Condensation-curing silicone adhesive

Abstract

This application describes and illustrates a silicone adhesive. The silicone adhesive composition comprises a silicone resin, a silicone fluid, and an aminosilane. The aminosilane contains two or more amino groups, where the amino groups may be bonded to a single silicon atom or to separate silicon atoms of a silicon core unit. The silicone adhesive composition is suitable for use as a hot-melt adhesive and can be used to coat or otherwise encapsulate articles.

Description

[Technical Field]

[0001] This invention relates to a silicone adhesive. More particularly, this invention relates to a composition that yields a silicone adhesive. This composition is curable by a condensation reaction and is suitable for forming a pressure-sensitive adhesive without requiring a conventional platinum catalyst. [Background technology]

[0002] Condensation-curing polyorganosiloxanes are used in a variety of applications and can be employed as adhesives, waterproof or moisture-proof coatings, electrical insulation films, building sealants, and other materials. Condensation-curing polyorganosiloxanes have good heat resistance, light resistance, and transparency. These properties make them suitable for applications such as encapsulating light-emitting diodes (LEDs). Most commercially available LEDs utilize platinum-catalyzed addition-curing polyorganosiloxanes to promote the crosslinking reaction. Under high operating temperatures and high light flux, platinum-catalyzed polyorganosiloxanes are known to often undergo excessive discoloration (yellowing) compared to condensation-curing products. That being said, large amounts of condensation catalyst, especially Lewis base catalysts, can also cause discoloration in condensation-curing products. Conventional condensation catalysts either color the adhesive or cause discoloration of the adhesive when the catalyst degrades and detaches from the chromophore residue. Therefore, many condensation catalysts are not suitable for manufacturing silicone adhesives for applications requiring transparency. [Overview of the Initiative]

[0003] The following is a summary of the disclosure, which provides a basic understanding of several embodiments. This summary is not intended to identify any major or significant elements of any embodiment or claim, nor to impose any limitations. Furthermore, this summary may provide a simplified overview of some embodiments, which may be described in more detail in other parts of the disclosure.

[0004] In one aspect, there is provided a condensation-curing silicone composition for forming an adhesive. This composition can be employed, for example, to form a hot melt adhesive. It may be post-cured by an applicator using relevant curing conditions.

[0005] In one aspect, there is provided a silicone adhesive composition comprising: a silicone resin; a silicone fluid; and an aminosilane of the following formula:

Chemical formula

[0006] In one embodiment, n is 0.

[0007] In one embodiment, R 16 , R 17 , R 18 , and R 19 Each of them is hydrogen, and R 20 and R 21 These are independently selected from monovalent C1-C14 alkyl and monovalent C6-C14 aromatic groups.

[0008] In one embodiment, R 16 , R 17 , R 18 , and R 19 Each is independently selected from monovalent C1-C14 alkyl groups, and R 20 and R 21 These are independently selected from monovalent C1-C14 alkyl and monovalent C6-C14 aromatic groups.

[0009] In one embodiment, R 16 , R 17 , R 18 , and R 19 Each is independently selected from monovalent C1-C14 alkyl groups, and R 20 and R 21 These are independently monovalent C1-C14 alkyl, monovalent C6-C14 aromatic, and -N(R 24 )(R 25 ) is selected from. In one embodiment, R 20 R is selected from monovalent C1-C14 alkyl and C6-C14 aromatic compounds, and R 21 is -N(R 24 )(R 25 ) is selected from. In one embodiment, R 18 and R 19 Each of them independently corresponds to -N(R 24 )(R 25 ) will be selected from.

[0010] In one embodiment, n is 1.

[0011] In one embodiment, X is a divalent C1-C30 organic group or oxygen.

[0012] In one embodiment, X is a divalent C1-C10 alkyl group or a divalent C6-C30 aromatic group.

[0013] In one embodiment, R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , and R 23 Each of these is independently selected from the monovalent C1-C14.

[0014] In one embodiment, the aminosilane is selected from one or more compounds of the following formula: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0015] In one embodiment, the aminosilane is present in an amount of from about 100 ppm to about 10 wt% based on the total weight of the composition.

[0016] In one embodiment, the silicone resin contains an aromatic group.

[0017] In one embodiment, the silicone resin is selected from compounds of the following formula: M 1 a M 2 a' D 1 b D 2 c T 1 d T 2 e Q f Where: M 1 is (R 1 )(R 2 )(R 3 )SiO 1 / 2 M 2 is (R 1' )(R 2' )(R 3' )SiO 1 / 2 D 1 is (R 4 )(R 5 )SiO 2 / 2 D 2 is (R 6 )(R 7 )SiO 2 / 2 T 1 is (R 8 )SiO 3 / 2 T 2 is (R 9 )SiO 3 / 2 Q is SiO 4 / 2 R 1 、R 2 、R 3 、R 4 、R 5 、and R 8Each is independently selected from hydrogen and a monovalent C1-C14 organic group; R 1' , R 2' , and R 3' Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a monovalent C6-C14 aromatic group, where R 1' , R 2' , and R 3' At least one of them is a monovalent C6-C14 aromatic group; R 6 and R 7 Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a monovalent C6-C14 aromatic group, where R 6 and R 7 At least one of them is a monovalent C6-C14 aromatic group; R 9 It is selected from monovalent C6-C14 aromatic groups; a and e are each independently greater than 0; and a', b, c, d, and f are each independently 0 or greater than 0.

[0018] In one embodiment, a, e, and f are greater than 0.1, b, c, and d are 0, and a' is 0 or greater.

[0019] In one embodiment, the silicone fluid has the following formula: HO-D 3 g D 4 h T 3 i T 4 j -OH During the ceremony: D 3 is (R 10 )(R 11 )SiO 2 / 2 D 4 is (R 12 )(R 13 )SiO 2 / 2 T 3 is (R 14 )SiO3 / 2 T 4 is (R 15 )SiO 3 / 2 Here R 10 and R 11 , and R 14 Each is independently selected from hydrogen and a monovalent C1-C14 organic group; R 12 and R 13 , and R 15 Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a monovalent C6-C14 aromatic group, where R 12 and R 13 At least one of them is a monovalent C6-C14 aromatic group; R 15 It is selected from monovalent C6-C14 aromatic groups; h is greater than 0; and g, i, and j are each independently 0 or greater than 0.

[0020] In another embodiment, a cured product obtained by curing a silicone adhesive composition is provided.

[0021] In yet another embodiment, an article is provided which includes a curing product disposed on the surface of the article.

[0022] In one embodiment, the article is a light-emitting diode.

[0023] Another embodiment provides a method for creating a silicone adhesive: The process involves reacting a mixture of silicone resin, silicone fluid, and aminosilane, where the aminosilane is selected from the compounds of the following formula: [ka] During the ceremony, R 16 , R 17 , R 18 , and R 19Each is independently selected from hydrogen and a monovalent C1-C14 organic group, where R 16 and R 17 Together they can form a ring containing a heteroatom selected arbitrarily from N, S, and O, and R 18 and R 19 These can come together to form a ring containing a heteroatom optionally selected from N, S, and O; R 20 , R 21 , R 22 , and R 23 Each of these is independently hydrogen, a monovalent C1-C14 organic group, and -N(R 24 )(R 25 ) is selected, and here R 24 and R 25 Each is independently selected from hydrogen and a monovalent C1-C14 organic group, where R 24 and R 25 These can come together to form a ring containing a heteroatom optionally selected from N, S, and O; X is a linking group selected from C1-C30 alkyl, C6-C30 aromatic, or oxygen; and n is either 0 or 1.

[0024] In one embodiment, the reaction is carried out at a temperature of approximately 25 to approximately 180°C.

[0025] The following description discloses various exemplary embodiments. Some improvements and novel embodiments may be explicitly identified, while others may be evident from the detailed description and drawings. [Modes for carrying out the invention]

[0026] The following describes exemplary embodiments. 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.

[0027] As used in this application, the terms “example” and “illustration” mean examples or illustrations. The terms “example” or “illustration” 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.

[0028] As used in this application, the term “organic group” generally refers to an acyclic, cyclic (or alicyclic) carbon-based group, which may be saturated or unsaturated, and may be substituted or interrupted by one or more heteroatoms or functional groups, such as carboxyl, cyano, hydroxy, halo, and oxy. As understood, based on the bonding required in the formula or structure, this term may encompass monovalent, divalent, and trivalent groups, and the appropriate valence state is specified and intended in the context of the given formula or structure.

[0029] As used in this application, the term “acyclic organic group” means a linear or branched organic group, preferably containing 1 to 60 carbon atoms per group, and may be saturated or unsaturated, and may optionally be substituted or interrupted by one or more heteroatoms or functional groups, such as carboxyl, cyano, hydroxy, halo, and oxy. Suitable monovalent acyclic organic groups include, but are not limited to, alkyl, alkenyl, alkynyl, hydroxyalkyl, cyanoalkyl, carboxyalkyl, alkyloxy, oxaalkyl, acryloxy, carboxamide, and haloalkyl, such as methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl, 3,3,3-trifluoropropyl, and others.

[0030] As used in this application, the terms “cyclic organic group” or “alicyclic organic group” mean an organic group comprising one or more saturated and / or unsaturated rings, preferably comprising 4 to 12 carbon atoms per ring, and optionally substituted on one or more rings with one or more alkyl radicals, halo radicals, or other functional groups, each of which preferably comprises 2 to 6 carbon atoms, and in the case of monovalent alicyclic hydrocarbon radicals comprising two or more rings, the rings may be fused. Suitable monocyclic alicyclic organic groups include, but are not limited to, cyclohexyl, cyclooctyl, norborneyl, and others.

[0031] As used herein, the term "aromatic group" means a cyclic group containing one or more aromatic rings per radical, which may optionally be substituted on the aromatic ring with one or more alkyl groups, halo groups, or other functional groups, each alkyl group preferably containing from 2 to 6 carbon atoms, and in the case of a monovalent aromatic group containing two or more rings, may be a fused ring. Suitable aromatic groups include, but are not limited to, for example, phenyl, tolyl, 2,4,6-trimethylphenyl, 1,2-isopropylmethylphenyl, 1-pentalenyl, naphthyl, anthryl, and others.

[0032] As used herein, the term "aralkyl" means an aromatic derivative of an alkyl group, preferably a (C2-C6) alkyl group, wherein the alkyl portion of the aromatic derivative may optionally be interrupted by an oxygen atom, and includes, for example but not limited to, phenylethyl, phenylpropyl, 2-(1-naphthyl)ethyl, phenylpropyl, phenoxypropyl, biphenyloxypropyl, and others.

[0033] As used herein, the viscosity may be evaluated using any suitable method. Unless otherwise specified, the viscosity is measured at 25 °C using a Brookfield (DV1) rotational viscometer.

[0034] The numerical values for the ranges of each component can combine to form new, unspecified ranges.

[0035] Provided is a composition for forming a silicone adhesive. This composition is suitable for forming an adhesive such as a hot melt adhesive. This composition contains a silicone resin, a silicone fluid, and an aminosilane. This aminosilane provides the behavior for the silicone composition to cure and provides a silicone adhesive. The use of this aminosilane provides a composition that does not require the use of a platinum or other noble metal catalyst.

[0036] Silicone resin

[0037] This composition uses a silicone resin. In this composition, the silicone resin refers to a silicone material having a network structure. The silicone resin contains at least M units and T units. In an embodiment, the silicone resin is an MT resin or an MDT resin or an MTQ resin or an MDTQ resin. The designations "M", "D", "T", and "Q" indicate the types of Si-O groups inside the silicone resin and have the general meanings as used and understood by those skilled in the art. In an embodiment, the silicone resin is an aromatic silicone containing a large amount of aromatic groups, such as, for example but not limited to, phenyl groups bonded to silicon atoms.

[0038] In an embodiment, the silicone resin is selected from compounds having the following formula: M 1 a M 2 a' D 1 b D 2 c T 1 d T 2 e Q f Where: M 1 is (R 1 )(R 2 )(R 3 )SiO 1 / 2 M 2 is (R 1' )(R 2' )(R 3' )SiO 1 / 2 D 1 is (R 4 )(R 5 )SiO 2 / 2 D 2 is (R 6 )(R 7 )SiO 2 / 2 T1 is (R 8 )SiO 3 / 2 T 2 is (R 9 )SiO 3 / 2 Q is SiO 4 / 2 R 1 , R 2 , R 3 , R 4 , R 5 , and R 8 Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a C6-C14 aromatic group; R 1' , R 2' , and R 3' Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a monovalent C6-C14 aromatic group, where R 1' , R 2' , and R 3' At least one of them is a monovalent C6-C14 aromatic group; R 6 and R 7 Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a monovalent C6-C14 aromatic group, where R 6 and R 7 At least one of them is a monovalent C6-C14 aromatic group; R 9 It is selected from monovalent C6-C14 aromatic groups; a and e are each independently greater than 0; and a', b, c, d, and f are each independently 0 or greater than 0.

[0039] In this embodiment, a is selected from 0.1 to 16, a' from 0 to 16, b from 0 to 5, c from 0 to 100, d from 0 to 100, e from 1 to 16, and f from 0.1 to 26.

[0040] In one embodiment, a, b, c, d, e, and f are each independently greater than 0; R 1 , R 2 , R 3 , R4 , R 5 , R 6 , and R 8 Each is independently selected from monovalent C1-C14 organic groups, monovalent C1-C10 organic groups, and monovalent C1-C6 organic groups, and R 7 and R 9 Each of these is independently selected from monovalent C6-C14 aromatic groups.

[0041] In one embodiment, the silicone resin is M 1 a D 1 b D 2 c T 1 d It is resin, and here R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 Each is independently selected from a C1-C4 organic group or a C1-C2 organic group, and R 7 It is selected from C6-C14 aromatic compounds.

[0042] In one embodiment, the silicone resin is of formula M 1 a D 1 b D 2 c T 1 d T 2 e It is a resin, and here R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 Each of these is a methyl group, and R 7 and R 9 These are each phenyl groups.

[0043] In one embodiment, the silicone resin is of formula M 1 a D1 b D 2 c T 1 d T 2 e It is a resin, and here R 1 , R 2 , R 3 , R 4 , R 5 , and R 8 Each of these is a methyl group, and R 6 , R 7 , and R 9 These are each phenyl groups.

[0044] In one embodiment, the silicone resin is M 1 a D 1 b D 2 c T 1 d T 2 e Q f It is a resin, where a is from 0.1 to 16, e is from 1 to 16, f is from 0.1 to 26, and b, c, and d are 0.

[0045] In one embodiment, the silicone resin is of formula M 1 a D 1 b D 2 c T 1 d T 2 e Q f The resin is such that a is between 0.1 and 16, c is between 0.1 and 100, e is between 1 and 16, f is between 0.1 and 26, and b and d are 0.

[0046] In one embodiment, the silicone resin is of formula M 1 a T 1 d T 2 e Q f It is MTQ resin, and here R1 , R 2 , R 3 , and R 8 is selected from monovalent C1-C12 organic groups, monovalent C1-C10 organic groups, and monovalent C1-C6 organic groups, and R 9 The group is selected from monovalent C6-C14 aromatic groups.

[0047] In one embodiment, the silicone resin is of formula M 1 a D 1 b D 2 c T 1 d T 2 e This is an MDT resin, and here R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 Each is independently selected from a C1-C4 organic group or a C1-C2 organic group, and R 7 and R 9 These are each phenyl groups.

[0048] In one embodiment, the silicone resin is of formula M 1 a T 1 d T 2 e This is MT resin, and here R 1 , R 2 , R 3 , and R 8 Each of these is a methyl group, and R 9 It is a phenyl group.

[0049] In one embodiment, a, a', b, c, d, e, and f are each independently greater than 0; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8Each is independently selected from monovalent C1-C14 organic groups, monovalent C1-C10 organic groups, and monovalent C1-C6 organic groups, R 1' , R 2' , and R 3' Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a monovalent C6-C14 aromatic group, where R 1' , R 2' , and R 3' At least one of them is a monovalent C6-C14 aromatic group, and R 7 and R 9 Each of these is independently selected from monovalent C6-C14 aromatic groups.

[0050] In one embodiment, the silicone resin is M 1 a M 2 a' D 1 b D 2 c T 1 d It is resin, and here R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 Each is independently selected from C1-C4 organic groups or C1-C2 organic groups, R 1' , R 2' , and R 3' Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a monovalent C6-C14 aromatic group, where R 1' , R 2' , and R 3' At least one of them is a monovalent C6-C14 aromatic group, and R 7 It is selected from C6-C14 aromatic compounds.

[0051] In one embodiment, the silicone resin is of formula M 1 a M 2 a' D 1 b D 2c T 1 d T 2 e is a resin, where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、and R 8 are each a methyl group, and R 1' 、R 2' 、and R 3' are each independently selected from methyl and phenyl, where R 1' 、R 2' 、and R 3' at least one of is a phenyl group, and R 7 and R 9 are each a phenyl group.

[0052] In one embodiment, the silicone resin is of the formula M 1 a M 2 a' D 1 b D 2 c T 1 d T 2 e is a resin, where R 1 、R 2 、R 3 、R 4 、R 5 、and R 8 are each a methyl group, and R 1' 、R 2' 、and R 3' are each independently selected from methyl and phenyl, where R 1' 、R 2' 、and R 3' at least one of is a phenyl group, and R 6 、R 7 、and R 9 are each a phenyl group.

[0053] In one embodiment, the silicone resin is M 1a M 2 a' D 1 b D 2 c T 1 d T 2 e Q f It is a resin, where a and a' are independently between 0.1 and 16, e is between 1 and 16, f is between 0.1 and 26, and b, c, and d are 0.

[0054] In one embodiment, the silicone resin is of formula M 1 a M 2 a' D 1 b D 2 c T 1 d T 2 e Q f The resin is such that a and a' are independently 0.1 to 16, c is 0.1 to 100, e is 1 to 16, f is 0.1 to 26, and b and d are 0.

[0055] In one embodiment, the silicone resin is of formula M 1 a M 2 a' T 1 d T 2 e Q f It is MTQ resin, and here R 1 , R 2 , R 3 , and R 8 is selected from monovalent C1-C12 organic groups, monovalent C1-C10 organic groups, and monovalent C1-C6 organic groups, and R 9 The group is selected from monovalent C6-C14 aromatic groups.

[0056] In one embodiment, the silicone resin is of formula M 1 a M 2 a'D 1 b D 2 c T 1 d T 2 e This is an MDT resin, and here R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 Each is independently selected from C1-C4 organic groups or C1-C2 organic groups, R 1' , R 2' , and R 3' Each is independently selected from methyl and phenyl, where R 1' , R 2' , and R 3' At least one of them is a phenyl group, and R 7 and R 9 These are each phenyl groups.

[0057] In one embodiment, the silicone resin is of formula M 1 a M 2 a' T 1 d T 2 e It is MT resin, and here R 1 , R 2 , R 3 , and R 8 Each of these is a methyl group, R 1' , R 2' , and R 3' Each is independently selected from methyl and phenyl, where R 1' , R 2' , and R 3' At least one of them is a phenyl group, and R 9 It is a phenyl group.

[0058] In the embodiment, the organic groups of the silicone resin are aromatic groups in amounts of about 2 to about 99 mol%, about 28 to about 83 mol%, or about 35 mol% to about 65 mol%.

[0059] Silicone resins can have viscosities of about 5 to about 2000 cP, about 10 to about 1000 cP, or about 20 to about 200 cP, based on a solid content of 50% by weight in xylene solvent.

[0060] Silicone resin may be present in the composition in an amount of about 3 to about 70% by weight, about 40 to about 65% by weight, or about 50 to about 60% by weight.

[0061] As understood, the composition may include a mixture of two or more silicone resins of different formulas and / or different sizes.

[0062] Silicone fluid

[0063] This composition contains a silicone fluid selected from silicone fluids containing silanol groups. The silicone fluid can be a linear or branched silicone fluid. In embodiments, the silicone fluid is a linear silicone fluid. The linear silicone fluid may be a hydroxyl-terminated silicone.

[0064] In one embodiment, the silicone fluid is given by the following formula: HO-D 3 g D 4 h T 3 i T 4 j -OH During the ceremony: D 3 is (R 10 )(R 11 )SiO 2 / 2 D 4 is (R 12 )(R 13 )SiO 2 / 2 T 3 is (R 14 )SiO 3 / 2 T 4 is (R15 )SiO 3 / 2 Here R 10 , R 11 , and R 14 Each is independently selected from hydrogen and a monovalent C1-C14 organic group; R 12 and R 13 and R 15 Each of these is independently selected from hydrogen, a monovalent C1-C14 organic group, and a monovalent C6-C14 aromatic group, where R 12 and R 13 At least one of them is a monovalent C6-C14 aromatic group; R 15 It is selected from monovalent C6-C14 aromatic groups; h is greater than 0; and g, i, and j are each independently 0 or greater than 0.

[0065] In one embodiment, R 10 , R 11 , and R 12 Each is independently selected from hydrogen and monovalent C1-C14 organic groups, monovalent C1-C10 organic groups, and monovalent C1-C6 organic groups; and R 13 It is a monovalent C6-C14 aromatic group.

[0066] In one embodiment, R 10 and R 11 Each is independently selected from hydrogen and a monovalent C1-C2 organic group; and R 12 and R 13 Each of these is independently selected from monovalent C6-C14 aromatic groups.

[0067] In one embodiment, R 10 , R 11 , and R 12 Each of these is a methyl group; and R 13 It is a phenyl group.

[0068] In one embodiment, R 10 and R 11Each of these is a methyl group; and R 12 and R 13 These are each phenyl groups.

[0069] In an embodiment, g is 0 to 1000, 1 to 1000, 5 to 750, 10 to 500, or 25 to 100; h is 0.1 to 1000, 5 to 750, 10 to 500, or 25 to 100; i is 0 to 5, 1 to 5, or 2 to 4; and j is 0 to 5, 1 to 5, or 2 to 4.

[0070] Silicone fluids can have viscosities of approximately 100 to approximately 1,000,000 cP, approximately 1,000 to approximately 100,000 cP, or approximately 2,000 to approximately 20,000 cP.

[0071] The silicone fluid may be present in the composition in an amount of about 30% to about 70% by weight, about 35% to about 60% by weight, or about 40% to about 50% by weight.

[0072] As understood, the composition may include a mixture of two or more silicone fluid materials of different formulas and / or different sizes.

[0073] aminosilane

[0074] This composition contains aminosilane. Although not bound by any particular theory, aminosilane has been found to promote the curing of silicone compositions. Aminosilane contains two or more amine groups. Aminosilane contains a core with one or more silicon atoms and an amine group bonded to at least one of the silicon atoms.

[0075] According to this technology, aminosilane is given by the following formula: [ka] During the ceremony, R 16, R 17 , R 18 , and R 19 Each is independently selected from hydrogen and a monovalent C1-C14 organic group, where R 16 and R 17 Together they can form a ring containing a heteroatom selected arbitrarily from N, S, and O, and R 18 and R 19 These can come together to form a ring containing a heteroatom optionally selected from N, S, and O; R 20 , R 21 , R 22 , and R 23 Each of these is independently hydrogen, a monovalent C1-C14 organic group, and -N(R 24 )(R 25 ) is selected, and here R 24 and R 25 Each is independently selected from hydrogen and a monovalent C1-C14 organic group, where R 24 and R 25 These can come together to form a ring containing a heteroatom optionally selected from N, S, and O; X is a linking group selected from a divalent C1-C30 alkyl group, a divalent C6-C30 aromatic radical, or oxygen; and n is either 0 or 1.

[0076] In the embodiment, n is 0, and the aminosilane has at least an N-Si-N bond group. Examples of aminosilanes where n is 0 include, but are not limited to: ●R 16 , R 17 , R 18 , and R 19 These are hydrogen and R respectively. 20 and R 21 Each is independently selected from a monovalent C1-C14 alkyl group and a monovalent C6-C14 aromatic group. In one embodiment, R 20 and R 21Each of these is independently selected from a monovalent C1-C14 alkyl group, a monovalent C1-C10 alkyl group, or a monovalent C1-C6 alkyl group. In one embodiment, R 20 is selected from C1-C14 alkyl groups, C1-C10 alkyl groups, or C1-C6 alkyl groups, and R 21 The group is selected from C6-C12 aromatic groups. ●R 16 and R 17 These are hydrogen and R respectively. 18 and R 19 Each is independently selected from a monovalent C1-C14 alkyl group and a monovalent C6-C14 aromatic group, and R 20 and R 21 Each of these is independently selected from a monovalent C1-C14 alkyl group and a monovalent C6-C14 aromatic group. ●R 16 , R 17 , R 18 , and R 19 These are hydrogen and R respectively. 20 is -N(R 24 )(R 25 ) is selected, and here R 24 and R 25 R is independently selected from hydrogen and monovalent C1-C14 alkyl groups, and R 21 This includes monovalent C1-C14 alkyl groups, monovalent C1-C6 alkyl groups, monovalent C1-C4 alkyl groups, monovalent C6-C14 aromatic groups, and -N(R 24 )(R 25 ) is selected, and here R 24 and R 25 These are independently selected from hydrogen and monovalent C1-C12 alkyl groups. ●R 16 , R 17 , R 18 , and R 19 Each of these is independently selected from monovalent C1-C14 alkyl groups, monovalent C1-C10 alkyl groups, or monovalent C1-C6 alkyl groups, and R 20 and R 21 Each is independently a monovalent C1-C14 alkyl group and -N(R 24 )(R 25) is selected, and here R 24 and R 25 R is independently selected from hydrogen and monovalent C1-C14 alkyl groups. In one embodiment, R 16 , R 17 , R 18 , and R 19 Each of these is independently selected from either a C1-C4 alkyl group or a C1-C2 alkyl group. ●R 20 and R 21 Each of them independently corresponds to -N(R 24 )(R 25 ) will be selected from.

[0077] In this embodiment, n is 1. Examples of exemplary embodiments of aminosilanes where n is 1 include, but are not limited to: ●R 16 , R 17 , R 18 , and R 19 These are hydrogen and R respectively. 20 and R 21 Each is independently selected from monovalent C1-C14 alkyl and monovalent C6-C14 aromatic, X is selected from divalent C1-C30 alkyl, divalent C1-C20 alkyl, divalent C1-C15 alkyl, divalent C1-C10 alkyl, divalent C6-C30 aromatic, or divalent C6-C14 aromatic, and R 22 and R 23 Each is independently selected from hydrogen and a monovalent C1-C14 alkyl group. In one embodiment, R 22 and R 23 Each of these is hydrogen. In one embodiment, R 22 and R 23 Each of these is selected from monovalent C1-C14 alkyl, monovalent C1-C10 alkyl, or monovalent C1-C6 alkyl. ●In one embodiment, R 20 and R 21 These are monovalent C1-C14 alkyl, C1-C10 alkyl, or C1-C6 alkyl groups, respectively. ●In one embodiment, R 20is selected from monovalent C1-C14 alkyl, monovalent C1-C4 alkyl, monovalent C1-C2 alkyl, monovalent C1-C10 alkyl, or monovalent C1-C6 alkyl, and R 21 It is selected from monovalent C6-C14 aromatics. ●In one embodiment, R 16 and R 17 Each of them is hydrogen, and R 18 and R 19 Each is independently selected from monovalent C1-C14 alkyl and monovalent C6-C14 aromatic, and R 20 and R 21 Each is independently selected from monovalent C1-C14 alkyl and monovalent C6-C14 aromatic, X is selected from divalent C1-C30 alkyl, divalent C1-C20 alkyl, divalent C1-C15 alkyl, divalent C1-C10 alkyl, divalent C6-C30 aromatic, or divalent C6-C12 aromatic, and R 22 and R 23 Each is independently selected from hydrogen and a monovalent C1-C14 alkyl group. In one embodiment, R 22 and R 23 Each of these is hydrogen. In one embodiment, R 22 and R 23 Each of these is selected from monovalent C1-C14 alkyl, monovalent C1-C4 alkyl, monovalent C1-C2 alkyl, monovalent C2-C10 alkyl, or monovalent C4-C6 alkyl. ●In one embodiment, R 16 , R 17 , R 18 , and R 19 Each of them is hydrogen, and R 20 is -N(R 24 )(R 25 ) is selected, and here R 24 and R 25 R is independently selected from hydrogen and monovalent C1-C14 alkyl groups, and R 19 These include monovalent C1-C14 alkyl, monovalent C1-C6 alkyl, monovalent C1-C4 alkyl, monovalent C6-C14 aromatic, and -N(R 24 )(R 25) is selected, and here R 24 and R 25 X is independently selected from hydrogen and monovalent C1-C14 alkyl, X is selected from divalent C1-C30 alkyl, divalent C1-C20 alkyl, divalent C1-C15 alkyl, divalent C1-C10 alkyl, divalent C6-C30 aromatic, or divalent C6-C14 aromatic, and R 22 and R 23 Each is independently selected from hydrogen and a monovalent C1-C14 alkyl group. In one embodiment, R 22 and R 23 Each of these is hydrogen. In one embodiment, R 22 and R 23 Each of these is selected from monovalent C1-C14 alkyl, monovalent C1-C4 alkyl, monovalent C1-C2 alkyl, monovalent C2-C10 alkyl, or monovalent C4-C6 alkyl. ●In one embodiment, R 16 , R 17 , R 18 , and R 19 Each is independently selected from monovalent C1-C14 alkyl, monovalent C2-C10 alkyl, or monovalent C4-C6 alkyl, and R 20 and R 21 These are independently monovalent C1-C14 alkyl and -N(R 24 )(R 25 ) is selected, and here R 24 and R 25 X is independently selected from hydrogen and monovalent C1-C14 alkyl, X is selected from divalent C1-C30 alkyl, divalent C1-C20 alkyl, divalent C1-C15 alkyl, divalent C1-C10 alkyl, divalent C6-C30 aromatic, or divalent C6-C14 aromatic, and R 22 and R 23 Each is independently selected from hydrogen and a monovalent C1-C14 alkyl group. In one embodiment, R 22 and R 23 Each of these is hydrogen. In one embodiment, R 22 and R 23Each of these is selected from monovalent C1-C14 alkyl, monovalent C1-C4 alkyl, monovalent C1-C2 alkyl, monovalent C2-C10 alkyl, or monovalent C4-C6 alkyl.

[0078] Some non-specific examples of suitable aminosilanes include: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0079] Aminosilane may be present in the composition in amounts of about 100 ppm to about 10% by weight based on the total weight of the composition, about 200 ppm to about 5% by weight based on the total weight of the composition, about 500 ppm to about 1.5% by weight based on the total weight of the composition, about 750 ppm to about 1.25% by weight based on the total weight of the composition, about 0.1% to about 1% by weight based on the total weight of the composition, or about 0.25% to about 0.75% by weight based on the total weight of the composition.

[0080] As can be understood, the composition may contain two or more different aminosilanes.

[0081] The composition may optionally contain additives such as pigments, fillers, dyes, plasticizers, thickeners, coupling agents, volume extenders, volatile organic solvents, wetting agents, tackifiers, crosslinking agents, thermoplastic polymers, UV stabilizers, and others, in appropriate amounts for a particular purpose or intended use. These typical additives may be used or selected at concentrations suitable for achieving a specific or intended effect for the intended use.

[0082] Typical fillers suitable for the compositions of the present invention include, but are not limited to, fumed silica, precipitated silica, clay, talc, aluminum silicate, calcium carbonate, and other reinforcing fillers. Plasticizers conventionally used in the condensation-curing compositions of the present invention can also be used in the present invention to modify their properties and facilitate the use of higher filler levels. Exemplary plasticizers include phthalates, dipropylene glycol dibenzoates and diethylene glycol dibenzoates, alkyl sulfonic acid phenols, alkylphenanthrenes, alkyl / diaryl phosphates, and mixtures thereof. The moisture-curing compositions of the present invention may contain various thixotropic or non-sag agents. Various castor oil waxes, fumed silica, modified clay, and polyamides are typical examples of this type of additive.

[0083] Adhesive compositions can be prepared by mixing components together. In one embodiment, an adhesive composition is prepared by mixing a silicone resin and a silicone fluid, and then adding aminosilane to this mixture. The silicone resin and silicone fluid can be mixed at a temperature of about 25°C to about 180°C. Aminosilane can be added to this mixture to promote a condensation reaction at a temperature of about 25°C to about 150°C, yielding a condensation product. This condensation product may be a partially cured adhesive. This partially cured adhesive can be post-cured to increase its cohesive strength. This can be achieved by exposing the partially cured adhesive to a temperature of about 150°C to about 180°C.

[0084] The adhesive composition can be applied to a target surface by any known or future-discovered method. The hot-melt adhesive composition of the present invention may be applied to various substrates by techniques currently used to distribute organic hot-melt formulations (e.g., hot-melt guns, extrusion, spreading with heated draw-down bars, doctor blades, comma coaters, lip coaters, roll coaters, die coaters, knife coaters, blade coaters, rod coaters, curtain coaters, kiss-roll coaters, and gravure coaters; screen printing, dipping, and casting methods). The composition is heated to a temperature sufficient to induce flow before application. Once cooled to atmospheric conditions, the composition of the present invention is an essentially non-stick, non-slump adhesive composition that may be used to bond parts or substrates together. After the desired parts are bonded with the hot-melt adhesive of the present invention, the combination is exposed to high temperatures, and the hot-melt adhesive is cured to create the adhesive's cohesive strength and modulus. Curing may be carried out using known means at a temperature of about 80 to about 180°C, about 120 to about 180°C, or about 150 to about 180°C for about 30 minutes to about 500 minutes, about 60 minutes to about 400 minutes, or about 120 minutes to about 300 minutes.

[0085] The amount of silicone PSA (pressure-sensitive adhesive) composition applied to the target surface may be such that the applied adhesive layer has a desired thickness. In one embodiment, the silicone composition is applied such that the applied adhesive layer has a thickness of about 10 to about 200 μm, and particularly about 25 to about 100 μm.

[0086] In one embodiment, the composition can be used to form a condensation product which may be laminated as a film between release liners. This film can be transferred to a target substrate and subjected to post-curing to increase its cohesive strength. Post-curing can be achieved by exposing the film to a temperature of about 80 to about 180°C.

[0087] The silicone composition of the present invention is suitable for use in a variety of applications. This composition can be used, for example, in sealants such as hot-melt sealants, primers, adhesives such as hot-melt adhesives, and coatings containing such cured compositions. Exemplarily, a cured composition includes a hot-melt composition. As used in this application, the term "hot-melt composition" refers to a material that is solid at room temperature, melts upon heating and applied to a substrate, and then solidifies again upon cooling to form a strong bond between the solid material and the substrate. Hot-melt compositions include, but are not limited to, hot-melt sealants and hot-melt adhesives.

[0088] The compositions of the present invention find useful in many of the same applications where silicone hot-melt adhesives are currently used, particularly in industries such as automotive, electronics, construction, aerospace, and medical. Exemplary electronic applications, though not limited to them, include the use of silicone hot-melt adhesives in portable electronic devices, such as smartphones, tablets, and watches. In these application areas, the hot-melt adhesives of the present invention provide a bond resistant to harsh environments, such as heat and moisture, and improve brightness by filling air gaps beneath the coating layer.

[0089] In one embodiment, the silicone composition is suitable for use as an encapsulation material for LED elements. The adhesive film can be applied to the LED substrate. Glass transition temperature (T g At temperatures exceeding 5°C, this film can melt and wet the substrate, creating a strong bond. g Post-curing, which involves condensing residual silanol groups at temperatures exceeding a certain level, increases the cohesive strength and storage modulus of the adhesive.

[0090] With respect to LED encapsulation materials, this composition can provide suitable additives desirable for specific uses or applications. For example, phosphorus may be used to provide a conversion material, which can function as a conversion layer for converting the wavelength of photons emitted from the device. The conversion particles can be selected to convert the wavelength of photons emitted from the diode upward or downward, thereby changing the color of the light emitted from the device. A non-limiting example is to provide phosphorus suitable for converting blue light emission to white light.

[0091] The technology of the present invention has been described in the above detailed description with reference to various aspects and embodiments. The technology may be further understood by referring to the following examples, which are intended to further illustrate aspects and embodiments of the technology and are not necessarily limited to such aspects and embodiments.

[0092] Examples

[0093] The composition was prepared according to the following example. The components used in the composition are listed in Table 1.

[0094] [Table 1]

[0095] Adhesive solution

[0096] Example 1

[0097] 150 g of phenyl resin A-1 (51.2% solids in xylene) and 56.9 g of phenyl fluid B-1 were added to a 500 mL round-bottom flask. The solution was stirred at 80°C for 1 hour under nitrogen purge using an overhead stirrer. 1.34 g of dimethylbis(isopropylamino)silane (C-1) was added dropwise to the flask, and the temperature was raised to 140°C. The solution gelled as the temperature rose to 120°C.

[0098] Example 2

[0099] 150 g of phenyl resin A-1 (51.2% solids content in xylene) and 56.9 g of phenyl fluid B-1 were added to a 500 mL round-bottom flask. The solution was stirred at 80°C for 1 hour under nitrogen purge using an overhead stirrer. 0.33 g of dimethylbis(isopropylamino)silane (C-1) was added dropwise to the flask, and the temperature was raised to 140°C. The solution was stirred continuously for 3 hours, and then the temperature was lowered to 80°C. 60.5 g of xylene, followed by 6.6 g of isopropanol, were added to the flask.

[0100] Jealousy example 3

[0101] 150 g of phenyl resin A-2 (49.9% solids in xylene) and 46.8 g of phenyl fluid B-2 were added to a 500 mL round-bottom flask. The solvent was removed under vacuum at 46 °C for 4 hours using a partial distillation setting. GC-MS showed that the product contained 2.5% xylene. 52.2 g of propyl propionate was added to the flask. The mixture was stirred at 100 rpm at 80 °C under nitrogen purge until homogenized. 0.43 g of dimethylbis(isopropylamino)silane (C-1) was added dropwise to the flask, and the solution was stirred at 80 °C for 1 hour. The solution was further stirred at 100 °C for 3 hours. 3.7 g of isopropanol was added to the flask. The solution was continued to be stirred for 3 hours.

[0102] Example 4

[0103] 150 g of phenyl resin A-2 (50.8% solids in xylene) and 47.6 g of phenyl fluid B-2 were added to a 500 mL round-bottom flask. The solvent was removed under vacuum at 35°C for 4 hours using a partial distillation setting. 52.2 g of propyl propionate was added to the flask. The mixture was stirred at 100 rpm under nitrogen purge at ambient temperature until homogenized. 0.08 g of bis(dimethylamino)dimethylsilane (C-2) was diluted with 1.6 g of propyl propionate. This stock solution was added dropwise to the flask at room temperature. After stirring for 10 minutes, the flask was heated to 60°C and stirred for 1 hour. 10 g of isopropanol was added to the flask and stirred for a further 2.5 hours.

[0104] Example 5

[0105] 150 g of phenyl resin A-2 (50.8% solids in xylene) and 47.6 g of phenyl fluid B-2 were added to a 500 mL round-bottom flask. This mixture was stirred at 100 rpm for 30 minutes under nitrogen purge using an overhead stirrer at ambient temperature until the mixture was homogenized. 0.07 g of phenylmethylbis(dimethylamino)silane (C-3) was diluted with 1.8 g of xylene. This stock solution was added dropwise to the flask at room temperature. After stirring for 10 minutes, the flask was heated to 60°C and stirred for 2 hours. The temperature was raised to 80°C. After stirring the solution for 30 minutes, 10 g of isopropanol was added to the flask.

[0106] Example 6

[0107] 150 g of phenyl resin A-2 (50.8% solids in xylene) and 47.6 g of phenyl fluid B-2 were added to a 500 mL round-bottom flask. The solvent was removed under vacuum at 35°C for 3 hours using a partial distillation setting. 52.2 g of propyl propionate was added to the flask. The mixture was stirred at 100 rpm under nitrogen purge at room temperature until homogenized. 0.16 g of bis(dimethylaminodimethylsilyl)ethane(C-4) was diluted with 1.6 g of propyl propionate. This stock solution was added dropwise to the flask at room temperature. After stirring for 20 minutes, the flask was heated to 60°C and stirred for 2 hours. The temperature was raised to 80°C. After stirring the flask for 10 minutes, 17 g of isopropanol was added to the flask and stirred for a further 30 minutes.

[0108] Comparative Example 1

[0109] 150 g of methyl resin (A'-3) (60.1% solids in toluene) and 66.7 g of methyl fluid (B'-3) were added to a 500 mL round-bottom flask. The mixture was homogenized using an overhead stirrer and reflux-dried under nitrogen purge at 125 °C for 1 hour. The temperature was reduced to 80 °C, and 1.34 g of dimethylbis(isopropylamino)silane (C-1) was added dropwise to the flask. The temperature was raised again to 130 °C, and the mixture was concentrated under reflux conditions for 4 hours.

[0110] Comparative Example 2

[0111] 150 g of phenyl resin (A-1) (51.2% solids in xylene) and 56.9 g of phenyl fluid (B-1) were added to a 500 mL round-bottom flask. This solution was stirred at 80°C for 1 hour under nitrogen purge using an overhead stirrer. 2.01 g of 1,3,5-trivinyl-1,3,5-trimethylcyclotrisilazane (C'-5) was added dropwise to the flask, and the temperature was raised to 100°C. This solution was continuously stirred for 3 hours, and then the temperature was lowered to 80°C. 14.1 g of isopropanol was added to the flask, and the mixture was stirred for 2 hours.

[0112] Comparative Example 3

[0113] 150 g of methyl resin (A'-3) (60.1% solids in toluene) and 66.7 g of methyl fluid (B'-3) were added to a 500 mL round-bottom flask. This mixture was homogenized using an overhead stirrer and reflux-dried under nitrogen purge at 125 °C for 1 hour. The temperature was reduced to 80 °C, and 1.47 g of 1,1,3,3,5,5-hexamethylcyclotrisilazane (C'-6) was added dropwise to the flask. The temperature was raised again to 130 °C, and the mixture was concentrated under reflux conditions for 4 hours.

[0114] Coating preparation

[0115] A 50 μm thick coating was prepared by casting the solution onto plastic films, such as polyethylene terephthalate (PET), polyimide (PI), and fluorosilicone-coated PET release liners, and then drawing down the film at a constant speed of 20 mm / s using a Gardner universal applicator at a TQC Sheen automated coating station. The wetted film was dried at 177°C for 10 minutes in a forced-air circulating oven and then evaluated.

[0116] Test method

[0117] Peeling force

[0118] A 1-inch x 8-inch (1 inch = 25.4 mm) adhesive-coated PET film sample was applied to a stainless steel panel using a roller with a constant load of 2 kg. This assembly was annealed separately in an oven at 100°C and 140°C for 5 minutes, cooled to room temperature for 30 minutes, and then tested for peel at room temperature. 180° peel tests were performed using a ChemInstruments AR-2000 adhesive tester at a constant peel rate of 12 inches / minute. Peel force is reported in grams-force per inch.

[0119] sticky

[0120] The tack (adhesion) of adhesive-coated samples was measured according to ASTM D-2979 using a TMI Polyken probe tack tester. Tack is reported in grams-weight.

[0121] Lapping shear strength

[0122] The lap shear strength test was performed using ChemInstruments' shear oven system (SOS-8). Adhesive-coated PI film was cut into 5-inch x 1-inch sample pieces. A 2-inch x 3-inch stainless steel test panel was then attached to one end of each sample piece, with a 1-inch x 1-inch overlap centered on the bottom edge of the panel. The other end of the sample piece was secured to a metal weight hanger. The sample piece was then loaded into the shear oven system set to 70°C, and a 1 kg weight was suspended from the weight hanger. The lap shear strength was reported as the time in minutes until the sample piece fell from the test panel and activated the timer switch.

[0123] Dynamic viscoelasticity measurement (DMA)

[0124] Dynamic viscoelasticity measurements were performed using a TA Instruments ARES G2 rheometer in the vibrational shear mode at a frequency of 1 Hz. A fixed amount of adhesive film coated on a fluorosilicone-coated PET liner was rolled into a sphere and loaded between 8 mm serrated parallel plates. The gap between the plates was set to approximately 0.5 mm. Dynamic temperature rise was performed in the linear viscoelastic region from -100°C to +200°C at a rate of 3°C / min. The storage modulus G' and loss modulus G'' were measured at 130°C, and the glass transition temperature T g This was defined as the temperature at which the tan-δ(G'' / G') value reaches its peak.

[0125] The physical properties of the adhesives prepared from each composition are shown in Table 2.

[0126] [Table 2]

[0127] The above description includes examples of the present invention. 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 comprehensive in the same way as “includes,” as is interpreted when “includes” is used as a substitute in the claims.

[0128] The above description illustrates various non-limiting embodiments of the silicone adhesive 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.

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