Oxazoline-containing aqueous polymer dispersions for composite film lamination

Patent metadata

Field	Value
Publication number	US-10364379-B2
Application number	US-201615558326-A
Country	US
Kind code	B2
Filing date	Mar 8, 2016
Priority date	Mar 18, 2015
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

Abstract

Described are aqueous polymer dispersions for composite film lamination and a multistage process for preparing them from ethylenically unsaturated, radically polymerizable monomers. In a first stage, a first polymer is prepared by radical emulsion polymerization. In a further stage, an aqueous polymer dispersion is prepared in the presence of the first polymer. The monomers of the first stage comprise monomers with acid groups. The monomers of the further stage comprise monomers having oxazoline groups. The polymerization of the first stage takes place at a low pH of less than 5. The acid groups of the first polymer are neutralized before the polymerization of the further stage. The aqueous polymer dispersions can be used as adhesives for producing composite films.

First claim

The invention claimed is:

1. A laminating adhesive, comprising an aqueous polymer dispersion comprising a polymer having a glass transition temperature of less than −10° C., wherein the polymer comprises, in polymerized form:
ethylenically unsaturated, radically polymerizable monomers;
at least one monomer having at least one acid group, in an amount of at least 0.1 part by weight, based on 100 parts by weight of all polymerizable monomers; and
at least one monomer having at least one oxazoline group.

2. The laminating adhesive of claim 1 , wherein the polymer comprises from 0.5 to 4 parts by weight of the at least one monomer having at least one oxazoline group, based on 100 parts by weight of all polymerizable monomers.

3. The laminating adhesive of claim 1 , wherein the at least one monomer having at least one oxazoline group is a monomer of formula:

wherein:
R is a C 2-20 alkenyl radical comprising at least one ethylenically unsaturated group; and
R 3 , R 4 , R 5 , and R 6 are selected independently of one another from the group consisting of H, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, C 7-32 arylalkyl, C 1 -C 20 hydroxyalkyl, C 1-20 aminoalkyl, and C 1-20 haloalkyl.

4. The laminating adhesive of claim 1 , wherein the at least one monomer having at least one oxazoline group is selected from the group consisting of 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-4,4-dimethyl-2-oxazoline, 2-vinyl-5,5-dimethyl-2-oxazoline, 2-vinyl-4,4,5,5-tetramethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline, 2-isopropenyl-5,5-dimethyl-2-oxazoline, and 2-isopropenyl-4,4,5,5-tetramethyl-2-oxazoline.

5. The laminating adhesive of claim 1 , wherein: the monomers comprising acid groups are selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, vinyllactic acid, unsaturated phosphonic acids, and mixtures of these monomers.

6. The laminating adhesive of claim 1 , wherein the ethylenically unsaturated, radically polymerizable monomers are exclusively derivatives of (meth)acrylic acid.

7. The laminating adhesive of claim 1 , wherein the polymer further comprises a latex.

8. A staged radical emulsion polymerization process for preparing the laminated adhesive of claim 1 , the process comprising:
a first stage in which a first composition comprising ethylenically unsaturated, radically polymerizable monomers is subjected to radical emulsion polymerization in an aqueous medium, to obtain a first polymer dispersed in water; and then
a second stage in which a second composition, which is different from the first composition and comprises ethylenically unsaturated, radically polymerizable monomers, is subjected to radical emulsion polymerization in an aqueous medium and in the presence of the first polymer,
wherein:
the first composition comprises the at least one monomer having at least one acid group, in an amount of at least 0.1 part by weight, based on 100 parts by weight of the monomers of all stages;
the second composition comprises the at least one monomer having at least one oxazoline group;
the radical emulsion polymerization of the first stage occurs at a pH less than 5 and, before the radical emulsion polymerization of the second stage, acid groups are neutralized with a volatile base to an extent such that the pH of the first polymer dispersed in water before the second stage is greater than 5; and
less than 0.5 part by weight, based on 100 parts by weight of monomers, of an emulsifier is optionally present in the staged radical emulsion polymerization process.

9. A composite film, comprising a first film and at least one second film, which are bonded to one another with the laminating adhesive of claim 1 .

10. A process for producing composite films, the process comprising bonding at least two films with one another using the laminating adhesive of claim 1 .

11. The laminating adhesive of claim 1 , wherein the glass transition temperature of the polymer is less than −14° C.

12. The process of claim 8 , wherein no emulsifier is present in the staged radical emulsion polymerization process.

13. The process of claim 8 , wherein, in the first stage, monomers comprising acid groups are copolymerized with monomers without acid groups, and a weight ratio of the monomers comprising acid groups to the monomers without acid groups ranges from 5:95 to 15:85.

14. The process of claim 8 , wherein at least 60% by weight of the monomers used in the second stage are selected from the group consisting of C1 to C20 alkyl acrylates, C1 to C20 alkyl methacrylates, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinylaromatics having up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols comprising 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds, and mixtures of these monomers.

15. The process of claim 8 , wherein a chain transfer agent is present during the first stage.

16. The process of claim 8 , wherein a weight ratio of monomers used in the first stage to monomers used in the second stage is from 10:90 to 65:35.

17. The process of claim 8 , wherein the monomers used in the second stage comprise not more than 1 part by weight, based on 100 parts by weight, of monomers with acid groups, or comprise no monomers with acid groups.

18. The process of claim 8 , wherein less than 0.3 part by weight, based on 100 parts by weight of monomers, of the emulsifier is optionally present in the staged radical emulsion polymerization process.

Assignees

• Basf Se

Inventors

• Zorn Matthias
• Schumacher Karl-Heinz

Classifications

• C09D151/003

  grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C09D151/04, C09D151/06 take precedence) · CPC title

• C09J137/00

  Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen (based on polymers of cyclic esters of polyfunctional acids C09J131/00; based on polymers of cyclic anhydrides of unsaturated acids C09J135/00); Adhesives based on derivatives of such polymers · CPC title

• C08F265/06 Primary

  Polymerisation of acrylate or methacrylate esters on to polymers thereof · CPC title

• C09J2205/31

  Chemistry & Metallurgy · mapped topic

• C08F224/00

  Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen (cyclic esters of polyfunctional acids C08F218/00; cyclic anhydrides of unsaturated acids C08F220/00, C08F222/00) · CPC title