• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Disclosed are compositions that are particularly useful as adhesives, as well as methods of making adhesive compositions and methods of using adhesive compositions.
    公开号:KR20030004141A
    申请号:KR1020020038358
    申请日:2002-07-03
    公开日:2003-01-14
    发明作者:데이츠제프리하롤드；쥬패닉조셉제임스；첸메이
    申请人:롬 앤드 하스 캄파니；
    IPC主号:
    专利说明:

    Adhesive Composition, Manufacturing Method, and Method of Using Adhesive Composition {Composition, Method of Making, and Method of Using Adhesive Composition}
    [1] The present invention relates to compositions that are particularly useful as adhesives, as well as to methods of making adhesive compositions and methods of using adhesive compositions.
    [2] Other unsaturated monomers such as acrylates, methacrylates and isocyanates are widely used in coatings, adhesives, sealants and elastomers. These unsaturated monomers are typically low molecular weight multifunctional compounds and can be either volatile or absorbed directly into the skin and have adverse health effects. Toxicity of substances such as aromatic isocyanates is particularly problematic when potential migration to food occurs. Another issue with these compounds is that those who handle products containing isocyanates require that they avoid contact with moisture in manufacture, storage and use. Functionalized polymers are generally nonvolatile compounds that are not directly absorbed by the skin and can overcome the above drawbacks. However, multi-step synthesis is required and many of the properties achievable using low molecular materials with low viscosity are lost. Thus, the coating, adhesive, waterproofing and elastomer industries continue to require new systems in which products are produced that avoid the use of toxic raw materials such as isocyanates and do not lose the desirable properties associated with these low molecular weight raw materials.
    [3] For example, U.S. Patent No. 4,644,036 discloses a curing component for a synthetic resin. The curing component was prepared by 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, and alkali metal hydroxides, alkalis. It was carried out in the presence of a metal alcoholate and a basic amino compound. The aforementioned curing components have also been disclosed for chemically bonded self-curing synthetic resins. However, the two step method is required to produce a synthetic resin useful as a lacquer. In the first step, a curing component (which must be resistant to hydrolysis) is produced. In the second step, the synthetic resin is crosslinked by the curing component.
    [4] In addition, compositions that can be crosslinked to produce coatings or adhesives have been prepared by Michael addition reactions. US Pat. No. 5,945,489 discloses a liquid oligomer composition which is an ungelled, crosslinked product due to the Michael addition reaction of excess di / tri / tetra acrylate acceptor and acetoacetate donor in the presence of an amine based catalyst. Is starting. U.S. Patent No. 5,945,410 discloses a process for preparing a composition of the '489 patent. However, the composition should have a polyacrylate receptor: acetoacetate donor ratio of at least 2: 1 equivalent, wherein the acetoacetate has at least 4 functionalities and a residual pendant unsaturated acrylate group. . It also requires additional steps for useful adhesives or coatings, and the composition must be further crosslinked (cured) by ultraviolet light.
    [5] The inventors have invented a single step method of producing a composition particularly useful as an adhesive, without the use of volatile low molecular raw materials and maintaining the desired properties associated with low molecular raw materials, which is in the presence of a non-amine based catalyst. The compound (A) having And , -Unsaturated multi-carboxylic acid ester are reacted.
    [6] [Formula 1]
    [7]
    [8] In the first aspect of the present invention,
    [9] Reacting a compound (A) having an structural formula with an α, β-unsaturated multi-carboxylic acid ester:
    [10] [Formula 1]
    [11]
    [12] In the formula, R is polyester or polyesteramide; R 'is CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 or Is; The reaction is carried out in the presence of at least one non-amine based catalyst; The composition is provided with a method for producing a composition having an α, β-unsaturated multi-carboxylic acid ester and a compound (A) in a reaction equivalent functional group ratio of 0.67: 1 to 1.75: 1.
    [13] In the second aspect of the present invention,
    [14] A composition is provided comprising a reaction product of an α, β-unsaturated multi-carboxylic acid ester with compound (A) having the structure:
    [15] [Formula 1]
    [16]
    [17] Wherein R is polyester or polyesteramide; R 'is CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 or Is; The reaction is carried out in the presence of at least one non-amine based catalyst; The composition is provided with a composition having an α, β-unsaturated multi-carboxylic acid ester and a compound (A) in a reaction equivalent functional group ratio of 0.67: 1 to 1.75: 1.
    [18] In the third aspect of the present invention,
    [19] Applying to the substrate a mixture of α, β-unsaturated multi-carboxylic acid ester with compound (A) having the structure
    [20] [Formula 1]
    [21]
    [22] Wherein R is polyester or polyesteramide; R 'is CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 or Is; The reaction is carried out in the presence of at least one non-amine base catalyst; The composition provides a method of adhering a substance to a substrate having an α, β-unsaturated multi-carboxylic acid ester and a compound (A) in a reaction equivalent functional group ratio of 0.67: 1 to 1.75: 1.
    [23] The methods and compositions of the present invention relate to the reaction of α, β-unsaturated multi-carboxylic acid esters with compound (A) having the structure:
    [24] [Formula 1]
    [25]
    [26] Wherein R is polyester or polyesteramide; R 'is CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 or Is; The reaction is carried out in the presence of at least one non-amine based catalyst; To provide a composition which is particularly useful as an adhesive. The method provides a reaction equivalent functional group 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 preferred. Preferably to a composition having a ratio of 1: 1 to 1.25: 1. At this equivalent ratio, less than 1 percent of the pendant unsaturated acrylate groups in the composition of the present invention remain uncrosslinked at the end of the Michael addition reaction. If the ratio is used above the ratios disclosed above, the resulting product has some pendant acrylate groups which may not be crosslinked, gelled and preferably not crosslinked by any method other than Michael addition or by adverse effects on the performance of the adhesive. . Preferably, the composition of the present invention is substantially free of solvent. By “substantially free of solvent” disclosed herein is meant that the composition contains at least 70%, preferably at least 95% solids.
    [27] α, β-unsaturated multi-carboxylic acid esters are provided in the present invention as a curing (crosslinking) agent of compound (A). Suitable α, β-unsaturated multi-carboxylic acid esters may be polyacrylates and may undergo Michael addition. As used herein, "polyacrylate" refers to di / tri / tetra-acrylate, polyether, polyester, epoxide, polyurethane, polyolefin, and acrylic based on hydrocarbon, and stands or cures The furnace forms homogeneous affinity solutions in which the phases do not separate. Examples of suitable polyacrylates include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol 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 di Acrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, acrylated polyester Oligomer, Bisphenol A Di Acrylates, ethoxylated bisphenol A diacrylates, tris (2-hydroxyethyl) isocyanurate triacrylates, acrylated aliphatic urethane oligomers, acrylated aromatic urethane oligomers and the like and mixtures thereof do.
    [28] Non-amine based catalysts are used in the present invention to catalyze the reaction. Preferably the catalyst is a strong base. By “non-amine based catalyst” disclosed herein is meant a catalyst that is not based on amine chemistry and is a compound (A) at room temperature (typically 20-25 ° C.) or above room temperature (typically 25-65 ° C.). Can be cured. Suitable non-amine based catalysts include sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, sodium alkoxide and potassium alkoxide, such as potassium butoxide, Sodium acetylaceto, such as quaternary ammonium hydroxide, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetraoctylammonium hydroxide, sodium acetylacetonate, potassium acetylacetonate And potassium acetylacetonate and the like and mixtures thereof.
    [29] Compound (A) may be acetoacetate terminated polyester or polyesteramide. Preferably, the acetoacetate terminated polyester or polyesteramides used contribute to hydrogen bonding and / or polar interactions. Acetoacetate terminated polyesters or polyesteramides contain multi-carboxylic acids, which may be from 5 to 80 mole percent of at least one aromatic multi-carboxylic acid. Acetoacetate terminated polyesters are prepared and used in a conventional manner by one skilled in the art. For example, one can be used in a two step process, the first step condensing a carboxylic acid selected from the group comprising a di / tri-carboxylic acid with a glycol selected from the group comprising a diol and a triol as a hydroxy radical. It relates to producing terminated polyesters and has a hydroxyl value of 50-225 and an acid value of 0.1-5 acid values, preferably 0.1-2, more preferably 0.1-1. The second step involves the conversion of hydroxy radicals to acetoacetate radicals by reaction with a modulator to form an acetoacetate terminated polyester. By "modifying agent" is meant herein a compound that converts hydroxy radicals into acetoacetyl radicals to modify the hydroxy terminated polyester. Suitable examples of modifiers are methylacetoacetate, ethyl acetoacetate, isopropyl Acetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, diketene, 2,2,6-trimethyl-4H-1,3-dioxin-4-one, ethyl benzoyl acetate and the like and mixtures thereof. Acetoacetate terminated polyesters can contain up to 10% by weight of urethane radicals (based on polyester) and are produced by reacting with diisocyanates to modify the hydroxy terminated polyesters. Diphenylmethane diisocyanate, 4,2'-diphenylmethane diisocyanate, toluene diisocyanate, hexa Methylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, etc., and combinations thereof, Preferably the acetoacetate terminated polyester does not contain isocyanate Preferably, the acetoacetate terminated polyester It contains 1.6 to 3 acetoacetate groups per chain, more preferably 1.7 to 2.5 acetoacetate groups per branch, most preferably 2 to 2.5 acetoacetate groups per branch. It has an average molecular weight (measured by gel permeation chromatography) of ˜10,000 and preferably has a molecular weight of 1,200 to 5,000, most preferably 1,800 to 4,000. Generally, the first step is performed at a temperature of about 100 to 240 ° C. The second step is carried out at a temperature of 80 to 150 ° C. Preferably, two stages The process proceeds in the presence of a catalyst, preferably the catalyst is dibutyltin oxide, hydroxybutyltin oxide, monobutyltin tris (2-ethylhexate), tetraethyl titate, 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 Is selected from the group. Examples of suitable polyesters are ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, triethylene glycol, 1 Based on 4-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, pentaerythritol, glycerin and the like, adipic acid, azelaic acid, sebacic acid, malonic acid, fumaric acid, maleic acid, maleic anhydride, Condensed with 1,4-cyclohexanedicarboxylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, trimellitic acid, caprolactam, malic acid, dimethylolpropionic acid, succinic anhydride and the like and mixtures thereof It includes.
    [30] Acetoacetate terminated pulleyesteramides are prepared by conventional methods that are readily available to those skilled in the art. For example, one can use a two step method, the first step condensing together a glycol selected from the group comprising diols and / or triols and a carboxylic acid selected from the group containing amino alcohols and di / tri-carboxylic acids together. To produce polyesteramides terminated with hydroxy radicals, having a hydroxyl value of 50-225 and an acid value of 0.1-5, preferably 0.1-2 or less, and more preferably 0.1-1. In reaction with the regulator during the second step, the hydroxy radicals are converted into acetoacetate radicals to form acetoacetate terminated polyesteramides. By "modulator" is meant herein a compound in which the hydroxy radical is converted to an acetoacetyl radical to cause modification of the hydroxy terminated polyesteramide. Examples of suitable modulators are methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, diketene, 2,2,6-trimethyl-4H-1,3-dioxin-4 -Warming lamps and mixtures thereof. Acetoacetate terminated polyesteramides can contain up to 10% by weight of urethane radicals (based on polyesteramides) and are produced by reacting with diisocyanates to modify the hydroxy terminated polyesteramides. Suitable diisocyanates include 4,4'-dipetylmethane diisocyanate, 4,2'-diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate and the like and theirs. Combinations. Preferably, the acetoacetate terminated polyesteramides do not contain isocyanates. Preferably, the acetoacetate terminated polyesteramides contain 1.6-3 acetoacetate groups per branch, more preferably 1.7-2.5 acetoacetate groups per branch, most preferably 2-2.5 acetoacetate groups per branch. . Acetoacetate terminated polyesters have an average molecular weight (measured by gel permeation chromatography) of 1,200 to 10,000, preferably of 1,200 to 5,000, most preferably of 1,800 to 4,000. In general, the first step is carried out at a temperature of 100 ~ 240 ℃, the second step is carried out at a temperature of 80 ~ 150 ℃. Preferably, the two step process is carried out in the presence of a catalyst. Preferably, the catalyst is dibutyltin oxide, hydroxybutyltin oxide, monobutyltin tris (2-ethylhexate), 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 are ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, triethylene glycol, 1 Diols and / or triols such as, 4-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, pentaerythritol, glycerin and the like and mixtures thereof; And ethanolamine, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-amineno-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 On the basis of and the like and mixtures thereof; Adipic acid, azelaic acid, sebacic acid, malonic acid, fumaric acid, maleic acid, maleic anhydride, 1,4-cyclohexanedicarboxylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, trimellitic acid Condensed with dicarboxylic acids, tricarboxylic acids and / or hydroxy carboxylic acids such as caprolactam, malic acid, dimethylolpropionic acid, succinic acid, succinic anhydride and the like and mixtures thereof.
    [31] Another embodiment of the invention is a method of using the composition of the invention to adhere a substance to a substrate. The α, β-unsaturated multi-carboxylic acid ester and compound (A) can be used as a two part system, where one part is an α, β-unsaturated multi-carboxylic acid ester and the other part is compound (A). The catalyst may be present in one or both parts. Preferably, the two parts are mixed together before application to the substrate in the presence of a catalyst. Compositions of the present invention typically have a potlife of 5 minutes to 8 hours, depending on the component, catalyst level and temperature. Preferably, the composition has a minimum potlife at 50 ° C. for 5-10 minutes. By “potlight” disclosed herein is meant a period in which the composition remains uncured and thus can be applied to an adhesive substrate. The composition is then applied to the substrate. The method of application can be any of a variety of methods known to those skilled in the art to form continuous or discontinuous films of the desired compositions (eg, brushing, spraying, roller coating, gravure coating, flexographic coating, Flow coating, dipping and combinations thereof). The composition can be applied at a level of 0.4-5.8 g / sq. Meter.
    [32] After the composition is applied to the first substrate, it can be contacted with other substrates to create a laminate structure. The laminate formed is applied under any application pressure, passing the laminate between rollers to increase the contact of the composition with the substrate. In another embodiment of the invention, the composition may be applied simultaneously or continuously to both parts of the first substrate, the composition is then adhered simultaneously or sequentially to two additional substrates, and the substrates may be the same or different. have. Furthermore, it is appreciated that laminate constructions can be continuously bonded to other substrate (s) using other compositions before or after the compositions of the present invention or the methods disclosed herein. The first and second substrates bonded in the process of the present invention may be the same or different and include, for example, plastics, metallized plastics, metals and papers, and may have smooth or structured surfaces, rolls, It may be provided in the form of a sheet, film, foil or the like. The substrate may be composed of a multi-laminate structure based on polyalkylenes such as polyethylene and polypropylene, polyesters and polyamides (nylon), metallized polypropylene, aluminum foil, and the like. Examples of bi-laminate configurations include polypropylene / polypropylene, polyester / nylon, polyester / polyethylene, polypropylene / metalized polypropylene, polypropylene / aluminum foil, polyester / aluminum foil, polyamide / aluminum foil And the like. A temperature above room temperature is not required to dry or cure the composition as disclosed herein, but heat may be applied.
    [33] It is appreciated that the present invention is particularly useful as an adhesive and also applicable to coatings, waterproofing agents and carbon polymers.
    [34] It includes all ranges disclosed herein, and the minimum and maximum of the ranges can be combined.
    [35] Example 1-8 Synthesis of Acetoacetate Terminated Polyester
    [36] Glycol, carboxylic acid and Fascat 4100 were charged to 1 liter of one-piece reactor and slowly heated to 100 ° C. The reaction temperature was slowly raised to 200 ° C. When the evaporation of water stopped, the temperature was reduced to 175 ° C. and vacuum was applied. The reaction was carried out at ca. 175 ° C. until the acid value (AV) was below 1.0. The vacuum was maintained at 3 mm. The reaction temperature was reduced to 120 ° C. after which ethyl acetoacetate was added slowly at 1 hour intervals. The reaction temperature was raised to 150 ° C. and maintained until the end of ethanol evaporation. While maintaining the reaction temperature at 150 ° C., vacuum was applied to remove residual ethanol and ethyl acetoacetate.
    [37]
    [38] Note: C1 and C2 are comparative examples.
    [39] Fascat 4100 was manufactured from Elf Atochem North America, Philadelphia, PA.
    [40]
    [41] Note: C1 and C2 are comparative examples.
    [42] Example 9-13. Synthesis of Acetoacetate Terminated Polyester
    [43] Glycol, carboxylic acid, amino alcohol and Fascat 4100 were charged to a one liter one-piece reactor and slowly heated to 100 ° C. The reaction temperature was slowly raised to 200 ° C. When the evaporation of water stopped, the temperature was reduced to 175 ° C. and vacuum was applied. The reaction was performed at 175 ° C. until the acid value (AV) was 1 or less. A 3 mm vacuum was maintained. The reaction temperature was lowered to 120 ° C. and ethyl acetoacetate was slowly added at 1 hour intervals. The reaction temperature was raised to 150 ° C. and maintained until the ethanol evaporation was complete. While maintaining the reaction at 150 ° C., vacuum was applied to remove residual ethanol and ethyl acetoacetate.
    [44]
    [45] Note: Fascat 4100 was manufactured from Elf Atochem North America, Philadelphia, PA.
    [46]
    [47] Examples 14-37. Composition Application Tests of the Invention
    [48] Polyester or polyesteramide (part 1) was mixed with polyacrylate and ethanol (part 2) and catalyst (21% sodium ethoxide dissolved in ethanol). The composition was coated on a plastic film with a number 3 rod and laminated to a nip temperature of 150 ° F. on the second laminate film. The peel strength of the laminate was determined after 1 to 7 days at room temperature.
    [49]
    [50]
    [51] Note: C14, C14a, C14b, C15, C15a and C15b are comparative examples.
    [52] SR259 (diacrylate of polyethylene glycol 200) was prepared from Sartomer Company, Inc., Exton, PA.
    [53] MorCure2000 (diacrylate of diglycidyl ether bisphenol-A) was prepared from Rohm and Haas of Philadelphia, PA.
    [54] CN983 (aliphatic polyester urethane diacrylate) was manufactured by Sartomer Company, Inc. of Exton, PA.
    [55] CN965 (aliphatic polyester urethane diacrylate) was manufactured by Sartomer Company, Inc. of Exton, PA.
    [56] CN978 (90% aromatic polyester urethane diacrylate / 10% 2 (2-ethoxyethoxy) ethyl acrylate) was made by Sartomer Company, Inc. of Exton, PA.
    [57]
    [58]
    [59] Note: C14, C14a, C14b, C15, C15a and C15b are comparative examples.
    [60]
    [61] Note: SR259 (diacrylate of polyethylene glycol 200) was manufactured by Sartomer Company, Inc. of Exton, PA.
    [62] MorCure 2000 (diacrylate of diglycityl ether bisphenol-A) was prepared from Rohm and Haas of Philadelphia, PA.
    [63]
    [64] The present invention makes it possible to produce compositions which are particularly useful as adhesives, without the use of volatile low molecular raw materials and maintaining the desired properties associated with low molecular raw materials.
    权利要求:
    Claims (20)
    [1" claim-type="Currently amended] A method of producing a composition comprising reacting an α, β unsaturated multi-carboxylic acid ester with a compound (A) having the structure
    [Formula 1]
    (Wherein R is polyester or polyesteramide;
    In the above structural formula, R 'is CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 or Is,
    The reaction proceeds in the presence of at least one non-amine based catalyst;
    The composition has α, β unsaturated multi-carboxylic acid ester and compound (A) in a reaction equivalent functional group ratio of 0.67: 1 to 1.75: 1.)
    [2" claim-type="Currently amended] The method of claim 1, wherein the composition has an α, β-unsaturated multi-carboxylic acid ester and a compound (A) at a reaction equivalent functional group ratio of 0.67: 1 to 1.5: 1.
    [3" claim-type="Currently amended] The method of claim 1, wherein the composition has an α, β-unsaturated multi-carboxylic acid ester and a compound (A) at a reaction equivalent functional group ratio of 0.67: 1 to 1.25: 1.
    [4" claim-type="Currently amended] The method of claim 1 wherein the reaction step is performed at room temperature.
    [5" claim-type="Currently amended] The method of claim 1 wherein the α, β-unsaturated multi-carboxylic acid ester is a polyacrylate.
    [6" claim-type="Currently amended] The method of claim 1, wherein the compound (A) is acetoacetate terminated polyester or polyesteramide.
    [7" claim-type="Currently amended] The method according to claim 1, wherein the acetoacetate terminated polyester or polyesteramide has an acid value of 0.1 to 5.
    [8" claim-type="Currently amended] The method of claim 1 wherein the acetoacetate terminated polyester or polyesteramide contains 5 to 80 mole percent of at least one aromatic multi-carboxylic acid.
    [9" claim-type="Currently amended] The method of claim 1 wherein the acetoacetate terminated polyester or polyesteramide contains 0-10% by weight of urethane radicals.
    [10" claim-type="Currently amended] The method of claim 1, wherein the acetoacetate terminated polyester or polyesteramide has an average molecular weight of 1,200 to 10,000.
    [11" claim-type="Currently amended] The method of claim 1 wherein the acetoacetate terminated polyester or polyesteramide contains 1.6 to 3 acetoacetate groups per branch.
    [12" claim-type="Currently amended] The method of claim 1, wherein the acetoacetate terminated polyester or polyesteramide has 1.7 to 2.5 acetoacetate groups per branch.
    [13" claim-type="Currently amended] The method of claim 1, wherein the acetoacetate terminated polyester or polyesteramide has 2 to 2.5 acetoacetate groups per branch.
    [14" claim-type="Currently amended] The method of claim 1 wherein the acetoacetate terminated polyester is
    (a) a glycol selected from the group consisting of diols, triols and mixtures thereof is condensed with a carboxylic acid selected from the group consisting of dicarboxylic acids and tricarboxylic acids to terminate with hydroxy radicals and the hydroxyl value exceeding the acid value And preparing a polyester having an acid value; And
    (b) subsequently reacting with a modifier to convert the hydroxy radicals into acetoacetate radicals to form the acetoacetate terminated polyester;
    Method generated by the method comprising a.
    [15" claim-type="Currently amended] The method of claim 1, wherein the acetoacetate terminated polyesteramide is
    (a) a glycol and amino alcohol selected from the group consisting of diols, triols and mixtures thereof are condensed with carboxylic acids selected from the group consisting of dicarboxylic acids and tricarboxylic acids to terminate with hydroxy radicals and the hydroxide value exceeds the acid value Preparing a polyesteramide having a hydroxyl value and an acid value; And
    (b) subsequently reacting with a modifier to convert the hydroxy radicals into acetoacetate radicals to form the acetoacetate terminated polyesteramide;
    Method generated by the method comprising a.
    [16" claim-type="Currently amended] 15. The process of claim 14, wherein the polyester or polyesteramide terminated with a hydroxy radical has a hydroxyl value of 50-225.
    [17" claim-type="Currently amended] 16. The process of claim 15, wherein the polyester or polyesteramide terminated with a hydroxy radical has a hydroxyl value of 50-225.
    [18" claim-type="Currently amended] A composition comprising the reaction product of an α, β-unsaturated multi-carboxylic acid ester with compound (A) having the structure
    [Formula 1]
    (Wherein R is polyester or polyesteramide;
    In the above structural formula, R 'is CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 or Is,
    The reaction proceeds in the presence of at least one non-amine based catalyst; And
    The composition has a reaction equivalent functional group ratio of α, β unsaturated multi-carboxylic acid ester and compound (A) of 0.67: 1 to 1.75: 1.)
    [19" claim-type="Currently amended] The composition of claim 1, wherein the composition is substantially free of solvent.
    [20" claim-type="Currently amended] applying to the substrate a mixture of α, β-unsaturated multi-carboxylic acid ester with compound (A) having the structure
    [Formula 1]
    (Wherein R is polyester or polyesteramide;
    In the above structural formula, R 'is CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 or Is,
    The reaction proceeds in the presence of at least one non-amine based catalyst; And
    The composition has an α, β-unsaturated multi-carboxylic acid ester and compound (A) in a reaction equivalent functional group ratio of 0.67: 1 to 1.75: 1.)
    Method of adhering a substance to a substrate comprising a.
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    US20030083436A1|2003-05-01|
    AU4885002A|2003-01-09|
    KR100974919B1|2010-08-09|
    AR036109A1|2004-08-11|
    BR0202518B1|2012-09-18|
    US7119144B2|2006-10-10|
    EP1283235A3|2004-01-02|
    EP1283235B1|2014-01-22|
    CN1394894A|2003-02-05|
    JP3657578B2|2005-06-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-07-03|Priority to US30272101P
    2001-07-03|Priority to US60/302,721
    2002-07-03|Application filed by 롬 앤드 하스 캄파니
    2003-01-14|Publication of KR20030004141A
    2010-08-09|Application granted
    2010-08-09|Publication of KR100974919B1
    优先权:
    申请号 | 申请日 | 专利标题
    US30272101P| true| 2001-07-03|2001-07-03|
    US60/302,721|2001-07-03|
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