Composition, method of making, and method of using adhesive composition

Abstract

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 are disclosed.

Description

[0001] 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.

[0002] 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.

[0003] 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.

[0004] 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.

[0005] 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 1

[0006] in the presence of a non-amine based catalyst.

[0007] 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: 2

[0008] wherein R is a polyester or polyesteramide; wherein R′ is CH3, CH2CH3, CH2CH2CH3, or 3

[0009] 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.

[0010] 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: 4

[0011] wherein R is a polyester or polyesteramide; wherein R′ is CH3, CH2CH3, CH2CH2CH3, or 5

[0012] 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.

[0013] 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: 6

[0014] wherein R is a polyester or polyesteramide; wherein R′ is CH3, CH2CH3, CH2CH2CH3, or 7

[0015] 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.

[0016] 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: 8

[0017] wherein R is a polyester or polyesteramide; wherein R′ is CH3, CH2CH3, CH2CH2CH3, or 9

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] While the invention is particularly useful as an adhesive, it is contemplated that it is also applicable to coatings, sealants and elastomers.

[0026] All ranges disclosed herein are inclusive, and the minimums and maximums of the nested ranges are combinable.

EXAMPLES 1-8

Synthesis of Acetoacetate Terminated Polyester

[0027] 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.

TABLE 1
Raw Material For Synthesis of Acetoacetate Terminated Polyester
	Glycol (g)	Carboxylic	Other (g)
		Tri-	Neo-	Methyl		Acid (g)		Ethyl	Total
	Diethylene	methylol-	pentyl	Propane	1,6-Hexane-	Adipic	Isophthalic	Fascat	Aceto-	Charge
Example	Glycol	propane	Glycol	Diol	diol	Acid	Acid	4100	acetate	(g)
C1	314.84					376.08		1.45	97.16	789.53
C2	317.30					217.85	121.94	1.15	184.60	842.84
3	287.04	43.55				257.47	144.78	0.66	148.05	881.55
4		43.56	279.92			384.45		0.70	138.00	846.63
5	286.65	43.75				384.30		0.87	139.22	854.79
6		43.60		248.74		385.02		0.73	157.17	835.26
7		162.15	140.93		43.60	371.61		0.81	167.35	886.45
8		43.70		246.55		231.95	126.93	0.86	223.23	873.22
NOTE: C1 and C2 are comparative examples. Fascat 4100 is made by Elf Atochem North America, Inc., located in Philadelphia, PA.

[0028]

TABLE 2
Synthesized Acetoacetate Terminated Polyester
	Polyester Prior	Final Acetoacetate Terminated Polyester
	to Acetoacetylation	ASTM	Brookfield	Molecular		Acetoacetate
	Acid	Hydroxyl	Solids	Viscosity	Weight	Dispersity	Groups/
Example	Value	Value	(%)	(cps)	Mn	Mw	(Mw/Mn)	Polyester Chain
C1	0.92	74.7	99.14	1930	1600	5200	3.25	0.92
C2	0.20	135.2	97.59	644.7	650	1300	2.0	1.14
3	0.3	90.3	99.67	10720	1200	5350	4.5	1.87
4	0.4	100.62	98.89	6680	2600	8000	3.1	2.41
5	0.19	89.09	99.17	3843	1400	6200	4.4	1.82
6	0.2	99.2	99.50	13480	2800	9850	3.5	1.71
7	0.3	85.3	99.40	4480	1700	5950	3.47	2.20
8	0.6	157.6	99.03	10153	1200	3200	2.77	1.96
NOTE: C1 and C2 are comparative examples.

EXAMPLES 9-13

Synthesis of Acetoacetate Terminated Polyesteramide

[0029] 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.

TABLE 3
Raw Material For Synthesis of Acetoacetate Terminated Polyesteramide
	Glycol (g)	Amino	Carboxylic	Other (g)
		Tri-	Neo-	Methyl	Alcohol (g)	Acid (g)		Ethyl	Total
	Diethylene	methylol-	pentyl	Propane	Ethanol-	Adipic	Isophthalic	Fascat	Aceto-	Charge
Example	Glycol	propane	Glycol	Diol	amine	Acid	Acid	4100	acetate	(g)
9	232.08	43.60			30.68	258.10	144.92	0.75	148.38	858.51
10		43.68		202.40	31.41	384.88		0.81	155.00	818.18
11		43.60	238.16		31.03	385.05		0.81	162.70	861.35
12		43.81		203.74	36.20	234.34	128.20	0.98	220.52	867.79
13		43.70		201.44	30.52	350.19		0.97	217.68	844.50
NOTE: Fascat 4100 is made by Elf Atochem North America, Inc., located in Philadelphia, PA.

[0030]

TABLE 4
Synthesized Acetoacetate Terminated Polyesteramide
	Polyesteramide Prior	Final Acetoacetate Terminated Polyesteramide
	to Acetoacetylation	ASTM	Brookfield	Molecular		Acetoacetate
	Acid	Hydroxyl	Solids	Viscosity	Weight	Dispersity	Groups/Polyester-
Example	Value	Value	(%)	(cps)	Mn	Mw	(Mw/Mn)	amide Chain
9	1.1	85.4	99.47	42400	3300	8900	2.7	1.80
10	0.8	96.8	99.52	22933	4300	12200	2.8	1.92
11	1.2	64.2	99.80	169600	5100	26000	5.1	2.94
12	1.2	162.2	99.23	41117	1100	3100	2.78	1.80
13	0.94	140.94	99.50	7787	1350	4600	3.4	2.06

EXAMPLES 14-37

Application Testing of Composition of the Invention

[0031] 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.

TABLE 5
Materials Used in Application Testing of Composition Made by Reaction of Acetoacetate Terminated Polyester with Polyacrylate
	Part II (g)
			MorCure 2000
	Part I (g)	SR259	(Diacrylate of
	Acetoacetate	Acetoacetate	Acetoacetate	Acetoacetate	Acetoacetate	Acetoacetate	(Diacrylate of	Diglycidyl
	Terminated	Terminated	Terminated	Terminated	Terminated	Terminated	Polyethylene	Ether
Example	Polyester 1	Polyester 2	Polyester 3	Polyester 4	Polyester 7	Polyester 8	Glycol 200)	Bisphenol-A)
C14	11.67						4.92
C14a	11.67						4.92
C14b	11.67						4.92
C15		10.07					2.45
C15a		10.07					2.45
C15b		10.07					2.45
16			5.05				1.28
16a			5.05				1.28
16b			5.05				1.28
17			5.23				1.33	0.70
17a			5.23				1.33	0.70
17b			5.23				1.33	0.70
18			5.11				1.44
18a			5.11				1.44
18b			5.11				1.44
19			5.18				1.44
19a			5.18				1.44
19b			5.18				1.44
20			5.16				1.45
20a			5.16				1.45
20b			5.16				1.45
21				5.09			1.65
21a				5.09			1.65
21b				5.09			1.65
22				5.14			1.34	0.70
22a				5.14			1.34	0.70
22b				5.14			1.34	0.70
23					5.06		1.83
23a					5.06		1.83
23b					5.06		1.83
24					5.82		1.54	0.82
24a					5.82		1.54	0.82
24b					5.82		1.54	0.82
25						7.63	4.01
25a						7.63	4.01
25b						7.63	4.01
26						7.56	3.18	1.67
26a						7.56	3.18	1.67
26b						7.56	3.18	1.67
27						7.69	2.41	3.31
27a						7.69	2.41	3.31
27b						7.69	2.41	3.31
28						5.02	1.90
28a						5.02	1.90
28b						5.02	1.90
29						5.07	1.53	0.79
29a						5.07	1.53	0.79
29b						5.07	1.53	0.79
	Part II (g)
		CN983	CN965	CN978 (90%
		(Aliphatic	(Aliphatic	Aromatic Polyester			Catalyst (g)
		Polyester	Polyester	Urethane Diacrylate/	Methyl		21% Sodium
		Urethane	Urethane	10% 2(2-ethoxyethoxy)	Ethyl		Ethoxide
	Example	Diaacrylate)	Diacrylate)	Ethyl Acrylate)	Ketone	Ethanol	in Ethanol
	C14				49.65		0.23
	C14a				49.65		0.23
	C14b				49.65		0.23
	C15				37.05		0.21
	C15a				37.05		0.21
	C15b				37.05		0.21
	16					3.75	0.14
	16a					3.75	0.14
	16b					3.75	0.14
	17					5.12	0.18
	17a					5.12	0.18
	17b					5.12	0.18
	18	0.79				6.48	0.16
	18a	0.79				6.48	0.16
	18b	0.79				6.48	0.16
	19		0.87			6.45	0.18
	19a		0.87			6.45	0.18
	19b		0.87			6.45	0.18
	20			0.82		5.89	0.16
	20a			0.82		5.89	0.16
	20b			0.82		5.89	0.16
	21					7.25	0.18
	21a					7.25	0.18
	21b					7.25	0.18
	22					7.58	0.17
	22a					7.58	0.17
	22b					7.58	0.17
	23					8.00	0.17
	23a					8.00	0.17
	23b					8.00	0.17
	24					8.15	0.17
	24a					8.15	0.17
	24b					8.15	0.17
	25					11.74	0.19
	25a					11.74	0.19
	25b					11.74	0.19
	26					12.62	0.18
	26a					12.62	0.18
	26b					12.62	0.18
	27					13.59	0.28
	27a					13.59	0.28
	27b					13.59	0.28
	28					7.36	0.23
	28a					7.36	0.23
	28b					7.36	0.23
	29					7.61	0.23
	29a					7.61	0.23
	29b					7.61	0.23
	NOTE:
	C14, C14a, C14b, C15, C15a, and C15b are comparative examples.
	SR259 (diacrylate of polyethylene glycol 200) is made by Sartomer Company, Inc., located in Exton, PA.
	MorCure 2000 (diacrylate of diglycidyl ether bisphenol-A) is made by Rohm and Haas, located in Philadelphia, PA.
	CN983 (aliphatic polyester urethane diacrylate) is made by Sartomer Company, Inc., located in Exton, PA.
	CN965 (aliphatic polyester urethane diacrylate) is made by Sartomer Company, Inc., located in Exton, PA.
	CN978 (90% aromatic polyester urethane diacrylate/10% 2(2-ethoxyethoxy) ethyl acrylate) is made by Sartomer Company, Inc., located in Exton, PA.

[0032]

TABLE 6
Results of Application Testing of Composition Made by Reaction of
Acetoacetate Terminated Polyester with Polyacrylate
	Laminate Coating
	Weight (lbs/rm)
	Poly-			Peel
	propylene/		Polyester/	Strength
	Poly-	Polyester/	High Slip	(g/ln. in.)
Example	propylene	Nylon	Polyethylene	1 Day	7 Days
C14	ND			0	10
C14a		ND		0	0
C14b			ND	0	0
C15	ND			0	10
C15a		ND		0	0
C15b			ND	0	0
16	3.368			40	50
16a		3.145		60	75
16b			3.445	70	90
17	2.584			30	40
17a		2.169		40	45
17b			2.699	100 ± 10	120 ± 10
18	1.630			40 ± 10	25 ± 5
18a		2.069		50 ± 5	35 ± 5
18b			1.392	140 ± 10	40 ± 10
19	1.561			50	40 ± 5
19a		2.261		55 ± 5	40 ± 5
19b			1.438	170 ± 10	150 ± 10
20	2.438			55 ± 5	60 ± 10
20a		2.815		70 ± 5	60 ± 5
20b			1.930	140 ± 10	150 ± 10
21	0.592			35	35
21a		1.361		40 ± 5	50
21b			0.930	125 ± 10	110
22	1.107			35	40
22a		0.869		45	20
22b			1.046	160	100 ± 10
23	1.115			20	20
23a		1.253		40 ± 5	35
23b			1.007	95	50
24	1.476			30	25
24a		1.369		45 ± 5	35
24b			1.400	105 ± 5	70
25	1.530			50	65
25a		1.607		70 ± 5	55
25b			1.377	250 ± 5	230
26	1.238			105	110
26a		1.730		80 ± 5	75
26b			1.707	305	290
27	2.615			400	350
27a		1.676		90 ± 10	85 ± 5
27b			0.761	370 ± 10	340
28	1.730			75	85
28a		0.992		130	120 ± 10
28b			0.492	330	310 ± 20
29	1.707			80 ± 5	110 ± 10
29a		1.569		170 ± 20	180 ± 10
29b			0.277	420	400 ± 10
NOTE: C14, C14a, C14b, C15, C15a, and C15b are comparative examples.

[0033]

TABLE 7
Materials Used in Application Testing of Composition Made by Reaction of
Acetoacetate Terminated Polyesteramide with Polyacrylate
	Part II (g)	Catalyst
	Part I (g)	SR259	MorCure 2000		(g)
	Acetoacetate	Acetoacetate	Acetoacetate	(Diacrylate of	(Diacrylate of		21% Sodium
	Terminated	Terminated	Terminated	Polyethylene	Diglycidyl Ether		Ethoxide
Example	Polyesteramide 9	Polyesteramide 11	Polyesteramide 12	Glycol 200)	Bisphenol-A)	Ethanol	in Ethanol
30	5.08			1.75		6.79	0.19
30a	5.08			1.75		6.79	0.19
30b	5.08			1.75		6.79	0.19
31	5.21			1.45	0.75	7.49	0.19
31a	5.21			1.45	0.75	7.49	0.19
31b	5.21			1.45	0.75	7.49	0.19
32		5.13		2.11		10.14	0.19
32a		5.13		2.11		10.14	0.19
32b		5.13		2.11		10.14	0.19
33		5.14		1.71	0.92	10.53	0.21
33a		5.14		1.71	0.92	10.53	0.21
33b		5.14		1.71	0.92	10.53	0.21
34		5.10		1.29	1.77	10.74	0.20
34a		5.10		1.29	1.77	10.74	0.20
34b		5.10		1.29	1.77	10.74	0.20
35			7.57	4.51		12.60	0.32
35a			7.57	4.51		12.60	0.32
35b			7.57	4.51		12.60	0.32
36			7.53	3.80	1.88	13.50	0.33
36a			7.53	3.80	1.88	13.50	0.33
36b			7.53	3.80	1.88	13.50	0.33
37			7.57	2.99	3.87	14.59	0.34
37a			7.57	2.99	3.87	14.59	0.34
37b			7.57	2.99	3.87	14.59	0.34
38			5.06	2.12		7.38	0.22
38a			5.06	2.12		7.38	0.22
38b			5.06	2.12		7.38	0.22
39			5.03	1.72	0.92	8.14	0.21
39a			5.03	1.72	0.92	8.14	0.21
39b			5.03	1.72	0.92	8.14	0.21
NOTE: SR259 (diacrylate of polyethylene glycol 200) is made by Sartomer Company, Inc., located in Exton, PA. MorCure 2000 (diacrylate of diglycidyl ether bisphenol-A) is made by Rohm and Haas, located in Philadelphia, PA.

[0034]

TABLE 8
Results of Application Testing of Composition Made by Reaction
of Acetoacetate Terminated Polyesteramide with Polyacrylate
	Laminate Coating
	Weight (lbs/rm)
	Poly-			Peel
	propylene/		Polyester/	Strength
	Poly-	Polyester/	High Slip	(g/ln. in.)
Example	propylene	Nylon	Polyethylene	1 Day	7 Days
30	2.238			25	50
30a		2.222		35	45
30b			1.653	40	110
31	3.030			60	125
31a		2.784		40	60
31b			2.061	70	240
32	1.392			25	50
32a		1.353		30	35
32b			1.077	105	150 ± 10
33	0.884			30	60 ± 10
33a		1.407		50	60 ± 5
33b			1.054	115 ± 5	215 ± 5
34	1.730			45 ± 5	100 ± 10
34a		1.730		65	90 ± 5
34b			1.007	240	270
35	1.253			75	75
35a		1.407		55 ± 5	50
35b			0.800	240 ± 10	230
36	1.323			140 ± 10	210
36a		1.907		70 ± 10	80 ± 10
36b			1.223	350	390
37	1.553			150	180
37a		2.022		370	150
37b			1.576	400 ± 20	700
38	1.384			90 ± 5	90 ± 5
38a		0.661		100 ± 10	80 ± 10
38b			0.569	300	300 ± 10
39	1.769			85 ± 5	120
39a		0.984		110 ± 10	120 ± 10
39b			0.731	380	380

Claims

1. 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:

2. The method, as recited in claim 1, 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 1.5:1.

3. The method, as recited in claim 1, 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 1.25:1.

4. The method, as recited in claim 1, wherein said reaction step is carried out at ambient temperature.

5. The method, as recited in claim 1, wherein said α,β-unsaturated multi-carboxylic acid ester is a polyacrylate.

6. The method, as recited in claim 1, wherein said compound (A) is an acetoacetate terminated polyester or polyesteramide.

7. The method, as recited in claim 1, wherein said acetoacetate terminated polyester or polyesteramide has an acid value of 0.1 to 5.

8. The method, as recited in claim 1, wherein said acetoacetate terminated polyester or polyesteramide contains 5 to 80 mole percent of at least one aromatic multi-carboxylic acid.

9. The method, as recited in claim 1, wherein said acetoacetate terminated polyester or polyesteramide contains 0 to 10 weight percent of urethane radicals.

10. The method, as recited in claim 1, wherein said acetoacetate terminated polyester or polyesteramide has a weight average molecular weight of 1,200 to 10,000.

11. The method, as recited in claim 1, wherein said acetoacetate terminated polyester or polyesteramide contains 1.6 to 3 acetoacetate groups per chain.

12. The method, as recited in claim 1, wherein said acetoacetate terminated polyester or polyesteramide contains 1.7 to 2.5 acetoacetate groups per chain.

13. The method, as recited in claim 1, wherein said acetoacetate terminated polyester or polyesteramide contains 2 to 2.5 acetoacetate groups per chain.

14. The method, as recited in claim 1, wherein said acetoacetate terminated polyester is produced by a process comprising the steps of: (a) condensing glycols selected from the group consisting of diols, triols, and mixtures thereof, with carboxylic acids selected from the group consisting of dicarboxylic acids and tricarboxylic acids, to produce a polyester terminated with hydroxyl radicals, and having a hydroxyl value and an acid value, wherein said hydroxyl value exceeds said acid value; and (b) subsequently converting said hydroxyl radicals into acetoacetate radicals by reaction with a modifying reagent, to form said acetoacetate terminated polyester.

15. The method, as recited in claim 1, wherein said acetoacetate terminated polyesteramide is produced by a process comprising the steps of: (a) condensing glycols selected from the group consisting of diols, triols, and mixtures thereof, and amino alcohol(s), with carboxylic acids selected from the group consisting of dicarboxylic acids and tricarboxylic acids, to produce a polyesteramide terminated with hydroxyl radicals, and having a hydroxyl value and an acid value, wherein said hydroxyl value exceeds said acid value; and (b) subsequently converting said hydroxyl radicals into acetoacetate radicals by reaction with a modifying reagent, to form said acetoacetate terminated polyesteramide.

16. The method, as recited in claim 14, wherein said polyester or polyesteramide terminated with hydroxyl radicals has a hydroxyl value of 50 to 225.

17. The method, as recited in claim 15, wherein said polyester or polyesteramide terminated with hydroxyl radicals has a hydroxyl value of 50 to 225

18. A composition comprising a reaction product of an α,β-unsaturated multi-carboxylic acid ester and a compound (A) having a structural formula:

19. The composition, as recited in claim 1, wherein said composition is substantially free of solvent.

20. 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: 14wherein R is a polyester or polyesteramide; wherein R′ is CH3, CH2CH3, CH2CH2CH3, or 15wherein said reaction is carried out in the presence of at least one non-amine based catalyst; and wherein said reaction product 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.