Internally incorporated phenolic resins in water-based (meth)acrylate adhesive compositions, pre-adhesive reaction mixtures, methods, and articles

Patent metadata

Field	Value
Publication number	US-11401447-B2
Application number	US-202016807839-A
Country	US
Kind code	B2
Filing date	Mar 3, 2020
Priority date	Dec 22, 2015
Publication date	Aug 2, 2022
Grant date	Aug 2, 2022

Abstract

Cationic or zwitterionic polymer adhesives, adhesive articles, aqueous polymerizable pre-adhesive reaction mixtures, and methods of preparation that include internal incorporation of a phenolic resin. The aqueous polymerizable pre-adhesive reaction mixtures include one or more cationic (meth)acrylate monomers, one or more low Tg nonionic monomer having a (meth)acryloyl group, optionally one or more anionic (meth)acrylate monomers, and one or more phenolic resins.

First claim

What is claimed is:

1. An aqueous polymerizable pre-adhesive reaction mixture comprising:
water;
one or more cationic (meth)acrylate monomers; and
a dispersed phase comprising one or more low Tg nonionic monomers and one or more phenolic resins, wherein the low Tg nonionic monomers have a (meth)acryloyl group and have a Tg of no greater than 20° C. when homopolymerized.

2. The aqueous pre-adhesive reaction mixture of claim 1 wherein the one or more phenolic resins comprise a terpene phenolic resin, an alkyl phenolic resin, or combinations thereof.

3. The aqueous pre-adhesive reaction mixture of claim 2 wherein the one or more phenolic resins comprise a terpene phenolic resin.

4. The aqueous pre-adhesive reaction mixture of claim 3 wherein the terpene phenolic resin has a hydroxyl value of 20 to 220 mg KOH per gram resin.

5. The aqueous pre-adhesive reaction mixture of claim 2 wherein the one or more phenolic resins comprise an alkyl phenolic resin.

6. The aqueous pre-adhesive reaction mixture of claim 5 wherein the alkyl phenolic resin comprises a para-alkylphenol-formaldehyde novolac resin.

7. The aqueous pre-adhesive reaction mixture of claim 1 wherein the phenolic resin is present in the pre-adhesive reaction mixture in an amount of 2 to 30 parts per one hundred parts of total monomers.

8. The aqueous pre-adhesive reaction mixture of claim 1 wherein the one or more cationic (meth)acrylate monomers comprise a (meth)acrylate ester having an alkyl ammonium functionality, or a mixture of two or more thereof.

9. The aqueous pre-adhesive reaction mixture of claim 1 wherein the low Tg nonionic monomer is an alkyl acrylate with the alkyl being a non-tertiary alkyl group having 1 to 18 carbon atoms.

10. The aqueous pre-adhesive reaction mixture of claim 1 wherein the pre-adhesive reaction mixture further comprises one or more anionic (meth)acrylate monomers.

11. A polymerized product of the aqueous pre-adhesive reaction mixture of claim 1 .

12. An adhesive composition comprising 70 wt-% to 98 wt-% of a cationic or zwitterionic polymer and 2 wt-% to 30 wt-% of a phenolic resin, based on the total weight of the cationic or zwitterionic polymer plus the phenolic resin.

13. The adhesive composition of claim 12 , wherein the cationic or zwitterionic polymer comprises:
2 wt-% to 45 wt-%, based on the total weight of monomers, of one or more cationic monomers comprising a (meth)acrylate ester having an alkyl ammonium functionality;
10 wt-% to 98 wt-%, based on the total weight of monomers, of one or more low Tg nonionic monomers having a (meth)acryloyl group and having a Tg of no more than 20° C. when homopolymerized;
0 wt-% to 30 wt-%, based on the total weight of monomers, of one or more optional monomers comprising a) one or more high Tg nonionic monomer having a (meth)acryloyl group and having a Tg of at least 30° C. when homopolymerized, b) one or more polar monomer having a hydroxyl group, primary amido group, secondary amido group, a tertiary amido group, an amino group, an ether group, or an epoxy group, c) one or more vinyl monomer that is free of a (meth)acryloyl group, or d) a mixture of two or more thereof;
0 wt-% to 10 wt-%, based on the total weight of monomer, of one or more crosslinking monomers; and
0 wt-% to 5 wt-%, based on the total weight of monomers, of one or more anionic monomers comprising acrylic acid, methacrylic acid, a carboxylate salt monomer, or a mixture of two or more thereof, wherein the amount of carboxylate salt is determined based on the weight of the corresponding free acid.

14. The adhesive composition of claim 12 , wherein the cationic or zwitterionic polymer comprises:
2 wt-% to 20 wt-%, based on the total weight of monomers, of one or more cationic monomers comprising a (meth)acrylate ester having an alkyl ammonium functionality;
45 wt-% to 98 wt-%, based on the total weight of monomers, of one or more low Tg nonionic monomers having a (meth)acryloyl group and having a Tg no greater than 20° C. when homopolymerized;
0 wt-% to 30 wt-%, based on the total weight of monomers, of one or more optional monomers comprising a) one or more high Tg nonionic monomer having a (meth)acryloyl group and having a Tg of at least 30° C. when homopolymerized, b) one or more polar monomer having a hydroxyl group, primary amido group, secondary amido group, a tertiary amido group, an amino group, an ether group, or an epoxy group, c) one or more vinyl monomer that is free of a (meth)acryloyl group, or d) a mixture of two or more thereof; and
0 wt-% to 5 wt-%, based on the total weight of the monomers, of one or more anionic monomers comprising acrylic acid, methacrylic acid, a carboxylate salt thereof, or a mixture of two or more thereof, wherein the amount of carboxylate salt is determined based on the weight of the corresponding free acid.

15. An adhesive article comprising a support having first and second opposed major surfaces, and an adhesive composition of claim 12 disposed on at least a portion of at least one of the first and second opposed major surfaces.

Assignees

• 3M Innovative Properties Co

Inventors

• El Hedok Ibrahim A
• Ali Mahfuza B
• Johnson Elizabeth E
• Purgett Mark D
• Kim Youhoon
• Antony Prince P

Classifications

• C09J133/14

  of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen · CPC title

• C09J161/06

  of aldehydes with phenols · CPC title

• C09J161/14 Primary

  Modified phenol-aldehyde condensates · CPC title

• C08G8/30

  by unsaturated compounds, e.g. terpenes · CPC title

• C08G8/12

  with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol · CPC title