Moisture-curable adhesive composition

Abstract

Disclosed herein is a curable composition, a method for applying the same, and a composition comprising the same. In some embodiments, the curable composition comprises component (A) having an organic polymer containing reactive silicon groups; component (B) having a chlorinated polyolefin polymer; component (C) having a silane compound having a dimethoxysilyl moiety; and component (D) having a silane compound having a trimethoxysilyl moiety.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of the filing date of U.S. Provisional Patent Application No. 63 / 325,340, filed March 30, 2022, entitled “Moisture-Curable Adhesive Composition,” which is incorporated herein by reference in its entirety.

[0002] The present invention relates to a moisture-curable adhesive composition comprising an organic polymer containing reactive silicon groups, and in particular to a moisture-curable adhesive composition having full strength and useful strength adhesion within a desired period of time to adhesion-resistant substrates such as thermoplastic polyolefins (TPO) and the like. [Background technology]

[0003] In recent years, research has been conducted to improve adhesion to adhesion-resistant substrates such as ethylene propylene diene rubber (EPDM) by the addition of thermoplastic elastomers to reactive silicon group-containing organic polymers (e.g., Kaneka Corporation and Kaneka Texas Corporation, Patent Publication No. 4,485,246).

[0004] Kaneka Corporation, US Pat. No. 7,759,425, describes moisture curable formulations that improve adhesion to TPO through the incorporation of tackifiers and chlorinated polyolefins into reactive silicon-group-containing organic polymers.

[0005] US Pat. No. 7,767,308 to Chemlink, Inc. describes the use of reactive silicon-group-containing organic polymers, phenolic tackifiers, and silane adhesion promoters for bonding with rubber materials.

[0006] WO 2020 / 176861 describes moisture-curable compositions for universal and good adhesion across different substrates including EPDM, polyvinyl chloride (PVC), and TPO.

[0007] Of these substrates, TPO is generally considered the most difficult low surface energy substrate to achieve good adhesion to, and thus, when adhesion to TPO is achieved, it is generally followed by adhesion to EPDM and PVC. Achieving adhesion to the smooth-backed versions of these substrates is particularly difficult compared to the fleece-backed versions, and involves additional surface treatments to improve adhesion.

[0008] Another problem with adhesive compositions is the time required for curing to achieve full strength or serviceability. For example, curing may take several weeks to achieve full strength adhesion. However, in certain applications, such as roofing installation, the roofing material may be removed by a catastrophic event, such as an unexpected wind event, during the time it takes for serviceability or full strength adhesion to be achieved.

[0009] There is a need to develop adhesive formulations that achieve practical and / or full strength adhesion in a shorter period of time. Summary of the Invention

[0010] Disclosed herein is a curable composition, a method for applying the same, and a composition comprising the same. In some embodiments, the curable composition comprises component (A) having an organic polymer containing reactive silicon groups; component (B) having a chlorinated polyolefin polymer; component (C) having a silane compound having a dimethoxysilyl moiety; and component (D) having a silane compound having a trimethoxysilyl moiety.

[0011] In some embodiments, a method of applying a curable composition includes applying the curable composition to a substrate.

[0012] In some embodiments, the composition comprises a substrate; and a curable composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] It is an object of the present invention to provide a moisture curable adhesive composition that provides excellent adhesion to all surfaces, including adhesion resistant surfaces such as EPDM, PVC, and TPO, either in smooth or fleece back versions of these substrates, and that achieves useful strength and full strength adhesion for a desired period of time, such as within about 24 hours, or more preferably within 4 hours.

[0014] In general, to achieve a desired adhesive strength for a desired period of time, a moisture-curable adhesive composition includes the following components: component (A) having an organic polymer with reactive silicon groups, component (B) having a chlorinated polyolefin polymer (CPO), component (C) having a silane compound with a dimethoxysilyl (DMS) moiety, and component (D) having a silane compound with a trimethoxysilyl (TMS) moiety. The latter three components (B) to (D) can be utilized as adhesion promoters in the moisture-curable composition.

[0015] Without wishing to be bound by a particular theory, the incorporation of a TMS moiety as an adhesion promoter can improve the cure speed in adhesive compositions. On the other hand, using a TMS moiety exclusively as an adhesion promoter can result in an increase in the modulus of the cured composition and poor adhesion to the substrate. By adding a DMS moiety as an additional adhesion promoter, the TMS moiety can be offset to maintain a threshold modulus in the cured composition and achieve good adhesion to the substrate.

[0016] Also, by using the DMS moiety, amino functionality is retained in the adhesion promoter, which works well in combination with CPO to promote adhesion to low energy surfaces such as TPO.

[0017] Additionally, by retaining a portion of the TMS portion, the dehumidifying effect is maintained, which is crucial for promoting better viscosity stability and thus enhancing shelf life, as well as facilitating application via the preferred methods of trowel, squeegee, roller, or spray.

[0018] The moisture-curable adhesive composition comprising components (A)-(D) can achieve excellent adhesion to smooth-backed surfaces such as TPO in about 24 hours using a variety of large scale application methods required for commercial applications such as trowels, squeegees, rollers or sprays. Moreover, it has been surprisingly found that the moisture-curable adhesive composition comprising components (A)-(D) achieves usable adhesion in about 4 hours. For example, achieving usable adhesion within this time frame allows the applicator to check their work at the end of the work day to ensure sufficient adhesion has been developed, thus eliminating the need for inefficient preventative measures such as temporary ballasting.

[0019] [Base material] EPDM substrates can include, for example, Carlisle Sure-Seal® EPDM, Carlisle Sure-White® EPDM, Johns Manville EPDM NR / R, Firestone RubberGard™ EPDM, Firestone Ecowhite™ EPDM, and / or Firestone Fullforce™ EPDM. PVC substrates can include, for example, GAF EverGuard® PVC, GAF EverGuard® PVC XK, Carlisle Sure-Flex® PVC, Carlisle Sure-Flex® KEE HP, Johns Manville PVC SD Plus, Johns Manville PVC with KEE, and / or Sika Sarnafil PVC. TPO substrates can include, for example, Firestone UltraPly™ TPO, Firestone UltraPly™ TPO XR, Firestone UltraPly™ TPO Flex Adhered, Firestone Platinum TPO, GAF EverGuard® TPO, GAF EverGuard Extreme® TPO, GAF EverGuard® TPO Ultra, and / or Carlisle Sure-Weld TPO.

[0020] [Component (A)] The moisture-curable composition includes a component (A) including an organic polymer containing a reactive silicon group represented by the following general formula (1): -Si(R 1 3~a )X a (1) In the formula, R 1 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; X represents a hydrolyzable group; a is an integer of 1 to 3; provided that when a is 1, each R 1may be the same or different; provided that when a is 2 or 3, each X may be the same or different.

[0021] In some embodiments, X represents -OR, where R is an alkyl group having 1 to 2 carbon atoms.

[0022] When X in general formula (1) is a hydrolyzable group, X is not particularly limited as long as X is a known hydrolyzable group.Specific examples of these include hydrogen and halogen atoms; and alkoxy, acyloxy, ketoximate, amino, amide, acid amide, aminooxy, mercapto, and alkenyloxy groups.Among these, alkoxy groups such as methoxy, ethoxy, propoxy, and isopropoxy groups are particularly preferred because they are mildly hydrolyzable and can easily handle the compound.

[0023] R in general formula (1) 1 is not particularly limited, and may be an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. These include, as specific examples, alkyl groups such as methyl, ethyl, propyl, and isopropyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. Of these groups, the methyl group is particularly preferred from the standpoint of availability of starting materials.

[0024] The specific structure of the reactive silicon group represented by general formula (1) is not particularly limited, as long as the structure is known.Particularly preferred are trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl, and methyldiethoxysilyl groups, from the viewpoint of their reactivity and availability.

[0025] One or more types of reactive silicon groups may be used in combination in formula (1).

[0026] The introduction of reactive silicon groups into the polyoxyalkylene polymer backbone of component (A) is carried out by known methods, examples of which include the following methods:

[0027] (i) A polyoxyalkylene polymer having a functional group such as a hydroxyl group is reacted with an organic compound having an active group reactive with the functional group and an unsaturated group, thereby obtaining a polyoxyalkylene polymer having an unsaturated group. Alternatively, for example, when an epoxide is subjected to ring-opening polymerization to obtain a polyoxyalkylene polymer, an epoxide containing an unsaturated group is ring-opening copolymerized with the epoxide to obtain a polyoxyalkylene polymer containing an unsaturated group. In this way, a monomer having an unsaturated group that is not involved in any polymerization reaction is copolymerized to obtain an organic polymer containing an unsaturated group. Next, a hydrosilane having a reactive silicon group is reacted with the obtained reaction production to hydrosilylate the reaction production.

[0028] In method (i), in order to introduce a reactive silicon group at a high introduction rate, 4 )-CH2- or CH(R 4 It is preferred to achieve incorporation by adding a hydrosilane compound to an organic polymer containing an unsaturated group represented by the formula: R 4 R represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. 4 is more preferably hydrogen or a methyl group. In order to set the introduction rate of reactive silicon groups to 85% or more, R 4 It is particularly important that is a methyl group.

[0029] Specific examples of the hydrosilane compounds used in method (i) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; and ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane. However, the hydrosilane compounds are not limited thereto. Among these compounds, halogenated silanes and alkoxysilanes are particularly preferred, and alkoxysilanes are most preferred because the hydrolysis of the composition obtained therefrom is mild, and as a result, the composition can be easily handled.

[0030] (ii) A compound having a mercapto group and a reactive silicon group is reacted with an unsaturated group-containing polyoxyalkylene polymer obtained by the same method as in the method (i).

[0031] The synthesis method (ii) is, for example, a method of introducing a compound having a mercapto group and a reactive silicon group into the unsaturated bond portion of an organic polymer by radical addition reaction in the presence of a radical initiator and / or a radical generating source. However, the method is not particularly limited. Specific examples of the compound having a mercapto group and a reactive silicon group include, but are not limited to, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane.

[0032] (iii) A polyoxyalkylene polymer having a functional group such as a hydroxyl group, an epoxy group, or an isocyanate group is reacted with a compound having a functional group reactive to the functional group and having a reactive silicon group. The functional group of the compound is not limited, but is preferably an isocyanate group or an amino group. The isocyanate group is particularly preferred.

[0033] Among the individual options for the synthesis method (iii), the method of reacting a polyoxyalkylene polymer having a hydroxyl group at its terminal with a compound having an isocyanate group and a reactive silicon group is, for example, the method described in JP-A-3-47825. However, the method is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include γ-isocyanatopropyl-trimethoxysilane, γ-isocyanatopropyl-methyldimethoxysilane, γ-isocyanatopropyl-triethoxysilane, γ-isocyanatopropyl-methyldiethoxysilane, α-isocyanatomethyl-dimethoxymethylsilane, and α-isocyanatomethyl-trimethoxysilane. However, the compound is not limited to these.

[0034] Among the above-mentioned methods, the polymer obtained by method (ii) emits a strong odor due to mercaptosilane, so method (i) or (iii) is preferred. In relation to the method of introducing reactive silicon groups, the organic polymer obtained by method (i) is preferred over the polymer obtained by method (iii) because it has reactive silicon groups and the polymer becomes a composition with low viscosity and good applicability. On the other hand, method (iii) is preferred in that the introduction of silyl groups into the hydroxyl group-containing polymer can be achieved in only one step, and as a result, component (A) can be produced with good productivity.

[0035] Among the individual options for method (iii), the method of reacting a polyoxyalkylene polymer having a hydroxyl group at its terminal with a compound having an isocyanate group and a reactive silicon group is preferred because it can achieve a high conversion rate in a relatively short reaction time. The oxyalkylene polymer obtained by such a reaction is a polymer having a reactive silicon group and a group represented by the following general formula (3): -NR 3 -C(=O)- (3) In the formula, R 3represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

[0036] The component (A) having a group represented by general formula (1) can also be obtained by methods other than those mentioned above. In particular, a compound obtained by a chain extension reaction between a polyol and a diisocyanate compound such as an aromatic polyisocyanate such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate or xylylene diisocyanate, or an aliphatic polyisocyanate such as isophorone diisocyanate or hexamethylene diisocyanate, is a compound having a group represented by general formula (3), regardless of the method of introducing a reactive silicon group.

[0037] Component (A) may be linear or branched, and its number average molecular weight is 500 or more, 3,000 or more, 15,000 or less, and / or 100,000 or less, based on gel permeation chromatography (GPC) in terms of polystyrene. The number average molecular weight is between 1,000 and 50,000, 1,000 to 10,000 or less, 10,000 or more, and 50,000 or less. The molecular weight is measured using an HLC-8120GPC (TOSOH CORPORATION), a TSK-GEL H-type column (TOSOH CORPORATION) as a liquid delivery system, and a THF solvent.

[0038] The reactive silicon group in component (A) may be bonded to the end of polyoxyalkylene polymer or along the polymer chain between the ends, or multiple reactive silicon groups may be bonded to both ends and along the polymer chain between the ends.In particular, when reactive silicon group is bonded only to the end, the network of the polymer components contained in the composition is effectively constructed.This case is preferred because it is easy to obtain a rubber-like cured product with high strength and elongation.

[0039] Various methods can be used to measure the introduction rate of reactive silicon groups in component (A). The introduction rate can be calculated from the integral value of the terminals to which the reactive silicon groups are introduced based on the 1H-NMR spectrum. The introduction rate of reactive silicon groups is a numerical value obtained by dividing the number of reactive silicon groups present in the molecule by the number of terminals of the molecule, and expressing the value obtained as a percentage. In particular, in the case of a linear polymer having an average of two reactive silicon groups in a single polymer chain (i.e., a polymer having two terminals), an introduction rate of 100% is calculated. For this reason, for polymers in which many reactive silicon groups exist in parts other than the terminals of the polymer chain, the calculated introduction rate may exceed 100%. In the present invention, a linear polymer having reactive silicon groups only at both terminals can be preferably used. Usually, a polymer having an introduction rate of less than 85% is used. A linear polyoxyalkylene polymer having reactive silicon groups only at both terminals can be prepared as follows.

[0040] (a) The hydroxyl groups present only at the ends of a linear polyoxyalkylene polymer are converted to -OM groups (wherein M is Na or K). The resulting polymer is reacted with a compound of the formula CH2=C(R 4 )-CH2-Z (wherein, R 4 is the same as defined above, and Z is a halogen atom.) to obtain a polyoxyalkylene polymer having unsaturated groups only at its terminals. 1 3~a )X a (In the formula, R 1 , X, and a are the same as defined above.) is added and reacted with the polyoxyalkylene polymer having unsaturated groups only at its terminals to obtain a linear polyoxyalkylene polymer having reactive silicon groups only at its terminals.

[0041] (b) a linear polyoxyalkylene polymer having hydroxyl groups only at its terminals and an isocyanate group and a carboxylic acid having the formula -Si(R 1 3~a )Xa (In the formula, R 1 , X, and a are as defined above.) to obtain a linear polyoxyalkylene polymer having reactive silicon groups only at its terminals.

[0042] The number of reactive silicon groups in a single polymer chain of component (A) is on average 0.5 or more, on average 1 or more, 0.8-3, or 1.1-5.

[0043] Polyoxyalkylene polymers having reactive silicon groups, component (A), have been proposed, as specific examples, in JP-B-36319, JP-B-12154, JP-A-50-156599, JP-A-54-6096, JP-A-55-13767, JP-A-55-13468, JP-A-57-164123, JP-B-3-2450, U.S. Pat. Nos. 3,632,557, 4,345,053, 4,366,307 and 4,960,844, as well as others. Other examples of these are the polyoxyalkylene polymers proposed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, and JP-A-61-218632. The polyoxyalkylene polymer is a polymer having a number average molecular weight of 6,000 or more and a molecular weight distribution (Mw / Mn) of 1.6 or less, and having a reactive silicon group, and has a high molecular weight and a narrow molecular weight distribution. However, component (A) is not particularly limited to these.

[0044] The above-mentioned polyoxyalkylene polymers each have a reactive silicon group, and may be used alone or in combination of two or more kinds.

[0045] The organic polymer of component (A) is commercially available and / or can be prepared according to techniques known in the art.These polymers containing reactive silicon groups include, but are not limited to, for example, silyl-terminated polyethers and silane-terminated polyurethanes.More specific examples of commercially available polymers containing reactive silicon groups for component (A) include, but are not limited to, KANEKA MS Polymer S327, KANEKA MS Polymer S227, KANEKA MS Polymer S203H, KANEKA SILYL SAX510, KANEKA SILYL SAX220, KANEKA SILYL SAT145, KANEKA SILYL SAT115, and combinations thereof.

[0046] The above exemplary list of commercially available polymers is by no means an exhaustive list, and other polymers with reactive silicon groups may be utilized. In some embodiments, it may be beneficial to combine different polymers. For example, in some embodiments, it may be necessary to balance a high viscosity grade polymer used to reduce the modulus for adhesion with a low viscosity grade polymer that facilitates application via brush, trowel, squeegee, spray gun, or other application techniques known in the art. In some embodiments, the organic polymer of component (A) may include a combination of different polymers. For example, one polymer may have a high viscosity and another polymer may have a low viscosity. In some embodiments, the high viscosity may be greater than 20,000 cP at 23°C. In some embodiments, the low viscosity may be less than 5,000 cP at 23°C. In some embodiments, the low viscosity may range from 6,000 to 10,000 cP at 23°C. When utilized, the high viscosity grade polymer and the low viscosity grade polymer can be present in a weight ratio of from 90:10 to 10:90, preferably from 75:25 to 25:75 (high viscosity:low viscosity, respectively), based on the total weight of component (A).

[0047] Component (A) may be included in the moisture-curable adhesive composition in an amount ranging from about 5 wt% to about 60 wt%, based on the total weight of the moisture-curable adhesive composition. This amount may more preferably range from about 10 wt% to about 50 wt%, and most preferably range from about 15 wt% to about 40 wt%.

[0048] [Component (B)] The curable composition includes component (B) having a chlorinated polyolefin polymer (CPO). Component (B) may be utilized as an adhesion promoter in the curable composition. The CPO of component (B) used in the present invention is not particularly limited and may be known in the art. Specific examples of these include chlorinated polyethylene and chlorinated polypropylene, copolymers thereof, and chlorinated polyolefins modified with acrylic acid moieties, maleic acid, and / or maleic anhydride. Specific examples of chlorinated polyolefin polymers include, but are not limited to, AdvaBond® 8203, AdvaBond® 8232, AdvaBond® 8214, and combinations thereof.

[0049] Component (B) may be included in the moisture-curable adhesive composition in an amount ranging from about 1 wt% to about 15 wt%, based on the total weight of the moisture-curable adhesive composition. More preferably, the amount may range from about 2 wt% to about 10 wt%. Most preferably, the amount may range from about 3 wt% to about 8 wt%.

[0050] [Component (C)] The curable composition includes component (C) having a silane compound having a dimethoxysilyl moiety. The silane compound having a dimethoxysilyl moiety has the chemical formula 1: [Chemical formula 1] R1(R2)Si(OCH3)2 It can be represented by:

[0051] R1 is a substituent that includes one or more amino groups. The one or more amino groups include -NH2 and -NH-. In some embodiments, R1 can be -CH2CH2CH2N(H)CH2CH2NH2 or -CH2CH2CH2NH2. R2 is an alkyl group. In one embodiment, R2 is -CH3.

[0052] In one embodiment, the silane compound having a DMS moiety has the following chemical formula 1-1: Represented by JPEG2025511225000001.jpg27170.

[0053] The silane compound of component (C) is not particularly limited and may be known in the art. Specific examples of the first silane include, but are not limited to, Dynasylan® 1401 or 1411 available from Evonik Industries; Geniosil® GF 95 available from Wacker Chemie; Z-6023 available from Dow Silicones Corporation; Silquest™ A-2120 available from Momentive Performance Materials; and KBM602 available from Shin-Etsu Chemical Company. Moreover, although described above as an aminosilane, the silane compound of component (C) is not limited thereto. Other silane compounds are possible, such as copolymer oligomers, alkyl silanes, glycidyl silanes, isocyanato silanes, thiocyanato silanes, methacryl silanes, ureido silanes, and mercapto silanes.

[0054] Component (C) may be included in the moisture-curable adhesive composition in an amount ranging from about 0.1 wt% to about 5.0 wt%, based on the total weight of the moisture-curable adhesive composition. More preferably, this amount may range from about 0.2 wt% to about 3.0 wt%, and most preferably, this amount may range from about 0.3 wt% to about 2.0 wt%.

[0055] [Component (D)] The curable composition includes component (D) having a silane compound having a trimethoxysilyl (TMS) moiety. The first silane has the formula 2: [Chemical formula 2] R1Si(OCH3)3 It is represented by:

[0056] R1 is a substituent that includes one or more amino groups. The one or more amino groups include -NH2 and -NH-. In one embodiment, R1 is -CH2CH2CH2N(H)CH2CH2NH2. In another embodiment, R1 is CH2CH2CH2N(H)CH2CH2CH2Si(OCH3)3. In yet another embodiment, R1 is CH2CH2CH2NH2.

[0057] In one embodiment, the silane compound having a TMS moiety has the following formula 2-1: Represented by JPEG2025511225000002.jpg30170.

[0058] The silane compound of component (D) is not particularly limited and may be known in the art. Specific examples of the second silane include, but are not limited to, Dynasylan® DAMO-T or DAMO or AMMO or 1124 available from Evonik Industries; Silquest® A-1120 available from Momentive Performance Materials; Z-6020 or Z-6094 available from Dow Silicones Corporation; Geniosil® GF 91 available from Wacker Chemie; and KBM603 available from Shin-Etsu Chemical Company. Moreover, although aminosilane is mentioned above, the silane compound of component (D) is not limited thereto. Other silane compounds are possible, such as copolymer oligomers, alkylsilanes, glycidylsilanes, isocyanatosilanes, thiocyanatosilanes, methacrylsilanes, ureidosilanes, and mercaptosilanes.

[0059] Component (D) may be included in the moisture-curable adhesive composition in an amount ranging from about 0.1 wt% to about 5.0 wt%, based on the total weight of the moisture-curable adhesive composition. More preferably, this amount may range from about 0.2 wt% to about 3.0 wt%, and most preferably, this amount may range from about 0.3 wt% to about 2.0 wt%.

[0060] The moisture-curable adhesive compositions of the present invention may optionally contain various other additives, such as fillers, pigments, dehydrating agents, plasticizers, anti-sag agents (thixotropic agents), stabilizers, other adhesion promoters, and curing catalysts.

[0061] In some embodiments, the moisture-curable adhesive composition may contain various fillers. Fillers include, for example, reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, and carbon black; fillers such as ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium dioxide, and bentonite; and fibrous fillers such as glass fibers and filaments. Fillers include, for example, calcium carbonate Hubercarb® Q3T available from Huber Engineered Materials of Atlanta, Georgia, USA; and calcium carbonate Hubercarb® G8 available from Huber Engineered Materials.

[0062] In some embodiments, the moisture-curable adhesive composition may include a dehydrating agent to improve storage stability. The dehydrating agent may be, but is not limited to, an alkoxysilane compound such as n-propyltrimethoxysilane, octyltrimethoxysilane, or vinyltrimethoxysilane. The dehydrating agent may include, for example, VTMO, a vinyltrimethoxysilane dehydrating agent available from Evonik Industries; and OCTMO, an octyltrimethoxysilane dehydrating agent available from Evonik Industries.

[0063] In some embodiments, the moisture-curable adhesive composition further comprises one or more catalysts. Additional catalysts include, for example, amine compounds such as aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, and aliphatic unsaturated amines; nitrogen-containing heterocyclic compounds such as pyridine, imidazole, and amidines such as 1,8-diazabicyclo(5,4,0)undecene-7 (DBU). Additional catalysts can include, for example, Polycat DBU, which is diazobicycloundecene, available from Evonik Industries; Dyhard OTB, which is 1-(o-tolyl)biguanide, available from AlzChem Group; Neostann U220H, which is dibutyltin diacetylacetonate, available from Nitto Kasei Co., Ltd; and Fomrez® SUL-11C, which is dibutyltin oxide, available from Galata Chemicals.

[0064] In some embodiments, the moisture-curable adhesive composition may include an antioxidant. The antioxidant is preferably a hindered phenolic antioxidant. Examples of hindered phenolic antioxidants include, but are not limited to, Irganox® 245, Irganox® 1010, and Irganox® 1076 available from BASF, and combinations thereof.

[0065] In some embodiments, the moisture-curable adhesive composition may include a light stabilizer. The light stabilizer can prevent photo-oxidative degradation of the cured product. Light stabilizers include, but are not limited to, benzotriazole compounds, hindered amine compounds, and benzoate compounds.

[0066] In some embodiments, the adhesive composition may include an ultraviolet absorbing agent. The ultraviolet absorbing agent can increase the surface weatherability of the cured product. Examples of ultraviolet absorbing agents include, but are not limited to, benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted tolyl compounds, and metal chelate compounds.

[0067] In some embodiments, the moisture-curable adhesive composition may include a thixotropic agent. Specific examples of thixotropic agents include, but are not limited to, hydrogenated castor oil, organic amide wax, organic bentonite, and calcium stearate. These thixotropic agents may be used alone or in combination of two or more thereof.

[0068] In some embodiments, the moisture-curable adhesive composition may include a plasticizer to adjust the viscosity. Specific examples of plasticizers include, but are not limited to, phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate, di(2-ethylhexyl) phthalate, and diisodecyl phthalate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylate compounds; unsaturated fatty acid ester compounds, polymeric plasticizers such as alkylsulfonic acid phenyl esters, hydrocarbon oils, and polyether polyols, and glycol ether esters. These plasticizers may be used alone or in combination of two or more of them. An example of the plasticizer is POLY-G® 20-37, a polypropylene glycol having a number average molecular weight (Mn) of 3,000 g / mol, available from Monument Chemical of Indianapolis, Indiana, USA.

[0069] Various other additives may be optionally added to the moisture-curable adhesive composition of the present invention to adjust the properties of the curable composition or the cured product. Such additives include, for example, flame retardants, curing modifiers, lubricants, pigments, and antifungal agents. These additives may be used alone or in combination of two or more of them. EXAMPLES

[0070] The curable composition according to the present invention will be described with reference to the following examples, although the present invention is not limited to these examples.

[0071] [Comparative Examples 1 to 5 and Examples 1 to 3 of the Present Invention] All the components were weighed according to the formulation shown in Table 1, and then mixed and kneaded in a mixer under dehydration conditions without using substantially any water. In Table 1, component (C) is a silane compound having a DMS moiety represented by chemical formula 1-1, and component (D) is a silane compound having a TMS moiety represented by chemical formula 2-1. The mixture was then placed in a moisture-proof container (polyethylene cartridge). In this manner, the curable compositions of Examples 1-3 and Comparative Examples 1-5 were produced. Unless otherwise stated, each composition was measured at 23°C after initial formation, and then again at 23°C after storage for 4 hours, 24 hours, and 13 days. The properties of the resulting curable compositions were measured as follows:

[0072] Viscosity: The viscosity of each composition was measured using an RV type Brookfield viscometer (spindle: No. 6, 1 rpm, 2 rpm, 10 rpm, and 20 rpm, temperature: 23° C.).

[0073] Peel: Specimens measuring 1.0" x 6.0" were cut from a single ply roofing membrane of TPO. Each composition was applied to a rigid substrate such as DensDeck Prime, plywood, or concrete to form a uniform layer, and then the TPO specimen was pressed onto the top of the adhesive layer. Two specimens were prepared for each formulation. The specimens were cured at 23°C and 50% RH for the given curing period shown in Table 2. After the curing period, the adhesive strength was measured using a Shimadzu tensile tester model AGS-20KNXD at a peel rate of 2 inches / minute, and the average peel strength was recorded. The rigid substrate with the mounted TPO specimen is secured to a movable stage that can move in a direction perpendicular to the direction of travel of the tester clamp. The TPO specimen is bent upward and secured to the tester clamp, forming an approximately 90 degree peel angle. As the tester peels the TPO specimen, the stage moves freely, maintaining an approximately 90 degree peel angle throughout the entire test. The experimental setup is similar to ASTM D6862, except that the free moving stage allows stiffer but flexible substrates, such as TPO membranes, to be positioned and peeled at a 90 degree angle more consistently. In contrast, the moving stage, such as ASTM D6862, requires alignment, and the larger bend radius of stiff membranes versus thin tapes can be more difficult. Thus, it is difficult to obtain consistent peel adhesion results for these materials using ASTM D6862. Peel adhesion strengths of less than 1 pli at 4 hours are unsatisfactory, 1-2 pli are good, and greater than 2 pli are excellent. Peel adhesion strengths of less than 4 pounds per linear inch ("pli") over 24 hours are considered unsatisfactory. Peel adhesion strengths between 4-5 pli are considered adequate. Peel adhesion strengths between 5-6 pli are considered good, and peel adhesion strengths of greater than 6 pli are considered excellent.

[0074] As shown in Table 2, the use of a combination of components (C) and (D) as adhesion promoters provides advantages with respect to adhesion after short periods of time. Examples 1-3, which use both components (C) and (D), have excellent adhesion after 4 hours and 24 hours, respectively. Comparative Examples 1-5, which use either component (C) or component (D), have negligible adhesion after 4 hours. Comparative Example 5 demonstrated adhesion comparable to Examples 1-3 at 24 hours and 13 days. However, Comparative Example 5 was of limited utility due to a significantly higher viscosity than the Examples. Comparative Examples 1-4 did not equal the adhesion strength of Examples 1-3 at 24 hours, even when measured after 13 days.

[0075] [Table 1]

[0076] [Table 2] JPEG2025511225000005.jpg175170

[0077] In summary, the present disclosure discloses a curable composition comprising: component (A) having an organic polymer containing reactive silicon groups; component (B) having a chlorinated polyolefin polymer; component (C) having a silane compound having a dimethoxysilyl moiety; and component (D) having a silane compound having a trimethoxysilyl moiety; and / or The reactive silicon group has the following general formula (1): -Si(R 1 3-a )X a (1) (In the formula, R 1 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; X represents a hydrolyzable group; when two or more Xs are present, each X is the same or different; a is an integer of 1 to 3; when a is 1, each R 1may be the same or different, and when a is 2 or 3, each X may be the same or different; and / or the hydrolyzable groups are selected from the group consisting of hydroxy groups, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups; and / or The hydrolyzable group is an alkoxy group and is selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. and / or the organic polymer comprises a polyoxypropylene backbone; and / or The organic polymer has the following general formula (3): -NR 3 C(=O)- (3) (In the formula, R 3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. and / or; and / or The additive is selected from the group consisting of a filler, a dehydrating agent, a plasticizer, a stabilizer, a catalyst, and combinations thereof; and / or Silane compounds having a dimethoxysilyl moiety have the chemical formula 1: [Chemical formula 1] R1(R2)Si(OCH3)2 (wherein R1 is a substituent containing one or more amino groups, the one or more amino groups are independently selected from the group consisting of -NH2 and -NH-, and R2 is an alkyl group.) and / or Silane compounds having a dimethoxysilyl moiety have the formula 1-1: JPEG2025511225000006.jpg27170[Chemical formula 1-1] and / or Silane compounds having a trimethoxysilyl moiety have the chemical formula 2: [Chemical formula 2] R1Si(OCH3)3 (wherein R1 is a substituent containing one or more amino groups, and the one or more amino groups are independently selected from the group consisting of -NH2 and -NH-.) and / or Silane compounds having a trimethoxysilyl moiety have the formula 2-1: JPEG2025511225000007.jpg30170[Chemical formula 2-1] It is represented by:

[0078] The present disclosure also discloses a method of applying a curable composition comprising applying the curable composition of claim 1 to a substrate; and / or the substrate is selected from the group consisting of polyvinyl chloride (PVC), ethylene propylene diene rubber (EPDM), and thermoplastic polyolefin (TPO); and / or the substrate is a thermoplastic polyolefin (TPO); and / or The substrate is a smooth back substrate.

[0079] The present disclosure also provides a substrate; and Also disclosed are compositions comprising the curable composition; and / or the substrate is selected from the group consisting of polyvinyl chloride (PVC), ethylene propylene diene rubber (EPDM), and thermoplastic polyolefin (TPO); and / or the substrate is a thermoplastic polyolefin (TPO); and / or The substrate is a smooth back substrate.

[0080] Although the invention is described herein with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications can be made to the illustrative embodiments and other arrangements can be devised without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims

1. Component (A) having an organic polymer containing reactive silicon groups; a component (B) having a chlorinated polyolefin polymer; Component (C) having a silane compound having a dimethoxysilyl moiety; Component (D) having a silane compound having a trimethoxysilyl moiety; 1. A curable composition comprising:

2. The reactive silicon group is represented by the following general formula (1): -Si(R １ ３－ａ )X ａ (1) (In the formula, R １ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; X represents a hydrolyzable group, and when two or more X are present, each X is the same or different; a is an integer from 1 to 3; When a is 1, each R １ may be the same or different, When a is 2 or 3, each X may be the same or different. The curable composition of claim 1 , represented by:

3. 3. The curable composition of claim 2, wherein the hydrolyzable groups are selected from the group consisting of hydroxy groups, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups.

4. 3. The curable composition of claim 2, wherein the hydrolyzable groups are alkoxy groups and are further selected from the group consisting of methoxy groups, ethoxy groups, propoxy groups, and isopropoxy groups.

5. The curable composition of claim 1 , wherein the organic polymer comprises a polyoxypropylene backbone.

6. The organic polymer is a group represented by the following general formula (3): -NR ３ C(=O)-(3) (In the formula, R ３ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. The curable composition of claim 1 comprising:

7. The curable composition of claim 1 further comprising an additive.

8. The curable composition of claim 1 , wherein the additive is selected from the group consisting of fillers, dehydrating agents, plasticizers, stabilizers, catalysts, and combinations thereof.

9. The silane compound having a dimethoxysilyl moiety is represented by the formula 1: [Chemical formula 1] R １ (R) ２ )Si(OCH ３ ) ２ (In the formula, R １ is a substituent containing one or more amino groups, and the one or more amino groups are -NH ２ and -NH-; R ２ is an alkyl group. The curable composition of claim 1 , represented by:

10. The silane compound having a dimethoxysilyl moiety is represented by the chemical formula 1-1: [Chemical formula 1-1] The curable composition of claim 9 , wherein the curable composition is represented by:

11. The silane compound having a trimethoxysilyl moiety is represented by the formula 2: [Chemical formula 2] R １ Si(OCH ３ ) ３ (In the formula, R １ is a substituent containing one or more amino groups, and the one or more amino groups are -NH ２ and -NH-. The curable composition of claim 1 , represented by:

12. The silane compound having a trimethoxysilyl moiety is represented by the chemical formula 2-1: [Chemical formula 2-1] The curable composition of claim 1 , represented by:

13. A method of applying a curable composition comprising applying the curable composition of claim 1 to a substrate.

14. 14. The method of claim 13, wherein the substrate is selected from the group consisting of polyvinyl chloride (PVC), ethylene propylene diene rubber (EPDM), and thermoplastic polyolefin (TPO).

15. The method of claim 13, wherein the substrate is a thermoplastic polyolefin (TPO).

16. The method of claim 13 , wherein the substrate is a smooth-back substrate.

17. A substrate; The curable composition according to claim 1. A composition comprising:

18. 18. The composition of claim 17, wherein the substrate is selected from the group consisting of polyvinyl chloride (PVC), ethylene propylene diene rubber (EPDM), and thermoplastic polyolefin (TPO).

19. 18. The composition of claim 17, wherein the substrate is a thermoplastic polyolefin (TPO).

20. 20. The composition of claim 17, wherein the substrate is a smooth-back substrate.

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