Room-temperature curable composition with a non-tin catalyst

Abstract

This application describes and illustrates condensation-curing silicone compositions. The condensation-curing composition comprises (i) an organopolysiloxane containing hydrolyzable and / or condensation-curing functional groups; (ii) a crosslinking agent; (iii) a non-tin metal catalyst comprising a central metal and an organic ligand, wherein the organic ligand is present in a molar amount sufficient to balance the charge of the central metal; (iv) an adhesion promoter comprising (a) a first adhesion promoter selected from secondary aminosilanes and (b) a second adhesion promoter other than a secondary aminosilane; and (v) an additive selected from organic acids, water, or a combination thereof. In embodiments, the metal catalyst is selected from bismuth, zinc, titanium, aluminum, or zirconium-based compounds.

Description

[Technical Field]

[0001] This invention relates to curable polyorganosiloxane compositions. In particular, this invention relates to water-curable polyorganosiloxane compositions using a non-tin catalyst at room temperature. [Background technology]

[0002] Water-curable polyorganosiloxane compositions are known to those skilled in the art. These compositions are used to provide curing materials suitable for use in a variety of applications, including adhesives, coatings, and others. These compositions can be provided as one-component or two-component systems. These systems generally comprise a hydrolyzable silyl-functional silicone polymer and a catalyst. Upon exposure to a humid atmosphere, the silyl groups react with water to form silanol groups, which then condense to form a cured siloxane network structure, in which case the condensation is facilitated or accelerated by the catalyst. However, silicone polymer systems typically cure slowly, i.e., several days to several weeks after exposure to a humid atmosphere.

[0003] Water-curable polyorganosiloxane compositions are cured using catalysts selected from materials such as metal complexes and / or non-metallic catalysts such as amines, acids, and others. Among the most widely used catalysts for promoting condensation curing are organotin compounds. Organotin compounds offer some of the most effective curing properties, and such catalysts promote curing in a way that provides materials with excellent curing properties, including, for example, a preferred touch-dry time (TFT), deep section curing (DSC), and adhesion to a given substrate.

[0004] Tin materials, including organotin catalysts, have been under investigation for many years as potentially harmful substances. Numerous regions and countries are considering regulating the use of such materials.

[0005] Under the expectation of stricter regulations on the use of tin-based materials, attempts are being made to find other catalysts to be used with or as substitutes for tin compounds. Alternative catalysts using metal compounds other than tin compounds, namely non-tin catalysts and non-metallic catalysts, are being explored. Conventional non-tin catalyst solutions may offer some advantages and some disadvantages in terms of the properties achieved in products into which such catalysts are formulated. Some catalysts may exhibit appropriate curing and adhesion properties, but the cured products may show yellowing. However, conventional non-tin catalyst solutions have not been found to provide robust curing overall, and non-tin catalyst compositions generally cannot meet all the necessary properties from a product development standpoint. In particular, conventional non-tin compositions cannot achieve sufficient properties across several important categories, such as rapid touch-dry time (TFT), rapid deep section curing (DSC), and rapid bulk curing (hardness), while simultaneously exhibiting good adhesion to various substrates. [Overview of the project]

[0006] The following is a summary of the disclosure, providing a basic understanding of several aspects. This summary is not intended to identify any major or significant elements, nor to impose any limitations on the embodiments or claims. Furthermore, this summary may provide a simplified overview of several aspects, which may be described in more detail in other parts of the disclosure.

[0007] Provided is a condensation-curing silicone composition containing a non-tin catalyst, and the cured material provided therein exhibits excellent properties including, but not limited to, rapid touch-dry time, deep cross-sectional curing, bulk curing, and / or adhesion. In some embodiments, this composition provides a cured material having excellent properties across all of these categories.

[0008] In one embodiment, the condensation-curing silicone composition comprises a non-tin metal catalyst, an adhesion promoter, and an additive selected from organic acids and / or water.

[0009] In one embodiment, the composition comprises (i) a polymer containing a siloxane group having hydrolyzable and condensation-curable functional groups, (ii) a non-tin metal catalyst containing a central metal and an organic ligand, (iii) an adhesion promoter comprising (a) a first adhesion promoter selected from secondary aminosilanes and (b) a second adhesion promoter selected from adhesion promoters other than secondary aminosilanes, and (iv) an additive selected from organic acids and / or water.

[0010] In one embodiment, a condensation-curing silicone composition is provided:

[0011] (i) Organopolysiloxanes containing silanol and / or hydrolyzable functional groups;

[0012] (ii) Crosslinking agents;

[0013] (iii) A non-tin metal catalyst comprising a central metal and an organic ligand, wherein the organic ligand is present in a molar amount sufficient to balance the charge of the central metal;

[0014] (iv) an adhesion promoter comprising (a) a first adhesion promoter selected from secondary aminosilanes, and (b) a second adhesion promoter other than a secondary aminosilane; and

[0015] (v) Contains an additive selected from an organic acid, water, or a combination thereof.

[0016] In one embodiment, the second adhesion promoter is selected from primary aminosilanes, tertiary aminosilanes, cyanurates, isocyanurates, or a combination of two or more of these.

[0017] In one embodiment of the composition according to any of the preceding embodiments, the secondary aminosilane is selected from the following compounds:

[0018] (R 22 )j(R23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k

[0019] R 22 、R 23 、R 26 、and R 27 is independently selected from monovalent C1-C20 hydrocarbons; R 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0-2.

[0020] In one embodiment, the secondary aminosilane is bis(gamma-trimethoxysilylpropyl)amine.

[0021] In one embodiment of the composition according to any of the preceding embodiments, the second adhesion promoter is selected from aminoalkyltrialkoxysilanes, aminoalkyl(alkyldialkoxysilanes), tris(alkyltrialkoxysilyl)amines, N(beta-aminoalkyl)-gamma-aminoalkyltrialkoxysilanes, N(beta-aminoalkyl)-gamma-aminodialkyldimethoxysilanes, tris(alkyltrialkoxysilyl)cyanurates, tris(alkyltrialkoxysilyl)isocyanurates, or combinations of two or more thereof.

[0022] In one embodiment according to any of the preceding embodiments, the first adhesion promoter is selected from compounds of the following formula: (R 22 ) j (R 23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k R 22 、R 23 、R26 , and R 27 R is independently selected from monovalent C1-C20 hydrocarbons; 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2; and The second adhesion promoter is selected from aminoalkyltrialkoxysilanes, aminoalkyl(alkyldialkoxysilanes), tris(alkyltrialkoxysilyl)amines, or a combination of two or more of these.

[0023] In one embodiment according to any of the preceding embodiments, the first adhesion promoter is selected from the following compound: (R 22 ) j (R 23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k R 22 , R 23 , R 26 , and R 27 R is independently selected from monovalent C1-C20 hydrocarbons; 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2; and The second adhesion promoter is selected from N(beta-aminoalkyl)-gamma-aminoalkyltrialkoxysilane, N(beta-aminoalkyl)-gamma-aminodialkyldimethoxysilane, or a combination thereof.

[0024] In one embodiment according to any of the preceding embodiments, the first adhesion promoter is selected from the following compound: (R 22 ) j (R 23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R27 ) k R 22 , R 23 , R 26 , and R 27 R is independently selected from monovalent C1-C20 hydrocarbons; 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2; and The second adhesion promoter is selected from tris(alkyltrialkoxysilyl) cyanurate, tris(alkyltrialkoxysilyl) isocyanurate, or a combination thereof.

[0025] In one embodiment, the first adhesion promoter is selected from the following compounds: (R 22 ) j (R 23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k R 22 , R 23 , R 26 , and R 27 R is independently selected from monovalent C1-C20 hydrocarbons; 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2; and The second adhesion promoter is selected from (i) aminoalkyltrialkoxysilane, aminoalkyl(alkyldialkoxysilane), or tris(alkyltrialkoxysilyl)amine, N(beta-aminoalkyl)-gamma-aminoalkyltrialkoxysilane, N(beta-aminoalkyl)-gamma-aminodialkyldimethoxysilane, or two or more combinations thereof, and / or (ii) tris(alkyltrialkoxysilyl)cyanurate, tris(alkyltrialkoxysilyl)isocyanurate, or combinations thereof.

[0026] In one embodiment of the composition according to any of the preceding embodiments, the adhesion promoter (iv) is present in an amount of about 0.1% to about 10% by weight based on the total weight of the composition.

[0027] In one embodiment of the composition according to any of the preceding embodiments, the first adhesion promoter is present in an amount of 0.05% to about 9.95% by weight based on the total weight of the composition, and the second adhesion promoter is present in an amount of about 0.05% to about 9.95% by weight based on the total weight of the composition.

[0028] In one embodiment of the composition according to any of the preceding embodiments, the central metal of the metal catalyst is bismuth, zinc, titanium, aluminum, or zirconium.

[0029] In one embodiment of the composition according to any of the preceding embodiments, the organic ligand of the non-tin metal catalyst is selected from C4-C30 carboxylates. In one embodiment, the organic ligand is a neodecanoate.

[0030] In one embodiment of the composition according to any of the preceding embodiments, the non-tin metal catalyst is present in an amount of about 0.001% to about 2.5% by weight based on the total weight of the composition.

[0031] In one embodiment of the composition according to any of the prior embodiments, the organic acid is selected from C4 to C30 organic acids.

[0032] In one embodiment of the composition according to any of the prior embodiments, the organic acid is selected from at least neodecanoates.

[0033] In one embodiment of the composition according to any of the preceding embodiments, additive (v), an organic acid may be present in an amount of about 0% to about 2% by weight, and water may be present in an amount of about 0% to about 1% by weight, provided that the sum of the weight percentages of the organic acid and the weight percentages of the water is greater than 0.

[0034] In one embodiment of the composition according to any of the preceding embodiments, additive (v) is provided as a diluent for a non-tin metal catalyst.

[0035] In one embodiment of the composition according to any of the preceding embodiments, the organopolysiloxane is selected from silanol-functionalized organopolysiloxanes.

[0036] In one embodiment of the composition according to any of the preceding embodiments, the organopolysiloxane comprises a first silanol-functional organopolysiloxane having a viscosity of about 100 to about 12,000 mPa·s, and a second silanol-functional organopolysiloxane having a viscosity of about 15,000 to 100,000 mPa·s.

[0037] In one embodiment of the composition according to any of the prior embodiments, the organopolysiloxane is present in an amount of about 5% to about 95% by weight based on the total weight of the composition.

[0038] In one embodiment of the composition according to any of the prior embodiments, the condensation-curing silicone composition contains a metal oxide.

[0039] In one embodiment, the metal oxide is selected from untreated fumed silica or fumed silica with surface treatment.

[0040] In one embodiment, the silica is selected from fumed silica, which includes a surface treatment selected from organosilane, organosilazane, or diorganocyclopolysiloxane.

[0041] In one embodiment, silica is present in an amount of about 0.05% to about 2% by weight based on the total weight of the composition.

[0042] In one embodiment of the composition according to any of the preceding embodiments, the composition comprises an MQ resin, which is present in an amount of about 0.1% to about 10% by weight based on the total weight of the composition.

[0043] In one embodiment of the composition according to any of the preceding embodiments, the composition is provided as a two-component composition comprising: (a) a first part comprising an organopolysiloxane, and (b) a second part comprising an adhesion promoter, a crosslinking agent, a catalyst, and an additive.

[0044] Provided in another embodiment is a method for forming a cured material, which includes exposing a condensation-curing silicone composition of any of the prior embodiments to moisture.

[0045] The following description discloses various exemplary embodiments. Some improvements and novel embodiments may be explicitly identified, while others may be evident from the description. [Modes for carrying out the invention]

[0046] Referencing the following exemplary embodiments, examples are illustrated in the accompanying drawings. As will be understood, other embodiments may also be used, and structural and functional modifications may be made. Furthermore, features of various embodiments may be combined or modified. Thus, the following description is presented merely as an example and does not in any way limit the various alternatives or modifications that may be made to the exemplary embodiments. In this disclosure, several specific details will lead to a complete understanding of the disclosed subject matter. It should be understood that embodiments of this disclosure may be implemented in other embodiments that do not necessarily include all aspects described in this application or elsewhere.

[0047] As used in this application, the terms “example” and “exemplify” mean examples or illustrations. The terms “example” and “exemplify” do not indicate essential or preferred embodiments or forms. The term “or” is intended to be inclusive, not exclusive, unless the context suggests otherwise. For example, the statement “A uses B or C” includes any inclusive substitution (e.g., A uses B; A uses C; or A uses both B and C). Separately, the articles “one” and “a” are generally intended to mean “one or more,” unless the context suggests otherwise.

[0048] The range values ​​for specific components can be combined to form new, unspecified ranges.

[0049] The composition provided is a condensation-curing silicone composition. This composition comprises (i) a polymer containing siloxane groups having hydrolyzable and / or condensation-curing functional groups, (ii) a non-tin metal catalyst containing a central metal and an organic ligand, (iii) an adhesion promoter, and (iv) an additive selected from organic acids and / or water. This composition may contain, but is not limited to, other substances suitable for curable siloxane compositions, including crosslinking agents, chain extenders, fillers, and other such additives.

[0050] Polymers containing siloxane groups can be selected as desired for specific purposes or intended applications. As used in this application, polymers containing siloxane groups may also be referred to as “siloxane polymers,” “polyorganosiloxanes,” and others. These polymers generally contain a siloxane main chain and at least one hydrolyzable and condensation-curable silyl group. This hydrolyzable / condensation-curable silyl group may contain a hydroxyl functional group.

[0051] This silicone polymer can be a polymer containing various silicone groups, which are known to be technically represented as M units, D units, T units, and Q units. The M unit is represented by the formula (R)3SiO 1 / 2 and the D unit is represented by the formula (R)2SiO 2 / 2 the T unit is represented by the formula (R)SiO 3 / 2 and the Q unit is represented by the formula SiO 4 / 2 The R group is generally selected from C1 - C60 hydrocarbon groups and hydrolyzable groups or condensation - curable groups. According to the composition of the present invention, at least one unit contains a hydrolyzable group or a condensation - curable group. In an embodiment, at least one or more R groups are - OH.

[0052] In one embodiment, the siloxane polymer is selected from compounds of the following formula: M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g wherein M 1 is (R 1 )(R 2 )(R 3 )SiO1 / 2 M<00 extraordinar000097>is (R<00000 extraordinar000098>)(R 5 )(R 6 )SiO 1 / 2 D 1 is (R 7 )(R 8 )SiO[[ID= extraordinar000066]] 2 / 2 D 2 is (R 9 )(R 10 )SiO 2 / 2 T 1 is (R 11 )SiO 3 / 2 T 2 is (R 12 )SiO 3 / 2 Q is SiO 4 / 2 R 1 , R 2 , R 3 , R 7 , R 8 , and R 11 Each is independently selected from saturated C1-C12 alkyl (substitutable with one or more halogens (e.g., Cl, F), O, S, or N atoms), C5-C16 cycloalkyl, C2-C12 alkenyl, C7-C16 arylalkyl, C7-C16 alkylaryl, phenyl, and C2-C4 polyalkylene ethers; R 4 , R 5 , R 6 , R 9 , R 10 , and R 12 Each is independently selected from (a) C1-C12 alkyl (substitutable with one or more halogens (e.g., Cl, F), O, S, or N atoms), C5-C16 cycloalkyl, C2-C12 alkenyl, C7-C16 arylalkyl, C7-C16 alkylaryl, phenyl, C2-C4 polyalkylene ether, and (b) OH, C1-C8 alkoxy, C2-C18 alkoxyalkyl, amino, alkenyloxy, oxymoalkyl, enoxyalkyl, aminoalkyl, carboxyalkyl, amidealkyl, amidearyl, carbamatealkyl or two or more combinations thereof. 2 Exemplary groups for this include OH, alkoxy, alkenyloxy, alkyloxymo, alkylcarboxy, alkylamide, and arylamide, where R 4 , R 5 , R 6 , R 9 , R 10 , and R 12 At least one of (ii) is selected from (ii); a+b+c+d+e+f+g are positive integers; and b+f+d is greater than zero.

[0053] In one embodiment, the curable composition of the present invention comprises at least one silanol-terminated diorganopolysiloxane (a). In one embodiment, the silanol-terminated organopolysiloxane is an MDM-type siloxane. Suitable silanol-terminated diorganopolysiloxanes (a) include those with the following general formula: M 2 b D 1 c D 2 d In the formula, b is 2, c is equal to or greater than 1, and d is zero or positive; M 2 is (R 4 ) 3-x-y (R 5 ) x (R 6 ) y SiO 1 / 2 Here, according to the constraint that x is 0, 1, or 2, and y is either 0 or 1, and x+y is equal to or less than 2, R 4 OH, R 5 and R 5 Each of these is independently a monovalent hydrocarbon group with up to 60 carbon atoms; D 1 is R 7 R 8 SiO 2 / 2 Here R 7 and R 8 Each of them is independently a monovalent hydrocarbon group of up to 60 carbon atoms; and D 2 is R 9 R 10 SiO 2 / 2 Here R 9 and R 10 Each of these is independently a monovalent hydrocarbon group with up to 60 carbon atoms.

[0054] In one embodiment, organopolysiloxane is present in an amount of about 5% to about 95% by weight, about 20% to about 85% by weight, about 30% to about 70% by weight, or about 40% to about 60% by weight of the total composition.

[0055] Siloxane polymers can have viscosities of approximately 15,000 to 100,000 mPa·s, approximately 20,000 to 90,000 mPa·s, approximately 30,000 mPa·s to 80,000 mPa·s, or approximately 40,000 mPa·s to 70,000 mPa·s.

[0056] Organopolysiloxanes can be provided by two or more organopolysiloxanes that differ in composition with respect to groups, functionality, size, and / or viscosity, or by using such organopolysiloxanes. In one embodiment, the siloxane polymer comprises a first siloxane of first viscosity and a second siloxane of second viscosity. In one embodiment, the first siloxane has a viscosity of about 100 to about 12,000 mPa·s, about 500 to about 10,000 mPa·s, about 1,000 to about 7,500 mPa·s, or about 2,500 to about 5,000 mPa·s, and the second siloxane has a viscosity of about 15,000 to about 100,000 mPa·s, about 20,000 to about 90,000 mPa·s, about 25,000 to about 80,000 mPa·s, or about 30,000 to about 75,000 mPa·s. The first siloxane can be present in amounts of approximately 1% to 60% by weight, approximately 10% to 50% by weight, or approximately 20% to 40% by weight, based on the total weight of the siloxanes, and the second siloxane can be present in amounts of approximately 40% to 99% by weight, approximately 50% to 90% by weight, or approximately 60% to 80% by weight, based on the total weight of the siloxanes.

[0057] This composition may also contain a crosslinking agent. As used herein, the term crosslinking agent encompasses compounds containing additional reactive components having at least two hydrolyzable groups and fewer than three silicon atoms per molecule not defined as siloxane polymer(i). In one embodiment, the crosslinking agent or chain extender may be selected from alkoxysilanes, alkoxysiloxanes, oxymosilanes, oxymosiloxanes, enoxysilanes, enoxysiloxanes, aminosilanes, carboxysilanes, carboxysiloxanes, alkylamidosilanes, alkylamidosiloxanes, arylamidosilanes, arylamidosiloxanes, alkoxyaminosilanes, alkalkylaminosiloxanes, alkoxycarbamatesilanes, alkoxycarbamatesiloxanes, imidatosilanes, ureidosilanes, isocyanatosilanes, thioisocyanatesilanes, and two or more combinations thereof.

[0058] Examples of suitable crosslinking agents include, but are not limited to, tetraethyl orthosilicate (TEOS); methyltrimethoxysilane (MTMS); methyltriethoxysilane; vinyltrimethoxysilane; vinyltriethoxysilane; methylphenyldimethoxysilane; 3,3,3-trifluoropropyltrimethoxysilane; methyltriacetoxysilane; vinyltriacetoxysilane; ethyltriacetoxysilane; dibutoxydiacetoxysilane; phenyltripropionoxysilane; methyltris(methylethylketoxime)silane; vinyl Tris(methylethylketoxime)silane; 3,3,3-trifluoropropyltris(methylethylketoxime)silane; methyltris(isopropeneoxy)silane; vinyltris(isopropeneoxy)silane; ethyl polysilicate; dimethyltetraacetoxydisiloxane; tetra-n-propyl orthosilicate; methyldimethoxy(ethylmethylketooxymo)silane; methylmethoxybis-(ethylmethylketooxymo)silane; methyldimethoxy(acetaldehyde)silane; methyldimethoxy(N-methylcarbamate)silane Ethyldimethoxy(N-methylcarbamate)silane; methyldimethoxyisopropeneoxysilane; trimethoxyisopropeneoxysilane; methyltriisopropeneoxysilane; methyldimethoxy(buto-2-ene-2-oxy)silane; methyldimethoxy(1-phenyletheneoxy)silane; methyldimethoxy-2(1-carboethoxypropeneoxy)silane; methylmethoxydi-N-methylaminosilane; vinyldimethoxymethylaminosilane; tetra-N,N-diethylaminosilane; methyldimethoxymethylaminosilane; Tyltricyclohexylaminosilane; Methyldimethoxyethylaminosilane; Dimethyldi-N,N-dimethylaminosilane; Methyldimethoxyisopropylaminosilane; Dimethyldi-N,N-diethylaminosilane; Ethyldimethoxy(N-ethylpropionamide)silane; Methyldimethoxy(N-methylacetamide)silane; Methyltris(N-methylacetamide)silane; Ethyldimethoxy(N-methylacetamide)silane; Methyltris(N-methylbenzamide)silane; Methylmethoxybis(N-methylacetamide)silane;This includes methyldimethoxy(caprolactamo)silane; trimethoxy(N-methylacetamide)silane; methyldimethoxyethylacetoimidatosilane; methyldimethoxypropylacetoimidatosilane; methyldimethoxy(N,N',N'-trimethylureido)silane; methyldimethoxy(N-allyl-N',N'-dimethylureido)silane; methyldimethoxy(N-phenyl-N',N'-dimethylureido)silane; methyldimethoxyisocyanatesilane; dimethoxydiisocyanatesilane; methyldimethoxythioisocyanatesilane; methylmethoxydithioisocyanatesilane, or any combination of two or more of these.

[0059] In one embodiment of the present invention, the crosslinking agent is present in an amount of about 0.1% to about 10% by weight of the total composition, about 0.3% to about 5% by weight of the total composition, or about 0.5% to about 1.5% by weight of the total composition.

[0060] This composition contains an adhesion promoter. The adhesion promoter is generally selected from aminosilane compounds, cyanurate-containing compounds, and / or isocyanurate-containing compounds. In one embodiment, the adhesion promoter is selected from aminosilanes. The aminosilane is selected from primary aminosilanes, secondary aminosilanes, tertiary aminosilanes, or mixtures of two or more of these. In one embodiment, the adhesion promoter is selected from at least secondary aminosilanes.

[0061] In one embodiment, the adhesion promoter component (D) is selected from aminoalkyltrialkoxysilane, aminoalkylalkyldialkoxysilane, bis(alkyltrialkoxysilyl)amine, tris(alkyltrialkoxysilyl)amine, N(beta-aminoalkyl)-gamma-aminoalkyltrialkoxysilane, N(beta-aminoalkyl)-gamma-aminodialkyldimethoxysilane, tris(alkyltrialkoxysilyl)cyanurate, and tris(alkyltrialkoxysilyl)isocyanurate, or two or more combinations thereof.

[0062] An aminosilane can be one of the following: (R 13 )(R 14 )NR 15 -Si(OR 16 ) 3-h (R 17 ) h R 18 -NH-R 19 -Si(OR 20 ) 3-i (R 21 ) i (R 22 ) j (R 23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k N-(R 28 -Si(OR 29 ) 3-m (R 30 m)3 R in the formula 13 , R 14 , and R 18 R is independently selected from H or monovalent C1-C20 hydrocarbons; 16 , R 17 , R 20 , R 21 , R 22 , R 23 , R 26 , R 27 , R 29 , and R 30 R is independently selected from monovalent C1-C20 hydrocarbons; 15 , R 19 , R 24 , and R 28 R is independently selected from divalent C1-C20 hydrocarbons; h, i, j, k, and m are independently selected from 0 to 2. In one embodiment, R 13 , R 14 , R 18 , R 16 , R 17 , R20 , R 21 , R 22 , R 23 , R 26 , R 27 , R 29 , and R 30 R is selected from C1-C20 alkyl, C2-C15 alkyl, C4-C10 alkyl, or C6-C8 alkyl. In one embodiment, R 13 , R 14 , R 18 , R 16 , R 17 , R 20 , R 21 , R 22 , R 23 , R 26 , R 27 , R 29 , and R 30 R is independently selected from C1-C4 alkyl groups. In one embodiment, R 15 , R 19 , R 24 , and R 28 These are independently selected from C1-C20 alkylenes, C2-C15 alkylenes, C3-C10 alkylenes, or C4-C8 alkylenes.

[0063] Examples of suitable adhesion promoters include, but are not limited to, N-(2-aminoethyl)aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N(beta-aminoethyl)gamma-aminopropyltrimethoxysilane, N(beta-aminoethyl)gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltrimethoxysilane, bis(gamma-trimethoxysilylpropyl)amine, N-phenyl-gamma-aminopropyltrimethoxysilane, triamino-functional trimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropyl Doxypropyltrimethoxysilane, gamma-glycidoxyethyltrimethoxysilane, gamma-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethylmethyl-dimethoxysilane, epoxylimonyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane, beta-cyanoethyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, alpha,omega-bis(aminoalkyldiethoxysilyl)polydimethylsiloxane, alpha,omega-bis(aminoalkyldiethoxysilyl)octamethyltetrasiloxane, 4-amino-3,3,-Dimethyl-butyl-trimethoxysilane, and N-ethyl-3-trimethoxysilyl-2-methylpropanamine, 3-(diethyl-aminopropyl)-trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrismethoxyethoxyethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane This includes lan, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (N-cyclohexylaminomethyl)methyldiethoxysilane, (N-cyclohexylaminomethyl)triethoxysilane, (N-phenylaminomethyl)methyldimethoxysilane, (N-phenylaminomethyl)trimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, combinations of two or more of these, and others.

[0064] The adhesion promoter may be present in an amount of about 0.1% to about 10% by weight, about 1% to about 5% by weight, or about 1.5% to about 4% by weight, based on the total weight of the composition.

[0065] In one embodiment, the composition comprises two or more adhesion promoters, including a first adhesion promoter selected from secondary aminosilanes and a second adhesion promoter selected from non-secondary aminosilanes. In one embodiment, the secondary aminosilane is a bis(alkyltrialkoxysilyl)amine, and the second adhesion promoter is selected from primary aminosilanes, tertiary aminosilanes, cyanurate silanes, and / or isocyanurate silanes.

[0066] In one embodiment, the first adhesion promoter is selected from the following compounds: (R 22 ) j (R 23 O) 3-j Si-R 24-NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k R 22 , R 23 , R 26 , and R 27 R is independently selected from monovalent C1-C20 hydrocarbons; 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2; and The second adhesion promoter is selected from aminoalkyltrialkoxysilanes, aminoalkyl(alkyldialkoxysilanes), tris(alkyltrialkoxysilyl)amines, or a combination of two or more of these.

[0067] In one embodiment, the first adhesion promoter is selected from the following compounds: (R 22 ) j (R 23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k R 22 , R 23 , R 26 , and R 27 R is independently selected from monovalent C1-C20 hydrocarbons; 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2; and The second adhesion promoter is selected from N(beta-aminoalkyl)-gamma-aminoalkyltrialkoxysilane, N(beta-aminoalkyl)-gamma-aminodialkyldimethoxysilane, or a combination thereof.

[0068] In one embodiment, the first adhesion promoter is selected from the following compounds: (R 22 ) j (R23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k R 22 , R 23 , R 26 , and R 27 R is independently selected from monovalent C1-C20 hydrocarbons; 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2; and The second adhesion promoter is selected from tris(alkyltrialkoxysilyl) cyanurate, tris(alkyltrialkoxysilyl) isocyanurate, or a combination thereof.

[0069]

[0070] In one embodiment, the first adhesion promoter is selected from the following compounds: (R 22 ) j (R 23 O) 3-j Si-R 24 -NH-R 25 -Si(OR 26 ) 3-k (R 27 ) k R 22 , R 23 , R 26 , and R 27 R is independently selected from monovalent C1-C20 hydrocarbons; 24 is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2; and The second adhesion promoter is selected from (i) aminoalkyltrialkoxysilane, aminoalkyl(alkyldialkoxysilane), or tris(alkyltrialkoxysilyl)amine, N(beta-aminoalkyl)-gamma-aminoalkyltrialkoxysilane, N(beta-aminoalkyl)-gamma-aminodialkyldimethoxysilane, or two or more combinations thereof, and / or (ii) tris(alkyltrialkoxysilyl)cyanurate, tris(alkyltrialkoxysilyl)isocyanurate, or combinations thereof.

[0071] In embodiments, the first aminosilane is selected from bis(propyltrimethoxysilane)amine. The first adhesion promoter may be present in an amount of about 0.05% to about 9.95% by weight, about 1% to about 5% by weight, or about 1.5% to about 3.5% by weight, based on the total weight of the adhesion promoters, and the second adhesion promoter may be present in an amount of about 0.05% to about 9.95% by weight, about 1% to about 5% by weight, or about 1.5% to about 3.5% by weight, based on the total weight of the adhesion promoters.

[0072] The catalyst is selected from non-tin metallic catalysts. Generally, metallic catalysts are selected from compounds having a central metal and an organic ligand. The metal can be selected from a variety of metallic materials, but the metal does not contain tin. In one embodiment, the metal can be selected from a metal cation or an oxometallic cation. In one embodiment, the metal cation or oxometallic cation may include metals selected from scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, aluminum, gallium, indium, germanium, tin, lead, antimony, and bismuth. In one embodiment, the metal is selected from bismuth, zinc, titanium, aluminum, or zirconium. The ligand can be selected from suitable organic ligands. In embodiments, ligands are selected from diketonates, diamines, triamines, aminoacetates, nitrile acetates, bipyridines, glyoximes, carboxylates, combinations of two or more of these, and others. In one embodiment, the organic ligand is selected from carboxylates. As is understood, organic ligands are generally provided in molar amounts corresponding to the valence of the central metal. If another suitable anion is provided, this metal may contain fewer organic ligands.

[0073] In one embodiment, the catalyst is selected from metallic compounds having a central metal of bismuth, titanium, aluminum, zirconium, or zinc, and an organic ligand. In one embodiment, the organic ligand is generally an anionic ligand and can be selected from C4-C25 carboxylates, C6-C30 carboxylates, C8-C18 carboxylates, or C10-C15 carboxylates. In one embodiment, the carboxylate is selected from C4-C30-alkyl, C7-C30-arylalkyl, C7-C30-alkylaryl, and / or C6-C10-arylcarboxylates. The carboxylate can be linear or branched. Examples of suitable carboxylate anions include, but are not limited to, pentanoates, hexanoates, heptanoates, octoates, 2-ethylhexanoates, neodecanoates, and others. Organic ligands generally exist to act as counterions, and the equivalence of ligands depends on the valence of the central metal (e.g., 3 for bismuth and 2 for zinc).

[0074] Some examples of suitable catalysts include the product name K-KAT 登録商標 REAXIS TM , or TIBKAT 登録商標 This includes, but is not limited to, items sold under the following, such as K-KAT. 登録商標 651 (Bismuth Carboxylate), K-KAT 登録商標 XK648 (zinc complex), K-KAT 登録商標 670 (zinc catalyst), REAXIS TM C3208 (Bismuth Carboxylate), REAXIS TM C716 (Bismuth Carboxylate), REAXIS TM 3202LA (Bismuth Octoate), REAXIS TM C616 (Zinc Neodecanoate), REAXIS TM REAXIS TM C708 (Zinc / Bismuth Neodecanoate Blend), REAXIS TM C716 (Bismuth Neodecanoate), REAXIS TMC717 (Zinc / Bismuth Octoate Blend), TIBKAT 登録商標 616 (Zinc Neodecanoate), TIBKAT 登録商標 620 (Zinc Octoate), TIBKAT 登録商標 623 (Zinc Acetylacetonate), TIBKAT 登録商標 634 (Zinc Oxalate), TIBKAT 登録商標 634 (Zinc Acetate), TIBKAT 登録商標 716 (Bismuth Carboxylate), TIBKAT 登録商標 710 (Bismuth Carboxylate), TIBKAT 登録商標 519 (Titanium Ethyl Acetoacetate), TIBKAT 登録商標 It contains 851 (aluminum ethyl acetate) and others.

[0075] The catalyst is present in amounts ranging from about 0.001% to about 2.5% by weight, from about 0.01% to about 1.5% by weight, or from about 0.1% to about 1% by weight, based on the total weight of the composition.

[0076] This composition contains an additive selected from an organic acid, water, or a mixture thereof. The organic acid can be selected from C4-C30, C6-C25, C8-C20, or C10-C15 organic acids. The C4-C30 group can be linear or branched. In one embodiment, the organic acid is a "neo" acid, i.e., a highly branched aliphatic carboxylic acid. Generally, the neo acid is a trialkylacetic acid containing a tetra-substituted alpha carbon. In one embodiment, the organic acid is a C8-C30 neo acid. In one embodiment, the organic acid is selected from neopentanoic acid, neodecanoic acid, and others. A suitable neopentanoic acid is Versatic, available from Hexion. TM Acid 5 is a particular type of acid. Neodecanoic acid, in particular, has an average molecular weight of 172 grams / mol. 10 H 20 This is a mixture of isomers of O2. Two examples of such isomers are shown below. [ka] A suitable example of neodecanoic acid is Versatic, available from Hexion. TM This is Acid 10.

[0077] The organic acid or water additive may be provided separately or as part of the catalyst mixture. For example, the catalyst may be provided as a mixture of the catalyst material and an organic acid or water as a diluent. The organic acid may be provided as part of such a mixture in an amount sufficient to provide the desired level of organic acid or water in the composition when the desired amount of catalyst is added.

[0078] Organic acids may be present in amounts of approximately 0% to approximately 2% by weight, approximately 0.1% to approximately 1% by weight, or approximately 0.2% to approximately 0.5% by weight, based on the total weight of the composition, and water may be present in amounts of approximately 0% to approximately 1% by weight, approximately 0.1% to approximately 0.75% by weight, or approximately 0.2% to approximately 0.5% by weight, based on the total weight of the composition, provided that the sum of the weight percentages of organic acids and water is greater than 0.

[0079] The composition optionally contains fillers. Fillers can be used to impart various properties or characteristics to the composition and the cured product. The type and amount of filler added depend on the desired physical properties of the cured silicone composition. In embodiments, the filler can function as a reinforcing or semi-reinforcing filler, that is, it has the ability to achieve higher tensile strength after curing and also increase viscosity, thereby establishing pseudoplasticity / shear viscosity reduction and thixotropic behavior. Non-reinforcing fillers may also be provided, which may act, for example, as bulking agents.

[0080] Examples of suitable fillers include, but are not limited to, crushed, settled, and colloidal calcium carbonate; reinforcing silica, e.g., fumed silica, settled silica, silica gel, hydrophobic silica, silica gel; crushed and crushed quartz, alumina, aluminum hydroxide, titanium hydroxide, diatomaceous earth, iron oxide, carbon black, and graphite; or clay, e.g., kaolin, bentonite, or montmorillonite, talc, mica, and others. The filler may be treated or untreated. In one embodiment, the filler is calcium carbonate treated with a compound such as stearate or stearic acid.

[0081] In one embodiment of the present invention, the filler is calcium carbonate filler, silica filler, or a mixture thereof.

[0082] Fillers may be present in the composition in amounts ranging from 0% to about 90% by weight of the total composition, from about 5% to about 60% by weight of the total composition, or from about 10% to about 40% by weight of the total composition. Fillers may be of a single type, or a mixture of two or more fillers of different chemical compositions, or a mixture of fillers of the same chemical composition but different in size, form, etc.

[0083] In one embodiment, the composition includes a metal oxide as an additive. The metal oxide may be treated or untreated. Suitable metal oxides include, but are not limited to, alumina, silica, titania, ceria, iron oxide, or mixtures of two or more of these. In one embodiment, the metal oxide is a fumed metal oxide selected from fumed alumina, fumed silica, fumed titania, fumed ceria, fumed iron oxide, or mixtures of two or more of these. In one embodiment, the metal oxide includes a surface treatment. The surface treatment may be, for example, organosilane, organosilazane, or diorganocyclopolysiloxane. Suitable surface treatments include, but are not limited to, hexamethylsilazane, hexamethylcyclotrisilazane, methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane, and others. Particularly suitable silica or metal oxide materials include fumed silica or fumed metal oxides. In the embodiment, fumed silica or fumed metal oxide is approximately 30 m 2 From / g to approximately 500m 2 / g, approx. 50m 2 From / g to approximately 350m 2 / g, or approximately 100m 2 From / g to approximately 250m 2 It can have a BET specific surface area of ​​ / g. Some examples of treated fumed silica include, but are not limited to, AEROSIL. 登録商標 R812 (Hexamethyldisilazane; 260ml) 2 / g;60), AEROSIL 登録商標 R812S (Hexamethyldisilazane; 220ml) 2 / g;65), and AEROSIL 登録商標 R8200 (Hexamethyldisilazane; 150ml) 2 / g;65) is included.

[0084] In some embodiments, silica or metal oxide fillers can be supplied in amounts ranging from about 0.05% to about 2% by weight, from about 0.075% to about 1% by weight, or from about 0.1% to about 0.5% by weight, based on the total weight of the composition.

[0085] The composition may optionally contain other silicone-based additives. In one embodiment, the composition may use a polyether-substituted siloxane. Polyether-substituted siloxanes generally include siloxane-type compounds having a polyether side chain to one of the silicon atoms. These siloxane compounds are known and understood in the art as M units (Si(R)3O 1 / 2 -), D unit (Si(R)2O 2 / 2 -), T unit (Si(R)O 3 / 2 -), and Q unit (SiO 4 / 2 The combination can be a general type including the following: where the R group is independently selected from monovalent hydrocarbon radicals, and one or more of the R groups bonded to the silicon atom are substituted with polyether groups. In one embodiment, the siloxane backbone is an MDM-type resin, where the M units and / or D units may be substituted with polyether groups. The polyether groups are not particularly limited and can be selected as desired. In one embodiment, the polyether groups are selected from ethylene oxide groups, polyether groups, or combinations thereof.

[0086] In one embodiment, the silicone additive is alkylpolydimethylsiloxane. The alkylpolydimethylsiloxane may be provided as a wax material and has 15-45, 20-40, or 25-30 "D" units ((Si(R)2O 2 / 2The composition may contain a polydimethylsiloxane main chain having terminal alkyl groups selected from C15-C40, C20-C35, or C25-C30 alkyl groups. In embodiments, the silicone additive may be provided in an amount of about 0.05% to about 2% by weight, about 0.075% to about 1% by weight, or about 0.1% to about 0.5% by weight, based on the total weight of the composition.

[0087] The composition may optionally contain a hydroxy-functional MQ resin. MQ resins are generally known in the technical sense. In this embodiment, the MQ resin is of formula R 31 3SiO 1 / 2 The M unit is represented by the formula SiO 4 / 2 It includes the Q unit represented by R 31 Each of these is independently selected from hydroxyl or monovalent hydrocarbon radicals, however the silanol content of the resin ranges from 0.2% to approximately 5% by weight. As recognized, MQ resins are basically made from M units and Q units, but formula R 32 2SiO 2 / 2 The D unit, represented by formula R 33 SiO 3 / 2 The T units expressed by can be up to 5 mole percent, where R 31 , R 32 and R 33 Each of these is independently a hydroxyl or monovalent hydrocarbon radical. Suitable examples of monovalent hydrocarbon radicals include, but are not limited to, alkyl radicals including methyl, ethyl, and isopropyl; alkenyl radicals including ethylene, propenyl, and hexenyl; alicyclic radicals such as cyclopentyl and cyclohexenyl; olefin-containing radicals such as vinyl and allyl; and monovalent hydrocarbon radicals having about 1 to about 6 carbon atoms. In one embodiment, the monovalent hydrocarbon radical in MQ resin is methyl.

[0088] In one embodiment, the ratio of M units to Q units ("M / Q ratio") of the MQ resin is less than 1.1:1, between about 0.8:1 and less than 1.1:1, or between about 0.8:1 and about 1.0:1. A silanol-functionalized silicone resin blend having an M:Q ratio within a selected range may be prepared by blending silicone MQ resins, one or more of which may independently have an M / Q ratio outside the preferred range.

[0089] Polyether-modified siloxane and MQ resin can be present in amounts of about 0% to about 10% by weight, about 0.1% to about 10% by weight, about 0.5% to about 8% by weight, or about 1.5% to about 6% by weight, based on the total weight of the composition.

[0090] The curing material is formed by exposing a mixture of components to moisture at or near room temperature (e.g., about 18°C ​​to about 30°C). Moisture can be provided by moisture from the atmosphere or by the separate addition of moisture to the mixture (e.g., the addition of water may contribute to the curing of the composition). The composition can be provided as a one-component or two-component composition. In one embodiment, the composition is formed by adding the components separately (or adding the components in combination) and by mixing the various components together. The components can be added in any order, but it may be preferable to add the catalyst last. For condensation-curing compositions, it may be preferable to provide the composition as a two-component composition, with the catalyst and reactive siloxane polymer as separate parts to avoid premature reaction of the composition. In one embodiment, the two-component composition is provided such that the first part (part A) comprises a silicone polymer and a filler, and the second part (part B) comprises an adhesion promoter, a catalyst, an additive (e.g., an organic acid and / or water), and a crosslinking agent.

[0091] The compositions of the present invention exhibit excellent properties, including, but are not limited to, touch-dry time, deep section hardening, and adhesive strength. As understood herein, the hardening of a sealant composition can be expressed as "touch-dry time," i.e., surface hardening, and "deep section hardening," i.e., hardening in the thickness direction of the sealant. Touch-dry time is tested by spreading the sealant to a desired thickness (e.g., 6.35 mm) on a Teflon mold and placing a 10 g stainless steel (SS) weight on the sealant at different time intervals. Touch-dry time is the time until the material no longer adheres to the surface of the weight. Alternatively, "deep section hardening," i.e., hardening in the thickness direction, is tested based on periodically cutting the spread material in the thickness direction to detect completion of hardening. The time required for the material to harden completely along the thickness direction is called deep section hardening and is also known as "thickness section hardening." Apart from visual observation, the inventors have devised a method for measuring deep section hardening by extracting the unhardened material of the sealant with a solvent, as will be described in more detail below.

[0092] In one embodiment, a composition according to the present invention exhibits a touch-dry time of less than 30 minutes, less than 25 minutes, less than 20 minutes, less than 15 minutes, less than 10 minutes, or less than 5 minutes. In one embodiment, a composition according to the present invention exhibits a touch-dry time of about 4 minutes to about 30 minutes, about 7 minutes to about 25 minutes, about 10 minutes to about 20 minutes, or about 12 minutes to about 18 minutes. In one embodiment, a composition according to the present invention exhibits a touch-dry time of about 4 minutes to about 12 minutes, about 5 minutes to about 10 minutes, or about 6 minutes to about 8 minutes.

[0093] In one embodiment, a composition according to the present invention exhibits deep cross-sectional hardening in less than 30 minutes, less than 25 minutes, less than 20 minutes, or less than 15 minutes. In one embodiment, a composition according to the present invention exhibits a touch-dry time of about 10 minutes to about 30 minutes, about 12 minutes to about 25 minutes, or about 15 minutes to about 20 minutes.

[0094] This curable composition may be used in a wide range of applications, including as a material for sealing, mold making, glazing, and prototyping; as an adhesive; as a coating for sanitary rooms; as a joint seal between different materials, for example, as a sealant between ceramic or mineral surfaces and thermoplastic resins; as a paper release agent; as an impregnation material; and others. Examples of curable compositions according to the present invention include general-purpose and industrial sealants, potting compounds, caulking agents, adhesives or coatings for architectural and insulating glass and structural glazing where glass plates are fixed and sealed to metal frames; caulking agents, adhesives for metal plates, car bodies, vehicles, electronic devices, and others. It may be suitable for a wide range of applications.

[0095] Examples

[0096] General method for evaluating the performance of various catalysts in the presence of adhesion promoters and other additives

[0097] Twenty g of a mixture of two silanol polymers of different viscosities and a CaCO3 filler was placed in a cup of a speed mixer. 0.4 g of aminosilane (secondary amine) and 0.2 g of adhesion promoter (primary amine / other amine) were added, followed by 0.068 g of crosslinking agent (n-propyl silicate), 1.27 g of PDMS, 0.01 g of polyether-based PDMS, 0.27 g of carbon black, and finally 0.052 g of catalyst. The mixture was thoroughly mixed with a spatula, and then with a speed mixer (method: 2350 RPM for 10 seconds).

[0098] The material was then applied to a Teflon-coated surface (approximately 1 mm thick), and its touch-dry time (TFT) was analyzed. This material was also cast into a mold to a thickness of 6 mm, and its bulk-cured hardness (Shore A, thickness) was analyzed. The material was placed on an aluminum / glass / polycarbonate plate to a thickness of 1 mm for adhesion testing. The bulk-cured hardness (Shore A, thickness) and overlapping tensile shear strength (LSS) were measured after 24 hours (ASTM-3163). Temperature and humidity were recorded during the preparation of each sample.

[0099] General method for evaluating the storage stability (aging test) of various catalysts in the presence of adhesion promoters and neodecanoic acid.

[0100] A two-component material was prepared using parts A and B as follows: Part A is a composition of 40 g of two silanol polymers with different viscosities, 2.54 g of PDMS, and 0.54 g of carbon black (processed with a speed mixer for 10 seconds). Part B is a mixture of 3.2 g of aminosilane (secondary amine), 1.6 g of aminosilane (primary amine), 0.544 g of crosslinking agent (n-propyl silicate), 0.08 g of polyether-containing PDMS, 0.416 g of catalyst, and 0.8 g of neodecanoic acid (versatic acid-VA10).

[0101] The total weight of Part B was 6.64 g, of which 1.66 g (25% of Part B) was used in the formulation, and the remaining Part B solution was kept in a hot oven at 70°C for 5 days. 1.66 g of Part B solution was added to the Part A mixture (in the cup of a speed mixer), and this mixture was thoroughly mixed with a spatula and then with a speed mixer (2350 RPM for 10 seconds) and cured. This material was then applied to a Teflon-coated surface (approximately 1 mm thick) for touch-dry time (TFT) analysis, and the material was also cast into a mold to a thickness of 6 mm for bulk curing hardness analysis (Shore A thickness). This material was also placed on an aluminum / glass / polycarbonate plate to a thickness of 1 mm for adhesion testing. The remainder of the material was then applied to a flexible sheet (approximately 2 mm thick) to a thickness of approximately 8 mm for deep section curing (DCS). TFT and DSC were measured by standard methods. The catalyzed material was cut at different time points, and the TFT was measured within the core. If the core was touch-dry, deep section hardening was complete. Otherwise, another cut was made at a 1 / 4-inch distance at a different time point until the test was complete. Bulk hardening hardness (Shore A at thickness) and overlapping tensile shear strength (LSS) were measured after 24 hours.

[0102] After 5 days at 70°C, the TFT, DSC, and adhesive properties of the solution from part B are measured by repeating the same procedure as above.

[0103] The compositions analyzed are listed in Tables 1 and 2: [Table 1] [Table 2]

[0104] In Tables 1 and 2, the following catalysts are indicated:

[0105] K-KAT-651 = Bismuth Carboxylate

[0106] K-KAT-670=Zn catalyst

[0107] K-KAT-648=Zn complex + alkanolamine

[0108] ReaxisC3208 = Bismuth Carboxylate

[0109] TIB-KAT-519 = Titanium ethyl acetoacetate

[0110] TIB-KAT-851 = Aluminum ethylacetoacetate

[0111] DBTO = Dibutyltin oxide

[0112] As shown in Tables 1 and 2, compositions using additives exhibit good interfacial fracture properties, including touch-dry time and deep cross-sectional hardening. In Table 1, compositions using titanium and aluminum catalysts have slightly longer touch-dry and deep cross-sectional hardening times. In these cases, the overall properties remained good. Therefore, the selection of catalysts may allow for control of desired properties (for example, when a fast touch-dry time or deep cross-sectional hardening is not required or desired). Example F#2 is similar to F#1 except that F#2 contains water along with an acid additive as an additive. In this case, excellent adhesion and slightly faster curing in terms of both touch-dry time and deep cross-sectional hardening are still obtained.

[0113] Examples F10-F13

[0114] Compositions were prepared according to the formulations shown in Table 3. These compositions utilize different levels of MQ resin. As shown in Table 3, good deep cross-sectional hardening can be achieved with different levels of MQ resin. For approximately 5% of the MQ resin, an increase in deep cross-sectional hardening over time can be observed. [Table 3]

[0115] Examples F14-F17

[0116] The compositions were prepared according to the formulations shown in Table 4. In the compositions shown in Table 4, the concentration of the acid additive (in this case, neodecanoic acid) was adjusted. As shown in Table 4, excellent touch-dry time was achieved even at low concentrations of the acid additive. Furthermore, good deep section hardening was achieved even at low concentrations of the acid additive, and this was shown to improve significantly with increasing amounts of the acid additive in the composition. [Table 4]

[0117] Examples F18-F21

[0118] The compositions were prepared according to the formulations shown in Table 5. Examples F18 to F21 use fumed silica and / or alkyl polydimethylsiloxane (alkyl PDMS) fillers. Alkyl polydimethylsiloxane is a wax material with 25 to 30 methyl-substituted "D" units and C25 to C30 alkyl terminal groups. Example F10 is included in Table 5 but does not contain fumed silica or alkyl PDMS fillers. Table 5 shows that the addition of these fillers maintains good touch-dry time, hardness, and adhesion. In addition, the inclusion of these fillers can improve deep section hardening. [Table 5]

[0119] Examples F22-F28

[0120] The compositions were prepared according to the formulations shown in Table 6. These compositions are similar to those in Table 1, except that compositions F22-F28 use a combination of a bissilane adhesion promoter and isocyanurate silane. In addition, as with the compositions in Table 1, different types of catalysts are used in the compositions. These compositions exhibit good storage stability, adhesion, and deep cross-sectional hardening. [Table 6]

[0121] The above description includes examples provided herein. Of course, for the purposes of this specification, it is impossible to describe all recognizable combinations of components or methodologies, but those skilled in the art will recognize that many further combinations and substitutions of this specification are possible. Thus, this specification is intended to encompass all such changes, modifications and variations that are included within the idea and scope of the appended claims. Furthermore, wherever the term “encompasses” is used in the detailed description or claims, such term is intended to be as comprehensive as “includes,” as is the case when “includes” is used as a substitute in the claims.

[0122] The above description illustrates various non-limiting embodiments of the curable polyorganosiloxane composition. Modifications may be conceived by those skilled in the art and those who create and use the present invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or subject matter described in the claims.

Claims

1. A condensation-curing type silicone composition, which includes: (i) Organopolysiloxanes containing condensation-curable and / or hydrolyzable functional groups; (ii) Crosslinking agent; (iii) A non-tin metal catalyst comprising a central metal and an organic ligand, wherein the organic ligand is present in a molar amount sufficient to balance the charge of the central metal; (iv) an adhesion promoter comprising (a) a first adhesion promoter selected from secondary aminosilanes, and (b) a second adhesion promoter other than a secondary aminosilane; and (v) A condensation-curing silicone composition comprising an additive selected from an organic acid, water, or a combination thereof.

2. The condensation-curing silicone composition of claim 1, wherein the second adhesion promoter is selected from primary aminosilanes, tertiary aminosilanes, cyanurates, isocyanurates, or combinations of two or more thereof.

3. Secondary aminosilanes are selected from the following compounds: (R ２２ ) ｊ (R ２３ O) ３－ｊ Si-R ２４ -NH-R ２５ -Si(OR ２６ ) ３－ｋ (R ２７ ) ｋ R ２２ , R ２３ , R ２６ , and R ２７ R is independently selected from monovalent C1-C20 hydrocarbons; ２４ The condensation-curing silicone composition of claim 1 or 2, wherein is selected from divalent C1-C20 hydrocarbons; and j and k are independently selected from 0 to 2.

4. The condensation-curing silicone composition according to claim 3, wherein the secondary aminosilane is bis(gamma-trimethoxysilylpropyl)amine.

5. The condensation-curing silicone composition according to any one of claims 2 to 4, wherein the second adhesion promoter is selected from aminoalkyltrialkoxysilane, aminoalkyl(alkyldialkoxysilane), tris(alkyltrialkoxysilyl)amine, N(beta-aminoalkyl)-gamma-aminoalkyltrialkoxysilane, N(beta-aminoalkyl)-gamma-aminodialkyldimethoxysilane, tris(alkyltrialkoxysilyl)cyanurate, tris(alkyltrialkoxysilyl)isocyanurate, or two or more combinations thereof.

6. The condensation-curing silicone composition according to any one of claims 1 to 5, wherein the adhesion promoter (iv) is present in an amount of about 0.1% to about 10% by weight based on the total weight of the composition.

7. A condensation-curing silicone composition according to any one of claims 1 to 6, wherein a first adhesion promoter is present in an amount of 0.05% to about 9.95% by weight based on the total weight of the composition, and a second adhesion promoter is present in an amount of about 0.05% to about 9.95% by weight based on the total weight of the composition.

8. A condensation-curing silicone composition according to any one of claims 1 to 7, wherein the central metal of the metal catalyst is selected from bismuth, zinc, titanium, aluminum, or zirconium.

9. A condensation-curing silicone composition according to any one of claims 1 to 8, wherein the organic ligand of the non-tin metal catalyst is selected from C4 to C30 carboxylates.

10. The condensation-curing silicone composition according to claim 9, wherein the organic ligand is a neodecanoate.

11. A condensation-curing silicone composition according to any one of claims 1 to 10, wherein a non-tin metal catalyst is present in an amount of about 0.001% to about 2.5% by weight based on the total weight of the composition.

12. The organic acid is selected from C4 to C30 organic acids, a condensation-curing silicone composition according to any one of claims 1 to 11.

13. The organic acid is selected from at least neodecanoic acid, a condensation-curing silicone composition according to any one of claims 1 to 12.

14. Additive (v), an organic acid may be present in an amount of about 0% to about 2% by weight, and water may be present in an amount of about 0% to about 1% by weight, provided that the sum of the weight percentages of the organic acid and the weight percentages of the water is greater than 0, the condensation-curing silicone composition according to any one of claims 1 to 13.

15. A condensation-curing silicone composition according to any one of claims 1 to 14, wherein additive (v) is provided as a diluent for a non-tin metal catalyst.

16. The organopolysiloxane is selected from silanol-functionalized organopolysiloxanes in any condensation-curing silicone composition according to any one of claims 1 to 15.

17. A condensation-curing silicone composition according to any one of claims 1 to 16, comprising a first silanol-functionalized organopolysiloxane having a viscosity of about 100 to about 12,000 mPa·s, and a second silanol-functionalized organopolysiloxane having a viscosity of about 15,000 to 100,000 mPa·s.

18. A condensation-curing silicone composition according to any one of claims 1 to 17, wherein the organopolysiloxane is present in an amount of about 5% to about 95% by weight based on the total weight of the composition.

19. A condensation-curing silicone composition according to any one of claims 1 to 18, comprising a metal oxide.

20. The metal oxide is selected from untreated fumed silica or fumed silica with surface treatment.

21. The condensation-curing silicone composition of claim 19, wherein the silica is selected from fumed silica including surface treatment, which is selected from organosilane, organosilazane, or diorganocyclopolysiloxane. The condensation-curing type silicone composition according to claim 20.

22. A condensation-curing silicone composition according to any one of claims 19 to 21, wherein silica is present in an amount of about 0.05% to about 2% by weight based on the total weight of the composition.

23. A condensation-curing silicone composition according to any one of claims 1 to 22, comprising MQ resin, wherein the MQ resin is present in an amount of about 0.1% to about 10% by weight based on the total weight of the composition.

24. The composition is provided as a two-component composition comprising: (a) a first part comprising an organopolysiloxane, and (b) a second part comprising an adhesion promoter, a crosslinking agent, a catalyst, and an additive, according to any one of claims 1 to 23.

25. A method for forming a cured material, comprising exposing a condensation-curing silicone composition according to any one of claims 1 to 24 to moisture.

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