Aqueous reactive putty (I)

• US 6,706,801 B1
• Filed: 06/14/2001
• Issued: 03/16/2004
• Est. Priority Date: 12/21/1998
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Wolff, Joachim, Clemens, Horst, Irle, Christoph, Blum, Harald, Ehlers, Michael, Probst, Joachim
• Primary Examiner(s): REDDICK, MARIE L
• Application Number:
  US09/868,404
• Time in Patent Office: 1,006 Days
• Field of Search: 524/507, 524/591, 523/201, 428/424.2, 428/424.8, 428/424.4
• US Class Current: 524/507
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/3225 Polyamines
• CPC Class Codes: C08G 18/3271 Hydroxyamines
• CPC Class Codes: C08G 18/6254 Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
• CPC Class Codes: C08G 18/706 the liquid medium being water
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 18/7837 containing allophanate groups
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/798 containing urethdione groups
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: C09D 5/34 Filling pastes materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12
• CPC Class Codes: Y10T 428/31573 Next to addition polymer of ethylenically unsaturated monomer
• CPC Class Codes: Y10T 428/31576 Ester monomer type [polyvinylacetate, etc.]
• CPC Class Codes: Y10T 428/31587 Hydrocarbon polymer [polyethylene, polybutadiene, etc.]

Abstract

The invention relates to aqueous reactive 2-component binder combinations for aqueous reactive filler compositions, processes for the preparation of aqueous reactive filler compositions based on aqueous reactive 2-component binder combinations and the use of such filler compositions.

Claims

1. An aqueous, reactive binder composition for aqueous, reactive, filler compositions comprising

a) at least one emulsion copolymer which contains isocyanate-reactive groups and which is present in an aqueous dispersion or an emulsion, said copolymer being produced by polymerizing a monomer mixture of a1), a2), a3) and a4):

a1) from 50 to 85 wt. % of one or more hardening monomers, said hardening monomers producing homopolymers having glass transition temperature above 0°

C.,

a2) from 5 to 30 wt. % of one or more plasticizing monomers, said plasticizing monomers producing homopolymers having glass transition temperatures below 0°

C.,

a3) from 2 to 30 wt. % of one or more hydroxy-functional monomers, and

a4) from 1 to 4 wt. % of one or more carboxyl- and/or carboxylate-functional monomers,

wherein the sum of monomers a1) through a4) is 100 wt. % and

b) at least one polyisocyanate which contains free isocyanate groups and has a viscosity of from 10 to 10,000 mPas/23°

C. and a functionality of from 2.4 to 5.5.

2. The reactive binder composition of claim 1, wherein said hardening monomers a1) are selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, iso-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, phenyl methacrylate, styrene, α

-methylstyrene, vinyl toluene, acrylonitrile, methacrylonitrile, dimethyl maleate, diethyl maleate and mixtures thereof, and

wherein said plasticizing monomers a2) are selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, iso-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, nonyl acrylate, n-otyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, iso-decyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, norbornyl acrylate, methoxypolypropylene glycol acrylate, methoxypolyethylene glycol acrylate, isobornyl acrylate, oleyl acrylate, palmityl acrylate, n-heptyl methacrylate, nonyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, Iso-decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, methoxypolyethylene glycol methacrylate, methoxypolypropylene glycol methacrylate, oleyl methacrylate, palmityl methacrylate, di-n-butyl maleate and mixtures thereof.

3. The aqueous, reactive binder composition of claim 1, wherein the monomer mixture of a1), a2), a3) and a4) contains at least 40 wt. % based on the total solids content of said copolymer, of styrene as at least part of monomer a1).

4. The aqueous, reactive binder composition of claim 1, wherein

a1) said hardening monomer is selected from the group consisting of styrene, methyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate and mixtures thereof,

a2) said plasticizing monomer is selected from the group consisting of n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and mixtures thereof,

a3) said hydroxy-functional monomer is selected from the group consisting of hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, and mixtures thereof,

a4) said carboxyl and/or carboxylate-functional monomer is selected from the group consisting of acrylic acid, methacrylic acid and mixtures thereof and wherein at amounts of up to 1.5 wt. % of a4), at least 50% are present in neutralized from, and

wherein said composition contains from 1.0 to 2.0 wt. %, based on the total amount of monomers, of emulsifier or emulsifier mixtures and from 0.15 to 0.45 wt. %, based on the total amount of monomers, of initiator or initiator mixtures, and

wherein said copolymer has i) a solids content Is from 30 to 56 wt. %, ii) a viscosity of from 10 to 5,000 mPas/23°

C., iii) an acid number of from 5 to 30 mg KOH/g, based on a solids content of 100 wt. %, and iv) an hydroxyl group content of from 0.2 to 3.5 wt. %, based on a solids content of 100 wt. %, and the aqueous dispersion or emulsion has a pH of from 5.5 to 9.

5. The aqueous, reactive binder composition of claim 1, wherein polyisocyanate b) is selected from the group consisting of i) low-viscosity hydrophobic polyisocyanates based on hexamethylene-diisocyanate and containing isocyanurate, uretdione, allophanate and/or urethane groups, ii) polyisocyanates based on hexamethylene-diisocyanate and hydrophilically modified by reaction with a hydrophilic polyether and iii) mixtures thereof.

6. The aqueous reactive binder composition of claim 1, wherein polyisocyanate b) comprises an allophanate-hydrophilic polyisocyanate prepared by the reaction of a hydrophilic polyether with an aliphatic and/or cycloaliphatic polyisocyanate employing suitable catalysts.

7. The aqueous, reactive binder composition of claim 1, wherein polyisocyanate b) comprises a hexamethylene-diisocyanate polyisocyanate with iminooxadiazinedione groups.

8. The aqueous, reactive binder composition of claim 1, wherein polyisocyanate b) comprises nonane-triisocyanate.

9. The aqueous, reactive binder composition of claim 1, wherein said copolymer a) has a core/shell structure, the core content is 20 to 80 wt. % and the core and shell comprise different amounts of the isocyanate-reactive groups and/or the plasticizing monomer.

10. The aqueous, reactive binder composition of claim 1, wherein components a) and b) are light-fast.

11. Wood, a woody substrate or cork coated with the aqueous reactive binder composition of claim 1.

12. A metallic substrate, vehicle body or plastic coated with the aqueous, reactive binder composition of claim 1.

13. A marble, granite and mineral substrate coated with the aqueous, reactive binder composition of claim 1.

14. A glass fibre-reinforced plastic, glass fibre-reinforced sheet-like structure or casting resin coated with the aqueous, reactive binder composition of claim 1.

15. An aqueous, reactive, filler composition comprising:

a) 10 to 50 wt. % of at least one emulsion copolymer which contains isocyanate-reactive groups and has a weight average molecular weight of >

50,000 g/mol, said copolymer being produced by polymerizing;

a1) from 50 to 85 wt. % of one or more hardening monomers, said hardening monomers producing homopolymers having glass transition temperature above 0°

C.,

a2) from 5 to 30 wt. % of one or more plasticizing monomers, said plasticizing monomers producing homopolymers having glass transition temperatures below 0°

C.,

a3) from 2 to 30 wt. % of one or more hydroxy-functional monomers, and

a4) from 1 to 4 wt. % of one or more carboxyl- and/or carboxylate-functional monomers,

wherein the sum of monomers a1) through a4) is 100 wt. % and

b) from 1 to 9.8 wt. % of at least one polyisocyanate which contains free isocyanate groups and has a viscosity of from 10 to 20,000 mPas/23°

C. and a functionality of 2 to 6,

c) from 40 to 90 wt. % of at least one pigment and/or filler,

d) from 0 to 3 wt. % of an auxiliary substance or additive,

e) from 0 to 50 wt. % of further oligomer or polymer other than a), optionally present in the form of an aqueous solution, dispersion or emulsion, and

f) from 0 to 20 wt. % of water and/or an organic solvent,

wherein the sum of a) to f) is 100 wt. % and the weight ratio of resin (solids from component a), component b) and component e)) to pigment/filler (solids from component c)) is from 1;

1.5 to 1;

15.

16. The aqueous, reactive, filler composition of claim 15, comprising

a) from 22 to 38 wt. % of component a),

b) from 1 to 7.5 wt. % of component b), and wherein component b) has a viscosity of from 10 to 10,000 mPas/23° C. and a functionality of from 2.4 to 5.5,

c) from 53 to 75 wt. % of component c),

d) from 0 to 2 wt. % of component d),

e) from 0 to 20 wt. % of component e), and

f) from 0 to 10 wt. % of component f), and

wherein the weight ratio of resin (solid from component a), component b) and component e)) to pigment/filler (solids from component c)) is from 1;

2.1 to 1;

10.

17. The aqueous, reactive, filler composition of claim 15, wherein no more than 10 wt. %, based on the total amount of c) is an inorganic coloring pigment.

18. The aqueous, reactive, filler composition of claim 15, wherein component e) comprises epoxy- and/or carbodiimide-functional oligomer or polymer.

19. The aqueous, reactive, filler composition of claim 15, which contains less than 5 wt. % of volatile organic substances.

20. A process for the preparation of the aqueous, reactive, filler composition of claim 15 comprising i) mixing components a), c), d), e) and f) and ii) homogeneously mixing component b).

21. A process for the preparation of the aqueous, reactive, filler composition of claim 15 comprising i) mixing components a), c), d), e), and up to 10 wt. %, based on the total solids content, of component f) and polyisocyanate b), and ii) adjusting to the required processing consistency by adding the remainder of component f).