Patent Grant
7119144
This invention pertains to a composition which is particularly useful as an adhesive, as well as a method of making an adhesive composition, and a method of using an adhesive composition.
Acrylate, methacrylate, and other unsaturated monomers, such as isocyanates, are widely used in coatings, adhesives, sealants and elastomers. These unsaturated monomers are typically low molecular weight multifunctional compounds, which may be volatile or readily absorbed through skin, and can cause adverse health effects. The toxicity of materials like aromatic isocyanates is particularly problematic when used in applications causing concerns for their potential migration into food. Another issue associated with using these compounds is that they require the handler of products containing them to avoid their contact with moisture during handling, such as manufacture, storage and use. Functionalized polymers, which are generally nonvolatile compounds that are not readily absorbed through the skin, may overcome these drawbacks. However, multi-step syntheses may be required, and many of the properties that can be achieved using low molecular weight materials, such as low viscosity, are lost. Therefore the coatings, adhesives, sealants and elastomers industries are continually in need of new systems to manufacture their products which avoid the use of toxic raw materials such as isocyanates, without losing the desirable properties associated with such low molecular weight raw materials.
For example, this has been addressed by U.S. Pat. No. 4,644,036, which discloses a curing component for synthetic resins. The curing component is the product of a Michael addition reaction of a mono- or di-carboxylic acid ester, with a compound selected from the group consisting of polyacrylates, bisacrylamides and urea derivatives, in the presence of a catalyst such as an alkali metal hydroxide, alkali metal alcoholate, and basic amino compounds. Also disclosed is a self-curing synthetic resin on which is chemically bound the above-mentioned curing component. However, a two step process is required to render the synthetic resin useful as a lacquer. In the first step, the curing component (which must be resistant to hydrolysis) is prepared. In the second step, the synthetic resin is crosslinked by the curing component.
Others have been able to accomplish the use of a Michael addition reaction to produce a composition that can be crosslinked to produce a coating or adhesive. U.S. Pat. No. 5,945,489 discloses a liquid oligomeric composition which is the ungelled, uncrosslinked product of a Michael addition reaction of excess di/tri/tetra acrylate acceptor, and an acetoacetate donor, in the presence of an amine based catalyst. U.S. Pat. No. 5,945,410 discloses a method of making the composition of the '489 patent. However, the composition must have equivalent ratios of polyacrylate acceptor:acetoacetate donor of greater than 2:1 where acetoacetate functionality is greater than four, and must have residual pendant unsaturated acrylate groups. Also, to be useful as an adhesive or a coating, an additional step is required, in that the composition must be further crosslinked (cured) by ultraviolet light.
Applicants have found a single step process to produce a composition, particularly useful as an adhesive, without using volatile low molecular weight raw materials but while maintaining the desirable properties associated with such low molecular weight raw materials, by reacting an α,β-unsaturated multi-carboxylic acid ester with a compound (A) having a structural formula
in the presence of a non-amine based catalyst.
In a first aspect of the present invention there is provided a method of making a composition, comprising the step of reacting an α,β-unsaturated multi-carboxylic acid ester with a compound (A) having a structural formula:
wherein R is a polyester or polyesteramide; wherein RI is CH3, CH2CH3, CH2CH2CH3, or
wherein said reaction is carried out in the presence of at least one non-amine based catalyst; and wherein said composition has a reactive equivalent functionality ratio of α,β-unsaturated multi-carboxylic acid ester to compound (A) of 0.67:1 to 1.75:1.
In a second aspect of the present invention, there is provided a composition comprising a reaction product of an α,β-unsaturated multi-carboxylic acid ester and a compound (A) having a structural formula:
wherein R is a polyester or polyesteramide; wherein RI is CH3, CH2CH3, CH2CH2CH3, or
wherein said reaction is carried out in the presence of at least one non-amine based catalyst; and wherein said composition has a reactive equivalent functionality ratio of α,β-unsaturated multi-carboxylic acid ester to compound (A) of 0.67:1 to 1.75:1.
In a third aspect of the present invention, there is provided a method of adhering a material to a substrate, comprising the step of: applying to a substrate a mixture of an α,β-unsaturated multi-carboxylic acid ester and a compound (A) having the structural formula:
wherein R is a polyester or polyesteramide; wherein RI is CH3, CH2CH3, CH2CH2CH3, or
wherein said reaction is carried out in the presence of at least one non-amine based catalyst; and wherein said composition has a reactive equivalent functionality ratio of α,β-unsaturated multi-carboxylic acid ester to compound (A) of 0.67:1 to 1.75:1.
The method and composition of this invention involves the reaction of an α,β-unsaturated multi-carboxylic acid ester with a compound (A) having the structural formula:
wherein R is a polyester or polyesteramide; wherein RI is CH3, CH2CH3, CH2CH2CH3, or
and wherein said reaction is carried out in the presence of at least one non-amine based catalyst; to produce a composition which is particularly useful as an adhesive. The method produces a composition having a reactive equivalent ratio of α,β-unsaturated multi-carboxylic acid ester to acetoacetate terminated polyester or polyesteramide of 0.67:1 to 1.75:1, preferably 1:1 to 1.5:1, most preferably 1:1 to 1.25:1. At these equivalent ratios, less than one percent of the pendant unsaturated acrylate groups on the composition of the invention remain uncrosslinked at the end of the Michael addition reaction. If ratios above those described above are used, the resulting product is uncrosslinked, ungelled and has several pendant acrylate groups that can further undesirably crosslink by methods other than Michael addition, or adversely impact the performance of the adhesive. Preferably, the composition of the invention is substantially free of solvent. By “substantially free of solvent”, herein is meant that the composition contains at least 70% solids, preferably at least 95% solids.
The α,β-unsaturated multi-carboxylic acid ester serves as the curing (crosslinking) agent for compound (A) in the invention. Suitable α,β-unsaturated multi-carboxylic acid esters, which may be polyacrylates, are capable of undergoing a Michael addition reaction. By “polyacrylates”, herein is meant di/tri/tetra-acrylates that are based upon hydrocarbons, polyethers, polyesters, epoxides, polyurethanes, polyolefins, and acrylics, and that form homogeneous compatible solutions which do not phase separate upon standing or curing. Examples of suitable polyacrylates include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, cyclohexane dimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated cyclohexane dimethanol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, acrylated polyester oligomer, bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, acrylated aliphatic urethane oligomer, acrylated aromatic urethane oligomer, and the like, and mixtures thereof.
Non-amine based catalysts are used to catalyze the reaction in the invention. Preferably, the catalyst is a strong base. By “non-amine based catalyst” herein is meant, a catalyst which is not based on amine chemistry, and which is capable of causing curing of compound (A) at ambient (typically 20° C. to 25° C.) or supra ambient temperatures (typically 25° C. to 65° C.). Examples of suitable non-amine based catalysts include sodium alkoxides and potassium alkoxides such as sodium methoxide, sodium ethoxide, sodium proproxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide, quatenary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetraoctylammoniium hydroxide, sodium acetylacetonates and potassium acetylacetonates, such as sodium acetylacetonate, potassium acetylacetonate, and the like, and mixtures thereof.
Compound (A) may be an acetoacetate terminated polyester or polyesteramide. Preferably, the acetoacetate terminated polyester or polyesteramide used contributes to hydrogen bonding and/or polar interactions. The acetoacetate terminated polyester or polyesteramide contains multi-carboxylic acids, of which 5 to 80 mole percent may be at least one aromatic multi-carboxylic acid. The acetoacetate terminated polyester may be prepared by conventional means, which are readily available to those skilled in the art. For example, one may use a two step process where the first step involves condensing glycols selected from the group including diols and triols, with carboxylic acids selected from the group including di/tri-carboxylic acids, to produce a polyester terminated with hydroxyl radicals, and having a hydroxyl value of 50 to 225, and an acid value of 0.1 to 5, preferably 0.1 to 2, more preferably 0.1 to 1. The second step involves converting the hydroxyl radicals into acetoacetate radicals by reaction with a modifying reagent, to form the acetoacetate terminated polyester. By “modifying reagent” herein is meant, a compound which causes modification of the hydroxyl terminated polyester by converting the hydroxyl radicals to acetoacetyl radicals. Examples of suitable modifying reagents include methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, diketene, 2,2,6-trimethyl-4H-1,3-dioxin-4-one, ethyl benzoylacetate, and the like, and mixtures thereof. The acetoacetate terminated polyester may contain up to 10 weight percent (based on polyester) of urethane radicals, which are created by modifying the hydroxyl terminated polyester by reacting it with a diisocyanate. Suitable diisocyanates include 4,4′-diphenylmethane diisocyanate, 4,2′-diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and the like, and combinations thereof. Preferably, the acetoacetate terminated polyester contains no isocyanates. Preferably, the acetoacetate terminated polyester contains 1.6 to 3 acetoacetate groups per chain, more preferably 1.7 to 2.5 acetoacetate groups per chain, most preferably 2 to 2.5 acetoacetate groups per chain. The acetoacetate terminated polyester has a weight average molecular weight (measured by gel permeation chromatography) of 1,200 to 10,000, preferably 1,200 to 5,000, most preferably 1,800–4,000. Generally, the first step takes place at temperatures of 100° C. to 240° C., and the second step at temperatures of 80° C. to 150° C. Preferably, the two step process takes place in the presence of a catalyst. Preferably, the catalyst is selected from the group consisting of dibutyltin oxide, hydroxybutyltin oxide, monobutyltin tris(2-ethylhexoate), tetraethyl titanate, tetrapropyl titanate, tetra(isopropyl) titanate, tetrabutyl titanate, tetra(2-ethylhexyl) titanate, titanium acetylacetonate, ethyl acetoacetic ester titanate, butyl zirconate, and propyl zirconate, and the like, and combinations thereof. Examples of suitable polyesters include those based on ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, triethylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, pentaerythritol, glycerin, etc. condensed with adipic acid, azelaic acid, sebacic acid, malonic acid, fumaric acid, maleic acid, maleic anhydride, 1,4-cyclohexanedicarboxylic acid, phthalic anhdyride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, trimellitic acid, caprolactone, malic acid, dimethylolpropionic acid, succinic anhydride, and the like, and mixtures thereof.
The acetoacetate terminated polyesteramide is prepared by conventional means, which are readily available to those skilled in the art. For example, one may use a two step process where the first step involves condensing glycols selected from the group including diols and/or triols, and amino alcohols, with carboxylic acids selected from the group including di/tri-carboxylic acids, to produce a polyesteramide terminated with hydroxyl radicals, and having a hydroxyl value of 50 to 225, and an acid value of 0.1 to 5, preferably less than 0.1 to 2, more preferably 0.1 to 1. During the second step, converting the hydroxyl radicals into acetoacetate radicals by reaction with a modifying reagent, to form the acetoacetate terminated polyesteramide. By “modifying reagent” herein is meant, a compound which causes modification of the hydroxyl terminated polyesteramide by converting the hydroxyl radicals to acetoacetyl radicals. Examples of suitable modifying reagents include methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, diketene, 2,2,6-trimethyl-4H-1,3-dioxin-4-one, and the like, and mixtures thereof. The acetoacetate terminated polyesteramide may contain up to 10 weight percent (based on polyesteramide) of urethane radicals, which are created by modifying the hydroxyl terminated polyesteramide by reacting it with a diisocyanate. Suitable diisocyanates include 4,4′-diphenylmethane diisocyanate, 4,2′-diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and the like, and combinations thereof. Preferably, the acetoacetate terminated polyesteramide contains no isocyanates. Preferably, the acetoacetate terminated polyesteramide contains 1.6 to 3 acetoacetate groups per chain, more preferably 1.7 to 2.5 acetoacetate groups per chain, most preferably 2 to 2.5 acetoacetate groups per chain. The acetoacetate terminated polyester has a weight average molecular weight (measured by gel permeation chromatography) of 1,200 to 10,000, preferably 1,200 to 5,000, most preferably 1,800–4,000. Generally, the first step takes place at temperatures of 100° C. to 240° C., and the second step at temperatures of 80° C. to 150° C. Preferably, the two step process takes place in the presence of a catalyst. Preferably, the catalyst is selected from the group consisting of dibutyltin oxide, hydroxybutyltin oxide, monobutyltin tris(2-ethylhexoate), tetraethyl titanate, tetrapropyl titanate, tetra(isopropyl)titanate, tetrabutyl titanate, tetra(2-ethylhexyl) titanate, titanium acetylacetonate, ethyl acetoacetic ester titanate, butyl zirconate, and propyl zirconate, and the like, and combinations thereof. Examples of suitable polyesteramides include those based on diols and/or triols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, triethylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, pentaerythritol, glycerin, and the like, and mixtures thereof; and amino alcohols such as ethanolamine, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-butanol, 4-amino-1-butanol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and the like, and mixtures thereof; condensed with dicarboxylic acids, tricarboxylic acids and/or hydroxy carboxylic acids such as adipic acid, azelaic acid, sebacic acid, malonic acid, fumaric acid, maleic acid, maleic anhydride, 1,4-cyclohexanedicarboxylic acid, phthalic anhdyride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, trimellitic acid, caprolactone, malic acid, dimethylolpropionic acid, succinic anhydride and the like, and mixtures thereof.
Another embodiment of the invention is the method of using the composition of the invention to adhere a material to a substrate. The α,β-unsaturated multi-carboxylic acid ester, and compound (A) may be employed as a two part system, wherein one part is the the α,β-unsaturated multi-carboxylic acid ester, and the other part is compound (A). The catalyst may be present in either or both parts. Preferably, the two parts are mixed together, in the presence of a catalyst, prior to application to a substrate. The composition of the invention typically has a potlife of five minutes to eight hours, depending upon the components, catalyst level and temperature. Preferably, the composition has a minimum potlife of 5 to 10 minutes at 50° C. By “potlife” herein is meant, the period of time during which the composition remains uncured, and can thus be applied to a substrate for adhesion. The composition is then applied to the substrate. The method of application may be by a number of ways known to those having ordinary skill in the art (for example brushing, spraying, roller coating, rotogravure coating, flexographic coating, flow coating, dipping and combinations thereof) to form a continuous or discontinuous film of the composition, as desired. The composition may be applied at a level of 0.4 to 5.8 g/sq. meter.
After the composition has been applied to the first substrate, it may then be contacted with another substrate to provide a laminate construction. The laminate so formed is optionally subjected to applied pressure, such as passing it between rollers to effect increased contact of the substrates with the composition. In another embodiment of the invention, the composition may be simultaneously or sequentially applied to both surfaces of the first substrate, which composition are then simultaneously or sequentially bonded to two further substrates, which may be the same, or different. It is further contemplated that the laminate construction may sequentially be bonded to other substrate(s) using the composition of the invention, or a different composition before or after the process described herein. The first and second substrates to be bonded in the method of this invention may be the same or different and include, for example plastics, metallized plastics, metal, and paper, which may have smooth or structured surfaces and may be provided in the form of rolls, sheets, films, foils etc. The substrates may be constructed in multi-ply laminate structures based upon polyalkylenes, such as polyethylenes, and polypropylenes, polyesters, and polyamides (nylon), metallized polypropylene, aluminum foil, etc. Examples of two-ply laminate constructions, include polypropylene/polypropylene, polyester/nylon, polyester/polyethylene, polypropylene/metallized polypropylene, polypropylene/aluminum foil, polyester/aluminum foil, polyamide/aluminum foil, etc. A temperature above ambient is not necessary to dry and cure the composition disclosed herein, however, heat may be applied.
While the invention is particularly useful as an adhesive, it is contemplated that it is also applicable to coatings, sealants and elastomers.
All ranges disclosed herein are inclusive, and the minimums and maximums of the nested ranges are combinable.
Glycol(s), carboxylic acid(s), and Fascat 4100, were charged to a 1-Liter one-piece reactor and slowly heated to 100° C. The reaction temperature was slowly increased to 200° C. When water evolution stopped, the temperature was decreased to 175° C. and vacuum applied. The reaction was maintained at 175° C. and ca. 3 mm of vacuum until the Acid Value (AV) was less than 1.0. The reaction temperature was decreased to 120° C., and then ethyl acetoacetate was added gradually over a 1 hr. interval. The reaction temperature was increased to 150° C., and maintained until ethanol evolution ceased. While maintaining the reaction at 150° C., vacuum was applied and residual ethanol and ethyl acetoacetate were removed.
Glycol(s), carboxylic acid(s), amino alcohol, and Fascat 4100, were charged to a 1-Liter one-piece reactor and slowly heated to 100° C. The reaction temperature was slowly increased to 200° C. When water evolution stopped, the temperature was decreased to 175° C. and vacuum applied. The reaction was maintained at 175° C. and ca. 3 mm of vacuum until the Acid Value (AV) was less than 1.0. The reaction temperature was decreased to 120° C., and then ethyl acetoacetate was added gradually over a 1 hr. interval. The reaction temperature was increased to 150° C., and maintained until ethanol evolution ceased. While maintaining the reaction at 150° C., vacuum was applied and residual ethanol and ethyl acetoacetate were removed.
The polyester or polyesteramide (Part I) was mixed with a polyacrylate and ethanol (Part II) and a catalyst (21% sodium ethoxide in ethanol). The composition was coated onto a plastic film with a number 3 rod and laminated to a second laminate film with a nip temperature of 150° F. The peel strength of the laminates were determined after 1 day and 7 days at ambient temperature.
This is a non-provisional application of prior pending U.S. provisional application Ser. No. 60/302,721 filed Jul. 3, 2001.
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| Number | Date | Country | |
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| Number | Date | Country | |
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| 60302721 | Jul 2001 | US |
