EP4291597A1 - Flexibler klebstoff zum verkleben - Google Patents

Flexibler klebstoff zum verkleben

Info

Publication number
EP4291597A1
EP4291597A1 EP22703851.0A EP22703851A EP4291597A1 EP 4291597 A1 EP4291597 A1 EP 4291597A1 EP 22703851 A EP22703851 A EP 22703851A EP 4291597 A1 EP4291597 A1 EP 4291597A1
Authority
EP
European Patent Office
Prior art keywords
silane
component
polymer
adhesive
terminated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22703851.0A
Other languages
English (en)
French (fr)
Inventor
DE Rudolph Frank BLOCK
VAN Ilse Adriënne HEES
Gabriela DA CRUZ DE AZEVEDO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Strongbond BV
Original Assignee
Strongbond BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from NL2027625A external-priority patent/NL2027625B1/en
Application filed by Strongbond BV filed Critical Strongbond BV
Publication of EP4291597A1 publication Critical patent/EP4291597A1/de
Pending legal-status Critical Current

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP22703851.0A 2021-02-11 2022-02-03 Flexibler klebstoff zum verkleben Pending EP4291597A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL2027539 2021-02-11
NL2027625A NL2027625B1 (en) 2021-02-23 2021-02-23 Flexible Adhesive for gluing
PCT/NL2022/050050 WO2022173289A1 (en) 2021-02-11 2022-02-03 Flexible adhesive for gluing

Publications (1)

Publication Number Publication Date
EP4291597A1 true EP4291597A1 (de) 2023-12-20

Family

ID=80446975

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22703851.0A Pending EP4291597A1 (de) 2021-02-11 2022-02-03 Flexibler klebstoff zum verkleben

Country Status (2)

Country Link
EP (1) EP4291597A1 (de)
WO (1) WO2022173289A1 (de)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006022095A1 (de) 2006-05-11 2007-11-15 Wacker Chemie Ag Alkoxysilanterminierte Polymere enthaltende transparente Polymerabmischungen
DE102009027357A1 (de) 2009-06-30 2011-01-05 Wacker Chemie Ag Alkoxysilanterminierte Polymere enthaltende Kleb- oder Dichtstoffmassen

Also Published As

Publication number Publication date
WO2022173289A1 (en) 2022-08-18

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