WO2005095484A1 - Epoxy adhesive composition - Google Patents

Epoxy adhesive composition Download PDF

Info

Publication number
WO2005095484A1
WO2005095484A1 PCT/EP2005/002361 EP2005002361W WO2005095484A1 WO 2005095484 A1 WO2005095484 A1 WO 2005095484A1 EP 2005002361 W EP2005002361 W EP 2005002361W WO 2005095484 A1 WO2005095484 A1 WO 2005095484A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
composition according
acrylonitrile
epoxy adhesive
adhesive composition
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/EP2005/002361
Other languages
English (en)
French (fr)
Inventor
Andreas Lutz
Karsten Frick
Cathy Grossnickel
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34814318&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2005095484(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to DE602004004501.2T priority Critical patent/DE602004004501T3/de
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to JP2007502252A priority patent/JP5102018B2/ja
Priority to BRPI0506523-2A priority patent/BRPI0506523B1/pt
Priority to CA002553251A priority patent/CA2553251A1/en
Priority to CN2005800073567A priority patent/CN1930206B/zh
Priority to KR1020067018504A priority patent/KR101151092B1/ko
Publication of WO2005095484A1 publication Critical patent/WO2005095484A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils

Definitions

  • the present invention relates to an epoxy adhesive composition according to claim 1, the use of the epoxy adhesive composition for the assembly of parts of a vehicle according to claim 13, and a vehicle according to claim 14.
  • Epoxy adhesive compositions are reaction adhesive compositions comprising an epoxy resin, a curing agent and usually an accelerator. Upon heat-activation, the epoxy groups of the epoxy resin react with the curing agent linking the epoxy resin compounds by a polyaddition reaction to obtain a cured product.
  • Such a cured product is known to have good mechanical properties and a chemical resistance superior to the cured product of other reaction adhesives. These characteristics make epoxy adhesive compositions particularly useful for demanding applications where stringent mechanical requirements must be satisfied, for example in the automotive industry.
  • the cured product of an epoxy adhesive other than a structural epoxy adhesive generally has a relatively high static strength, for example a high tensile and lap shear strength. Its dynamic strength however, i.e. its impact peel strength, is generally low.
  • Adhesives used for the assembly of parts of a vehicle, such as cars, vans, lorries, trucks and trains, are called structural adhesives.
  • the cured product of such a structural adhesive has to bear high static and dynamic loads.
  • additional flexibilizers and/or tougheners are to be added to the epoxy adhesive composition.
  • EP-A-0 197 892 describes a structural adhesive comprising an epoxy resin, a nitrogen comprising toughener and an accelerator.
  • the problem described by this application is to provide a structural adhesive having a good storage stability and a high curing rate.
  • EP-A-0 308 664 describes an epoxy adhesive composition comprising a butadierie-acrylonitrile copolymer in combination with a polyphenol-terminated polyurethane or polyurea.
  • EP-A-0 353 190 describes an epoxy adhesive composition comprising a butadiene-acrylonitrile copolymer in combination with a polyether-, polyester, polythioester or polyamid prepolymer terminated with a functionalized carbocyclic aromatic or araliphatic residue.
  • EP-A-0 308 664 and EP-A-0 353 190 The technology according to EP-A-0 308 664 and EP-A-0 353 190 is called M ⁇ hlhaupt-technology.
  • the problem described by both EP-A-0 308 664 and EP-A-0 353 190 is to improve the impact peel strength of the cured product. At low temperatures however, the impact peel strength is low.
  • WO 00/20483 relates to a composition comprising an epoxide-reactive copolymer having a glastransition- temperature of -30°C or less, and a reaction product of a carboxylic acid anhydride with a di- or polyamine and a polyphenol or aminophenol .
  • the cured product of WO 00/20483 has an impact peel strength of less than 20 N/mm at -40°C.
  • the cured product of a structural adhesive is required to have good mechanical properties at room temperature as well as at low temperatures. Because of their low impact peel strength values at low temperatures, the above known epoxy adhesives do not fully meet this requirement. Vehicles, parts of which are assembled by the above known epoxy adhesives, do consequently not fully comply with safety requirements, for example in a crash test.
  • a further disadvantage of the above known epoxy adhesive compositions is their relatively low impact behaviour on high strength metals both at moderate and at extreme temperatures. Due to this disadvantage, the use of the known epoxy adhesive compositions for assembling the parts of a high strength metal construction is limited.
  • composition according to claim 1 comprising a) a first epoxy resin, b) a second epoxy resin modified with an acrylonitrile-butadiene rubber, the latter comprising on average less than 25 wt% acrylonitrile, and c) a toughener,
  • the total amount of component b) and component c) being more than 30 % based on the total weight of the composition, and the weight ratio of component c) to component b) being greater than 1:1.
  • the epoxy adhesive composition of the present invention results upon curing in a product having an impact peel strength of more than 35 N/mm at room temperature and of more than 25 N/mm at -40 °C.
  • the vastly improved impact strength at low temperatures allows the epoxy adhesive composition to be used as a structural adhesive which upon curing has a high crash resistance at any temperature of use and satisfies the most stringent safety requirements.
  • the cured product of the epoxy adhesive composition of the present invention Due to its improved toughening, the cured product of the epoxy adhesive composition of the present invention has a superior impact peel strength on high strength metals. Assembly of high strength metal parts by the epoxy adhesive composition of the present invention allows the resulting high strength metal construction to be higher loaded than a construction bonded with conventional adhesives. The applicability of the epoxy adhesive compositions of the present invention for the assembly of high strength metal parts is highly desirable, since bonding of high strength metal by welding is often not feasible.
  • the cured epoxy adhesive composition has an excellent static strength in a temperature range of from -40 °C to +80°C.
  • the lap shear strength is higher than 25 Pa and the tensile strength is higher than 30 MPa. It has a young modulus of about 1500 MPa and a tensile elongation at break of more than 10%.
  • the epoxy adhesive composition of the present invention shows an excellent adhesion on coated steels like hot- dipped, electro-galvanized and bonazinc steel, pretreated aluminum, magnesium and composites.
  • the strength values of the epoxy adhesive composition of the present invention are decreased by only 20 to 30%.
  • the first epoxy resin (component a) of claim 1 can be any kind of epoxy resin, such as DER 330 (low viscosity, undiluted, bisphenol A liquid epoxy resin) , DER 331 (standard, undiluted, bisphenol A liquid epoxy resin) or
  • the Dow Chemical Company Preferred examples of the first epoxy resin are polyglycidyl ether of bisphenols, such as
  • component a) is a mixture of at least two different epoxy resins. It is preferred that at least one epoxy resin is liquid at room temperature.
  • the second epoxy resin is modified with an acrylonitrilebutadiene rubber (component b) .
  • component b) comprises at least 30 wt%, preferably at least 40 wt% of acrylonitrile-butadiene rubber.
  • the acrylonitrilebutadiene rubber is preferably X8, X31 or any mixture of X8, X31 and X13 (wherein X stands for a copolymer rubber of the CTBN (carboxy-terminated butadiene-rubber) type and the term "mixture” means a "mixture of two or three of the components") .
  • X8 is a CTBN type acrylonitrile-butadiene-rubber containing 17% acrylonitrile.
  • X13 is a CTBN type acrylonitrile-butadiene-rubber containing 26% acrylonitrile.
  • X31 is a CTBN type acrylonitrile-butadiene-rubber containing 10% acrylonitrile.
  • the epoxy adhesive composition comprises less than 20%, preferably less than 15% of acrylonitrile based on the total weight of the acrylonitrile-butadiene rubber.
  • composition preferably comprises as toughener (component c) a compound of formula I
  • R 1 is an n-valent radical of an elastomeric prepolymer after the removal of the terminal isocyanate, amino or hydroxyl group, the elastomeric prepolymer being soluble or dispersible in epoxy resin
  • W and X are independently -0- or -NR 3 -, at least one of W and X being -NR 3 -
  • R 2 is an m+1-valent radical of a polyphenol or aminophenol after the removal of the phenolic hydroxyl group and optionally of the amino group
  • R 3 is hydrogen, a Ci to C alkyl or phenol.
  • composition comprises as component c) a compound of formula II
  • p is 1 or 2
  • q is 2 to 6
  • Y is -0-, -S- or -NR 6 -
  • Z is a radical selected from the group consisting of -OH, -NHR 6 , -OCN,
  • R 4 is a residue of a hydroxyl-, mercapto- or amino- terminated polyether prepolymer or of a hydroxyl-, ercapto- or amino-terminated prepolymeric, segmented polyester, polyt ioester or polyamid
  • R 5 is a carbocyclic aromatic or araliphatic p+1-valent radical with groups Z bonded directly to the aromatic ring
  • R 6 is hydrogen, Ci to C 6 alkyl or phenyl
  • R 7 is methyl or hydrogen.
  • composition can comprise a mixture of both a compound of formula I and formula II as component c) .
  • RAM A, RAM B or RAM C examples of component c) are RAM A, RAM B or RAM C.
  • RAM A, RAM B and RAM C are compounds of formula I, RAM A being allylphenol-terminated, RAM B being bisphenol A-terminated and RAM C being alkylphenol-terminated.
  • RAM 965 which is known to a skilled person.
  • component b) is in an amount of from 14 to 20 % and component c) is in an amount of from 18 to 28 % based on the total weight of the composition.
  • the epoxy adhesive composition comprises a total amount of component b) and component c) of at least 35 wt%, preferably 38 wt%.
  • the weight ratio of component c) to component b) is greater than 1.3:1, preferably greater than 1.5:1.
  • the epoxy adhesive composition according to the present invention can further include additives, such as fillers and accelerators, which are known to a person skilled in the art.
  • the composition comprises as an accelerator a solid solution of a nitrogen base having a boiling point above 130°C and a phenolic polymer which is an addition polymer of a phenol having an unsaturated substituent.
  • solid solution means the combination of the components in a solid one-phase system.
  • EP-A-0 197 892 page 1 , line 7, to page 10, line 28
  • EP 796 which is known to a skilled person is particularly preferred.
  • the epoxy adhesive composition is preferably used for the assembly of parts of a vehicle, such as cars, vans, lorries, trucks and trains. It can also be used for assembling parts of boats and aircrafts.
  • the epoxy adhesive composition of the present invention is preferably applied at a temperature of 40° to 65°C. It can be applied manually or automatically by a robot as normal beads, by swirling or by jet-streaming. The curing is starting at temperatures above 140°C.
  • the adhesive itself is showing the following standard values after curing at temperatures higher than 140 °C.
  • VDA testings were performed on pretreated aluminum, hot dipped, electro galvanised and bonazinc coated steel and showed a decrease in strength by only 20 to 30%.
  • Other artificial aging tests like KKT, P 1210, 3C and cataplasma showed similar results.
  • Struktol 3604 is a rubber modified epoxy resin consisting of 60% diglycidyl ether of bisphenol A (DGEBA) and 40% X8.
  • Struktol 3614 is a rubber modified epoxy resin consisting of 60% DGEBA and 40% X13.
  • the values of the impact peel strength were determined according to ISO 113 43.
  • the epoxy adhesive compositions according to the present invention have a significantly higher impact peel strength at -40°C than the conventional epoxy adhesive compositions.
  • H300XD Z100, H400TD Z100, RAGAL600DP Z100, DOCOL 1000DP ZE75/75 are high strength steels known to a skilled person.
  • the epoxy adhesive composition according to the present invention shows a significantly higher impact peel strength on high strength steel compared to known structural adhesive compositions.
  • Lap shear strength on high strength steel values in MPa at room temperature
  • Table 3 shows the lap shear strengths values of known structural adhesive compositions being maintained in the epoxy adhesive composition according to the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)
PCT/EP2005/002361 2004-03-12 2005-03-07 Epoxy adhesive composition Ceased WO2005095484A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE602004004501.2T DE602004004501T3 (de) 2004-03-12 2004-03-12 Epoxidharz Klebstoffzusammensetzung
JP2007502252A JP5102018B2 (ja) 2004-03-12 2005-03-07 エポキシ接着剤組成物
BRPI0506523-2A BRPI0506523B1 (pt) 2004-03-12 2005-03-07 Composição adesiva de époxi e uso de uma composição adesiva epóxi
CA002553251A CA2553251A1 (en) 2004-03-12 2005-03-07 Epoxy adhesive composition
CN2005800073567A CN1930206B (zh) 2004-03-12 2005-03-07 环氧粘合剂组合物
KR1020067018504A KR101151092B1 (ko) 2004-03-12 2005-03-07 에폭시 접착제 조성물

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04005984.2A EP1574537B2 (en) 2004-03-12 2004-03-12 Epoxy adhesive composition
EP04005984.2 2004-03-12

Publications (1)

Publication Number Publication Date
WO2005095484A1 true WO2005095484A1 (en) 2005-10-13

Family

ID=34814318

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/002361 Ceased WO2005095484A1 (en) 2004-03-12 2005-03-07 Epoxy adhesive composition

Country Status (11)

Country Link
US (1) US7910656B2 (https=)
EP (1) EP1574537B2 (https=)
JP (1) JP5102018B2 (https=)
KR (1) KR101151092B1 (https=)
CN (1) CN1930206B (https=)
AT (1) ATE352576T1 (https=)
BR (1) BRPI0506523B1 (https=)
CA (1) CA2553251A1 (https=)
DE (1) DE602004004501T3 (https=)
ES (1) ES2276182T5 (https=)
WO (1) WO2005095484A1 (https=)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7125461B2 (en) 2003-05-07 2006-10-24 L & L Products, Inc. Activatable material for sealing, baffling or reinforcing and method of forming same
US7199165B2 (en) 2003-06-26 2007-04-03 L & L Products, Inc. Expandable material
JP2010523800A (ja) * 2007-04-11 2010-07-15 ダウ グローバル テクノロジーズ インコーポレイティド 耐熱性構造用エポキシ樹脂
JP2010529285A (ja) * 2007-06-12 2010-08-26 ゼフィロス インコーポレイテッド 強化接着性材料
US9096039B2 (en) 2010-03-04 2015-08-04 Zephyros, Inc. Structural composite laminates
US9427902B2 (en) 2009-09-15 2016-08-30 Zephyros, Inc. Cavity filling
US10577523B2 (en) 2013-07-26 2020-03-03 Zephyros, Inc. Relating to thermosetting adhesive films
US11028220B2 (en) 2014-10-10 2021-06-08 Zephyros, Inc. Relating to structural adhesives
US11248145B2 (en) 2008-04-09 2022-02-15 Zephyros, Inc. Structural adhesives

Families Citing this family (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1431325A1 (de) * 2002-12-17 2004-06-23 Sika Technology AG Hitze-härtbare Epoxidharzzusammensetzung mit verbesserter Tieftemperatur-Schlagzähigkeit
US7557169B2 (en) 2003-07-07 2009-07-07 Dow Global Technologies, Inc. Capping isocyanate prepolymer or polyisocyanate/polyether polyol or polyamine mixture
EP2843022B1 (en) * 2003-07-07 2020-12-16 Dow Global Technologies LLC Adhesive epoxy composition and process for applying it
EP1498441A1 (de) * 2003-07-16 2005-01-19 Sika Technology AG Hitzehärtende Zusammensetzungen mit Tieftemperatur-Schlagzähigkeitsmodifikatoren
EP1602702B2 (en) * 2004-06-01 2020-09-16 Dow Global Technologies LLC Epoxy adhesive composition
US8070994B2 (en) 2004-06-18 2011-12-06 Zephyros, Inc. Panel structure
EP1695990A1 (en) * 2005-02-28 2006-08-30 Dow Global Technologies Inc. Two-component epoxy adhesive composition
DE602005020260D1 (de) * 2005-06-02 2010-05-12 Dow Global Technologies Inc Schlagzähmodifizierter Strukturklebstoff auf Epoxid Basis
EP1741734A1 (de) * 2005-07-05 2007-01-10 Sika Technology AG Tieftemperaturschlagzähe hitze-härtbare Epoxidharzzusammensetzung mit Epoxidfestharzen
KR101303246B1 (ko) * 2005-08-24 2013-09-06 헨켈 아일랜드 리미티드 개선된 내충격성을 갖는 에폭시 조성물
EP1876194A1 (de) * 2006-06-30 2008-01-09 Sika Technology AG Hitzehärtende Zusammensetzung geeignet zum Verkleben von beschichteten Substraten
JP5307714B2 (ja) 2006-07-31 2013-10-02 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 硬化性エポキシ樹脂系粘着組成物
CN101547990B (zh) 2006-10-06 2012-09-05 汉高股份及两合公司 可泵送的耐洗掉的环氧膏状粘合剂
EP1916272A1 (de) * 2006-10-24 2008-04-30 Sika Technology AG Hitzehärtende Epoxidharzzusammensetzung enthaltend ein blockiertes und ein epoxidterminiertes Polyurethanprepolymer
ATE486899T1 (de) * 2006-12-21 2010-11-15 Dow Global Technologies Inc Zusammensetzung, die zur verwendung als klebstoff beim einbau von fahrzeugfenstern brauchbar ist
WO2008127925A2 (en) * 2007-04-11 2008-10-23 Dow Global Technologies, Inc. Structural epoxy resins containing core-shell rubbers
EP2344561B1 (en) 2007-06-20 2015-07-29 Dow Global Technologies LLC Crash durable epoxy adhesives with very low sensitivity to temperature variations
CN101778877B (zh) * 2007-07-23 2013-01-02 陶氏环球技术公司 在使用温度范围内g-模量基本一致的两部分聚氨酯可固化组合物
JP2010536953A (ja) * 2007-08-17 2010-12-02 ダウ グローバル テクノロジーズ インコーポレイティド 二液型耐衝撃性エポキシ接着剤
MX2010004855A (es) * 2007-10-30 2010-06-30 Henkel Ag & Co Kgaa Adhesivos de pasta epoxi resistentes al lavado.
ATE484547T1 (de) * 2008-01-30 2010-10-15 Sika Technology Ag Auswaschbeständige hitzehärtende epoxidharzklebstoffe
EP2262852A1 (en) * 2008-03-26 2010-12-22 Lord Corporation Coating for elastomeric substrates
WO2010019539A2 (en) 2008-08-11 2010-02-18 Dow Global Technologies Inc. One-part structural epoxy resin adhesives containing elastomeric tougheners capped with phenols and hydroxy-terminated acrylates or hydroxy-terminated methacrylates
BRPI0912919B1 (pt) * 2008-08-22 2019-04-24 Dow Global Technologies Llc Composição bicomponente e método para ligar dois ou mais substratos entre si
BRPI1005818A2 (pt) 2009-02-26 2016-03-08 Dow Global Technologies Llc adesivo estrutural monocomponente e método de aplicação de adesivo estrutural
KR20110018061A (ko) 2009-08-17 2011-02-23 헨켈테크놀러지스 (유) 접착용 다기능 처리제를 이용한 신발의 제조방법
KR101093348B1 (ko) * 2009-08-17 2011-12-14 헨켈테크놀러지스 (유) 접착용 다기능 처리제 및 이를 이용한 신발의 제조방법
CN102648262B (zh) 2009-11-05 2014-12-10 陶氏环球技术有限责任公司 含有用酮肟封端的弹性增韧剂的结构环氧树脂胶粘剂
CN103025840A (zh) 2010-06-29 2013-04-03 陶氏环球技术有限责任公司 用于环氧树脂的储存稳定且热活化的叔胺催化剂
US8440746B2 (en) 2010-12-02 2013-05-14 Ppg Industries Ohio, Inc One component epoxy structural adhesive composition prepared from renewable resources
US9074040B2 (en) * 2010-12-20 2015-07-07 Mitsui Chemicals, Inc. Curable adhesive compositions
EP2655516B1 (en) 2010-12-26 2018-12-26 Dow Global Technologies LLC Structural epoxy resin adhesives containing chain-extended elastomeric tougheners capped with phenol, polyphenol or aminophenol compounds
TWI607073B (zh) 2011-10-14 2017-12-01 Ｌｇ化學股份有限公司 用於偏光板之黏著劑及包含其之偏光板
BR112014018126B1 (pt) 2012-03-23 2021-07-13 Dow Global Technologies Llc Adesivo estrutural termocurável e processo para unir e soldar membros metálicos
JP6173424B2 (ja) 2012-03-23 2017-08-02 ダウ グローバル テクノロジーズ エルエルシー 応力耐久性が高い破壊耐久性接着剤
EP2730594A1 (de) 2012-11-12 2014-05-14 Sika Technology AG Reaktive Flüssigkautschuke aus blockierten Isocyanat-terminierten Präpolymeren mit Glycolfänger
WO2014072515A1 (de) 2012-11-12 2014-05-15 Sika Technology Ag Neue schlagzähigkeitsmodifikatoren für epoxy-basierte klebstoffe
CN106715577A (zh) * 2014-07-08 2017-05-24 陶氏环球技术有限责任公司 延迟固化的高Tg碰撞耐用粘合剂
US10150893B2 (en) 2014-07-23 2018-12-11 Dow Global Technologies Llc Structural adhesives having improved wash-off resistance and method for dispensing same
US10047250B2 (en) * 2014-11-11 2018-08-14 Dow Global Technologies Llc Adhesive composition with glass spheres
US10392539B2 (en) 2014-12-31 2019-08-27 Dow Global Technologies Llc Crash durable epoxy adhesive compositions having improved low-temperature impact resistance and wash off resistance
US10081704B2 (en) 2015-03-24 2018-09-25 Evonik Degussa Gmbh Epoxy systems having improved fracture toughness
US20180163104A1 (en) * 2015-06-02 2018-06-14 Dow Global Technologies Llc Blocked polyurethane tougheners for epoxy adhesives
JP2017031264A (ja) * 2015-07-30 2017-02-09 デンカ株式会社 組成物
EP3347398B1 (en) 2015-09-10 2024-07-31 DDP Specialty Electronic Materials US, LLC One-component toughened epoxy adhesives with improved adhesion to oily surfaces and high wash-off resistance
WO2017044359A1 (en) 2015-09-10 2017-03-16 Dow Global Technologies Llc High modulus, toughened one-component epoxy structural adhesives with high aspect ratio fillers
EP3170877B1 (en) 2015-11-19 2020-11-18 3M Innovative Properties Company Structural adhesive with improved failure mode
WO2017127253A1 (en) 2016-01-19 2017-07-27 Dow Global Technologies Llc One-component epoxy-modified polyurethane and/or polyurea adhesives having high elongation and excellent thermal stability, and assembly processes using same
EP3529328B1 (en) 2016-10-24 2020-06-24 Dow Global Technologies LLC Epoxy adhesive resistant to open bead humidity exposure
WO2018081032A1 (en) 2016-10-25 2018-05-03 Dow Global Technologies Llc Epoxy adhesive having improved low-temperature impact resistance
EP3532527A1 (en) 2016-10-28 2019-09-04 Dow Global Technologies, LLC Crash durable epoxy adhesive having improved low-temperature impact resistance
KR102445875B1 (ko) 2017-01-03 2022-09-21 코닝 인코포레이티드 만곡된 커버 유리 및 디스플레이 또는 터치 패널을 갖는 차량 인테리어 시스템 및 이를 형성시키는 방법
US11274236B2 (en) 2017-02-26 2022-03-15 Ddp Specialty Electronic Materials Us, Llc One-component toughened epoxy adhesives containing a mixture of latent curing agents
US11332609B2 (en) 2017-06-29 2022-05-17 Dow Global Technologies Llc Epoxy-fiber reinforced composites, method to form the composites and epoxy resin composition used therefor
CN117962601A (zh) 2017-07-18 2024-05-03 康宁公司 复杂弯曲玻璃制品的冷成型
KR102627557B1 (ko) 2017-08-15 2024-01-24 디디피 스페셜티 일렉트로닉 머티리얼즈 유에스, 엘엘씨 이액형 상온 경화성 에폭시 접착제
US11492525B2 (en) 2017-09-12 2022-11-08 Ddp Specialty Electronic Materials Us, Llc Adhesive formulation
EP3681847B1 (en) 2017-09-12 2025-01-29 Corning Incorporated Tactile elements for deadfronted glass and methods of making the same
WO2019055128A1 (en) 2017-09-12 2019-03-21 Dow Global Technologies Llc EPOXY ADHESIVES REINFORCED WITH A COMPONENT
KR102529169B1 (ko) 2017-09-13 2023-05-08 코닝 인코포레이티드 충격 성능이 개선된 만곡된 커버 유리를 갖는 차량 인테리어 시스템 및 이를 형성하는 방법
US11065960B2 (en) 2017-09-13 2021-07-20 Corning Incorporated Curved vehicle displays
TWI844520B (zh) 2017-10-10 2024-06-11 美商康寧公司 具有改善可靠性的彎曲的覆蓋玻璃的車輛內部系統及其形成方法
KR20240025034A (ko) 2018-01-08 2024-02-26 디디피 스페셜티 일렉트로닉 머티리얼즈 유에스, 엘엘씨 에폭시 수지 접착제 조성물
US11718071B2 (en) 2018-03-13 2023-08-08 Corning Incorporated Vehicle interior systems having a crack resistant curved cover glass and methods for forming the same
EP3802723B1 (en) * 2018-05-29 2022-09-21 DDP Specialty Electronic Materials US, LLC Method for bonding using one-component epoxy adhesive mixtures
JP2021526168A (ja) 2018-06-05 2021-09-30 ダウ グローバル テクノロジーズ エルエルシー エポキシ繊維複合体をポリオレフィンにリサイクルするための方法
US10822517B2 (en) 2018-11-28 2020-11-03 Industrial Technology Research Institute Resin composition and cured resin composition
JP2022533832A (ja) 2019-05-21 2022-07-26 ディディピー スペシャルティ エレクトロニック マテリアルズ ユーエス，エルエルシー エポキシ接着剤組成物及び使用方法
US20220195267A1 (en) 2019-06-18 2022-06-23 Ddp Specialty Electronic Materials Us, Llc One-component toughened epoxy adhesives with improved humidity resistance
KR102304734B1 (ko) * 2019-08-19 2021-09-29 한국과학기술연구원 니켈-코발트-몰리브덴 산화물을 포함하는 이차전지용 음극 활물질, 이를 포함하는 이차전지용 음극, 상기 이차전지용 음극을 포함하는 이차전지 및 이들의 제조방법
KR102445303B1 (ko) * 2019-10-31 2022-09-20 주식회사 엘지화학 열 경화성 접착제 조성물과, 접착층을 포함한 구조체 및 이의 제조 방법
CN116472301A (zh) 2020-10-26 2023-07-21 Ddp特种电子材料美国有限责任公司 单组分结构粘合剂
JP2024512348A (ja) * 2021-03-05 2024-03-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 衝撃耐性、耐応力性、及び溶接性を備えたエポキシ接着剤
US12110425B2 (en) 2021-08-17 2024-10-08 Uniseal, Inc. Electromagnetic curable novel toughened epoxy-hybrid structural adhesives and applications using the same
WO2023033919A1 (en) 2021-08-30 2023-03-09 Ddp Specialty Electronic Materials Us, Llc Two-component structural adhesive
DE102021129372A1 (de) * 2021-11-11 2023-05-11 Thyssenkrupp Steel Europe Ag Verfahren zum Verkleben von Blechbauteilen
EP4543955A1 (de) 2022-06-22 2025-04-30 Basf Se Epoxy-terminierte isocyanat-prepolymere und verfahren zu deren herstellung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0308664A1 (de) * 1987-08-26 1989-03-29 Ciba-Geigy Ag Modifizierte Epoxidharze
EP0353190A2 (de) * 1988-07-28 1990-01-31 Ciba-Geigy Ag Flexibilisatorkombinationen für Epoxidharze
US20030187154A1 (en) * 2000-04-10 2003-10-02 Rainer Schoenfeld Impact-resistant epoxy resin compositions

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3514427A (en) * 1967-06-26 1970-05-26 Us Air Force Wide temperature range multiphase viscoelastic damping compositions
CA1259897A (en) * 1985-04-02 1989-09-26 Madan M. Bagga Bonding process using curable epoxide resin adhesive
US4788083A (en) * 1986-03-27 1988-11-29 Ashland Oil, Inc. Tin or bismuth complex catalysts and trigger cure of coatings therewith
US4948449A (en) * 1986-05-07 1990-08-14 Minnesota Mining And Manufacturing Company Epoxy resin composition
US4739019A (en) * 1986-12-08 1988-04-19 Ppg Industries, Inc. Curable epoxy based compositions having reduced shrinkage during cure
US5278257A (en) * 1987-08-26 1994-01-11 Ciba-Geigy Corporation Phenol-terminated polyurethane or polyurea(urethane) with epoxy resin
US5202390A (en) * 1988-07-28 1993-04-13 Ciba-Geigy Corporation Butadiene/polar comonomer copolymer and aromatic reactive end group-containing prepolymer
EP0381625B1 (de) * 1989-02-02 1996-07-31 Ciba-Geigy Ag Zähe Epoxidharze
JPH0343481A (ja) 1989-06-26 1991-02-25 Raytheon Co エポキシ接着剤
US5198510A (en) * 1990-04-27 1993-03-30 The B. F. Goodrich Company Modification of vinyl ester resins with reactive liquid polymers
ZA913801B (en) * 1990-05-21 1993-01-27 Dow Chemical Co Latent catalysts,cure-inhibited epoxy resin compositions and laminates prepared therefrom
JPH04110358A (ja) * 1990-08-31 1992-04-10 Shinto Paint Co Ltd 塗料用樹脂組成物およびこれを含有してなる電着塗料組成物
JP2750217B2 (ja) * 1990-11-20 1998-05-13 サンスター技研株式会社 自動車構造用一液型エポキシ系接着剤
DE4407490A1 (de) * 1994-03-07 1995-09-14 Bayer Ag Verfahren zur Herstellung heißhärtender Einkomponenten-Polyurethan-Reaktivmassen
WO1996000754A1 (en) 1994-06-30 1996-01-11 Minnesota Mining And Manufacturing Company Polyurethane/urea elastomeric sealants
DE19532294A1 (de) * 1995-09-01 1997-03-06 Huels Chemische Werke Ag Flüssige Einkomponenten-PUR-Einbrennlacke
US6258918B1 (en) * 1998-04-22 2001-07-10 3M Innovative Properties Company Flexible polyurethane material
US20040181013A1 (en) * 1998-10-06 2004-09-16 Henkel Teroson Gmbh Impact resistant epoxide resin compositions
DE19845607A1 (de) * 1998-10-06 2000-04-20 Henkel Teroson Gmbh Schlagfeste Epoxidharz-Zusammensetzungen
DE19858921A1 (de) * 1998-12-19 2000-06-21 Henkel Teroson Gmbh Schlagfeste Epoxidharz-Zusammensetzungen
CA2471368A1 (en) 2001-12-21 2003-07-03 Henkel Teroson Gmbh Expandable epoxy resin-based systems modified with thermoplastic polymers
US20030192643A1 (en) * 2002-03-15 2003-10-16 Rainer Schoenfeld Epoxy adhesive having improved impact resistance
EP2843022B1 (en) 2003-07-07 2020-12-16 Dow Global Technologies LLC Adhesive epoxy composition and process for applying it
EP1695990A1 (en) * 2005-02-28 2006-08-30 Dow Global Technologies Inc. Two-component epoxy adhesive composition
DE602005020260D1 (de) * 2005-06-02 2010-05-12 Dow Global Technologies Inc Schlagzähmodifizierter Strukturklebstoff auf Epoxid Basis

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0308664A1 (de) * 1987-08-26 1989-03-29 Ciba-Geigy Ag Modifizierte Epoxidharze
EP0353190A2 (de) * 1988-07-28 1990-01-31 Ciba-Geigy Ag Flexibilisatorkombinationen für Epoxidharze
US20030187154A1 (en) * 2000-04-10 2003-10-02 Rainer Schoenfeld Impact-resistant epoxy resin compositions

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7125461B2 (en) 2003-05-07 2006-10-24 L & L Products, Inc. Activatable material for sealing, baffling or reinforcing and method of forming same
US7199165B2 (en) 2003-06-26 2007-04-03 L & L Products, Inc. Expandable material
JP2010523800A (ja) * 2007-04-11 2010-07-15 ダウ グローバル テクノロジーズ インコーポレイティド 耐熱性構造用エポキシ樹脂
JP2010529285A (ja) * 2007-06-12 2010-08-26 ゼフィロス インコーポレイテッド 強化接着性材料
US11248145B2 (en) 2008-04-09 2022-02-15 Zephyros, Inc. Structural adhesives
US11667813B2 (en) 2008-04-09 2023-06-06 Zephyros, Inc. Structural adhesives
US12497543B2 (en) 2008-04-09 2025-12-16 Zephyros, Inc. Structural adhesives
US9427902B2 (en) 2009-09-15 2016-08-30 Zephyros, Inc. Cavity filling
US9096039B2 (en) 2010-03-04 2015-08-04 Zephyros, Inc. Structural composite laminates
US10577523B2 (en) 2013-07-26 2020-03-03 Zephyros, Inc. Relating to thermosetting adhesive films
US10577522B2 (en) 2013-07-26 2020-03-03 Zephyros, Inc. Thermosetting adhesive films including a fibrous carrier
US11873428B2 (en) 2013-07-26 2024-01-16 Zephyros, Inc. Thermosetting adhesive films
US11028220B2 (en) 2014-10-10 2021-06-08 Zephyros, Inc. Relating to structural adhesives

Also Published As

Publication number Publication date
CA2553251A1 (en) 2005-10-13
ATE352576T1 (de) 2007-02-15
DE602004004501T3 (de) 2015-05-28
US20050209401A1 (en) 2005-09-22
DE602004004501D1 (de) 2007-03-15
US7910656B2 (en) 2011-03-22
DE602004004501T2 (de) 2007-11-15
EP1574537A1 (en) 2005-09-14
EP1574537B1 (en) 2007-01-24
KR20070021152A (ko) 2007-02-22
JP5102018B2 (ja) 2012-12-19
KR101151092B1 (ko) 2012-06-01
BRPI0506523B1 (pt) 2021-10-13
BRPI0506523A (pt) 2007-02-27
ES2276182T5 (es) 2015-04-10
ES2276182T3 (es) 2007-06-16
CN1930206A (zh) 2007-03-14
EP1574537B2 (en) 2014-12-24
CN1930206B (zh) 2011-05-18
JP2007528923A (ja) 2007-10-18

Similar Documents

Publication Publication Date Title
EP1574537B1 (en) Epoxy adhesive composition
EP2137277B1 (en) Heat-resistant structural epoxy resins
KR101467609B1 (ko) 온도 변화에 대한 민감도가 매우 낮은 충돌 내구성 에폭시 접착제
US8858752B2 (en) Structural epoxy resin adhesives containing elastomeric tougheners capped with ketoximes
EP1602702B1 (en) Epoxy adhesive composition
JP2002527551A (ja) 高強度エポキシ接着剤およびその使用
JP2002526618A (ja) 耐衝撃性エポキシ樹脂組成物
EP3737725A1 (en) Epoxy resin adhesive compositions
US7956143B1 (en) Toughened two-part adhesive compositions demonstrating improved impact and/or peel strengths when cured
EP4688993A1 (en) Expanded cure window crash durable epoxy adhesives

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2553251

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 200580007356.7

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 1020067018504

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2007502252

Country of ref document: JP

Ref document number: 3296/CHENP/2006

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Ref document number: DE

WWP Wipo information: published in national office

Ref document number: 1020067018504

Country of ref document: KR

ENP Entry into the national phase

Ref document number: PI0506523

Country of ref document: BR

122 Ep: pct application non-entry in european phase