WO2007076108A1 - Adhesive compositions for bonding metals - Google Patents

Adhesive compositions for bonding metals Download PDF

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Publication number
WO2007076108A1
WO2007076108A1 PCT/US2006/049224 US2006049224W WO2007076108A1 WO 2007076108 A1 WO2007076108 A1 WO 2007076108A1 US 2006049224 W US2006049224 W US 2006049224W WO 2007076108 A1 WO2007076108 A1 WO 2007076108A1
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WO
WIPO (PCT)
Prior art keywords
diol
adhesive composition
adhesion promoter
butyne
acetylenic
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/US2006/049224
Other languages
French (fr)
Inventor
Samuel B. Osae
Paul C. Briggs
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.)
IPS Corp
Original Assignee
IPS Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IPS Corp filed Critical IPS Corp
Priority to AU2006330904A priority Critical patent/AU2006330904A1/en
Priority to EP06848132.4A priority patent/EP1963450B1/en
Priority to JP2008547652A priority patent/JP5417849B2/en
Priority to CA2633738A priority patent/CA2633738C/en
Priority to CN200680052543.1A priority patent/CN101365764B/en
Publication of WO2007076108A1 publication Critical patent/WO2007076108A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • a preferred embodiment of this invention relates to two-part structural adhesive compositions, utilizing new and unique adhesion promoters, exhibiting improved adhesion to metals, as well as .other important characteristics .
  • These adhesive compositions are mixtures of acrylate or methacrylate monomers and polymers that comprise at least the following components:
  • one or more polymerizable acidic adhesion promoters are also added to the composition.
  • additives may also be added to the composition to enhance its performance.
  • acetylenic diol adhesion promoters of a preferred 5 embodiment of this invention correspond to the general formula:
  • Ri, R 2 , R 3 and R 4 are selected from H and alkyl groups and wherein n is equal to or greater than 0.
  • SURFYNOL® 104 Air Products and Chemicals, Inc.
  • 25 diols is the 2-butyne-l, 4-diol backbone structure, wherein the hydroxyl groups are attached to the carbon atom adjacent to the acetylenic triple bond.
  • acetylenic diols are sold commercially as defoaming agents and surfactants for a wide variety of aqueous or waterborne applications, such as paints and coatings.
  • their use in adhesives has been limited to waterborne compositions based on polymer emulsions and water-compatible additives. They are not recommended for use in organic coatings or adhesives when organic solvents or monomers - are the primary liquid species in the composition.
  • acetylenic diol adhes ' ion promoters may derive from one or more of the theoretical explanations for metal adhesion. These theories include, but are not limited to, various electron donor-acceptor, hydrogen bonding or dipole-dipole interactive phenomena.
  • the acetylenic diols adhesion promoters have the potential to function in at least two ways, wherein either the electron donating capability of the acetylenic moiety, or the hydrogen bonding capability of the hydroxyl moieties, or both, can participate in the adhesion process.
  • While the preferred inventive additives may be added to the composition as the sole adhesion promoter, they find particular utility in combination with other acidic adhesion promoters.
  • the ability of acidic adhesion promoters to affect the bond strength of acrylate or methacrylate based structural adhesives to metals is known in the art.
  • Traditional acidic adhesion promoters include unsaturated mono-carboxylic acids, such as acrylic acid and methacrylic acid, unsaturated- dicarboxylic acids such as maleic acid and fumaric acid, and unsaturated phosphoric acid esters such as mono- and bis- methacroyloxyethyl phosphate .
  • the factors influencing the ability of acrylate or methacrylate structural adhesives to bond metals are complex and interactive.
  • Acrylic and methacrylic acids generally enhance the ability of acrylate and methacrylate structural adhesives to bond ferrous metals and generally increase their rate of cure.
  • Maleic acid generally enhances adhesion to zinc surfaces
  • unsaturated phosphoric acid esters generally enhance adhesion and durability of bonds to unprepared aluminum and stainless steel surfaces.
  • Combinations of these acidic adhesion promoters can be used to formulate adhesives for specific applications and. combinations of metallic and non-metallic materials.
  • One basis for a preferred embodiment of the current invention is that even when prior art metal adhesion promoters have been evaluated or incorporated in certain adhesive formulations, a specific formulation, even with certain other desirable characteristics, may not provide the desired level of adhesion to one or more metallic substrates.
  • the addition of the preferred inventive acetylenic diol adhesion promoter can impart the desired improvements in metal adhesion.
  • the specific improvements include, but are not limited to, increased bond strength and an , increase in the desired cohesive failure mode over the less desirable adhesive failure mode, and preferably both.
  • Cohesive failure is the mode of bond failure wherein upon separation of the bond in testing or in use, the failure occurs within the adhesive layer, leaving adhesive on both of the substrate pieces. In the adhesive failure mode, the adhesive separates cleanly from one of the substrate pieces, leaving no adhesive residue on that surface.
  • a particularly preferred composition of the current invention comprises:
  • the composition also includes 0.5 to 20 percent of an polymerizable acidic adhesion promoter or a mixture thereof.
  • Acetylenic component features Inventive Diol Inventive Diol Inventive Diol Single OH No 0
  • Example A is a control Example while the preferred inventive Examples include Examples B-D. These Examples, particularly Examples B and C, disclose improved adhesion for the compositions of preferred embodiments of the invention over compositions that do not include the inventive acetylenic diol component. However, these Examples, particularly Examples B and C, disclose improved adhesion for the compositions of preferred embodiments of the invention over compositions that do not include the inventive acetylenic diol component. However, these Examples, particularly Examples B and C, disclose improved adhesion for the compositions of preferred embodiments of the invention over compositions that do not include the inventive acetylenic diol component. However, these examples, particularly Examples B and C, disclose improved adhesion for the compositions of preferred embodiments of the invention over compositions that do not include the inventive acetylenic diol component. However, these Examples, particularly Examples B and C, disclose improved adhesion for the compositions of preferred embodiments of the invention over compositions that do not include the inventive acetylenic diol component. However, these

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A two-part structural adhesive composition particularly for use with metals comprising one or more vinyl monomers, preferably an acrylate or methacrylate ester monomer, one or more soluble or dispersible polymers, and acetylenic diol adhesion promoter, and preferably one or more polymerizable acid adhesion promoters.

Description

Title
ADHESIVE COMPOSITIONS FOR BONDING METALS
Background and A Preferred Embodiment A preferred embodiment of this invention relates to two-part structural adhesive compositions, utilizing new and unique adhesion promoters, exhibiting improved adhesion to metals, as well as .other important characteristics . These adhesive compositions are mixtures of acrylate or methacrylate monomers and polymers that comprise at least the following components:
A. one or more vinyl monomers, preferably an acrylate or methacrylate ester monomer, B. one or more soluble or dispersible polymers, and
C. an acetylenic diol adhesion promoter.
Preferably one or more polymerizable acidic adhesion promoters are also added to the composition.
Other additives may also be added to the composition to enhance its performance.
In the course of evaluating the effects of traditional acidic adhesion promoters for bonding metallic substrates, it was surprisingly discovered that the addition of an acetylenic diol produced a marked improvement in the ability of the composition to bond to a variety of metals, even when conventional metal bonding adhesion promoters fail to provide the desired level of adhesion.
The acetylenic diol adhesion promoters of a preferred 5 embodiment of this invention correspond to the general formula:
Ri Ra
H(C2H4O)n O - C - C ≡ C - C - 0(C2H4O)nH 10 R2 R4
wherein Ri, R2 , R3 and R4 are selected from H and alkyl groups and wherein n is equal to or greater than 0.
One group of preferred acetylenic diol adhesion
,15 promoters are disclosed by US Patent Nos . 4,650,543 and 3; 268, 593, the entirety of each is incorporated by reference herein. A particularly preferred acetylenic diol adhesion promoter is 2-butyne-l, 4-diol wherein Ri, R2, R3, and R4 are all H and n = 0. Another particularly preferred
20 acetylenic diol adhesion promoter, sold commercially as SURFYNOL® 104 by Air Products and Chemicals, Inc., is 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol, • wherein Ri and R3 are methyl groups and R2 and R4 are isobutyl groups and n = 0. One important feature of the preferred acetylenic
25 diols is the 2-butyne-l, 4-diol backbone structure, wherein the hydroxyl groups are attached to the carbon atom adjacent to the acetylenic triple bond. Other particularly preferred acetylenic diol adhesion promoters include ethoxylated 2-butyne-l, 4-diols, wherein the hydroxyl moiety is separated from the acetylenic carbon atom by one or more oxyethylene groups (n = 1 or more) , such as SURFYNOL 485, which is an ethoxylated 2,4,7,9 tetramethyl- 5-decyn-4,7 diol.
Conventionally, acetylenic diols are sold commercially as defoaming agents and surfactants for a wide variety of aqueous or waterborne applications, such as paints and coatings. Heretofore, their use in adhesives has been limited to waterborne compositions based on polymer emulsions and water-compatible additives. They are not recommended for use in organic coatings or adhesives when organic solvents or monomers - are the primary liquid species in the composition. Even when acetylenic alcohols or diols are used in water-based compositions, their benefits are. generally limited to effects deriving from their function as a defoamer or surfactant. Therefore, the significant improvement in adhesion to a variety of metallic surfaces by use of the compositions of preferred embodiments of invention was surprising.
While not intending to be bound by a specific theory, possible explanations for the beneficial effects from the use of the acetylenic diol adhes'ion promoters may derive from one or more of the theoretical explanations for metal adhesion. These theories include, but are not limited to, various electron donor-acceptor, hydrogen bonding or dipole-dipole interactive phenomena. In this sense, the acetylenic diols adhesion promoters have the potential to function in at least two ways, wherein either the electron donating capability of the acetylenic moiety, or the hydrogen bonding capability of the hydroxyl moieties, or both, can participate in the adhesion process. Evidence may be found in the fact that the olefinic or double bond analog of the preferred 2-butyne, 1,4-diol, namely 2- butene, 1,4-diol, wherein the triple bond of the structure above is replaced by a double bond, does not impart the inventive improvements. Similarly, the bis (acetate ester) of 2,butyne-l, 4-diol does not impart the same inventive improvements. Thus, it is believed that the presence of at least one hydroxyl moiety and the triple bond are necessary to impart the desired improvements.
While the preferred inventive additives may be added to the composition as the sole adhesion promoter, they find particular utility in combination with other acidic adhesion promoters. The ability of acidic adhesion promoters to affect the bond strength of acrylate or methacrylate based structural adhesives to metals is known in the art. Traditional acidic adhesion promoters include unsaturated mono-carboxylic acids, such as acrylic acid and methacrylic acid, unsaturated- dicarboxylic acids such as maleic acid and fumaric acid, and unsaturated phosphoric acid esters such as mono- and bis- methacroyloxyethyl phosphate . The factors influencing the ability of acrylate or methacrylate structural adhesives to bond metals are complex and interactive. They involve the catalytic or inhibitive effect of metallic surfaces and the acidic adhesion promoters on the reactivity of the adhesive composition as well as the effects of the specific metallic surfaces on the initial adhesion and durability of the bonds. For example, zinc and copper can either catalyze or inhibit the cure of an adhesive depending on the specific formulation. Iron oxide and aluminum oxide on ferrous and aluminum surfaces behave differently with respect to initial bond strength and durability of bonds.
Acrylic and methacrylic acids generally enhance the ability of acrylate and methacrylate structural adhesives to bond ferrous metals and generally increase their rate of cure. Maleic acid generally enhances adhesion to zinc surfaces, and unsaturated phosphoric acid esters generally enhance adhesion and durability of bonds to unprepared aluminum and stainless steel surfaces. Combinations of these acidic adhesion promoters can be used to formulate adhesives for specific applications and. combinations of metallic and non-metallic materials.
One basis for a preferred embodiment of the current invention is that even when prior art metal adhesion promoters have been evaluated or incorporated in certain adhesive formulations, a specific formulation, even with certain other desirable characteristics, may not provide the desired level of adhesion to one or more metallic substrates. In such formulations, the addition of the preferred inventive acetylenic diol adhesion promoter can impart the desired improvements in metal adhesion. The specific improvements include, but are not limited to, increased bond strength and an , increase in the desired cohesive failure mode over the less desirable adhesive failure mode, and preferably both. Cohesive failure is the mode of bond failure wherein upon separation of the bond in testing or in use, the failure occurs within the adhesive layer, leaving adhesive on both of the substrate pieces. In the adhesive failure mode, the adhesive separates cleanly from one of the substrate pieces, leaving no adhesive residue on that surface.
Detailed • information concerning groups of adhesives to which this preferred inventive composition may be directed can be found in the US Patents 3,890,407, 4,182,604, 4,223,115, 4,536,546, 4,645,810, 4,714,730, 4,942,201, and a review of the subject by D.J. Damico, Engineered Materials Handbook, Volume 3, 119 ASM International, 1990, all of which references are incorporated herein by reference. For purpose of this discussion, the polymerizable vinyl, acrylate and methacrylate monomers include those disclosed in the '604 patent cited above; and the soluble or dispersible polymers include those disclosed in the Λ604 and Λ546 patents. The catalysts or initiating species include all of those generally recognized in the prior art including those described in the above cited references.
A particularly preferred composition of the current invention comprises:
A. 20 percent to 90 percent of a polymerizable vinyl monomer, preferably an acrylate or methacrylate ester monomer,
B. 10 percent to 60 percent of a soluble or dispersible polymer or mixture of polymers, and
C. 0.1 percent to 10 percent of an acetylenic diol . Preferably, the composition also includes 0.5 to 20 percent of an polymerizable acidic adhesion promoter or a mixture thereof.
Other additives to enhance the . performance of the composition can be added, as needed. EXAMPLES
The components used in the following examples are:
Component Description Supplier
Methyl Methacrylate Monomer Lucite
5.
Methacrylic Acid Polymerizable carboxylic Lucite acid adhesion promoter
Tyrin 3615 Chlorinated polyethylene duPont/Dow 0
Kraton D1155 Thermoplastic SBS block Kraton Polymers copolymer 5 Paraloid BTA 753 MBS Core-shell Rohm & Haas impact modifier
Phosphate ester CD-9052 Polymeri zable acidic Sartomer
. adhesion promoter 0
0.05% CuAcAc solution Copper acetyl acetonate Lab prep/Aldrich solution in MMA 5 Reillcat ASY-2 Dihydropyridine activator Reilly Industries
Component
2-Butyne-4-diol Inventive adhesion promoter BASF 0
Sύrfynol® Inventive commercial Air Products adhesion promoters
2 2--BBuuttvynnee--ll /, 44--ddiiooll ddiiaacceettate Comparative acetylenic Aldrich 5 compound
Example A B C D E P
Coxαponontia Control
Methyl Methacrylate 63.4 61 .4 61. 4 61. 4 61. 4 61 .4
Methacrylic Acid 2.5 2 . 5 2 .5 2 . 5 2 .5 2 . 5
Tyrin 3615 5 5 5 5 5 5
Kraton D1155 5 5 5 5 5 5 p-Toluenesulfonyl Chlotide 1.5 1.5 1.5 1. 5 1. 5 1. 5
Rohm S Haas BTA-753 20 20 20 20 20 20 Phosphate Ester CD-9052 1.25 1.25 1.25 1.25 1.25 1.25
0.05% CuAcAc Solution 0. 1 0.1 0.1 0.1 0.1 0. 1
Reillcat ASY-2 1. 25 1.25 1.25 1.25 1.25 1. 25
2-Butyne-l, 4-diol - 2 - - - -
Surfynol* 104 - - 2 - - -
SurEynol 485 - - - .2 - -
Surfynol 61 - - - - 2 -
2-Butyne-l,4-diol diacetate - - - - - 2
Acetylenic component features Inventive Diol Inventive Diol Inventive Diol Single OH No 0
Group Results
Aluminum Lap Shear Strength, psi2112 2513 2308 2184 2048 2153
ASTM D1002
Failure Mode Adhesive Cσhesive/Adh Adhesive Adhesive Adhesive Adhe
Example A is a control Example while the preferred inventive Examples include Examples B-D. These Examples, particularly Examples B and C, disclose improved adhesion for the compositions of preferred embodiments of the invention over compositions that do not include the inventive acetylenic diol component. However, these
Examples place no limitations on the scope of the inventions disclosed herein.

Claims

Claims
Claim 1. ■ An adhesive composition, preferably an organic adhesive composition, comprising one or more vinyl monomers, one or more soluble or dispersible polymers, and an acetylenic diol adhesion promoter, preferably wherein the acetylenic diol is selected from the group consisting of
Ri Ra
H(C2H4O)n O - C - C ≡ C - C - 0(C2H4O)nH R2 R4
wherein R1, R2 , R3 , and R4 are selected from H and alkyl groups and wherein n is equal to or greater than 0; 2- butyne-1, 4-diol; 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol; an ethoxylated 2-butyne-l, 4-diol, and preferably a polymerizable acidic adhesion promoter.
Claim 2. The adhesive composition of Claim 1 wherein the acidic adhesion promoter is selected from the group consisting of unsaturated monσ-carboxylic acids, such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids, such as maleic acid and fumaric acid, unsaturated phosphoric acid esters, such as mono- and bis- methacroyloxyethyl phosphate and mixtures thereof.
Claim 3. An organic adhesive composition comprising from 20 to 90% of a polymerizable vinyl monomer, from 10% to 60% of a soluble or dispersible polymer or mixture of polymers, and from 0.1 to 10% of an acetylenic diol, wherein the acetylenic diol is preferably selected from
Ri R3
H(C2H4O)n O - C - C ≡ C - C - 0(C2H4O)nH R2 R4
wherein Ri, R∑ , R3 , and R4 are selected from H and alkyl groups and wherein n is equal to or greater than 0; 2- butyne-1, 4-diol; 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol; and an ethoxylated 2-butyne-l, 4-diol .
Claim 4. The composition of Claim 3 further comprising from 0.5 to 20% of a polymerizable acidic adhesion promoter.
Claim 5. The adhesive composition of Claim 4 wherein the acidic adhesion promoter is selected from the group consisting of unsaturated mono-carboxylic acids, such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids, such as maleic acid and fumaric acid, unsaturated phosphoric acid esters, such as mono- and bis- methacroyloxyethyl phosphate and mixtures thereof.
Claim 6. A process of adhesively securing metallic substrates comprising a) preparing the adhesive composition of Claim 1, and b) securing the adhesive composition to metallic substrates.
PCT/US2006/049224 2005-12-22 2006-12-22 Adhesive compositions for bonding metals Ceased WO2007076108A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU2006330904A AU2006330904A1 (en) 2005-12-22 2006-12-22 Adhesive compositions for bonding metals
EP06848132.4A EP1963450B1 (en) 2005-12-22 2006-12-22 Adhesive compositions for bonding metals
JP2008547652A JP5417849B2 (en) 2005-12-22 2006-12-22 Adhesive composition for metal bonding
CA2633738A CA2633738C (en) 2005-12-22 2006-12-22 Adhesive compositions for bonding metals
CN200680052543.1A CN101365764B (en) 2005-12-22 2006-12-22 Adhesive composition for bonding metals

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US75331005P 2005-12-22 2005-12-22
US60/753,310 2005-12-22
US11/643,543 US20070155879A1 (en) 2005-12-22 2006-12-21 Adhesive compositions for bonding metals
US11/643,543 2006-12-21

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WO2007076108A1 true WO2007076108A1 (en) 2007-07-05

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US (1) US20070155879A1 (en)
EP (1) EP1963450B1 (en)
JP (1) JP5417849B2 (en)
CN (1) CN101365764B (en)
AU (1) AU2006330904A1 (en)
CA (1) CA2633738C (en)
WO (1) WO2007076108A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008016436A1 (en) 2008-03-31 2009-10-01 Ems-Patent Ag Polyamide molding compound for paint-free, tough housings with a high-gloss surface
US9074112B2 (en) 2010-02-26 2015-07-07 Scott Bader Company Limited Methacrylate-based adhesive compositions
CN109468097A (en) * 2018-10-22 2019-03-15 广东星宇耐力新材料股份有限公司 A kind of aluminium foil XPS extruded sheet composite water soluble adhesive and preparation method thereof

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090087671A1 (en) * 2007-09-27 2009-04-02 Ppg Industries Ohio, Inc. Coating compositions exhibiting corrosion resistance properties and methods of coil coating
US8921490B2 (en) * 2009-06-30 2014-12-30 Henkel US IP LLC Ultrafast heat/room temperature adhesive composition for bonding applications
KR101206591B1 (en) 2009-08-25 2012-11-29 (주)엘지하우시스 Aqueous pressure-sensitive adhesive composition, preparation method thereof and pressure-sensitive adhesive film
US8986827B2 (en) * 2010-10-06 2015-03-24 Toray Plastics (America), Inc. Barrier coating composition with organic particles
WO2015164031A1 (en) 2014-04-22 2015-10-29 Dow Global Technologies Llc Polyurethane-acrylate epoxy adhesive
SG11201703125WA (en) * 2014-10-23 2017-05-30 Agency Science Tech & Res Method of bonding a first substrate and a second substrate
JP7234654B2 (en) * 2019-01-28 2023-03-08 株式会社リコー Electrode and its manufacturing method, electrode element, non-aqueous electrolyte storage element

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2125420A (en) * 1982-08-16 1984-03-07 Air Prod & Chem Pressure sensitive adhesives
US4507429A (en) * 1984-01-12 1985-03-26 Air Products And Chemicals, Inc. Pressure sensitive adhesives with improved shear resistance
US4714730A (en) * 1986-06-04 1987-12-22 Illinois Tool Works Inc. Acid modified adhesive compositions
EP1486801A2 (en) * 2001-04-24 2004-12-15 Hoya Corporation Optical composition, process for producing optical element using the same, and optical element

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1127347B (en) * 1961-06-26 1962-04-12 Air Reduction Process for the preparation of alkynol-ethylene oxide adducts
US3890407A (en) * 1972-07-20 1975-06-17 Du Pont Novel adhesive compositions
US4182644A (en) * 1975-03-27 1980-01-08 E. I. Du Pont De Nemours And Company Polymer in monomer adhesive composition and method employing same
US4041103A (en) * 1976-06-07 1977-08-09 Shell Oil Company Blends of certain hydrogenated block copolymers
US4223115A (en) * 1978-04-24 1980-09-16 Lord Corporation Structural adhesive formulations
US4242470A (en) * 1979-03-19 1980-12-30 Shell Oil Company Polyamide/block copolymer blends
IE51059B1 (en) * 1980-07-11 1986-09-17 Loctite Corp Butadiene toughened adhesive composition
US4451615A (en) * 1980-05-09 1984-05-29 Loctite (Ireland) Limited Polyisoprene toughened adhesive composition
US4440830A (en) * 1981-04-16 1984-04-03 Wempe Lawrence K Substrates coated with release composition based on polyvinyl alcohol and composites with pressure sensitive adhesives
US4536546A (en) * 1983-09-22 1985-08-20 Illinois Tool Works Inc. (Meth)acrylate-based compositions
US4491646A (en) * 1983-09-29 1985-01-01 Ashland Oil, Inc. Aqueous hydroxyl-acrylic latex and multi-isocyanate adhesive composition
JPS60183726A (en) * 1984-03-02 1985-09-19 Toshiba Corp Electrode pattern forming method of semiconductor device
GB2163439B (en) * 1984-08-23 1988-04-27 Bostik Ltd Adhesive bonding
US4942201A (en) * 1988-08-29 1990-07-17 Illinois Tool Works, Inc. Adhesive for low temperature applications
US5026609A (en) * 1988-09-15 1991-06-25 Owens-Corning Fiberglas Corporation Road repair membrane
JPH0781115B2 (en) * 1988-12-29 1995-08-30 カネボウ・エヌエスシー株式会社 Two-component acrylic adhesive composition
US5945461A (en) * 1991-03-21 1999-08-31 Illinois Tool Works Inc. Foamed acrylic polymer compositions
US6034159A (en) * 1995-01-06 2000-03-07 H.B. Fuller Licensing & Financing, Inc. Fast setting multipurpose bookbinding adhesive with excellent flexibility
US5866262A (en) * 1995-10-16 1999-02-02 Galic Maus Ventures Fully-hydrolized ketimine silane/epoxide silane copolymer liquid hardcoating compositions and processes for dipcoating polycarbonate spectacle lenses
US5742943A (en) * 1996-06-28 1998-04-28 Johnson & Johnson Medical, Inc. Slip-coated elastomeric flexible articles and their method of manufacture
JP3928751B2 (en) * 1996-07-22 2007-06-13 大日本インキ化学工業株式会社 Water-based adhesive composition and laminating method
US6559257B2 (en) * 1998-06-12 2003-05-06 Lord Corporation Adhesive formulations
WO2000032688A1 (en) * 1998-12-03 2000-06-08 The Dexter Corporation Adhesive compositions with retarding additive
US7348300B2 (en) * 1999-05-04 2008-03-25 Air Products And Chemicals, Inc. Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture
FR2804963B1 (en) * 2000-02-15 2004-01-30 Rhodia Chimie Sa USE OF HYDROPHILIC (CO) POLYMERS AS ADDITIVES IN AQUEOUS SILICONE EMULSIONS, CROSSLINKABLE IN WATERPROOF AND ANTI-ADHERENT COATINGS FOR SOFT SUPPORTS
US6512043B2 (en) * 2000-05-10 2003-01-28 Illinois Tool Works Inc. Two-part structural adhesive having long working time
JP3779231B2 (en) * 2001-04-24 2006-05-24 Ｈｏｙａ株式会社 Coating composition, method for producing optical member using the same, and optical member
US6433091B1 (en) * 2001-05-10 2002-08-13 Henkel Loctite Corporation Adhesive composition
JP4545356B2 (en) * 2001-07-11 2010-09-15 電気化学工業株式会社 Adhesive composition for galvanized steel sheet
AU2002357615A1 (en) * 2002-01-07 2003-07-24 Denki Kagaku Kogyo Kabushiki Kaisha Electroconductive resin composition
US6989416B2 (en) * 2002-05-07 2006-01-24 Sika Technology Ag Methacrylate structural adhesive
US6949602B2 (en) * 2002-12-19 2005-09-27 Illinois Tool Works, Inc. Heat resistant, impact resistant, acrylic/epoxy adhesives
US6886937B2 (en) * 2003-06-20 2005-05-03 Vision - Ease Lens, Inc. Ophthalmic lens with graded interference coating

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2125420A (en) * 1982-08-16 1984-03-07 Air Prod & Chem Pressure sensitive adhesives
US4507429A (en) * 1984-01-12 1985-03-26 Air Products And Chemicals, Inc. Pressure sensitive adhesives with improved shear resistance
US4714730A (en) * 1986-06-04 1987-12-22 Illinois Tool Works Inc. Acid modified adhesive compositions
EP1486801A2 (en) * 2001-04-24 2004-12-15 Hoya Corporation Optical composition, process for producing optical element using the same, and optical element

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008016436A1 (en) 2008-03-31 2009-10-01 Ems-Patent Ag Polyamide molding compound for paint-free, tough housings with a high-gloss surface
EP2107083A2 (en) 2008-03-31 2009-10-07 Ems-Patent Ag Polyamide moulding material for lacquer-free ductile housing with highly reflective surface
US8563653B2 (en) 2008-03-31 2013-10-22 Ems-Patent Ag Polyamide moulding compound for varnish-free, tough casings with a high-gloss surface
US9074112B2 (en) 2010-02-26 2015-07-07 Scott Bader Company Limited Methacrylate-based adhesive compositions
CN109468097A (en) * 2018-10-22 2019-03-15 广东星宇耐力新材料股份有限公司 A kind of aluminium foil XPS extruded sheet composite water soluble adhesive and preparation method thereof

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EP1963450B1 (en) 2014-10-22
CA2633738A1 (en) 2007-07-05
CA2633738C (en) 2014-07-15
CN101365764B (en) 2014-01-22
JP2009521582A (en) 2009-06-04
US20070155879A1 (en) 2007-07-05
AU2006330904A1 (en) 2007-07-05
JP5417849B2 (en) 2014-02-19
CN101365764A (en) 2009-02-11
EP1963450A1 (en) 2008-09-03

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