WO2005040295A1 - Adhesive compositions for bonding and filling large assemblies - Google Patents
Adhesive compositions for bonding and filling large assemblies Download PDFInfo
- Publication number
- WO2005040295A1 WO2005040295A1 PCT/US2004/032660 US2004032660W WO2005040295A1 WO 2005040295 A1 WO2005040295 A1 WO 2005040295A1 US 2004032660 W US2004032660 W US 2004032660W WO 2005040295 A1 WO2005040295 A1 WO 2005040295A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- percent
- methacrylate
- mixtures
- adhesive
- filling composition
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- 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
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/286—Chlorinated polyethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- 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
- 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
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Definitions
- This invention relates to polymerizable vinyl adhesive or filling compositions that are useful for a variety of adhesive, coating, filling, repair and related applications. More particularly, this invention relates to two-part room- temperature curing polymerizable vinyl adhesive compositions comprising mixtures of free-radical polymerizable monomers and additives that generate heat and undergo expansion and contraction during the polymerization process.
- the improved compositions comprise mixtures of elastomers, thermoplastic resins, acrylate, methacrylate and styrenic monomers, and polyester or vinyl ester resins that can be applied in large masses or thick cross sections without gassing and void formation from the exothermic cure reaction. It also relates to improvements in the ability of adhesives based on the compositions to bond thermoplastic and thermoset materials, and to bond such materials with a reduced tendency to cause "read-through" in the bonded area. It further relates to improvements in the ability of the compositions to cure with a tack-free surface and low residual odor, especially when formulated to have a long open working time applications involving large parts or assemblies. It still further relates to improvements in the physical properties and adhesive bonding capabilities of the modified compositions.
- Prior art compositions include formulations based on acrylate and methacrylate monomers, styrene monomer and styrene derivatives as well as polyester and vinyl ester resins.
- the compositions are generally liquids or pastes that polymerize and cure when two separately packaged components, one of which contains a polymerization initiator, generally a peroxide, and the other of which contains a promoter, generally an amine, are mixed just prior to use.
- a particularly useful group of polymerizable vinyl compositions comprises mixtures of dissolved or dispersed polymers in acrylate or methacrylate monomers.
- compositions can provide a number of performance benefits for adhesive bonding and related applications, including high bond strength, adhesion to a variety of materials with minimal surface preparation, and rapid curing.
- Methyl methacrylate is a preferred monomer for these adhesives because it is relatively low in cost and provides high strength properties in formulated compositions.
- This group of polymerizable compositions is recognized by those skilled in the art as being superior in many respects to those based on polyester resins and vinyl ester resins, particularly in terms of their ductility and adhesion to a variety of material surfaces.
- Polyester resins generally contain styrene, which is lower in cost than methyl methacrylate. They are widely used in automobile body fillers, polyester marine putties, and other filling, bonding and repair materials.
- Polyester/styrene compositions are preferred for applications that emphasize the ability to economically fill large voids and gaps with adequate functional performance rather than those that emphasize physical properties and related performance attributes at a premium cost.
- one surprising aspect of this invention is the achievement of improvements in the performance of the inventive compositions through the incorporation of polyester resins.
- Many of the benefits provided by the inventive compositions are useful for the non-adhesive applications cited above.
- adhesive applications are among the most demanding of those anticipated for such compositions. For this reason, the discussion and examples that follow, and the inventive improvements therein will emphasize adhesive applications, with the understanding that they can readily be extended to the other applications cited.
- the growing acceptance of methacrylate adhesives has extended their use to larger and larger assemblies and applications, which has resulted in more demanding application requirements.
- open time, working time, and open working time are interchangeable terms that define the elapsed time between the mixing of the separate adhesive components and the attainment of a degree of polymerization or cure that prevents effective bond formation.
- the adhesive either attains a very high viscosity, forms a skin on the surface, or both, preventing effective wetting for good bond formation.
- this interval is often referred to as the gel time or pot life for the composition, which is the time after mixing at which it becomes too thick or viscous to continue applying it.
- the occurrence and severity of the problem generally increases with the thickness of the bond and the overall mass of adhesive involved.
- the causes of such appearance problems can be complex, including contributions from the specific nature of the bonded substrates. These include part thickness, the state of cure of thermoset parts when bonded, the thermal conductivity and expansion coefficients of the bonded materials, the properties of coatings applied on the parts, and other factors. Irrespective of what other factors may be involved in the development of read-through or print through, it is generally observed that adhesives with less tendency to exotherm and undergo dimensional changes during the curing process have less tendency to contribute to the phenomenon. A number of techniques have been used in efforts to overcome this problem.
- Patent 5,932,638 also referenced below, include weakening of the adhesive bond, increased odor resulting from escaping, unreacted monomer, and problems related to tackiness of the surface of the adhesive.
- the problem is especially acute when low levels of catalytic species and added retarding agents are used to extend the open working time of methacrylate based adhesive compositions to periods of about 45 minutes to one hour or more.
- the problem is further exacerbated by low ambient application temperatures that further reduce the cure rate, and may prevent completion of the free-radical curing process.
- Patent 5,932,638 discloses the use of certain para-halogenated aniline derivatives to overcome the problems associated with poor surface cure of adhesive compositions resulting from air inhibition.
- Compositions containing up to about 10 percent by weight of unsaturated polyester resin are disclosed.
- the cited improvement in the surface cure is a reduction in the thickness of the uncured surface layer exposed to air from about 0.025 inch to about 0.002 to about 0.003 inches.
- actual commercial experience has shown that even the lesser amounts of uncured adhesive cited can be sufficient to cause serious lingering odor problems. Such problems can occur when, for example, the incompletely cured surface of a squeezed out bead or "fillet" of adhesive is in a confined area such the stringer grid of a boat.
- the problem can be further exacerbated when the fillet or other uncured adhesive bond area is trimmed or smoothed with a spatula or other device that smears a thin film of the adhesive against an exposed surface such as the boat hull.
- the resulting thin film of adhesive is especially susceptible to the effects of air inhibition. Trapped vapors can eventually migrate to the enclosed cabin area of the boat and create an objectionable or unacceptable level of odor in spite of the very low levels that are present. This is because the detectable odor threshold level for methyl methacrylate monomer is about 0.5 parts per million or less.
- Patent 5,932,638 discloses the optional inclusion of from 0 to about 10 percent by weight of a polyester resin in methacrylate compositions.
- U.S. Patent 5,859,160 also discloses the optional inclusion of from 0 to about 10 percent by weight of an unsaturated polyester resin in methacrylate adhesive compositions .
- the '638 Patent and the '160 Patent cite U.S. Patents
- the methacrylate composition contains at least about 10 percent, and generally 15-20 percent or more of a polymeric species to provide toughness in the cured composition.
- Preferred polymers include polychloroprene, chlorosulfonated polyethylene, mixtures of chlorinated polyethylene with sulfonyl chlorides, polybutadiene, butadiene copolymers, and polyacrylate rubbers. No particular preference is stated for selection among these polymers, whether or not an unsaturated polyester resin is present.
- U.S. Patent 3,321,351 discloses compositions containing unsaturated polyester resins, vinyl monomers and their polymerizates (specifically methyl methacrylate and polymers thereof, styrene monomer and polymers thereof) , polychloroprene rubber and polyvinyl ethers.
- the specification generally discloses 10-85% vinyl monomer, 0- 50% vinyl polymer, 0-80% unsaturated polyester and 0-40% polyvinyl vinyl ethers. In the examples, however, when methyl methacrylate is included in the compositions, and no neoprene is included, no more than 15 percent polyester resin is included. When both methyl methacrylate and neoprene are present, no more than 1 percent unsaturated polyester is included. In no case does the amount of neoprene exceed 3 percent of the composition.
- U.S. Patent 4,548,992 discloses methacrylate adhesive compositions containing a modified carboxyl containing nitrile rubber and an alkali metal or amine salt of an unsaturated polyester resin.
- the carboxyl containing nitrile rubber is modified by reaction with a methacrylated phosphate ester.
- the free carboxyl groups of the polyester resin are neutralized by a metal compound, ammonia or an amine to create a modified polyester resin containing an ionic bond.
- the ionic bond-containing polyester resin is said to promote adhesion to oily metal surfaces and to improve the storage stability of the methacrylate adhesive composition.
- the essential feature of this invention is the use of unsaturated polyester resins or vinyl ester resins to modify the curing behavior, bonding capabilities and physical properties of polymerizable acrylate or methacrylate compositions.
- the acrylate or methacrylate compositions are solutions of thermoplastic or partially thermoplastic polymers or elastomers in acrylate or methacrylate monomers that polymerize when mixed with a catalyst.
- the preferred polyester resins and vinyl ester resins are commercial products that are typically supplied as liquids that are catalyzed with peroxides and promoters and used for a variety of applications including laminated and cast parts and structural components, coatings, adhesives and repair materials.
- the preferred polymers are synthetic elastomeric and thermoplastic polymers.
- the preferred monomers are low molecular weight acrylate and methacrylate monomers.
- the most preferred monomer is methyl methacrylate.
- This invention provides compositions that include 5 percent to 75 percent of a thermoplastic or partially thermoplastic polymer or elastomer, 0.5 percent to 35 percent of an unsaturated polyester resin or vinyl ester resin, and 20 percent to 80 percent of an acrylate or methacrylate monomer.
- the inventive compositions exhibit better control of the exothermic curing and dimensional changes associated with adhesives and filling compositions.
- polyester and vinyl ester resins utilized in this invention are well known to those skilled in the art.
- the resins and their applications are described in detail in a number of publications, including "Handbook of Composites", second edition, S.T. Peters, Editor, published by Chapman and Hall which is included herein by reference.
- Unsaturated polyesters are condensation reaction products of polybasic acids or anhydrides with polyhydric alcohols. After the condensation reaction is completed, the resulting resin, generally a solid or semisolid, is diluted with an unsaturated monomer to establish the desired viscosity, reactivity and end use properties.
- Preferred unsaturated monomers include styrene, alpha- methylstyrene, 2-methylstyrene, 3-methylstyrene, 4- methylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t- butylstyrene, 1, 3-divinylbenzene, 1, 4-divinylbenzene, 1,3- diisopropenylbenzene, 1, 4-diisopropenylbenzene, and the like, and mixtures comprising at least one of the foregoing alkenyl aromatic monomers.
- Preferred alkenyl aromatic monomers further include styrenes having from 1 to 5 halogen substituents on the aromatic ring, and mixtures comprising at least one such halogenated styrene.
- the monomer mixture may also contain an acrylate or methacrylate monomer such as methyl methacrylate.
- the monomer is generally present in an amount of 30 to 60 parts per 100 parts resin.
- unsaturated polybasic acids that may be used to form the unsaturated polyester resins include maleic acid, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, nadic acid, tetrahydrophthalic acid, endo-methylenetetrahydrophthalic acid, hexachloro-endo- methylenetetrahydrophthalic acid and other unsaturated di- and polybasic acids and halogenated acids, as well as their corresponding esters and anhydrides.
- Preferred unsaturated acids include maleic acid and fumaric acid, and their corresponding esters and anhydrides.
- Polyfunctional saturated and aromatic acids are employed in conjunction with the polybasic unsaturated acids to reduce the density of the ethylenic unsaturation and provide desired chemical and mechanical properties for specific applications.
- saturated and aromatic polybasic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, eicoic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (CHDA) , and the like, halogenated acids such as tetrabromophthalic acid, as well as their esters and anhydrides.
- Preferred aromatic polybasic acids include phthalic acid, terephthalic acid and isophthalic acid, and their corresponding esters and anhydrides. Polyester resins that employ them are referred to as “orthophthalic” and “isophthalic” or “ortho” and “iso” resins, respectively.
- Examples of useful polyhydric alcohols include ethylene glycol, propylene glycol, 1, 2-propanediol, 2-methyl-l, 3- propanediol, diethylene glycol, dipropylene glycol, 1,2- butanediol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, glycerol, triethylene glycol, pentanediol, hexylene glycol, hydrogenated bisphenol A, bisphenol A-alkylene oxide adducts, tetrabromobisphenol A-alkylene oxide adducts, and the like.
- Preferred polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-l, 3-propane diol, and neopentyl glycol. Triols, when used are employed in very limited quantity relative to diol to control and limit chain branching and its effects on molecular weight and viscosity.
- Preferred triols include glycerol and trimethylol propane. More recently, dicyclopentadiene (DCPD) monomer has been used to synthesize polyester resins that can be incorporated in higher proportions in styrene monomer to produce "low styrene” resins. Such resins are generally referred to as "DCPD" resins.
- Vinyl ester resins are described in a number of U.S. patents, including 3,564,074, 4,151,219, 4,347,343, 4,472,544, 4,483,963, 4,824,919, 3,548,030, and 4,197,390 which are incorporated herein by reference.
- Vinyl ester resins typically comprise a terminally unsaturated vinyl ester resin, generally derived from a polyepoxide, and at least one copolymerizable monomer, generally styrene.
- the terminally unsaturated vinyl ester resins are prepared by reacting about equivalent proportions of a polyepoxide, such as a bisphenol A/epichlorohydrin adduct with an unsaturated monocarboxylic acid such as acrylic or methacrylic acid.
- the resulting resin has terminal, polymerizable unsaturated groups.
- the resins also may include halogenated polyester and vinyl ester resins. While any of the above-referenced polyester or vinyl ester resins or mixtures thereof may be used to advantage in the inventive compositions, specific combinations of polyester or vinyl ester resins, methacrylate monomers and polymers can be formulated to provide specific and significant performance benefits and improvements over the prior art.
- any number of the above described polyester or vinyl ester resins may be used to provide compositions with reduced tendency of the composition to gas or boil when the adhesive cures.
- This can be achieved with either a relatively short or long open working time.
- the adhesive has the unique advantage of providing relatively fast curing with the ability to fill thick cross sections or voids with reduced exotherm and without gassing or boiling.
- Fully cured, void-free bonds can be achieved within about 15 to about 60 minutes, respectively, in thicknesses of up to about one and one half inches.
- Prior art adhesives with similar cure times are prone to gassing and boiling in thicknesses of one-half inch or less.
- the adhesive When the open time is long, for example, from about 45 to about 90 minutes, the adhesive, has the ability to cure with a hard, tack-free surface, as well as the unique ability to cure in thin cross sections or in a thin film, without weak bonds from cure retardation and lingering odor resulting from unreacted, air-inhibited monomer.
- void-free bonds can be obtained within about 90 minutes to about three hours in thicknesses up to three inches.
- Prior art adhesives with long open time generally do not cure well in thin cross sections or in thin films, and tend to gas and boil in thicknesses greater than about one inch.
- the polyester resins provide multiple benefits without negatively impacting the cure of the composition, and in fact even improve the final state of cure of the compositions.
- Other benefits can include improved adhesion and physical properties such as tensile strength and tensile elongation.
- the choice of resin can influence application, curing and performance characteristics to varying degrees depending upon the specific formulation involved. For example, with other variables constant, compositions containing orthophthalic and isophthalic resins generally achieve a better final state of cure than those containing DCPD resins when benzoyl peroxide is used as the catalyst.
- DCPD resins provide compositions with significantly less exotherm and shrinkage or dimensional change than orthophthalic or isophthalic resins.
- Compositions containing vinyl ester resins or halogenated vinyl ester resins or mixtures thereof tend to exhibit greater exotherm and dimensional change than those containing polyester resins, but their cure speed, ultimate state of cure and heat resistance, defined as the proportion of room temperature strength retained at high temperatures, are superior. If exotherm and dimensional change is not an issue, very strong, fast-curing bonds with low tendency to gas and boil can be obtained with vinyl ester resins.
- the resin employed may be either promoted or unpromoted.
- Many commercial polyester and vinyl ester resins contain amines and/or organometallic compounds as well as inhibitors that are added by the manufacturer to impart a desired level of reactivity when a peroxide initiator is added just prior to use. Such resins are called promoted or pre-promoted resins.
- the resins employed in this invention are additives in reactive methacrylate compositions that have specific catalytic requirements, it may be preferable in some cases that the polyester and vinyl ester resins contain no catalytic species.
- the inventive modified methacrylate compositions utilizing such non-promoted resins can then be formulated with the desired level of preferred catalytic species for the desired application characteristics.
- the unsaturated polyester and vinyl ester resins of this invention are commercially available from a number of U.S. and global suppliers.
- U.S. suppliers include Alpha Owens Corning (AOC) , Ashland Chemical, Cook Composites (CCP) , Eastman Chemical, Interplastic Corporation, and Reichhold.
- Vinyl ester resins are available from AOC,
- Preferred unsaturated polyester resins of this invention are unsaturated orthophthalic, isophthalic, terephthalic, DCPD halogenated polyester resins and mixtures thereof.
- Preferred orthophthalic and DCPD resins include the Altek 500 and 800 series from AOC, the Polylite 31000, 32000, 33000 and 44000 series from Reichhold, and similar resins from other manufacturers.
- Preferred isophthalic resins include Vipel F737 from AOC and similar resins sold under the trade names DION, ATLAC and Polylite from Reichhold.
- Preferred DCPD resins include the Altek H800 series from AOC and Polylite 44383, 44006 and 44285 from Reichhold.
- Resin manufacturers generally produce unpromoted "base" versions of the above polyester resin types and vinyl ester resins that are blended with other resins to obtain a desired set of properties. Within a given family of resins, grades with varying reactivity and flexibility characteristics are made at high solids levels, generally up to about 70 percent. Most preferred orthophthalic resins are unpromoted, flexibilized, low-to medium reeactivity versions such as Polylite 31008 from Reichhold and Verimac 711-1530 from Eastman. Most preferred isophthalic and terephthalic resins are unpromoted, flexibilized low to medium reactivity versions such as AOC T750-70, Polylite 31830 from Reichhold and Verimac 126-0863 from Eastman.
- DCPD resins are unpromoted base resins such as CoREZYN 61AA340 from Interplastics and Polylite 44-006 from Reichhold.
- Preferred vinyl ester resins, halogenated vinyl ester resins or mixtures thereof include Derakane 411-350 from Dow, Hetron 922 from Ashland, CoREZYN VE8300 from Interplastic, DION and Atlac 9100 from Reichhold and Verimac 785-8430 from Eastman.
- Most preferred vinyl ester resins include Derakane 411-350 from Dow and DION/Atlac 9100 from Reichhold.
- the vinyl ester or polyester resins can be used individually or in combinations to achieve the optimum effects in terms of curing behavior and physical properties of the cured composition.
- the methacrylate portion should comprise at least 20 percent of the overall mixture.
- the compositions of the invention preferably encompass a combination of 0.5 percent to 35 percent, preferably from 1 percent to 25 percent, and most preferably from 2 percent to 20 percent of an unsaturated polyester resin, a vinyl ester resin, or a combination thereof.
- the preferred polymers of this invention are thermoplastic or partially thermoplastic polymers and elastomers and may be selected from a thermoplastic or partially thermoplastic polymer or elastomer or a blend of two or more thermoplastic or partially thermoplastic polymers, a blend of two or more elastomers, and a blend of one or more elastomers with one or more thermoplastic or partially thermoplastic polymers.
- the term partially thermoplastic refers to polymers, elastomers, or elastomer-containing polymers that have some degree of crosslinking in their structure.
- a polymer is a core-shell impact modifier wherein the core, which is typically a butadiene based or acrylic based rubber, is crosslinked to some degree to provide the desired impact modifying properties or other specific properties.
- the core which is typically a butadiene based or acrylic based rubber
- Neoprene AG a polychloroprene elastomer sold by duPont Dow Elastomers.
- the polychlorprene which is normally thermoplastic and soluble, is specifically modified with an agent that imparts light crosslinking to provide unique, gel-like properties that beneficially modify the rheology of solutions or rubber compounds that contain it.
- Additional examples include elastomeric polymers that are crosslinked to modify them for use as impact modifiers or other property modifiers in formulated rubber, plastic or other resin compositions.
- thermoplastic, partially thermoplastic, and substantially soluble polymers and elastomers and mixtures thereof include, but are not limited to, diene based polymers including those based on butadiene or isoprene, such as copolymers and multipolymers containing acrylonitrile, styrenic and acrylic monomers; thermoplastic block copolymers, multipolymers and impact modifiers based on butadiene, isoprene, ethylene-propylene and ethylene- butylene in combination with styrene, acrylonitrile and acrylic monomers; acrylonitrile butadiene styrene (ABS) resins and impact modifiers, methacrylate butadiene styrene (MBS) and MABS impact modifiers and polymers, chlorinated polymers such as polychloroprenes, chlorinated polyolefins and copolymers, chlorosulfonated polyethylenes, polyolefins, and copolymers,
- the preferred polymers are those which impart toughness and elastic properties and improve adhesion of the compositions to bonded substrates.
- Other polymers that improve adhesion or other properties but do not impart toughness may be used to advantage in the inventive compositions. Examples include polymers, copolymers and multi polymers of styrene, acrylonitile, vinyl chloride and acrylic monomers. Low molecular weight, liquid reactive and unreactive elastomers and oligomers may also be used to advantage in the compositions of this invention.
- Examples include liquid vinyl reactive butadiene polymers and copolymers with acrylonitrile and acrylate monomers sold by Noveon and Ricon resins, and any number of other reactive liquid polymers and oligomers sold commercially by Sartomer, Radcure and others.
- elastomers and polymers include polychloroprenes such as Neoprene AD-5, AD-10 and AG, chlorinated polyethylenes such as Tyrin 3611, 3615 and 4211, and chlorosulfonated polyethylenes such as Hypalon 20, 30, 40 and 48 sold by duPont Dow elastomers, nitrile elastomers such as Nipol 401LL, 1201, DN-4555, and 1401LG, sold by Zeon Chemical, crosslinked nitrile elastomers such as Zealloy 1422 sold by Zeon and Chemigum P-83 sold by Eliokem, liquid nitrile elastomers such as Hycar 1300X33 sold by Noveon, styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS) , styrene-ethylene-propylene (SEP) and styrene- ethylene-butadiene-
- Preferred monomers are lower molecular weight Ci-C ⁇ acrylate and methacrylate monomers. More preferred monomers include methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, hydroxypropyl acrylate, butyl acrylate, hexylacrylate, cyclohexyl methacrylate and mixtures thereof. Even more preferred monomers are methyl methacrylate and ethyl methacrylate.
- the most preferred monomer is methyl methacrylate.
- Other higher molecular weight monofunctional or polyfunctional acrylate monomers and oligomers may be used in quantities of up to about 25 percent of the composition in order to crosslink the cured compositions or impart certain desirable application and performance characteristics such as reduced odor, improved wetting and adhesion properties for particular substrates, reduced tendency to solvate sensitive plastic surfaces, including incompletely cured polyester resin surfaces, and improved flexibility or other mechanical properties.
- compositions of this invention encompass a combination of 5 percent to 75 percent, preferably 7 percent to 60 percent, and most preferably 10 percent to 50 percent of a thermoplastic or partially thermoplastic polymer or elastomer, 0.5 percent to 35 percent, preferably 1 percent to 25 percent, and most preferably 2 percent to 20 percent of an unsaturated polyester resin or a vinyl ester resin, and 20 percent to 80 percent of at least one acrylate or methacrylate monomer, preferably from 30 to 80 percent, and most preferably from 40 to 70 percent.
- compositions of this invention encompass a combination of 5 percent to 75 percent, preferably 7 percent to 60 percent, and most preferably 10 percent to 50 percent of a blend of at least two polymers, 0.5 percent to 35 percent, preferably 1 percent to 30 percent, and most preferably 2 percent to 20 percent of an unsaturated polyester resin or a vinyl ester resin, and 20 percent to 80 percent of at least one acrylate or methacrylate monomer, preferably from 30 to 80 percent, and most preferably from 40 to 70 percent. More preferred compositions encompass a combination of
- compositions of the invention encompass a combination of 5 to 75 percent, preferably from 7 percent to 60 percent, most preferably from 10 percent to 50 percent by weight of a blend of at least one elastomer and at least one elastomer modified thermoplastic polymer or an elastomer-containing core-shell impact modifier, 0.5 percent to 35 percent, preferably 1 percent to 25 percent, and most preferably 2 percent to 20 percent of an unsaturated polyester resin or a vinyl ester resin, and 20 percent to 80 percent of at least one methacrylate monomer, preferably from 30 to 80 percent, and most preferably from 40 to 70 percent.
- compositions of the invention encompass a combination of 5 to 75 percent, preferably from 7 percent to 60 percent, most preferably from 10 percent to 50 percent by weight of a blend of polymers that includes at least one chlorinated polymer and at least one nitrile elastomer or thermoplastic acrylonitrile polymer as disclosed in U.S. Patent No. 6,602,958, 0.5 percent to 35 percent, preferably 1 percent to 25 percent, and most preferably 2 percent to 20 percent of an unsaturated polyester resin or a vinyl ester resin, and 20 percent to 80 percent of at least one methacrylate monomer, preferably from 30 to 80 percent, and most preferably from 40 to 70 percent.
- the compositions may also contain from 0.01 to 20 percent, preferably from 0.1 to 15 percent of a polymerizable organic acid monomer or oligomer.
- a polymerizable organic acid monomer or oligomer include vinyl reactive carboxylic acid monomers that are well known to those skilled in the art.
- Preferred polymerizable carboxylic acid monomers are acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.
- Other preferred polymerizable acid monomers or oligomers inlude the vinyl functional derivatives of phosphoric acid disclosed in U.S. Patents 4,223,115 and 4,293,665 cited earlier.
- Specific preferred examples are the mixed mono- and di- substituted phosphate esters derived from hydroxyethyl methacrylate, sold under the tradename Light Ester P-1M and P-2M by Kyoeisha Chemical Co., LTD,
- the selection of the acid monomer or oligomer or mixture thereof depends on the anticipated substrate bonding requirements and other effects imparted by the polymerizable acid employed.
- methacrylic acid is preferred in many instances because it increases the cure speed of the adhesive composition and improves adhesion to mild steel.
- the partially substituted phosphated esters are preferred when improved adhesion and durability are required on unprepared aluminum and stainless steel substrates.
- the acid functional phosphate esters can retard the cure speed of certain formulations.
- Maleic acid is shown in US Patent 4,714,730 to enhance adhesion to difficult to bond substrates such as nylon. In some cases, mixtures of acidic monomers and oligomers can be used to advantage when adhesion to a variety of substrates is required.
- the precise selection and effects of the mixed acids is influenced by the other components in the formulation and the acceptable perfomance compromises for a given application.
- Various viscosity control agents such as organoclays, fumed silica or the like may be added in amounts ranging from 0.1 to 10 percent based on the system weight to control the viscosity of the adhesive.
- Additional fillers may be added in significantly larger amounts to reduce the cost of the adhesive or to modify certain physical properties. In this case, quantity of the filler or extender would be considered separately as an additive to the base polymer and monomer composition as described above.
- Common particulate fillers or extenders such as clay, talc, calcium carbonate, silica and alumina trihydrate can be added in amounts up to about 50 percent or more of the composition by weight in order to achieve specific economic, application or bonding characteristics.
- Inorganic or organic microspheres or microballoons may be used to reduce the density and cost of the adhesives, as well as to improve their sanding or finishing characteristics when used as repair materials such as automobile body repair products. Any number of available and well-known catalyst combinations may be chosen to cause the polymerization and curing of the compositions of the instant invention.
- the primary catalytic species for initiating the polymerization of the vinyl monomers of this invention are peroxide or hydroperoxide initiators. Examples are benzoyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, tertiary butyl peroxyacetate, tertiary butyl perbenzoate, and the like.
- the peroxide initiators are used in amounts ranging from 0.01 to 10 weight percent based on the weight of the adhesive composition.
- the initiators will be used in the amount of 0.05 to 5 weight percent.
- one or more free radical inhibitors or antioxidant stabilizers may be required in the formulation.
- the selection and use of such additives is well known to those skilled in the art.
- the methacrylate monomers used in the compositions contain inhibitors, generally phenolic compounds, that are added to the monomers to stabilize them during storage. Many of the polymers used in the formulations contain heat stabilizers that protect the polymers during processing and storage.
- the polyester resins of the inventive compositions also may contain inhibitors. The most common inhibitors and stabilizers are phenols, quinones and their derivatives, and many can be used interchangeably in the raw materials cited.
- the inhibitors present in these raw materials are sufficient to stabilize the formulated adhesives, and in some cases additional materials may need to be added to assure stability. Because of the variety of raw materials (with in situ inhibitors) that may be chosen, and the variety of catalyst systems that may be selected to prepare a composition, the selection of the complete inhibitor package is generally the final step in the formulating process. The selection is specific to each formulation, beyond the scope of this invention, and generally proprietary to those skilled in the art.
- a chelating agent may be used to further stabilize the methacrylate compositions. Chelating agents are used as scavengers for trace metal impurities that can destabilize the reactive methacrylate formulations.
- a reducing agent is used to induce the room temperature decomposition of the peroxide or hydroperoxide initiator at ambient or room temperature.
- the most common reducing agents for this purpose are well known to those skilled in the art and include tertiary aromatic amines and aldehyde- amine reaction products.
- Useful tertiary amines include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N- diethyltoluidine, N, N-bis (2-hydroxyethyl) toluidine and other similar aromatic amines used for this purpose which are well known in the art.
- Aldehyde-amine reaction products include such compositions as butyraldehyde-aniline and butyraldehyde-butylamine derivatives whose active ingredient is a dihydropyridine (DHP) formed from condensation of three moles of aldehyde with one mole of amine. More recently, DHP-enriched versions of these compositions have been made available.
- DHP dihydropyridine
- One such material is Reillcat ASY-2, available from Reilly Industries, Inc. This catalyst or initiator system is most often used in combination with a sulfonyl chloride compound and a hydroperoxide as described in U.S.
- the reducing agents are employed in amounts of up to 5 weight percent based on the weight of the adhesive. Preferred amounts are 0.01 to 5 percent.
- Transition metal salts including organometallic compounds such as cobalt, nickel, manganese or iron naphthenate, copper octoate, copper acetylacetonate, iron hexoate, or iron propionate, and other well-known metallic compounds act as promoters for the inventive polymerizable compositions. Promoters, whose effect varies greatly from system to system are used in amounts up to 1-2 weight percent, preferably 1 part per million to 0.5 weight percent. Most preferred amounts range from 5 parts per million to 0.5 percent by weight.
- Metallic promoters may be used with certain peroxide initiators as the primary initiating species or in combination with tertiary amine or amine-aldehyde reducing agents to enhance the rate of polymerization.
- the most preferred free radical initiation systems comprise (1) a tertiary amine reacting with benzoyl peroxide or another peroxide, (2) a DHP derivative in combination with a sulfonyl chloride compound and a hydroperoxide or another peroxide or (3) an organometallic compound such as cobalt naphthenate in combination with a hydroperoxide, all three combinations being capable of inducing the free- radical curing process at room temperature.
- Combinations of amine or amine aldehyde and metallic species may be used to advantage in any of the above systems.
- the precise selection and partitioning of the initiating and inhibiting components for a given composition depend on its specific intended application, subject to the formulating principles well known to those skilled in the art.
- the adhesive compositions of the invention are characterized by their ability to polymerize in large masses or thick cross sections without forming voids, and their ability to cure with a tack-free surface or in thin films with low residual odor, especially when formulated to have a long open working time applications involving large parts or assemblies.
- the compositions are also capable of curing in thick bonds or relatively large masses without exhibiting objectionable read-through or print-through on exposed cosmetic surfaces. They further exhibit improved physical properties and adhesive bonding capabilities.
- Such improvements include the attainment of higher tensile strength without sacrificing tensile elongation, and the capability to bond a variety of composite materials, including certain difficult to bond composites with or without preparation of the surface prior to bonding, as well as a variety of other materials alone or in combination.
- the compositions of this invention have been developed primarily to improve the properties of adhesives. However, the improvements thereby discovered make these products more useful than previous products of their class for repair materials, coatings, bulk casting and any number of other applications beyond adhesives.
- Neoprene Polychloroprene elastomer DuPont Dow Elastomers
- Typical solution concentrations in MMA of 15- 35 percent by weight of polymer were selected to provide final solution viscosities ranging from about 50,000 to 500,000 cps . It is generally preferable to prepare the stock solutions in the higher concentration and viscosity range in order to be able to make final viscosity adjustments by diluting the finished adhesive with MMA monomer. The polymer and monomer were rolled until all of the polymer was dissolved and no lumps or particles of undissolved material were present. Experimental adhesives were prepared in plastic beakers in quantities ranging from about 100-600 grams of finished adhesive. Sufficient stock solution or a mixture of stock solutions was added to the beaker in the quantity required to provide the desired proportion of elastomer in the finished adhesive.
- Adhesives formulated with no impact modifier were prepared by adding the remaining ingredients directly to the mixture of stock elastomer solutions and thoroughly mixing to form the finished adhesive. Final viscosity adjustments were made by adding with MMA monomer to reduce viscosity, or fumed silica or additional impact modifier to increase viscosity, as required.
- thermocouple wire attached to an exotherm recorder was inserted into the center of the mass of adhesive to record the peak temperature attained and the time to reach peak temperature.
- test molds were prepared from adhesively bonded 0.25 inch thick polypropylene sheet to provide a rectangular cavity to form a test casting with dimensions of 8 inches (length) by 2 inches (width) by 1.5 inch (height).
- a mass of adhesive (approximately 500-600 grams, depending on specific gravity) was mixed and degassed as noted above and transferred to the test mold using a spatula to pack the mold and smooth the top exposed surface even with the top of the mold. The adhesive mass was allowed to cure, and the appearance and condition of the cured casting was observed and recorded. The presence or absence of voids resulting from gassing or boiling was noted.
- TLCF THIN LAYER COHESIVE FAILURE.
- TENSILE PROPERTIES OF THE BULK ADHESIVES Bulk stress-strain properties of the adhesives were measured according to ASTM test method D638. Test specimens were prepared by mixing a sufficient quantity of adhesive to prepare a uniformly flat film of adhesive approximately 6 to 7 inches in diameter and approximately .0625 inches thick.
- the adhesive components were combined in the specified ratios by simple hand mixing in a beaker. After the adhesive was thoroughly mixed, the beaker was placed in a vacuum chamber and vacuum was applied intermittently to remove air until the last one or two applications of vacuum did not produce additional frothing or expansion. The adhesive was then transferred to one of two glass or plastic plates approximately 12 inches in diameter with a similar sized layer of Mylar release film on top of it. The adhesive was placed in the center of the film, and a mating Mylar film and plate were placed over the adhesive and pressed down uniformly to spread the film. Metal shims were placed around the perimeter of the plates to establish the desired film thickness. After the films were cured, the plates were removed.
- Test dumbbells were cut from the films as specified in the test method, taking care to cut the specimens from the most void-free section of the film. The films were allowed to cure overnight at ambient temperature followed by a thermal postcure at 82°C for one hour prior to cutting the dumbbells. Each test number is the average of five individual test specimens .
- EXAMPLES 1-2 Examples 1 and 2 are comparative examples for inventive examples 3-7 and 8-12, respectively. They illustrate that when the respective inventive examples are formulated without the addition of a vinyl ester resin, they undergo significant gassing and boiling, even though they effectively bond open molded FRP composite in normally thin bonded (0.125 inch) cross sections.
- EXAMPLE 1 2 MMA Monomer 68.60 65.60 Neoprene AD-10 20.00 Nipol DN 4555 10.00 BTA 753 18.00 Lauryl 5.00 5.00
- Examples 3-7 illustrate the effectiveness of a preferred vinyl ester resin in improving the curing performance of methacrylate formulations containing a range of elastomeric polymers .
- the inventive compositions do not boil or gas to cause expansion and undesirable voids in the thick cast bead that simulates a thick bonded cross section .
- example 3 which contains a nitrile elastomer, did not cure as effectively as the other examples in this series. This is believed to be the result of the antioxidant type and or level employed in the elastomer as supplied by the manufacturer. As noted in the specification and the examples that follow, adjustments in the type or level of amine promoter, or in the level of BPO paste can be used to influence the curing behavior of individual compositions .
- EXAMPLES 8-12 Examples 8-12 illustrate that alternative catalyst systems can be used effectively to take advantage of the modification of the curing behavior of the inventive compositions.
- Examples 8 and 9 illustrate that with other variables constant, HET can be more effective than DMT in combination with BPO in promoting full cure of a specific composition as measured by hardness of the cured composition.
- Examples 10- 12 illustrate that a preferred vinyl ester resin and a preferred DCPD resin can be used to very effectively and beneficially modify the curing behavior of compositions that employ the chlorosulfonated polyethylene/sulfonyl chloride/DHP cure system. It is well known to those skilled in the art that such cure systems are highly reactive and are difficult to control with respect to boiling and gassing in other than very thin bonds or small masses.
- Examples 13-17 illustrate the effects of four different and preferred modifier resins on the curing properties of a specific and compositionally constant methacrylate formulation compared with a comparative formulation that contains no modifier resin. TABLE 4 (Comparative)
- Examples 14 and 15 illustrate that the preferred orthophthalic and isophthalic resins provide similar reactivity as measured by the time to peak exotherm and peak exotherm temperatures.
- Examples 16 and 17 illustrate that, relative to the orthophthalic and isophthalic resins, the preferred DCPD resin imparts much lower reactivity and the preferred vinyl ester resin provides much higher reactivity as measured by time to peak exotherm and peak exotherm temperature. As noted in the specification and in the other examples the reactivity of examples 16 and 17 would be readily adjusted with appropriate changes in the amount or type of initiator and promoter.
- Examples 18-19 demonstrate the formulation of an adhesive for bonding Class A fiberglass panels without read- through by incorporating a flexible polyester base resin in the composition.
- a 1 inch by 4 inch by 0.062 inch aluminum strip was bonded to the rough side a 4 inch by 4 inch by 0.125 inch fiberglass panel with a class A show surface using a 20 grams mass of adhesive. Spacers were used to shim the bond at a thickness of 3/8 inch.
- the adhesive was allowed to complete the cure cycle to peak exotherm followed by cooling to ambient temperature, with the results as noted at the end of Table 5.
- the comparative print through was observed by the casual visual technique that is traditionally used by those skilled in the art.
- the bonded assembly is positioned with the show surface perpendicular to a strong light source such as a fluorescent light fixture, and viewed at an oblique, nearly parallel angle. Under such conditions, the presence or absence of print through is readily apparent.
- Examples 20-21 illustrates an improved formulation that provides an adhesive with long open time that does not boil in a thick bead, and provides full cure without softness or tackiness or lingering odor from unreacted monomer in a thin film.
- Example 20 is an inventive composition that contains a flexible polyester resin.
- Example 21 is a comparative example that utilizes vinyl toluene to provide extended open time. The examples illustrate that the inventive composition does not exhibit boiling when applied in a thick (1 inch) bead, yet cures to a hard state in a thin (0.10 inch) film. The comparative example (formulated for slow cure) does not exhibit boiling in a thick bead, but it does not effectively cure in the thin film as illustrated by the finger hardness test.
- inventive example has significantly longer open working time than the comparative example, yet cures fully with a lower peak exotherm temperature.
- the inventive example does not boil, but the comparative example does.
- Comparison of examples 20B and 21B illustrates a significant improvement in the tensile strength and elongation of the inventive composition containing the polyester resin.
- results labeled 20A and 21A were obtained when formulations 20 and 21 were mixed in ratio of 43:5 by weight with IPS Weld-On® SS 218 HVB activator, a proprietary curative paste containing 5.6 percent benzoyl peroxide by weight.
- Results 20B and 21B were obtained with an experimental curing paste containing 7.7 percent benzoyl peroxide .
- the cure state observations were made four hours after the achievement of peak exotherm.
- Example 22 illustrates the improvement in adhesive bond strength at elevated temperature obtained with the addition of a vinyl ester resin.
- Example 22B which contains 10 percent of a preferred vinyl ester resin, has more than twice the bond strength at 250°F than comparative example 22A which contains no additive resin.
- the fiber tearing bond failure mode exhibited by Example 22B further illustrates the higher elevated temperature strength of the cured inventive adhesive formulation.
- Example 23 illustrates an inventive composition that is capable of bonding fiberglass panels with no observable print-through as well as bonding aluminum with no surface preparation. Adhesion to unprepared aluminum is achieved through the addition of a methacryloyloxyethyl phoshpate ester.
- the adhesive was mixed at a ratio of 8.3 to 1 by weight with Weld-On SS 605B activator, a proprietary paste containing 13.5 percent BPO by weight. Print through test was performed as in Example 18.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2004284427A AU2004284427B2 (en) | 2003-10-17 | 2004-10-05 | Adhesive compositions for bonding and filling large assemblies |
DK04794130.7T DK1682626T3 (en) | 2003-10-17 | 2004-10-05 | Adhesive compositions for connecting and filling large units |
CN2004800351801A CN1898350B (en) | 2003-10-17 | 2004-10-05 | Adhesive compositions for bonding and filling large assemblies |
JP2006535543A JP5391517B2 (en) | 2003-10-17 | 2004-10-05 | Adhesive composition for joining and filling large assemblies |
EP04794130.7A EP1682626B1 (en) | 2003-10-17 | 2004-10-05 | Adhesive compositions for bonding and filling large assemblies |
CA2542381A CA2542381C (en) | 2003-10-17 | 2004-10-05 | Adhesive compositions for bonding and filling large assemblies |
ES04794130.7T ES2463473T3 (en) | 2003-10-17 | 2004-10-05 | Adhesive compositions for bonding and filling large assemblies |
HK07106082.9A HK1101042A1 (en) | 2003-10-17 | 2007-06-07 | Adhesive compositions for bonding and filling large assemblies |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/688,441 US20050014901A1 (en) | 2001-07-10 | 2003-10-17 | Adhesive compositions for bonding and filling large assemblies |
US10/688,441 | 2003-10-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005040295A1 true WO2005040295A1 (en) | 2005-05-06 |
Family
ID=34521169
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/032660 WO2005040295A1 (en) | 2003-10-17 | 2004-10-05 | Adhesive compositions for bonding and filling large assemblies |
Country Status (11)
Country | Link |
---|---|
US (4) | US20050014901A1 (en) |
EP (1) | EP1682626B1 (en) |
JP (1) | JP5391517B2 (en) |
CN (1) | CN1898350B (en) |
AT (1) | AT13638U3 (en) |
AU (1) | AU2004284427B2 (en) |
CA (1) | CA2542381C (en) |
DK (1) | DK1682626T3 (en) |
ES (1) | ES2463473T3 (en) |
HK (1) | HK1101042A1 (en) |
WO (1) | WO2005040295A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011104510A1 (en) | 2010-02-26 | 2011-09-01 | Scott Bader Company Limited | Methacrylate-based adhesive compositions |
WO2011129767A1 (en) * | 2010-04-12 | 2011-10-20 | Showa Highpolymer Singapore Pte. Ltd. | Room temperature curable resin composition for pipe renewal |
WO2011148112A1 (en) * | 2010-05-28 | 2011-12-01 | Saint-Gobain Recherche | Adhesive composition containing a carboxylic-acid-terminated unsaturated polyester and uses thereof |
US9290631B2 (en) | 2008-03-12 | 2016-03-22 | General Electric Company | Adhesive formulations for bonding composite materials |
US9777202B2 (en) | 2012-04-10 | 2017-10-03 | Sika Technology Ag | Curable composition suitable for the bonding of plasticized PVC |
US9970411B2 (en) | 2011-09-29 | 2018-05-15 | General Electric Company | UV-IR combination curing system and method of use for wind blade manufacture and repair |
Families Citing this family (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050014901A1 (en) * | 2001-07-10 | 2005-01-20 | Ips Corporation | Adhesive compositions for bonding and filling large assemblies |
US20070155899A1 (en) * | 2005-12-21 | 2007-07-05 | Ips Corporation | Elastic methacrylate compositions |
EP2102298B1 (en) * | 2006-12-27 | 2017-09-06 | Jacret | Composition for structural adhesive |
FR2910908B1 (en) * | 2006-12-27 | 2010-08-20 | Jacret | COMPOSITION FOR STRUCTURAL ADHESIVE |
US20080281052A1 (en) * | 2007-05-10 | 2008-11-13 | Impact Matrix Systems, Llc | Multipurpose resin composition and process for manufacturing the same |
US8251969B2 (en) | 2007-08-03 | 2012-08-28 | Kimberly-Clark Worldwide, Inc. | Body adhering absorbent article |
US8062275B2 (en) | 2007-08-03 | 2011-11-22 | Kimberly Clark Worldwide, Inc. | Body adhering absorbent article and method for donning such article |
US8292862B2 (en) * | 2007-08-03 | 2012-10-23 | Kimberly-Clark Worldwide, Inc. | Dynamic fitting body adhering absorbent article |
US8734413B2 (en) | 2007-08-03 | 2014-05-27 | Kimberly-Clark Worldwide, Inc. | Packaged body adhering absorbent article |
US8672911B2 (en) | 2007-08-03 | 2014-03-18 | Kimberly-Clark Worldwide, Inc. | Body adhering absorbent article |
US20090182296A1 (en) * | 2007-08-03 | 2009-07-16 | Melissa Jean Dennis | Body Adhering Article |
US8702672B2 (en) | 2007-08-03 | 2014-04-22 | Kimberly-Clark Worldwide, Inc. | Body adhering absorbent article |
US7947027B2 (en) | 2007-12-28 | 2011-05-24 | Kimberly-Clark Worldwide, Inc. | Body adhering absorbent article |
GB2453921B (en) * | 2007-09-05 | 2010-02-24 | Rolls Royce Plc | A component matrix |
US20090099309A1 (en) * | 2007-10-16 | 2009-04-16 | Yulex Corporation | Guayule resin multipolymer |
US9173706B2 (en) * | 2008-08-25 | 2015-11-03 | Covidien Lp | Dual-band dipole microwave ablation antenna |
US11147722B2 (en) * | 2008-11-10 | 2021-10-19 | Kimberly-Clark Worldwide, Inc. | Absorbent article with a multifunctional acrylate skin-adhesive composition |
US10022468B2 (en) | 2009-02-02 | 2018-07-17 | Kimberly-Clark Worldwide, Inc. | Absorbent articles containing a multifunctional gel |
DE102009057632A1 (en) * | 2009-12-09 | 2011-06-16 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Solvent-free reactive adhesive, useful for fiber flocking of a substrate for dissipating the electrostatic fiber charges, comprises a mixture, which is produced from various radically reactive chemical polymers and monomeric compounds |
CN102115641A (en) * | 2010-12-03 | 2011-07-06 | 烟台德邦科技有限公司 | High-toughness acrylate structural adhesive and preparation method thereof |
CN103547606B (en) | 2011-05-03 | 2016-01-20 | 陶氏环球技术有限责任公司 | Can be used for the dual cure adhesive bonding glass |
JP2014511931A (en) | 2011-05-03 | 2014-05-19 | ダウ グローバル テクノロジーズ エルエルシー | Accelerated curing composition containing an isocyanate functional prepolymer |
US9371476B1 (en) * | 2011-09-22 | 2016-06-21 | Engineered Bonding Solutions, LLC | Structural adhesive compositions |
DE102011088123A1 (en) | 2011-12-09 | 2013-06-13 | Henkel Ag & Co. Kgaa | Method for integrally bonding plastic pipes |
CN102618201B (en) * | 2012-01-13 | 2013-09-18 | 十堰福波新材料有限公司 | Enhanced vibration-proof adhesive with following property and preparation method thereof |
WO2014074140A1 (en) | 2012-11-08 | 2014-05-15 | Dow Global Technologies Llc | Ultrafast dual cure adhesive useful for bonding to glass |
FR3000408B1 (en) * | 2013-01-03 | 2015-02-27 | Commissariat Energie Atomique | METHOD FOR PRODUCING FILTER FOR FILTRATION OF NANOPARTICLES, FILTER OBTAINED AND METHOD FOR COLLECTING AND QUANTITATIVE ANALYSIS OF NANOPARTICLES THEREOF |
CN103275626B (en) * | 2013-06-21 | 2014-09-17 | 苏州市景荣科技有限公司 | PVC sole adhesive |
JP6350161B2 (en) * | 2013-10-02 | 2018-07-04 | ダイキン工業株式会社 | Waterproof and moisture-proof durable coating composition |
CN104530893A (en) * | 2014-12-09 | 2015-04-22 | 东莞市蓝铂化工科技有限公司 | Aqueous plastic suction oil and preparation method thereof |
CN104742379B (en) * | 2015-03-25 | 2018-04-17 | 上海德竑玻璃钢制品有限公司 | The preparation method of fiberglass mould and fiberglass |
CN104830239A (en) * | 2015-05-08 | 2015-08-12 | 南通长航船舶配件有限公司 | Automatic control cabinet body for ships |
GB2542629B (en) * | 2015-09-28 | 2020-05-06 | Henkel IP & Holding GmbH | Polystyrene copolymer curable primer compositions for injection molding |
US10392532B2 (en) * | 2015-10-07 | 2019-08-27 | Illinois Tool Works, Inc. | Adhesive compositions with repair-rework ability |
CN106367003A (en) * | 2016-08-27 | 2017-02-01 | 安徽天瞳智能科技有限公司 | Waterproof anti-corrosion resin adhesive with long durability |
US10042957B2 (en) | 2017-01-12 | 2018-08-07 | Innovationdock, Inc. | Devices and methods for implementing dynamic collaborative workflow systems |
CN107418475A (en) * | 2017-09-21 | 2017-12-01 | 南通如港船舶配套机械有限公司 | A kind of ship metallic plate bonding agent |
CN109232789B (en) * | 2018-07-18 | 2020-06-12 | 四川大学 | Amphoteric polyelectrolyte-based high-performance self-repairing rubber and preparation method thereof |
CN110551473B (en) * | 2019-09-09 | 2021-11-30 | 广东莱尔新材料科技股份有限公司 | High-weather-resistance high-adhesion-force adhesive and FFC wire reinforcing plate |
CN110841575A (en) * | 2019-11-20 | 2020-02-28 | 郎蕾 | Equipment for bonding glass fiber reinforced plastic by using polyesterification polycondensation reaction |
CN111040705B (en) * | 2019-12-26 | 2021-04-27 | 杭州之江新材料有限公司 | Marble glue composition and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3321351A (en) * | 1955-12-31 | 1967-05-23 | Degussa | Method of adhesively joining surfaces |
US4548992A (en) * | 1981-12-05 | 1985-10-22 | Okura Koygo Kabushiki Kisha | Two-part type adhesives |
US5206288A (en) * | 1988-08-29 | 1993-04-27 | Illinois Tool Works, Inc. | Adhesive for low temperature applications |
WO2003040248A2 (en) * | 2001-07-10 | 2003-05-15 | Ips Corporation | Improved adhesives for bonding composites |
Family Cites Families (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL123024C (en) * | 1960-09-23 | |||
US3564074A (en) * | 1966-11-28 | 1971-02-16 | Dow Chemical Co | Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides |
US3548030A (en) * | 1968-03-27 | 1970-12-15 | Dow Chemical Co | Vinyl ester resins containing esterified secondary hydroxy groups |
US3890407A (en) * | 1972-07-20 | 1975-06-17 | Du Pont | Novel adhesive compositions |
US3838093A (en) * | 1972-10-25 | 1974-09-24 | Lord Corp | Method and composition for improving adhesion between adhesives and polyester or thermoplastic substrates |
US4038475A (en) * | 1974-09-24 | 1977-07-26 | Loctite Corporation | Highly stable anaerobic 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 |
US4126504A (en) * | 1977-01-27 | 1978-11-21 | Pratt & Lambert, Inc. | Adhesive compositions and method employing same |
US4151219A (en) * | 1977-05-11 | 1979-04-24 | The Dow Chemical Company | Vinyl ester resins containing polyoxyalkylene low profile additives |
US4223115A (en) * | 1978-04-24 | 1980-09-16 | Lord Corporation | Structural adhesive formulations |
US4293665A (en) * | 1978-04-24 | 1981-10-06 | Lord Corporation | Structural adhesive formulations |
US4233418A (en) * | 1978-05-31 | 1980-11-11 | Cosden Technology, Inc. | Process for preparing rubber-modified styrene copolymers by suspension copolymerization |
US4197390A (en) * | 1979-02-22 | 1980-04-08 | Shell Oil Company | Thickenable thermosetting vinyl ester resins |
DE2935196A1 (en) * | 1979-08-31 | 1981-03-19 | Robert Bosch Gmbh, 7000 Stuttgart | SAFETY DEVICE FOR ELECTRICAL CONSUMERS IN MOTOR VEHICLES |
US4304709A (en) * | 1979-11-01 | 1981-12-08 | Hooker Chemicals & Plastics Corp. | Polymer blends with improved hydrolytic stability |
US4347343A (en) * | 1981-01-21 | 1982-08-31 | The Dow Chemical Company | Thickened vinyl ester resin compositions |
US4374940A (en) * | 1981-06-16 | 1983-02-22 | The Henkel Corporation | Anaerobic compositions |
DE3127843A1 (en) * | 1981-07-15 | 1983-05-26 | AEG-Telefunken Nachrichtentechnik GmbH, 7150 Backnang | METHOD FOR PREVENTING "COMPROMISING RADIATION" IN PROCESSING AND TRANSMITTING SECRET DATA INFORMATION |
FR2529558B1 (en) * | 1982-06-30 | 1985-10-25 | Chloe Chemie | CURABLE POLYESTER COMPOSITIONS |
FR2531092B1 (en) * | 1982-07-27 | 1985-10-11 | Ugine Kuhlmann | ANTI-SHRINKAGE ADDITIVE FOR AN UNSATURATED POLYESTER, A METHOD FOR PRODUCING THE SAME, ANTI-SHRINKAGE COMPOSITION |
DE3229078A1 (en) * | 1982-08-04 | 1984-02-09 | Bayer Ag, 5090 Leverkusen | MOLDS OF VINYL CHLORIDE POLYMERISAT, GRAFT POLYMERS AND POLYMERS SOFTENERS WITH HIGH AGING RESISTANCE |
US4467071A (en) * | 1982-09-13 | 1984-08-21 | Lord Corporation | Epoxy modified structural adhesives having improved heat resistance |
JPS6033147B2 (en) * | 1982-12-14 | 1985-08-01 | 大倉工業株式会社 | Two-component acrylic adhesive composition |
US4961938A (en) * | 1982-12-22 | 1990-10-09 | Genentech, Inc. | Preparation of cheese with rennin from recombinant microbial cells |
US4513108A (en) * | 1983-05-16 | 1985-04-23 | Ethyl Corporation | Thermoplastic PVC molding compositions |
US4824919A (en) * | 1983-06-09 | 1989-04-25 | The Dow Chemical Company | Toughening of cured vinyl ester resins by inclusion in the uncured resins of oligomeric vinyl-reactive urethanes which phase out upon curing |
US4536546A (en) * | 1983-09-22 | 1985-08-20 | Illinois Tool Works Inc. | (Meth)acrylate-based compositions |
US4773957A (en) * | 1983-09-22 | 1988-09-27 | Illinois Tool Works, Inc. | Bonding method employing novel methacrylate based adhesive compositions |
US4714730A (en) * | 1986-06-04 | 1987-12-22 | Illinois Tool Works Inc. | Acid modified adhesive compositions |
US4964938A (en) * | 1987-04-13 | 1990-10-23 | Dymax Corporation | Bonding method using photocurable acrylate adhesive containing perester/tautomeric acid adhesion promoter |
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 |
US5391608A (en) * | 1989-04-26 | 1995-02-21 | National Starch And Chemical Investment Holding Corporation | Woodworking adhesives based on multistage emulsion polymer |
IT1244842B (en) | 1990-11-21 | 1994-09-06 | Mini Ricerca Scient Tecnolog | HIGH RESILIENCE ADHESIVE COMPOSITIONS. |
US5945461A (en) * | 1991-03-21 | 1999-08-31 | Illinois Tool Works Inc. | Foamed acrylic polymer compositions |
US5340901A (en) * | 1991-12-09 | 1994-08-23 | Gencorp Inc. | Two-component, primerless, organic phosphorus containing polyurethane adhesive |
JP2956344B2 (en) * | 1992-02-08 | 1999-10-04 | 日本ゼオン株式会社 | Rubber composition |
DE69332415T2 (en) * | 1992-03-12 | 2003-06-18 | Ashland Oil Inc., Columbus | PRIMER-FREE STRUCTURAL POLYURETHANE PURETHANE ADHESIVE |
US5262479A (en) * | 1992-11-24 | 1993-11-16 | National Starch And Chemical Investment Holding Corporation | Plasticizer resisant hot melt pressure sensitive adhesive |
JP3674081B2 (en) * | 1995-04-18 | 2005-07-20 | 大日本インキ化学工業株式会社 | Resin composition, civil engineering and building materials and covering materials |
US5656345A (en) * | 1995-06-07 | 1997-08-12 | Illinois Tool Works, Inc. | Adhesive compositions and adhesively joined pipe segments |
EP0859085B1 (en) * | 1995-11-01 | 2005-03-16 | Mitsubishi Rayon Co., Ltd. | Method of repairing/reinforcing existing structures and anisotropic woven fabrics used therefor |
JP3256548B2 (en) * | 1996-04-15 | 2002-02-12 | ロード コーポレーション | Free radical polymerizable composition containing p-halogenated aniline derivative |
US5935711A (en) * | 1996-10-23 | 1999-08-10 | 3M Innovative Properties Company | Organoborane amine complex initiator systems and polymerizable compositions made therewith |
US5859160A (en) * | 1997-01-09 | 1999-01-12 | Lord Corporation | Additives for controlling cure rate of polymerizable composition |
US6203911B1 (en) * | 1998-06-17 | 2001-03-20 | E. I. Du Pont De Nemours And Company | Thermoset volatile monomer molding compositions |
WO2000032688A1 (en) | 1998-12-03 | 2000-06-08 | The Dexter Corporation | Adhesive compositions with retarding additive |
US6433091B1 (en) * | 2001-05-10 | 2002-08-13 | Henkel Loctite Corporation | Adhesive composition |
US20050014901A1 (en) * | 2001-07-10 | 2005-01-20 | Ips Corporation | Adhesive compositions for bonding and filling large assemblies |
-
2003
- 2003-10-17 US US10/688,441 patent/US20050014901A1/en not_active Abandoned
-
2004
- 2004-10-05 WO PCT/US2004/032660 patent/WO2005040295A1/en active Application Filing
- 2004-10-05 AU AU2004284427A patent/AU2004284427B2/en not_active Ceased
- 2004-10-05 JP JP2006535543A patent/JP5391517B2/en not_active Expired - Fee Related
- 2004-10-05 CA CA2542381A patent/CA2542381C/en not_active Expired - Fee Related
- 2004-10-05 AT ATGM50141/2013U patent/AT13638U3/en not_active IP Right Cessation
- 2004-10-05 EP EP04794130.7A patent/EP1682626B1/en not_active Expired - Lifetime
- 2004-10-05 ES ES04794130.7T patent/ES2463473T3/en not_active Expired - Lifetime
- 2004-10-05 DK DK04794130.7T patent/DK1682626T3/en active
- 2004-10-05 CN CN2004800351801A patent/CN1898350B/en not_active Expired - Fee Related
-
2006
- 2006-12-28 US US11/646,664 patent/US7795351B2/en not_active Ceased
-
2007
- 2007-06-07 HK HK07106082.9A patent/HK1101042A1/en not_active IP Right Cessation
-
2008
- 2008-03-27 US US12/056,342 patent/US7816453B2/en not_active Expired - Fee Related
-
2012
- 2012-09-12 US US13/611,205 patent/USRE46269E1/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3321351A (en) * | 1955-12-31 | 1967-05-23 | Degussa | Method of adhesively joining surfaces |
US4548992A (en) * | 1981-12-05 | 1985-10-22 | Okura Koygo Kabushiki Kisha | Two-part type adhesives |
US5206288A (en) * | 1988-08-29 | 1993-04-27 | Illinois Tool Works, Inc. | Adhesive for low temperature applications |
WO2003040248A2 (en) * | 2001-07-10 | 2003-05-15 | Ips Corporation | Improved adhesives for bonding composites |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9290631B2 (en) | 2008-03-12 | 2016-03-22 | General Electric Company | Adhesive formulations for bonding composite materials |
WO2011104510A1 (en) | 2010-02-26 | 2011-09-01 | Scott Bader Company Limited | Methacrylate-based adhesive compositions |
US9074112B2 (en) | 2010-02-26 | 2015-07-07 | Scott Bader Company Limited | Methacrylate-based adhesive compositions |
EP3572476A1 (en) | 2010-02-26 | 2019-11-27 | Scott Bader Company Limited | Methacrylate-based adhesive compositions |
WO2011129767A1 (en) * | 2010-04-12 | 2011-10-20 | Showa Highpolymer Singapore Pte. Ltd. | Room temperature curable resin composition for pipe renewal |
WO2011148112A1 (en) * | 2010-05-28 | 2011-12-01 | Saint-Gobain Recherche | Adhesive composition containing a carboxylic-acid-terminated unsaturated polyester and uses thereof |
FR2960547A1 (en) * | 2010-05-28 | 2011-12-02 | Saint Gobain Rech | ADHESIVE COMPOSITION COMPRISING AN UNSATURATED CARBOXYLIC ACID TERMINATING POLYESTER AND USES THEREOF. |
US9970411B2 (en) | 2011-09-29 | 2018-05-15 | General Electric Company | UV-IR combination curing system and method of use for wind blade manufacture and repair |
US9777202B2 (en) | 2012-04-10 | 2017-10-03 | Sika Technology Ag | Curable composition suitable for the bonding of plasticized PVC |
Also Published As
Publication number | Publication date |
---|---|
HK1101042A1 (en) | 2007-10-05 |
AU2004284427A1 (en) | 2005-05-06 |
CA2542381A1 (en) | 2005-05-06 |
US7795351B2 (en) | 2010-09-14 |
US20070142556A1 (en) | 2007-06-21 |
US7816453B2 (en) | 2010-10-19 |
AU2004284427A2 (en) | 2005-05-06 |
DK1682626T3 (en) | 2014-05-19 |
US20080177004A1 (en) | 2008-07-24 |
EP1682626A1 (en) | 2006-07-26 |
EP1682626B1 (en) | 2014-04-30 |
JP5391517B2 (en) | 2014-01-15 |
CN1898350A (en) | 2007-01-17 |
JP2007508445A (en) | 2007-04-05 |
AU2004284427B2 (en) | 2011-05-26 |
USRE46269E1 (en) | 2017-01-10 |
AT13638U3 (en) | 2015-01-15 |
CA2542381C (en) | 2012-07-17 |
AT13638U2 (en) | 2014-05-15 |
ES2463473T3 (en) | 2014-05-28 |
CN1898350B (en) | 2012-07-11 |
US20050014901A1 (en) | 2005-01-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2542381C (en) | Adhesive compositions for bonding and filling large assemblies | |
JP4525076B2 (en) | Improved adhesives for composite bonding | |
EP1861474B1 (en) | Acrylate/methacrylate adhesives initiated by chlorosulfonated polymer | |
EP3931228B1 (en) | Acrylate structural adhesive | |
CA2606748C (en) | Adhesives for metal bonding applications | |
EP2289957B1 (en) | Elastic methacrylate compositions | |
US20040197587A1 (en) | Two-part structural adhesive systems and laminates incorporating the same | |
US9845413B1 (en) | Structural adhesive compositions | |
WO2000032688A1 (en) | Adhesive compositions with retarding additive | |
JP2864179B2 (en) | Acrylic adhesive composition | |
JPH0322915B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200480035180.1 Country of ref document: CN |
|
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 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): BW GH 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 IT 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: 2542381 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006535543 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004284427 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004794130 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2004284427 Country of ref document: AU Date of ref document: 20041005 Kind code of ref document: A |
|
WWP | Wipo information: published in national office |
Ref document number: 2004284427 Country of ref document: AU |
|
WWP | Wipo information: published in national office |
Ref document number: 2004794130 Country of ref document: EP |