CA2410180C

CA2410180C - Binder for mineral wool products

Info

Publication number: CA2410180C
Application number: CA002410180A
Authority: CA
Inventors: Thor Husemoen; Erling Lennart Hansen; Povl Nissen
Original assignee: Rockwool International AS
Current assignee: Rockwool AS
Priority date: 2000-06-16
Filing date: 2001-06-15
Publication date: 2009-11-03
Anticipated expiration: 2021-06-15
Also published as: US20050137318A1; JP2004503643A; AU8575801A; EP1164163A1; CN1302061C; EP1290082A2; CZ20024091A3; CA2410180A1; UA81597C2; RU2291883C2; HUP0301498A2; WO2001096460A2; US6849683B2; US20030153690A1; AU2001285758B2; WO2001096460A3; EP1290082B1; US7459490B2; PL210069B1; HUP0301498A3

Abstract

Process for providing a binder for mineral wool products, said process comprising the steps of: mixing together under reactive conditions a carboxylic acid with an alkanolamine, whereby optionally these are firstly mixed to provide a resin which resin is subsequently reacted with a separate carboxylic acid group containing polymer.

Description

BINDER FOR MINERAL WOOL PRODUCTS

The invention relates to a process for providing a binder for mineral fibers, i.e. man made vitreous fibers, for example glass, slag or stone wool, a binder obtainable via such a process, and a mineral wool product comprising such a binder.
Mineral wool products generally comprise mineral fibers bonded together by a cured thermoset polymeric material. One or more streams of molten glass, slag or stone are drawn into fibers and blown into a forming chamber where they are deposited as a web on to a travelling conveyer. The fibers, while airborne in the forming chamber and while still hot are sprayed with a binder. The coated fibrous web is then transported from the chamber to a curing oven where heated air is blown through the mat to cure the binder and rigidly bond the mineral wool fibers together.
Phenol-formaldehyde binders are widely used in the mineral wool industry since they have a low viscosity in the uncured state, yet still form a rigid thermoset polymeric matrix for the mineral fibers when cured.
However the use of phenol formaldehyde binders is becoming increasingly undesirable due to the use and release of environmentally unfavourable chemicals during the process.
The use of 9-hydroxyalkylamides to cure polycarboxy polymers such as polyacrylic acid in order to provide a binder is known.
A problem with polyacrylics cured by f3-hydroxyalkylamides is that mineral wool products bound with such a resin normally exhibit good mechanical properties before ageing, but after exposure to high humidities and increased temperatures, for example above CONFIRMATION COPY

40 degrees centigrade, the mechanical properties are drastically reduced.

There is therefore a desire to develop a binder which improves on the known binders.

The present invention provides an alternative binder which overcomes or at least mitigates one or more of these problems.

According to a first aspect of the present invention, there is provided a process for providing a binder for mineral wool products said process comprising the steps of:

- mixing t.ngRther_ under reactive conditions a carboxylic acid with an alkanolamine.

In a more specific embodiment of this first aspect, there is provided a process for providing a binder for a mineral wool product, said process comprising the step of: mixing together under reactive conditions a carboxylic acid with an alkanolamine, wherein the carboxylic acid comprises at least one of a di, tri and tetra carboxylic acid having a molecular weight of about 1,000 or less, and wherein the reaction between the carboxylic acid and the alkanolamine is actively stopped by addition of water.

2a The resulting binder when utilized for a mineral wool product, provi.des the mineral wool product with desirable mechanical properties after ageing, subjection to tear strain and exposure to high humidities J and increased temperatures.
The carboxylic acid and the alkanolamine are preferably firstly mixed together under reactive conditions to provide a?-esin, which resin optionally is subsequently mixed with a separate carboxylic acid group 1.0 containing polymer to form a binder.
The carboxylic acid is preferably a di-, tri-, or tetra carboxylic acid having a molecular weight of about 1000 or less, preferably about 500 or less, and most preferably about 200 or less, most preferably a di-15 carboxylic acid having the general formula:
COOH - (CRlRZ) n - COOH
wherein nz2 and preferably nz4, and wherein R, and R.
are independently selected from H or a lower alkyl group, preferably a methyl or ethyl group.
20 The carboxylic acid is preferably selected from the group consisting essentially of: adipic acid, citric acid, trimellitic acid, sebacic acid, azelaic acid, and, succinic acid and is most preferably adipic acid.
The alkanolamine is preferably selected from 25 the group comprising di, and tri-alkanolamines, and can be a secondary beta-hydroxy alkylamine, preferably an N-substituted alkanolamine selected from the group consisting essentially of, di-ethanolamine, 1-(m)ethyldiethanolamine, n-butyldiethanolamine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tris(hydroxymethyl)aminomethane, most preferably being diethanolamine.

The mole ratio of the carboxylic acid to the alkanolamine in the binder preferably lies in the range of 0.1-1:1-0.1 and the weight percentage of the carboxylic acid group containing polymer in the binder can lie in the range of 0.5-50, for example 10-40, preferably 15-30, most preferably about 20.

The alkanolamine may be firstly heated to a first predetermined lower temperature whereafter the carboxylic acid is added and the temperature of the mixture obtained is raised to a second predetermined higher temperature.

The alkanolamine is preferably firstly heated to around 60 C, whereafter the carboxylic acid is added and the temperature of this mixture is subsequently raised to about at least 90 C, preferably a temperature lying in the range of about 95-200, for example about 120-150 C.

The carboxylic acid group containing polymer preferably has a molecular weight lying in the ranges of 1000-300000, for example 1000-250000, preferably 1000-200000 most preferably having a molecular weights of around 60000, around 100000 and around 190000.

The carboxylic acid group containing polymer preferably comprises one or more of the following:
polyacrylic acid, polymethacrylic acid, polymaleic acid and/or co-polymers thereof, e.g. a polyacrylic emulsion, a styrene/acrylic emulsion, a poly(acrylic acid) with an average molecular weight about 60,000, or a poly(acrylic acid) with an average molecular weight about 250,000, preferably being selected from one or more of the following:

- PrimalJ HF-05A, Rohm & Haas/, - AcusolU 190, Rohm & Haas, - Acumer 1510, Rohm & Haas, .1 - 41.600-2, from the Aldrich Chemical Company Inc.
One or more of the following additives can be added to the binder:

- a coupling agent, for example an aminosilane, preferably gamma-aminopropyltriethoxysilane, - a polymerisation accelerator, a curing accelerator and optionally further standard mineral wool binder additives.

In order to improve the water solubility of the resin a base might be added till a pH up to 7. The base is preferably mixed with a polyacrylic acid, e.g. Acumer 1510, and added to the resin reaction mixture after the resin reaction is preferably stopped by water addition.
Accordingly, the base can first be added after the resin is prepared. Suitable bases include NH3, diethanolamine (DEA), triethanolamine (TEA).

The reaction between carboxylic acid and the alkanolamine may be stopped by adding water to the reaction mixture in an amount up 50% by weight of the mixture, e.g.
up to 25%, preferably 4%.

4a The weight percent of the base in the reaction mixture, calculated by weight of the acids in the reaction mixture, may lie in the range up 20%, e.g. 10%, preferably 1-5%, more preferably 4%.

The weight percent of the polyacrylic acid in the mixture may lie in the range up to 50%, e.g. up to 40%, preferably up to 30%, more preferably up to 25%.

In order to improve the ageing constancy properties a silane may be added. The silane usually but is not restricted to be added during the binder preparation or directly (separately) at the line. The amount would normally be in the range from 0.1% to 5% (0.2%-3%).
Preferred amount is approximately 1%. The silane is preferably prehydrolysed gamma-aminopropyltriethoxysilane.

According to further aspects of the present invention there is provided a binder obtainable according to this process, a process for providing a mineral wool product by contacting mineral fibres with a binder of the invention, a mineral wool product comprising a binder of the invention, which may be cured at at least 150 C and preferably at at least 200 C, and the use of a reaction mixture of an alkanolamine and a carboxylic acid, optionally mixed with a carboxylic acid group containing polymer, as a binder for a mineral wool product.

The binder obtained according to the process of the invention may have a curing time of at most 100 seconds, e.g. 90 seconds, preferably 50 seconds, more preferably 45 seconds, most preferably 35 seconds at 250 C, preferably 200 C.

The mineral wool binder of the invention may have an aged strength according to the Grit bar test of at least 4b 0.5 N/mm2, e.g. 1.0 N/mm2, preferably 1.5 N/mm2, more preferably 2.0 N/mm2 and most preferably 2.5 N/mm2, and a remaining strength measured according to the Grit bar test of at 10%, e.g. at least 20%, preferably at least 30%, more preferably at least 40% and most preferably at least 50%.
The invention will now be further illustrated by way of the following examples and results.

Exam-cl? 1 158 g diethanolamine was placed in a 1-liter glass reactor provided with a double jac}:et and an agitator. Temperature of the diethanolamine was raised to 60 C whereafter 99 g adipic acid was added slowly. The temperature was raised to 95 C. After a reaction time of 1 hour at about 95 C the reaction was stopped by the addition of 200 g water. The reaction product was a clear, colourless, low viscous liquid, dilutable with water.

Exam-ole 2 158 g diethanolamine was placed in a 1-liter glass reactor provided with a double jacket and an agitator. Temperature of the diethanolamine was raised to 60 C whereafter 175 g adipic acid was added slowly. The temperature was raised to 95 C. After a reaction time of 1 hour at about 95 C the reaction was stopped by the addition of 200 g water. The reaction product was a clear, colourless, low viscous liquid, dilutable with water.

Example 3 67.2 g triethanolamine was.mixed with 33.0 g adipic acid at room temperature. After the solution had turned clear 60 ml temperate water was added. The mixture was a clear, colourless, low viscous liquid, dilutable in water.
ExamT)le 4-6 Resins were made using the same procedure as in example 1. The following amounts of chemicals were used:

Ta~~~ 1 i -All.ano;amine Polycarbo-mylic acid 'Vate.
r xampie 4 158 g Diethanolam.ine 243 ff Azelaic Acid 200 ml Example 5 158 g Diethanolam.in 141 g Sebacic Acid 200 ml Example 6 158 ; Dicthan,ami.ne 89 g Succinic Acid 200 ml Examrole 7 158 g diethanolamin.e was placed in a 7-liter lo glass reactor provided with a double j ach-et and an aga.tator. . The temperature of the diethanolamine was raised to 60 C whereafter 99 g adipic acid was slowly added. The temperature was.subsequently raised to about i30 C, the temperature being maintained between 128 and 13- 135 C. P*ter a reaction time of 3 hours the reaction was stopped by the addition of water.

21_11 the produced reaction products in examples 4-7 were clear colourless low viscous liquids, dilutable 20 in water.

Examrole 8 Preparation and testing of selected binder samples to evaluate'the binding strength towards shots 25 with mi.neral riibre composition (Vrit bar test) . ps shots are considered ur_fiberized fiber material wi th identical composition as the fibers.
Shots with size between 0.25 and 0.5 mm diameter were used to make bars with dimensions 140 mm x 30 28 mm x 10 mm.
A binder solution was prepared comprising 800 of the resins =rom examples 1-7 mixed at room temperature with 20o of a commercial polyacrylic resin.
T~s polyacryi=~c ac~ds were used the commerriG, types from Rohm & Haas: Primal HF-05A, Acusol 190 and Acumer !510, and a polvacrylic acid w;th an average mole weigrt of~ 250.000 (Al.drich Chemical Comrany Inc. 41.600-2).
For making the bars 90 ml binder solu'tion with 15 o sol-lds content and 0.2 o silane coupling agent of binder solids were mixed with 450 g shots.
The coupling agent was gamma-aminopropyltriethoxysilane.
Out of the 450 g shots mixed with binder solution, B bars were made which were cured 2 hours at 200 C in an incubator.
Four of the bars were broken directly (dry strength),, the.other 4 are placed 3 hours in 80 C water before they are broken (wet strength).
The binding strength was determined by breaking the bars in a measuring device, where the clamping length is 100 mm and the velocity of the compressing beam was 10 mm/min. Using the clamping length, width and thickness of the bars, the bending strength was determined in N/mm2.
TM
For comparison a commercial product Primid XL-552 from EMS Chemie AG was used. Primid XL-552 is the reaction product of a dimethylester of adipic acid and diethanolamine, whereby the inventors have shown that 100% Primid is not curable since only free OH-groups are present which do not cross-link. A mixture of 80% primid amd 20% PAA yielded a very fast curing time (45s (HF-05) and 20s (Mw 250, 000) at 200 C) but the products have no remaining strength after ageing. The results are shown in table 2.

. 8 Ta:ole 2 Resin Polyacry- Unaged Aged Remaining lic acid strength stre-Ligth strength N/mmz N/mm 2 (aged/
unaged) 8 0 0 209. Primal HM5 9.6 2.0 21%
Example 1 80% 20o PAA MW 9.7 4.6 47%
Example 1 250000 8 0% 20% Prizral. HF05 10.0 5.3 53%
Examp 1 e 2 80% 20%.PAA MW 6.9 4.5 66%
Example 2 250000 80% 20% HF05 7.7 6.2 81%
Example 3 comparison 20% Pri.rral HFO5 3.6 0 0%
example 80% Primid 60% 40% HF05 8.1 4.0 49%
Example 2 20% 80% HF05 8.5 1.5 18%
Example 2 20% 80% PAA, 4.5 4.0 89%
Example '2 Mw 250,000 80% 20% P.AA 6.6 3.1 47 %
Example 4 MW 2,000 80% 20% PAA. 8.0 4.7 590 Example 5 Mw 2,000 80% 20% PAA 7.5 0.4 5%
Example 6 Mw 250,000 80% 20% 8.0 2.4 300 Example 7 Acusol 190 80% 20% Acumer 9.2 3.2 35%
Example 7 1510 Measurement of curina- times for selected examoles A few droplets of the binder to be examined were placed on a microscope cover glass. The glass was dried in a heating cupboard at 90 C for 45 min.

v` ~_`lc ?7 . ..~=1" st a ~C" ~e :a.-~ 2 3 G ~.'_7w_r .~
_~' õ L_1"'re.r5 w ~~!
_ a ~
metal wire (sr_w; ghtened pap`_ clips) the time was measured until the __n.dG= was cur=ct, The results are shovan in tahle 3.
Table 3: Results Resin Polyacrylic Curing time Curing time acid 200 C 250 C

I0 80 o Example 1 20-06 Primal HF05 - 90 s 80% Exampl e 1 2 0 o P_AA, Mw - 25 s 250,000 80 o Example 2 20% Primal HF05 140-160 S 45 s 8 0% Examp l e 2 2 0 o PAA, Mw - 25 s j250000 80 o Example 4 20% Primal HF05 173 s 43 s 80pt Example 5 20% Primal HF05 285 s 50 s 80% Example 7 200 35 s -Acusol 190 80o Example 7 20o.Acumer 30 s -As polyacrylic acids were used the commercial types from Rohrn & Haas: Primal HF-05A, Acusol 190 and Acumer 1510, and two pure polyacrylic acids with average mole weiahts of 1800 and 250,000 respectivel_y (Aldrich Chemical Compa.ny Inc. 32,366-7 and 41,600-2) E~~am~le 9 20.8 kg Diethanolami-ne were transferred to a 80 l1 t er steel reactor Drovld _d w1L 7 an ag=LazoY' and a heatinng/cooling jacket and neGted to 60 C. 23.0 }.g Adipi c Ac'! d were added to the re3ctor 7 n 5 portlons and the tem-.)erature raised to a reaction temoerature of 95 C.
A*ter reaction for 1 hour 26.3 kg temperate water were added, whereafter the resin was cooled to room temperature.
The resulting resin was a clear colourless low viscous liquid dilutable with water.
At room temperature 80% of the above resin was mixed with 20 0 of a commercial Polyacrylic resi n=rom Rohm & Haas: Primal HF-05.
The produced resin was after mixing with water and addition of 0.2% of a silane Coupling agent used as a binder in a production trial on a standard stonewool line. The product produced was a standard slab with a density of 100 kg/m3; 100 mm thickness and with approximately 3o binder content.
As a comparison a trial was made with two commercial polyacrylic resins. Primal HF-05 and QRXP 1513 both from Rohm & Haas. Both resins were diluted with water and added 0.2% of a silane coupling agent.
The coupling agent was-y-aminopropyltriethoxysilane.
The mechanical strengths were measured according to EN1607 (delamination strength). The delamination strength was measured on both unaged and after exposure to high humidity and increased temperature in a climate chamber (70 C/95 RH; aged samples) Results from the testing are shown in tables 4, 5 and 6 below.

T~rla L

Binder Binder Oil Density Delamination Delamination Remaining content content Kg/m' strength strength strength Unaged Aged kPa (70 C/95 %
RH) kPa Binder 3.1% 0.2% 98 9.7 4.0 41%
according Example 8 Comparison 3.3% 0.2% 101 7.2 1.3 18%
example Primal HF-05 Comparison 3.1% 0.2% 98 12.6 1.6 13%
1.0 example QRXP
Comparison 3.3% 0.2% 99 10.9 4.6 42%
example Standard uhenolic resin Example 10 Table 5 Ex Amine Poly- Water Accele- Base Reaction Curing Curing Silane acid rator conditions time time [%]

10 25.5kg 17.6kg 32.51 20% DEA 60 /130 140s 35 s 0.2 DEA ADP PAA for 3 hours ?2 Table 6 Ex Binder Oil Densiry Delamination Delamination Remaining content content [kg/m'] strength, unaged strength, aged strength [ o) [ o] [kPa) (70 C/95 uRH) [ 10]
[1tiPa]
3.5 0.2 140 10.1 3.3 36 Example 11 10 Resin:
116 kg DEA was transferred to a 400 1 reactor and heated to 60 C and stirred.
16.3 kg ADP was added and the mixture heated and reacted at l30 C for 60 minutes.
Thereafter cooled to 85 C and added tetrahydrophthalic anhydride (THPA) 33.8 kg. Thereafter 82.5 kg p-phthalic acid (PrA) was added and the tecperature raised to 130 C and kept there for 120 minutes.
Thereafter the reaction mixture was cooled to 110 C and 100 kg water added.
The temperature stabilised at approx. 50 C.
'The mixture was stirred for further 15 minutes until homogenous..
The resin was cooled and transferred to a storage tank.
Resin solids content 62.2o determined at 200 C.
Rest monomers 39o DEA of added, 12o THPA of added, 250 PTA of added. Average molweight about 6o0.
On a sample, a factory trial was carried out, wherebv 4% DEA and 25% solids Acumer 1510 calculated on resin soli ds, 0. 4 0 of sum solids silane and water to 25%
solids content, was added and ar_alysed_ Results of factory trial Binder yield 60%
Delamination strength (EN 1607) 13.4 kPa (Terraenbatts Industri) - Aged 3.6 kPa (70 C/95%RH) Tensile strength 5.5 kPa (Flexi A Batts) Example 12 Resin 24 kg DEA was transferred to a 80 1 reactor and heated to 60 C and stirred.

6.7 kg ADP was added and the mixture heated and reacted at 130 C for 60 minutes.
Thereafter cooled to 85 C and added 6.9 kg THPA. Thereafter 16.9 kg PTA was added and the temperature raised to 130 C and kept there for 120 minutes.
Thereafter the reaction mixture was cooled to 110 C and 20.5 kg water added. The temperature stabilises at approx. 50 C.
The mixture was stirred for further 15 minutes until homogenous.
The resin was cooled and transferred to a storage tank.
Resin solids content 63.4% determined at 200 C.
Rest monomers 37% DEA of added, 14% THPA of added, 25%
PTA of added. Average molweight about 600.
On a sample, a factory trial was carried out, whereby 4% DEA and 25% solids Acumer 1510 calculated on resin solids, 0.4% of sum solids silane and water to 25%
solids content, was added and analysed.

Results of factory trial Binder yield 70%
Delamination strength (EN 1607) 12.1 kPa (Terraenbatts Industri) - Aged 4.3 kPa (70 C/95oRH) The invention is not limited to the above description, the requested rights are determined by the following claims.

Claims

CLAIMS:

1. A process for providing a binder for a mineral wool product, said process comprising the step of:
mixing together under reactive conditions a carboxylic acid with an alkanolamine, wherein the carboxylic acid comprises at least one of a di, tri and tetra carboxylic acid having a molecular weight of about 1,000 or less, and wherein the reaction between the carboxylic acid and the alkanolamine is actively stopped by addition of water.

2. The process according to claim 1, wherein the carboxylic acid and the alkanolamine are firstly mixed together under reactive conditions to provide a resin, which resin is subsequently mixed with a separate carboxylic acid group containing polymer.

3. The process according to claim 2, wherein the carboxylic acid group containing polymer has a molecular weight lying in the range of 1,000-300,000.

4. The process according to claim 3, wherein the carboxylic acid group containing polymer has a molecular weight lying in the range of 1,000-250,000.

5. The process according to claim 4, wherein the carboxylic acid group containing polymer has a molecular weight lying in the range of 1,000-200,000.

6. The process according to claim 5, wherein the carboxylic acid group containing polymer has a molecular weight selected from one of 6,000, 10,000 and 190,000.

7. The process according to any one of claims 2 to 6, wherein the carboxylic acid group containing polymer comprises at least one of a polyacrylic acid, a polymethacrylic acid, a polymaleic acid and a co-polymer thereof.

8. The process according to claim 7, wherein the polyacrylic acid is selected from one or more of the following:

a polyacrylic acid emulsion, a styrene/acrylic emulsion, a poly(acrylic acid) with an average molecular weight about 60,000, and a poly(acrylic acid) with an average molecular weight about 250,000.

9. The process according to any one of claims 1 to 8, wherein the carboxylic acid has a molecular weight of about 500 or less.

10. The process according to claim 9, wherein the carboxylic acid has a molecular weight of about 200 or less.

11. The process according to any one of claims 1 to 10, wherein the carboxylic acid is a di-carboxylic acid having the general formula:

COOH-(CR1R2)n-COOH

wherein n >= 2, and wherein R1 and R2 are independently selected from H and a lower alkyl group.

12. The process according to claim 11, wherein n >= 4, and wherein R1 and R2 are independently selected from H, a methyl group and an ethyl group.

13. The process according to any one of claims 1 to 11, wherein the carboxylic acid is selected from the group consisting of adipic acid, citric acid, trimellitic acid, sebacic acid, azelaic acid and succinic acid.

14. The process according to claim 13, wherein the carboxylic acid is adipic acid.

15. The process according to any one of claims 1 to 14, wherein the alkanolamine is selected from the group consisting of di- and tri-alkanolamines.

16. The process according to claim 15, wherein the alkanolamine is a secondary beta-hydroxy alkylamine.

17. The process according to claim 15, wherein the alkanolamine is an N-substituted alkanolamine.

18. The process according to any one of claims 1 to 14, wherein the alkanolamine is selected from the group consisting of diethanolamine, 1-methyldiethanolamine, 1-ethyldiethanolamine, n-butyldiethanolamine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol and tris(hydroxymethyl)aminomethane.

19. The process according to claim 18, wherein the alkanolamine is a diethanolamine.

20. The process according to any one of claims 1 to 19, wherein the mole ratio of the carboxylic acid to the alkanolamine in the binder lies in the range of 0.1-1:1-0.1.

21. The process according to any one of claims 2 to 20, wherein the weight percentage of the carboxylic acid group containing polymer in the binder lies in the range of 0.5-50.

22. The process according to claim 21, wherein the weight percentage of the carboxylic acid group containing polymer in the binder lies in the range of 10-40.

23. The process according to claim 22, wherein the weight percentage of the carboxylic acid group containing polymer in the binder lies in the range of 15-30.

24. The process according to claim 23, wherein the weight percentage of the carboxylic acid group containing polymer in the binder is 20.

25. The process according to any one of claims 1 to 24, wherein the alkanolamine is firstly heated to a first predetermined lower temperature whereafter the carboxylic acid is added and the temperature of the mixture obtained is raised to a second predetermined higher temperature.

26. The process according to claim 25, wherein the first temperature is around 60°C and wherein the second temperature is at least about 90°C.

27. The process according to claim 26, wherein the second temperature is in the range of about 95-200°C.

28. The process according to claim 27, wherein the second temperature is in the range of about 120-150°C.

29. The process according to any one of claims 1 to 28, comprising the further step of adding at least one of the following to the binder: a coupling agent, a polymerisation accelerator, a curing accelerator and a standard mineral wool binder additive.

30. The process according to claim 29, wherein the coupling agent is an aminosilane.

31. The process according to claim 30, wherein the aminosilane is gamma-aminopropyltriethoxysilane.

32. The process according to any one of claims 1 to 31, wherein a base is subsequently added to the reaction mixture.

33. The process according to claim 32, wherein the base is selected from the group consisting of NH3, diethanolamine (DEA), triethanolamine (TEA), and any of NH3, DEA and TEA mixed with a polyacrylic acid.

34. The process according to claim 33, wherein the polyacrylic acid is Acumer® 1510 with a molecular weight of about 60,000.

35. The process according to any one of claims 32 to 34, wherein the weight % of the base in the reaction mixture, calculated by weight of solids in the reaction mixture, lies in the range of up to 20%.

36. The process according to claim 35, wherein the weight % of the base in the reaction mixture, calculated by weight of solids in the reaction mixture, lies in the range of up to 10%.

37. The process according to claim 36, wherein the weight % of the base in the reaction mixture, calculated by weight of solids in the reaction mixture, lies in the range of 1-5%.

38. The process according to claim 37, wherein the weight % of the base in the reaction mixture, calculated by weight of solids in the reaction mixture, is 4%.

39. The process according to any one of claims 33 to 38, wherein the weight % of the polyacrylic acid in the mixture lies in the range up to 50%.

40. The process according to claim 39, wherein the weight % of the polyacrylic acid in the mixture lies in the range up to 40%.

41. The process according to claim 40, wherein the weight % of the polyacrylic acid in the mixture lies in the range up to 30%.

42. The process according to claim 41, wherein the weight % of the polyacrylic acid in the mixture lies in the range up to 25%.

43. The process according to any one of claims 2 to 42, further comprising the step of adding a silane, in the range of 0.1%-5% by weight of resin solids.

44. The process according to claim 43, wherein the silane is added in the range of 0.2% to 3%.

45. The process according to claim 44, wherein the silane is added at about 1%.

46. The process according to any one of claims 43 to 45, wherein the silane is prehydrolized gamma-aminopropyltriethoxysilane.

47. The process according to any one of claims 1 to 46, wherein the reaction between the carboxylic acid and the alkanolamine is stopped by adding water to the reaction mixture in an amount up to 50% by weight of the mixture.

48. The process according to claim 47, wherein the reaction between the carboxylic acid and the alkanolamine is stopped by adding water to the reaction mixture in an amount up to 25% by weight of the mixture.

49. The process according to claim 48, wherein the reaction between the carboxylic acid and the alkanolamine is stopped by adding water to the reaction mixture in an amount of 4% by weight of the mixture.

50. A binder obtained by the process according to any one of claims 1 to 49.

51. The binder according to claim 50, having a curing time of at most 100 seconds at 250°C.

52. The binder according to claim 51, having a curing time of at most 90 seconds at 250°C.

53. The binder according to claim 52, having a curing time of at most 50 seconds at 250°C.

54. The binder according to claim 53, having a curing time of at most 45 seconds at 250°C.

55. The binder according to claim 54, having a curing time of 35 seconds at 250°C.

56. The binder according to claim 50, having a curing time of at most 100 seconds at 200°C.

57. The binder according to claim 56, having a curing time of at most 90 seconds at 200°C.

58. The binder according to claim 57, having a curing time of at most 50 seconds at 200°C.

59. The binder according to claim 58, having a curing time of at most 45 seconds at 200°C.

60. The binder according to claim 59, having a curing time of 35 seconds at 200°C.

61. The binder according to any one of claims 50 to 60, having an aged strength measured according to the Grit bar test of at least 0.5 N/mm2.

62. The binder according to claim 61, having a remaining strength measured according to the Grit bar test of at least 10%.

63. The binder according to claim 61, having an aged strength measured according to the Grit bar test of at least 1.0 N/mm2, and a remaining strength measured according to the Grit bar test of at least 20%.

64. The mineral wool binder according to claim 61, having an aged strength measured according to the Grit bar test of at least 1.5 N/mm2, and a remaining strength measured according to the Grit bar test of at least 30%.

65. The mineral wool binder according to claim 64, having an aged strength measured according to the Grit bar test of at least 2.0 N/mm2, and a remaining strength measured according to the Grit bar test of at least 40%.

66. The mineral wool binder according to claim 65, having an aged strength measured according to the Grit bar test of at least 2.5 N/mm2, and a remaining strength measured according to the Grit bar test of at least 50%.

67. A process for providing a mineral wool product comprising the steps of contacting mineral fibres with the binder of any one of claims 50 to 65, followed by a curing step.

68. A mineral wool product comprising the binder of any one of claims 50 to 65.

69. The mineral wool product according to claim 68, which mineral wool product has been cured at a temperature of at least 100°C.

70. The mineral wool product according to claim 69, which mineral wool product has been cured at a temperature of at least 150°C.

71. The mineral wool product according to claim 70, which mineral wool product has been cured at a temperature of at least 200°C.

72. Use of a reaction mixture as defined in any one of claims 1 to 49, as a binder for a mineral wool product.