Anaerobic curable compositions containing blocked (meth)acrylic acid compounds

Patent metadata

Field	Value
Publication number	US-9994510-B2
Application number	US-201615340385-A
Country	US
Kind code	B2
Filing date	Nov 1, 2016
Priority date	May 1, 2014
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

The present invention relates to anaerobic curable compositions, such as adhesives and sealants, containing blocked acrylic acid compounds. The blocked acrylic acid compounds are labile (meth)acrylic acid compounds having an acetal linkage, which cleaves to release (meth)acrylic acid during anaerobic cure. In this way, the block acrylic acid compounds acts as an adhesion promoter thereby promoting adhesion to various substrates.

First claim

The invention claimed is:

1. An anaerobic curable composition comprising:
(i) a (meth)acrylate component;
(ii) an anaerobic cure system; and
(iii) an adhesion promoter comprising a labile (meth)acrylic acid compound, wherein the labile (meth)acrylic acid compound is the reaction product of (meth)acrylic acid and a vinyl ether compound selected from the group consisting of ethyl vinyl ether; isobutyl vinyl ether; n-butyl vinyl ether; tert-Butyl vinyl ether; cyclohexyl vinyl ether; 1,4-cyclohexane dimethanol divinyl ether; butanediol divinyl ether; hydroxybutyl vinyl ether; diethylene glycol divinyl ether; triethylene glycol divinyl ether; dodecyl vinyl ether; octadecyl vinyl ether; 4-(hydroxy methyl) cyclohexyl methyl vinyl ether; 2-ethyl hexyl vinyl ether; diethylene glycol monovinyl ether; poly-THF 290-divinyl ether; 3-amino propyl vinyl ether; tertamyl vinyl ether; diethylaminoethyl vinyl ether; ethyleneglycol butyl vinyl ether; ethyleneglycol divinyl ether; ethyleneglycol monovinyl ether; hexanediol divinyl ether; hexanediol monovinyl ether; isopropyl vinyl ether; polyethyleneglycol-520 methyl vinyl ether; pluriol-E200 divinyl ether; n-propyl vinyl ether; tetraethyleneglycol divinyl ether; triethyleneglycol methyl vinyl ether; and trimethylolpropane trivinyl ether.

2. The composition of claim 1 wherein the labile (meth)acrylic acid compound is an acetal compound.

3. An anaerobic curable composition comprising:
(i) a (meth)acrylate component;
(ii) an anaerobic cure system; and
(iii) an adhesion promoter comprising a labile (meth)acrylic acid compound, wherein the labile (meth)acrylic acid compound is the reaction product of a vinyl ether compound and (meth)acrylic acid.

4. An anaerobic curable composition comprising:
(i) a (meth)acrylate component;
(ii) an anaerobic cure system; and
(iii) an adhesion promoter comprising a labile (meth)acrylic acid compound, wherein the labile (meth)acrylic acid compound is embraced by:

wherein B is a blocking unit and n is 1-2.

5. The composition of claim 1 wherein the (meth)acrylate component is represented by:
H 2 C=CGCO 2 R 1 , wherein G may be hydrogen, halogen, or alkyl groups having from 1 to about 4 carbon atoms, and R1 may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, or aryl groups having from 1 to about 16 carbon atoms, any of which may be optionally substituted or interrupted as the case may be with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, sulfonate and sulfone;
reaction products of the diglycidylether of bisphenol-A with methacrylic acid and a (meth)acrylate ester corresponding to structure as shown below:

where R 4 may be selected from hydrogen, alkyl groups having from 1 to about 4 carbon atoms, hydroxyalkyl groups having from 1 to about 4 carbon atoms or

R 5 may be selected from hydrogen, halogen, and alkyl groups of from 1 to about 4 carbon atoms;
R 6 may be selected from hydrogen, hydroxy and

m is an integer equal to at least 1, e.g., from 1 to about 8 or higher, for instance, from 1 to about 4;
v is 0 or 1; and
n is an integer equal to at least 1, e.g., 1 to about 20 or more; and
polyfunctional (meth)acrylate monomers, di- or trifunctional (meth) acrylates, polyethylene glycol di(meth)acrylates, tetrahydrofuran (meth)acrylates and di(meth)acrylates, hydroxypropyl (meth)acrylate, hexanediol di(meth)acrylate, trimethylol propane tri(meth)acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di-(pentamethylene glycol) dimethacrylate, tetraethylene diglycol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, bisphenol-A mono and di(meth)acrylates, ethoxylated bisphenol-A (meth)acrylate, and bisphenol-F mono and di(meth)acrylates, and ethoxylated bisphenol-F (meth)acrylate.

6. The composition of claim 1 wherein the anaerobic cure system comprises a free-radical initiator.

7. A composition comprising the reaction product of:
(i) a (meth)acrylate component;
(ii) an anaerobic cure system; and
(iii) an adhesion promoter comprising a labile (meth)acrylic acid compound, wherein the labile (meth)acrylic acid compound is the reaction product of (meth)acrylic acid and a vinyl ether compound selected from the group consisting of ethyl vinyl ether; isobutyl vinyl ether; n-butyl vinyl ether; tert-Butyl vinyl ether; cyclohexyl vinyl ether; 1,4-cyclohexane dimethanol divinyl ether; butanediol divinyl ether; hydroxybutyl vinyl ether; diethylene glycol divinyl ether; triethylene glycol divinyl ether; dodecyl vinyl ether; octadecyl vinyl ether; 4-(hydroxy methyl) cyclohexyl methyl vinyl ether; 2-ethyl hexyl vinyl ether; diethylene glycol monovinyl ether; poly-THF 290-divinyl ether; 3-amino propyl vinyl ether; tertamyl vinyl ether; diethylaminoethyl vinyl ether; ethyleneglycol butyl vinyl ether; ethyleneglycol divinyl ether; ethyleneglycol monovinyl ether; hexanediol divinyl ether; hexanediol monovinyl ether; isopropyl vinyl ether; polyethyleneglycol-520 methyl vinyl ether; pluriol-E200 divinyl ether; n-propyl vinyl ether; tetraethyleneglycol divinyl ether; triethyleneglycol methyl vinyl ether; and trimethylolpropane trivinyl ether.

8. A method of making an anaerobic curable composition comprising:
(i) Providing a composition comprising:
(a) a (meth)acrylate component; and
(b) an anaerobic cure system; and

(ii) Adding to the composition of step (i) an adhesion promoter comprising a labile (meth)acrylic acid compound, wherein the labile (meth)acrylic acid compound is the reaction product of (meth)acrylic acid and a vinyl ether compound selected from the group consisting of ethyl vinyl ether; isobutyl vinyl ether; n-butyl vinyl ether; tert-Butyl vinyl ether; cyclohexyl vinyl ether; 1,4-cyclohexane dimethanol divinyl ether; butanediol divinyl ether; hydroxybutyl vinyl ether; diethylene glycol divinyl ether; triethylene glycol divinyl ether; dodecyl vinyl ether; octadecyl vinyl ether; 4-(hydroxy methyl) cyclohexyl methyl vinyl ether; 2-ethyl hexyl vinyl ether; diethylene glycol monovinyl ether; poly-THF 290-divinyl ether; 3-amino propyl vinyl ether; tertamyl vinyl ether; diethylaminoethyl vinyl ether; ethyleneglycol butyl vinyl ether; ethyleneglycol divinyl ether; ethyleneglycol monovinyl ether; hexanediol divinyl ether; hexanediol monovinyl ether; isopropyl vinyl ether; polyethyleneglycol-520 methyl vinyl ether; pluriol-E200 divinyl ether; n-propyl vinyl ether; tetraethyleneglycol divinyl ether; triethyleneglycol methyl vinyl ether; and trimethylolpropane trivinyl ether.

9. A composition comprising the reaction product of:
(i) a (meth)acrylate component;
(ii) an anaerobic cure system; and
(iii) an adhesion promoter comprising a labile (meth)acrylic acid compound, wherein the labile (meth)acrylic acid compound is the reaction product of a vinyl ether compound and (meth)acrylic acid.

10. A composition comprising the reaction product of:
(i) a (meth)acrylate component;
(ii) an anaerobic cure system; and
(iii) an adhesion promoter comprising a labile (meth)acrylic acid

Assignees

• Henkel IP & Holding GmbH

Inventors

• Messana Andrew D
• Burdzy Sean M
• Schall Joel D
• Jacobine Anthony F

Classifications

• C08F220/281

  and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate · CPC title

• C09K3/1006

  characterised by the chemical nature of one of its constituents · CPC title

• C08F220/286

  and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate · CPC title

• C09K2200/0625

  Polyacrylic esters or derivatives thereof · CPC title

• C08F222/02

  Acids; Metal salts or ammonium salts thereof {, e.g. maleic acid or itaconic acid} · CPC title