US20070155899A1 - Elastic methacrylate compositions - Google Patents
Elastic methacrylate compositions Download PDFInfo
- Publication number
- US20070155899A1 US20070155899A1 US11/642,489 US64248906A US2007155899A1 US 20070155899 A1 US20070155899 A1 US 20070155899A1 US 64248906 A US64248906 A US 64248906A US 2007155899 A1 US2007155899 A1 US 2007155899A1
- Authority
- US
- United States
- Prior art keywords
- styrene
- block copolymer
- butadiene
- linear
- part adhesive
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- 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
- C08L51/04—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 grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
- C09J127/00—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 a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/04—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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
-
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- 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
- 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
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; 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
Definitions
- This invention relates to liquid and paste compositions comprising mixtures of polymers and acrylic or methacrylate monomers that are hardened by free radical polymerization to form high strength, flexibilized materials.
- the hardened compositions are generally useful as adhesives, filling and repair materials, coatings and the like.
- the mixing ratio of monomer composition to peroxide is typically from about 100:1, if pure BPO is used, to about 10:1 or less, if it is diluted with a plasticizer for more convenient mixing.
- the minimum practical ratio of monomer composition to peroxide component is about 4:1, because the inert plasticizer and other ingredients in the peroxide component have a negative effect on the properties of the cured composition.
- Benzoyl peroxide is not stable when mixed with methacrylate monomers. Stability of the peroxide catalyst species in admixtures with methacrylate mixtures is necessary for safe and practical storage prior to use in typical 1:1 mix ratio formulations. For this reason, benzoyl peroxide is not a catalyst component in the preferred embodiments of the inventive compositions.
- an initiator system comprising a sulfonyl chloride initiating species, a hydroperoxide or other stable non-BPO co-initiating species, and an amine-aldehyde activator.
- the initiating species are included in the adhesive portion or component A of the adhesive
- the aldehyde-amine activator is included in the activator portion or component B of the adhesive.
- a common source of sulfonyl chloride is chlorosulfonated polyethylene, sold commercially as Hypalon by dupont.
- a preferred aldehyde-amine activator is Reillcat ASY-2, a reaction product of butyraldehyde and aniline that is enriched in the content of the active dihydropyridine component, generically referred to as DHP.
- U.S. Pat. No. 4,574,142 to Charnock discloses toughened two-part acrylic monomer based adhesive compositions that employ styrene-butadiene (SBS) block copolymer rubbers. Only block copolymers of styrene and butadiene are disclosed, and no preference for the relative ratios of butadiene or styrene, or structure of the polymer is disclosed. An aldehyde-amine component is used as part of the curing catalyst system. However, it is specified that the compositions include a free-radical catalyst system that is free from organic sulfonyl chloride.
- SBS styrene-butadiene
- Sulfonyl chlorides and polymers containing sulfonyl chlorides, such as chlorosulfonated polyethylene, which are preferred accelerators for prior art adhesives, are specifically excluded from the compositions.
- Charnock either excludes or teaches away from any chlorine bearing species in the compositions, especially sulfonyl chlorides.
- U.S. Pat. No. 5,206,288 discloses improvements in low temperature flexible bond properties with compositions that combine elastomers with low glass transition temperatures Tg and core-shell impact modifiers.
- the catalyst system comprises BPO paste as an additive in one polymer in monomer component and a tertiary amine, N,N-dimethyl-p-toluidine in the other.
- BPO is not a preferred component of the compositions of the preferred embodiments.
- U.S. Pat. No. 6,989,416 discloses methacrylate adhesives with improved flexibility based on block copolymers of styrene and butadiene.
- the adhesives contain peroxides and tertiary amine initiators but do not contain sulfonyl chlorides or any other sulfur bearing components or DHP components. Further, they preferably utilize benzoyl peroxide paste as the catalyst component in a mix ratio of 10:1.
- Preferred embodiments of this invention provide two-part structural adhesive compositions that exhibit improved elasticity and retention of elasticity.
- the adhesive compositions are mixtures of acrylate or methacrylate monomers and polymers that comprise
- compositions are particularly well suited for formulation as ambient temperature curing adhesives with a convenient 1:1 mix ratio. While it is not required for the compositions to be mixed in a 1:1 mix ratio to benefit from the advantages of this invention, this is a highly preferred and practical feature for commercial products. Further, these embodiments do not require the presence of benzoyl peroxide.
- thermoplastic block copolymer component utilized in combination with certain free radical initiation systems.
- Preferred thermoplastic block copolymer components are selected from a group consisting of
- thermoplastic block copolymers examples are sold commercially by Kraton Polymers, Inc. under the KratonmTM trade name, by Dexco Polymers under the trade name VectormTM, and by others.
- the preferred free radical initiation systems include sulfur bearing compounds, preferably sulfonyl chlorides or sulfimides, combined with a dihydropyridine.
- an adhesion promoting polymer is preferably used to improve the bond strength of the cured compositions on a variety of plastic, metallic ceramic, wood or other materials or combinations of materials.
- the choice of adhesion promoting polymers depends upon the nature of the materials to be bonded and the required physical properties of the cured adhesive composition.
- Preferred adhesion promoting polymers are thermoplastic resins and elastomers that are soluble or dispersible in the methacrylate monomers. Preferred polymers for this purpose are disclosed in U.S. Patent No. 4,182,644, which is incorporated herein by reference. More preferred adhesion-promoting polymers are chlorinated polymers, and most preferred polymers are chlorinated elastomers, including chlorosulfonated polyethylene, chlorinated polyethylene, and polychloroprene polymers. Mixtures of any or all of the preferred polymers may be employed to advantage.
- impact modifiers preferably core-shell impact modifiers.
- this class of polymers can provide additional benefits of Theological or handling properties and further improvements in the ductility or toughness of the cured compositions.
- the benefits of impact modifiers and in particular core-shell impact modifiers are disclosed in U.S. Pat. No. 4,536,546, which is incorporated herein by reference.
- acrylate and methacrylate monomers used in preferred embodiments of the inventive formulations are well known to those skilled in the art and disclosed in the '644 patent cited above. Most preferred monomers are methyl methacrylate monomer and higher molecular weight monomers wherein the alcohol portion of the monomer is based on a C 6 or higher hydrocarbon moiety. A most preferred monomer of the latter type is lauryl methacrylate.
- Non-methacrylate unsaturated or vinyl monomers such as styrene, vinyl toluene, alpha-methyl styrene, and others may be used as necessary to provide specific benefits such as control of cure rate.
- the initiating species of a preferred embodiment of the inventive compositions include sulfur bearing compounds and peroxides.
- the activators of a preferred embodiment of the invention include tertiary aromatic amines, amine-aldehyde activators and active metallic species.
- Preferred sulfur bearing compounds include sulfonyl chlorides or chlorosulfonated polymers, such as chlorosulfonated polyethylene, and sulfimides, including benzoic sulfimide or saccharin.
- Preferred peroxides include hydroperoxides, such as cumene hydroperoxide and methyl ethyl ketone peroxide, benzoate esters including t-butyl perbenzoate, and other peroxidic species well known to those in the art. Benzoyl peroxide is not preferred.
- Preferred activators are adducts of butyraldehyde and aniline, including products that are enriched in the active dihydropyridine (DHP) component sold commercially as Reillcat ASY-2.
- the compositions may also contain an organometallic species capable of increasing the reactivity and cure speed of the adhesive.
- Preferred active metallic species are transition metal compounds, most preferably derivatives of long chain carboxylic acids such as copper naphthenate copper octoate, or similar organometallic compounds familiar to those skilled in the art.
- compositions that when fully cured exhibit exceptional improvements in mechanical properties over prior art compositions that are capable of formulation as 1:1 mix ratio adhesive products.
- ASTM method D638 fully cured methacrylate adhesive compositions of the prior art display a broad and mixed range of thermoplastic, viscoelastic and elastic behaviors.
- the significant improvements in the preferred compositions of the preferred embodiments of this invention consist of a combination of high tensile strength and elongation at failure, coupled with a high degree of linear elasticity, recoverable deformation prior to yielding, and preferably significant strain hardening prior to failure. From the engineering standpoint, these are highly desirable features for a structural adhesive.
- any number of additional components may be used to formulate the adhesive compositions of the preferred embodiments of this invention.
- these include non-polymeric adhesion promoters, such as polymerizable carboxylic acids and acrylated or methacrylated phosphate esters, corrosion inhibitors, including zinc and molybdate compounds, epoxy resins, fillers, plasticizers, vapor barrier waxes and the like. They may also include polyester resins and acetylenic alcohols.
- compositions comprise (A) about 20 percent to about 90 percent of a methacrylate monomer, (B) about 0.02 to about 30 percent of a sulfur bearing compound or a chlorosulfonated polymer, (C) about 0.05 percent to about 10 percent of an amine promoter, preferably a dihydropyridine, and (D) about 5 percent to about 50 percent of a thermoplastic block copolymer component. Additional promoters may be added as needed, particularly adhesion promoters. The use of benzoyl peroxide is not preferred.
- thermoplastic block copolymers are prepared in one gallon glass jars by using a jar roller to dissolve sufficient quantities of polymer in methyl methacrylate to provide solutions with concentrations ranging from about 30-45%.
- the final viscosity is adjusted by adding additional MMA after additional formulating ingredients are added.
- the DHP component or BPO component is added as the final additive to initiate the polymerization.
- Test specimens are 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 0.125 inches thick.
- the adhesive components are combined in the specified ratios by simple hand mixing in a beaker. After the adhesive is thoroughly mixed, the beaker is placed in a vacuum chamber and vacuum is applied intermittently to remove air until the last one or two applications of vacuum does not produce additional frothing or expansion.
- the adhesive is 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 is placed in the center of the film, and a mating Mylar film and plate are placed over the adhesive and pressed down uniformly to spread the film. Metal shims are placed around the perimeter of the plates to establish the desired film thickness.
- Test dumbbells are 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 are 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 1-5 compare preferred formulations (2-4) with a prior art formulation (5). Comparison of examples 1 and 2 illustrates the effect of added plasticizer to provide the desired properties when the thermoplastic block copolymer is a radial SBS block copolymer.
Abstract
Description
- This application claims priority from Provisional Application No. 60/752,713, filed on Dec. 21, 2005.
- This invention relates to liquid and paste compositions comprising mixtures of polymers and acrylic or methacrylate monomers that are hardened by free radical polymerization to form high strength, flexibilized materials. The hardened compositions are generally useful as adhesives, filling and repair materials, coatings and the like.
- Commercial and prior art methacrylate adhesive compositions capable of being mixed in a 1:1 ratio and also having practical storage life or shelf life heretofore have not been as elastic or ductile as adhesives with the common but less practical 10:1 mix ratio. This is especially evident upon aging of the adhesive over time or at elevated temperatures. The latter compositions generally employ benzoyl peroxide as the primary initiating species. The earliest and most widely used catalyst combination comprises benzoyl peroxide and a tertiary aromatic amine. The amine is generally incorporated in the polymer and monomer mixture, and the benzoyl peroxide is supplied separately and added to the monomer composition at the time of use. The mixing ratio of monomer composition to peroxide is typically from about 100:1, if pure BPO is used, to about 10:1 or less, if it is diluted with a plasticizer for more convenient mixing. The minimum practical ratio of monomer composition to peroxide component is about 4:1, because the inert plasticizer and other ingredients in the peroxide component have a negative effect on the properties of the cured composition. Benzoyl peroxide is not stable when mixed with methacrylate monomers. Stability of the peroxide catalyst species in admixtures with methacrylate mixtures is necessary for safe and practical storage prior to use in typical 1:1 mix ratio formulations. For this reason, benzoyl peroxide is not a catalyst component in the preferred embodiments of the inventive compositions.
- Commercial and prior art methacrylate adhesives with a 1:1 mix ratio typically employ an initiator system comprising a sulfonyl chloride initiating species, a hydroperoxide or other stable non-BPO co-initiating species, and an amine-aldehyde activator. The initiating species are included in the adhesive portion or component A of the adhesive, and the aldehyde-amine activator is included in the activator portion or component B of the adhesive. A common source of sulfonyl chloride is chlorosulfonated polyethylene, sold commercially as Hypalon by dupont. A preferred aldehyde-amine activator is Reillcat ASY-2, a reaction product of butyraldehyde and aniline that is enriched in the content of the active dihydropyridine component, generically referred to as DHP.
- While the hydroperoxide/sulfonyl chloride/DHP curing system has provided a means of producing adhesives with a convenient and non-critical 1:1 mix ratio, the resulting formulations have not been preferred for the most demanding structural adhesives applications. This is because these formulations are typically more rigid and may become brittle upon aging relative to compositions cured with BPO and tertiary amines. Therefore, there is a recognized need for adhesives with a convenient 1:1 mix ratio and a high degree of flexibility and retained flexibility after aging. It has now been discovered that specific block copolymers of styrene, butadiene and isoprene can be used to formulate adhesive compositions with these desired characteristics using components that provide a convenient 1:1 mix ratio. Further, in preferred embodiments, these compositions can be formulated without the use of benzoyl peroxide.
- U.S. Pat. No. 4,574,142 to Charnock discloses toughened two-part acrylic monomer based adhesive compositions that employ styrene-butadiene (SBS) block copolymer rubbers. Only block copolymers of styrene and butadiene are disclosed, and no preference for the relative ratios of butadiene or styrene, or structure of the polymer is disclosed. An aldehyde-amine component is used as part of the curing catalyst system. However, it is specified that the compositions include a free-radical catalyst system that is free from organic sulfonyl chloride. Sulfonyl chlorides and polymers containing sulfonyl chlorides, such as chlorosulfonated polyethylene, which are preferred accelerators for prior art adhesives, are specifically excluded from the compositions. Polychloroprene, another chlorinated polymer used in prior art compositions, is also disclosed, which has undesirable effects. Thus, Charnock either excludes or teaches away from any chlorine bearing species in the compositions, especially sulfonyl chlorides.
- U.S. Pat. No. 5,206,288 discloses improvements in low temperature flexible bond properties with compositions that combine elastomers with low glass transition temperatures Tg and core-shell impact modifiers. In one embodiment employing Kraton in a formulation mixed in an approximately 1:1 mix ratio, the catalyst system comprises BPO paste as an additive in one polymer in monomer component and a tertiary amine, N,N-dimethyl-p-toluidine in the other. BPO is not a preferred component of the compositions of the preferred embodiments.
- U.S. Pat. No. 6,989,416 discloses methacrylate adhesives with improved flexibility based on block copolymers of styrene and butadiene. The adhesives contain peroxides and tertiary amine initiators but do not contain sulfonyl chlorides or any other sulfur bearing components or DHP components. Further, they preferably utilize benzoyl peroxide paste as the catalyst component in a mix ratio of 10:1.
- Preferred embodiments of this invention provide two-part structural adhesive compositions that exhibit improved elasticity and retention of elasticity. The adhesive compositions are mixtures of acrylate or methacrylate monomers and polymers that comprise
-
- A. one or more acrylate or methacrylate ester monomers,
- B. a sulfur bearing compound, preferably a sulfonyl chloride,
- C. an amine promoter, preferably an amine aldehyde reaction product,
- D. a thermoplastic block copolymer component selected from a group consisting of
- a. a linear styrene-butadiene-styrene copolymer
- b. a radial styrene-butadiene-styrene block copolymer plus a plasticizer
- c. a linear or radial styrene-isoprene-styrene block copolymer, and
- d. a linear or radial styrene-butadiene-isoprene-styrene block copolymer, and
- E. optionally, an adhesion promoting polymer, preferably a chlorinated polymer.
- The compositions are particularly well suited for formulation as ambient temperature curing adhesives with a convenient 1:1 mix ratio. While it is not required for the compositions to be mixed in a 1:1 mix ratio to benefit from the advantages of this invention, this is a highly preferred and practical feature for commercial products. Further, these embodiments do not require the presence of benzoyl peroxide.
- It has now been discovered that an important element useful for improved and permanent elasticity in formulations capable of more convenient 1:1 ratio mixing is a thermoplastic block copolymer component utilized in combination with certain free radical initiation systems. Preferred thermoplastic block copolymer components are selected from a group consisting of
-
- a. a linear styrene-butadiene-styrene copolymer with a styrene content from about 20 percent to about 45 percent
- b. a radial styrene-butadiene-styrene block copolymer with a styrene content from about 20 percent to about 45 percent plus a plasticizer
- c. a linear or radial styrene-isoprene-styrene block copolymer with a styrene content from about 10 percent to about 45 percent, and
- d. a linear or radial styrene-butadiene-isoprene-styrene block copolymer with a styrene content from about 10 percent to about 45 percent.
- Examples of acceptable thermoplastic block copolymers are sold commercially by Kraton Polymers, Inc. under the Kratonm™ trade name, by Dexco Polymers under the trade name Vectorm™, and by others. The preferred free radical initiation systems include sulfur bearing compounds, preferably sulfonyl chlorides or sulfimides, combined with a dihydropyridine.
- When the inventive compositions are formulated as adhesives, an adhesion promoting polymer is preferably used to improve the bond strength of the cured compositions on a variety of plastic, metallic ceramic, wood or other materials or combinations of materials. The choice of adhesion promoting polymers depends upon the nature of the materials to be bonded and the required physical properties of the cured adhesive composition.
- Preferred adhesion promoting polymers are thermoplastic resins and elastomers that are soluble or dispersible in the methacrylate monomers. Preferred polymers for this purpose are disclosed in U.S. Patent No. 4,182,644, which is incorporated herein by reference. More preferred adhesion-promoting polymers are chlorinated polymers, and most preferred polymers are chlorinated elastomers, including chlorosulfonated polyethylene, chlorinated polyethylene, and polychloroprene polymers. Mixtures of any or all of the preferred polymers may be employed to advantage.
- Other polymers that may be used to advantage in the inventive formulations are impact modifiers, preferably core-shell impact modifiers. In addition to providing improved adhesion to some materials, this class of polymers can provide additional benefits of Theological or handling properties and further improvements in the ductility or toughness of the cured compositions. The benefits of impact modifiers and in particular core-shell impact modifiers are disclosed in U.S. Pat. No. 4,536,546, which is incorporated herein by reference.
- The acrylate and methacrylate monomers used in preferred embodiments of the inventive formulations are well known to those skilled in the art and disclosed in the '644 patent cited above. Most preferred monomers are methyl methacrylate monomer and higher molecular weight monomers wherein the alcohol portion of the monomer is based on a C6 or higher hydrocarbon moiety. A most preferred monomer of the latter type is lauryl methacrylate. Non-methacrylate unsaturated or vinyl monomers such as styrene, vinyl toluene, alpha-methyl styrene, and others may be used as necessary to provide specific benefits such as control of cure rate.
- The initiating species of a preferred embodiment of the inventive compositions include sulfur bearing compounds and peroxides. The activators of a preferred embodiment of the invention include tertiary aromatic amines, amine-aldehyde activators and active metallic species. Preferred sulfur bearing compounds include sulfonyl chlorides or chlorosulfonated polymers, such as chlorosulfonated polyethylene, and sulfimides, including benzoic sulfimide or saccharin. Preferred peroxides include hydroperoxides, such as cumene hydroperoxide and methyl ethyl ketone peroxide, benzoate esters including t-butyl perbenzoate, and other peroxidic species well known to those in the art. Benzoyl peroxide is not preferred.
- Preferred activators are adducts of butyraldehyde and aniline, including products that are enriched in the active dihydropyridine (DHP) component sold commercially as Reillcat ASY-2. The compositions may also contain an organometallic species capable of increasing the reactivity and cure speed of the adhesive. Preferred active metallic species are transition metal compounds, most preferably derivatives of long chain carboxylic acids such as copper naphthenate copper octoate, or similar organometallic compounds familiar to those skilled in the art.
- An important feature of the preferred embodiments of this invention is the provision of compositions that when fully cured exhibit exceptional improvements in mechanical properties over prior art compositions that are capable of formulation as 1:1 mix ratio adhesive products. When tested for bulk mechanical properties according to ASTM method D638, fully cured methacrylate adhesive compositions of the prior art display a broad and mixed range of thermoplastic, viscoelastic and elastic behaviors. These phenomena are described in US Patent Application Publication US 2005/0004303 A1, which is incorporated herein by reference. For the purpose of this discussion, the significant improvements in the preferred compositions of the preferred embodiments of this invention consist of a combination of high tensile strength and elongation at failure, coupled with a high degree of linear elasticity, recoverable deformation prior to yielding, and preferably significant strain hardening prior to failure. From the engineering standpoint, these are highly desirable features for a structural adhesive.
- In addition to the polymeric components cited above, any number of additional components that are well known to those skilled in the art may be used to formulate the adhesive compositions of the preferred embodiments of this invention. These include non-polymeric adhesion promoters, such as polymerizable carboxylic acids and acrylated or methacrylated phosphate esters, corrosion inhibitors, including zinc and molybdate compounds, epoxy resins, fillers, plasticizers, vapor barrier waxes and the like. They may also include polyester resins and acetylenic alcohols.
- Preferred compositions comprise (A) about 20 percent to about 90 percent of a methacrylate monomer, (B) about 0.02 to about 30 percent of a sulfur bearing compound or a chlorosulfonated polymer, (C) about 0.05 percent to about 10 percent of an amine promoter, preferably a dihydropyridine, and (D) about 5 percent to about 50 percent of a thermoplastic block copolymer component. Additional promoters may be added as needed, particularly adhesion promoters. The use of benzoyl peroxide is not preferred.
- The preferred embodiments can be further understood from a review of the following examples. However, the Examples are not intended to limit the scope of the invention in any way.
- Stock solutions of thermoplastic block copolymers are prepared in one gallon glass jars by using a jar roller to dissolve sufficient quantities of polymer in methyl methacrylate to provide solutions with concentrations ranging from about 30-45%. For individual examples, the final viscosity is adjusted by adding additional MMA after additional formulating ingredients are added. Just prior to making the test specimens, the DHP component or BPO component is added as the final additive to initiate the polymerization.
- Bulk stress-strain properties of the adhesives are measured according to ASTM test method D638. Test specimens are 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 0.125 inches thick. The adhesive components are combined in the specified ratios by simple hand mixing in a beaker. After the adhesive is thoroughly mixed, the beaker is placed in a vacuum chamber and vacuum is applied intermittently to remove air until the last one or two applications of vacuum does not produce additional frothing or expansion. The adhesive is 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 is placed in the center of the film, and a mating Mylar film and plate are placed over the adhesive and pressed down uniformly to spread the film. Metal shims are placed around the perimeter of the plates to establish the desired film thickness.
- After the films are cured, the plates are removed. Test dumbbells are 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 are 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 1-5 compare preferred formulations (2-4) with a prior art formulation (5). Comparison of examples 1 and 2 illustrates the effect of added plasticizer to provide the desired properties when the thermoplastic block copolymer is a radial SBS block copolymer.
EXAMPLES 1 2 3 4 5 Component MMA Monomer 63.81 53.85 58.50 59.25 61.50 Methacrylic Acid 5.00 5.00 5.00 5.00 5.00 Kraton D 1116 27.35 27.40 Kraton D 1101 31.50 Kraton D 1111 31.90 33.00 DOP 10.00 p-TSCl 3.00 3.00 3.00 3.00 CHP 0.75 0.75 0.50 0.75 DHP 2.50 2.50 2.40 2.50 HET 0.5 CuAcAc Soln 0.10 0.10 0.10 0.10 Benox B55 2.5 Tensile Properties ASTM D638 after 82° C./1 hr postcure Tensile stress (psi) 1190 905 1545 1295 1467 Elongation, % 91.8 407 342 534 100 Strain harden Y/N No Yes Yes Yes No Block Copolymer Type SBS SBS SBS SIS SIS Linear/Radial Radial Radial Linear Linear Linear Plasticizer Y/N No Yes No No No Other Components MMA Monomer Methyl methacrylate monomer Lucite Kraton Polymers Thermoplastic block copolymer Kraton DOP Dioctylphthalate plasticizer Aldrich p-TSCl p-Toluenesulfonyl chloride Aldrich CHP Cumene Hydroperoxide Hercules DHP Enriched dihydropyridine (DHP) Reilly Industries HET N,N-bis Hydroxyethyl Toluidine Bayer CuAcAc′ solution 0.5% solution of copper acetyl Laboratory Acetonate in MMA monomer Prep/Aldrich Benox B55 55% Benzoyl peroxide/benzoate Norac Plasticizer
Particularly preferred compositions are shown in Examples 2, 3 and 4.
Claims (20)
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/642,489 US20070155899A1 (en) | 2005-12-21 | 2006-12-20 | Elastic methacrylate compositions |
DK10191458.8T DK2289957T3 (en) | 2005-12-21 | 2006-12-21 | elastic methacrylatsammensætninger |
EP10191458.8A EP2289957B1 (en) | 2005-12-21 | 2006-12-21 | Elastic methacrylate compositions |
PCT/US2006/048825 WO2007075909A1 (en) | 2005-12-21 | 2006-12-21 | Elastic methacrylate compositions |
CN200680052563.9A CN101365731B (en) | 2005-12-21 | 2006-12-21 | Elastic methacrylate compositions |
EP06847929A EP1979388B1 (en) | 2005-12-21 | 2006-12-21 | Elastic methacrylate compositions |
JP2008547555A JP5343563B2 (en) | 2005-12-21 | 2006-12-21 | Elastic methacrylate composition |
ES10191458.8T ES2471465T3 (en) | 2005-12-21 | 2006-12-21 | Elastic Methacrylate Compositions |
ES06847929T ES2389090T3 (en) | 2005-12-21 | 2006-12-21 | Elastic Methacrylate Compositions |
DK06847929.4T DK1979388T3 (en) | 2005-12-21 | 2006-12-21 | ELASTIC METHACRYLATE COMPOSITIONS |
AU2006331622A AU2006331622B2 (en) | 2005-12-21 | 2006-12-21 | Elastic methacrylate compositions |
CA2633719A CA2633719C (en) | 2005-12-21 | 2006-12-21 | Elastic methacrylate compositions |
US13/904,161 US9133373B2 (en) | 2005-12-21 | 2013-05-29 | Elastic methacrylate compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US75271305P | 2005-12-21 | 2005-12-21 | |
US11/642,489 US20070155899A1 (en) | 2005-12-21 | 2006-12-20 | Elastic methacrylate compositions |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/904,161 Continuation US9133373B2 (en) | 2005-12-21 | 2013-05-29 | Elastic methacrylate compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070155899A1 true US20070155899A1 (en) | 2007-07-05 |
Family
ID=37944885
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/642,489 Abandoned US20070155899A1 (en) | 2005-12-21 | 2006-12-20 | Elastic methacrylate compositions |
US13/904,161 Expired - Fee Related US9133373B2 (en) | 2005-12-21 | 2013-05-29 | Elastic methacrylate compositions |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/904,161 Expired - Fee Related US9133373B2 (en) | 2005-12-21 | 2013-05-29 | Elastic methacrylate compositions |
Country Status (9)
Country | Link |
---|---|
US (2) | US20070155899A1 (en) |
EP (2) | EP1979388B1 (en) |
JP (1) | JP5343563B2 (en) |
CN (1) | CN101365731B (en) |
AU (1) | AU2006331622B2 (en) |
CA (1) | CA2633719C (en) |
DK (2) | DK1979388T3 (en) |
ES (2) | ES2471465T3 (en) |
WO (1) | WO2007075909A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110083804A1 (en) * | 2008-03-21 | 2011-04-14 | Jacret | Composition for structural adhesive |
WO2012134735A1 (en) * | 2011-03-25 | 2012-10-04 | Huntsman Advanced Materials Americas Llc | Peroxide-free methacrylate structural adhesives |
US9045672B2 (en) | 2011-05-03 | 2015-06-02 | Dow GlobalTechnologies LLC | Dual cure adhesive useful for bonding to glass |
US9296932B2 (en) | 2011-05-03 | 2016-03-29 | Dow Global Technologies Llc | Accelerated cure composition containing an isocyanate functional prepolymer |
US9416301B2 (en) | 2012-11-08 | 2016-08-16 | Dow Global Technologies Llc | Ultrafast dual cure adhesive useful for bonding to glass |
US20210198525A1 (en) * | 2018-09-17 | 2021-07-01 | Henkel Ag & Co. Kgaa | Two-Part Adhesive Composition |
EP3921566A4 (en) * | 2019-02-07 | 2022-11-02 | IPS Corporation | Gasketed pipe joint formed in place and method of making same |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2910908B1 (en) * | 2006-12-27 | 2010-08-20 | Jacret | COMPOSITION FOR STRUCTURAL ADHESIVE |
WO2008080913A1 (en) * | 2006-12-27 | 2008-07-10 | Jacret | Composition for structural adhesive |
US9676922B2 (en) | 2014-06-11 | 2017-06-13 | IPS, Corporation—Weld-On Division | Heat and moisture resistant acrylic adhesive composition |
US10487969B2 (en) | 2014-09-26 | 2019-11-26 | Ips, Corporation-Weld-On Division | Pipe fitting apparatus and methods |
US10392532B2 (en) | 2015-10-07 | 2019-08-27 | Illinois Tool Works, Inc. | Adhesive compositions with repair-rework ability |
TW201816024A (en) * | 2016-05-09 | 2018-05-01 | 漢高智慧財產控股公司 | Adhesive compositions containing reactive silsesquioxanes |
US10913876B2 (en) | 2016-05-27 | 2021-02-09 | Ips Corporation | Polyurea-poly(meth)acrylate interpenetrating polymer network adhesive compositions and methods of using the same |
KR102176356B1 (en) * | 2018-12-20 | 2020-11-09 | 주식회사 오아시스 | Sealing tape composition and product comprisign the same |
CN114213778B (en) * | 2021-11-30 | 2024-03-19 | 上海金发科技发展有限公司 | High-impact high-gloss HIPS material and preparation method and application thereof |
Citations (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268593A (en) * | 1961-06-26 | 1966-08-23 | Cumberland Chemical Corp | Ethylene oxide adducts of tertiary acetylenic alcohols |
US3890407A (en) * | 1972-07-20 | 1975-06-17 | Du Pont | Novel adhesive compositions |
US4041103A (en) * | 1976-06-07 | 1977-08-09 | Shell Oil Company | Blends of certain hydrogenated block copolymers |
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 |
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 |
US4451615A (en) * | 1980-05-09 | 1984-05-29 | Loctite (Ireland) Limited | Polyisoprene toughened adhesive composition |
US4507429A (en) * | 1984-01-12 | 1985-03-26 | Air Products And Chemicals, Inc. | Pressure sensitive adhesives with improved shear resistance |
US4536546A (en) * | 1983-09-22 | 1985-08-20 | Illinois Tool Works Inc. | (Meth)acrylate-based compositions |
US4574142A (en) * | 1980-07-11 | 1986-03-04 | Loctite (Ireland) Ltd. | Curable adhesive composition toughened with styrene-butadiene block copolymer rubbers |
US4645810A (en) * | 1984-08-23 | 1987-02-24 | Usm Corporation | Adhesive bonding |
US4650543A (en) * | 1984-03-02 | 1987-03-17 | Kabushiki Kaisha Toshiba | Method of forming electrode pattern of semiconductor device |
US4714730A (en) * | 1986-06-04 | 1987-12-22 | Illinois Tool Works Inc. | Acid modified adhesive compositions |
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 |
US5059656A (en) * | 1988-12-29 | 1991-10-22 | National Starch And Chemical Investment Holding Corporation | Two-solution 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 |
US6291593B1 (en) * | 1998-12-03 | 2001-09-18 | Loctite Corporation | Adhesive compositions with retarding additive |
US6433091B1 (en) * | 2001-05-10 | 2002-08-13 | Henkel Loctite Corporation | Adhesive composition |
US6512043B2 (en) * | 2000-05-10 | 2003-01-28 | Illinois Tool Works Inc. | Two-part structural adhesive having long working time |
US6559257B2 (en) * | 1998-06-12 | 2003-05-06 | Lord Corporation | Adhesive formulations |
US6635352B2 (en) * | 2001-04-24 | 2003-10-21 | Hoya Corporation | Coating composition, process for producing optical element using the same, and optical element produced thereby |
US20040118514A1 (en) * | 2002-12-19 | 2004-06-24 | Gosiewski Donald E. | Heat resistant, impact resistant, acrylic/epoxy adhesives |
US20050004303A1 (en) * | 2002-01-07 | 2005-01-06 | Takeshi Miyakawa | Electroconductive resin composition |
US6989416B2 (en) * | 2002-05-07 | 2006-01-24 | Sika Technology Ag | Methacrylate structural adhesive |
US20080153971A1 (en) * | 2006-12-21 | 2008-06-26 | Kraton Polymers U.S. Llc | Solvent sprayable contact adhesive formulations from (S-I/B)x polymers |
US20110281045A1 (en) * | 2010-05-11 | 2011-11-17 | Bostick S.A. | HMPSA for debondable self-adhesive label |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2044861C (en) * | 1990-07-05 | 2000-11-14 | Donald E. Gosiewski | Adhesive for low temperature applications |
CA2136882A1 (en) * | 1993-12-20 | 1995-06-21 | William J. Catena | Structural acrylic adhesives |
US6232391B1 (en) * | 1998-12-23 | 2001-05-15 | National Starch And Chemical Investment Holding Corporation | Multipurpose hot melt adhesive |
WO2000077109A2 (en) * | 1999-06-10 | 2000-12-21 | Lord Corporation | Adhesive formulations |
US20050014901A1 (en) * | 2001-07-10 | 2005-01-20 | Ips Corporation | Adhesive compositions for bonding and filling large assemblies |
-
2006
- 2006-12-20 US US11/642,489 patent/US20070155899A1/en not_active Abandoned
- 2006-12-21 DK DK06847929.4T patent/DK1979388T3/en active
- 2006-12-21 CA CA2633719A patent/CA2633719C/en not_active Expired - Fee Related
- 2006-12-21 ES ES10191458.8T patent/ES2471465T3/en active Active
- 2006-12-21 CN CN200680052563.9A patent/CN101365731B/en not_active Expired - Fee Related
- 2006-12-21 EP EP06847929A patent/EP1979388B1/en not_active Not-in-force
- 2006-12-21 JP JP2008547555A patent/JP5343563B2/en not_active Expired - Fee Related
- 2006-12-21 DK DK10191458.8T patent/DK2289957T3/en active
- 2006-12-21 ES ES06847929T patent/ES2389090T3/en active Active
- 2006-12-21 EP EP10191458.8A patent/EP2289957B1/en not_active Not-in-force
- 2006-12-21 AU AU2006331622A patent/AU2006331622B2/en not_active Ceased
- 2006-12-21 WO PCT/US2006/048825 patent/WO2007075909A1/en active Application Filing
-
2013
- 2013-05-29 US US13/904,161 patent/US9133373B2/en not_active Expired - Fee Related
Patent Citations (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3268593A (en) * | 1961-06-26 | 1966-08-23 | Cumberland Chemical Corp | Ethylene oxide adducts of tertiary acetylenic alcohols |
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 |
US4451615A (en) * | 1980-05-09 | 1984-05-29 | Loctite (Ireland) Limited | Polyisoprene toughened adhesive composition |
US4574142A (en) * | 1980-07-11 | 1986-03-04 | Loctite (Ireland) Ltd. | Curable adhesive composition toughened with styrene-butadiene block copolymer rubbers |
US4536546A (en) * | 1983-09-22 | 1985-08-20 | Illinois Tool Works Inc. | (Meth)acrylate-based compositions |
US4507429A (en) * | 1984-01-12 | 1985-03-26 | Air Products And Chemicals, Inc. | Pressure sensitive adhesives with improved shear resistance |
US4650543A (en) * | 1984-03-02 | 1987-03-17 | Kabushiki Kaisha Toshiba | Method of forming electrode pattern of semiconductor device |
US4645810A (en) * | 1984-08-23 | 1987-02-24 | Usm Corporation | Adhesive bonding |
US4714730A (en) * | 1986-06-04 | 1987-12-22 | Illinois Tool Works Inc. | Acid modified adhesive compositions |
US4942201A (en) * | 1988-08-29 | 1990-07-17 | Illinois Tool Works, Inc. | Adhesive for low temperature applications |
US5206288A (en) * | 1988-08-29 | 1993-04-27 | Illinois Tool Works, Inc. | Adhesive for low temperature applications |
US5026609A (en) * | 1988-09-15 | 1991-06-25 | Owens-Corning Fiberglas Corporation | Road repair membrane |
US5059656A (en) * | 1988-12-29 | 1991-10-22 | National Starch And Chemical Investment Holding Corporation | Two-solution 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 |
US6559257B2 (en) * | 1998-06-12 | 2003-05-06 | Lord Corporation | Adhesive formulations |
US6291593B1 (en) * | 1998-12-03 | 2001-09-18 | Loctite Corporation | Adhesive compositions with retarding additive |
US6512043B2 (en) * | 2000-05-10 | 2003-01-28 | Illinois Tool Works Inc. | Two-part structural adhesive having long working time |
US6635352B2 (en) * | 2001-04-24 | 2003-10-21 | Hoya Corporation | Coating composition, process for producing optical element using the same, and optical element produced thereby |
US6433091B1 (en) * | 2001-05-10 | 2002-08-13 | Henkel Loctite Corporation | Adhesive composition |
US20050004303A1 (en) * | 2002-01-07 | 2005-01-06 | Takeshi Miyakawa | Electroconductive resin composition |
US6989416B2 (en) * | 2002-05-07 | 2006-01-24 | Sika Technology Ag | Methacrylate structural adhesive |
US20040118514A1 (en) * | 2002-12-19 | 2004-06-24 | Gosiewski Donald E. | Heat resistant, impact resistant, acrylic/epoxy adhesives |
US20080153971A1 (en) * | 2006-12-21 | 2008-06-26 | Kraton Polymers U.S. Llc | Solvent sprayable contact adhesive formulations from (S-I/B)x polymers |
US20110281045A1 (en) * | 2010-05-11 | 2011-11-17 | Bostick S.A. | HMPSA for debondable self-adhesive label |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110083804A1 (en) * | 2008-03-21 | 2011-04-14 | Jacret | Composition for structural adhesive |
US8480844B2 (en) * | 2008-03-21 | 2013-07-09 | Jacret | Composition for structural adhesive |
US9732255B2 (en) | 2008-03-21 | 2017-08-15 | Jacret | Composition for structural adhesive |
US10000673B2 (en) | 2008-03-21 | 2018-06-19 | Jacret | Composition for structural adhesive |
WO2012134735A1 (en) * | 2011-03-25 | 2012-10-04 | Huntsman Advanced Materials Americas Llc | Peroxide-free methacrylate structural adhesives |
US9045672B2 (en) | 2011-05-03 | 2015-06-02 | Dow GlobalTechnologies LLC | Dual cure adhesive useful for bonding to glass |
US9296932B2 (en) | 2011-05-03 | 2016-03-29 | Dow Global Technologies Llc | Accelerated cure composition containing an isocyanate functional prepolymer |
US9416301B2 (en) | 2012-11-08 | 2016-08-16 | Dow Global Technologies Llc | Ultrafast dual cure adhesive useful for bonding to glass |
US20210198525A1 (en) * | 2018-09-17 | 2021-07-01 | Henkel Ag & Co. Kgaa | Two-Part Adhesive Composition |
EP3921566A4 (en) * | 2019-02-07 | 2022-11-02 | IPS Corporation | Gasketed pipe joint formed in place and method of making same |
Also Published As
Publication number | Publication date |
---|---|
CN101365731B (en) | 2015-06-17 |
ES2389090T3 (en) | 2012-10-23 |
JP5343563B2 (en) | 2013-11-13 |
EP1979388A1 (en) | 2008-10-15 |
EP1979388B1 (en) | 2012-08-01 |
US9133373B2 (en) | 2015-09-15 |
DK2289957T3 (en) | 2015-01-19 |
WO2007075909A1 (en) | 2007-07-05 |
EP2289957A1 (en) | 2011-03-02 |
CN101365731A (en) | 2009-02-11 |
CA2633719C (en) | 2013-09-10 |
JP2009521573A (en) | 2009-06-04 |
AU2006331622A1 (en) | 2007-07-05 |
EP2289957B1 (en) | 2014-05-14 |
DK1979388T3 (en) | 2012-08-27 |
ES2471465T3 (en) | 2014-06-26 |
US20130261247A1 (en) | 2013-10-03 |
AU2006331622B2 (en) | 2013-03-07 |
CA2633719A1 (en) | 2007-07-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9133373B2 (en) | Elastic methacrylate compositions | |
US6433091B1 (en) | Adhesive composition | |
US9676922B2 (en) | Heat and moisture resistant acrylic adhesive composition | |
JPH0233749B2 (en) | ||
JP5193461B2 (en) | Adhesive composition | |
US8519023B2 (en) | Fast,curing two part anaerobic adhesive composition | |
JP6684800B2 (en) | Composition | |
JPH1060381A (en) | Primer composition for anaerobic acrylic adhesive | |
JP6579613B2 (en) | Composition | |
JP6681898B2 (en) | Composition and adhesive composition | |
US4496694A (en) | Process for producing a storage-stable, miscible curing agent for acrylate resin adhesives | |
US4625008A (en) | Adhesives which contain acrylic acid derivatives of 5,6-dihydro-dicyclopentadienol | |
JP6579610B2 (en) | Composition | |
JPS621772A (en) | Adhesive composition | |
JP6579611B2 (en) | Composition | |
JP6579612B2 (en) | Composition | |
JPS62265314A (en) | Anaerobically curable composition | |
US20230323165A1 (en) | High-strength acrylic adhesives incorporating polyvinyl butyral | |
US20210301183A1 (en) | Low surface energy accelerated bonding adhesive formulation and process for the use thereof | |
JP2018119118A (en) | Composition | |
JPH0222373A (en) | Acrylic adhesive composition | |
JP2017031263A (en) | Composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: IPS CORPORATION, CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BRIGGS, PAUL C.;OSAE, SAMUEL B.;REEL/FRAME:019049/0651 Effective date: 20070321 |
|
AS | Assignment |
Owner name: GENERAL ELECTRIC CAPITAL CORPORATION, AS ADMINISTR Free format text: SECURITY AGREEMENT;ASSIGNOR:IPS CORPORATION;REEL/FRAME:028810/0727 Effective date: 20120817 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: GENERAL ELECTRIC CAPITAL CORPORATION, AS ADMINISTR Free format text: SECURITY AGREEMENT;ASSIGNOR:IPS CORPORATION;REEL/FRAME:031768/0633 Effective date: 20131206 |
|
AS | Assignment |
Owner name: IPS CORPORATION, CALIFORNIA Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GENERAL ELECTRIC CAPITAL CORPORATION, AS ADMINISTRATIVE AGENT;REEL/FRAME:034960/0294 Effective date: 20150206 |