WO2022173289A1 - Flexible adhesive for gluing - Google Patents
Flexible adhesive for gluing Download PDFInfo
- Publication number
- WO2022173289A1 WO2022173289A1 PCT/NL2022/050050 NL2022050050W WO2022173289A1 WO 2022173289 A1 WO2022173289 A1 WO 2022173289A1 NL 2022050050 W NL2022050050 W NL 2022050050W WO 2022173289 A1 WO2022173289 A1 WO 2022173289A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silane
- component
- polymer
- adhesive
- terminated
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 67
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 66
- 238000004026 adhesive bonding Methods 0.000 title claims abstract description 7
- 239000003707 silyl modified polymer Substances 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000000565 sealant Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 17
- -1 organotin Chemical class 0.000 claims description 16
- 239000004014 plasticizer Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000005498 phthalate group Chemical class 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000012963 UV stabilizer Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 5
- 239000006254 rheological additive Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000003619 algicide Substances 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 239000003899 bactericide agent Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 230000000855 fungicidal effect Effects 0.000 claims description 4
- 239000000417 fungicide Substances 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 102000011045 Chloride Channels Human genes 0.000 claims description 3
- 108010062745 Chloride Channels Proteins 0.000 claims description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 3
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 229910052610 inosilicate Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 238000000518 rheometry Methods 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- 229960004063 propylene glycol Drugs 0.000 claims 1
- 235000013772 propylene glycol Nutrition 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 4
- 239000000306 component Substances 0.000 description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000011521 glass Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 235000013350 formula milk Nutrition 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- 235000001465 calcium Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229960005088 urethane Drugs 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SYOKIDBDQMKNDQ-XWTIBIIYSA-N vildagliptin Chemical class C1C(O)(C2)CC(C3)CC1CC32NCC(=O)N1CCC[C@H]1C#N SYOKIDBDQMKNDQ-XWTIBIIYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Definitions
- 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.
- 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.
- DE 102009027 357 A1 recites a two-component adhesive or sealant masses (K) with a first component (Kl) containing silane-terminated pre polymers (A) which have end groups of the general formula (II) -0-CO-NH-(CH)-SiR(OR), where R R are independently hydrocarbon radicals having 1-18 carbon atoms or co-oxaalkyl- alkyl radicals having a total of 2-20 carbon atoms, x is 2 or 3 and y is a number from 1 to 10, and a second component (K2) containing water, with which Provided that at least 50% of all prepolymer molecules (A) in the backbone of the prepolymer chain have no additional ure thane or urea units, DE 102006022095 A1 recites polymer blends (P) which A) alkoxysilane-terminated polymers (A) having at least one end group of the formula (1) -A- (CH2)m-SiR
- 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(ORi)2R3) polymer (STP) with at least one alpha nitrogen at the reactive silane end group according to fig. 1,
- u OMe preferably with two or more silane terminated end groups, preferably wherein the nitrogen forms part of a urethane bond, wherein Me is C3 ⁇ 4, 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, (lb) 3-50 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, and/or
- the polymer for figs. 2 and 3 is selected as above for fig. 1, (le) 5-60 wt.% of at least one filler, (If) 0-5 wt.% of at least one pigment or colorant, (lg) 0-5 wt.% of at least one rheology modifier, (lh) 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, (li) 0-5 wt.% of at least one adhesion promotor, (lj) 0-8 wt.% of at least one drying agent, (lk) 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
- STP silane-terminated polymer
- Geniosil silane-terminated polymer
- 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.
- 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.
- 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.
- part B also referred to as second part or component
- the second compo nent typically holds the water needed for the reaction.
- 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.
- a silane terminated amine such as 3 -aminopropyl-tri - m ethoxy silane or 3 -aminopropyl-tri ethoxy silane could be present.
- An example of a single 1C sealant of the prior art adhesive has an open time of ⁇ 42 minutes.
- 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).
- KOH potassium hydroxide
- g KOH/g second plasticiser g KOH/g second plasticiser
- HV [ ⁇ (56.1 )(N)(V B -V acet ) ⁇ /W acet ]+AV ⁇
- HV is the hydroxyl value
- VB is the amount (ml) potassium hydroxide solution re quired for the titration of the blank
- V aCet is the amount (ml) of potassium hydroxide solution required for the titration of the acetylated sample
- W aCet 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.
- 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.
- 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 F max > 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.
- the present invention provides a solution to one or more of the above-men tioned problems.
- the present invention relates in a first aspect to an adhesive composition according to claim 1.
- the at least one first silane-terminated polymer (STP) is reactive.
- 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.
- the present adhesive in the first component com prises (la) 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.%.
- the present adhesive in the first component com prises (lb) 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.%.
- the present adhesive in the first component com- prises(lc) 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.%.
- 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.
- the polyether has an average molecular mass Mn of 400-4000 kDa (ISO 472).
- 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.
- the additives are selected from catalysts, co-catalysts, rheology control agents, pigments, pig ment pastes, HALS, UV stabilizers, antioxidants, adhesion promotors, and drying agents.
- the adhesion promotor is selected from Amino-propyl-tri-ethoxy-silane (APTES) and Amino- propyl-tri-methoxy-silane (APTMS).
- APTES Amino-propyl-tri-ethoxy-silane
- APITMS Amino- propyl-tri-methoxy-silane
- the rheology modifier is selected from fumed silica, carbon black, and polyamide waxes.
- 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.%
- the present adhesive in the first component com prises in the first component (In) 0-5 wt.% hardening catalyst, such as an amine, and (lo) 0- 5 wt.% of at least one further additive.
- the filler is selected from chalk, precipitated chalk, grounded chalk, coated precipitated chalk, coated grounded chalk, silica, alumina, carbon black, and combinations thereof.
- inorganic material selected from clay, CaC0 3 , carbon black, silica, zeolite, talc, mica, kaolin, dolomite, aluminium trihydrate, and a calcium inosil- icate mineral (CaSi03), such as wollastonite, preferably 4-7 wt.%, preferably precipitated CaC0 3.
- the inorganic material has an average particle size of 0.01-300 pm, preferably 0.02-10 pm, more preferably 0.05-1 pm, such as 0.07-0.2 pm.
- 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
- the present adhesive in the second component com prises (2c) 0.05-2 wt.% of at least one surfactant, preferably 0.1-1.5 wt.% spoil and/or
- 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.%.
- 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.%.
- 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 (2i) 0-10 wt.% of an accelerator, preferably 1-8 wt.%, such as 3-6 wt.%.
- 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.
- 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.
- the present adhesive may comprise a combination of the above.
- the present use is in one-sided or two-sided bonding, especially of bonding of large surfaces of 0.5-30 m 2 , such as 0.5-15 m 2 .
- the present use is for adhering a workpiece, such as a car window, and a car panel.
- Figure 1 A first silane-terminated (Si(ORi)2R3) 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.
- STP silane-terminated polymer
- 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
- Table 1 and table 2 show a list of sealants and boosters according to the invention.
- sealants SO [prior art] and S1-S5, according to the invention
- 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.
- sealant 3 is still the fastest when the open time is extended from 20 till 30 minutes by choosing a different booster.
- the curing speed is already halved compared to sealant 3, but still considerably faster than the prior art.
- the sealant containing gamma O polymer needs about 25 hours to reach half of the strength which the sealant with 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 FI 00 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.
- 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 (com ponent lb)
- Results table 4 open time and curing speeds
- Results table 5 Fmax of Dumbbells after DIN 53504 after 1 day cure at 10°C and 30%RH
- Open time and curing time were determined by using a Beck Roller recorder, usually known as BK-recorder such as sup-plied by for example TQC-sheen.
- an adhesive film of 450pm is applied to a glass plate.
- the B.K Drying recorder pulls a needle through the adhesive film at a set speed correlating with time.
- a film of fresh adhesive is applied on to a degreased glass plate (25 x 300 mm).
- 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.
- 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.
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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.
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.
Some documents may be referred to. DE 102009027 357 A1 recites a two-component adhesive or sealant masses (K) with a first component (Kl) containing silane-terminated pre polymers (A) which have end groups of the general formula (II) -0-CO-NH-(CH)-SiR(OR), where R R are independently hydrocarbon radicals having 1-18 carbon atoms or co-oxaalkyl- alkyl radicals having a total of 2-20 carbon atoms, x is 2 or 3 and y is a number from 1 to 10, and a second component (K2) containing water, with which Provided that at least 50% of all prepolymer molecules (A) in the backbone of the prepolymer chain have no additional ure thane or urea units, DE 102006022095 A1 recites polymer blends (P) which A) alkoxysilane-terminated polymers (A) having at least one end group of the formula (1) -A- (CH2)m-SiR la(OR2)3-a, where A is a divalent linking group selected from -0-, -S-, -(R3)N-, - 0-CO-N(R3)-, -N(R3)-CO-0-, -N(R3)-CO-NH-, -NH-CO-N(R3)-, -N(R3)-CO-N(R3)-, R1 is an optionally halogen-substituted alkyl, cycloalkyl, alkenyl or aryl radical with 1- 10 carbon atoms, R2 is an alkyl radical having 1-6 carbon atoms or an omega-oxaalkyl-alkyl radical having a total of 2-10 carbon atoms, R3 is hydrogen, an optionally halogen-substituted cy clic, linear or branched Ci- to Cis-alkyl or alkenyl radical or a Ce- to Cis- aryl radical, a is an integer from 0 to 2 and m is an integer from 1 bi s is 6, B) pyrogenically produced or precipi tated silica with a BET surface area of at least 50 m2/g and C) contain a catalyst with at most 0.05% by weight of amino compounds and no other fillers. It is therefore an object of the present invention to provide an adhesive which overcomes one or more of the above disad vantages, 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(ORi)2R3) polymer (STP) with at least one alpha nitrogen at the reactive silane end group according to fig. 1,
H C — Si — CH C — OvO Polymer v/\ O— C ^ \ H - Si— CH
3 I 2 \ / II 2 I 3
N W
OMe |-| u OMe preferably with two or more silane terminated end groups, preferably wherein the nitrogen forms part of a urethane bond, wherein Me is C¾, 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, (lb) 3-50 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, and/or
(lc) 0.1-45 wt.% of at least one third silane-terminated polymer (STP) with no nitrogen close to the reactive silane end group, (Id) 0-5 wt.% of at least one fourth silane-terminated polymer (STP) with no nitrogen at the reactive silane end group according to fig. 3, in partic ular 0.1-3 wt.%,
OMe Fig. 3 Ϊ2 OMe
I H 2 / \ I
H C— Si — CFI C—O v/\ Polymer 7O-C x E H - Si— CH
3 I 2 / H 2 2 I 3
OMe |-| OMe wherein the polymer for figs. 2 and 3 is selected as above for fig. 1, (le) 5-60 wt.% of at least one filler, (If) 0-5 wt.% of at least one pigment or colorant, (lg) 0-5 wt.% of at least one rheology modifier, (lh) 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, (li) 0-5 wt.% of at least one adhesion promotor, (lj) 0-8 wt.% of at least one drying agent, (lk) 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, (lm) 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 <104 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, CaCC , carbon black, silica, zeolite, talc, mica, kaolin, dolomite, aluminium trihydrate, and a calcium inosilicate mineral (Ca- Si03), such as wollastonite, preferably precipitated or grounded CaCC , which 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-aminopropyl-trimethox- ysilane or 3 -aminopropyl-tri ethoxy silane, (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 - m ethoxy silane or 3 -aminopropyl-tri ethoxy silane 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 (F max) 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) } /Wacet]+AV} wherein HV is the hydroxyl value; VB is the amount (ml) potassium hydroxide solution re quired for the titration of the blank; VaCet 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 (la) 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 (lb) 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(lc) 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 (la,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- 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 (In) 0-5 wt.% hardening catalyst, such as an amine, and (lo) 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, CaC03, carbon black, silica, zeolite, talc, mica, kaolin, dolomite, aluminium trihydrate, and a calcium inosil- icate mineral (CaSi03), such as wollastonite, preferably 4-7 wt.%, preferably precipitated CaC03.
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 pm, preferably 0.02-10 pm, more preferably 0.05-1 pm, such as 0.07-0.2 pm.
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 (2c) 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 (2i) 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 m2, such as 0.5-15 m2.
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(ORi)2R3) 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 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 FI 00 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 Fmax 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:
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 (com ponent lb)
Results table 3: open time, curing time, Fmax
Results table 4: open time and curing speeds
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 Roller 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 450pm is 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 450pm 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).
Claims
1. A two component flexible adhesive for gluing comprising a first component, comprising
(la) 0.1-50 wt.% of at least one first silane-terminated (Si(ORi)2R-3) polymer (STP) with at least one alpha nitrogen at the reactive silane end group according to fig. 1,
preferably with two or more silane terminated end groups, preferably wherein the nitrogen forms part of an urethane bond [-C-0-C=0-NH-), wherein Me is CLP, 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,
(lb) 3-50 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, and/or
OMe 0 Fig. 2 [J OMe
H C— Si — CH C— 0 v/\ Polymer \0— C ^ N: H — Si— CH
3 3 6\ / „ 3 6 3
I N O
OMe |-| u OMe
(lc) 0,1-25 wt.% of at least one third silane-terminated polymer (STP) with no nitrogen close to the reactive silane end group,
(Ld) 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,
H e Fig. 3 '.
OM 2
C OMe
H 2 / \ 1
H C— Si — CH C— O v/\ Polymer v/O — C k XC H — Si— CH
3 I 2\c / H 2 3
2
OMe |-| OMe
(le) 5-60 wt.% of at least one filler,
(Lf) 0-5 wt.% of at least one pigment or colorant,
(lg) 0-5 wt.% of at least one rheology modifier,
(lh) 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,
(li) 0-5 wt.% of at least one adhesion promotor,
(lj) 0-8 wt.% of at least one drying agent,
(lk) 0-5 wt.% of at least one of an antioxidant, an UV-stabilizer, and a hindered amine light stabilizer,
(ll) 0.0 -2 wt.% of one or more of a fungicide, a bactericide, and an algaecide,
(lm) 0-5% of a catalyst, preferably chosen from organometal compounds, such as organotin, organo zinc, and organo bismuth, and amines,
(Ln) <0.2 wt.% free water, preferably <0.01 wt.%, more preferably <104 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, CaCCh, carbon black, silica, zeolite, talc, mica, kaolin, dolomite, aluminium trihydrate, and a calcium inosilicate mineral (Ca- Si03), such as wollastonite, preferably precipitated and/or grounded CaCCh, wherein the CaCC 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-trimethoxy silane or 3 -aminopropyl-tri ethoxy silane,
(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 claim 1, wherein the at least one first silane-terminated polymer (STP) comprises <10 silane end groups with an alpha nitrogen.
3. Adhesive according to claim 2, wherein the at least one first silane-terminated polymer (STP) comprises 1-5 silane end groups with an alpha nitrogen, such as 2-4 silane end groups.
4. Adhesive according to any of claims 1-3, comprising in the first component
(la) 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.%. and/or
(lb) 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
(lc) 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
(la,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),
(la,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, CaCCb, sil ica, zeolite, and carbon black, wherein the CaCCb may be coated or not, preferably 35-45 wt.%, preferably precipitated CaCCb, and/or
(2b) preferably wherein the inorganic material has an average particle size of 0.01-300 pm, preferably 0.02-10 pm, more preferably 0.05-1 pm, such as 0.07-0.2 pm, and/or
(2b) 0.2-10 wt.% at least one silica, preferably a fumed silica, preferably 0.5-3 wt.%, and/or
(2c) 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 claims 1-4, with the proviso that no heavy metal catalyst is present.
6. Adhesive according to any of claims 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 claims 1-6, further comprising in the first component
(Ln) 0-5 wt.% hardening catalyst, such as an amine, and
(lo) 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 (2i) 0-10 wt.% of an accelerator.
8. Adhesive according to any of claims 1-7, wherein the filler is selected from chalk, precipi tated 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 claims 1-8, wherein the first and second component are pro vided 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 claims 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 claims 1-9, in one-sided or two sided bonding, therewith providing one or more of rapid hardening, long open time, such as >30 minutes, rapid strength built-up, such as Fmax>l .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 claim 11, for bonding of large surfaces of 0.5-10 m2.
13. Use of a sealant or adhesive according to any of claims 11-12 for adhering a workpiece, such as a car window, and a car panel.
Priority Applications (1)
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EP22703851.0A EP4291597A1 (en) | 2021-02-11 | 2022-02-03 | Flexible adhesive for gluing |
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NL2027539 | 2021-02-11 | ||
NL2027539 | 2021-02-11 | ||
NL2027625A NL2027625B1 (en) | 2021-02-23 | 2021-02-23 | Flexible Adhesive for gluing |
NL2027625 | 2021-02-23 |
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WO2022173289A1 true WO2022173289A1 (en) | 2022-08-18 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006022095A1 (en) | 2006-05-11 | 2007-11-15 | Wacker Chemie Ag | Alkoxysilane-terminated polymers containing transparent polymer blends |
DE102009027357A1 (en) | 2009-06-30 | 2011-01-05 | Wacker Chemie Ag | Alkoxysilane-terminated polymers containing adhesives or sealants |
-
2022
- 2022-02-03 EP EP22703851.0A patent/EP4291597A1/en active Pending
- 2022-02-03 WO PCT/NL2022/050050 patent/WO2022173289A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006022095A1 (en) | 2006-05-11 | 2007-11-15 | Wacker Chemie Ag | Alkoxysilane-terminated polymers containing transparent polymer blends |
DE102009027357A1 (en) | 2009-06-30 | 2011-01-05 | Wacker Chemie Ag | Alkoxysilane-terminated polymers containing adhesives or sealants |
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