Primer composition and articles made therefrom

Abstract

There are provided primer compositions comprising a primer component comprising: a rubber; an amine-functional (meth)acrylic resin; and a plasticizer. There are also provided articles made using these primer compositions.

Claims

1. A primer composition comprising a primer component comprising: a rubber; an amine-functional (meth)acrylic resin; and a plasticizer; wherein the amine-functional (meth)acrylic resin is a polymerization reaction product of an amine-functional (meth)acryloyl compound and a non-amine-vinyl monomer; wherein the amine-functional (meth)acryloyl compound is of Formula (I): ##STR00007## wherein R1 is hydrogen, alkyl, or aralkyl; R2 is alkyl or aralkyl; or R1 and R2 together with the nitrogen atom with which they are joined may form a 5, 6, or 7 member ring; R3 is alkylene or aralkylene; X is nitrogen or oxygen; R4 does not exist if X is oxygen and is hydrogen, alkyl, aryl, alkaryl, or aralkyl if X is nitrogen; and R5 is hydrogen or methyl; or wherein the amine-functional (meth)acryloyl compound is of Formula (II): ##STR00008## wherein R1 is hydrogen, alkyl, or aralkyl; each R3 is independently alkylene or aralkylene; X is nitrogen; and R5 is hydrogen or methyl; or combinations thereof.

2. The primer composition of claim 1, wherein the amine-functional (meth)acrylic resin has a calculated Tg greater than or equal to 12 C.

3. The primer composition of claim 1, wherein the non-amine-vinyl monomer is selected from the group consisting of a (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, a vinyl ester, a styrene, a (meth)acrylonitrile, and mixtures thereof.

4. The primer composition of claim 1, wherein the non-amine-vinyl monomer is a (meth)acrylic acid ester of a C1 to C18 alcohol.

5. The primer composition of claim 1, wherein the rubber comprises a block copolymer of a styrene and an alkene.

6. The primer composition of claim 1, wherein the rubber comprises a styrene-ethylene/butylene-styrene block copolymer grafted with maleic anhydride.

7. The primer composition of claim 1, wherein the plasticizer is of Formula III:
(RX).sub.nZ (III) wherein: each R may be hydrogen, C1-C14 alkyl, aryl, alkaryl, or aralkyl; each optionally interrupted by oxygen, nitrogen, carbonyl, carboxyl, or carbamide; each X may be oxygen, nitrogen, carbonyl, carboxyl, or carbamide; Z may be a hydrogen, C1-C14 alkyl, aryl, alkaryl, aralkyl, C1-C14 alkylene, arylene, alkarylene, aralkylene; each optionally interrupted by oxygen, nitrogen, carbonyl, carboxyl, or carbamide; and n is an integer of 1 to 5.

8. The primer composition of claim 7, wherein n is an integer of 1 to 4.

9. The primer composition of claim 7, wherein the plasticizer is selected from at least one of the following a benzoic acid ester, a myristic acid ester, a citric acid ester, an acetic acid ester, a succinic acid ester, a gluratic acid ester, an adipic acid ester, a sebacic acid ester, and combinations thereof.

10. The primer composition of claim 1, wherein the plasticizer is selected from at least one of the following a benzoic acid ester, a myristic acid ester, a citric acid ester, and combinations thereof.

11. The primer composition of claim 1, wherein the primer component comprises: 35 wt. % to 70 wt. % of the rubber; 20 wt. % to 35 wt. % of the amine-functional (meth)acrylic resin; and 10 wt. % to 40 wt. % of the plasticizer, wherein the weight percentages are all based on the total weight of the primer component.

12. The primer composition of claim 1 wherein the primer component comprises: 40 wt. % to 60 wt. % of the rubber; 20 wt. % to 35 wt. % of the amine-functional (meth)acrylic resin; and 15 wt. % to 35 wt. % of the plasticizer, wherein the weight percentages are all based on the total weight of the primer component.

13. The primer composition of claim 12 further comprising a liquid carrier.

14. The primer composition of claim 13 wherein the liquid carrier is one or more solvent.

15. The primer composition of claim 14, wherein the primer composition comprises: 1 wt. % to 25 wt. % of the primer component; and 75 wt. % to 99 wt. % of the solvent, wherein the weight percentages are all based on the total weight of the primer composition.

16. The primer of claim 14, wherein the primer composition comprises: 2 wt. % to 7 wt. % of the primer component; and 93 wt. % to 98 wt. % of the solvent, wherein the weight percentages are all based on the total weight of the primer composition.

Description

DETAILED DESCRIPTION

(1) Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of including, comprising, or having and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. Any numerical range recited herein includes all values from the lower value to the upper value. For example, if a concentration range is stated as 1% to 50%, it is intended that values such as 2% to 40%, 10% to 30%, or 1% to 3%, etc., are expressly enumerated. These are only examples of what is specifically intended, and all possible combinations of numerical values between and including the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.

(2) Primer compositions of the present disclosure are conveniently applied in liquid form, for example from the melt; as aqueous emulsions, dispersions, or suspensions; or, preferably, as solvent solutions. Preferred solvent solutions are homogeneous and storage stable and minimally attack substrate during use. Solvent solutions may comprise a single solvent or a blend of solvents.

(3) As used herein, a primer surface preparation, derived from the presently disclosed primer composition comprising non-volatile primer component, is considered to provide strong adhesion to double sided tapes, such as for example, double sided foam tapes, when there is a peel adhesion of at least 35 Newtons per centimeter (N/cm) (20 pounds per inch width (piw)) between two bonded substrates, preferably peel adhesion exceeding 52 N/cm (30 piw) between two bonded substrates, and more preferably peel adhesion exceeding 52 N/cm (30 piw) between two bonded substrates and resulting in cohesive failure in the tape.

(4) The present disclosure provides a primer composition having a primer component comprising a rubber, an amine-functional (meth)acrylic resin, and a plasticizer. In some embodiments, the present disclosed primer composition comprises a rubber, an amine-functional (meth)acrylic resin, a plasticizer, and an aliphatic hydrocarbon.

(5) Rubbers useful in the present disclosure include block copolymers of styrene and alkene, preferably hydrogenated styrene/alkene block copolymers, and more preferably hydrogenated styrene/alkene block copolymers further bearing pendant anhydride moieties. Most preferably, the rubber is a styrene-ethylene/butylene-styrene block copolymer grafted with maleic anhydride, such as those available under the trade designation KRATON FG1901 from Kraton Performance Polymers Inc., Houston, Tex.

(6) Amine-functional acrylic resins useful in the present disclosure include those derivable by copolymerization of amine-functional (meth)acrylic acid esters and amides with non-amine-functional vinyl monomers. Amine-functional acrylic acid esters and amides are selected from those of Formula (I)

(7) ##STR00003##

(8) wherein R1 is hydrogen, alkyl, or aralkyl; R2 is alkyl or aralkyl; or R1 and R2 together with the nitrogen atom with which they are joined may form a 5, 6, or 7 member ring; R3 is alkylene or aralkylene; X is nitrogen or oxygen; R4 does not exist if X is oxygen and is hydrogen, alkyl, aryl, alkaryl, or aralkyl if X is nitrogen; and R5 is hydrogen or methyl;

(9) and those of Formula (II)

(10) ##STR00004##

(11) wherein R1 is hydrogen, alkyl, or aralkyl; each R3 is independently alkylene or aralkylene; X is nitrogen; and R5 is hydrogen or methyl.

(12) Preferred amine-functional (meth)acrylic acid esters and amides include 2-(N,N-dimethylaminoethyl) (meth)acrylate; 2-(N,N-diethylaminoethyl) (meth)acrylate; 2-(t-butylaminoethyl) (meth)acrylate; 2-(N,N-dimethylaminoethyl) (meth)acrylamide; 2-(N,N-diethylaminoethyl) (meth)acrylamide; 2-(t-butylaminoethyl) (meth)acrylamide; and N-(meth)acryloylpiperidine. 2-(N,N-dimethylaminoethyl) methacrylate and 2-(t-butylaminoethyl) methacrylate are particularly preferred.

(13) In some embodiments, the amine-functional (meth)acrylic resin has a calculated Tg greater than or equal to 12 C. In some embodiments, the amine-functional (meth)acrylic resin has a calculated Tg greater than or equal to 20 C. The calculated Tg of an amine-functional (meth)acrylic resin can be conveniently estimated according to Formula V
Tg.sub.amine-functional (meth)acrylic resin=1/((W.sub.i/(Tg.sub.i+273))273
wherein Tg.sub.amine-functional (meth)acrylic resin is the calculated Tg for the amine-functional (meth)acrylic resin and W.sub.i and Tg.sub.i are weight fraction and homopolymer Tg for individual amine-functional (meth)acrylic acid esters and amides and non-amine-functional vinyl monomers present in the amine-functional (meth)acrylic resin. Each Tg has units in degrees Celsius. Values for homopolymer Tg for individual amine-functional (meth)acrylic acid esters and amides and non-amine-functional vinyl monomers are conveniently tabulated, for example, in Polymer Handbook, 2nd edition. John Wiley, 1975.

(14) Non-amine-functional vinyl monomers include, for example, (meth)acrylic acid and their esters and amides, vinyl esters, styrene, and (meth)acrylonitrile. (meth)acrylic acid esters are preferred non-amine-functional vinyl monomers. More preferred (meth)acrylic acid esters are formally esters of (meth)acrylic acid with C1 to C18 alcohols.

(15) Plasticizers useful in the present disclosure remain in the primer coating after evaporation of a liquid carrier, for example, a solvent, and minimize attack (e.g. dissolution, crazing, marring, discoloration) on a substrate used therewith. Preferred plasticizers have Predicted Enthalpies of Evaporation greater than about 50 kJ/mol and general structure of Formula III
(RX).sub.nZ wherein

(16) each R may be hydrogen, C1-C14 alkyl, aryl, alkaryl, or aralkyl; each optionally interrupted by oxygen, nitrogen, carbonyl, carboxyl, or carbamide;

(17) each X may be oxygen, nitrogen, carbonyl, carboxyl, or carbamide;

(18) each Z may be a hydrogen, C1-C14 alkyl, aryl, alkaryl, aralkyl, C1-C14 alkylene, arylene, alkarylene, aralkylene; each optionally interrupted by oxygen, nitrogen, carbonyl, carboxyl, or carbamide; and

(19) n is an integer ranging from 1 to 5, or in some embodiments, n is an integer ranging from 1 to 4.

(20) Preferred plasticizers include benzoic acid ester, myristic acid ester, citric acid ester, acetic acid ester, succinic acid ester, gluratic acid ester, adipic acid ester, and sebacic acid ester, and combinations thereof. More preferred plasticizers include benzoic acid ester, myristic acid ester, and citric acid ester.

(21) Plasticizers useful in the present disclosure preferably resist evaporation and remain in the primer component for prolonged periods. While volatile plasticizers can be useful, for example, when a priming step immediately precedes a tape bonding step, preferred plasticizers remain in the primer component even when the tape bonding step is delayed. Useful plasticizers preferably retain efficacy for at least three minutes after application, more preferably for at least 60 minutes, most preferably for at least 24 hours. Resistance to evaporation can be conveniently quantified according to the predicted enthalpy of vaporization values provided by commercially available chemical computation software, such as that available under the name Percepta PredictorsSoftware Modules to Predict Physicochemical, ADME, and Toxicity Properties from Structure Advanced Chemistry Development (publicly available by accessing the website called http.//www.chemspider.com (last accessed on Nov. 20, 2015). Preferred plasticizers useful in the present disclosure have predicted enthalpies of vaporization greater than about 50 kJ/mol, and more preferably greater than about 55 kJ/mol. Predicted enthalpy of vaporization for plasticizers useful in the present disclosure are listed in the table below:

(22) TABLE-US-00001 Predicted Enthalpy of Vaporization Compound (kJ/mol) tributyl acetylcitrate 89 tributyl citrate 74 dipropylene glycol dibenzoate 73 diethylene glycol dibenzoate 66 propylene glycol dicaprate/caprylate 65 dibutyl tartarate 65 triethyl citrate 62 diethyl tartarate 60 diethyl malate 60 isodecyl benzoate 59 dibutyl phthalate 58 triethyl acetylcitrate 57 isopropyl myristate 56 diethyl sebacate 55 ethyl toluenesulfonamide 55 ethylhexyl benzoate 55 dibutyl itaconate 55 dibutyl adipate 54 dimethyl sebacate 54 dibutyl fumarate 52 tributyl phosphate 51 phenoxypropanol 51 glycerol triacetate 50 butyl lactate 49 dimethyl adipate 47 diethyl succinate 46

(23) In some embodiments, the present disclosure provides a primer composition having a primer component comprising a rubber, an amine-functional (meth)acrylic resin, a plasticizer, and a liquid carrier. In some embodiments, the present disclosed primer composition comprises a rubber, an amine-functional (meth)acrylic resin, a plasticizer, and an aliphatic hydrocarbon. Preferred liquid carrier useful in the present disclosure is solvent.

(24) In some embodiments, the presently disclosed primer composition comprises: 1 wt. % to 25 wt. % of the primer component; and 75 wt. % to 99 wt. % of the solvent, where the weight percentages are all based on the total weight of the primer composition. In some embodiments, the presently disclosed primer composition comprises: 2 wt. % to 7 wt. % of the primer component; and 93 wt. % to 98 wt. % of the solvent, where the weight percentages are all based on the total weight of the primer composition.

(25) Solvent solutions useful in the present disclosure are those having a Hildebrand total solubility parameter between about 15 MPa.sup.1/2 and about 17.5 MPa.sup.1/2. Hildebrand total solubility parameters for single solvents are conveniently tabulated, for example, in Handbook of Solubility Parameters and Other Cohesion Parameters, 2nd edition. CRC Press, 1991. Hildebrand total solubility parameters for solvent blends can be estimated from the volume averaged Hildebrand total solubility parameters of the individual solvent components in the solvent blend according to Formula IV
SP.sub.blend=(W.sub.i/SG.sub.iSP.sub.i)/(W.sub.i/SG.sub.i)

(26) wherein SP.sub.blend is the Hildebrand total solubility parameter of the solvent blend and W.sub.i, SG.sub.i, and SP.sub.i are weight fraction, specific gravity, and Hildebrand total solubility parameter for each individual solvent in the blend. Representative Hildebrand total solubility parameter and specific gravity for select individual solvents and various solvent blends follow.

(27) TABLE-US-00002 Individual Solvent SP.sub.i (MPa.sup.1/2) SG.sub.i (g/ml) hexamethyldisiloxane (HMDS) 11.7 0.77 heptane 15.3 0.68 methylcyclohexane (MCH) 16.0 0.77 t-butyl acetate (tBAC) 16.2 0.87 methyl acetate (MAC) 19.4 0.94 acetone 19.7 0.79 Solvent Blend Estimated SP.sub.blend (MPa.sup.1/2) 40/40/20 MCH/MAC/HMDS 16.3 30/40/30 MCH/MAC/HMDS 15.8 60/40 heptane/MAC 16.6 40/40/20 heptane/MAC/tBAC 16.9 46/15/39 heptane/MCH/MAC 16.7

(28) Individual solvents preferably useful in the present disclosure include acetone, methyl acetate, t-butyl acetate, hexamethyldisiloxane, heptane, and methylcyclohexane.

(29) More preferred solvent solutions for use in the present disclosure comprise less than 0.1 wt. % of any one aromatic hydrocarbon including, for example, benzene, toluene, xylene, ethylbenzene, and chlorobenzene. Even more preferred solvent solutions comprise less than 0.1 wt. % total aromatic hydrocarbon. Most preferably, the solvent solution comprises less than 0.01 wt. % total aromatic hydrocarbon.

(30) More preferred solvent solutions comprise, for example 0-50 wt. % acetone, 0-50 wt. % methyl acetate, 0-40 wt. % hexamethyldisiloxane, and 0-40 wt. % t-butyl acetate. More preferred solvent solutions additionally comprise 25-90 wt. % aliphatic alkane, including straight chain, branched, and cyclic hydrocarbons, especially those having five to twelve carbon atoms. Heptane and methylcyclohexane are especially preferred aliphatic alkanes. More preferred solvent solutions comprise 25-45 wt. % acetone or methyl acetate, 0-25 wt. % hexamethyldisiloxane, and 35-75 wt. % aliphatic alkane. Most preferred solvent solutions comprise methyl acetate and methylcyclohexane or methyl acetate and heptane.

(31) Preferred primer compositions of the present disclosure comprise 92 to 99 wt. % volatile solvents and 1 to 8 wt. % non-volatile primer components, more preferably 94 to 97 wt. % volatile solvents and 3 to 6 wt. % non-volatile primer components.

(32) In some embodiments, the presently disclosed primer composition comprises a primer component, where the primer component comprises: 35 wt. % to 70 wt. % of the rubber; 20 wt. % to 35 wt. % of the amine-functional (meth)acrylic resin; and 10 wt. % to 40 wt. % of the plasticizer, where the weight percentages are all based on the total weight of the primer component. In some embodiments, the presently disclosed primer composition comprises a primer component , where the primer component comprises: 40 wt. % to 60 wt. % of the rubber; 20 wt. % to 35 wt. % of the amine-functional (meth)acrylic resin; and 15 wt. % to 35 wt. % of the plasticizer, where the weight percentages are all based on the total weight of the primer component.

(33) In some embodiments, the primer composition further comprises a colorant. In some embodiments, the colorant is fluorescent.

(34) The present disclosure provides primer compositions comprising primer component that exhibit good adhesion to both low energy surfaces (e.g., polyolefins, such as polypropylene), as well as higher energy surfaces (i.e., having surface energies greater than 35 dynes/cm such as metal). The primer compositions are useful as primers (e.g., for use with adhesives, paints, and coatings).

(35) In some embodiments, articles can be made comprising: a substrate; and a primer surface treatment of any of the previously disclosed embodiments of the primer component disposed on at least one surface of the substrate. These articles can also include a layer of adhesive disposed on the layer of the primer surface treatment opposite the substrate. In some embodiments, these articles can also include a backing layer disposed on the layer of adhesive opposite the layer of the primer surface treatment.

(36) Following are non-limiting, exemplary embodiments and combinations of embodiments for the present disclosure:

(37) Embodiment 1. A primer composition comprising a primer component comprising: a rubber; an amine-functional (meth)acrylic resin; and a plasticizer.

(38) Embodiment 2. The primer composition of Embodiment 1, wherein the amine-functional (meth)acrylic resin is a polymerization reaction product of an amine-functional (meth)acryloyl compound and a non-amine-vinyl monomer; wherein the amine-functional (meth)acryloyl compound is of Formula (I):

(39) ##STR00005## wherein R1 is hydrogen, alkyl, or aralkyl; R2 is alkyl or aralkyl; or R1 and R2 together with the nitrogen atom with which they are joined may form a 5, 6, or 7 member ring; R3 is alkylene or aralkylene; X is nitrogen or oxygen; R4 does not exist if X is oxygen and is hydrogen, alkyl, aryl, alkaryl, or aralkyl if X is nitrogen; and R5 is hydrogen or methyl; wherein the amine-functional (meth)acryloyl compound is of Formula (II):

(40) ##STR00006## wherein R1 is hydrogen, alkyl, or aralkyl; each R3 is independently alkylene or aralkylene; X is nitrogen; and R5 is hydrogen or methyl; or combinations thereof.

(41) Embodiment 3. The primer composition of Embodiment 1 or 2, wherein the amine-functional (meth)acrylic resin has a calculated Tg greater than or equal to 12 C.

(42) Embodiment 4. The primer composition of Embodiment 2, wherein the non-amine-vinyl monomer is selected from the group consisting of a (meth)acrylic acid, a (meth)acrylic acid ester, a (meth)acrylamide, a vinyl ester, a styrene, a (meth)acrylonitrile, and mixtures thereof.

(43) Embodiment 5. The primer composition of any of Embodiments 2, 3 or 4, wherein the non-amine-vinyl monomer is a (meth)acrylic acid ester of a C1 to C18 alcohol.

(44) Embodiment 6. The primer composition of any of the preceding Embodiments, wherein the rubber comprises a block copolymer of a styrene and an alkene.

(45) Embodiment 7. The primer composition of any of the preceding Embodiments, wherein the rubber comprises a styrene-ethylene/butylene-styrene block copolymer grafted with maleic anhydride.

(46) Embodiment 8. The primer composition of any of the preceding Embodiments, wherein the plasticizer is of Formula III:
(RX-)nZ (III) wherein: each R may be hydrogen, C1-C14 alkyl, aryl, alkaryl, or aralkyl; each optionally interrupted by oxygen, nitrogen, carbonyl, carboxyl, or carbamide; each X may be oxygen, nitrogen, carbonyl, carboxyl, or carbamide; Z may be a hydrogen, C1-C14 alkyl, aryl, alkaryl, aralkyl, C1-C14 alkylene, arylene, alkarylene, aralkylene; each optionally interrupted by oxygen, nitrogen, carbonyl, carboxyl, or carbamide; and n is an integer of 1 to 5.

(47) Embodiment 9. The primer composition of Embodiment 8, wherein n is an integer of 1 to 4.

(48) Embodiment 10. The primer composition of any of the preceding Embodiments, wherein the plasticizer is selected from at least one of the following a benzoic acid ester, a myristic acid ester, a citric acid ester, an acetic acid ester, a succinic acid ester, a gluratic acid ester, an adipic acid ester, a sebacic acid ester, and combinations thereof.

(49) Embodiment 11. The primer composition of any Embodiments 1 to 9, wherein the plasticizer is selected from at least one of the following a benzoic acid ester, a myristic acid ester, a citric acid ester, and combinations thereof.

(50) Embodiment 12. The primer composition of any of the preceding Embodiments, wherein the primer component comprises: 35 wt. % to 70 wt. % of the rubber; 20 wt. % to 35 wt. % of the amine-functional (meth)acrylic resin; and 10 wt. % to 40 wt. % of the plasticizer, wherein the weight percentages are all based on the total weight of the primer component.

(51) Embodiment 13. The primer composition of any of Embodiments 1 to 11 wherein the primer component comprises: 40 wt. % to 60 wt. % of the rubber; 20 wt. % to 35 wt. % of the amine-functional (meth)acrylic resin; and 15 wt. % to 35 wt. % of the plasticizer, wherein the weight percentages are all based on the total weight of the primer component.

(52) Embodiment 14. The primer composition of any of the preceding Embodiments further comprising a liquid carrier.

(53) Embodiment 15. The primer composition of Embodiment 14 wherein the liquid carrier is a solvent.

(54) Embodiment 16. The primer composition of Embodiment 15, wherein the primer composition comprises: 1 wt. % to 25 wt. % of the primer component; and 75 wt. % to 99 wt. % of the solvent, wherein the weight percentages are all based on the total weight of the primer composition.

(55) Embodiment 17. The primer of Embodiment 15, wherein the primer composition comprises: 2 wt. % to 7 wt. % of the primer component; and 93 wt. % to 98 wt. % of the solvent, wherein the weight percentages are all based on the total weight of the primer composition.

(56) Embodiment 18. The primer composition of any of Embodiments 15 to 17 wherein the solvent is a solvent blend having a Hildebrand total solubility parameter in a range from about 15 MPa.sup.1/2 to about 17.5 MPa.sup.1/2.

(57) Embodiment 19. The primer composition of any of the preceding Embodiments wherein the plasticizer has a Predicted Enthalpy of Evaporation greater than about 50 kJ/mol.

(58) Embodiment 20. The primer composition of Embodiment 1 or 2, wherein the amine-functional (meth)acrylic resin has a calculated Tg greater than or equal to 20 C.

(59) Embodiment 21. The primer composition of any of the preceding Embodiments wherein the plasticizer has a Predicted Enthalpy of Evaporation greater than about 55 kJ/mol.

(60) Embodiment 22. An article comprising: a substrate; and a layer of any of the aforementioned primer components disposed on at least one outer surface of the substrate.

(61) Embodiment 23. The article of Embodiment 22 further comprising a layer of adhesive disposed on the layer of any of the aforementioned primer components opposite the substrate.

(62) Embodiment 24. The article of Embodiment 23 further comprising a backing layer disposed on the layer of adhesive opposite the layer of the primer component.

(63) Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.

EXAMPLES

(64) TABLE-US-00003 TABLE 1 Materials Designation Description Source MMA methyl methacrylate Dow Chemical, Midland, MI IOA iso-octyl acrylate 3M Co., St. Paul, MN tBAEMA 2-(t-butylamino)ethyl methacrylate BASF, Florham Park, NJ MAC Methyl acetate Alfa-Aesar, Ward Hill, MA VAZO 2,2-azobis(2-methylbutyronitrile) DuPont, Wilmington, DE NVC N-vinylcaprolactam BASF, Florham Park, NJ KRATON FG1901 a clear, linear triblock copolymer based on Kraton Polymers, Houston, styrene and ethylene/butylene TX TINOPAL OB 2,5-thiophenediylbis(5-tert-butyl-1,3- BASF, Florham Park, NJ benzoxazole ATBC tributyl acetylcitrate Lanxess, Orange, TX A186 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Momentive, Columbus, OH MCH methylcyclohexane Alfa-Aesar, Ward Hill, MA HMDS hexamethyldisiloxane Alfa-Aesar, Ward Hill, MA AA Acrylic acid Dow Chemical, Midland, MI

(65) Test Methods

(66) Polymer Inherent Viscosity

(67) The inherent viscosity was determined by conventional means using a Cannon-Fenske #50 viscometer in a 25 C. water bath to measure the flow time of 10 milliliters polymer solution (0.60 grams per deciliter of ethyl acetate.)

(68) Primer Component Adhesion Performance (Peel Test)

(69) Substrates were cleaned with SURPASS facial tissues (Kimberly-Clark) wetted with aqueous isopropyl alcohol (50:50 vol/vol) then allowed to dry. The Primer Composition was poured onto a fresh SURPASS facial tissue, applied to substrates in even coats, and allowed to dry for three minutes. 3M VHB TAPE 4611 tape strips (1 inch4 inches, 2.5 cm10 cm) were backed on one face with anodized aluminum foil and the other face was placed onto the primed surface, then pressed down twice under a 15 pound (6.8 kg) roller moving at 12 inches (30 cm) per minute. 90 peel strengths were assessed after standing overnight at room temperature, pulling the anodized aluminum foil backing perpendicular to the substrate at 12 inches (30 cm) per minute. The average peel force was recorded along with failure mode. Failure mode fs indicates cohesive failure within the foam tape during testing, cp means the tape peeled cleanly from the surface and the tape did not fail cohesively during testing, and mix indicates a mixture of fs and cp failure modes were observed during testing. A list of adhesion performance test substrates immediately follows:

(70) TABLE-US-00004 Adhesion Performance Test Substrates Designation Description Source stainless steel Polished stainless steel ChemInstruments, Fairfield, OH acrylic Acrylic Clear, Ext PE Mask, 0.118 thick Plastics International, Eden Prairie, MN polycarbonate MAKROLON GP, clear, 0.118 thick Plastics International ABS ABS Natural (Tan) S/S Ext, 0.125 thick Plastics International Nylon Nylon Type 6/6 Natural, 0.125 thick Plastics International Rigid PVC Type 1 Grade 1 Gray PVC, 0.125 thick Plastics International polyester FRP GPO-3 Polyester/Glass red, 0.125 thick, Plastics International glass fiber reinforced polyester Epoxy FRP FR4 Epoxy/Glass, 0.125 thick, glass fiber Plastics International reinforced thermoset epoxy resin phenolic CE Phenolic/Canvas Natural, 0.125 thick, Plastics International canvas reinforced phenolic TPO BASEL HIFAX ETA 3131 BLK Standard Plaque, Melvindale, MI thermoplastic polyolefin polypropylene Polypropylene SR Natural, 0.125 thick Plastics International white truck paint DC105W-2196 19G1393 POLAR Dura Coat Products, Huntsville, AL WHITE, roll-coated, heat-cured, wax- containing coating (0.75 mil thick) on 0.019 thick aluminum

Preparative Example 1 (PE-1)

Preparation of Amine-Functional Acrylic Resin 1 (AFAR1) (55:30:15 MMA/IOA/tBAEMA, at 40 wt. % Solids in MAC)

(71) A reactor was charged with 132 grams MMA, 72 grams IOA, 36 grams of tBAEMA, 360 grams of MAC, and 1.92 grams of VAZO 67. The solution was deoxygenated with nitrogen, the reactor was sealed, and the solution was heated 46 hours at 65 C., then allowed to cool. The resulting solution was found to contain 40.3 wt. % solids and had inherent viscosity of 0.36.

Preparative Examples 2 to 9 (PE-2 to PE-9)

Amine-Functional Acrylic Resins 2 to 9 (AFAR2-AFAR9)

(72) The general procedure for preparation of PE-1 was repeated (with the same relative amounts of MAC and VAZO 67), but altering monomer weight ratios and/or incorporating alternative monomers, according to the amounts indicated in Table 2, with the resulting inherent viscosity and wt. % solid (phr is per hundred weight resin) values listed.

(73) TABLE-US-00005 TABLE 2 Preparative AFAR MMA, BMA, IOA, tBAEMA, DMAEMA, Calculated Inherent Wt. % Example number phr phr phr phr phr Tg viscosity solids PE-1 AFAR1 55 0 30 15 0 26 C. 0.36 40.3 PE-2 AFAR2 42 0 42 16 0 6 C. 0.38 40.1 PE-3 AFAR3 35 53 0 12 0 49 C. 0.42 34.2 PE-4 AFAR4 35 53 0 0 12 47 C. 0.37 34.9 PE-5 AFAR5 42 42 0 16 0 55 C. 0.33 40.6 PE-6 AFAR6 56 14 14 16 0 47 C. 0.35 40.4 PE-7 AFAR7 28 28 28 16 0 12 C. 0.37 40.1 PE-8 AFAR8 0 42 42 16 0 16 C. 0.38 39.9 PE-9 AFAR9 14 14 56 16 0 21 C. 0.39 39.8

Preparative Examples 10 (PE-10)

Amide-Functional Acrylic Resin (AMDA)

(74) The general procedure for preparation of PE-1 was repeated, but replacing amino-functional monomer with amide-functional monomer, N-vinylcaprolactam (NVC), and using the monomer weight ratios, according to the amounts indicated in Table 3.

(75) TABLE-US-00006 TABLE 3 IOA, NVC, AA, Inherent Wt. % Preparative Example phr phr phr viscosity solids PE-10 (AMDA) 78 21 1 0.58 37.5

Example 1

Primer Composition: (50:24:24:2 KRATON FG1901/ATBC/PE-1/A186 in Solvent Solution)

(76) A 5-liter flask equipped with overhead stirring, thermocouple, condenser, and nitrogen inlet was charged with 100.0 grams KRATON FG1901, 3.0 grams TINOPAL OB, 48.0 grams ATBC, and 4.0 grams A186. Stirring was started, 567 grams of MCH was added, and the mixture was heated 3 hours at 60 C. to ensure homogeneous solution. The solution was diluted with an additional 953 grams MCH, cooled to ambient temperature, then sequentially diluted with 1448 grams of methyl acetate, 120 grams of the AFAR of PE-1, and 760 grams HMDS. The final solution was found to have 4.7 wt. % solids.

(77) Example 1 Primer Composition was applied to various substrates and performance of the dried coatings were assessed according to the Primer Component Adhesion Performance test method. Peel forces and failure modes were as recorded in Table 4.

(78) TABLE-US-00007 TABLE 4 Example 1 primer composition peel force test results Substrate piw (N/cm) failure mode stainless steel 46 (80) fs acrylic 46 (80) fs polycarbonate 46 (80) fs ABS 46 (80) fs Nylon 47 (82) mix Rigid PVC 46 (80) fs polyester FRP 43 (75) mix Epoxy FRP 46 (80) fs phenolic 46 (80) fs TPO 45 (78) fs polypropylene 27 (47) mix white truck paint 36 (63) cp piw: pounds force per inch width N/cm: Newtons/cm mode: fs = foam split mix = mixed mode cp = clean peel

Examples 2-5

(79) Example 1 was repeated, preserving the 50/24/24/2 KRATON FG1901/AFAR/ATBC/A186 ratio, but replacing AFAR1 with AFAR2, omitting TINOPAL OB, and varying concentration of total solids as shown in Table 5. The peel force test results were as shown in Table 5.

(80) TABLE-US-00008 TABLE 5 Example 2 Example 3 Example 4 Example 5 3 wt. % 4 wt. % 5 wt. % 6 wt. % solids solids solids solids piw piw piw piw Substrate (N/cm) mode (N/cm) mode (N/cm) mode (N/cm) mode Nylon 32 (56) cp 32 (56) cp 34 (59) cp 34 (59) cp polypropylene 32 (56) mix 36 (63) mix 19 (33) mix 28 (49) mix white truck 28 (49) cp 32 (56) cp 33 (57) cp 31 (54) cp paint

Examples 6-7 and Comparative Example 1

(81) Example 3 was repeated, except replacing AFAR2 with AMDA, AFAR3, AFAR4, or a mixture thereof, and adjusting the non-volatile ingredient ratio as shown in Table 6. The peel force test results were as shown in Table 6.

(82) TABLE-US-00009 TABLE 6 poly- propylene phenolic piw piw Example Non-volatiles, weight ratio (N/cm) mode (N/cm) mode Example 6 50/7/15/26/2 KRATON 35 (61) fs 35 (61) fs FG1901/AMDA/AFAR3/ATBC/A186 Example 7 50/7/15/26/2 KRATON 35 (61) fs 35 (61) fs FG1901/AMDA/AFAR4/ATBC/A186 Comparative 1 50/20/28/2 KRATON 18 (31) cp 19 (33) cp FG1901/AMDA/ATBC/A186

Examples 8-16 and Comparative Examples 2-3

(83) Example 4 was repeated, except replacing ATBC with alternative plasticizer, or omitting plasticizer, with peel force test results as shown in Table 7.

(84) TABLE-US-00010 TABLE 7 white truck Nylon polypropylene paint Example Plasticizer piw (N/cm) mode piw (N/cm) mode piw (N/cm) mode Example 8 isopropyl myristate 38 (66) mix 40 (70) fs 32 (56) cp Example 9 dibutyl adipate 36 (63) cp 43 (75) fs 30 (52) cp Example 10 phenoxypropanol 32 (56) cp 31 (54) mix 38 (66) cp Example 11 isodecyl benzoate 32 (56) cp 26 (45) cp 37 (64) mix Example 12 dipropylene glycol 42 (73) mix 21 (36) cp 39 (68) mix dibenzoate Example 13 diethylene glycol 32 (56) cp 32 (56) mix 38 (66) mix dibenzoate/dipropylene glycol dibenzoate Example 14 2,2,4-trimethylpentyl 41 (71) cp 19 (33) cp 40 (70) mix dibenzoate Example 15 triethylene glycol 32 (56) cp 21 (36) cp 31 (54) cp diethylhexanoate Example 16 diethylhexyl 32 (56) cp 32 (56) cp 29 (50) cp terephthalate Comparative 2 none 42 (73) mix 14 (24) cp 26 (45) cp Comparative 3 2-octyldodecanol 31 (54) cp 16 (28) cp 30 (52) cp

Examples 17-24 and Comparative Examples 4-9

(85) Example 3 was repeated, all at 4 wt. % solids, but replacing AFAR2 with AFAR3 and varying KRATON FG1901/AFAR3/ATBC weight ratio, with peel force test results as shown in Table 8.

(86) TABLE-US-00011 TABLE 8 Non-volatiles, weight white truck ratio Nylon polypropylene paint KRATON piw piw piw Example FG1901/AFAR3/ATBC (N/cm) mode (N/cm) mode (N/cm) mode Example 17 48/32/20 36.8 (64) mix 37.5 (65) mix 39.5 (69) mix Example 18 40/24/36 33.3 (58) mix 39 (68) mix 28.7 (50) cp Example 19 64/24/12 29.4 (51) cp 25.1 (44) cp 24.9 (43) cp Example 20 64/10/26 25.6 (44) cp 24.7 (43) mix 22.1 (38) cp Example 21 48/24/28 31.6 (55) cp 36 (63) mix 26.3 (46) cp Example 22 40/32/28 29.5 (51) cp 27.6 (48) mix 28.1 (49) cp Example 23 48/16/36 29.2 (51) cp 24 (42) cp 23.7 (41) cp Example 24 5624/20 32.8 (57) cp 29.1 (51) mix 24.4 (42) cp Comparative 4 32/40/28 25.6 (44) cp 10.8 (18) cp 20.2 (35) cp Comparative 5 5517/28 35.8 (62) mix 16.4 (28) cp 28.7 (50) cp Comparative 6 40/48/12 24.8 (43) cp 13.9 (24) cp 18.4 (32) cp Comparative 7 55/40/5 28.1 (49) cp 18.5 (32) cp 16.9 (29) cp Comparative 8 32/24/44 33.1 (58) cp 16.5 (28) cp 16.7 (29) cp Comparative 9 48/10/42 28.2 (49) cp 18.4 (32) mix 25.3 (44) cp

Example 25

(87) Example 4 was repeated, except replacing the 40/40/20 MCH/MAC/HMDS solvent blend with the solvent blend indicated in Table 9.

(88) TABLE-US-00012 TABLE 9 Solvent Blend white truck Weight Ratio Nylon polypropylene paint Example MCH MAC HMDS piw (N/cm) mode piw (N/cm) mode piw (N/cm) mode Example 25 30 40 30 32 (56) cp 28 (49) cp 30 (52) cp

Examples 26-27

(89) Example 1 was repeated, except replacing the 40/40/20 MCH/MAC/HMDS solvent blend with the solvent blend indicated in Table 10.

(90) TABLE-US-00013 TABLE 10 Solvent Blend Weight Ratio polycarbonate TPO polypropylene Example MCH MAC heptane tBAC piw (N/cm) mode piw (N/cm) mode piw (N/cm) mode Example 26 0 40 60 0 41 (71) fs 41 (71) fs 42 (73) fs Example 27 0 40 40 20 41 (71) fs 42 (73) fs 18 (31) cp

Examples 28-30 and Comparative Example 10-11

(91) Example 3 was repeated, except replacing AFAR2 as shown in Table 11.

(92) TABLE-US-00014 TABLE 11 AFAR white truck Calculated Nylon polypropylene paint Example AFAR Tg piw (N/cm) mode piw (N/cm) mode piw (N/cm) mode Example 28 AFAR5 55 C. 38 (66) fs 30 (52) mix 31 (54) cp Example 29 AFAR6 47 C. 36 (63) fs 40 (70) mix 30 (52) cp Example 30 AFAR7 12 C. 31 (54) cp 29 (50) mix 24 (42) cp Comparative 10 AFAR8 16 C. 23 (40) cp 20 (35) mix 17 (29) cp Comparative 11 AFAR9 21 C. 23 (40) cp 7 (12) cp 15 (26) cp

Examples 31-32 and Comparative Example 12

(93) Example 3 was repeated, except varying ATBC as shown in Table 12.

(94) TABLE-US-00015 TABLE 12 Non-volatiles, weight ratio white truck KRATON Nylon polypropylene paint Example FG1901/AFAR2/ATBC/A186 piw (N/cm) mode piw (N/cm) mode piw (N/cm) mode Example 31 50/24/24/2 37 (64) cp 38 (66) fs 27 (47) cp Example 32 58/28/12/2 40 (70) mix 25 (43) cp 29 (50) cp Comparative 12 66/32/0/2 39 (68) mix 16 (28) mix 22 (38) cp