Adhesives based on carbodimide chemistry

Patent metadata

Field	Value
Publication number	US-12054576-B2
Application number	US-202017435758-A
Country	US
Kind code	B2
Filing date	Mar 5, 2020
Priority date	Mar 7, 2019
Publication date	Aug 6, 2024
Grant date	Aug 6, 2024

Abstract

Described herein is a thermosetting resin composition, obtained from the reaction of at least: a polycarbodiimide (i), where the number of carbodiimide groups per molecule is in the range of from 1 to 10; a mixture of crystalline and amorphous polyols (ii), where the molar ratio of carbodiimide groups in the polycarbodiimide according to (i) to hydroxyl groups in the mixture according to (ii) is in the range of from 1:2 to 2:1 and where at least 25 weight-% of the mixture according to (ii) consists of at least one crystalline polyesterol, based on the overall weight of the mixture being 100 weight-%. Also described herein is a method of using the thermosetting resin composition as an adhesive, as well as processes for preparation of adhesives, an element including an adhesive layer on at least one substrate, and an adhesive film, obtained from one of the processes.

First claim

The invention claimed is:

1. A thermosetting resin composition, obtained from the reaction of at least:
i) a polycarbodiimide, wherein the number of carbodiimide groups per molecule is in the range of from 2 to 10; and
ii) a mixture of crystalline and amorphous polyols,
wherein the molar ratio of carbodiimide groups in the polycarbodiimide according to (i) to hydroxyl groups in the mixture according to (ii) is in the range of from 1:2 to 2:1, and wherein at least 25 weight-% of the mixture according to (ii) consists of at least one crystalline polyesterol, based on the overall weight of the mixture being 100 weight-%.

2. The thermosetting resin composition according to claim 1 , wherein the polycarbodiimide according to (i) is obtained from the reaction of at least:
i.1) a polyisocyanate composition comprising at least one diisocyanate; and
i.2) a monofunctional compound selected from the group consisting of a monoisocyanate, an isocyanate reactive monofunctional compound, wherein the isocyanate reactive monofunctional compound is selected from the group consisting of a monoalcohol, a monothiol, a monoamine, and mixtures of two or more of these isocyanate reactive monofunctional compounds, and a mixture of monoisocyanate and isocyanate reactive monofunctional compound;
in the presence of a carbodiimidization catalyst (i.3).

3. The thermosetting resin composition according to claim 2 , wherein the polycarbodiimide according to (i) is obtained by
a) mixing the polyisocyanate composition according to (i.1) with at least a part of the monofunctional compound according to (i.2) at a temperature Ti thereby obtaining a first mixture;
b) adding the catalyst (i.3) to the first mixture obtained in (a) at a temperature T 2 wherein T 2 is >T 1 , thereby obtaining a precursor compound;
c) adjusting the precursor compound obtained in (b) to a temperature T 3 ; and
d) adding the remaining part of the monofunctional compound according to (i.2) at temperature T 3 ; thereby obtaining the polycarbodiimide according to (i);
wherein:
T 1 is a temperature below 70° C.;
T 2 is a temperature ≥70° C.; and
T 3 is a temperature below 100° C.

4. The thermosetting resin composition according to claim 1 , wherein the at least one crystalline polyesterol of the mixture according to (ii) has a melting temperature >30° C.

5. The thermosetting resin composition according to claim 1 , wherein the at least one crystalline polyesterol of the mixture according to (ii) has a molecular weight in the range of from 500 to 5000 g/mol.

6. The thermosetting resin composition according to claim 1 , wherein at least 50 weight-% of the mixture of crystalline and amorphous polyols consists of at least one crystalline polyesterol, based on the overall weight of the mixture being 100 weight-%.

7. The thermosetting resin composition according to claim 1 , wherein the at least one crystalline polyesterol of the mixture according to (ii) is a saturated polyesterol based on at least:
(ii.1) a compound having at least two hydroxyl groups reactive towards ester formation; and
(ii.2) a compound having at least two carboxyl groups reactive towards ester formation.

8. The thermosetting resin composition according to claim 1 , wherein the at least one crystalline polyesterol of the mixture according to (ii) is a polyesterol based on a C2 to C10 dicarboxylic acid selected from the group consisting of adipic acid, azelaic acid sebacic acid, 12-dodecanedioic acid and mixtures of two or more of these dicarboxylic acids and a diol which is hexane-1,6-diol, neopentylglycol or a mixture of hexane-1,6-diol and neopentylglycol; or
wherein the at least one crystalline polyesterol of the mixture according to (ii) is a saturated polyesterol based on at least an alpha-omega-hydroxy-carboxylic acid, a cyclic oligomer of an alpha-omega-hydroxy-carboxylic acid or a mixture of two or more thereof.

9. The thermosetting resin composition according to claim 1 , obtained from the reaction of at least:
i) a polycarbodiimide, wherein the number of carbodiimide groups per molecule is in the range of from 2 to 10; and
ii) a mixture of crystalline and amorphous polyols,
wherein the molar ratio of carbodiimide groups in the polycarbodiimide according to (i) to hydroxyl groups in the mixture according to (ii) is in the range of from 1:2 to 2:1, and wherein at least 25 weight-% of the mixture according to (ii) consists of at least one crystalline polyesterol, based on the overall weight of the mixture being 100 weight-%;
optionally in the presence of a catalyst (iii);
wherein the polycarbodiimide according to (i) is a toluene diisocyanate-based polycarbodiimide obtained from the reaction of at least:
i.1) a polyisocyanate composition comprising at least TDI; and
i.2) a monofunctional compound which is 2-ethyl hexan-1-ol;

in the presence of a carbodiimidization catalyst (i.3); and
wherein the at least one crystalline polyesterol of the mixture according to (ii) is a crystalline saturated copolyester based on hexane-1,6-dicarboxylic acid and hexane-1,6-diol.

10. An adhesive comprising the thermosetting resin composition according to claim 1 .

11. A process for preparation of an adhesive, comprising
a) mixing at least:
i) a polycarbodiimide, wherein the number of carbodiimide groups per molecule is in the range of from 2 to 10;
ii) a mixture of crystalline and amorphous polyols; and
iii) a catalyst;
wherein the molar ratio of carbodiimide groups in the polycarbodiimide according to (i) to hydroxyl groups in the polyesterol according to (ii) is in the range of from 1:2 to 2:1, and wherein at least 25 weight-% of the mixture according to (ii) consists of at least one crystalline polyesterol, based on the overall weight of the mixture being 100 weight-%;
wherein the mixing according to (a) is done at a temperature above the melting temperature Tm of the at least one polyesterol of the mixture according to (ii), thereby obtaining a mixture;

b) applying the mixture obtained from (a) to at least one substrate, wherein the substrate has a temperature above 0° C., wherein applying is done at a temperature of the mixture above the melting temperature Tm of the at least one crystalline polyesterol of the mixture according to (ii); and
c) optionally curing the mixture on the at least one substrate at a temperature above the melting temperature Tm of the at least one crystalline polyesterol of the mixture according to (ii);
thereby obtaining an element comprising an adhesive layer on at least one substrate.

12. The process according to claim 11 , wherein the at least one substrate comprises a first and a second substrate, wherein (b) comprises:
b.1) applying the mixture obtained from (a) at least partially on at least one surface of the first substrate, wherein the substrate has a temperature above 0° C., wherein applying is done at a temperature of the mixture above the melting temperature Tm of the at least one crystalline polyesterol of the mixture according to (ii), thereby obtaining a first substrate having a surface at least partially coated with the mixture obtained from (a); and
b.2) positioning the second substrate at least partially onto the coated surface of the first substrate, thereby obtaining an element comprising the first and second substrate and the mixture obtained from (a) between them;
and (c) comprises curing the mixture between first and second substrate at a temperature above the melting temperature Tm of the at least one crystalline polyesterol of the mixture according to (ii), thereby obtaining an element comprising first and second substrates and an adhesive layer between them.

Assignees

• Basf Se

Inventors

• Eling Berend
• Auffarth Stefan
• Linnenbrink Martin
• Albuerne Julio
• Mu Linyu

Classifications

• C08L67/00

  Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain (of polyester-amides C08L77/12; of polyester-imides C08L79/08); Compositions of derivatives of such polymers · CPC title

• C08G18/22

  containing metal compounds · CPC title

• C08G18/227

  of antimony, bismuth or arsenic · CPC title

• C09J167/02 Primary

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C09J167/06 takes precedence) · CPC title

• C08G18/2825

  having at least 6 carbon atoms · CPC title