Conductive moisture-curable composition

Abstract

The present invention provides a conductive moisture-curing composition comprising the following: (A) A polyfunctional silane compound having at least two alkoxysilane groups, (B) Moisture absorber, (C) Alkoxysilane isocyanurate compounds and optionally epoxy-functionalized silane coupling agents, (D) A photoacid generator which is a sulfonium salt, (E) Moisture-curing catalyst, and (F) Conductive filler. The present invention further provides a method for applying the composition, a cured product of the composition, an article containing the cured product, and a use of the composition or the cured product.

Description

[Technical Field]

[0001] The present invention relates to conductive moisture-curable compositions, and more particularly to conductive moisture-curable compositions that dry quickly on the surface, have good stability, can be cured at room temperature, and have low resistivity; a method for applying the composition; a cured product of the composition; an article containing the cured product; and the use of the composition or the cured product. [Background technology]

[0002] Currently, many electronic products use heat-sensitive plastics as frames, thus creating a need for low-temperature curable compositions, particularly room-temperature curable compositions. Existing conductive room-temperature curable compositions typically contain modified silane polymers, conductive fillers, and a base (e.g., 3-aminopropyltrimethoxysilane). However, balancing tack-free time and stability in these compositions is challenging; that is, these compositions cannot exhibit both fast surface drying and good stability.

[0003] Furthermore, for rapid production, photocurable or moisture-curable adhesives are the first choice. However, photocurable conductive adhesives have limitations in curing depth due to their low transmittance. While hybrid chemistry of acrylates and NCOs can exhibit rapid surface drying, their stability deteriorates when mixed with conductive fillers. [Overview of the project] [Problems that the invention aims to solve]

[0004] Therefore, it is desirable to provide a conductive moisture-curable composition that dries quickly, has good stability, can be cured at room temperature, and has low resistivity. [Means for solving the problem]

[0005] The present invention provides a conductive moisture-curing composition comprising the following: (A) A polyfunctional silane compound having at least two alkoxysilane groups, (B) Moisture scavenger, (C) An alkoxysilane isocyanurate compound and optionally an epoxy-functional silane coupling agent, (D) A photoacid generator that is a sulfonium salt, (E) A moisture curing catalyst, and (F) A conductive filler.

[0006] The present invention also provides a method for applying the conductive moisture-curable composition of the present invention, comprising a step of applying the composition onto a substrate, a step of subjecting the composition to ultraviolet curing to obtain a cured product, and then a step of subjecting the cured product to moisture curing.

[0007] The present invention further provides a cured product of the conductive moisture-curable composition of the present invention.

[0008] The present invention also provides an article containing the cured product of the present invention.

[0009] Furthermore, the present invention provides the use of the conductive moisture-curable composition of the present invention or the cured product of the present invention in electronic products.

[0010] The conductive moisture-curable composition of the present invention, the method for applying such a composition, the cured product, the article and the use are all based on the following surprising findings of the inventors: The conductive moisture-curable composition of the present invention containing the combination of components (A) to (F) has a fast surface drying speed, good stability, can be cured at room temperature, and has a low resistivity; in particular, the tack-free time (without ultraviolet light) > 4 hours, the tack-free time (LED 365 nm, 3 w / cm 2* 2 s) ≤ 2 minutes, a fluid liquid state at room temperature (RT) after 4 hours (without ultraviolet light), a conductivity ≤ 0.005 Ω * cm after 7 days, and a cured depth ≥ 0.5 mm after 24 hours.

Embodiments for Carrying Out the Invention

[0011] Those skilled in the art will understand that this discussion is for illustrative purposes only and is not intended to limit the broader aspects of the present invention. Each of the aspects described herein can be combined with other aspects unless explicitly indicated otherwise. In particular, features indicated as preferred or advantageous can be combined with other features indicated as preferred or advantageous.

[0012] Unless otherwise specified, the terms “a,” “an,” and “the” as used herein include singular and plural referents. That is, the terms “a,” “an,” and “the” are used interchangeably with “at least one,” meaning one or more of the elements being described.

[0013] As used herein, the terms “comprising” and “comprises” are synonymous with “including,” “includes,” “containing,” or “contains,” and are inclusive or open-ended, not excluding any additional undescribed components, elements, or process steps.

[0014] Unless otherwise specified, the notation of endpoints in a number includes not only the notated endpoint but also all numbers and fractions within that range.

[0015] Unless otherwise specified, the term "room temperature" as used herein refers to 23±2°C.

[0016] Unless otherwise defined, all terms used in the disclosure of this invention, including technical and scientific terms, have the meanings generally understood by those skilled in the art to which this invention pertains.

[0017] Surprisingly, according to the present invention, the inventors of the present invention have provided a conductive moisture-curable composition comprising the following: (A) A polyfunctional silane compound having at least two alkoxysilane groups, (B) Moisture absorber, (C) Alkoxysilane isocyanurate compounds and optionally epoxy-functionalized silane coupling agents, (D) A photoacid generator which is a sulfonium salt, (E) Moisture-curing catalyst, and (F) Conductive filler We found that it dries quickly, has good stability, can cure at room temperature, and has low resistivity.

[0018] In a first embodiment, the disclosure generally relates to a conductive moisture-curable composition comprising: (A) A polyfunctional silane compound having at least two alkoxysilane groups, (B) Moisture absorber, (C) Alkoxysilane isocyanurate compounds and optionally epoxy-functionalized silane coupling agents, (D) A photoacid generator which is a sulfonium salt, (E) Moisture-curing catalyst, and (F) Conductive filler.

[0019] (A) Polyfunctional silane compounds having at least two alkoxysilane groups According to the present invention, the conductive moisture-curable composition comprises (A) a polyfunctional silane compound having at least two alkoxysilane groups.

[0020] Preferably, the polyfunctional silane compound (A) having at least two alkoxysilane groups comprises one or more at least bifunctional α-alkoxysilane compounds, the compound preferably having the following formula (III): [ka] (In the formula, R 16 is at least a divalent organic residue, Each R 17 This is independently a monovalent residue selected from the group consisting of hydrogen, linear, branched, cyclic, saturated, unsaturated, and aromatic hydrocarbons, which may optionally be halogen-substituted and / or interrupted by 1 to 3 heteroatoms. Each R18 is, independently, a monovalent residue selected from the group consisting of linear, branched, cyclic, saturated, unsaturated and aromatic hydrocarbons, optionally halogen-substituted and / or optionally interrupted by 1 to 3 heteroatoms, Each R 19 is, independently, a monovalent residue selected from the group consisting of hydrogen, linear, branched, cyclic, saturated, unsaturated and aromatic hydrocarbons, optionally halogen-substituted and / or optionally interrupted by 1 to 3 heteroatoms, X is a divalent or trivalent residue containing a heteroatom, linked via a heteroatom, especially oxygen, nitrogen or sulfur, to the -CR 17 2-SiR 18q (OR 19 ) (3-q) group, p is at least 2, q is 0 to 2) corresponds to.

[0021] More preferably, in formula (III), R 16 is (i) a linear or branched, saturated or unsaturated alkyl residue having 1 to 8 C atoms, optionally interrupted by 1 to 3 heteroatoms, (ii) a saturated or unsaturated cycloalkyl residue having 3 to 9 C atoms, optionally interrupted by 1 to 3 heteroatoms, (iii) an aromatic residue having 5 to 10 C atoms, (iv) a residue selected from the group consisting of polyolefins, polyethers, polyamides, polyesters, polycarbonates, polyurethanes, polyureas, siloxanes, polybutadienes, hydrogenated polybutadienes or polyacrylates, where each R 16 can be unsubstituted or can have further substituents.

[0022] Particularly preferably, R 16 is a polymer residue of group (iv) above, preferably having a terminal alkoxysilane group of formula (III).

[0023] Compounds of general formula (III) are so-called α-alkoxysilane compounds, characterized in that the (alkoxy)silane group is located at the α-position relative to a heteroatom such as oxygen, sulfur, or nitrogen. The alkoxysilane group is separated from the heteroatom by a substituted or unsubstituted methylene group.

[0024] Preferably, residue R 16 These are polymer or copolymer skeletons based on polyethers, polyesters, polycarbonates, polyurethanes, polyamides, and polyureas.

[0025] Particularly preferred, residue R 16 It is a polyurethane or polyether residue.

[0026] The heteroatom-containing residue X is preferably -O-, -S-, -N(R)-, -C(O)-O-, -OC(O)-O-, -OC(O)-ON(R)-, -N(R)-C(O)-O-, -S(O)-, -S(O)2-, -S(O)2-O-, -OS(O)2-O-, -C(O)-N(R)-, -S(O)2-N(R)-, -S(O)2-N[C(O)R]-, -OS(O)2-N(R)-, -N(R)-S(O)2-O-, -P(O)(OR)-O-, -OP(O)(O R)-, -OP(O)(OR)-O-, -P(O)(OR)-N(R)-, -N(R)-P(O)(OR)-, -OP(O)(OR)-N(R)-, -N(R)-P(O)(OR)-O-, -N[C(O)R]-, -N=C(R)-O-, -(R)=NO-, -C(O)-N[C(O)R]-, -N[S(O)2R']-, -C(O)-N[S(O)2R']- or -N[P(O)R''2]-, where R represents a heteroatom-containing divalent residue, and R is a hydrogen or optionally substituted C1-C 20 Alkyl or C6-C 20 This represents an aryl residue, where R'' is an optionally substituted C1-C 20 Alkyl, C6-C 20 Ariel, C1-C 20 Alkoxy or C6-C 20 This represents an aryloxy residue.

[0027] Particularly preferably, X in general formula (III) represents an oxygen or nitrogen atom, or a carboxy, carbamate, ureid, urethane, or sulfonate bond.

[0028] R 17 R is preferably hydrogen. 18 The C1-C6 alkyl group is preferably a C1-C6 alkyl group, particularly methyl or ethyl, or phenyl.

[0029] Residue R in general formula (III) 19 q preferably means a methyl group or an ethyl group. Preferably, q is 0 or 1. Furthermore, two R 19 It is also possible to crosslink residues to form a ring.

[0030] According to another preferred embodiment, residue R 17 is hydrogen, R 18 and R 19 ' is a methyl group, and q is 1.

[0031] Many preferred α-silanes based on polyethers or polyurethanes are commercially available from Wacker Chemie. They are sold under the trade name Geniosil STPE. Examples include STPE-10 and STPE-30 types.

[0032] Examples of commercially available ingredients (A) include Geniosil XB502, Geniosil XT50, and Geniosil XT55, all of which are available from Wacker.

[0033] In a preferred embodiment of the present invention, component (A) comprises a mixture of Geniosil STPE-10 and Geniosil XB502.

[0034] Preferably, the amount of component (A) is 3 to 50% by weight, preferably 5 to 35% by weight, and more preferably 5 to 25% by weight, based on the total weight of the composition. If the amount of component (A) is greater than 50% by weight, the conductivity of the product obtained from the composition deteriorates. If the amount of component (A) is less than 3% by weight, the composition cannot cure into a film, and the final product of the composition does not have conductivity.

[0035] Component (A) in the present invention does not include an epoxy-functionalized silane coupling agent, which will be explained below.

[0036] (B) Moisture absorber According to the present invention, the conductive moisture-curable composition comprises (B) a moisture scavenger, which is added to remove moisture from the surroundings or from the raw materials in order to enhance the storage stability of the composition.

[0037] Examples of moisture-scavenging agents (B) include, but are not limited to, vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and 3-vinylpropyltriethoxysilane. Preferably, the moisture-scavenging agent (B) used in the present invention is a vinylsilane. More preferably, the moisture-scavenging agent (B) is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and combinations thereof. Most preferably, the moisture-scavenging agent (B) is vinyltrimethoxysilane.

[0038] Examples of commercially available ingredients (B) include, but are not limited to, Dynasylan VTMO, available from Evonik, and Geniosil XL (VTMO), available from Wacker.

[0039] Preferably, the amount of component (B) is 0.3 to 2% by weight, preferably 0.4 to 1.0% by weight, based on the total weight of the composition. If the amount of component (B) is greater than 2% by weight, the moisture curing rate of the composition will be adversely affected. If the amount of component (B) is less than 0.3% by weight, the stability of the product will be adversely affected.

[0040] (C) Alkoxysilane isocyanurate compounds and optionally epoxy-functionalized silane coupling agents According to the present invention, the conductive moisture-curable composition comprises (C) an alkoxysilane isocyanurate compound and optionally an epoxy-functionalized silane coupling agent.

[0041] Preferably, the alkoxysilane isocyanurate compound used in the present invention is of the following general formula (I): [ka] (In the formula, R1, R2, and R3 are each independently a C1-C8 alkyl, preferably a C2-C6 alkyl, more preferably a C3-C4 alkyl; R4-R 12 Each of them is independently a C1-C4 alkyl or C1-C4 alkoxy, preferably a C1-C2 alkyl or C1-C2 alkoxy, more preferably a C1-C2 alkoxy; however, R4-R 12 (At least one of them is a C1-C4 alkoxy) It is represented as follows.

[0042] In preferred embodiments of the present invention, the alkoxysilane isocyanurate compound is selected from the group consisting of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, 1,3,5-tris(methyldimethoxysilylpropyl)isocyanurate, 1,3,5-tris(methyldiethoxysilylpropyl)isocyanurate, 1,3,5-tris(trimethoxysilylbutyl)isocyanurate, 1,3,5-tris(methyldimethoxysilylbutyl)isocyanurate, 1,3,5-tris(triethoxysilylpropyl)isocyanurate, and combinations thereof. Preferably, the alkoxysilane isocyanurate compound is selected from the group consisting of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, 1,3,5-tris(trimethoxysilylbutyl)isocyanurate, and combinations thereof. More preferably, the alkoxysilane isocyanurate compound is 1,3,5-tris(trimethoxysilylpropyl)isocyanurate.

[0043] Examples of commercially available alkoxysilane isocyanurate compounds include, but are not limited to, Dynasylan VPS 7163 (1,3,5-tris(trimethoxysilylpropyl)isocyanurate) and Dynasylan VPS 7161 (1,3,5-tris(trimethoxysilylpropyl)isocyanurate) (both available from Evonik); T-33 (1,3,5-tri(trimethoxysilylpropyl)cyanurate) (available from Huaian Hongtu New Material Co., Ltd.); and KBM-9658 (1,3,5-tri(trimethoxysilylpropyl)cyanurate) (available from Shin-Etsu Chemical Co., Ltd.). Preferably, the alkoxysilane isocyanurate compound is Dynasylan VPS 7163 or Dynasylan VPS 7161, both available from Evonik.

[0044] If present, the epoxy-functionalized silane coupling agent used in the present invention is preferably selected from the group consisting of 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, and combinations thereof. More preferably, the epoxy-functionalized silane coupling agent is 3-glycidyloxypropyltrimethoxysilane.

[0045] Examples of commercially available epoxy-functionalized silane coupling agents used in the present invention include: Silkquest A-187, Silkquest Wetlink 78, Silkquest A-1871, and Silkquest A-186 (all available from Momentive); Dynasylan 4721, Dynasylan GLYMO, and Dynasylan GLYEO (all available from Evonik); SCA-403, SCA-412, SCA-413, and SCA-4603 (all available from Itochu Corporation); Dow Corning Z-6040, Dow Corning Z-6042, Dow Corning Z-6041, and Dow Corning Z-6043 (all available from Dow Corning); KBM-403, KBM-303, KBE-402, and KBE-403 (all available from Shin-Etsu Chemical Co., Ltd.); GF80, GF84, and GF82 (all available from Wacker). Examples include, but are not limited to, those available from Chemie. Preferably, the epoxy-functionalized silane coupling agent used in the present invention is the Silke A-187, available from Momentive.

[0046] In a preferred embodiment of the present invention, the amount of component (C) is 0.5 to 20% by weight, preferably 1 to 8% by weight, based on the total weight of the composition. If the amount of component (C) is greater than 20% by weight, the crosslinking density of the product becomes too high, and the film obtained from the composition becomes brittle. If the amount of component (C) is less than 0.5% by weight, the tack-free time of the composition becomes too long, and the time required to obtain conductivity of the composition becomes too long.

[0047] (D) Photoacid generators which are sulfonium salts According to the present invention, the conductive moisture-curable composition contains a photoacid generator which is a (D) sulfonium salt.

[0048] Preferably, the photoacid generator (D) is an aromatic sulfonium compound. More preferably, the aromatic sulfonium compound has the following general formula (II): [ka] (In the formula, R 13 , R 14 and R 15 Each independently represents a monovalent aromatic group which may have substituents on the aromatic ring, and the monovalent aromatic group may optionally have one or more bonds selected from -S- (thioether bond), -SO- (sulfoxide bond), -O- (ether bond), and -O- (carbonyl bond); Rf is a fluoroalkyl group, preferably C1-C 10 m represents a fluoroalkyl group, more preferably a C1-C8 fluoroalkyl group, most preferably a C1-C4 fluoroalkyl group; m is a "cation [S + (R 13 )(R 14 )(R 15 It is represented as (the same number as the cation charge of ) and n is an integer in the range of 0 to 6).

[0049] In a preferred embodiment of the present invention, the cation [S] in the aromatic sulfonium compound + (R 13 )(R 14 )(R 15)] is selected from the group consisting of the following cations (a-1) to (a-20): [ka] TIFF2026519669000005.tif208164 TIFF2026519669000006.tif216164 TIFF2026519669000007.tif106164 (Here, hal represents a chlorine atom or a fluorine atom, and f, which represents the number of substituents (hal)f on the cationic group, is independently 0 or 1.)

[0050] In another preferred embodiment of the present invention, in an aromatic sulfonium compound, the formula [PF 6-n ](Rf) n The anion represented by ] is selected from the group consisting of the following anions (b-1) to (b-12): [ka] TIFF2026519669000009.tif191103

[0051] In a preferred embodiment of the present invention, the photoacid generator (D) is a combination of a cation (a-11) and an anion (b-2).

[0052] Examples of commercially available aromatic sulfonium compounds include, but are not limited to, CPI-100P, CPI-110P, CPI-200K, CPI-210S, CPI-500K, and CP1-500P (all available from SAN-APRO); as well as ADEKAOPTOMER SP-150, ADEKAOPTOMER SP-152, and ADEKAOPTOMER SP-300 (all available from ADEKA Corporation). Preferably, the aromatic sulfonium compound is the one traded under the name CPI-200K from SAN-APRO.

[0053] Preferably, the amount of component (D) is 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the composition. If the amount of component (D) is greater than 5% by weight, the amount of acid generated after UV exposure (after UV treatment) becomes too large, which is detrimental to the conductivity of the cured composition. If the amount of component (D) is less than 0.5% by weight, the tack-free time of the composition becomes too long, preventing rapid surface drying.

[0054] (E) Moisture-curing catalyst According to the present invention, the conductive moisture-curable composition comprises (E) a moisture-curing catalyst.

[0055] Preferably, the moisture-curing catalyst used in the present invention is a metal-containing catalyst, preferably a bismuth-containing catalyst.

[0056] Examples of moisture-curing catalysts include, but are not limited to, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin diacetate, tin(II) acetate, tin(II) octanoate, tin(II) acetylacetonate, titanium(V) isopropylate, potassium neodecanoate, indium neodecanoate, zirconium(IV) acetylacetonate, copper naphthenate, iron(III) acetylacetonate, iron naphthenate, zinc acetylacetonate, zinc 2-ethylhexanoate, zinc neodecanoate, bismuth 2-ethylhexanoate, bismuth neodecanoate, and bismuth tetramethylheptanedione. Preferably, examples of moisture-curing catalysts include bismuth 2-ethylhexanoate, bismuth neodecanoate, and bismuth tetramethylheptanedione.

[0057] Examples of commercially available moisture-curing catalysts include, but are not limited to, Borchi Kat 22, Borchi Kat VP 0243, Borchi Kat VP 0244, and Borchi Kat 315 (all available from OMG-Borchers); BICAT products (available from Shepherd Chemical); and K-Kat K-348 (available from King Industries). Preferably, the moisture-curing catalyst used in the present invention is the one traded as Borchi Kat 315, available from OMG Borchers.

[0058] Preferably, the amount of component (E) is 0.01 to 10% by weight, preferably 0.3 to 7% by weight, more preferably 0.5 to 5% by weight, and most preferably 1.5 to 2.5% by weight, based on the total weight of the composition. If the amount of component (E) is greater than 10% by weight, the stability of the product will be poor, and the composition will become a viscous liquid within 4 hours. If the amount of component (E) is less than 0.01% by weight, the curing rate of the composition will be too slow, and it will not be able to exhibit conductivity after 7 days.

[0059] (F) Conductive filler According to the present invention, the conductive moisture-curable composition comprises (F) a conductive filler.

[0060] The conductive filler is a component that imparts conductivity to the cured product of the composition of the present invention. Examples of conductive fillers include, but are not limited to, metal particles such as silver, gold, platinum, palladium, nickel, copper and their alloys; particles coated with metal (e.g., silver, gold, platinum, palladium, nickel, copper and their alloys); and carbon black, carbon fibers, carbon nanotubes, graphene, etc. Preferably, the conductive filler used in the present invention may be silver, copper, gold, or silver-coated particles. More preferably, the conductive filler is silver or silver-coated core particles. Most preferably, the conductive filler is silver.

[0061] In the present invention, the conductive filler may be spherical particles, flakes, rods, wires, nanoparticles, or a combination thereof. In a preferred embodiment of the present invention, the conductive filler is 0.4 to 3.5 m 2 It has a specific surface area of ​​0.5 to 2.9 m² / g. Preferably, when silver powder is used as the conductive filler, it is 0.5 to 2.9 m². 2 It may have a specific surface area of ​​ / g.

[0062] Examples of commercially available conductive fillers include, but are not limited to, Silflake 135 (available from Technic); SF-29 (available from Ames Advanced Materials); SF-3, SF-3J, and SF-C (all available from Ames Goldsmith); RA-0127, AA3462, P629-3, P629-4, AC-4044, and SF-11 (all available from Metalor); and combinations thereof. Preferably, the conductive filler used in the present invention is the one traded as RA-0127, available from Metalor.

[0063] Preferably, the amount of component (F) is 50 to 95% by weight, preferably 55 to 90% by weight, and more preferably 65 to 80% by weight, based on the total weight of the composition. If the amount of component (F) is greater than 95% by weight, the conductive filler cannot be well dispersed in the composition. If the amount of component (F) is less than 50% by weight, the composition will not have sufficient conductivity.

[0064] (G) Additives In some embodiments of the present invention, the conductive moisture-curable composition may optionally further contain (G) additives commonly used in the art to which the present invention belongs, such as antioxidants, light stabilizers, ultraviolet absorbers, and rheological aids, provided that they do not adversely affect the desired technical effects of the composition of the present invention.

[0065] An example of an antioxidant used in this invention is Irganox 1010, manufactured by BASF.

[0066] Examples of light stabilizers used in the present invention include, but are not limited to, hindered amine light stabilizers.

[0067] Examples of UV absorbers used in the present invention include, but are not limited to, salicylic acid UV absorbers, phenyl ketone UV absorbers, and benzotriazole UV absorbers.

[0068] The presence (or absence), type, and quantity of additives can be determined by a person skilled in the art according to the actual requirements.

[0069] A preferred embodiment of the present invention, the conductive moisture-curing composition of the present invention, includes the following: (A) A polyfunctional silane compound having at least two alkoxysilane groups, in an amount of 3 to 50% by weight, preferably 5 to 35% by weight, and more preferably 5 to 25% by weight, based on the total weight of the composition; (B) A moisture-scavenging agent in an amount of 0.3 to 1% by weight, preferably 0.4 to 0.8% by weight, based on the total weight of the composition; (C) Based on the total weight of the composition, 0.5 to 20% by weight, preferably 1 to 8% by weight, of an alkoxysilane isocyanurate compound and optionally an epoxy-functionalized silane coupling agent; (D) A photoacid generator, which is a sulfonium salt, in an amount of 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the composition; (E) A moisture-curing catalyst in an amount of 0.01 to 10% by weight, preferably 0.3 to 7% by weight, more preferably 0.5 to 5% by weight, and most preferably 1.5 to 2.5% by weight, based on the total weight of the composition; (F) 50 to 90% by weight, preferably 55 to 90% by weight, more preferably 65 to 80% by weight of conductive fillers, based on the total weight of the composition; and (G) Antioxidant (optional).

[0070] The conductive moisture-curable composition of the present invention can be prepared by any conventional preparation method in the art. Preferably, the composition of the present invention can be prepared by a method comprising the following steps: adding components (C), (D), and (G) (if any) and dispersing them uniformly; adding component (F) and dispersing the resulting mixture uniformly; adding component (B) and dispersing the resulting mixture uniformly; adding component (A) and dispersing the resulting mixture uniformly; adding component (E) and dispersing the resulting mixture uniformly; and discharging the final mixture as quickly as possible and degassing to remove the air contained therein. The preparation of the composition is preferably carried out in a controlled temperature and humidity environment, and more preferably, the preparation is carried out at a temperature below 25°C and a relative humidity below 50%. The mixer used for preparation may be any conventional mixing device used in the art, such as a Speedmixer or Ross Mixer. The composition obtained in this manner is preferably stored at -40°C.

[0071] In a second embodiment, the present disclosure relates to a method for applying a conductive moisture-curable composition of the present invention, comprising the steps of: applying the composition onto a substrate; ultraviolet curing the composition to obtain a cured product; and subsequently moisture curing the cured product.

[0072] In a preferred embodiment, the composition of the present invention may be applied onto a substrate by dispensing. The applied composition may be cured with ultraviolet light using an ultraviolet LED light source preferably having a wavelength of 365 nm, and the light intensity of the LED light source is preferably 1.0 to 5 W / cm². 2 The curing time is preferably 1 to 10 seconds. The cured product obtained from the UV curing step may then be moisture-cured under ambient conditions, during which the cured product is preferably kept at 18 to 25°C and 30 to 40% relative humidity. In moisture curing, the curing rate is affected by temperature and humidity, and generally the higher the temperature and / or humidity, the faster the curing rate.

[0073] In a third embodiment, the disclosure relates to a cured product of a conductive moisture-curable composition of the present invention, an article containing the cured product, and the use of the composition or the cured product in an electronic product.

[0074] The conductive moisture-curing composition of the present invention can be used in electronic products, preferably products where conductivity or antistatic properties are desired.

[0075] The conductive moisture-curable composition of the present invention, comprising a combination of components (A) to (F), exhibits rapid surface drying, good stability, can be cured at room temperature, and has low resistivity; in particular, tack-free time (without UV) > 4 hours, tack-free time (LED 365nm, 3w / cm2 * Fluid liquid state at room temperature (RT) after 4 hours (without UV light), with conductivity ≤ 0.005Ω after 7 days (2s) ≤ 2 minutes, and conductivity ≤ 0.005Ω after 7 days. * This shows the combination of cm and a curing depth of ≥0.5 mm after 24 hours. [Examples]

[0076] The following examples are intended to help those skilled in the art to better understand and implement the present invention. The scope of the present invention is not limited by the examples but is defined by the appended claims. Unless otherwise stated, parts and percentages are all based on weight.

[0077] Raw materials: Ingredient (A): Component a-1: Geniosil STPE-10, CAS number 611222-18-5, available from Wacker, has the following structure: [ka]

[0078] Component a-2: Geniosil XB502, available from Wacker, is a mixture of the polymer of formula (III) of the present invention and a methoxy-terminated silsesquioxane in a weight ratio of approximately (25-30) / (70-75).

[0079] Ingredient (B): Component b-1: Dynasylan VTMO, available from Evonik, has the following structure: [ka]

[0080] Ingredients (C): Component c-1: Dynasylan VPS 7163, available from Evonik, has the following structure: [ka]

[0081] Ingredient c-2: [ka]

[0082] Ingredient c-3: [ka]

[0083] Ingredients (D): Component d-1: CPI 200K, available from SAN-APRO, has the following structure: [ka]

[0084] Component d-2': SpeedCure 939, 4-isopropyl-4'-methyldiphenyliodonium tetrakis-(pentafluorophenyl)borate, available from Lambson, has the following structure: [ka]

[0085] Component d-3': Omnirad 184, 1-hydroxycyclohexyl phenyl ketone, available from LGM, has the following structure: [ka]

[0086] Ingredients (E): Ingredient e-1: Borchi Kat 315, available from OMG.

[0087] Component e-2': Dynasylan AMMO, 3-aminopropyltrimethoxysilane, available from Evonik.

[0088] Ingredient (F): Ingredient f-1: RA-0127, silver filler, available from Metalor.

[0089] Ingredients (G): Ingredient g-1: Irganox 1010, available from BASF.

[0090] Examples 1-2 (Ex.1-Ex.2) and Comparative Examples 1-4 (CEx.1-CEx.4) Table 1 shows the specific amounts and types of components in the conductive moisture-curable compositions of Examples 1-2 and Comparative Examples 1-4 of the present invention. The compositions were prepared as follows: Components (C), (D), and (G) were added and dispersed uniformly. Component (F) was added and the resulting mixture was dispersed uniformly. Component (B) was added and the resulting mixture was dispersed uniformly. Component (A) was added and the resulting mixture was dispersed uniformly. Component (E) was added and the resulting mixture was dispersed uniformly. The final mixture was discharged as quickly as possible, degassed, and the air inside was removed. The compositions were prepared at 23°C and 40% relative humidity. The mixer used for preparation was a Speedmixer, DAC150.1 FVZ-K, available from Flacktek. The compositions obtained in this manner were stored at -40°C.

[0091] Test method Tack-free time (no UV rays): Each composition from Examples 1-2 and Comparative Examples 1-4 was dispensed onto a glass substrate. The substrate with the composition was then placed in an environment of 25°C / 50%RH, and the surface of the composition was touched every 3 minutes to check whether a solid film had formed on the surface.

[0092] Tack-free time (with UV protection): Each composition from Examples 1-2 and Comparative Examples 1-4 was dispensed onto a glass substrate, and the substrate coated with the composition was subjected to a 3 w / cm² load. 2 After UV curing for 2 seconds under an LED 365nm light source with a specified output, the material was placed in a 25°C / 50%RH environment, and finally, the surface of the composition was touched every minute for the first 5 minutes, and then every 3 minutes thereafter, to confirm whether the surface had become a solid film.

[0093] Condition after 4 hours at room temperature (RT) (without UV light): Each composition from Examples 1-2 and Comparative Examples 1-4 was dispensed onto a glass substrate, and the substrates coated with the compositions were placed in an environment of 25°C / 50%RH. After 4 hours, the paste-like state was checked.

[0094] Conductivity after 7 days (Ω) * cm): For each composition in Examples 1-2 and Comparative Examples 1-4, the conductivity after 7 days was measured using an Agilent 34401A according to ASTM D991.

[0095] Curing depth after 24 hours: Each composition from Examples 1-2 and Comparative Examples 1-4 was dispensed onto an aluminum plate, and the substrate coated with the composition was placed in an environment of 25°C / 50%RH. The thickness of the composition was measured after 24 hours.

[0096] The tack-free time (without UV light), tack-free time (with UV light), state after 4 hours RT (without UV light), conductivity after 7 days, and curing depth after 24 hours of curing were tested using the methods described above, and the results are shown in Table 1 below.

[0097] [Table 1]

[0098] From the data in Table 1, the conductive moisture-curable compositions of the present invention (Examples 1 and 2) containing combinations of components (A) to (F) exhibit rapid surface drying, good stability, can be cured at room temperature, and have low resistivity; in particular, tack-free time (without UV) > 4 hours, tack-free time (LED 365nm, 3w / cm²) 2* Fluid liquid state at room temperature (RT) after 4 hours (without UV light), with conductivity ≤ 0.005Ω after 7 days (2s) ≤ 2 minutes, and conductivity ≤ 0.005Ω after 7 days. * It can be seen that this combination shows a curing depth of ≥0.5 mm after 24 hours.

[0099] In contrast, epoxy compositions not conforming to the present invention (Comparative Examples 1 to 4) had a tack-free time (without UV light) > 4 hours, and a tack-free time (LED 365nm, 3w / cm²). 2* Fluid liquid state at RT after 2s ≤ 2 minutes and 4 hours (without UV light), conductivity after 7 days ≤ 0.005Ω *The combination of a tack-free time of 18 minutes (without UV light) and a curing depth of ≥0.5 mm after 24 hours was not shown. For example, Comparative Example 1 (without components (C) and (D) of the present invention) showed a tack-free time of 18 minutes (without UV light) and a 0.5 mm film at RT after 4 hours (without UV light). Comparative Examples 2 and 3 (neither of which contained the alkoxysilane isocyanurate compounds of the present invention) showed tack-free times far exceeding 2 minutes (LED 365 nm, 3 w / cm²). 2* 2s), 0.005Ω * The conductivity after 7 days was far greater than or undetectable than cm, and the curing depth after 24 hours was unsuitable. Comparative Example 4 (containing an iodonium photoacid generator and a photopolymerization initiator instead of component (D) of the present invention) had a tack-free time of 60 minutes (LED 365 nm, 3 w / cm). 2* 2s), 4 hours later (without UV light), sticky liquid at RT, and 0.2Ω * This shows the conductivity of cm after 7 days.

[0100] While several preferred embodiments have been described, many modifications and variations are possible in light of the above teachings. Therefore, it should be understood that the present invention can be implemented in ways other than those specifically described without departing from the scope of the appended claims.

Claims

1. Conductive hygroscopic compositions including the following: (A) A polyfunctional silane compound having at least two alkoxysilane groups, (B) Moisture-absorbing agent, (C) Alkoxysilane isocyanurate compounds and optionally epoxy-functionalized silane coupling agents, (D) A photoacid generator which is a sulfonium salt, (E) Moisture-curing catalyst, and (F) Conductive filler.

2. The alkoxysilane isocyanurate compound is given by the following general formula (I): 【Chemistry 1】 (wherein, R １ , R ２ and R ３ are each independently C １ -C ８ alkyl, preferably C ２ -C ６ alkyl, more preferably C ３ -C ４ alkyl; each of R ４ to R １2 is independently C １ -C ４ alkyl or C １ -C ４ alkoxy, preferably C １ -C ２ alkyl or C １ -C ２ alkoxy, more preferably C １ -C ２ alkoxy group; provided that at least one of R ４ to R １２ is C １ -C ４ alkoxy) The conductive moisture-curing composition according to claim 1, represented by [the specified formula].

3. The alkoxysilane isocyanurate compounds include 1,3,5-tris(trimethoxysilylpropyl) isocyanurate, 1,3,5-tris(methyldimethoxysilylpropyl) isocyanurate, 1,3,5-tris(methyldiethoxysilylpropyl) isocyanurate, 1,3,5-tris(trimethoxysilylbutyl) isocyanurate, 1,3,5-tris(methyldimethoxysilylbutyl) isocyanurate, 1,3,5-tris(triethoxysilylpropyl) isocyanurate, and The conductive moisture-curable composition according to claim 1 or 2, wherein the alkoxysilane isocyanurate compound is selected from the group consisting of combinations thereof; preferably, the alkoxysilane isocyanurate compound is selected from the group consisting of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, 1,3,5-tris(trimethoxysilylbutyl)isocyanurate, and combinations thereof; more preferably, the alkoxysilane isocyanurate compound is 1,3,5-tris(trimethoxysilylpropyl)isocyanurate.

4. The photoacid generator (D) is defined by the following general formula (II): 【Chemistry 2】 (In the formula, R １３ , R １４ and R １５ Each independently represents a monovalent aromatic group which may have substituents on the aromatic ring, and the monovalent aromatic group may optionally have one or more bonds selected from -S- (thioether bond), -SO- (sulfoxide bond), -O- (ether bond), and -O- (carbonyl bond); Rf is a fluoroalkyl group, preferably C １ -C １０ Fluoroalkyl groups, more preferably C １ -C ８ Fluoroalkyl groups, most preferably C １ -C ４ Represents a fluoroalkyl group; m is a cation [S ＋ (R １３ ) (Caution １４ ) (Caution １５ (The number is the same as the cation charge of ) and n is an integer in the range of 0 to 6.) A conductive moisture-curable composition according to any one of claims 1 to 3, wherein the aromatic sulfonium compound is represented by .

5. The cation [S] in the aromatic sulfonium compound ＋ (R １３ ) (Caution １４ ) (Caution １５ )] refers to the following cations (a-1) to (a-20): 【Transformation 3】 【change】 【change】 【change】 (In the formula, hal represents a chlorine atom or a fluorine atom, and f, which represents the number of substituents (hal)f in the cationic group, is independently 0 or 1.) Selected from the group consisting of; and / or, The formula [P-F] in the aforementioned aromatic sulfonium compound ６－ｎ (Rf) ｎ The anions represented by ] are the following anions (b-1) to (b-12): 【Chemistry 4】 【change】 A conductive moisture-curable composition according to claim 4, selected from the group consisting of the following.

6. The polyfunctional silane compound having at least two alkoxysilane groups (A) comprises one or more at least bifunctional α-alkoxysilane compounds, preferably the α-alkoxysilane compound having the following formula (III): 【Transformation 5】 (In the formula, R １６ is at least a divalent organic residue, Each R １７ This is a monovalent residue independently selected from the group consisting of hydrogen, linear, branched, cyclic, saturated, unsaturated, and aromatic hydrocarbons, which may optionally be halogen-substituted and / or interrupted by 1 to 3 heteroatoms. Each R １８ This is independently a monovalent residue selected from the group consisting of linear, branched, cyclic, saturated, unsaturated, and aromatic hydrocarbons, which may optionally be interrupted by halogen substitution and / or 1 to 3 heteroatoms. Each R １９ This is a monovalent residue independently selected from the group consisting of hydrogen, linear, branched, cyclic, saturated, unsaturated, and aromatic hydrocarbons, which may optionally be halogen-substituted and / or interrupted by 1 to 3 heteroatoms. X is particularly affected by heteroatoms of oxygen, nitrogen, or sulfur, -CR １７ ２ -SiR １８ｑ (OR １９ ) （３－ｑ） A divalent or trivalent residue containing a heteroatom, bonded to a base, p is at least 2, (q is between 0 and 2) A conductive moisture-curable composition according to any one of claims 1 to 5, which corresponds to the above.

7. The conductive moisture-curable composition according to any one of claims 1 to 6, wherein the moisture-scavenging agent (B) is vinylsilane; preferably, the moisture-scavenging agent (B) is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and combinations thereof; more preferably, the moisture-scavenging agent (B) is vinyltrimethoxysilane.

8. The conductive moisture-curable composition according to any one of claims 1 to 7, wherein the amount of component (C) is 0.5 to 20% by weight, preferably 1 to 8% by weight, based on the total weight of the composition.

9. The conductive moisture-curable composition according to any one of claims 1 to 8, wherein the amount of component (D) is 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the composition.

10. A conductive moisture-curable composition according to any one of claims 1 to 9, further comprising an additive (G) selected from the group consisting of antioxidants, light stabilizers, ultraviolet absorbers, rheological aids, and combinations thereof.

11. A conductive moisture-curable composition according to any one of claims 1 to 10, which can be cured at room temperature.

12. A method for applying a conductive moisture-curable composition according to any one of claims 1 to 11, comprising the steps of: applying the composition onto a substrate; curing the composition with ultraviolet light to obtain a cured product; and subsequently moisture-curing the cured product.

13. A cured product of a conductive moisture-curable composition according to any one of claims 1 to 11.

14. An article comprising the curing product described in claim 13.

15. Use of the conductive moisture-curable composition according to any one of claims 1 to 11 or the cured product according to claim 13 in electronic products, preferably those where conductivity or antistatic properties are desired.

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