ADHESIVE FOR BONDING TO FLEXIBLE POLYMER SURFACES

• US 20110104508A1
• Filed: 08/21/2009
• Published: 05/05/2011
• Est. Priority Date: 08/29/2008
• Status: Abandoned Application

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies, Inc. (Dow, Inc.)
• Inventors: Walter, Barbara Jean, Cawley, Arthur Francis, Wang, Yee Yang
• Application Number:
  US13/002,408
• Publication Number:
  US 20110104508A1
• Time in Patent Office: Days
• US Class Current: 428/522
• CPC Class Codes: C08F 220/281 and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• CPC Class Codes: C08F 4/52 selected from boron, aluminium, gallium, indium, thallium or rare earths C08F4/14 takes precedence
• CPC Class Codes: C09D 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• CPC Class Codes: C09J 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

This invention relates to stabilized polymerizable compositions comprising compounds containing moieties capable of free radical polymerization and organoborane initiators capable of initiating free radical polymerization and adhesives based on such compositions. In another embodiment the invention relates to a method of polymerizing compounds containing moieties capable of free radical polymerization and to methods of bonding substrates (including flexible substrates) using such compositions. The invention also relates to coatings, laminates, and components including these compositions.

Claims

1. A polymerizable adhesive composition comprising:

(i) an organoboron compound capable of forming a free radical generating species;

(ii) an organic acid;

(iii) one or more compounds that undergo a free radical polymerization; and

(iv) a monoalkenyl arene block copolymer;

wherein the one or more compounds that undergo a free radical polymerization optionally includes methyl methacrylate at a concentration less than about 80 percent based on the total weight of the compounds that undergo a free radical polymerization;

wherein the monoalkenyl arene block copolymer is present at a concentration greater than about 3 wt percent, based on the total weight of the polymerizable adhesive composition, and the monoalkenyl arene block copolymer has one or more blocks including a monoalkenyl arene and one or more blocks including a conjugated diene; and

wherein the adhesive composition upon curing for 6 days at about 20°

C. when applied to a thermoplastic polyolefin exhibits a lap shear strength greater than about 1.8 MPa tested according to ASTM 3163 with a bondline of about 254 μ

m.

2. A polymerizable adhesive composition of claim 1, wherein the adhesive composition is a two-part adhesive composition wherein the two-part adhesive includes a first part and a second part;

the organoboron compound is in the first part;

the organic acid is in the second part;

the one or more compounds that undergo a free radical polymerization is in the first part, the second part, or both; and

the monoalkenyl arene block copolymer is in the first part, the second part, or both.

3. A polymerizable adhesive composition of claim 1 wherein the composition comprises two or more compounds that undergo a free radical polymerization.

4. A polymerizable adhesive composition of claim 3 wherein the two or more compounds that undergo a free radical polymerization includes two or more compounds which are esters of unsaturated carboxylic acids, wherein the esters of unsaturated carboxylic acids each have at least one acrylate or methacrylate functional group.

5. A polymerizable adhesive composition of claim 1 wherein the methyl methacrylate is present at a concentration of less than about 60 wt percent based on the total weight of the compounds that undergo a free radical polymerization.

8. A polymerizable adhesive composition of claim 1, wherein the polymerizable composition further comprises a plurality of fillers including a talc, a calcium carbonate, a fumed silica, or any combination thereof;

and the plurality of fillers are present at a concentration from about 0 weight percent to about 25 weight percent based on the total weight of the polymerizable composition.

9. A polymerizable adhesive composition of claim 1 wherein the organoboron compound is an organoborane amine complex or an organoborate salt.

10. A polymerizable adhesive composition of claim 9, wherein the organoboron compound is an organoborane amine complex comprising a trialkyl borane or an alkyl cycloalkyl borane.

12. A polymerizable adhesive composition of claim 1, wherein the monoalkenyl arene block copolymer includes an A-B-A triblock copolymer, an A-B diblock copolymer, or a combination thereof wherein the total concentration of the diblock and triblock copolymer ranges from about 4 weight percent to about 20 weight percent based on the total weight of the composition.

14. A polymerizable adhesive composition of claim 2, wherein

the organoboron compound is present from about 1 to about 10 weight percent based on the total weight of the composition;

the organoboron compound includes a complex of tri-n-butyl borane and methoxypropyl amine, a complex of triethylborane and methoxypropyl amine, or both;

the organic acid is present from about 1 to about 8 weight percent based on the total weight of the composition;

the second part includes from about 2 to about 15 weight percent filler based on the total weight of the composition;

the second part includes an alkoxylated tetrahydrofurfuryl;

the second part includes methyl ether of hydroquinone, the organic acid is acrylic acid, methacrylic acid, or both;

the filler includes calcium carbonate, talc, clay, fumed silica or any combination thereof;

the methyl methacrylate is present at a concentration from about 10 to about 40 weight percent based on the total weight of the composition;

the first part, the second part, or both includes from about 10 to about 50 weight percent of a methacrylate having an oxirane ring based on the total weight of the composition, and from about 0 to about 15 weight percent of a polybutadiene oligomer having a terminal acrylate functionality based on the total weight of the composition;

the monoalkenyl arene block copolymer includes a styrene-butadiene-styrene triblock copolymer present at a concentration from about 5 to about 25 weight percent based on the total weight of the composition; and

the methyl methacrylate is present at a concentration less than about 40 weight percent based on the total weight of the methyl methacrylate, the alkoxylated tetrahydrofurfuryl acrylate, the methacrylate having an oxirane ring, and the polybutadiene oligomer having a terminal acrylate functionality.

15. A polymerizable adhesive composition of claim 1, wherein the composition optionally includes a solvent, wherein the concentration of the solvent, if present, is less than about 20 wt. % based on the total weight of the composition.

16. A polymerizable adhesive composition of claim 1, wherein

the composition is a one-part adhesive composition;

the one or more compounds that undergo a free radical polymerization includes one or more ester of an unsaturated carboxylic acid, and from about 1 to about 10 weight percent based on the total weight of the composition of a polybutadiene oligomer having a terminal acrylate functionality; and

the organoboron compound includes an organoborane amine complex.

17. A method of polymerization comprising contacting the components of the polymerization composition of claim 1 under conditions such that the compounds capable of free radical polymerization undergo polymerization.

18. A method of claim 17 wherein the polymerization occurs at an ambient temperature.

19. A method of claim 18 wherein the process further comprises a step of heating the composition.

20. A method of bonding together a first substrate and a second substrate which comprises:

i) contacting the first part and the second part of any of the two-part composition of claim 2 under conditions such that polymerization is initiated;

ii) contacting the adhesive composition with the first and second substrate;

iii) positioning the first and second substrates such that the composition is interposed between the substrates;

iv) allowing the composition to polymerize so as to bind the substrates together;

wherein the first substrate, the second substrate, or both comprises a thermoplastic having a flexural modulus less than about 1200 MPa as measured according to ISO 178 at a rate of 2 mm/min.

21. A method of coating a TPO substrate comprising the steps of contacting the components of the composition of claim 2;

contacting the contacted composition with one or more surfaces of a substrate; and

allowing the contacted composition to cure on the surface of the substrate.

22. A coating composition which comprises the composition of claim 1.

23. A laminate comprising at least two substrates having disposed between the substrates and bound to each substrate a composition of claim 1.

24. A method of modifying the surface of a low energy polymer comprising the steps of:

contacting a composition of claim 1 with at least a portion of the surface of the low surface energy polymer; and

causing the organoboron compound to convert to a free radical generating species thereby initiating a polymerization of at least one compound in the composition such that the polymer formed is on the surface of the low surface energy polymer.

6. (canceled)

7. (canceled)

11. (canceled)

13. (canceled)