Silylated sealing compositions with improved adhesion to metal substrates

Abstract

1) A moisture-curable silylated composition, comprising 35 to 65% by weight of a polymer (A) having at least two alkoxysilyl end groups of formula (I): TIFF2023517322000027.tif28170 (in the formula, R 1 represents a divalent hydrocarbon group containing 5 to 15 carbon atoms, and R 2 represents C2-C4 alkylene, and R 3 represents C1-C6 alkylene, and R 4 and R 5 each represents a C1-C4 alkyl, and R 6 represents H or a group containing 1 to 6 carbon atoms, and n is a group of the formula -[OR 2 ] n - is an integer such that the Mw of the block is 300 to 40,000 g / mol, m is an integer different from 0 such that the Mw of polymer (A) is between 500 and 50,000 g / mol, and p is an integer equal to 0, 1, or 2), 15 to 2.5 to 12 wt. % of polymer (B) containing at least two alkoxysilyl end groups of formula (II), TIFF2023517322000028.tif18170 (in the formula, R 2 , R 4 , R 5 , n, and p are as defined for formula (I). 20 2) A moisture-curable silylated composition comprising: (I) a silsesquioxane (C) having 7.5 to 28 wt. % of an alkoxy-modified silsesquioxane; and (II) a silsesquioxane (C) having 7.5 to 28 wt. % of an alkoxy-modified silsesquioxane. 20 2) Use as an adhesive, sealant, and / or coating material.

Description

[Technical Field]

[0001] The present invention relates to moisture-curable silylated compositions and their use as adhesives, sealants and / or coating materials, preferably for assembling metal substrates and / or filling gaps between metal substrates. [Background technology]

[0002] Sealing (or sealant or caulking) compositions are widely used in the construction industry. They are used to assemble substrates, for example made of concrete, via expansion joints. In such applications, the compositions, due to their mechanical and especially elastic properties, make it possible to obtain joints that are stable against dimensional changes caused by temperature changes. Sealant compositions can also be used for adhesive bonding of floor coverings, especially wooden floors.

[0003] For manual application, the sealant composition is typically packaged in a cartridge with a nozzle at one end and applied after the cartridge is inserted into a gun, where the operator operates the gun's trigger to actuate a piston, which extrudes the sealant through the nozzle onto one of the substrates being assembled and / or into the gap between two substrates being joined.

[0004] The sealant composition comprises a moisture-crosslinkable prepolymer, the chemical structure of which generally has isocyanate-reactive or alkoxysilyl-reactive end groups.

[0005] After the sealant is extruded onto a substrate to create an assembly and / or into the gap between two substrates to be filled, these reactive groups undergo a crosslinking or curing reaction with water from moisture in the air or the substrate, resulting in the creation of a solid three-dimensional polymer network containing siloxane bonds, thereby forming an adhesive bond between the two substrates.

[0006] Silylated sealing compositions are known in industries such as the transportation industry.

[0007] By way of example, EP 1657155 describes a method for caulking ship decks with a moisture-curing sealing composition comprising one or more silyl-modified polyacrylates.

[0008] In the method described by this European patent, in a first step, wooden planks are joined onto a subdeck of a ship. Between adjacent planks, an empty gap or gap (also called a joint) remains around the periphery of the planks. The method then includes, in a second step, sealing (or bonding or caulking) the joined wooden planks by applying a sealing (or sealant) composition to fill the joints around the periphery of the wooden planks. The hardening of the composition results in the formation of a joint that prevents undesirable products, such as dust, dirt, moisture, chemicals, or seawater, from penetrating the joint and coming into contact with the subdeck. This prevents possible damage or corrosion of the subdeck.

[0009] However, there are many applications throughout industry, and particularly in the transportation industry, where it is desirable to obtain an adhesive bond between two substrates when assembling substrates other than concrete or wood and / or sealing the gap (or joint) between those substrates with a sealant composition.

[0010] In particular, there is a need to obtain an adhesive joint between two metal substrates, the formation of which may be desirable in order to provide the joint with advantageous properties such as air and / or water tightness.

[0011] One example is the assembly of ventilation pipes used to transfer and exchange air from air conditioning systems developed for high-speed trains. Such ventilation pipes have a rectangular cross section and extend throughout the entire train. They are assembled by screwing laminated insulation panels to a rigid metal frame, e.g., aluminum. These insulation panels typically consist of polyurethane foam boards about 10 mm thick, covered on both sides with metal foil, e.g., aluminum foil, about 0.5 mm thick.

[0012] In such an assembly, seams are formed at the interface between the metal surfaces of the insulation panels and the rigid metal frame to which they are screwed. Other seams are formed along the inner edges resulting from the perpendicular intersection of the four metal foils covering the four insulation panels positioned on the four sides of the rectangular cross section of the vent pipe.

[0013] It is therefore necessary for such seams to be sealed with adhesive joints to prevent leakage of the strong air currents flowing inside the vent pipes and to ensure that said vent pipes, which run the entire length of the train, are completely airtight (or gas-tight). This requirement is all the more important due to the high speeds (approximately 300 km / h) of trains that will have vent pipes integrated into their air-conditioning systems. As cold and / or warm air currents flow throughout the entire vent pipe, loss of joint adhesive can cause detrimental problems while the train is moving, such as very loud wind noise, like a whistling sound.

[0014] Therefore, for such seals to be hermetically effective, a high level of adhesion of the sealing joint to the metal substrate is of paramount importance.

[0015] Furthermore, high-speed trains can travel vast distances and across different climates in the course of a day, encountering a wide range of temperature and humidity conditions, so there is a risk that water may condense on the metal foil surface of the insulation panel inside the vent pipe and come into contact with the seal.

[0016] Therefore, there is also a need to maintain a high level of adhesion of the sealing joint to the metal substrate, even after prolonged contact with water. Summary of the Invention

[0017] Therefore, one object of the present invention is to propose new moisture-curable silylated compositions which, after curing, exhibit a high level of adhesion on metal substrates, in particular on aluminium.

[0018] Another object of the present invention is to propose novel silylated moisture-curing compositions which, after curing, exhibit a high level of adhesion on metal substrates, in particular on aluminum, which is maintained even after prolonged contact with water.

[0019] Another object of the present invention is to propose a novel silylated moisture-curable composition having suitable viscosity and curing time suitable for use as a sealant.

[0020] Another object of the present invention is to propose new silylated moisture-curing compositions that can be used for assembling metal substrates and / or filling gaps between metal substrates, in particular for aluminum substrates.

[0021] It has been found that the above objectives can be achieved in whole or in part by the moisture-curable compositions according to the invention described below. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 shows an enlarged cross-sectional view of a portion of a vent pipe exhibiting a rectangular cross-section. DETAILED DESCRIPTION OF THE INVENTION

[0023] The present invention relates to a moisture-curable silylated composition, the moisture-curable silylated composition comprising, based on the total weight of the composition: 35 to 65% by weight of a polymer (A) containing at least two alkoxysilyl end groups of formula (I), TIFF0007749573000001.tif26170(I) During the ceremony, -R 1 represents a hydrocarbon-based divalent group containing 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic, -R 2 represents a divalent linear or branched alkylene group containing 2 to 4 carbon atoms, -R 3 represents a divalent linear or branched alkylene group containing 1 to 6 carbon atoms, -R 4 and R 5 are the same or different and each represents a linear or branched alkyl group having 1 to 4 carbon atoms, and some R 4 (or R 5 ) groups, when present, may be the same or different; -R 6 represents a hydrogen atom or a group containing 1 to 6 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic, or a group selected from the following groups: Formula (Ia): TIFF0007749573000002.tif18170(Ia) Formula (Ib): TIFF0007749573000003.tif26170 formula (Ic): TIFF0007749573000004.tif23170(Ic) (In the formula, R 7 is a linear or branched alkyl group containing 1 to 6 carbon atoms. -n is the expression -[OR 2 ] n the average molecular weight of the polyether blocks is an integer between 300 g / mol and 40,000 g / mol, -m is an integer different from 0 such that the average molecular weight of polymer (A) is between 500 g / mol and 50,000 g / mol, -p is an integer equal to 0, 1 or 2 a polymer (A); 2.5 to 12% by weight of a polymer (B) containing at least two alkoxysilyl end groups of formula (II), TIFF0007749573000005.tif16170(II) In the formula, R 2 , R 4 , R 5 , n and p are as defined for formula (I). a polymer (B); 7.5 to 28% by weight of alkoxy-modified silsesquioxane (C); The present invention is characterized by comprising:

[0024] It has been found that the moisture-curable compositions defined above, after being cured with moisture, unexpectedly provide cured compositions that advantageously have a high level of adhesion to metal substrates, particularly aluminum substrates.

[0025] Such a high level of adhesion can be experimentally estimated from the failure mode of tensile tests carried out on a two-layer system consisting of a layer of the cured composition coated on an aluminum substrate. Indeed, in the field of adhesives and sealants, several types of failures have been observed in tensile tests, namely: - Adhesion failure at the sealant / substrate interface, - cohesive failure occurring within the actual layer of sealant, with each substrate retaining a fraction of the sealant; -Adhesive-independent substrate failure (also known as substrate failure) can be distinguished by.

[0026] Many intermediate situations also exist, which are rated according to the proportion of the substrate surface involved.

[0027] It has now been found that adhesive joints made from the cured composition coated on aluminium exhibit highly advantageous cohesive or substrate failure in tensile tests.

[0028] The moisture-curable composition according to the present invention is therefore suitable for use in assembling metal substrates and / or filling gaps between metal substrates.

[0029] It is particularly suitable for use in the assembly of ventilation pipes to be incorporated into air conditioning systems developed for high speed trains.

[0030] Figure 1 shows an enlarged cross-sectional view of a portion of such a vent pipe (1) presenting a rectangular cross-section.

[0031] Polyurethane foam boards (2) and (2') are used, covered on both sides with aluminum foil (3) and (3').

[0032] Each end of the polyurethane foam boards (2) and (2') is cut at a 45° angle so that they will match and form a right angle after being fixed to the aluminum frame (4) by screws (not shown).

[0033] Such assembly results in the formation of seams at the contact surfaces between the aluminum foils (3) and (3') on the inside of the vent pipe, and at the contact surfaces between the aluminum frame (4) from one side and the aluminum foils (3) and (3') from the other side on the outside of the vent pipe.

[0034] Such joints are sealed / filled by introducing a moisture-curing composition according to the invention and subsequently moisture curing it, resulting in beads (5) and strips (6), (6') that prevent leakage of strong air currents flowing through the vent pipe in a direction (7) perpendicular to the plane of the drawing.

[0035] Furthermore, it has been found that the setting time of the moisture-curing composition according to the invention, as assessed by the skinning time test, is comprised between 15 and 45 minutes, and its viscosity, as measured by a rheometer, is comprised between 20 and 50 Pa·s. These properties make the composition particularly suitable for application as a sealant by means of a cartridge equipped with a nozzle at one end.

[0036] A polymer (A) containing at least two alkoxysilyl end groups of formula (I) The moisture-curable composition according to the present invention contains 35 to 65% by weight of the polymer (A).

[0037] According to a preferred variant, the polymer (A) is: -R 1 is selected from one of the following divalent groups, each formula of which indicates two free valences: a) a divalent group derived from isophorone diisocyanate (IPDI): TIFF0007749573000006.tif32170-b) Divalent group derived from methylenebis(cyclohexyl isocyanate) (HMDI): TIFF0007749573000007.tif16170-c) Divalent group derived from tolylene diisocyanate (TDI): TIFF0007749573000008.tif35170-d) Divalent radical derived from diphenylmethane diisocyanate (MDI): TIFF0007749573000009.tif23170-e) Divalent group derived from hexamethylene diisocyanate (HDI): -(CH2)6- -f) a divalent group derived from m-xylylene diisocyanate (XDI): TIFF0007749573000010.tif22170-R 2 is a divalent radical of ethylene and / or isopropylene, -R 3 is a divalent group of methylene and / or n-propylene, -R 4 and R 5 represents a methyl group or an ethyl group, -R 6 represents a hydrogen atom, a phenyl group, or a linear, branched, or cyclic alkyl group containing 1 to 6 carbon atoms.

[0038] Said polymer (A), sometimes referred to by the term "SPUR", may be obtained according to the following method. a) to form a polyurethane-polyether block having at least two terminal -NCO groups, H-[-OR 2 ]n-OH of polyether polyol of the formula NCO-R 1 -NCO and then reacting with a stoichiometric excess of diisocyanate according to the formula: b) the block obtained in the previous step with a stoichiometric or slight excess amount of alpha, beta or gamma-aminosilane; (R 5 O) 3-p (R 4 ) p Si-R 3 -NHR 6 The reaction was:

[0039] For further details, see international applications WO2013 / 136108 or WO2014 / 031568.

[0040] Many SPURs are commercially available, for example: -SPUR+1015 LM from MOMENTIVE, DESMOSEAL® S XP 2774, DESMOSEAL® S XP 2636 or DESMOSEAL® S XP 2749 from Covestro There is.

[0041] According to a preferred embodiment, the content of polymer (A) contained in the composition according to the invention varies from 40 to 60% by weight.

[0042] A polymer (B) containing at least two alkoxysilyl end groups of formula (II) The moisture-curable composition according to the present invention contains 2.5 to 12% by weight of the polymer (B).

[0043] The polymer (B) may be called α-STPE (if it is a silyl-terminated polyether), and may be obtained according to the method described in EP 2 336 208 to BOSTIK.

[0044] According to a preferred embodiment, the polymer (B) has the formula (II) R 2 is a divalent radical of isopropylene, and R 4 and R 5 are methyl or ethyl, respectively.

[0045] Among the polymers of formula (II) available on the market, mention may be made of: GENIOSIL® STP-E10 (available from Wacker) which has a number average molecular weight of 8889 g / mol and contains two terminal alkoxysilyl groups of formula Si(CH3)(OCH3)2 attached to the polypropylene glycol backbone via the group -O-CO-NH-CH2-. GENIOSIL® STP-E30 (available from Wacker) with a number average molecular weight of 14,493 g / mol and containing two terminal alkoxysilyl groups of formula Si(CH3)(OCH3)2 attached to the polyether backbone via the group -O-CO-NH-CH2-.

[0046] According to a preferred embodiment, the content of polymer (B) contained in the composition according to the invention varies from 3.7 to 10.5% by weight.

[0047] Alkoxy-modified silsesquioxane (C) The moisture-curable composition according to the present invention contains 7.5 to 28% by weight of the alkoxy-modified silsesquioxane (C).

[0048] Silsesquioxanes (C) are organosilicon compounds that have a cage or polymer structure with Si-O-Si bonds.

[0049] Preferably, the alkoxy-modified silsesquioxane (C) has the formula (III): TIFF0007749573000011.tif48170(III) It is of In the formula, R' 1 ~R' 8 are the same and different, - hydrogen atom, a group selected from the group consisting of a linear or branched C1-C4 alkoxy, a linear or branched alkyl containing 1 to 30 carbon atoms, an alkenyl containing 2 to 30 carbon atoms, an aromatic group containing 6 to 30 carbon atoms, an aryl group containing 3 to 30 carbon atoms, a cycloaliphatic group containing 3 to 30 carbon atoms, and an acyl group containing 1 to 30 carbon atoms, or --OSiR' 9 R' 10 is a group, R ’9 and R' 10 is selected from a hydrogen atom, a linear or branched C1-C4 alkyl, a linear or branched C1-C4 alkoxy, a C2-C4 alkenyl, a phenyl, a C3-C6 aryl group, a C3-C8 cycloaliphatic group, and a C1-C4 acyl group; -OSiR' 9 R' 10 base represents However, R' 1 ~R' 8 At least one, preferably at least two of the groups are C1-C4 alkoxy groups.

[0050] The alkoxy-modified silsesquioxanes (C) of formula (III) are known compounds, which are described in particular in WO 2008 / 107331.

[0051] Preferably, R' in formula (III) 1 ~R' 8 is R' 1 ~R' 8 represents a group selected from among methyl, methoxy or phenyl, provided that at least one, preferably at least two of are methoxy.

[0052] According to a preferred embodiment, the content of silsesquioxane (C) contained in the composition according to the invention varies from 11.3 to 24.5% by weight.

[0053] According to a more preferred embodiment, the composition according to the invention comprises the polymer (B) and the silsesquioxane (C) in a weight percent amount such that the weight ratio (B) / [(B)+(C)] is in the range of 10 to 35%, preferably in the range of 15 to 30%. In such an embodiment, (B) and (C) can be advantageously introduced during the preparation of the composition according to the invention or can be mixed in a single composition that is already available as a premix.

[0054] As an example of such a combination of (B) and (C), mention may be made of the commercial product Geniosil® XB502 from WACKER, which is -methylphenylsilsesquioxane (C) having a methoxy end group and a number average molecular weight of about 800 g / mol; a number average molecular weight of about 14000 g / mol, 4 and R 5 represents methyl, and -[OR 2 ] n -groups derived from polypropylene glycol) and a mixture of The products (B) and (C) are mixed in a weight ratio (B) / [(B)+(C)] of about 15 to 30%.

[0055] According to a preferred embodiment, the moisture-curing composition according to the invention comprises: 40 to 60% by weight of polymer (A); 3.7 to 10.5 wt% of a polymer (B); 11.3 to 24.5 wt% of silsesquioxane (C) Includes.

[0056] According to a particularly preferred embodiment, the moisture-curable composition according to the invention comprises, in addition to (A), (B) and (C), about 10-20 wt. % of a polyether (D), which contains at least one alkoxysilyl end group attached to the polyether backbone by a divalent group of -O-CO-NH-(CH2)3-, where -(CH2)3- is directly bonded to the Si atom of the alkoxysilyl end group.

[0057] According to a first embodiment, the polyether (D) comprises two alkoxysilyl end groups and has the formula (IV): TIFF0007749573000012.tif16170(IV) is a polyether of In the formula, R 2 , R 4 , R 5 , n and p are as defined for formula (I).

[0058] The polymer (D) may be called γ-STPE (if it is a silyl-terminated polyether), and may also be obtained according to the method described in EP 2 336 208 to BOSTIK.

[0059] According to a more preferred embodiment, in formula (IV), R 2 is a divalent radical of isopropylene, and R 4 and R 5 are methyl or ethyl, respectively.

[0060] Among the commercially available polymers of formula (IV), mention may be made of GENIOSIL® STP-E35 (available from Wacker) which contains two terminal alkoxysilyl groups of formula Si(OCH3)3 linked to the polyether backbone via the group -O-CO-NH-(CH2)3- and has a number average molecular weight of 32,240 g / mol.

[0061] According to a second preferred embodiment, the polyether (D) contains only one alkoxysilyl end group. An example of such a polyether is Geniosil® XM25, sold by Wacker, which is a monosilyl polymer with a number average molecular weight of about 6000 g / mol. It contains a polyether-type backbone and hydrolyzable propylene-methyldimethoxysilane end groups.

[0062] According to another preferred embodiment, the moisture-curable composition according to the invention comprises a curing catalyst, which may be any catalyst known to those skilled in the art for the condensation of silanols, such as amines or organometallic derivatives, in particular organic derivatives of iron, titanium, aluminum, or divalent or tetravalent tin.

[0063] Such compounds are commercially available, e.g. - such as TEGOKAT® 223, a dioctyltin-based catalyst from Evonik, - such as TYZOR® 726, a catalyst based on ethyl acetoacetate titanium complex from Dorf Ketal, or - Neostan S-1, a catalyst based on the reaction product of tetraethyl silicic acid (H4SiO4) with bis(acetyloxy)dioctylstannane (CAS number: 93925-43-0) from Nitto Kasei. There is.

[0064] The total weight of the curing catalyst is typically in the range of 0.1 to 2%.

[0065] According to a further preferred embodiment, the moisture-curable composition according to the invention comprises as a flame retardant a phosphate ester or a derivative of a phosphate ester, such as tris(2-ethylhexyl) phosphate, in an amount ranging from 10 to 20% by weight. Such an embodiment is particularly appreciated when the composition is used as a sealant for the transportation industry, particularly for train equipment, to ensure passenger safety in the event of a fire.

[0066] According to a further preferred embodiment, the moisture-curable composition according to the invention is transparent in both its uncured and cured form. In such a case, the sealing composition may contain a filler, preferably fumed silica, in an amount not exceeding 10% by weight. An example of such a fumed silica is KONASIL K-D15, available from OCI.

[0067] Optionally, moisture-curable compositions according to the present invention may contain additional ingredients such as one or more moisture scavengers, adhesion promoters or UV stabilizers.

[0068] It is preferable to check the water content of the composition according to the invention in order to prevent immediate crosslinking of the silylated polymers (A) and (B) and / or the silsesquioxane (C), which would lead to an increase in viscosity during storage of the composition. Moisture can be introduced into the composition by some of its components.

[0069] For this reason, the composition according to the present invention can contain one or more dehydrating agents (or moisture scavengers). Suitable dehydrating agents are, in particular, alkoxysilanes, such as trialkoxysilanes (especially trimethoxysilanes) and alkoxysilanes containing amino, mercapto, or epoxy groups. Examples include vinyltrimethoxysilane (VTMO), γ-glycidyloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, or trimethoxymethylsilane.

[0070] Some of these compounds, particularly trialkoxysilanes containing amino, mercapto, or epoxy groups, such as [3-(2-aminoethyl)aminopropyl]trimethoxysilane (also known as DAMO), can also act as adhesion promoters.

[0071] Finally, the compositions according to the invention may also contain a UV stabilizer, such as Tinuvin® 384-2 commercially available from BASF.

[0072] According to a preferred embodiment, the composition comprises: 0.1 to 2% moisture scavenger, 0.5-3% adhesion promoter Includes.

[0073] The moisture-curable composition according to the invention can be prepared by mixing the silylated polymer(s) (A) and (B) and the silsesquioxane (C) at a temperature ranging from 10°C to 40°C and a relative humidity ranging from 0.1% to 50%. The catalyst, if present, is preferably added in a second step after mixing the silylated polymer and the filler (if present). Other additives are introduced according to conventional methods.

[0074] As mentioned above, according to a preferred embodiment, the polymer (B) and the silsesquioxane (C) are introduced during the preparation of the composition in which they are mixed as a single composition in which the weight ratio (B) / [(B)+(C)] is in the range of 10-35%.

[0075] The present invention also relates to the use of the moisture-curing silylated composition according to the invention as an adhesive, sealant and / or coating material, preferably for assembling and / or filling gaps between metal substrates, more preferably for aluminum substrates.

[0076] According to one embodiment, the use according to the invention is for assembling ventilation pipes that are to be incorporated into air conditioning systems for high-speed trains. [Example]

[0077] The following examples are given purely to illustrate the present invention, but should not be construed as limiting the scope of the invention.

[0078] Example 1: Moisture-curable composition based on polymer (A), polymer (B), silsesquioxane (C) and polyether (D) 1) Preparation The composition of Example 1 is prepared as previously disclosed by mixing the components shown in Table 1, with the polymer (B) and silsesquioxane (C) being introduced into the mixture as a commercially available premix, Geniosil® XB502. After its preparation, the composition is stored in a sealed cartridge and then subjected to the following tests:

[0079] The viscosity of the composition was measured using a measuring device equipped with a 25 mm diameter plate and a viscosity of 5.0 s -1 The measurements were performed at 23 °C using a standard rheometer operating at a shear rate of 20–50 Pa·s.

[0080] The skinning time of the compositions was tested in a conditioned room (23°C and 50% relative humidity) by first applying a strip of the composition to a substrate (e.g., aluminum) and then using a finger to touch the surface of the composition every 5 minutes to see if a skin had formed on the surface. The time required for the skin to form was recorded. Results ranging between 20 and 30 minutes were obtained.

[0081] 2) Determining the failure mode of cured compositions adhered to aluminum substrates A sample of polyurethane foam board 10 mm thick is used, which is covered on both sides with aluminium foil 0.5 mm thick.

[0082] Grease or dust is removed from the aluminum foil surface of the sample with ethanol, and then the sample is left to stand for 15 minutes to allow the solvent to evaporate completely.

[0083] A bead of the composition is applied from the cartridge onto a sample of clean aluminum foil and then scraped from one side to the other with a spatula to form a strip approximately 10 cm long, 2 cm wide and 2-3 mm thick.

[0084] The coated samples are left to cure for 7 days in a conditioned room (23°C and 50% relative humidity) to form a strip of cured composition that adheres to the aluminum foil (adhesive joint).

[0085] The failure mode of the strip is then determined manually by inserting a spatula between the strip and the aluminum foil substrate in an attempt to peel the strip from the aluminum foil.

[0086] The strip broke off and the resulting remaining piece was still attached to the aluminum foil substrate, making it impossible to peel the strip from the aluminum foil.

[0087] Therefore, the failure mode result was determined to be 100% cohesive failure, and is listed in Table 1 as 100% CF.

[0088] The results demonstrate excellent adhesion of the cured composition to aluminum.

[0089] 3) Determination of the failure mode of the cured composition adhered to an aluminum substrate after contact with water for 7 days. After 7 days of cure, the previous determinations were repeated except that the coated substrates were immersed in water for 7 days and then allowed to rest at room conditions for 30 minutes before proceeding to determine failure mode.

[0090] The failure mode result was also determined to be 100% cohesive failure, and is listed in Table 1 as 100% CF.

[0091] The results demonstrate excellent adhesion of the cured composition to aluminum, as well as excellent adhesion of the cured composition to aluminum after exposure to water.

[0092] Examples 2 and 3: Moisture-curable compositions based on polymer (A), polymer (B) and silsesquioxane (C) 1) Preparation Example 1 was repeated using the composition shown in Table 1, i.e. without Geniosil® XM25. The same tests as in Example 1 were then carried out.

[0093] The same results were obtained for viscosity and skinning time.

[0094] 2) Determining the failure mode of cured compositions adhered to aluminum substrates As shown in Table 1, the same results as in Example 1 were obtained.

[0095] 3) Determination of the failure mode of the cured composition adhered to an aluminum substrate after contact with water for 7 days. Inserting a spatula between the strip of cured composition and the aluminum foil substrate revealed that the strip could be easily peeled off with no residual pieces adhering to the aluminum foil substrate.

[0096] Therefore, the failure mode result was determined to be 100% adhesive failure, and is listed in Table 1 as 100% AF.

[0097] Examples A, B and C (Comparative) 1) Preparation Example 1 was repeated using compositions A, B and C as shown in Table 1.

[0098] The same tests as in Example 1 were then carried out.

[0099] Similar results were obtained for viscosity and skinning time.

[0100] 2) Determining the failure mode of cured compositions adhered to aluminum substrates Inserting a spatula between the strip of cured composition and the aluminum foil substrate revealed that the strip could be easily peeled off with no residual pieces adhering to the aluminum foil substrate.

[0101] Therefore, the failure mode result was determined to be 100% adhesive failure, and is listed in Table 1 as 100% AF.

[0102] 3) Determination of the failure mode of the cured composition adhered to an aluminum substrate after contact with water for 7 days. The failure mode result was also determined to be 100% adhesive failure, and is listed in Table 1 as 100% AF. TIFF0007749573000013.tif122170

Claims

1. 1. A moisture-curable silylated composition comprising, based on the total weight of the composition: 35 to 65% by weight of a polymer (A) containing at least two alkoxysilyl end groups of formula (I): (I) (In the formula, -R １ represents a hydrocarbon-based divalent radical containing 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic, -R ２ represents a divalent linear or branched alkylene radical containing 2 to 4 carbon atoms, -R ３ represents a divalent linear or branched alkylene group containing 1 to 6 carbon atoms, -R ４ and R ５ are the same or different and each represents a linear or branched alkyl group having 1 to 4 carbon atoms, and some R ４ (or R ５ ) groups, when present, may be the same or different; -R ６ represents a hydrogen atom or a group containing 1 to 6 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic, or a group selected from the following groups: Formula (Ia): (Ia) Formula (Ib): Formula (Ic): (Ic) (In the formula, R ７ is a linear or branched alkyl group containing 1 to 6 carbon atoms. -n is a group of the formula -[OR ２ ] ｎ - is an integer such that the average molecular weight of the polyether block is between 300 g / mol and 40,000 g / mol, -m is an integer different from 0 such that the average molecular weight of polymer (A) is between 500 g / mol and 50,000 g / mol, - p is an integer equal to 0, 1 or 2. 2.5 to 12 wt. % of a polymer (B) containing at least two alkoxysilyl end groups of formula (II): (II) (In the formula, R ２ , R ４ , R ５ , n and p are as defined for formula (I), 7.5 to 28 wt. % of an alkoxy-modified silsesquioxane (C); A moisture-curable silylated composition comprising:

2. 2. The moisture-curable silylated composition of claim 1, wherein the polymer (A) is -R １ is selected from one of the following divalent groups, each formula of which shows two free valences: -a) a divalent group derived from isophorone diisocyanate (IPDI): -b) a divalent group derived from methylenebis(cyclohexyl isocyanate) (HMDI): -c) a divalent group derived from tolylene diisocyanate (TDI): -d) a divalent group derived from diphenylmethane diisocyanate (MDI): -e) a divalent group derived from hexamethylene diisocyanate (HDI): -(CH ２ ) ６ - -f) a divalent group derived from m-xylylene diisocyanate (XDI): -R ２ is a divalent radical of ethylene and / or isopropylene, -R ３ is a divalent group of methylene and / or n-propylene, -R ４ and R ５ represent a methyl group or an ethyl group, -R ６ represents a hydrogen atom, a phenyl group, or a linear, branched, or cyclic alkyl group containing 1 to 6 carbon atoms; A moisture-curable silylated composition characterized in that it is a polymer.

3. The polymer (B) is represented by the formula (II), R ２ is a divalent group of isopropylene, and R ４ and R ５ 3. The moisture-curable silylated composition of claim 1, wherein each of the groups is methyl or ethyl.

4. 4. The moisture-curable silylated composition of claim 1, wherein the alkoxy-modified silsesquioxane (C) is a compound represented by formula (III): (III) (In the formula, R' １ ~R' ８ are the same or different, - hydrogen atom, - linear or branched C １ -C ４ a group selected from alkoxy, linear or branched alkyl containing 1 to 30 carbon atoms, alkenyl containing 2 to 30 carbon atoms, aromatic group containing 6 to 30 carbon atoms, aryl group containing 3 to 30 carbon atoms, cycloaliphatic group containing 3 to 30 carbon atoms, acyl group containing 1 to 30 carbon atoms, or --OSiR' ９ R' １０ is a group, R ’９ and R' １０ is a hydrogen atom or a linear or branched C １ -C ４ Alkyl, linear or branched C １ -C ４ Alkoxy, C ２ -C ４ Alkenyl, phenyl, C ３ -C ６ Allyl group, C ３ -C ８ Cycloaliphatic group, C １ -C ４ acyl groups, —OSiR′ ９ R' １０ base represents However, R' １ ~R' ８ At least one of the following is C １ -C ４ is an alkoxy group.) A moisture-curable silylated composition comprising:

5. R' in formula (III) １ ~R' ８ But R' １ ~R' ８ 5. The moisture-curable silylated composition according to claim 4, characterized in that at least one of the groups represents a radical selected from among methyl, methoxy or phenyl, with the proviso that at least one of the groups is methoxy.

6. 6. The moisture-curable silylated composition according to claim 1, wherein the polymer (B) and the silsesquioxane (C) are contained in amounts of % by weight such that the weight ratio (B) / [(B)+(C)] is in the range of 10 to 35%.

7. 40 to 60% by weight of polymer (A); 3.7 to 10.5 wt. % of polymer (B); 11.3 to 24.5 wt. % of silsesquioxane (C); 7. The moisture-curable silylated composition of claim 1, comprising:

8. In addition to (A), (B), and (C), the composition contains 10 to 20% by weight of a polyether (D), wherein the polyether (D) is —O—CO—NH—(CH ２ ) ３ at least one alkoxysilyl end group attached to the polyether backbone by a divalent group of -, where -(CH ２ ) ３ 8. The moisture-curable silylated composition according to claim 1, wherein - is directly bonded to the Si atom of the alkoxysilyl end group.

9. The polyether (D) contains two alkoxysilyl end groups and has the formula (IV): (IV) 9. The moisture-curable silylated composition of claim 8, wherein

10. In formula (IV), R ２ is a divalent group of isopropylene, and R ４ and R ５ 10. The moisture-curable silylated composition of claim 9, wherein each of is methyl or ethyl.

11. 9. The moisture-curable silylated composition of claim 8, wherein the polyether (D) contains only one alkoxysilyl end group.

12. 12. Use of the moisture-curable silylated composition according to any one of claims 1 to 11 as an adhesive, sealant and / or coating material.

13. 13. Use according to claim 12 for assembling metal substrates and / or filling gaps between metal substrates.

14. 14. Use according to claim 13, characterized in that the metal substrate is an aluminum substrate.

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