Two-component binder system with cyclocarbonate and epoxy groups

Abstract

The present invention relates to a binder system containing a resin component and a curing agent component, wherein the resin comprises at least one compound carrying at least two cyclic carbonate groups and at least one compound carrying at least two epoxy groups, and the curing agent comprises at least one multifunctional amine as well as the use of the binder system as an adhesive/sealant and the use of this adhesive/sealant.

Claims

1. A two component binder system containing resin component (A) and curing agent component (B), wherein: (i) Component (A) comprises at least one compound containing at least two cyclic carbonate groups and at least one compound containing at least two epoxy groups; and (ii) Component (B) comprises: a first compound containing at least two (NHR) atomic groups and having a molecular weight of 60 g/mol to 500 g/mol, and a second compound containing at least two (NHR) atomic groups and having a molecular weight of greater than 500 g/mol, wherein R is H, an alkyl or aryl radical.

2. The binder system according to claim 1, wherein the at least one compound containing at least two cyclic carbonate groups is a polymer containing cyclic carbonate groups selected from the group consisting of optionally alkoxylated castor oil, optionally alkoxylated dimer diol, polyethers, polyether polyols, polyesters, polyester polyols, polycarbonates, polycarboxylic acids, polyacrylates, polymethacrylates, polyamides, polyamines, polyurethanes, and mixtures thereof.

3. The binder system according to claim 1, wherein the at least one compound containing at least two cyclic carbonate groups is a reaction product of cyclic hydroxyalkyl carbonate with a polymer containing isocyanate groups.

4. The binder system according to claim 1, wherein the at least one compound containing at least two cyclic carbonate groups is a reaction product of cyclic hydroxyalkyl carbonate having a five-membered or six-membered carbonate ring with a polymer containing isocyanate groups.

5. The binder system according to claim 1, wherein the at least one compound containing at least two cyclic carbonate groups is a reaction product of a glycerin carbonate with a polymer containing isocyanate groups.

6. The binder system according to claim 1, wherein the at least one compound containing at least two cyclic carbonate groups is a reaction product of cyclic hydroxyalkyl carbonate with an isocyanate group-terminated polyurethane prepolymer that is the reaction product of a polyol with an aromatic diisocyanate.

7. The binder system according to claim 1, wherein the at least one compound containing at least two cyclic carbonate groups is a reaction product of cyclic hydroxyalkyl carbonate with an isocyanate group-terminated polyurethane prepolymer that is the reaction product of a polyol with an average molecular weight Mw of 75 to 2000 g/mol with methylene diphenyl diisocyanate.

8. The binder system according to claim 1, wherein the compound containing at least two epoxy groups is an aliphatic epoxy.

9. The binder system according to claim 1, wherein the compound containing at least two epoxy groups is an aliphatic epoxy with an EEW of 120 to 350 g/mol.

10. The binder system according to claim 1, wherein the first and second compounds of Component (B) are: (i) selected from the group consisting of alkylene diamines, cycloalkylene diamines, amine-functionalized polyalkylene glycols, and polyfunctional amines; (ii) a polymer or a highly branched polymer or a dendrimer, selected from the group consisting of polyamines, polyimines, polyethers, polyamides, polyaminoamides, polyurethanes, polyolefins, polyvinyl amines, and mixtures thereof; or (iii) a mixture of the compounds according to (i) and (ii).

11. A cured reaction product of a mixture comprising Component (A) and Component (B) of claim 1.

12. A two-component adhesive comprising the binder system of claim 1.

13. A two-component adhesive comprising the binder system of claim 1, wherein the adhesive is solvent-free.

14. A two-component adhesive comprising the binder system of claim 1, wherein the adhesive further comprises solvent.

15. A food package comprising a laminate of at least two films with the binder system of claim 1 disposed therebetween.

16. A food package comprising a laminate of at least two films bonded together by cured reaction products of an adhesive comprising the binder system of claim 1.

17. A method for producing an adhesive or sealant using the binder system of claim 1, comprising: providing the binder system of claim 1; mixing component (A) with component (B) in a ratio of carbonate groups to primary amino groups of 30:1 to 0.2:1, wherein the mixing ratio is to be applied to secondary amino groups in the absence of primary amino groups.

18. A method for producing an adhesive or sealant using the binder system of claim 1, comprising: providing the binder system of claim 1; mixing component (A) with component (B) in a ratio of carbonate groups to primary amino groups of 5:1 to 0.5:1, wherein the mixing ratio is to be applied to secondary amino groups in the absence of primary amino groups.

19. A method for producing an adhesive or sealant using the binder system of claim 1, comprising: providing the binder system of claim 1; and mixing component (A) with component (B) in a ratio of carbonate groups to primary amino groups of about 1:1, wherein the mixing ratio is to be applied to secondary amino groups in the absence of primary amino groups.

20. The binder system according to claim 1, wherein the first compound containing at least two (NHR) atomic groups has a molecular weight of 60 g/mol to 300 g/mol.

21. The binder system according to claim 20, wherein the second compound containing at least two (NHR) atomic groups has a molecular weight of 500 g/mol to 5,000,000 g/mol.

22. The binder system according to claim 21, wherein the second compound containing at least two (NHR) atomic groups has a molecular weight of 600 g/mol to 20,000 g/mol.

Description

EXAMPLES

(1) Raw Materials:

(2) PPG2000: Voranol 2000 L, propylene glycol, Mw=2000 g/mol, Dow

(3) Lupranat MIS: diphenylmethane diisocyanate, isomer mixture, BASF

(4) Glycerin carbonate: Jeffsol glycerin carbonate (4-hydroxymethyl-1,3-dioxolan-2-one), Huntsman

(5) TIB Kat 216: dioctyltin dilaurate, TIB Chemicals

(6) Epoxy 1: commercially available difunctional propylene glycol-based epoxy resin (EEW 320 g/mol)

(7) Amine 1: commercially available difunctional amine with only primary amino groups, Mw=176 g/mol

(8) Amine 2: commercially available hyperbranched polyethyleneimine (primary/secondary/tertiary amine ratio: 1/0.9/0.5), Mw=800 g/mol

(9) Preparation of the Components:

(10) Synthesis of the Solvent-free Prepolymer 1 (KA1)

(11) PPG2000 (435.46 g) is placed in a three-neck flask, dehydrated (10 mbar, 80 C.) for 1 hour and aerated with nitrogen. After cooling and storing overnight under a protective gas, Lupranat MIS (104.69 g) was added, and after dissolving completely, the reaction mixture was adjusted to 80 C. again. NCO titrations are performed regularly and at NCO=2.91%, glycerin carbonate (46.30 g) is added at a lower temperature (50.6 C.). Immediately following that, 0.05% by weight TIB Kat 216 (0.30 g) was additionally added and after the exothermic reaction was finished, the reaction mixture was again heated to 80 C. until reaching NCO <0.1%.

(12) Synthesis of the Solvent-Based Prepolymer 2 (KA2)

(13) PPG2000 (1548.14 g) is placed in a three-neck flask, dehydrated (<10 mbar, 80 C.) for 1 hour and aerated with nitrogen. After cooling and storing overnight under a protective gas, the reaction mixture was adjusted immediately to approx. 34 C. and Lupranat MIS (371.92 g) was added. After complete homogenization, the reaction mixture is again set or 80 C. NCO titrations are carried out regularly and at NCO=3.01%, glycerin carbonate (164.69 g) is added at a lower temperature (50.2 C.). Immediately after that, 0.05% by weight TIB Kat 216 (0.30 g) was additionally added, and after the exothermic reaction was completed, the reaction mixture was again heated to 80 C. until reaching NCO<0.1%. Next at approx. 55 C., ethanol (1390.46 g) was added to achieve a solids content 60% by weight.

(14) Component A with Epoxy (KA3)

(15) KA1 (2100 g) was placed in a vessel and epoxy resin was added to epoxy 1 (176 g). The mixture was stirred with a wooden spatula until it was homogenized and was stored until use.

(16) Preparation of the Curing Agent (KB1)

(17) Amine 1 (20.00 g) and amine 2 (80.09 g) were mixed at one temperature using a magnetic stirrer until the mixture was homogenous.

(18) Preparing the adhesives and laminations:

(19) Preparation of the Solvent-Based Adhesive 1 and Lamination (KS1) (Comparative Example)

(20) KA1 (11.00 g) was dissolved in ethyl acetate (35.4805 g). In addition KB1 (0.8268 g) was added (ratio of primary amine/cyclocarbonate=1/1-equivalent). This produces an adhesive that has a solids content of 25% by weight and can be laminated (KS1). KS1 was applied to a PET film using a spiral doctor applicator (0.08 mm), and the solvent was evaporated for 5 minutes at 90 C. in a drying cabinet. Immediately thereafter the lamination was completed with a PE film (surface corona pretreated) with the help of a laboratory lamination device. The laminate (2 to 3.5 g/m.sup.2, dry) was stored at 40 C. under pressure (5 kg weight) and strips were cut off regularly to determine the laminate adhesion (15 mm wide strips, 90 peel tests on a tensile testing machine at 100 mm/min). An IR spectrum was recorded of the PE layer of laminate (ATR). Laminate adhesion after one day at 40 C.: PET/PE 0.72 N/15 mm, co-adhesive break, both strips still tacky. The IR spectrum after 3 days at 40 C. still had the cyclocarbonate carbonyl group band at 1818.30 cm.sup.1.

(21) Preparing the Solvent-Based Adhesive 2 and Lamination (KS2) (According to the Invention)

(22) KA3 (2276 g) was dissolved in ethanol (2330 g) and the curing agent KB1 (157 g) was added to it (ratio of primary amine/cyclocarbonate=1/1-equivalent) and homogenized using wooden spatula. The result was an adhesive containing 32% by weight solids which could be laminated (KS2). KS2 was applied by means of a laboratory combination lamination system with roller application (engraving roller with 50 lines per cm) and the parameters were adjusted so that the application weight (dry) was approx. 2.5 g/m.sup.2. The laminated wound roll was stored at 40 C. immediately after lamination. Laminate adhesion after 1 day at 40 C.: PET/PE: 2.05 N/15 mm, adhesive break, PE still tacky. IR spectrum after 2 days at 40 C. no longer had a band for the cyclocarbonate carbonyl group at 1818.30 cm.sup.1.