NL2027625B1

NL2027625B1 - Flexible Adhesive for gluing

Info

Publication number: NL2027625B1
Application number: NL2027625A
Authority: NL
Inventors: Adriënne Van Hees Ilse; Frank De Block Rudoplh
Original assignee: Strongbond B V
Priority date: 2021-02-23
Filing date: 2021-02-23
Publication date: 2022-09-19

Abstract

The present invention is in the ﬁeld of ﬂexible adhesive for gluing, in particular in the construction of trucks, buses, trains and the like, more in particular for adhering a relatively large workpiece. The present invention also relates to a product comprising said adhesive, and a use of said adhesive. 5

Description

Flexible Adhesive for gluing

FIELD OF THE INVENTION The present invention is in the field of flexible adhesives for gluing, in particular in the construction of trucks, buses, trains and the like, more in particular for adhering a relatively large workpiece. The present invention also relates to a product comprising said adhesive, and a use of said adhesive.

BACKGROUND OF THE INVENTION In the construction industry, and in particular in the construction of trucks, buses, trains and the like, there is a need for flexible adhesives for gluing. For example, a flexible glue for adhering large parts to one and another, or even series of parts, typically of different types of materials, for which the glue (or adhesive) hardens quickly once the bond has been made. In view of the large parts, adhesives are required to have a long open time on the one hand and, on the other hand, have a rapid strength build-up after the open time has elapsed and have good adhesive built-up. The adhesive must also meet further technical properties as required. Examples thereof are elasticity, strength, durability, adhesion, and being free of tackiness. Additionally, such as when applied in the field of vehicles, leakage of water trough punctured sealants may cause severe damage, which leakage is to be prevented from happening. It is therefore an object of the present invention to provide an adhesive which overcomes one or more of the above disadvantages, without jeopardizing functionality and advantages.

SUMMARY OF THE INVENTION The present invention relates to a two component flexible adhesive for gluing com- prising a first and second component, the first component, comprising (la) 0.1-50 wt.% of at least one first silane-terminated (Si(OR1)2R3) polymer (STP) with at least one alpha nitrogen at the reactive silane end group according to fig. 1, OMe 0 Fig. 1 n OMe | i ZN | H C—Si—CH C—O Polymer NO—C CH—Si—CH 3 | Ny yd i 2 | 3 OMe | © OMe preferably with two or more silane terminated end groups, preferably wherein the nitrogen forms part of a urethane bond, wherein Me is CHz, wherein the polymer is a polyether or a polyurethane or a combination thereof, wherein the polyether preferably is selected from branched or unbranched propylene glycol polyether, more preferably with less than 3 branches, (1b) 0-50 wt.% of at least one second silane-terminated polymer (STP) with at least one gamma nitrogen at the reactive silane end group according to fig. 2, OMe 0 Fig. 2 N OMe | I / Ne | HC Si CH CO AN Polymer AOC H— Si CH 3 | 3 == / 1 36 | 3 OMe 0 OMe

(lc) 0-45 wt.% of at least one third silane-terminated polymer (STP) with no nitrogen close to the reactive silane end group, (1d) 0-5 wt.% of at least one fourth silane-terminated poly- mer (STP) with no nitrogen at the reactive silane end group according to fig. 3, OMe Fig. 3 2 OMe > | H> ZN | H C—Si —CH CON Polymer AOC CH—Si—CH 3 | a / Hs 2 | 3 OMe H OMe 2 wherein the polymer for figs. 2 and 3 is selected as above for fig. 1, (1e) 5-60 wt.% of at least one filler, (If) 0-5 wt.% of at least one pigment or colorant, (1g) 0-5 wt.% of at least one rheology modifier, (1h) 0-50 wt.% of at least one first plasticizer, wherein the plasticizer is preferably selected from benzoates, phthalates, terephthalates, polyols, hydrated versions of phthalates, terephthalates, benzoates, and combinations thereof, (11) 0-5 wt.% of at least one adhesion promotor, (1j) 0-8 wt.% of at least one drying agent, (1k) 0-5 wt.% of at least one of an anti-oxidant, an UV-stabilizer, and a hindered amine light stabilizer, (11) 0.0 -2 wt.% of one or more of a fungicide, a bactericide, and an algaecide, (1m) 0 -5% of a catalyst, preferably chosen from organometal compounds, such as organotin, organo zinc, and organo bismuth compounds, and amines, (In) <0.2 wt.% free water, preferably <0.01 wt.%, more preferably <10% wt.%, the second booster component, comprising (2a) 20-70 wt.% of at least one second plasticizer, preferably at least one polyol, having a molecular weight of 2000 — 25000 Da, having a functionality of two, three, or more, and a hydroxyl number of 5- 50 mgKOH/g, (2b) 20-60 wt.% of at least one of clay, CaCOs, carbon black, silica, zeolite, talc, mica, kaolin, dolomite, aluminium trihydrate, and a calcium inosilicate mineral (Ca- S103), such as wollastonite, preferably precipitated or grounded CaCO:3, which may be coated or not, and/or preferably a fumed silica, (2¢) 0.01-5 wt.% of at least one surfactant, (2d) 0.0-10 wt.% of at least one silane terminated amine, such as 3-aminopropyl-trimethox- ysilane or 3-aminopropyl-triethoxysilane, (2f) 3-60 wt.% water, wherein first and second component are provided in a volume ratio of 0.1:1 to 100:0, and wherein all weight percent- ages are based on the respective first and second component.

It has now unexpectedly been found that the use of the present more reactive polyether polymer in a 2C-system leads to the desired combination of properties by using a silane-terminated polymer (STP) with an alpha nitrogen at the reactive silane end group.

This type of STP-polymer, for example sold under the trade name Geniosil, is found to be very reactive.

This reactivity is considered due to the secondary alpha-amino group in the polymer chain.

In praxis, in an alternative embodiment,

a combination may be chosen between polymers with an alpha nitrogen, and a polymer with a gamma-nitrogen, or no nitrogen at all, to optimize the reactivity, and to balance the open time and cure speed.

An additional advantage is there is no need for the use of a catalyst, such as a heavy metal catalyst, like a tin catalyst.

Other ingredients such as fillers, stabi-

lizers, pigments, rheology modifiers, plasticizers, adhesion promotors, drying agents, antiox- idants, UV-stabilizers, and biocides may be added in desired quantities. Also, a hardening catalyst, for example an amine could be present. The A-part (also referred to as first part or component) of the 2C-adhesive can therefore be able to cure without part B (also referred to as second part or component), using water from the air. In the 2C-system the second compo- nent typically holds the water needed for the reaction. To obtain a mixture which is fully miscible with part A, this part consists, apart from water, of a plasticizer, such as a polyol, or a mixture of polyols, a filler, such as a fine calcium carbonate, preferably a precipitated cal- cium carbonate, as to increase the viscosity, a fumed silica and one or more surfactants to homogenize the mixture. Additionally, a silane terminated amine such as 3-aminopropyl-tri- methoxysilane or 3-aminopropyl-triethoxysilane could be present. An example of a single 1C sealant of the prior art adhesive has an open time of ~42 minutes. It will reach a strength (Fmax) of ~2.8 MPa after 24 hours at RT, and 50%RH. Once boosted as described above the open time is not compromised and is still 37-43 min. However, the present Fmax is already 1,4-1,65 MPa after two hours, and reaches 3,7-3,85 MPa after 24 hours, hence much higher. It has been found that the sealant of the present invention has improved self-healing proper- ties.

The hydroxyl value or hydroxyl number is defined as the number of milligrams of po- tassium hydroxide required to neutralize acetic acid taken up on acetylation of one gram of a chemical substance that contains free hydroxyl groups, in this case the at least one second plasticizer. Hydroxyl value is a measure of the content of free hydroxyl groups in a chemical substance, usually expressed in units of the mass of potassium hydroxide (KOH) in milli- grams equivalent to the hydroxyl content of one gram of the chemical substance (g KOH/g second plasticiser). The hydroxyl value can be calculated using the following equation. The acid value (AV) of the substance, determined in a separate experiment, enters into this equa- tion as a correction factor in the calculation of the hydroxyl value (HV): HV=[{(56.1)(N)(VB-Vacet) }/Wacer FAV } wherein HV is the hydroxyl value; Vg is the amount (ml) potassium hydroxide solution re- quired for the titration of the blank; Vac is the amount (ml) of potassium hydroxide solution required for the titration of the acetylated sample; Wacet is the weight of sample (in grams) used for acetylation; N is the normality of the titrant; 56.1 is the molecular weight of potas- sium hydroxide; AV is a separately determined acid value of the chemical substance. The content of free hydroxyl groups in a substance can also be determined by methods other than acetylation. ASTM D 1957 and ASTM E222-10 describe several versions of this method of determining hydroxyl value.

In a second aspect the present invention relates to a product comprising an adhe- sive according to the invention, preferably wherein the product comprises large adhered parts, and/or is selected from vehicles, such as trucks, buses, and trains.

In a third aspect the present invention relates to a use of an adhesive composition according to the invention, for one or more of rapid hardening, long open time, such as >30 minutes, rapid strength built-up, such as Fmax:>1.2 MPa after two hours, good elasticity, good strength, such as > 4.3 MPa after 24 hours (@590% elongation), good durability, good adhesion, free of tackiness, self-healing, water-tightness, a high bulk modulus after 24 hours, such as of > 1.2 MPa, and combinations thereof.

Thereby the present invention provides a solution to one or more of the above-men- tioned problems.

Advantages of the present description are detailed throughout the description.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates in a first aspect to an adhesive composition according to claim 1.

In an exemplary embodiment of the present adhesive in the first component the at least one first silane-terminated polymer (STP) is reactive.

In an exemplary embodiment of the present adhesive in the first component the at least one first silane-terminated polymer (STP) comprises <10 silane end groups with an al- pha nitrogen, preferably 1-5 silane end groups with an alpha nitrogen, such as 2-4 silane end groups.

In an exemplary embodiment the present adhesive in the first component com- prises (14) 1-20 wt.% of the at least one first silane-terminated polymer, preferably 3-15 wt.%, more preferably 4-12 wt.%, such as 5-10 wt.%.

In an exemplary embodiment the present adhesive in the first component com- prises (1b) 3-45 wt.% of at least one second silane-terminated polymer, preferably 12-40 wt.%, more preferably 20-35 wt.%, such as 25-30 wt.%.

In an exemplary embodiment the present adhesive in the first component com- prises(1c) 0.1-4 wt.% of at least one third silane-terminated polymer, preferably 0.2-2 wt.%, more preferably 0.3-1.5 wt %, such as 0.5-1.1 wt.%.

In an exemplary embodiment of the present adhesive in the first component com- prises (1a,b,c) the silane-terminated polymer (STP) each individually comprise a polyether, wherein the polyether preferably is selected from branched or unbranched glycol polyethers, more preferably polypropylene glycol polyethers, such as with <3 side-branches (see e.g. fig. 4).

In an exemplary embodiment of the present adhesive in the first component the polyether has an average molecular mass Mn of 400-4000 kDa (ISO 472).

In an exemplary embodiment of the present adhesive in the first component (la,b,c) the silane-terminated polymer (STP) each individually comprise a carboxyl moiety between the polymer and silane group, wherein the carboxyl moiety preferably comprises 1- 3 carbons. In an exemplary embodiment of the present adhesive in the first component the additives are selected from catalysts, co-catalysts, rheology control agents, pigments, pig- ment pastes, HALS, UV stabilizers, antioxidants, adhesion promotors, and drying agents.

In an exemplary embodiment of the present adhesive in the first component the adhesion promotor is selected from Amino-propyl-tri-ethoxy-silane (APTES) and Amino- 5 propyl-tri-methoxy-silane (APTMS).

In an exemplary embodiment of the present adhesive in the first component the rheology modifier is selected from fumed silica, carbon black, and polyamide waxes.

In an exemplary embodiment the present adhesive in the first component com- prises (le) 15-55 wt.% of at least one filler, preferably 30-50 wt.%, more preferably 40-45 wt. % In an exemplary embodiment the present adhesive in the first component com- prises in the first component (1n) 0-5 wt.% hardening catalyst, such as an amine, and (19) 0- 5 wt.% of at least one further additive.

In an exemplary embodiment of the present adhesive in the first component the filler is selected from chalk, precipitated chalk, grounded chalk, coated precipitated chalk, coated grounded chalk, silica, alumina, carbon black, and combinations thereof.

In an exemplary embodiment the present adhesive in the second component com- prises (2a) 30-60 wt.% of at least one second plasticizer, preferably 40-50 wt. %.

In an exemplary embodiment the present adhesive in the second component com- prises (2b) 30-50 wt.% at least one inorganic material selected from clay, CaCOs, carbon black, silica, zeolite, talc, mica, kaolin, dolomite, aluminium trihydrate, and a calcium inosil- icate mineral (CaSi103), such as wollastonite, preferably 4-7 wt.%, preferably precipitated CaCO:.

In an exemplary embodiment of the present adhesive in the second component (2b) the inorganic material has an average particle size of 0.01-300 um, preferably 0.02-10 Lm, more preferably 0.05-1 pum, such as 0.07-0.2 um.

In an exemplary embodiment the present adhesive in the second component com- prises (2b) 0.2-10 wt.% at least one silica, preferably a fumed silica, preferably 1-4 wt.%, and/or In an exemplary embodiment the present adhesive in the second component com- prises (2¢) 0.05-2 wt.% of at least one surfactant, preferably 0.1-1.5 wt.%,, and/or In an exemplary embodiment the present adhesive in the second component com- prises (2d) 0.5-8 wt.% of at least one silane terminated amine, preferably 2-6 wt.%, such as 4-5 wt. %.

In an exemplary embodiment the present adhesive in the second component com- prises (2e) 0.1 -1.7 wt.% of one or more of a fungicide, a bactericide, and an algaecide, pref- erably 0.3-1.5 wt.%, such as 0.5-1.4 wt.%.

In an exemplary embodiment of the present adhesive with the proviso that no heavy metal catalyst is present.

In an exemplary embodiment the present adhesive comprises in the second compo- nent (2g) 0-60 wt.% of at least one second plasticizer, preferably 5-45 wt.%, such as 35-45 wt.%, and optionally, and (21) 0-10 wt.% of an accelerator, preferably 1-8 wt.%, such as 3-6 wt. %.

In an exemplary embodiment of the present adhesive the at least one first and at least one second plasticizer each individually are selected from benzoic acid esters, phthalic acid diesters, terephthalic acid diesters, benzoates, phthalates, terephthalates, polyols, hydro- genated versions of phthalates, terephthalates and benzoates, and combinations thereof.

In an exemplary embodiment of the present adhesive the first and second compo- nent are provided in a weight ratio of 40:1 to 0.5:1, preferably 30:1 to 0.6:1, more preferably 25:1 to 0.7:1, such as 20:1 to 2:1.

In an example of the present adhesive it may comprise a combination of the above. In an exemplary embodiment the present use is in one-sided or two-sided bonding, especially of bonding of large surfaces of 0.5-30 m?, such as 0.5-15 m?.

In an exemplary embodiment the present use is for adhering a workpiece, such as a car window, and a car panel.

The invention is further detailed by the accompanying figures and examples, which are exemplary and explanatory of nature and are not limiting the scope of the invention. To the person skilled in the art it may be clear that many variants, being ob- vious or not, may be conceivable falling within the scope of protection, defined by the present claims.

FIGURES Figure 1: A first silane-terminated (Si(OR1)2R5) polymer (STP) with at least one alpha nitrogen at the reactive silane end group according to the invention.

Figure 2 shows a second silane-terminated polymer (STP) with at least one gamma nitrogen at the reactive silane end group.

Figure 3 shows a third silane-terminated polymer (STP) with no nitrogen close to the reactive silane end group.

Fig. 4 shows a propylene glycol moiety.

EXAMPLES/EXPERIMENTS The invention although described in detailed explanatory context may be best un- derstood in conjunction with the accompanying examples.

Table 1 and table 2 show a list of sealants and boosters according to the invention.

There are 6 sealants (SO [prior art] and S1-S5, according to the invention) tested with an open time around 20 minutes. In table 3 the results of open time, curing time and Fmax are presented for these sealants combined with one of the boosters of table 2. The sealant with the fastest strengthening is sealant 3, which contains the alpha N polymer of the present in- vention. Moreover, sealant 3 is still the fastest when the open time is extended from 20 till

30 minutes by choosing a different booster. When only a minor amount of gamma N poly- mer is added, such as in sealant 1, the curing speed is already halved compared to sealant 3, but still considerably faster than the prior art. Additionally, the sealant containing gamma O polymer (sealant 0) needs about 25 hours to reach half of the strength which the sealant with 5 the alpha N polymer (sealant 3) reaches in 3 hours.

Table 4 shows the open time and curing speeds, combined with the final properties of the sealants after one week (168 h) of curing. It is clear that sealant 3 has the highest curing speed, for both boosted and non-boosted sealant, after 1 day and 1 week of curing because sealant 3 has the highest F100 value. Moreover, the sealant has the highest curing speed, re- gardless of the type of booster. Additionally, it is especially remarkable that sealant 3 is free of (tin-) catalyst.

Additionally the formula SO and S3 were tested without booster according to EN ISO 1465, RVS 2mm layer of adhesive, 12,5 mm x 25 mm overlap. Cure was performed at low temperature and humidity, 10°C and 30%RH, so the cure was far from complete. For for- mula SO a Fax was found of 0,38 N/mm2 but for formula S3 this was 0,82 N/mm2 , thus showing the increased speed of adhesive strength build-up of the present invention. Finally dumbbells were prepared without booster and tested according to DIN 53504, dumb- bell type 2, but measured after 1 day at 10°C and 30%RH. The results in table 5 clearly demonstrate the increased cure rate or strength build-up..

Formulation of sealants Table 1: Formulation SO Sl S2 S3 S4 S5 Composition wit% wia wit% wia wit% wi% Gamma O 46,5 Alpha-N 25 20 35 15 Gamma N 10 15 35 20 Stabilizers and colourants 2,5 24 2.4 2.4 2.4 2.4 Plasticizer [polyol] 12.8 12.8 12.8 12.8 12,8 VIMO 2,7 3,1 3,1 3,1 3,1 3,3 Fillers 46,4 45,2 45,2 45,2 45,2 45.0 Aminosilane 1,4 1,5 1,5 1,5 1,5 1.5 Tin catalyst 0,6 0,02 Non-tin catalyst 0,05 Gamma O: polymer with the silyl group on the gamma position from the oxygen (prior art) Alpha N: polymer with the silyl group on the alpha position from the nitrogen (component la)

Gamma N: polymer with the silyl group on the gamma position from the nitrogen (compo- nent 1b) Formulation of boosters table2: Composition wit% wit% wit% wit% Polyol 6kDa _ 40 37.6 Polyol 8kDa 40,0 42,5 Stabilizer/microbial agent 2.0 2.0 2.0 2,0 Water 10.0 10.0 10.0 15.0 Fillers 43,0 45,5 48,0 45,4 Aminosilane 5.0 a Oee ee Curing Sealant | Booster | Open time time Fmax [min] [h] [MPa] S3 B4 19 3 4.0 53 B2 32 2,5 3.1 S3 B3 31 2 3.0 S2 B2 17 2.5 2.6 S1 B4 20 2,75 2.2 SO B3 22 25 2,1 Sl B3 22 3 2.1 S1 B2 37 2,5 1,7 Ss B3 23 2 1.6 S1 Bl 23 2,5 1.4 Results table 3: open time, curing time, Fmax

Open Curing

Sealant | Booster time time F100 Fmax EAB [min] [h] [MPa] [MPa] [%o] SO - 14 24 14 2,6 250 SO - 168 2.4 3.6 200

SO B3 23 2 - - - SO B3 25 0,72 2,08 340 SO B3 168 1.9 4.1 320 S1 - 41 24 18 4,5 450 Sl - 168 2,2 4,6 320 Sl B2 37 2,5 0,70 1.6 320 S1 B2 26,5 1,2 3,9 540 Sl B3 26 3 0,75 2.1 390 SI B3 168 1.9 4,9 400 S1 B4 20 2.75 0,75 2,2 460 Sl B4 168 1,93 4.62 360 S3 - 21 24 1,9 4,2 400 53 - 168 2 4,7 380 S3 B2 32 2,5 1.00 3.1 500 S3 B2 26,5 14 3,9 490 S3 B2 168 1.7 4.8 460 S3 B3 24 2 0,95 3,04 340 S3 B3 25 1.4 4,68 620 S3 B3 168 1.7 5.1 470 S3 B4 19 3 1,2 4 610 S3 B4 168 1,9 4,6 360

S4 - >120 24 - - - S4 - 168 2,2 4,5 300

S4 B3 >120 2 - - -

S4 B3 25 - - - S4 B3 168 1.8 4,9 460

Results table 4: open time and curing speeds 1 day. 10°C and 30%RH, N/mm?

Results table 5: Fmax of Dumbbells after DIN 53504 after 1 day cure at 10°C and 30%RH Test Methods Open time and curing time Open time and curing time were determined by using a Beck Koller recorder, usually known as BK-recorder such as sup-plied by for example TQC-sheen.

With use of a film applicator an adhesive film of 450um 1s applied to a glass plate. The B.K Drying recorder pulls a needle through the adhesive film at a set speed correlating with time.

After the test different stages are observed. By measuring the start and end of the dif- ferent stages open time and curing time can be calculated.

Using a 450um film applicator a film of fresh adhesive is applied on to a degreased glass plate (25 x 300 mm). Immediately after application the glass plate is inserted in the BK-recorder, the needle is placed on the adhesive, and if desired BK-recorder weights may be applied to increase needle pressure to be able to scratch through the adhesive, and the re- corder is started. After the needle has reached the end of the line the open time and the cure time can be calculated from the distance the needle has passed scratching through the adhe- sive onto the glass plate (open time) and scratching through the adhesive to the glass plate added with the distance scratching through the adhesive, but no longer through to the glass plate (curing time), respectively. This method is an adaptation of ASTM D5895, EN 14022, and ISO 9117-4.

Force at 100% elongation (F100), maximum force (Fmax) and elongation at break (EAB) were determined conform DIN 53504 using a dumbbell type 2 (Schulterstab S2).

For the sake of searching the following section is added which represents embodiments of the invention and of which a translation is given into Dutch in the subsequent section.

1. A two component flexible adhesive for gluing comprising a first component, comprising (1a) 0.1-50 wt.% of at least one first silane-terminated (Si(OR1)2R3) polymer (STP) with at least one alpha nitrogen at the reactive silane end group according to fig. 1, OMe Fig. 1 H OMe | © py iN | H C—Si—CH CON Polymer AOC CH — Si — CH 3 | 2 / 4 2 3 OMe | 0 OMe preferably with two or more silane terminated end groups, preferably wherein the nitrogen forms part of an urethane bond [-C-O-C=0-NH-), wherein Me is CHs, wherein the polymer is a polyether or a polyurethane or a combination thereof, wherein the polyether preferably is selected from branched or unbranched propyl- ene glycol polyethers, more preferably with less than 3 branches,

(1b) 0-50 wt.% of at least one second silane-terminated polymer (STP) with at least one gamma nitrogen at the reactive silane end group according to fig. 2, OMe 0 Fig. 2 An OMe | i / Ne | HC Si CH CO AN Polymer OC H— Si CH 3 | 3 OW / u 36 | 3 OMe 0 OMe (1c) 0-25 wt.% of at least one third silane-terminated polymer (STP) with no nitrogen close to the reactive silane end group,

(1d) 0-5 wt.% of at least one fourth silane-terminated polymer (STP) with no nitrogen at the reactive silane end group such as according to fig. 3,

OMe Fig. 3 2 OMe

| H2 J Nene H C—Si—CH CON Polymer NO—C CH—Si—CH 3 | a / Hs 2 | 3

OMe H, OMe (le) 5-60 wt.% of at least one filler, (1f) 0-5 wt.% of at least one pigment or colorant, (1g) 0-5 wt.% of at least one rheology modifier,

(1h) 0-50 wt.% of at least one first plasticizer, wherein the plasticizer is prefer- ably selected from benzoates, phthalates, terephthalates, polyols, hydrated versions of phthalates, terephthalates, benzoates, and combinations thereof,

(11) 0-5 wt.% of at least one adhesion promotor, (13) 0-8 wt.% of at least one drying agent,

(1k) 0-5 wt.% of at least one of an antioxidant, an UV-stabilizer, and a hindered amine light stabilizer,

(11) 0.0 -2 wt.% of one or more of a fungicide, a bactericide, and an algaecide, (1m) 0-5% of a catalyst, preferably chosen from organometal compounds, such as organotin, organo zinc, and organo bismuth, and amines,

(In) <0.2 wt.% free water, preferably <0.01 wt.%, more preferably <10™ wt.%,

a second booster component, comprising (2a) 20-70 wt.% of at least one second plasticizer, preferably at least one pol- yol, having a molecular weight of 2000 — 25000 Da, having a functionality of two, three, or more, and a hydroxyl number of 5-50 mgKOH/g,

(2b) 20-60 wt.% of at least one of clay, CaCO3, carbon black, silica, zeolite, talc, mica, kaolin, dolomite, aluminium trihydrate, and a calcium inosilicate mineral (Ca- S103), such as wollastonite, preferably precipitated and/or grounded CaCOs, wherein the CaCOs may be coated or not, and/or preferably a fumed silica,

(2c) 0.01-5 wt.% of at least one surfactant,

(2d) 0.0-10 wt.% of at least one silane terminated amine, such as 3-aminopro- pyl-trimethoxysilane or 3-aminopropyl-triethoxysilane, (2e) 0.0 -2 wt.% of one or more of a fungicide, a bactericide, and an algaecide, (2f) 3-60 wt.% water, wherein first and second component are provided in a volume ratio of 0.1:1 to 100:0, and wherein all weight percentages are based on the respective first and second component.

2. Adhesive according to embodiment 1, wherein the at least one first silane-terminated pol- ymer (STP) is reactive.

3. Adhesive according to embodiment 1 or 2, wherein the at least one first silane-terminated polymer (STP) comprises <10 silane end groups with an alpha nitrogen, preferably 1-5 silane end groups with an alpha nitrogen, such as 2-4 silane end groups.

4. Adhesive according to any of embodiments 1-3, comprising in the first component (1a) 1-20 wt.% of the at least one first silane-terminated polymer, preferably 3- wt.%, more preferably 4-12 wt.%, such as 5-10 wt.%. 15 and/or (1b) 3-45 wt.% of at least one second silane-terminated polymer, preferably 12-40 wt.%, more preferably 20-35 wt.%, such as 25-30 wt.%, and/or (1c) 0.1-4 wt.% of at least one third silane-terminated polymer, preferably 0.2-2 wt.%, more preferably 0.3-1.5 wt.%, such as 0.5-1.1 wt.%, and/or (1a,b,c) wherein the silane-terminated polymer (STP) each individually com- prise a polyether, wherein the polyether preferably is selected from branched or unbranched glycol polyethers, more preferably polypropylene glycol polyethers, such as with <3 side- branches, and/or wherein the polyether has an average molecular mass Mn of 400-4000 kDa (ISO 472), (14,b,c) wherein the silane-terminated polymer (STP) each individually com- prise a carboxyl moiety between the polymer and silane group, wherein the carboxyl moiety preferably comprises 1-3 carbons, in the second component (2a) 30-60 wt.% of at least one second plasticizer, preferably 40-50 wt.%, and/or (2b) 30-50 wt.% at least one inorganic material selected from clay, CaCO, sil- ica, zeolite, and carbon black, wherein the CaCO; may be coated or not, preferably 35-45 wt.%, preferably precipitated CaCO3, and/or (2b) preferably wherein the inorganic material has an average particle size of

0.01-300 um, preferably 0.02-10 um, more preferably 0.05-1 um, such as 0.07-0.2 um, and/or (2b) 0.2-10 wt.% at least one silica, preferably a fumed silica, preferably 0.5-3 wt.%, and/or (2¢) 0.05-1 wt.% of at least one surfactant, preferably 0.1-0.5 wt %, and/or (2d) 0.5-8 wt.% of at least one silane terminated amine, preferably 2-6 wt.%.

5. Adhesive according to any of embodiments 1-4, with the proviso that no heavy metal cata- lyst is present.

6. Adhesive according to any of embodiments 1-5, comprising in the first component (le) 15-55 wt.% of at least one filler, preferably 30-50 wt.%, more preferably 40-45 wt.%

7. Adhesive according to any of embodiments 1-6, further comprising in the first component (1n) 0-5 wt.% hardening catalyst, such as an amine, and (10) 0-5 wt.% of at least one further additive, and/or in the second component (2g) 0-60 wt.% of a second plasticizer, and optionally, and (21) 0-10 wt.% of an accelerator.

8. Adhesive according to any of embodiments 1-7, wherein the filler is selected from chalk, precipitated chalk, coated precipitated chalk, grounded chalk, silica, alumina, carbon black, and combinations thereof, and/or wherein the at least one first and at least one second plasticizer each individually are selected from benzoic acid esters, phthalic acid diesters, terephthalic acid diesters, benzoates, phthalates, terephthalates, polyols, hydrogenated versions of phthalates, terephthalates and benzoates, and combinations thereof, and/or wherein the additives are selected from catalysts, co-catalysts, rheology control agents, pig- ments, pigment pastes, HALS, UV stabilizers, antioxidants, adhesion promotors, and drying agents, and/or wherein the adhesion promotor is selected from Amino-propyl-tri-ethoxy-silane (APTES) and Amino-propyl-tri-methoxy-silane (APTMS), and/or wherein the rheology modifier is selected from fumed silica, carbon black, and poly- amide waxes, and combinations thereof.

9. Adhesive according to any of embodiments 1-8, wherein the first and second component are provided in a weight ratio of 40:1 to 0.5:1, preferably 30:1 to 0.6:1, more preferably 25:1 to 0.7:1, such as 20:1 to 2:1.

10. Product comprising an adhesive according to any of embodiments 1-9, preferably wherein the product comprises large adhered parts, and/or is selected from vehicles, such as trucks, buses, and trains.

11. Use of an adhesive composition according to any of embodiments 1-9, for one or more of rapid hardening, long open time, such as >30 minutes, rapid strength built-up, such as Fmax>1.2 MPa after two hours, good elasticity, good strength, such as > 4.3 MPa after 24 hours (@590% elongation), good durability, good adhesion, free of tackiness, self-healing, water-tightness, a high bulk modulus after 24 hours, such as of > 1.2 MPa, and combinations thereof.

12. Use according to embodiment 11, in one-sided or two sided bonding, especially of bond- ing of large surfaces of 0.5-10 m*.

13. Use of a sealant or adhesive according to any of embodiments 1-9 for adhering a work- piece, such as a car window, and a car panel.

Claims

Conclusies:Conclusions:

1. Een tweecomponenten flexibel hechtmiddel voor verlijming, omvattend een eerste component, omvattend (1a) 0,1-50 gew.% van ten minste een eerste silaan-getermineerd (Si(OR1)2R3) polymeer (STP) met ten minste een alfa-stikstof aan de reactieve silaaneindgroep volgens fig. 1, OMe Fig. 1 HN OMe 0 N | U ZN | H C— Si CH COT Polymer NO—C CH —Si—CH 3 | 2 “yg 4 2 3 OMe H 0 OMe bij voorkeur met twee of meer silaaneindgroepen, bij voorkeur waarin de stikstof deel uit- maakt van een urethaanbinding [-C-O-C=0-NH-], waarin Me CH: is, waarbij het polymeer een polyether of een polyurethaan of een combi- natie daarvan is, waarbij de polyether bij voorkeur is gekozen uit vertakte of onvertakte pro- pyleenglycolpolyethers, bij voorkeur met minder dan 3 vertakkingen, (1b) 0-50 gew.-% van ten minste een tweede silaan-getermineerd polymeer (STP) met ten minste één gammastikstof aan de reactieve silaaneindgroep volgens fig. 2, OMe 0 Fig. 2 N OMe | I JN | HC— Si CH CO UN Polymer „OC CH Si CH 3 | 3 aN / n 36 | 3 OMe | © OMe (1c) 0-45 gew.-% van ten minste een derde polymeer met silaan-eindgroep (STP) zon- der stikstof in de nabijheid van de reactieve silaaneindgroep, (1d) 0-5 gew.-% van ten minste een vierde polymeer (STP) met silaaneind- groep zonder stikstof in de nabijheid van de reactieve silaaneindgroep, zoals volgens fig. 3, OMe Fig. 3 2 OMe | H JN | H C—Si —CH CO UN Polymer “OC CH — Si —CH 3 | DN / H, 2 | 3 OMe H OMe 2 (le) 5-60 gew.-% van ten minste één vulstof, (1f) 0-5 gew.-% van ten minste een pigment of kleurstof, (1g) 0-5 gew.-% van ten minste één reologiemodificator, (1h) 0-50 gew.-% van ten minste één eerste weekmaker, waarbij de weekmaker bij voorkeur is gekozen uit benzoaten, ftalaten, tereftalaten, polyolen, gehydrateerde versies van ftalaten, tereftalaten, benzoaten, en combinaties daarvan,A two-part flexible bonding adhesive comprising a first component comprising (1a) 0.1-50% by weight of at least a first silane-terminated (Si(OR1)2R3) polymer (STP) having at least one alpha -nitrogen at the reactive silane end group of FIG. 1, OMe FIG. 1 HN OMe 0 N | U ZN | HC—Si CH COT Polymer NO—C CH—Si—CH 3 | 2 “yg 4 2 3 OMe H 0 OMe preferably with two or more silane end groups, preferably in which the nitrogen is part of a urethane bond [-C-O-C=O-NH-], where Me is CH: where the polymer is a polyether or a polyurethane or a combination thereof, wherein the polyether is preferably selected from branched or unbranched propylene glycol polyethers, preferably with less than 3 branches, (1b) 0-50% by weight of at least one second silane-terminated polymer (STP) with at least one gamma nitrogen at the reactive silane end group according to Fig. 2, OMe 0 Figs. 2 N OMe | I JN | HC— Si CH CO UN Polymer 'OC CH Si CH 3 | 3 aN/n 36 | 3 OMe | © OMe (1c) 0-45% by weight of at least one third silane-terminated polymer (STP) with no nitrogen in the vicinity of the reactive silane-terminated group, (1d) 0-5% by weight of at least a fourth polymer (STP) with silane end group without nitrogen in the vicinity of the reactive silane end group, as shown in Fig. 3, OMe Figs. 3 2 OMe | H JN | HC—Si—CH CO UN Polymer “OC CH—Si—CH 3 | DN/H, 2| 3 OMe HO OMe 2 (lee) 5-60% by weight of at least one filler, (1f) 0-5% by weight of at least one pigment or dye, (1g) 0-5% by weight of at least one rheology modifier, (1h) 0-50% by weight of at least one primary plasticizer, the plasticizer preferably being selected from benzoates, phthalates, terephthalates, polyols, hydrated versions of phthalates, terephthalates, benzoates, and combinations thereof ,

(11) 0-5 gew.-% van ten minste één adhesiepromotor, (1j) 0-8 gew.-% van ten minste één droogmiddel, (1k) 0-5 gew.-% van ten minste één van een antioxidant, een UV-stabilisator, en een lichtstabilisator van een gehinderd amine, (11) 0,0 -2 gew.-% van één of meer van een fungicide, een bactericide, en een algicide, (1m) 0-5% van een katalysator, bij voorkeur gekozen uit organometaal verbin- dingen, zoals organotin-, organozink, en organobismuthverbindingen en aminen, (In) <0,2 wt.% vrij water, bij voorkeur <0,01 gew.%, liever <10™ gew.%, een tweede boostercomponent, omvattend (2a) 20-70 gew.% van ten minste één tweede weekmaker, bij voorkeur ten min- ste één polyol, met een molecuulgewicht van 2000 - 25000 Da, met een functionaliteit van twee, drie of meer, en een hydroxylgetal van 5-50 mgKOH/g, (2b) 20-60 gew.-% van ten minste een van klei, CaCOs, roet, kiezelzuur, zeo- liet, talk, mica, kaolien, dolomiet, aluminiumtrihydraat, en een calcium inosilicaat mineraal (CaSi0s), zoals wollastoniet, bij voorkeur geprecipiteerd en/of gemalen CaCO;, waarbij de CaCO: al dan niet gecoat kan zijn, en/of bij voorkeur een pyrogeen kiezelzuur, (2c) 0,01-5 gew.-% van ten minste een oppervlakactieve stof, (2d) 0,0-10 gew.-% van ten minste een silaan-getermineerd amine, zoals 3-ami- nopropyl-trimethoxysilaan of 3-aminopropyl-triethoxysilaan, (2e) 0,0 -2 gew.-% van één of meer van een fungicide, een bactericide, en een algicide, (2f) 3-60 gew.% water, waarin de eerste en tweede component in een volumeverhouding van 0,1:1 tot 100:0 aanwe- zig zijn, en waarbij alle gewichtspercentages zijn gebaseerd op het respectieve eerste en tweede bestand- deel.(11) 0-5 wt% of at least one adhesion promoter, (1j) 0-8 wt% of at least one drying agent, (1k) 0-5 wt% of at least one of an antioxidant, a UV stabilizer, and a light stabilizer of a hindered amine, (11) 0.0-2% by weight of one or more of a fungicide, a bactericide, and an algicide, (1m) 0-5% of a catalyst , preferably selected from organometallic compounds, such as organotin, organozinc, and organobismuth compounds and amines, (In) <0.2 wt.% free water, preferably <0.01 wt.%, more preferably <10™ wt. %, a second booster component comprising (2a) 20-70% by weight of at least one second plasticizer, preferably at least one polyol, with a molecular weight of 2000 - 25000 Da, with a functionality of two, three or more , and a hydroxyl number of 5-50 mgKOH/g, (2b) 20-60% by weight of at least one of clay, CaCO 3 , carbon black, silicic acid, zeolite, talc, mica, kaolin, dolomite, aluminum trihydrate, and a calcium inosilicate mineral (CaSiO 3 ), such as wollasto un, preferably precipitated and/or ground CaCO2, where the CaCO2 may be coated or uncoated, and/or preferably a fumed silica, (2c) 0.01-5% by weight of at least one surfactant , (2d) 0.0-10% by weight of at least one silane-terminated amine, such as 3-aminopropyl-trimethoxysilane or 3-aminopropyl-triethoxysilane, (2e) 0.0-2% by weight of one or more of a fungicide, a bactericide, and an algicide, (2f) 3-60 wt.% water, wherein the first and second components are present in a volume ratio of 0.1:1 to 100:0, and wherein all weight percentages are based on the respective first and second component.

2. Hechtmiddel volgens conclusie 1, waarin het ten minste één eerste silaan-getermineerd polymeer (STP) reactief is.The adhesive of claim 1, wherein the at least one first silane-terminated polymer (STP) is reactive.

3. Hechtmiddel volgens conclusie 1 of 2, waarin het tenminste één eerste silaan-getermi- neerd polymeer (STP) <10 silaan eindgroepen met een alpha stikstof omvat, bij voorkeur 1-5 silaan eindgroepen met een alpha stikstof, zoals 2-4 silaan eindgroepen.An adhesive according to claim 1 or 2, wherein the at least one first silane-terminated polymer (STP) comprises < 10 silane end groups with an alpha nitrogen, preferably 1-5 silane end groups with an alpha nitrogen, such as 2-4 silane end groups.

4. Hechtmiddel volgens één van de claims 1-3, omvattend (la) 1-20 gew.-% van ten minste één eerste silaan-getermineerd polymeer, bij voorkeur 3-15 gew.-%, liever 4-12 gew.-%, zoals 5-10 gew.-%, en/of (1b) 3-45 gew.% ten minste een tweede silaan-beëindigd polymeer, bij voor- keur 12-40 gew.%, liever 20-35 gew.%, zoals 25-30 gew.%, en/of (1c) 0,1-4 gew.-% van ten minste een derde silaan-getermineerd polymeer, bij voorkeur 0,2-2 gew.-%, liever 0,3-1,5 gew.-%, zoals 0,5-1,1 gew.-%, en/of (la,b,c) waarin het silaan-getermineerde polymeer (STP) elk afzonderlijk een polyether bevat, waarbij de polyether bij voorkeur is gekozen uit vertakte of onvertakte gly- colpolyethers, liever polypropyleenglycolpolyethers, zoals met <3 zijvertakkingen, en/of waarbij de polyether een gemiddelde molecuulmassa Mn heeft van 400-4000 kDa (ISO 472), (14,b,c) waarin het silaan-getermineerde polymeer (STP) elk afzonderlijk een carboxylgroep tussen het polymeer en de silaangroep omvat, waarbij de carboxylgroep bij voorkeur 1-3 koolhydraten omvat, (2a) 30-60 gew.% van ten minste tweede weekmaker, bij voorkeur 40-50 gew.%, en/of (2b) 30-50 gew.-% van ten minste een anorganisch materiaal, gekozen uit klei, CaCOs, silica, en koolstof, waarbij de CaCO: al dan niet gecoat kan zijn, bij voorkeur 35-45 gew.-%, bij voorkeur geprecipiteerd CaCOs, en/of (2b) bij voorkeur waarin het anorganisch materiaal een gemiddelde deeltjes- grootte heeft van 0.01-300 um, bij voorkeur 0.02-10 um, liever 0.05-1 um, zoals 0.07-0.2 um, en/of (2b) 0,2-10 gew.% van ten minste een silica, bij voorkeur een pyrogene silica, bij voorkeur 1-4 gew.%, en/of (2c) 0,05-2 gew.-% van ten minste een oppervlakactieve stof, bij voorkeur 0,1- 1,5 gew.-%, en/of (2d) 0,5-8 gew.-% van ten minste een met silaan getermineerd amine, bij voor- keur 2-6 gew.-%.An adhesive according to any one of claims 1-3 comprising (1a) 1-20% by weight of at least one first silane-terminated polymer, preferably 3-15% by weight, more preferably 4-12% by weight %, such as 5-10 wt%, and/or (1b) 3-45 wt% at least one second silane-terminated polymer, preferably 12-40 wt%, more preferably 20-35 wt% , such as 25-30% by weight, and/or (1c) 0.1-4% by weight of at least one third silane-terminated polymer, preferably 0.2-2% by weight, more preferably 0.3 -1.5 wt%, such as 0.5-1.1 wt%, and/or (1a,b,c) wherein the silane-terminated polymer (STP) each individually contains a polyether, wherein the polyether is preferably selected from branched or unbranched glycol polyethers, more preferably polypropylene glycol polyethers, such as having <3 side branches, and/or wherein the polyether has an average molecular weight Mn of 400-4000 kDa (ISO 472), (14,b,c) wherein the silane-terminated polymer (STP) each individually includes a carboxyl group between the polymer and the silane group, with the carboxyl group at preferably 1-3 carbohydrates, (2a) 30-60% by weight of at least second plasticizer, preferably 40-50% by weight, and/or (2b) 30-50% by weight of at least one inorganic material , selected from clay, CaCO 3 , silica, and carbon, wherein the CaCO: may be coated or uncoated, preferably 35-45 wt%, preferably precipitated CaCO 3 , and/or (2b) preferably in which the inorganic material has an average particle size of 0.01-300 µm, preferably 0.02-10 µm, more preferably 0.05-1 µm, such as 0.07-0.2 µm, and/or (2b) 0.2-10 wt% of at least one silica , preferably a fumed silica, preferably 1-4% by weight, and/or (2c) 0.05-2% by weight of at least one surfactant, preferably 0.1-1.5% by weight %, and/or (2d) 0.5-8% by weight of at least one silane-terminated amine, preferably 2-6% by weight.

5. Hechtmiddel volgens een van de conclusies 1-4, met dien verstande dat er geen zware me- talen katalysator aanwezig is.An adhesive according to any one of claims 1 to 4, provided that no heavy metal catalyst is present.

6. Hechtmiddel volgens een van de conclusies 1-5, omvattend (le) 15-55 gew.-% van ten minste één vulstof, bij voorkeur 30-50 gew.-%, bij voorkeur 40-45 gew.-%An adhesive according to any one of claims 1-5, comprising (1e) 15-55% by weight of at least one filler, preferably 30-50% by weight, preferably 40-45% by weight

7. Hechtmiddel volgens een van de conclusies 1-6, verder omvattend in de eerste component (1n) 0-5 gew.% verhardingskatalysator, zoals een amine, en (10) 0-5 gew.% van ten minste één ander additief, en/of in het tweede bestanddeel (2g) 0-60 gew.-% van een tweede weekmaker, en naar keuze, en (21) 0-10 gew.-% van een versneller.An adhesive according to any one of claims 1-6, further comprising in the first component (1n) 0-5% by weight of a curing catalyst, such as an amine, and (10) 0-5% by weight of at least one other additive, and/or in the second component (2g) 0-60% by weight of a second plasticizer, and optionally, and (21) 0-10% by weight of an accelerator.

8. Hechtmiddel volgens één van de conclusies 1-7, waarbij het vulstof is gekozen uit krijt, geprecipiteerd krijt, gecoat geprecipiteerd krijt, gemalen krijt, silica, aluminiumoxide, kool- stof, en combinaties daarvan, en/of waarin de ten minste één eerste en ten minste één tweede weekmaker elk afzonderlijk zijn gekozen uit benzoézuuresters, ftaalzuurdiesters, tereftaalzuurdiesters, benzoaten, ftala- ten, tereftalaten, polyolen, gehydrogeneerde versies van ftalaten, tereftalaten, en benzoaten, en combinaties daarvan, en/of waarin de additieven zijn gekozen uit katalysatoren, co-katalysatoren, reologiecontro- lemiddelen, pigmenten, pigmentpasta's, HALS, UV-stabilisatoren, anti-oxidanten, adhesie- promotoren, en droogmiddelen, en/of waarin de adhesiepromotor is gekozen uit Aminopropyltriethoxy-silaan (APTES) en Aminopropyltrimethoxy-silaan (APTMS), en/of waarin de reologiemodificator is gekozen uit pyrogeen kiezelzuur, roet, en polyamide- wassen, en combinaties daarvan.The adhesive of any one of claims 1 to 7, wherein the filler is selected from chalk, precipitated chalk, coated precipitated chalk, ground chalk, silica, alumina, carbon, and combinations thereof, and/or wherein the at least one first and at least one second plasticizer are each individually selected from benzoic acid esters, phthalic acid diesters, terephthalic acid diesters, benzoates, phthalates, terephthalates, polyols, hydrogenated versions of phthalates, terephthalates, and benzoates, and combinations thereof, and/or wherein the additives are selected from catalysts, cocatalysts, rheology control agents, pigments, pigment pastes, HALS, UV stabilizers, antioxidants, adhesion promoters, and drying agents, and/or wherein the adhesion promoter is selected from Aminopropyltriethoxysilane (APTES) and Aminopropyltrimethoxysilane silane (APTMS), and/or wherein the rheology modifier is selected from fumed silica, carbon black, and polyamide waxes, and combinations thereof.

9. Hechtmiddel volgens een van de conclusies 1-8, waarbij de eerste en tweede component zijn verschaft in een gewichtsverhouding van 40:1 tot 0,5:1, bij voorkeur 30:1 tot 0,6:1, lie- ver 25:1 tot 0,7:1, zoals 20:1 tot 2:1.An adhesive according to any one of claims 1 to 8, wherein the first and second components are provided in a weight ratio of 40:1 to 0.5:1, preferably 30:1 to 0.6:1, more preferably 25 :1 to 0.7:1, such as 20:1 to 2:1.

10. Product omvattend een hechtmiddel volgens een van de conclusies 1-9, bij voorkeur waarin het product grote gelijmde onderdelen bevat, en/of is gekozen uit voertuigen, zoals vrachtwagens, bussen, en treinen.A product comprising an adhesive according to any one of claims 1-9, preferably wherein the product contains large glued parts, and/or is selected from vehicles, such as trucks, buses, and trains.

11. Gebruik van een kleefstofsamenstelling volgens een van de conclusies 1-9, voor een of meer van snelle uitharding, lange open tijd, zoals >30 minuten, snelle sterkteopbouw, zoals Fmax>1,2 MPa na twee uur, goede elasticiteit, goede sterkte, zoals > 4,3 MPa na 24 uur (@590% uitrekking), goede duurzaamheid, goede hechting, vrij van kleverigheid, zelther- stellend, waterdichtheid, een hoge volumemodulus na 24 uur, zoals van > 1,2 MPa, en com- binaties daarvan.Use of an adhesive composition according to any one of claims 1-9, for one or more of fast curing, long open time, such as >30 minutes, fast strength build-up, such as Fmax>1.2 MPa after two hours, good elasticity, good strength, such as > 4.3 MPa after 24 hours (@590% elongation), good durability, good adhesion, tack free, self-healing, water tightness, a high volume modulus after 24 hours, such as > 1.2 MPa, and combinations thereof.

12. Gebruik volgens conclusie 11, bij eenzijdige of tweezijdige verlijming, in het bijzonder bij verlijming van grote oppervlakken van 0,5-10 m*.Use according to claim 11, for one-sided or two-sided bonding, in particular for bonding large surfaces of 0.5-10 m*.

13. Gebruik van een afdichtmiddel of hechtmiddel volgens één van de conclusies 1-9 voor het hechten van een werkstuk, zoals een autoruit, en een autopaneel.Use of a sealant or adhesive according to any one of claims 1-9 for bonding a workpiece, such as a car window, and a car panel.