an array of hollow cells each in a hexagon shape having a side length of 1 mm to 8 mm, such that the bonding strength between the core layer and the outer layer is enhanced.
  • the present disclosure provides in embodiments a method for preparing the composite honeycomb sandwich board mentioned above.
  • the method includes: providing an outer layer made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition, and the epoxy resin compositionincludes an epoxy resin, a latent curing agent, an accelerator and a coupling agent, optionally a toughening agent and a filler; providing a core layer, in a honeycomb structure and made of aluminum; and placing the outer layer at at least one of upper and lower surfaces of the core layer followed by heat pressing treatment, so as to obtain the composite honeycomb sandwich board.
  • providing the outer layer further includes: melting the epoxy resin composition by heating (under stirring at a speed of 500 rpm to 1500 rpm) to form a melt; coating the melt on the reinforcing material to obtain a green body; and impregnating the green body to obtain the epoxy resin reinforcing material.
  • the melt is formed by mixingcomponents of the epoxy resin composition followed by heating under stirring so that the epoxy resin composition is melted to be of certain fluidity.
  • the meltis coated on the reinforcing material at a linear speed of 3 m/sto 10 m/sunder a temperature of 60 °C to 80 °C; and the green bodyis impregnated for 0.2 min to 5 minunder a temperature of60 °C to 100 °C.
  • the heat pressing treatment is performed for 5 min to 20 min under a temperature of 80 °C to 200 °C and a pressure of 0.1MPa to 1MPa, such that the melted epoxy resin reinforcing material is in a direct contact with the core layer in the honeycomb structure without any adhesive.
  • amino-containing silane coupling agent N- (6-aminohexyl) amino methyl triethoxysilane (SIA0592.6, purchased from Gelest Company) ) ,
  • the bisphenol A epoxy resin, the phenolic epoxy resin, the polyurethane modified epoxy resin, dicyandiamide, phenyldimethylurea, aluminum hydroxide, the amino-containing silane coupling agent, the epoxy-containing silane coupling agentand the coupling auxiliary agent were mixed, followed by heating to 70 °C under stirring at a speed of 100 rpm, thereby forming a melt, i.e., melted epoxy resin composition.
  • a melt was then coated on glassfiber cloth (purchased from ChongQingPolycomp International Corporation, having a weightof 800g/m 2 ) at a linear speed of 5 m/sunder 65 °Cby a coating device, therebyfroming a green body.
  • Such a green body was subsequently impregnated for 3 min at 80 °C, thereby obtaining the epoxy resin reinforcing material, which was cut into pieces having a size of 600mm ⁇ 600mm, as the outer layer for use.
  • the core layer in thehoneycomb structure which is an array of hollow cells each in a hexagon shape with a side length of 4 mm, was placed between two outer layers manufactured as above-mentioned, followed by heat pressing treatment at a temperature of 140 °C and a pressure of 0.3 MPafor 8 min in a mould. After cooling down and demoulding, the composite honeycomb sandwich board was obtained.
  • compositions of the epoxy resin compositions are same as that in Example 1, only with differences in amounts of various components as shown in Table 1 below.
  • the epoxy resin composition in this Example includes all compositions in same amounts as those in Example 1, except for the bisphenolA epoxy resin and the phenolic epoxy resin.
  • the bisphenol A epoxy resin with a Grade NPEL-128 used in Example 1 was replaced by that with a Grade NPEL-134 (with an epoxy value of 0.46) purchased from NanYa Epoxy Resin Co., Ltd in the same amount; and the phenolic epoxy resin with a Grade 631 used in Example 1 was replaced by that with a Grade 638S (with an epoxy value of 0.55) purchased fromNanYa Epoxy Resin Co., Ltd in the same amount.
  • the outer layer for Example 10 was manufactured same as that in Example 1.
  • the composite honeycomb sandwich boardfor Example 10 was obtained same as that in Example 1.
  • the epoxy resin composition in this Example includes all compositions in same amounts as those in Example 1, except for theamino-containing silane coupling agent and the epoxy-containing silane coupling agent.
  • N- (6-aminohexyl) amino methyl triethoxysilane (SIA0592.6, purchased from Gelest Company) used in Example 1for the amino-containing silane coupling agent was replaced by N-(2-N-benzylaminoethyl) -3-aminopropyltrimethoxysilane (SIB0956.0, purchased from the Gelest Company) in the same amount; and 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane (A-1861, purchased from Momentive Company) used in Example 1 for the epoxy-containing silane coupling agent was replaced by (3-epoxypropoxypropyl) trimethoxysilane (KH560, purchased from Shenzhen City YouYueChangHao Co., Ltd. ) in the same amount
  • the outer layer for Example 11 was manufactured same as that in Example 1.
  • the composite honeycomb sandwich boardfor Example 11 was obtained same as that in Example 1.
  • the epoxy resin composition in this Example includes all compositions in same amounts as those in Example 1, except for the amino-containing silane coupling agent and the epoxy-containing silane coupling agent.
  • N- (6-aminohexyl) amino methyl triethoxysilane (SIA0592.6, purchased from Gelest Company) used in Example 1 for the amino-containing silane coupling agent was replaced by diethylenetriamine propyl trimethoxysilane (SIA0400.0, purchased from Gelest Company) in the same amount; and 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane (A-1861, purchased from Momentive Company) used in Example 1 for the epoxy-containing silane coupling agent was replaced by 3-glycidoxypropyldimethoxymethylsilane (SIG5836.0, purchased from Gelest Company) in the same amount.
  • SIG5836.0 3-glycidoxypropyldimethoxymethylsilane
  • the outer layer for Example 12 was manufactured same as that in Example 1.
  • the composite honeycomb sandwich boardfor Example 12 was obtained same as that in Example 1.
  • the epoxy resin composition in this Example includes all compositions in same amounts as those in Example 1, except only KH 550 was used as the silane coupling agent in the total amounts of the amino-containing silane coupling agent.
  • the outer layer for Example 13 was manufactured same as that in Example 1.
  • the composite honeycomb sandwich boardfor Example 13 was obtained same as that in Example 1.
  • the epoxy resin compositionin this Comparative Example includes all compositions in same amounts as those in Example 1, except the amino-containing silane coupling agent and the epoxy-containing silane coupling agent.
  • the outer layer for this Comparative Example was manufactured same as that in Example 1.
  • the core layer (in the honeycomb structure) having a volume of 600mm ⁇ 600mm ⁇ 6mm was applied with FS4000 adhesive (purchased from Dongguan XinYuanJing Technology Co., Ltd) at its upper and lower surfaces, and placed between two outer layers, followed by heat pressing treatment at a temperature of 140 °C and a pressure of 0.3 MPafor 8 min in a mould. After cooling down and demoulding, the composite honeycomb sandwich board was obtained.
  • the outer layer made of the epoxy resin reinforcing material is combined at at least one of upper and lower surfaces of the core layerin the honeycomb structure by means of curing the epoxy resin reinforcing material through the heating press treatment, resulting in no need to use a solventadhesive, thereby being friendly to environment.
  • the amino-containing silanecoupling agent is added to the resin composition, such that the outer layer outer layer is combined with the core layer with a relative stable structure during curing the epoxy resin reinforcing material, thereby improving the bonding strength between the outer layer and the core layer, and avoiding occurrence of delamination for the composite honeycomb sandwich board.

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Abstract

Provided is a composite honeycomb sandwich board and a method for preparing the same. The composite honeycomb sandwich board includes: acore layer, in a honeycomb structure, having upper and lower surfaces, and made of aluminum; and an outer layer, combined at at least one of the upper and lower surfaces and made of an epoxy resin reinforcing material. The epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition. The epoxy resin composition includes an epoxy resin, a latent curing agent, an accelerator, a coupling agent, and optionally a toughening agent and a filler. The coupling agent includes an amido-containing silane coupling agent.

Description

COMPOSITE HONEYCOMB SANDWICH BOARD AND METHOD FOR PREPARING THE SAME
CROSS-REFERENCE TO RELATED APPLICATION
This application claims a priority to and benefits of Chinese Patent Application Serial No. 201511032527.3, filed with the State Intellectual Property Office of P.R. China on December31, 2015, the entire content of which is incorporated herein by reference.
TECHNICAL FIELD
The present disclosure relates to a composite material in a sandwich structure, specifically to a composite honeycomb sandwich board and a method for preparing the same.
BACKGROND
Currently, a honeycomb sandwich boardwith structure characteristics of light weight, high specificstrength and stiffness and function characteristics such as sound and heat insulationhas been widely used in the engineering field, such as aerospace, ships, high-speed trains, wind turbine blades, civil construction. The honeycomb sandwich board is commonly constitutedbyplacing a corelayer (ina honeycomb structure) between two outer layers (which may be made of a metal material or a resin composite material) . The two outer layers provide strength in tension (e.g., most bending moment) for the core layer, while the core layer mainly resists to shearing force and guaranteesreliable connection with the twoouter layers. When manufacturing the honeycomb sandwich board, it is generally to process thetwoouter layers and the core layerseparatelyat first, which are then subjected to combination by means of jointingwith an adhesive directly.
However, the existingadhesive, usually a solvent adhesive, has disadvantages such as being unfriendly to environment, low bonding strength, and delamination tendency between the two outer layers (e.g., made of aluminum or resin composite material) and the core layer (in a  honeycomb structure) .
SUMMARY
An object of the present disclosure is to provide a composite honeycomb sandwich board and a method for preparing the composite honeycomb sandwich board, so as to improve bondingstrengthbetween a core layerin a honeycomb structureandan outer layer made of an epoxy resin reinforcing material, thereby being friendly to environment.
In order to achieve the above object, in a first aspect, the present disclosure providesin embodiments a composite honeycomb sandwich board, including: a core layer, in a honeycomb structure, having upper and lower surfaces, and made of aluminum； and an outer layer, combined at at least one of the upper and lower surfaces and made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition； the epoxy resin composition includes an epoxy resin, a latent curing agent, an accelerator, a coupling agent, and optionally a toughening agent and a filler； and the coupling agent includes an amido-containing silane coupling agent.
In a second aspect, the present disclosure provides in embodimentsa method for preparing the composite honeycomb sandwich board mentioned above. In some embodiments, the method includes: providing an outer layer made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition, and the epoxy resin compositionincludes an epoxy resin, a latent curing agent, an accelerator, a coupling agent, optionally a toughening agent and a filler； providing a core layer, in a honeycomb structure and made of aluminum； and placing the outer layer at at least one of upper and lower surfaces of the core layer followed by heat pressing treatment, so as to obtain the composite honeycomb sandwich board.
The composite honeycomb sandwich board according to embodiments of the present disclosure has the following advantages. The outer layer made oftheepoxy resin reinforcing material is combined at at least one of upper and lower surfaces of the core layerin the honeycomb structure by means of curing the epoxy resin reinforcing material through the heating press treatment, resulting in no need to use the solventadhesive, thereby being friendly to  environment. Meanwhile, the amino-containing silane coupling agent is added to the resin composition, such that the outer layer outer layer is combined with the core layer with a relative stable structure during curing the epoxy resin reinforcing material, thereby improving the bonding strength between the outer layer and the core layer, and avoiding occurrence of delamination for the composite honeycomb sandwich board.
Other features and advantages will be illustrated in detail in the following embodiments.
DETAILED DESCRIPTION
Reference will be made in detail to embodiments of the present disclosure. The embodiments described herein are explanatory, illustrative, and used to generally understand the present disclosure. The embodiments shall not be construed to limit the present disclosure.
In order to avoid occurrence of delaminationbetween the outer layer (made of aluminum or a resin composite material) and the core layer due to poor bonding strength resulting from the use of the solvent adhesive, the present disclosure provides in embodiments a composite honeycomb sandwich board, including: a core layer, in a honeycomb structure, having upper and lower surfaces, and made of aluminum； and an outer layer, combined at at least one of the upper and lower surfaces and made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition； the epoxy resin composition includes an epoxy resin, a latent curing agent, an accelerator, a coupling agent, and optionally a toughening agent and a filler； and the coupling agent includes an amido-containing silane coupling agent.
The outer layer made of the epoxy resin reinforcing material is combined at at least one of upper and lower surfaces of the core layerin the honeycomb structure by means of curing the epoxy resin reinforcing material through the heating press treatment, resulting in no need to use a solventadhesive, thereby being friendly to environment. Meanwhile, the amino-containing silane coupling agent is added to the resin composition, such that the outer layer outer layer is combined with the core layer with a relative stable structure during curing the epoxy resin reinforcing material, thereby improving the bonding strength between the outer layer and the core layer, and avoiding occurrence of delamination for the composite honeycomb sandwich board.
In some embodiments of present disclosure, the coupling agent includes but not limited to one or more ofγ-amigrammagenopropyltriethoxysilane (i.e., H2N (CH2) 3Si (OC2H5) 3, for example GradesA-1100 andKH-550) , γ-aminopropyltrimethoxysilane (i.e., H2N (CH2) 3Si (OCH3) 3, for example Grade A-1110) , N-β (aminoethyl) -γ-aminopropyltrimethoxysilane (NH2 (CH2) 2NH (CH2) 3Si (OCH3) 3, for example Grades A-1120 andKBM-603) , N-β (aminoethyl) -γ-aminopropyl methyl dimethoxysilane (NH2 (CH2) 2NH (CH2) 3Si (OCH3) 3, for example GradeKBM-602) , N-β (aminoethyl) -γ-aminopropyltriethoxysilane (NH2 (CH2) 2NH (CH2) 3Si (OC2H5) 3, for example Grade KH-791) , N- (6-aminohexyl) amino methyl triethoxysilane (for example Grade SIA0592.6 purchased from Gelest Company) , N- (2-N-benzyl aminoethyl) -3-aminopropyl trimethoxysilane (for example Grade SIB0956.0 purchased from Gelest Company) , diethylenetriaminepropyl trimethoxysilane (for example Grade SIA0400.0 purchased from Gelest Company) , bis[3- (trimethoxysilyl) propyl] ethylenediamine and N-3- [amino isopropyl (polyoxy isopropyl) ] aminopropyltrimethoxysilane.
In some embodiments of present disclosure, the coupling agent includes the amino-containingsilane coupling agent. In some embodiments of present disclosure, the amino-containingsilane coupling agent contains at least two amino groups, thereby further enhancingthe bonding strength between the core layer and the outer layer. In some embodiments of present disclosure, the amino-containingsilane coupling agent withat least two amino groups includes but not limited to one or more of N- (6-aminohexyl) aminomethyltriethoxysilane (for example GradeSIA0592.6 purchased from Gelest Company) , N- (2-N-benzyl aminoethyl) -3-aminopropyl trimethoxysilane (for example Grade SIB0956.0 purchased from Gelest Company) , diethylenetriaminepropyl trimethoxysilane (for example Grade SIA0400.0 purchased from Gelest Company) , bis [3-trimethoxysilyl) propyl] ethylenediamine and N-3- [amino isopropyl (polyoxy isopropyl) ] aminopropyltrimethoxysilane. In addition to the aforementioned commercially available products, one or more of Y-11763 purchased from Momentive Company, Z-6137 purchased from Dow Corning Company, SIA0592.6 andSIT8398.0 purchased from Gelest Company can also be used.
As to the composite honeycomb sandwich board provided in some embodiments of the  present disclosure, in addition to the amino-containing silane coupling agent, the coupling agentfurther includesanepoxy-containingsilane coupling agent. The amino-containingsilane coupling agent and the epoxy-containingsilane coupling agent are used in combination, thereby further enhancingthe bonding strength between the core layerand the outer layer. In some embodiments of present disclosure, a weight ratio of the epoxy-containingsilane coupling agent to the amino-containingsilane coupling agent ranges from 0.5: 1 to 2: 1.
In some embodiments of present disclosure, the epoxy-containingsilane coupling agent is selected from one or more of 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane (A-1861 purchased from Momentive Company) , 2- (3, 4-epoxy cyclohexane) ethyltrimethoxysilane, (3-epoxypropoxy propyl) trimethoxysilane, (3-epoxypropoxy propyl) triethoxysilane (KH560 purchased from Shenzhen YouYueChangHao Co., Ltd. ) , 3-glycidoxypropyldimethoxymethylsilane (SIG5836.0 purchased from Gelest Company) and (3-glycidoxypropyl) methyldiethoxysilane. In other embodiments of present disclosure, the epoxy-containingsilane coupling agent further includes one or more of A-187 and A-186 purchased from Momentive Company, as well as Z-6041 andZ-6042 purchased from Dow Corning Company. In still other embodiments of present disclosure, the epoxy-containingsilane coupling agentcontains two epoxy groups.
Asto the composite honeycomb sandwich board provided in some embodiments of the present disclosure, in the case that the silane coupling agent includes the amino-containing silane coupling agent only or includes both the amino-containing silane coupling agent and the epoxy-containing silane coupling agent, the coupling agentfurther includes the coupling auxiliary agent. The coupling auxiliary agent is selected from one or more of (C2H5O) 3Si-CH2CH2-Si- (C2H5O) 3, (C2H5O) 3Si-CH2RCH2-Si- (C2H5O) 3 and (CH3O) 3Si-CH2RCH2-Si- (CH3O) 3, in whichR is a reactive organic group (for example selected from one or a moreof -NH-, -CH2-, -CHOH, -CH (O) CH-, -COO-and -CHCOOH) and/or a non-reactive organic group (for example selected from one or more of -CH2-, -CH2CH2-and -CH2CH2CH2-) . The amino-containingsilane coupling agent and/or the epoxy-containingsilane coupling agent are/is used in the silane coupling agent, in combination with thecoupling auxiliary agent, such that the bonding strength between the core layerand the outer layers are further enhanced. In some embodiments of present disclosure, aweight ratio of the coupling auxiliary  agent to the amino-containingsilane coupling agent ranges from 0.1: 1 to 0.5: 1.
In some embodiments of present disclosure, the coupling auxiliary agent includes but not limit to one or more of (CH3O) 3Si-CH2CH2-Si- (CH3O) 3, (CH3O) 3Si-CH2NHCH2-Si- (CH3O) 3, (CH3O) 3Si-CH2-CH (O) CH-CH2-Si- (CH3O) 3. For example, (CH3O) 3Si-CH2CH2-Si- (CH3O) 3 may be Grade 1817 purchased from Gelest Company.
In some embodiments of present disclosure, based on the total weight of the epoxy resin composition, the epoxy resin compositionincludes 35wt％to 90wt％of the epoxy resin (e.g, a hot-melt type) , 1wt％to 10wt％of the latent curing agent, 0.1wt％to 5wt％of the silane coupling agent, 0wt％to 40wt％of the toughening agent, 0.5wt％to 20wt％of the accelerator, and 0wt％to 60wt％of the fillers. In other embodiments of present disclosure, based on the total weight of the epoxy resin composition, the epoxy resin compositionincludes 35wt％to 90wt％of the epoxy resin, 3wt％to 8wt％of the latent curing agent, 0.3wt％to 3wt％of the silane coupling agent, 3wt％to 15wt％of the toughening agent, 0.5wt％to 5wt％of the accelerator, and 0wt％to 60wt％of the fillers, in which the epoxy resin composition does not include a solvent.
In some embodiments of present disclosure, the epoxy resinis capable of impregnatinginto the reinforcing materialafter hot meltedby heating. In some embodiments of present disclosure, the epoxy resin includes but not limited to one of more of bisphenol A epoxy resin, bisphenolF epoxy resin, phenolic epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenolF epoxy resin, cycloaliphatic epoxy resin, o-cresol epoxy resin, triglycidylisocyanurate, bisphenolfluorenyl epoxy resin, adamantaneepoxy resin and hydantoin epoxy resins. The epoxy resin used in embodiments of the present disclosure may be a commercially available product, including but not limit to, epoxy resin purchased from TaiWanNanYa Epoxy Resin Co., Ltd, such as NPEL-127, NPEL-127E, NPEL-127H, NPEL-128, NPEL-128E, NPEL-128G, NPEL-128R, NPEL-128S, NPEL-134, NPEL-136, NPEL-134, NPEL-231, NPEF-164X, NPEF-170, NPEF-175, NPEF-176, NPEF-185, NPEF-187, NPEF-198, NPPN-631, NPPN-638, andNPPN-638S； epoxy resinpurchased from Nantong XingChenSynthetic Material Co., Ltd, such as0161, 0161L, 0161E, 0164, 0164E, 0164EA, 0164D, 0164C, 0174, 0174E, 0176E, 0177, 0177E, 0179, 0230, 0235, 0235E, 0235L, 0235C, 0248, 0830 and830； epoxy resinpurchased  fromLanXing Chemical New MaterialsCo., Ltd, such as840L, 840, 850S, 850A, 850D, 860L, 860, N-740, N-740S andN-740G； epoxy resin purchased from Dow Chemical Company, such as D.E.R. 383, SD. E.R. 331, D.E.R. 331JD.E.R. 337, D.E.N. 438, D.E.N. 439 and D.E.R. 354； epoxy resin (with a brand of Phoenix) purchased from LanXing Chemical New Materials Co., Ltd, such F-51, F-50, F-44 andF-48； epoxy resin purchased from Shandong ShengQuan New materials Co., Ltd, such as SQCN-704M, SQCN-704MLandSQCN051； epoxy resin purchased from Nanjing MeiKai Technology Co., Ltd, such as TGIC powders； and hydantoin epoxy resin purchased from Wuxi Meihua Chemical Co., Ltd, such as MHR07. The resin mentioned above can be used separately or in any combination.
In some embodiments of present disclosure, the epoxy resinincludes bisphenolA epoxy resin and phenolic epoxy resin. In some embodiments of present disclosure, based on the total weight of the epoxy resin, the epoxy resinincludes 60wt％to 85wt％of the bisphenolA epoxy resin and 15wt％to 40wt％of the phenolic epoxy resin. The bisphenolA epoxy resin and the phenolic epoxy resinare used in combination, such thatthe bonding strength between the core layer and the outer layers are enhanced, while the outer layer is provided with improved heat resistance, therebyimprovingheat resistance forthe composite honeycomb sandwich board. In some embodiments of present disclosure, the bisphenolA epoxy resin is of an epoxide value of 0.3 to 0.6, the phenolic epoxy resin is of an epoxide value of 0.4 to 0.7.
In some embodiments of present disclosure, the bisphenolA epoxy resin and the phenolic epoxy resin eachcan be a commercially available product. The bisphenolA epoxy resin may be, for example, purchased from NanYa Epoxy Resin Co., Ltd, such asNPEL-127, NPEL-128, NPEL-134, NPEL-136 andNPEL-231； or purchased from LanXing Chemical New Materials Co., Ltd, such as840L, 840, 850S, 850A, 850D, 860L and860. The phenolic epoxy resinmaybe: for example, purchased from NanYa Epoxy Resin Co., Ltd, such asNPPN-631, NPPN-638 andNPPN-638S； or purchased from Dow Chemical Company, such asD. E. N. 438 orD. E. N. 439.
In some embodiments of present disclosure, the latent curing agent is one or more of dicyandiamide, an imidazolium compound and organic hydrazine. In some embodiments of present disclosure, the imidazolium compound includes but not limited to one or more of an imidazole derivative such as imidazole, 2-methylimidazole, 2-ethylimidazole,  2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole. The organic hydrazine includes but not limited to a hydrazine compound such as adipodihydrazide and sebacicdihydrazide. In some embodiments of present disclosure, the latent curing agent can be a commercially available product, including but not limited to the dicyandiamidepurchased from Air Products and Chemicals, Inc； the imidazolium compound purchased from Shikoku Chemicals Corporation, such as2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ and2P4MHZ； and adipodihydrazide (organic hydrazide) purchased from Shandong Xiya Chemical Industry Co., Ltd.
In some embodiments of present disclosure, in the case that the latent curing agent is dicyandiamide, the accelerator can be one or more of phenyldimethylurea, 2, 4-toluene bisdimethylurea, 4, 4 -methylene bisphenyl dimethylurea and alicyclicbiuret. The accelerator can bea commercially available product purchased from German Evonik Degussa Company, suchUR300, UR500 andUR700. In another embodiments of present disclosure, in the case that the latent curing agent is organic hydrazine, the accelerator can be one or more of phenyldimethylurea, 2, 4-toluene bisdimethylurea, 4, 4 -methylene bisphenyl dimethylurea and alicyclicbiuret.
In some embodiments of present disclosure, the toughening agent is one or more of polyurethane modified epoxy resin (with 5wt％to 30wt％of polyurethane, and an epoxy value of0.4 to 0.6) , carboxyl terminated nitrile rubber modified epoxy resin (with 5wt％to 40wt％of carboxyl terminated nitrile rubber, and an epoxy valueof0.2 to 0.3) , silicone modified epoxy resin (with 10wt％to 40wt％of silicone, and with an epoxy valueof 0.05 to 0.15) and dimer acid modified epoxy resin (with 20 wt％to 40wt％of dimer acid, and an epoxy value of 0.15 to 0.35) . In other embodiments of present disclosure, the toughening agent ispolyurethane modified epoxy resin and/or dimer acid modified epoxy resin.
In some embodiments of present disclosure, the toughening agent can be a commercially available product, for example, polyurethane modified epoxy resin HypoxUA10 purchased from American CVC Corporation or polyurethane modified epoxy resin 102D-1 purchased from HengChuangInsulating Materials Co. Ltd； for another example, carboxyl terminated nitrile rubber modified epoxy resin 1340 purchased from ShenZhenJiaDiDa Chemical Co. Ltd； for still another  example, silicone modified epoxy resin Si1200 purchased from Mitsubishi Corporation； andfor a further example, dimer acid modified epoxy resin DA323 purchased from American CVC Corporation.
In some embodiments of present disclosure, the filler is of an average particle size D50below 30 microns, for example below 25 microns. In some embodiments of present disclosure, the filler can be an inorganicor organicfiller. In some embodiments of present disclosure, the inorganic filler includes but not limited to one or more of barium sulfate, barium titanate, silicon oxide, quartz, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum, alumina, aluminum hydroxide, mica and kaolin. In some embodiments of present disclosure, the organic filler includes but not limited to polyimide (PI) and polytetrafluoro ethylene (PTFE) both in a form of powders. Accordingly, the outer layer is provided with improved characteristics such as good adhesion and high hardness.
In some embodiments of present disclosure, the epoxy resin compositionfurther includes viscosity increasing filler. In some embodiments of present disclosure, based on the total weight of the epoxy resin composition, the epoxy resin composition includes 1wt％to 15wt％of the viscosity increasing filler. In some embodiments of present disclosure, the viscosity increasingfilleris one or more of aluminum, alumina, mica and kaolin.
In some embodiments of present disclosure, the epoxy resin compositionfurther includes an adjuvant according to requirements to manufacturing or applying the composite honeycomb sandwich board. In some embodiments of present disclosure, the adjuvantincludes but not limited to one or more ofa pigment, an antifoaming agent, a dispersant and a retardant. In some embodiments of present disclosure, based on the total weight of the epoxy resin composition, the epoxy resin composition includes 0wt％to 0.5wt％of the pigment, 0wt％to 0.8wt％of the antifoaming agent, 0wt％to 0.5wt％of the dispersant, 0wt％to 30wt％of theretardant.
In some embodiments of present disclosure, the pigment is one or more of phthalocyanine green, phthalocyanineblue, carbon black, ultramarine, lithopone, permanent violet, permanent yellow and titanium pigment. In some embodiments of present disclosure, the pigment can be a commercially available product, e.g., atitanium pigmentpurchased from American Dupont Corporation, such as R-706, R-900, R-902, R-931, R-960, R-102, R-103, R-104, R-105  andR-350； atitanium pigment purchased from Japanese ISHIHARA SANGYO KAISHA, LTD, such asR-930, CR-60-2, R-200, R-600, R-980, CR-50, CR-50-2, CR-58, CR-58-2, CR-93, CR-80, CR-80, CR -95 and CR-97； a pigment purchased from BASF Company, such as BASF L6480 blue, BASF L3980 red, Green L8730, BlueK7014LW, BlueK7090, BlueK6907, BlueD7079, BlueK6912, BlueL7080, GreenD9360/6G, BlueL7085, BlueL6960F/BSNF, BlueK7072, BlueL7087/PG, BlueK6902, BlueL6700F, BlueK6911D, BlueL6875F, GreenK8740, BlueL6900, GreenK9360, BlueL6901F, BlueK7096/GBP, BlueL6920, GreenL9361, BlueL6930, BlueL7101F, BlueL6989F andGreenL8690P. G7.
In some embodiments of present disclosure, the antifoaming agentcan be organosilicone and/or acrylics. In some embodiments of present disclosure, the antifoaming agent can be a commercially available product, e.g., an antifoaming agentKS-66 purchased from Japanese Shin-Etsu Company； an antifoaming agent purchased fromGermany TEGO Corporation, such asFoamexN, Foamex815N, Foamex825, Foamex840 and Foamex842； anantifoaming agent purchased from Elementis Specialties Company, such asDEUCHEM3200, DEUCHEM3500, DEUCHEM5300, DEUCHEM5400, DEUCHEM5600, DEUCHEM6500, DEUCHEM6800 and DEUCHEM6600； andan acrylicsantifoaming agentpurchased from German BYK Corporation, such asBYK-051, BYK-052, BYK-053 and BYK-057.
In some embodiments of present disclosure, the dispersant can be one or more of the following: a dispersant purchased from German BYK Corporation, such asANTI-TERRA-U, ANTI-TERRA-U80, ANTI-TERRA-U100, DISPERBYK-101, DISPERBYK-130, BYK-220S, LACTIMON, LACTIMON-WS, BYK-W 966, DISPERBYK, BYK-154, BYK-9076, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-102, DISPERBYK-111, DISPERBYK-180, DISPERBYK-106, DISPERBYK-187, DISPERBYK-181, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-115, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-167, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-168, DISPERBYK-169, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-190, DISPERBYK-2150, BYK-9077, DISPERBYK-112,  DISPERBYK-116, DISPERBYK-191, DISPERBYK-192, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2010, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050 and DISPERBYK-2070； a dispersantpurchased from NetherlandishAkzo Nobel Corporation, such as PHOSPHOLAN PS-236； adispersant purchased from American Witco Chemical Corporation, such as PS-21A； adispersant purchased from Britain Croda Corporation, such as Hypermer KD andZephrym PD； adispersant purchased from TEGO Corporation, such as Dispers-655 and Dispers-670.
In some embodiments of present disclosure, the retardant includes, in addition to thefiller mentioned above, and one or more of hypophosphite, zinc borate, zinc molybdate, zinc oxide, antimonic oxide, magnesium hydroxide, aluminum hydroxide, microsilica and nanoscalemontmorillonoid.
In some embodiments of present disclosure, based on the total weight of the epoxy resin reinforcing material, the epoxy resin reinforcing material includes 40wt％to 60wt％of the epoxy resin composition. For example, the epoxy resin composition is of a grammage of 400 g/m2 to 2000g/m2. In some embodiments of present disclosure, the reinforcing material includes but not limited to fiberglass cloth.
In some embodiments of present disclosure, the core layer is of a thickness of 2 mm to 9mm, and in a honeycomb structure which is an array of hollow cells each in a hexagon shape having a side length of 1 mm to 8 mm, such that the bonding strength between the core layer and the outer layer is enhanced.
In a second aspect, the present disclosure provides in embodiments a method for preparing the composite honeycomb sandwich board mentioned above. In some embodiments, the method includes: providing an outer layer made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition, and the epoxy resin compositionincludes an epoxy resin, a latent curing agent, an accelerator and a coupling agent, optionally a toughening agent and a filler； providing a core layer, in a honeycomb structure and made of aluminum； and placing the outer layer at at least one of upper and lower surfaces of the core layer followed by heat pressing treatment, so as to obtain the composite honeycomb sandwich board.
In some embodiments, providing the outer layer further includes: melting the epoxy resin composition by heating (under stirring at a speed of 500 rpm to 1500 rpm) to form a melt； coating the melt on the reinforcing material to obtain a green body； and impregnating the green body to obtain the epoxy resin reinforcing material. In some embodiments of present disclosure, the melt is formed by mixingcomponents of the epoxy resin composition followed by heating under stirring so that the epoxy resin composition is melted to be of certain fluidity. In some embodiments of present disclosure, the meltis coated on the reinforcing material at a linear speed of 3 m/sto 10 m/sunder a temperature of 60 ℃ to 80 ℃； and the green bodyis impregnated for 0.2 min to 5 minunder a temperature of60 ℃ to 100 ℃.
In some embodiments, the heat pressing treatment is performed for 5 min to 20 min under a temperature of 80 ℃ to 200 ℃ and a pressure of 0.1MPa to 1MPa, such that the melted epoxy resin reinforcing material is in a direct contact with the core layer in the honeycomb structure without any adhesive.
Advantages of the composite honeycomb sandwich board and it manufacturing method will be further illustrated hereinafter in conjunction with specific examples in detail.
Example 1
Manufacturing inventive composite honeycomb sandwich board1
Providing the epoxy resin composition:
40 parts by weightof the bisphenol A epoxy resin (NPEL-128, purchased fromNanYa Epoxy Resin Co., Ltd, and having anepoxide value of 0.51) ,
20 parts by weight of the phenolic epoxy resin (631, purchased from NanYa Epoxy Resin Co., Ltd, and having anepoxide value of 0.57) ,
6 parts by weight of polyurethane modified epoxy resin (HypoxUA10, purchased from American CVC Corporation, and having anepoxide value of 0.46) ,
5 parts by weight of dicyandiamide (3636AS, purchased fromAiDiKeFine Chemical Industry Corporation) ,
1.5 parts by weight of phenyldimethylurea (u405, purchased from American CVC Corporation) ,
15 parts by weight of aluminum hydroxide (having a particle size D50of 8 microns) ,
8 parts by weight of aluminum powders (having a particle size D50of 5 microns) ,
1 part by weight of the amino-containing silane coupling agent (N- (6-aminohexyl) amino methyl triethoxysilane (SIA0592.6, purchased from Gelest Company) ) ,
1 part by weight of the epoxy-containing silane coupling agent (2- (3, 4-epoxycyclohexane) ethyltriethoxysilane (A-1861, purchased from Momentive Company) ) , and
0.5 parts by weight of the coupling auxiliary agent ( (C2H5O) 3Si-CH2CH2-Si- (C2H5O) 3, (1817, purchased from Gelest Company) ) .
Providing the outer layer
The bisphenol A epoxy resin, the phenolic epoxy resin, the polyurethane modified epoxy resin, dicyandiamide, phenyldimethylurea, aluminum hydroxide, the amino-containing silane coupling agent, the epoxy-containing silane coupling agentand the coupling auxiliary agent were mixed, followed by heating to 70 ℃ under stirring at a speed of 100 rpm, thereby forming a melt, i.e., melted epoxy resin composition. Such a melt was then coated on glassfiber cloth (purchased from ChongQingPolycomp International Corporation, having a weightof 800g/m2) at a linear speed of 5 m/sunder 65 ℃by a coating device, therebyfroming a green body. Such a green body was subsequently impregnated for 3 min at 80 ℃, thereby obtaining the epoxy resin reinforcing material, which was cut into pieces having a size of 600mm×600mm, as the outer layer for use.
Providing the composite honeycomb sandwich board
The core layer in thehoneycomb structure, which is an array of hollow cells each in a hexagon shape with a side length of 4 mm, was placed between two outer layers manufactured as above-mentioned, followed by heat pressing treatment at a temperature of 140 ℃ and a pressure of 0.3 MPafor 8 min in a mould. After cooling down and demoulding, the composite honeycomb sandwich board was obtained.
Examples 2 to 9
Manufacturing inventive composite honeycomb sandwich boards 2 to 9
Providing the epoxy resin compositions:
The compositions of the epoxy resin compositions are same as that in Example 1, only with differences in amounts of various components as shown in Table 1 below.
Table 1
Figure PCTCN2016112651-appb-000001
Providing the outer layers
The outer layers for Examples 2 to 9 were manufactured same as that in Example 1.
Providing the composite honeycomb sandwich board
The composite honeycomb sandwich boards for Examples 2 to 9 were obtained same as that in Example 1.
Example 10
Manufacturing inventive composite honeycomb sandwich board10
Providing the epoxy resin composition:
The epoxy resin composition in this Example includes all compositions in same amounts as those in Example 1, except for the bisphenolA epoxy resin and the phenolic epoxy resin. In specific, the bisphenol A epoxy resin with a Grade NPEL-128 used in Example 1 was replaced by that with a Grade NPEL-134 (with an epoxy value of 0.46) purchased from NanYa Epoxy Resin Co., Ltd in the same amount； and the phenolic epoxy resin with a Grade 631 used in Example 1 was replaced by that with a Grade 638S (with an epoxy value of 0.55) purchased fromNanYa Epoxy Resin Co., Ltd in the same amount.
Providing the outer layer
The outer layer for Example 10 was manufactured same as that in Example 1.
Providing the composite honeycomb sandwich board
The composite honeycomb sandwich boardfor Example 10 was obtained same as that in Example 1.
Example 11
Manufacturing inventive composite honeycomb sandwich board11
Providing the epoxy resin composition:
The epoxy resin composition in this Example includes all compositions in same amounts as those in Example 1, except for theamino-containing silane coupling agent and the epoxy-containing silane coupling agent. In specific, N- (6-aminohexyl) amino methyl triethoxysilane (SIA0592.6, purchased from Gelest Company) used in Example 1for the amino-containing silane coupling agent was replaced by  N-(2-N-benzylaminoethyl) -3-aminopropyltrimethoxysilane (SIB0956.0, purchased from the Gelest Company) in the same amount； and 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane (A-1861, purchased from Momentive Company) used in Example 1 for the epoxy-containing silane coupling agent was replaced by (3-epoxypropoxypropyl) trimethoxysilane (KH560, purchased from Shenzhen City YouYueChangHao Co., Ltd. ) in the same amount. In addition, the coupling auxiliary agent 1817 obtained from Gelest Company was not added in Example 11.
Providing the outer layer
The outer layer for Example 11 was manufactured same as that in Example 1.
Providing the composite honeycomb sandwich board
The composite honeycomb sandwich boardfor Example 11 was obtained same as that in Example 1.
Example 12
Manufacturing inventive composite honeycomb sandwich board12
Providing the epoxy resin composition:
The epoxy resin composition in this Example includes all compositions in same amounts as those in Example 1, except for the amino-containing silane coupling agent and the epoxy-containing silane coupling agent. In specific, N- (6-aminohexyl) amino methyl triethoxysilane (SIA0592.6, purchased from Gelest Company) used in Example 1 for the amino-containing silane coupling agent was replaced by diethylenetriamine propyl trimethoxysilane (SIA0400.0, purchased from Gelest Company) in the same amount； and 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane (A-1861, purchased from Momentive Company) used in Example 1 for the epoxy-containing silane coupling agent was replaced by 3-glycidoxypropyldimethoxymethylsilane (SIG5836.0, purchased from Gelest Company) in the same amount.
Providing the outer layer
The outer layer for Example 12 was manufactured same as that in Example 1.
Providing the composite honeycomb sandwich board
The composite honeycomb sandwich boardfor Example 12 was obtained same as that in  Example 1.
Example 13
Manufacturing inventive composite honeycomb sandwich board13
Providing the epoxy resin composition:
The epoxy resin composition in this Example includes all compositions in same amounts as those in Example 1, except only KH 550 was used as the silane coupling agent in the total amounts of the amino-containing silane coupling agent.
Providing the outer layer
The outer layer for Example 13 was manufactured same as that in Example 1.
Providing the composite honeycomb sandwich board
The composite honeycomb sandwich boardfor Example 13 was obtained same as that in Example 1.
Comparative Example 1
Manufacturing a composite honeycomb sandwich board
Providing the epoxy resin composition
The epoxy resin compositionin this Comparative Example includes all compositions in same amounts as those in Example 1, except the amino-containing silane coupling agent and the epoxy-containing silane coupling agent.
Providing the outer layer
The outer layer for this Comparative Example was manufactured same as that in Example 1.
Providing the composite honeycomb sandwich board
The core layer (in the honeycomb structure) having a volume of 600mm×600mm×6mm was applied with FS4000 adhesive (purchased from Dongguan XinYuanJing Technology Co., Ltd) at its upper and lower surfaces, and placed between two outer layers, followed by heat pressing treatment at a temperature of 140 ℃ and a pressure of 0.3 MPafor 8 min in a mould. After cooling down and demoulding, the composite honeycomb sandwich board was obtained.
Performance Tests:
The composite honeycomb sandwich boards in Examples 1 to 13 and the comparative 1 were subjected to performance tests as below.
(1) Bending strength was tested according to GBT 1449-2005.
(2) Flexural modulus was tested according to GBT 1449-2005.
(3) Roll peel strength was tested according to GBT 1457-2005.
Testing results are shown in Table 2.
Table 2
Figure PCTCN2016112651-appb-000002
It can be seen from Table 2, the composite honeycomb sandwich boards in Examples 1 to 13 each have superiorbending strength, flexural modulus and roll peel strength than that in Comparative Example 1.
The outer layer made of the epoxy resin reinforcing material is combined at at least one of  upper and lower surfaces of the core layerin the honeycomb structure by means of curing the epoxy resin reinforcing material through the heating press treatment, resulting in no need to use a solventadhesive, thereby being friendly to environment. Meanwhile, the amino-containing silanecoupling agent is added to the resin composition, such that the outer layer outer layer is combined with the core layer with a relative stable structure during curing the epoxy resin reinforcing material, thereby improving the bonding strength between the outer layer and the core layer, and avoiding occurrence of delamination for the composite honeycomb sandwich board.
It should be noted that all specific technical features described in aforementioned embodiments can be combined in any appropriate waywithout contradiction. Various possible combinations will not be described in details for brevity.
Moreover, the different embodiments of present disclosure can also becombined in any proper manner without departing concept of present disclosure, which should be within the scope of the present disclosure.

Claims (20)

  1. A composite honeycomb sandwich board, comprising:
    a core layer, in a honeycomb structure, having upper and lower surfaces, and made of aluminum； and
    an outer layer, combined atat least one of the upper and lower surfaces and made of an epoxy resin reinforcing material, wherein
    theepoxy resin reinforcing material is constituted witha reinforcing material and an epoxy resin composition；
    the epoxy resin composition comprisesan epoxy resin, a latent curing agent, an accelerator, a coupling agent, and optionally a toughening agentand a filler； and
    thecoupling agent comprises anamido-containing silane coupling agent.
  2. The composite honeycomb sandwich board according to claim 1, wherein the amido-containingsilane coupling agentcontains at least two amino groups； preferably, the amido-containingsilane coupling agent is selected from one or more of N- (6-aminohexyl) amino methyl triethoxysilane, N- (2-N-benzylaminoethyl) -3-aminopropyltrimethoxysilane, diethylenetriaminepropyl trimethoxysilane, bis (3-trimethoxysilyl) propyl) -ethylenediamine and N-3- [aminoisopropyl (polyoxy isopropyl) ] aminopropyltrimethoxysilane.
  3. The composite honeycomb sandwich board according to claim 1 or2, wherein the coupling agentfurther comprisesanepoxy-containing silane coupling agent.
  4. The composite honeycomb sandwich board according to claim 3, wherein a weight ratio of the epoxy-containingsilane coupling agent to the amido-containingsilane coupling agent ranges from 0.5: 1 to 2: 1.
  5. The composite honeycomb sandwich board according to claim 3 or 4, wherein the epoxy-containingsilane coupling agent contains two epoxy groups； preferably, the epoxy-containingsilane coupling agent is selected from one or more of 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane and (3-glycidoxypropyl) methyldiethoxysilane.
  6. The composite honeycomb sandwich board according to anyone of claims 1 to 5, wherein the coupling agentfurther comprises a coupling auxiliary agent selected from one or more of (C2H5O) 3Si-CH2CH2-Si- (C2H5O) 3, (C2H5O) 3Si-CH2RCH2-Si- (C2H5O) 3 and (CH3O) 3Si-CH2RCH2-Si- (CH3O) 3, wherein R is selected from one or more of -NH-, -CH2-, -CHOH, -CH (O) CH-, -COO-and -CHCOOH.
  7. The composite honeycomb sandwich board according to claim 6, whereina weight ratio of the coupling auxiliary agent to the amino-containing silane coupling agent ranges from 0.1: 1 to 0.5: 1.
  8. The composite honeycomb sandwich board according to anyone of claims 1 to 7, wherein based onthe total weight of the epoxy resin composition, the epoxy resin composition comprises 35wt％ to 90wt％ of the epoxy resin, 3wt％ to 8wt％ of the latent curing agent, 0.3wt％ to 3wt％ of the silane coupling agent, 3wt％ to 15wt％ of the toughening agent, 0.5wt％ to 5wt％ of the accelerator, and 0wt％ to 60wt％ of the filler.
  9. The composite honeycomb sandwich board according to anyone of claims 1 to 8, wherein the filler comprises a viscosity increasing filler； preferably, based on the total weight of the epoxy resin composition, the epoxy resin composition comprises 1wt％ to 15wt％ of viscosity increasingfiller； more preferably, the viscosity increasingfilleris one or more of aluminum, alumina, mica and kaolin.
  10. The composite honeycomb sandwich board according to anyone of claims 1 to 9, wherein the epoxy resin is selected from one or more of bisphenol Aepoxy resin, bisphenolF epoxy resin, phenolic epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenolF epoxy resin, cycloaliphatic epoxy resin, o-cresol epoxy resin, triglycidylisocyanurate, bisphenolfluorenyl epoxy resin, adamantaneepoxy resin and hydantoin epoxy resins.
  11. The composite honeycomb sandwich board according to anyone of claims 1 to 10, wherein the epoxy resin comprises the bisphenol A epoxy resin and the phenolic epoxy resin； preferably, based on the total weight of the epoxy resin, the epoxy resin comprises 60wt％ to 85wt％ of the bisphenol A epoxy resin and 15wt％ to 40wt％ of the phenolic epoxy resin.
  12. The composite honeycomb sandwich board according to claim 10 or 11, wherein the bisphenol A epoxy resin is of an epoxide value of 0.3 to 0.6, and the phenolic epoxy resin is of an epoxide value of 0.4 to 0.7.
  13. The composite honeycomb sandwich board according to anyone of claims1 to 12, wherein the latent curing agent is one or more of dicyandiamide, an imidazolium compound and organic hydrazine.
  14. The composite honeycomb sandwich board according to anyone of claims 1 to 13, wherein the toughening agent is one or more of polyurethane modified epoxy resin, carboxyl terminated nitrile rubber modified epoxy resin, silicone modified epoxy resin and dimeracid modified epoxy resin.
  15. The composite honeycomb sandwich board according to anyone of claims 1 to 14, wherein based on the total weight of the epoxy resin reinforcing material, the epoxy resin reinforcing material comprises 40wt％ to 60wt％ of the epoxy resin composition； preferably, the epoxy resin composition is of a grammage of400g/m2 to 2000g/m2.
  16. The composite honeycomb sandwich board according to anyone of claims 1 to 15, wherein the core layer is of a thickness of2mm to 9mm.
  17. A method for preparing a composite honeycomb sandwich board, comprising:
    providing an outer layer made of an epoxy resin reinforcing material, wherein the epoxy resin reinforcing material is constituted with a reinforcing material and an epoxy resin composition, and the epoxy resin compositioncomprises an epoxy resin, a latent curing agent, an acceleratorand a coupling agent, optionallya toughening agent and a filler；
    providing a core layer, in a honeycomb structure and made of aluminum； and
    placing the outer layer at at least one of upper and lower surfaces of the core layer followed by heatpressing treatment, so as to obtain the composite honeycomb sandwich board.
  18. The method according to claim 17, wherein providing the outer layerfurther comprises:
    melting the epoxy resin composition by heating to form a melt；
    coatingthe melton the reinforcing materialto obtain a green body； and
    impregnating the green body to obtain the epoxy resin reinforcing material.
  19. The method according to claim 18, wherein the meltis coated on the reinforcing material at a linear speed of 3 m/sto 10m/sunder a temperature of 60℃ to 80℃； and the green bodyis impregnated for 0.2 min to 5minunder a temperature of60℃ to 100℃.
  20. The method according to claim 17, wherein the heat pressing treatment is performed for 5 min to 20 min under a temperature of 80℃ to 200℃ and a pressure of 0.1MPato 1MPa.
PCT/CN2016/112651 2015-12-31 2016-12-28 Composite honeycomb sandwich board and method for preparing the same WO2017114416A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11040765B2 (en) 2018-06-27 2021-06-22 Goodrich Corporation Advanced composite heated floor panel

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2568727B (en) * 2017-11-24 2020-06-24 Gurit Uk Ltd Fire-retardant composite materials
CN108441154B (en) * 2018-04-20 2020-10-20 郑州中原思蓝德高科股份有限公司 Bonding method of honeycomb plate
CN109266274B (en) * 2018-08-21 2020-11-06 溧阳二十八所系统装备有限公司 High-strength room-temperature fast-curing two-component epoxy structural adhesive
CN109722940A (en) * 2018-12-19 2019-05-07 中航复合材料有限责任公司 A kind of honeycomb impregnating resin, honeycomb and cellular preparation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005083002A1 (en) * 2004-03-02 2005-09-09 Toray Industries, Inc. Epoxy resin composition for fiber-reinforced composite material, prepreg and fiber-reinforced composite material
WO2007125926A1 (en) * 2006-04-25 2007-11-08 The Yokohama Rubber Co., Ltd. Epoxy resin composition for fiber-reinforced composite material
EP2017296A1 (en) * 2006-04-25 2009-01-21 The Yokohama Rubber Co., Ltd. Epoxy resin composition for fiber-reinforced composite material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4141479B2 (en) * 2006-04-25 2008-08-27 横浜ゴム株式会社 Epoxy resin composition for fiber reinforced composite materials
CN101402839B (en) * 2008-11-18 2012-05-09 广州鹿山新材料股份有限公司 Adhesion agent for aluminum cellular composite board and method of producing the same
CN104364312B (en) * 2012-03-30 2017-03-01 三菱瓦斯化学株式会社 Resin combination, prepreg and plywood
CN102702683B (en) * 2012-06-04 2015-02-11 中国航空工业集团公司北京航空材料研究院 Epoxy resin for prepreg and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005083002A1 (en) * 2004-03-02 2005-09-09 Toray Industries, Inc. Epoxy resin composition for fiber-reinforced composite material, prepreg and fiber-reinforced composite material
WO2007125926A1 (en) * 2006-04-25 2007-11-08 The Yokohama Rubber Co., Ltd. Epoxy resin composition for fiber-reinforced composite material
EP2017296A1 (en) * 2006-04-25 2009-01-21 The Yokohama Rubber Co., Ltd. Epoxy resin composition for fiber-reinforced composite material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11040765B2 (en) 2018-06-27 2021-06-22 Goodrich Corporation Advanced composite heated floor panel
EP3587097B1 (en) * 2018-06-27 2022-01-19 Goodrich Corporation Advanced composite heated floor panel

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