Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0014—Use of organic additives
  • C08J9/0023—Use of organic additives containing oxygen
• • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • 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
  • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
  • C08L5/16—Cyclodextrin; Derivatives thereof

Definitions

• This invention relates to adhesives and sealants and, more particularly, to a process for improving the adhesion of adhesives and sealants as well as an adhesive and sealant composition which displays improved adhesion.
• the invention has been found to be especially useful for expanded adhesives and sealants which traditionally employed a blowing agent.
• Blowing agents are substances that produce a cellular structure " in a fluidized plastic or rubber composition.
• Conventional blowing agents include fluorocarbons, nitrogen gas, hydrazine derivatives, trihydrazide triazine, 5-phenyl tetrazole, p-toluene sulfonyl ⁇ emicarbazide, modified azodicarbonamide, and azodicarbonamide.
• Chemical blowing ⁇ agents are a class of blowing agents which are solids or liquids at room temperature and, upon heating, release a gas.
• a well-known class of chemical blowing agents is sold under the trademark CELOGEN by Uniroyal, Inc.
• Blowing agents are used in making a variety of 0 consumer products and automotive sealants. Further, blowing agents are used with adhesive plastic materials in a hot melt adhesive. Blowing agents are also used in foodstuff wrapping which is applied to the exterior of animal parts after they have been butchered and prior 5 to wholesale. Such product is referred to by some as "bone wrap".
• chemical blowing agents are used by mixing the chemical blowing agent with a solid plastic material and then heating the admixture while maintaining 0 the mix under pressure. Heating fluidizes the plastic material and causes the blowing agents to release a gas. The gas forms bubbles or cells in the fluid plastic materia .
• Chemical blowingagents have the advantage over gaseous blowing agents in that they can be added to the solid plastic material prior to heating. Gaseous blowing agents such as nitrogen and some fluorocarbons must be injected into the fluidized plastic material. With hot melt adhesives and sealants, a gas is mixed with the adhesive composition prior to the end of the nozzle.
• the process according to the present invention comprises admixing a cyclodextrin with an adhesive or sealant plastic material and then applying the admixture to a surface.
• the process comprises the steps of forming an admixture comprising an adhesive and/or sealant plastic material and a complex of a blowing agent and a cyclodextrin and heating the admixture so as to fluidize the plastic material and cause the complex to release a gas.
• the gas forms cells in the fluidized plastic material.
• a step of forming a complex between the cyclodextrin and the blowing agent is accomplished prior to the step of mixing the complex with the plastic material.
• the step of heating the admixture is accomplished either by applying heat to the admixture as is typically the case in conventional extrusion or blow molding processes, or through an exothermic reaction, such as is normally the case with a polyurethane.
• An adhesive and/or sealant composition made in accordance with the present invention comprises an adhesive and/or sealant plastic material and a complex of a blowing agent and a cyclodextrin.
• a blowing agent e.g., a blowing agent for a blowing agent for a blowing agent for a blowing agent for a blowing agent for a blowing agent for a blowing agent for a blowing agent for a blowing agent.
• the amount of cyclodextrin added to the adhesive and/or sealant plastic material is an effective amount to improve the adhesion of the adhesive and/or sealant.
• the amount of cyclodextrin added to the adhesive and/or ' sealant plastic material to improve its adhesion is about 1 to about 30 parts by weight based on 100 parts of adhesive and/or sealant plastic material (php). More preferably, about 1 to about 15 php of cyclodextrin is added to the adhesive and/or sealant plastic material to improve its adhesion. Most preferred, is to add about 1 to about 10 php of cyclodextrin to the adhesive and/or sealant plastic material to improve the adhesion.
• the amounts listed herein are also the amount of complex of cyclodextrin and blowing agent which is added to the adhesive and/or sealant plastic material in accordance with the present invention.
• the amount of complex of cyclodextrin and blowing agent which is added to the adhesive and/or sealant plastic material in accordance with the present invention.
• any conventional mixing procedure normally employed with the adhesive and/or sealant materials is any conventional mixing procedure normally employed with the adhesive and/or sealant materials.
• Cyclodextrins also called “Schardingers dextrins", cycloamyloses, cyclomaltoses and cycloglucans, are oligomers of anhydroglucose, bonded together by alpha 1,4 bonds to form a ringed compound.
• a six membered ring is called alpha cyclodextrin; seven, beta cyclodextrin, and eight, gamma cyclodextrin. These six, seven and eight membered rings are also referred to as cyclomaltohexaose, cyclomaltoheptaose and cyclomaltoctaose, respectively.
• cyclodextrins are obtained by treating a starch slurry with enzyme or acid to produce a gelatinized and liquefied slurry having a DE between 1 and 5.
• the gelatinized and liquefied starch slurry is then treated with cyclodextrin glycosyltransferase (CGT), at the appropriate pH, temperature and time for the selected CGT.
• CGT cyclodextrin glycosyltransferase
• the enzyme, CGT is obtained from microorganisms such as Bacillus macerans, B. magaterium, B. circulans, B. stearothermophilus, and Bacillus sp. (alkalophilic) as well as others.
• the resulting digest from treatment of a gelatinized and liquefied starch slurry with CGT is then subjected to a separation and purification process to obtain cyclodextrins.
• cyclodextrins are their ability to act as a clathrate or host to other commercial compounds. Physically a cyclodextrin is donut-shaped. The consequence of this is that cyclodextrins are able to act as a clathrate with substances that have outer geometric dimensions corresponding to the diameter of the cyclodextrin cavity. Often the exterior is modified by adding a side chain such as hydroxy-propyl cyclodextrin onto the donut-shaped exterior of the cyclodextrin.
• cyclodextrin as used in the specification and claims means not only cyclodextrin per se but also modified cyclodextrins and branched cyclodextrins.
• complex or the expression "complex of cyclodextrin and blowing agent” as used in the specification and claims means not only a composition of cyclodextrin and blowing agent where the cyclodextrin acts as a host to the blowing agent but also where the blowing agent is closely associated with the exterior of the cyclodextrin by weak bonding forces.
• a method for formation of a complex between a cyclodextrin and a blowing agent involves dissolving the cyclodextrin in water with a blowing agent and collecting the precipitate that forms.
• Another method is by charging a ball mill with a cyclodextrin and a blowing agent and milling the charge in the ball mill for a period of time. After milling, a complex will form between the cyclodextrin and the blowing agent.
• Other known methods for forming a complex between a cyclodextrin and a guest molecule include kneading, freeze-drying and co-grinding. Good results have been obtained by co-grinding using a mortar and pestle.
• the cyclodextrins used in the present invention are alpha, beta or gamma cyclodextrin. Beta cyclodextrin is preferred because of its commercial availability.
• a complex made from a combination of all three cyclodextrins provides different rates of release of the blowing agent. This is thought to be due in part to the different bond strengths between the blowing agent and the different cyclodextrins.
• Suitable blowing agents include liquids such as water, propylene glycol, dipropylene glycol, tripropylene glycol, cyclohexyl amine, dicyclohexyl amine and ethylene glycol and solids such as benzoyl peroxide and other peroxides which are difficult to process. It is both surprising and unexpected that water, propylene glycol, dipropylene glycol, tripropylene glycol, and ethylene glycol are useful as blowing agents. Heretofore, water, propylene glycol, dipropylene glycol, tripropylene glycol, and ethylene glycol were not used as blowing agents due to their poor dispersion in plastic materials.
• blowing agents such as hydrazine derivatives, trihydrazide triazine, 5-phenyl tetrazole, p-toluene sulfonyl semicarbazide, modified azodicarbonamide, and azodicarbonamide which form a complex with cyclodextrin may be used as a blowing agent in accordance with the present invention.
• Conventional blowing agents complexed with cyclodextrin reduce dusting and stabilize the composition.
• the amount of blowing agent that is complexed with the cyclodextrin is about 1 to about 30 parts by weight based on 100 parts by weight cyclodextrin (phc). More preferably about 3 to 15 phc is complexed. Most preferred is to complex between about 5 to about 7 phc of the blowing agent with the cyclodextrin.
• an excess amount of blowing agent is used to form the complex.
• a suitable source of the complex of cyclodextrin and water has been found to be the cyclodextrin as taken from a commercial operation for making cyclodextrin.
• the cyclodextrin obtained from a commercial process generally has about 10 to about 12 phc water.
• Using this cyclodextrin in an adhesive composition has been found to provide adequate gas upon heating such that the commercially obtained cyclodextrin, which is complexed with about 10 to about 12 phc water, works as a blowing agent.
• Suitable plastic materials include polymers such as polystyrene, polyvinyl chloride, polyethylene, polyurethane, polyphenol ⁇ , polypropylene, polyisoprene (rubber), polybutadiene as well as copolymers such as acrylonitrile-butadiene-styrene, styrene-isoprene, ethylene-butylene, styrene-butadiene rubber and ethylene vinyl acetate.
• Specific examples of adhesive plastic materials include ethylene vinyl acetate (EVA), acrylanitrile-butadiene- styrene and styrene-isoprene. Good results have been obtained using the complex of the present invention with EVA.
• a typical adhesive made in accordance with the present invention comprises:
• a bookbinding adhesive made in accordance with the present invention comprises:
• Antioxidant 0.05-0.25 php Blowing Agent-Cyclodextrin Complex 1-10 php Mildewcide (optional) 1-10 php
• the blowing agent-cyclodextrin complex is a water-cyclodextrin complex and has between about 8 and about 15 phc water. More preferably the amount of complex used in the bookbinding adhesive is between about 3 and about 7 phc and has a water content of about 10 to about 15 phc.
• a microbial or fungicide complexed with a cyclodextrin helps prevent degradation. Water will act as the blowing agent and will aid in the release of the microbial or f ngicide.
• the bookbinding adhesive is made by mixing all the components together in a conventional manner. Such adhesives have an application temperature around 120 to about 205°C.
• a carton and case sealing adhesive is made in accordance with the present invention comprising:
• the blowing agent-cyclodextrin complex is a propylene glycol-cyclodextrin complex and has between about 8 and about 15 phc of propylene glycol.
• Preferably about 3 to about 7 php of the complex is used having propylene glycol content of about 10 to about 13 phc.
• the carton and case sealing adhesive is made by mixing all the components together in a conventional manner.
• Such carton and case sealing adhesive has an application temperature between about 175 to about 205°C.
• a carpet backing adhesive made in accordance with the present invention comprises:
• blowing agent-cyclodextrin complex used in this carpet backing adhesive is a complex of cyclodextrin with about 8 to about 15 phc of either water, propylene glycol or a combination of water and propylene glycol or a combination of water, propylene gylcol and hydrazine derivatives.
• such a carpet backing adhesive preferably contains a complex of cyclodextrin and mildewcide in an amount up to about 1 php.
• Suitable mildewcides include diiodomethyl-p-tolysulfone, phenols and butylhydroxytoluene; diidomethyl-p-tolysulfone is preferred, the release of which would be triggered by water released by the cyclodextrin.
• the carpet backing adhesive is made by mixing all the components together in a conventional manner.
• the application temperature of this carpet backing adhesive is between about 300 to 350°F.
• EXAMPLE 1 This example illustrates a hot melt adhesive in accordance with the present invention and specifically, a bookbinding adhesive.
• EVA-507 was a commercial grade of a copolymer of ethylene-vinyl acetate obtained from Union Carbide Corp.
• Staybelite resin was a hydrogenated resin and plasticizer consisting of diethylene glycol esters of hydrogenated resins obtained from Hercules Powder Co.
• Pentalyn H was a synthetic resin obtained from Hercules Powder Co.
• Microcrystalline wax was a commercially available wax obtained from Petrolite Corp. of Tulsa, Oklahoma.
• the antioxidant was Irganox 1010 obtained from Ciba-Geigy Corp.
• the beta cyclodextrin was a commercial grade beta cyclodextrin obtained from American Maize-Products Company of Hammond, Indiana.
• the water was regular tap water. It is surprising and unexpected that a complex of cyclodextrin and water worked in this formulation because water, by itself, did not work as a blowing agent in the bookbinding adhesive.
• EXAMPLE 2 This example illustrates making a carton and case adhesive in accordance with the present invention.
• the following adhesive composition was made: Material Parts by Weight
• a complex of propylene glycol-beta cyclodextrin was mixed.
• the complex contained 1 mole of beta cyclodextrin and 2 moles of propylene glycol.
• the complex of propylene glycol and beta cyclodextrin was made by mixing an excess of propylene glycol with the beta cyclodextrin.
• EVA-305 was a commercial grade of a copolymer of ethylene-vinyl acetate obtained from Union Carbide.
• CKM-2400 was obtained from Union Carbide.
• Piccolyte A-115 was a thermoplastic terpene resin obtained from Hercules.
• Super STATAC was obtained from Reichold Chemical Inc.
• Polywax 1000 was obtained from Bareco and Castor wax was obtained from Universal Preservachems.
• the antioxidant was Irganox 1010.
• the beta cyclodextrin was a commercial grade beta cyclodextrin obtained from American Maize-Products Company of Hammond, Indiana.
• the propylene glycol was a commercial grade obtained from Dow Chemical.
• EXAMPLE 3 This example illustrates making a carpet backing adhesive in accordance with the present invention.
• the following adhesive composition was made: Material . Parts by Weight
• 0.1 php of an antioxidant, about 20 php of a filler, and 5 php of a complex of water and beta cyclodextrin are added along with 5 parts of a complex of propylene glycol-beta cyclodextrin.
• the complexes of blowing agent and cyclodextrin are made in accordance with Examples 1 and 2 above.
• the complexes of blowing agent and cyclodextrin are both mixed with the adhesive composition simultaneously in a manner according to Examples 1 and 2 above. Upon heating the admixture of adhesive composition and both blowing agents to about 195°C the adhesive admixture expands.
• the EVA is a commercial grade of a copolymer of ethylene-vinyl acetate.
• the modified resins are commercial grades of wood rosin.
• the waxes are commercial grades of waxes used conventionally in carpet backing adhesives.
• the antioxidant is Irgonox 1010 and the fillers are conventional calcium carbonate.
• This example illustrates making a pressure sensitive adhesive in accordance with the present invention.
• the following adhesive composition was made: Material Parts by Weight EVA 501 15
• Total Plastic Adhesive 100 To the adhesive materials, 0.1 php of an antioxidant, Irganox 1010, 5 php of a complex of water and beta cyclodextrin and 5 php of cyclohexylamine and beta cyclodextrin were added. The water and beta cyclodextrin complex had 12.8 phc water. The complex of beta cyclodextrin and cyclohexylamine, volatile corrosion inhibitor, had 8 phc cyclohexylamine complexed with cyclodextrin. Making the complex and mixing ' of the adhesive composition was done in accordance with Example 1.
• the released moisture provided a "trigger" mechanism whereby the complexed cyclohexylamine was partially released so as to be in equilibrium with the released moisture from the water-cyclodextrin complex.
• a mechanism provided corrosion protection to metallic surfaces.
• the complex of cyclodextrin and cyclohexylamine stabilizes the cyclohexylamine during the heating process. Uncomplexed cyclohexylamine is not stable during the heating of the adhesive.
• the EVA 501 and 605 were a commercial grade of a copolymer of ethylene-vinyl acetate obtained from Union Carbide.
• the Staybelite Ester 10 and the Abitol were obtained from Hercules.
• the application temperature of the adhesive was about 300°F to 325°F.
• Beta cyclodextrin:dicyclohexylamine complex (2:1 molar ratio) 2 Aluminum paste (50:50 aluminum in
• Equal amounts of the hot melt base and plasticizer were mixed and allowed to cool and then placed on a cold rolled steel sheet or galvanized cold rolled steel sheet.
• the sheets were placed in an oven and heated at 200°C for 15 minutes.
• the material expanded on the plate in both a vertical and horizontal plane such that the mix about doubled in volume.
• Example 5 A mix of 50 parts hot melt base from Example 5 above was mixed with 50 parts over-based calcium sulfonate. The over-based calcium sulfonate was heated to evaporate water from it prior to mixing it with the hot melt base. The mixture was placed on a cold rolled steel plate and a cold rolled galvanized steel plate and heated in an oven at 200°C for 15 minutes. The mix upon heating melted and spread out over the plates without expanding.
• Adhesion Comparison Examples 5 and 6 The material made in accordance with Example 6 was tested for adhesion to cold rolled and galvanized steel plates against the material made in accordance with Example 5 above. The cured material of Example 5 above adhered much more strongly to the cold rolled and galvanized steel plates than the material of Example 6. It was found that the material of Example 6 was able to be easily peeled from the plates while the material made in accordance with Example 5 above (the present invention) did not easily peel.
• EXAMPLE 7 The material made in accordance with Example 6 was tested for adhesion to cold rolled
• a mix was made the same as Example 6 above, except that water was not removed from the over-based calcium sulfonate before mixing and placing it on the cold rolled steel plate and cold rolled galvanized steel plate in the oven at 200°C.
• the mix in this example simply hardened in place. Curing was accelerated due to the water release as evidenced by the lack of flowing or deformation of the material placed on the sheets.
• EXAMPLE 8 A mix was made the same as Example 5 above, except that the mixture was not allowed to cool. The mix was placed on a cold rolled steel sheet and a cold rolled galvanized steel sheet and then placed in the oven at 200°C. This material expanded to about double in volume.
• the blowing agent water
• a conventional sealant was made from:
• This material was mixed and placed on cold rolled steel and cold rolled galvanized steel sheets and placed in an oven at 200°C for 15 minutes. This material melted and spread out on the plate.
• This example uses Formula A to make a sealant in accordance with the present invention.
• Example 10 The sealant of Example 10 was also tested for relative adhesion between cold rolled steel and galvanized steel. It was- found that the sealant of Example 10 adhered better to a cold rolled steel plate than to a galvanized steel plate. — IB —
• This example illustrates using another chemical blowing agent complexed with the cyclodextrin.
• Example 11 (present invention) adhered to the steel plate better than the sealant of Example 9.
• the sealant of Example 11 was also tested for relative adhesion between cold rolled steel and galvanized steel.
• composition Amount a complex of beta cyclodextrin and benzoyl peroxide as both a blowing agent and a curing agent for a thermoplastic.
• the benzoyl peroxide was stabilized during mixing. It was also difficult to obtain a uniform distribution of the uncomplexed benzoyl peroxide during mixing...
• the beta c clodextrin-benzoyl peroxide complex was easily mixed and uniformly distributed during mixing of the composition.
• composition D containing uncomplexed benzoyl peroxide cured very rapidly and did not spread out laterally to a great extent. Bubbles in the cured composition were not of uniform size and distribution.
• composition A containing the beta cyclodextrin complex of benzoyl peroxide also cured rapidly and did not spread out laterally to a great extent. Blowing and curing were occurring simultaneously. This composition had raised higher than sample D containing uncomplexed benzoyl peroxide. Bubbles in composition A were of uniform size and distribution.
• Composition C spread laterally more than any of the other compositions. Water released from the cyclodextrin formed bubbles of uniform size and distribution. The water released was acting as a traditional blowing agent but no curing agent was present to cure the composition to retard spreading. Composition B spread out laterally more than compositions A and D but not as much as Composition C. No curing agent was present which would retard spreading and no blowing agent was present which would increase spreading.
• Composition A containing the complex of benzoyl peroxide and beta cyclodextrin.
• the benzoyl peroxide was stabilized to be released upon heating to act both as a curing agent and a blowing agent.
• the complex was also easily mixed into and dispersed in the composition.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Emergency Medicine (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Sealing Material Composition (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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Citations (10)

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• 1992
  • 1992-09-21 NZ NZ244424A patent/NZ244424A/en unknown
  • 1992-09-22 CZ CZ1994623A patent/CZ289633B6/cs not_active IP Right Cessation
  • 1992-09-22 HU HU9400824A patent/HUT68787A/hu unknown
  • 1992-09-22 CA CA002116458A patent/CA2116458C/en not_active Expired - Fee Related
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  • 1992-09-22 BR BR9206524A patent/BR9206524A/pt not_active IP Right Cessation
  • 1992-09-22 KR KR1019940700908A patent/KR0137426B1/ko not_active IP Right Cessation
  • 1992-09-22 JP JP5506344A patent/JP2743035B2/ja not_active Expired - Fee Related
  • 1992-09-22 EP EP92921024A patent/EP0613486A4/de not_active Withdrawn
  • 1992-09-22 WO PCT/US1992/008075 patent/WO1993006162A1/en active IP Right Grant
  • 1992-09-23 PT PT100895A patent/PT100895B/pt active IP Right Grant
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  • 1992-09-24 AR AR92323246A patent/AR248039A1/es active
• 1994
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  • 1994-03-21 FI FI941312A patent/FI941312A/fi not_active Application Discontinuation

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