Curable adhesive composition comprising a maleimide and a thiol

Abstract

The present invention relates to a curable adhesive composition comprising (A) at least one maleimide compound, (B) at least one thiol compound having at least two mercapto groups and no siloxane group in the molecule, (C) at least one latent curing agent, and (D) optionally at least one photoradical polymerization initiator. The cured product obtained from the adhesive composition of the present invention has high moisture resistance. Furthermore, the present invention also provides an article comprising the cured adhesive composition, and the use thereof.

Description

[Technical Field]

[0001] The present invention relates to curable adhesive compositions comprising maleimides and thiols, articles comprising the cured adhesive compositions, and uses thereof. [Background technology]

[0002] Improving the moisture resistance of low-temperature-cured adhesives is challenging in electronic applications. Recent image sensor modules are made from a variety of materials, including glass, metal, and liquid crystal polymer (LCP). When modules made from these various materials are used as substrates, adhesives with high moisture resistance and reliability are required. Thiol-containing compositions are known to be promising for achieving the recently required low-temperature, rapid curing properties. For example, acrylates and thiols have been selected as the main components for producing low-temperature-curing adhesives for UV / thermal dual-cure applications. However, adhesives based on this combination exhibit poor moisture resistance, likely due to the hydrolyzable ester structure in the polymer backbone.

[0003] To solve the above-mentioned problems, U.S. Patent No. 15,556,964 discloses a custom-made chemical structure of thiol with a smaller amount of ester group to improve moisture resistance. However, the synthesis method of the thiol is too complicated, and the thiol structure is too limited for more widespread application.

[0004] Maleimides have attracted considerable attention for their high modulus and excellent resistance to thermal degradation, and are primarily used in the production of adhesive joints, heat-resistant composites, and high-performance coatings. To explore this application, many efforts have been made to modify bis-maleimides (BMIs), which are disclosed in the patents identified and discussed below.

[0005] WO 2009 / 145779 A1 discloses diamines or dithiols used to extend the BMI and obtain oligomeric compounds with better solubility and greater toughness.

[0006] WO 2010 / 016946 A2 discloses metal / carboxylate complexes and peroxides used to cure maleimide compounds at temperatures below 100°C.

[0007] WO 2018 / 201428A1 discloses a thermosetting sealant composition comprising: (a) a thermosetting epoxy resin selected from maleimide resins, maleimide-modified epoxy resins, and any combination thereof; (b) a latent curing agent; (c) a polysiloxane containing mercapto groups; and optionally, a stabilizer. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 15,556,964 [Patent Document 2] International Publication No. 2009 / 145779A1 [Patent Document 3] International Publication No. 2010 / 016946A2 [Patent Document 4] International Publication No. 2018 / 201428A1 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, the present inventors came up with a new idea of ​​combining maleimide and a thiol compound to develop a low-temperature curing adhesive that will exhibit high moisture resistance in the cured product. [Means for solving the problem]

[0010] After intensive research, the inventors have found that the above problems can be solved by a curable adhesive composition comprising: (A) at least one maleimide compound; (B) at least one thiol compound having at least two mercapto groups and no siloxane group in the molecule; (C) at least one latent hardener; and (D) optionally, at least one photoradical polymerization initiator.

[0011] In another aspect of the present invention, an article is provided that includes a first substrate, a cured adhesive, and a second substrate bonded to the first substrate via the cured adhesive obtained from a curable adhesive composition according to the present invention.

[0012] In an additional aspect of the present invention, there is provided an electronic device comprising the article of the present invention or manufactured using the curable adhesive composition according to the present invention.

[0013] In yet another aspect of the present invention, there is provided the use of the curable adhesive compositions and articles according to the present invention in the manufacture of electronic devices. DETAILED DESCRIPTION OF THE INVENTION

[0014] Those skilled in the art will appreciate that the present invention describes only exemplary embodiments and is not intended to limit the broader aspects of the present invention. Each embodiment so described may be combined with any other embodiment, unless expressly stated otherwise. In particular, any feature identified as being preferred or advantageous may be combined with any other feature identified as being preferred or advantageous.

[0015] Unless otherwise specified, in the context of the present invention, the terms used should be construed in accordance with the following definitions.

[0016] Unless otherwise specified, as used herein, the terms "a," "an," and "the" include both singular and plural referents.

[0017] As used herein, the terms "comprising" and "comprises" are synonymous with "including," "includes," or "containing," and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps.

[0018] Unless otherwise specified, recitation of numerical endpoints includes not only the recited endpoint but all numbers and fractions subsumed within each range.

[0019] All documents cited herein are incorporated by reference in their entirety.

[0020] Unless otherwise defined, all terms used herein, including technical and scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs.

[0021] The present invention relates to a curable adhesive composition comprising: (A) at least one maleimide compound; (B) at least one thiol compound having at least two mercapto groups and no siloxane group in the molecule; (C) at least one latent hardener; and (D) optionally, at least one photoradical polymerization initiator.

[0022] [(A) Maleimide Compound] In accordance with the present invention, one notable feature is the inclusion of a maleimide compound in the curable adhesive composition.

[0023] Maleimide compounds suitable for use in the present invention have the general structure (I): [ka] [wherein n is an integer of 2 or more, and X is an aromatic group or an aliphatic group] It has.

[0024] In a preferred embodiment, the adhesive composition comprises a bis-, tris-, or tetramaleimide compound, more preferably a bismaleimide (BMI) compound.

[0025] BMI compounds suitable for use in the present invention have the formula structure (II): [ka] where X1 is a divalent hydrocarbyl linking group.

[0026] Exemplary divalent hydrocarbyl linking groups can be selected from the following: linear or branched alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, cycloalkenylene, cycloalkylarylene, biphenylene, heterocycloalkylene, or heterocycloarylene having from 1 to 36 carbon atoms, optionally containing at least one carbonyl group, carboxyl group, amide group, carbamate group, urea group, ester group, ether group, and combinations thereof.

[0027] As used herein, "alkylene" refers to any divalent group derived from a saturated aliphatic hydrocarbon by removing two hydrogen atoms. In the present invention, higher alkylene groups having 12 to 36 carbon atoms are preferred.

[0028] As used herein, "cycloalkylene" refers to any divalent group derived by removing two hydrogen atoms from a cycloalkane.

[0029] As used herein, "bicycloalkylene" refers to any divalent group derived by removing two hydrogen atoms from a cycloalkane whose molecule contains two rings.

[0030] As used herein, "tricycloalkylene" refers to any divalent group derived by removing two hydrogen atoms from a cycloalkane whose molecule contains three rings.

[0031] As used herein, "alkenylene" refers to any divalent group derived by removing two hydrogen atoms from different carbon atoms of an alkene.

[0032] As used herein, "arylene" refers to any divalent group derived by removing two hydrogen atoms from polyunsaturated, aromatic monocyclic or polycyclic rings (preferably 1 to 3 rings) that are fused together or covalently linked.

[0033] As used herein, "aralkylene" refers to any divalent radical derived from an aryl group attached to an alkylene group, as defined above.

[0034] As described herein, "arylbicycloalkylene" refers to any divalent group derived by removing two hydrogen atoms from a cycloalkane, the molecule of which contains two rings and an aryl group.

[0035] As described herein, "aryltricycloalkylene" refers to any divalent group derived by removing two hydrogen atoms from a cycloalkane whose molecule contains three rings and an aryl group.

[0036] As used herein, "cycloalkenylene" refers to any divalent group derived by removing two hydrogen atoms from different carbon atoms of a cycloalkene.

[0037] As described herein, "cycloalkylarylene" refers to any divalent group derived by removing two hydrogen atoms from an aryl group contained in a fused cycloalkylaryl, which contains both a saturated ring and a benzene ring.

[0038] As used herein, "biphenylene" refers to any divalent group derived by removing two hydrogen atoms from a polycyclic hydrocarbon consisting of two benzene rings joined by a pair of interconnecting bonds.

[0039] As used herein, "heterocycloalkylene" refers to any divalent group derived by removing two hydrogen atoms from a non-aromatic monocyclic or polycyclic ring containing carbon and hydrogen atoms and at least one heteroatom, preferably 1 to 4 heteroatoms selected from nitrogen, oxygen, and sulfur.

[0040] As used herein, "heterocycloarylene" refers to any divalent group derived by removing two hydrogen atoms from an aromatic group containing a polycyclic ring, which contains carbon and hydrogen atoms and at least one heteroatom, preferably 1 to 4 heteroatoms selected from nitrogen, oxygen, and sulfur.

[0041] Preferred BMI compounds for use in the present invention include, but are not limited to, the following formula structures (A1)-(A4): [ka] [In the formula, C 36 represents a straight or branched chain (with or without cyclic moieties) of 36 carbon atoms] [ka] .

[0042] Exemplary BMI compounds for use in the present invention can be prepared by the reaction of maleic anhydride with dimer amines (i.e., dimer acids, α,ω-diamino hydrocarbons prepared from mixtures of mono-, di-, and tri-functional oligomeric aliphatic carboxylic acids; dimer acids are typically prepared by the thermal reaction of unsaturated fatty acids (e.g., oleic acid, linoleic acid, etc.), which involves an Enne / Diels-Alder reaction, to give a mixture of the above components).

[0043] Exemplary BMI compounds for use in the present invention can be prepared from dimer amines such as 1,20-bismaleimido-10,11-dioctyl-eicosane, and are believed to be present in admixture with other isomeric species produced in the Enne / Diels-Alder reaction used to prepare dimer acids. Other BMI compounds contemplated for use in the present invention include BMIs made from α,ω-aminopropyl-terminated polydimethylsiloxanes (e.g., PS510 available from Huls), polyoxypropyleneamines (e.g., D-230, D-400, D-2000, and T-403 available from Huntsman), polytetramethyleneoxide-di-p-aminobenzoate (e.g., Versalink P-650 available from Air Products), and the like.

[0044] The BMI compounds used in the present invention are commercially available, for example, CM1016 manufactured by Henkel, SR525 manufactured by Sartomer, and BMI4 manufactured by Henkel.

[0045] In other embodiments, maleimide compounds suitable for use in the present invention include those having the general structure (I), where n is an integer greater than 2 and X is an aliphatic or aromatic group. Exemplary X groups include, but are not limited to: poly(butadiene), poly(carbonate), poly(urethane), poly(ether), poly(ester), simple hydrocarbons, and simple hydrocarbons containing functional groups such as carbonyl, carboxyl, amide, carbamate, urea, or ether. Specific preferred maleimide compounds include the following formula structure (A5): [ka]

[0046] The maleimide compounds used in the present invention are commercially available, for example, TrisMI-1 is available from Henkel.

[0047] These maleimide compounds can be used alone or in combination, but the maleimide compounds that can be used in the present invention are not limited to these.

[0048] Particularly preferably, component (A) incorporated into the curable adhesive composition is present in an amount of 10 to 80 wt %, preferably 20 to 70 wt %, based on the total weight of the composition.

[0049] [(B) Thiol Compound] According to the present invention, the composition contains at least one thiol compound having at least two mercapto groups in the molecule and no siloxane group. The thiol compound having no -Si-O-Si- bond in the compound disperses better with the maleimide compound than a thiol compound having a polysiloxane thiol, and can form an adhesive composition.

[0050] As used herein, the term "siloxane group" refers to a substituted organosilicon compound composed of a -Si-O-Si- backbone with side chains R attached to the silicon atoms, where each R is independently a water atom or an organic group which may have functional groups.

[0051] In a preferred embodiment, the curable adhesive composition comprises at least one thiol compound having at least two mercapto groups, preferably three mercapto groups, and more preferably four mercapto groups in the molecule, and no siloxane groups.

[0052] In some embodiments, the composition comprises at least one thiol compound having at least two mercapto groups in the molecule and no siloxane groups, wherein the at least two mercapto groups are C 1- C 36 aliphatic group, C 4- C 36 Alicyclic group, C 6- C 40 It may be linked to a divalent linking unit selected from an aromatic group, a urethane group, an imide group, a carbonyl group, a carboxyl group, an amide group, a carbamate group, a urea group, an ester group, an ether group, a poly(butadiene) group, a polycarbonate group, a polyurethane group, a polyether group, a polyester group, and combinations thereof.

[0053] As used herein, an "aliphatic group" refers to an optionally substituted straight or branched C 1-36 It refers to a hydrocarbon, which is either fully saturated or contains one or more units of unsaturation, but is not aromatic. For example, suitable aliphatic groups include optionally substituted, straight-chain or branched alkyl, alkenyl, alkynyl groups, and combinations thereof.

[0054] As used herein, "alkyl" used alone or as part of a larger moiety refers to an optionally substituted straight or branched chain hydrocarbon group having from 1 to 36 carbon atoms.

[0055] As used herein, "alkenyl," used alone or as part of a larger moiety, refers to an optionally substituted straight or branched chain hydrocarbon group having at least one carbon-carbon double bond and 2 to 36 carbon atoms.

[0056] As used herein, "alkynyl," used alone or as part of a larger moiety, refers to an optionally substituted straight or branched chain hydrocarbon group having at least one carbon-carbon triple bond and 2 to 36 carbon atoms.

[0057] It will be understood that the phrase "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted." In general, the term "substituted," whether accompanied by the term "optionally," means that a hydrogen radical of the designated moiety is replaced with a specified substituent group, provided that the substitution results in a stable or chemically feasible compound. Unless otherwise specified, an "optionally substituted" group may have a substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted with more than one substituent selected from a specified group, the substituents may be the same or different at each position. Combinations of substituents contemplated by the present disclosure are, for example, those that result in the formation of stable or chemically feasible compounds.

[0058] As used herein, "alicyclic" refers to a group that combines the properties of aliphatic and cyclic compounds, including, but not limited to, monocyclic or polycyclic aliphatic hydrocarbons and bridged cycloalkyl groups, which are optionally substituted with one or more functional groups. As will be understood by those skilled in the art, "alicyclic" as used herein refers to a group having a C 4- C 36 , preferably C 4- C 30 It is intended to include, but is not limited to, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties, which are optionally substituted with one or more functional groups.

[0059] The "cycloalkyl" used in component (B) specifically refers to a group having 4 to 36, preferably 4 to 30, carbon atoms. Suitable cycloalkyls include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

[0060] The term "aromatic group" as used in component (B) refers to a stable monocyclic or polycyclic unsaturated moiety, preferably having 6 to 40 carbon atoms, preferably 6 to 30 carbon atoms, each of which may be substituted or unsubstituted. In certain embodiments, the term "aromatic moiety" refers to a planar ring having p orbitals at each ring atom perpendicular to the ring plane and satisfying Huckel's rule that the number of pi electrons in the ring is (4n+2), where n is an integer. Monocyclic or polycyclic unsaturated moieties that do not meet one or all of these criteria for aromaticity are defined herein as "non-aromatic" and are encompassed by the term "alicyclic."

[0061] Preferably, the thiol compound may have an ester group, an s-triazinetrione group, a pentaerythritol group, or a bicyclic heteroaryl group, such as a group derived from imidazoimidazole, and has 2 to 4 mercapto groups in one molecule.

[0062] Examples of thiol compounds for use in the present invention include, but are not limited to, methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2-cyclohexanedithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,2-dimercaptopropyl methyl ether, 2,3-dimethylethyl ... mercaptopropyl methyl ether, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) sulfide, bis(mercaptoethyl) disulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,3-bis(mercaptomethylthio) )propane, 1,3-bis(2-mercaptoethylthio)propane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,ll-dimercapto-3,6,9-trithiaundecane KOH, 4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-bismercaptomethyl-1,4-Dithiane, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 2,3-dimercapto-1-propanol(3-mercaptopropionate), 3-mercapto-1,2-propanediol bis(2-mercaptoacetate), 3-mercapto-1,2-propanediol di(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), ditrimethylolpropane tetrakis(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), ditrimethylolpropane tetrakis(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), dipentaerythritol hexa(2-mercaptoacetate), pentaerythritol di(3-mercaptopropionate) ester), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), glycerin di(2-mercaptoacetate), glycerin tris(2-mercaptoacetate), glycerin di(3-mercaptopropionate), glycerin tris(3-mercaptopropionate), 1,4-cyclohexanediol bis(2-mercaptoacetate), 1,4-cyclohexanediol bis(3-mercaptopropionate) propionate), hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide(2-mercaptoacetate), hydroxyethyl sulfide(3-mercaptopropionate), hydroxymethyl disulfide(2-mercaptoacetate), hydroxymethyl disulfide(3-mercaptopropionate), thioglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), N,N',N"-Tris(3-mercaptopropylcarbonyloxyethyl)isocyanurate, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene ) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene, 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2,4,5-tetrakis(mercaptoethyl)benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, etc.

[0063] Specific examples of thiol compounds that can be used in the present invention include, but are not limited to, the formula structures B1 to B19 shown below: [ka] [ka] [ka] [ka]

[0064] In a preferred embodiment, component (B) can be a thiol compound having in the molecule at least two mercapto groups attached to a divalent linking unit, wherein the divalent linking unit is C 12- C 36 Thiol compounds having a substantially flexible backbone, which is an aliphatic group and contains one or more ether groups, produce high bond strength in the cured adhesive after hydrothermal aging.

[0065] Examples of such compounds include, but are not limited to, 3,3'-[[2,2-bis[(3-mercaptopropoxy)methyl]propane-1,3-diyl]dioxy]bis(propane-1-thiol), 1-[3-(2-sulfanylpropoxy)-2,2-bis(2-sulfanylpropoxymethyl)propoxy]propane-2-thiol, 3-[2-(methoxymethyl)-3-(3-sulfanylpropoxy)-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol, 2-(sulfanylpropoxymethyl)propoxy]bis(propane-1-thiol), 2-[3-(2-sulfanylethoxy)-2,2-bis(2-sulfanylethoxymethyl)propoxy]ethanethiol, 2-[2-[3-[2-(2-sulfanylethoxy)ethoxy]-2,2-bis[2-(2-sulfanylethoxy)ethoxymethyl]propoxy]ethoxy]ethanethiol 3-[2-(butoxymethyl)-3-(3-sulfanylpropoxy)-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol, 3-[2-[2-(2-sulfanylethoxy)ethoxymethyl]-2-(2-sulfanylethylperoxymethyl)-3-(3-sulfanylpropoxy)propoxy]propane-1-thiol, 3-[2-(2-sulfanylethylperoxymethyl)-3-(3-sulfanylpropoxy)-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol 3-[3-(3-sulfanylpropoxy)-2-[[3-(3-sulfanylpropoxy)-2,2-bis(3-sulfanylpropoxymethyl)propoxy]methyl]-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol, 2-[3-(2-sulfanylethoxy)-2-[[3-(2-sulfanylethoxy)-2,2-bis(2-sulfanylethoxymethyl)propoxy]methyl]-2-(2-sulfanylethoxymethyl)propoxy]ethanethiol, 3-[2,2-bis[2-(2-sulfanylethoxy)ethoxymethyl]-3-(2-sulfanylethylperoxy)propoxy]propane-1-thiol, 3-[2-[3-[2-(3-sulfanylpropoxy)ethoxy]-2,2-bis[2-(3-sulfanylpropoxy)ethoxymethyl]propoxy]ethoxy]propane-1-thiol, O-[3-(3-sulfanylpropanethioyloxy)-2-[[3-(3-sulfanylpropanethioyloxy)-2,2-bis(3-sulfanylpropanethioyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanethioyloxymethyl)propyl]3-sulfanylpropanethioate, etc.

[0066] In another preferred embodiment, the component (B) used in the present invention may be a thiol compound having, in the molecule, at least two mercapto groups bonded to a divalent linking unit, wherein the divalent linking unit is selected from arylbicycloalkylene, aryltricycloalkylene, cycloalkenylene, cycloalkylarylene, biphenylene, heterocycloalkylene, heterocycloarylene, and combinations thereof. 4- C 36 Alicyclic group or C 6- C 40 Thiol compounds with such rigid rings produce high bond strength in the cured adhesive after hydrothermal testing.

[0067] Examples of such compounds include, but are not limited to, 1,3,4,6-tetra(2-mercaptoethyl)octahydroimidazo[4,5-d]imidazole-2,5-dione, 1,3,4,6-tetrakis(3-sulfanylpropyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione, 3a-methyl-1,3,4,6-tetrakis(2-sulfanylethyl)-6aH-imidazo[4,5-d]imidazole- 2,5-dione, 1,3,4,6-tetrakis(2-methylsulfanylethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione, 1,6-dipropyl-3,4-bis(2-sulfanylethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione, 6-propyl-1,3,4-tris(2-sulfanylethyl)-3a,6a-dihydro-2H-imidazo[4,5-d]imidazole-5-one, and the like.

[0068] These thiol compounds can be used alone or in combination, but the thiol compounds having at least two mercapto groups and no siloxane group in the molecule are not limited to these examples.

[0069] The above thiol compounds can be prepared using techniques well known to those skilled in the art or are commercially available.

[0070] A commercially available example of a thiol compound is Karenz available from Showa Denko KK. MT BD1,Karenz MT Examples of suitable acrylic acid esters include NR1, Multhiol Y4 available from SC Organic Chemical Co., and C3TS-G available from Shikoku.

[0071] In a preferred embodiment, the ratio of the maleimide equivalent in component (A) to the mercapto equivalent in component (B) is 0.2 to 1.8, preferably 1.0 to 1.5.

[0072] Particularly preferably, component (B) may be included in the curable adhesive composition in an amount of 15% to 70% by weight, preferably 15% to 40% by weight, based on the total weight of the composition.

[0073] [(C) Latent hardener] In accordance with the present invention, the curable adhesive composition comprises at least one latent curing agent.

[0074] The latent curing agent as component (C) is a compound that is inactive at room temperature and is activated by heating to act as a curing accelerator.

[0075] Examples of the latent curing agent may include an imidazole compound, an amine adduct obtained by the reaction product of an amine compound with an epoxy compound, an isocyanate compound, and / or a urea compound, a core-shell type latent curing agent, and a masterbatch type latent curing agent.

[0076] Examples of imidazole compounds include, but are not limited to, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2' ... N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adipoyldiamide. However, the imidazole compounds that are solid at room temperature and used as latent curing agents in the present invention are not limited to these examples.

[0077] Commercially available examples of the imidazole compounds described above that may be used as latent curing agents in the present invention include IMICURE® EMI-24 curing agent available from Evonik.

[0078] Examples of epoxy compounds used as one of the raw materials for producing an amine adduct latent curing agent (amine-epoxy-adduct type latent curing agent) include: polyglycidyl ethers obtained by the reaction between polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol, and epichlorohydrin; glycidyl ether esters obtained by the reaction between hydroxycarboxylic acids such as p-hydroxybenzoic acid and 3-hydroxynaphthoic acid and epichlorohydrin; polyglycidyl esters obtained by the reaction between polycarboxylic acids such as phthalic acid and terephthalic acid and epichlorohydrin; and glycidyl amine compounds obtained by the reaction between 4,4'-diaminodiphenylmethane, m-aminophenol, etc., and epichlorohydrin. Further examples include polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins, as well as monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate, but the epoxy compounds used as latent curing agents in the present invention are not limited to these examples.

[0079] The amine compound used as a separate raw material for producing the amine adduct latent curing agent may be any compound having one or more active hydrogens in its molecule capable of undergoing addition reaction with an epoxy group, and having one or more functional groups selected from primary amino groups, secondary amino groups, and tertiary amino groups in its molecule. Examples of such amine compounds are listed below. These examples may include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine. However, the amine compounds used as latent curing agents in the present invention are not limited to these examples.

[0080] Among these, compounds having a tertiary amino group in their molecule are raw materials that provide latent curing agents with particularly excellent curing acceleration properties. Examples of such compounds include primary or secondary amines having a tertiary amino group in their molecule, such as amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, and imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. Further examples may include alcohols, phenols, thiols, carboxylic acids, hydrazides, and the like having a tertiary amino group in the molecule, such as 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, Nn-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, and the like.However, the above compounds having a tertiary amino group in the molecule, which are used as latent curing agents in the present invention, are not limited to these examples.

[0081] Examples of isocyanate compounds that can be used as another raw material for the amine adduct latent curing agent include, but are not limited to, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate, as well as polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate. Furthermore, compounds containing isocyanate groups at their terminals obtained by the reaction between these polyfunctional isocyanate compounds and active hydrogen compounds can also be used. Examples of such compounds having an isocyanate group at their terminals include an addition compound having an isocyanate group at their terminals obtained by the reaction between toluene diisocyanate and trimethylolpropane, and an addition compound having an isocyanate group at their terminals obtained by the reaction between toluene diisocyanate and pentaerythritol. However, the compounds having an isocyanate group at their terminals that are used as the amine adduct latent curing agent in the present invention are not limited to these examples.

[0082] Examples of urea compounds used as raw materials to make amine adduct latent curing agents include, but are not limited to, urea, urea phosphate, urea oxalate, urea acetate, diacetyl urea, dibenzoyl urea, and trimethyl urea.

[0083] Commercially available examples of the amine adduct latent curing agents include Ajicure PN-23 manufactured by Ajinomoto Fine-Techno Co., Ltd., Ajicure PN-40 manufactured by Ajinomoto Fine-Techno Co., Ltd., Ajicure PN-50 manufactured by Ajinomoto Fine-Techno Co., Ltd., Hardener X-3661 S manufactured by ACR Co., Ltd., Hardener X-3670S manufactured by ACR Co., Ltd., FXR1 121 manufactured by T&K TOKA Corporation, Fujicure FXE-1000 manufactured by T&K TOKA Corporation, and Fujicure FXR-1030 manufactured by T&K TOKA Corporation.

[0084] Furthermore, a core-shell type latent curing agent can be obtained by further treating the surface of an amine compound (or amine adduct) with an acid compound such as a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, or an epoxy compound to form a shell of a modified product (adduct, etc.) on the surface. Furthermore, a masterbatch type latent curing agent is a core-shell type latent curing agent in a state of being mixed with an epoxy resin.

[0085] Commercially available examples of the masterbatch-type curing agent include Novacure HX-3722 manufactured by Asahi Kasei Epoxy Co., Ltd., Novacure HX-3742 manufactured by Asahi Kasei Epoxy Co., Ltd., and Novacure HX-3613 manufactured by Asahi Kasei Epoxy Co., Ltd.

[0086] The latent hardeners can be used alone, or two or more types of components can be used in combination.

[0087] Particularly preferably, component (C) may be incorporated into the curable adhesive composition in an amount of 5% to 20% by weight, preferably 5% to 15% by weight, based on the total weight of the composition.

[0088] [(D) Photoradical polymerization initiator] According to the present invention, the curable adhesive composition optionally comprises at least one photoradical polymerization initiator; if present, the curing process can be initiated by UV irradiation.

[0089] In some embodiments, both photoinitiators and thermal initiators may be desirable. For example, the curing process can be initiated by UV irradiation, usually via a free radical reaction, and the curing can be completed in a post-processing step by applying heat to achieve further curing, usually via a thiol-Michael addition reaction. Therefore, both UV initiators and thermal initiators may be added to the curable adhesive composition.

[0090] In a preferred embodiment, the curable adhesive composition does not contain a photoinitiator and can only be thermally cured.

[0091] The photoradical polymerization initiator used in the present invention is not particularly limited as long as it can promote free radical polymerization, crosslinking, or both. The photoradical polymerization initiator and its amount are preferably selected so as to achieve a uniform reaction conversion rate according to the thickness of the composition to be cured, and so as to achieve a sufficiently high total conversion rate to achieve the desired initial handling strength.

[0092] Useful photoinitiators include, but are not limited to, "alpha-cleavage" photoinitiators, such as benzil dimethyl ketal, benzoin ether, hydroxyalkyl phenyl ketone, benzoylcyclohexanol, dialkoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, trimethylbenzoylphosphine oxide, methylthiophenyl morpholinoketone, and morpholinophenyl aminoketone; hydrogen abstraction photoinitiators, including photoinitiators and coinitiators based on benzophenone, thioxanthone, benzil, camphorquinone, and ketocoumarin; and combinations thereof.

[0093] Preferred photoradical polymerization initiators include acylphosphine oxides, including, for example, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, and 2,4,4-trimethylbenzoyldiphenylphosphine oxide.

[0094] These photoradical polymerization initiators may be used alone or in combination of two or more thereof.

[0095] Useful commercially available photoradical polymerization initiators are available under the following tradenames: IRGACURE 369 morpholinophenyl amino ketone, IRGACURE 819 bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and its preferred form CGI819XF, IRGACURE CGI 403 bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, IRGACURE 651 benzil dimethyl ketal, IRGACURE 184 benzoylcyclohexanol, DAROCUR 1173 hydroxyalkyl phenyl ketone, DAROCUR 4265 a 50:50 blend of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and CGI1700 a 25:75 blend of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine and 2-hydroxy-2-methyl-1-phenylpropan-1-one, all available from Ciba-Geigy Corp (Ardsley, NY);

[0096] Generally, when a photoradical polymerization initiator is present in the composition, these compositions will cure at room temperature at wavelengths ranging from 200 nm to 650 nm, preferably 300 to 500 nm, in less than 30 seconds, preferably less than 10 seconds, and more preferably less than 5 seconds, followed by a thermal cure process as described herein. As will be appreciated, the time and amount cure profile of each curable adhesive composition will vary, and different compositions can be designed to provide a cure profile suitable for a particular industrial manufacturing process.

[0097] Particularly preferably, component (D), when present, may be in an amount of 0 to 5% by weight, preferably 1 to 3% by weight, of the total composition.

[0098] [(E) Acrylic resin] According to the present invention, the composition optionally comprises at least one acrylic resin selected from acrylate monomers, methacrylate monomers, or oligomers thereof.

[0099] Examples of acrylic acid ester monomers and / or methacrylic acid ester monomers, or oligomers thereof, that can be used in the present invention may include the following: diacrylate and / or dimethacrylate of tris(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)isocyanurate triacrylate and / or trimethacrylate, trimethylolpropane triacrylate and / or trimethacrylate, or oligomers thereof, pentaerythritol triacrylate and / or trimethacrylate, or oligomers thereof, polyacrylate and / or polymethacrylate of dipentaerythritol, tris(acryloxyethyl)isocyanurate, caprolactone-modified tris(acryloxyethyl)isocyanurate, caprolactone-modified tris(methacryloxyethyl)isocyanurate, polyacrylate and / or polymethacrylate of alkyl-modified dipentaerythritol, and polyacrylate and / or polymethacrylate of caprolactone-modified dipentaerythritol.

[0100] Commercially available examples of acrylic resins include polyester acrylate (product name: EBECRYL 81O) manufactured by Daicel-Allnex Ltd., polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., tricyclodecane dimethanol diacrylate (product name: SR 833S) manufactured by Sartomer, and diacrylate ester of bisphenol A epoxy resin (product name: Ebecryl 3700) manufactured by Allnex.

[0101] These acrylic resins mentioned above may be used alone or in combination of two or more components.

[0102] In a preferred embodiment, the ratio of the maleimide equivalent in compound (A) and the —C═C— carbon bond equivalent in compound (E) to the mercapto equivalent in compound (B) is 0.2 to 1.8, preferably 1.0 to 1.5.

[0103] Particularly preferably, the curable adhesive composition does not contain any acrylic resin. When present, component (E) may be incorporated into the curable adhesive composition in an amount of 0 to 35 wt %, preferably 15 to 25 wt %, based on the total weight of the composition.

[0104] [Additives] If necessary, the curable adhesive composition may contain additives such as fillers such as silica fillers, stabilizers, carbon black, titanium black, silane coupling agents, ion trapping agents, leveling agents, antioxidants, antifoaming agents, thixotropic agents, and the like, as long as the additives do not impair the subject matter of the present invention. Furthermore, the additives may be mixed with viscosity modifiers, flame retardants, or solvents.

[0105] The additives may be in a variety of forms, including, for example, particles (spherical particles, beads, and elongated particles), fibers, and combinations thereof.

[0106] One useful class of stabilizers includes carbodiimide stabilizers.

[0107] Examples of useful antioxidants include hindered phenolic antioxidants, phosphite antioxidants, and thioether antioxidants. Commercially available examples include RGANOX 565, 1010, and 1076 available from Ciba-Geigy (Hawthorne, NY). The moisture-curable polyurethane hot melt adhesive composition optionally contains up to about 2 wt. % of an antioxidant.

[0108] Examples of useful pigments include inorganic, organic, reactive, and non-reactive pigments, and combinations thereof, which may be selected from metal oxide pigments, titanium dioxide, optionally surface-treated zirconium oxide or cerium oxide, zinc oxide, iron oxide (black, yellow, or red), chromium oxide, manganese.

[0109] According to the present invention, the additives may be present in an amount of 0 to 10% by weight, preferably 2% to 6% by weight, based on the total weight of the composition.

[0110] Compositions and Cured Products Preferred according to the present invention are curable adhesive compositions comprising: 10% to 80% by weight, preferably 20% to 70% by weight, of at least one maleimide compound; 15% to 70% by weight, preferably 15 to 40% by weight, of at least one thiol compound having at least two mercapto groups in the molecule and having no siloxane group; 5% to 20% by weight, preferably 5% to 15% by weight, of at least one latent hardener; 0 to 5 wt. %, preferably 1 to 3 wt. %, of at least one photoradical polymerization initiator; and 0-10% by weight, preferably 2% to 6% by weight, of at least one additive; wherein the weight percentages are based on the total weight of the composition.

[0111] [Method for producing curable adhesive composition] The curable adhesive composition of the present invention can be produced by mixing the following at room temperature: (A) at least one maleimide compound; (B) at least one thiol compound having at least two mercapto groups in the molecule and no siloxane groups; (C) at least one latent curing agent; and optionally, (D) at least one photoradical polymerization initiator; (E) an acrylic resin, and, if present, other additives. There is no particular limitation on the equipment used for mixing, stirring, dispersing, etc., these components. Examples of equipment that can be used include an automatic motor equipped with a stirrer and heater, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill. These equipment may also be used in combination. The method for producing the curable adhesive composition is not particularly limited, as long as a composition in which the above components are uniformly mixed is obtained.

[0112] [Curing profile] In another aspect of the present invention, there is provided a method of joining two substrates comprising applying to at least one substrate a curable adhesive composition of the present invention.

[0113] The curable adhesive composition can be applied to a substrate using any suitable application method, including, for example, automated fine line application, jet application, slot die coating, roll coating, gravure coating, transfer coating, pattern coating, screen printing, spray coating, filament coating, coating by extrusion, air knife, trailing blade, brushing, dipping, doctor blade, offset gravure coating, rotogravure coating, and combinations thereof. The curable adhesive composition can be applied as a continuous or discontinuous coating, in single or multiple layers and combinations thereof.

[0114] Optionally, the surface of the substrate to which the curable adhesive composition is applied has been treated to enhance adhesion using any suitable method for increasing adhesion to the substrate surface, including, for example, corona treatment, chemical treatment (e.g., chemical etching), flame treatment, abrasion, and combinations thereof.

[0115] According to the present invention, the curable adhesive composition of the present invention can be cured at a temperature of less than 100°C, preferably from 60°C to 80°C.

[0116] In a preferred embodiment, when a photoradical polymerization initiator is present in the curable adhesive composition, the curing process can be initiated by UV irradiation at a wavelength of 200 nm to 650 nm, preferably 300 nm to 500 nm, at room temperature for a time of less than 30 seconds, preferably less than 10 seconds, more preferably less than 5 seconds, and a subsequent thermal curing process at a temperature of less than 100° C., preferably 60° C. to 80° C., for a time of 20 minutes to 3 hours, preferably 30 minutes to 1.5 hours. As will be appreciated, the time and temperature cure profile for each adhesive composition can vary, and different compositions can be designed to provide a cure profile suitable for a particular industrial manufacturing process.

[0117] In some embodiments, the cured product of the curable adhesive composition exhibits an aspect ratio of 0% or greater, preferably 20% or greater, and more preferably 40% or greater after hydrothermal aging at 85°C and 85% humidity for 120 hours or greater.

[0118] [Articles, electronic devices, and their uses] In another aspect of the present invention, an article is provided that includes a first substrate, a cured adhesive, and a second substrate bonded to the first substrate via the cured adhesive obtained from the curable adhesive composition of the present invention.

[0119] The first substrate and / or the second substrate may be a single layer of a single material, or may include multiple layers of the same or different materials, which may be continuous or discontinuous.

[0120] The substrate of the articles described herein can have a variety of properties, including rigidity (e.g., a stiff substrate, i.e., the substrate cannot be bent by an individual using both hands or will break if an individual attempts to bend the substrate using both hands), flexibility (e.g., a flexible substrate, i.e., the substrate can be bent with less than the strength of both hands), porosity, electrical conductivity, lack of electrical conductivity, and combinations thereof.

[0121] The substrate of the article may be in a variety of forms, such as, for example, a fiber, a thread, a yarn, a woven fabric, a nonwoven fabric, a film (e.g., a polymeric film, a metalized polymeric film, a continuous film, a discontinuous film, and combinations thereof), a foil (e.g., a metal foil), a sheet (e.g., a metal sheet, a polymeric sheet, a continuous sheet, a discontinuous sheet, and combinations thereof), and combinations thereof.

[0122] Useful substrate materials for use in the present invention include, for example, polymers (e.g., polycarbonate, ABS resin (acrylonitrile-butadiene-styrene resin), liquid crystal polymers, polyolefins (e.g., polypropylene, polyethylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, and oriented polypropylene, copolymers of polyolefins with other comonomers), polyether terephthalate, ethylene vinyl acetate, ethylene methacrylic acid ionomer, ethylene vinyl alcohol, polyesters (e.g., polyethylene terephthalate), polycarbonate, polyamides (e.g., nylon-6 and nylon-6,6), polyvinyl chloride, polyvinylidene chloride, cellulose derivatives, polystyrene, and epoxies), polymer composites (e.g., composites of polymers with metals, cellulose, glass, polymers, and combinations thereof), metals (aluminum, Copper, zinc, lead, gold, silver, platinum, and metal alloys such as magnesium, steel (such as stainless steel), tin, brass, magnesium, aluminum alloys, carbon fiber composites, other fiber-based composites, graphene, fillers, glass (e.g., alkali aluminosilicate reinforced glass and borosilicate glass), quartz, boron nitride, gallium nitride, sapphire, silicon, carbides, ceramics, and combinations thereof, preferably liquid crystal polymers, glass, and combinations thereof.

[0123] An additional aspect of the present invention provides an electronic device comprising an article of the present invention or an article made using the curable adhesive composition of the present invention.

[0124] Exemplary electronic devices include computers and computing equipment such as printers, fax machines, scanners, keyboards, etc.; medical sensors; automotive sensors, etc.; wearable electronic devices (e.g., watches, eyeglasses, etc.), handheld electronic devices (e.g., phones (e.g., cell phones, mobile smartphones, etc.), cameras, tablets, e-readers, monitors (e.g., monitors used in hospitals and by medical professionals, athletes, and individuals), watches, calculators, mice, touchpads, and joysticks), computers (e.g., desktop and laptop computers), computer monitors, televisions, media players, household appliances (e.g., refrigerators, washers, dryers, ovens, microwaves, etc.), light bulbs (e.g., incandescent lamps, light emitting diodes, fluorescent lamps, etc.), and articles containing visible, transparent or transparent components, glass housing structures, protective transparent covers for displays or other optical components.

[0125] In yet another aspect of the present invention, there is provided the use of the curable adhesive composition of the present invention and of the article of the present invention for manufacturing electronic devices. [Example]

[0126] The following examples are intended to aid those skilled in the art in better understanding and practicing the present invention. The scope of the present invention is not limited by the examples, but is defined by the appended claims. All parts and percentages are by weight unless otherwise specified.

[0127] [Ingredients:] SR 833S is tricyclodecane dimethanol diacrylate available from Sartomer. Ebecryl 3700 is a diacrylate ester of bisphenol A epoxy resin bisphenol available from Allnex.

[0128] CM1016 is a maleimide compound having the formula structure (A1) described herein, available from Henkel. SR525 is a phenylene dimaleimide having the formula structure (A4) described herein, available from Sartomer. BMI4 is a maleimide compound having the formula structure (A3) described herein, available from Henkel. TrisMI-1 is a maleimide compound having the formula structure (A5) described herein, available from Henkel.

[0129] SMS-042 is a (mercaptopropyl)methylsiloxane dimethylsiloxane copolymer available from Gelest.

[0130] KARENZ MT BD1 is a thiol compound available from Showa Corporation and having the following chemical structure: [ka]

[0131] KARENZ MT NR1 is a thiol compound having the formula structure (B12) described herein, available from Showa Corporation. Multiol Y4 is a thiol compound having the formula structure (B8) described herein, available from SC organic chemical. C3TS-G is a thiol compound having the formula structure (B15) described herein, available from Shikoku.

[0132] EH-5057P is a latent hardener available from ADEKA corporation. HX-3722 is a latent hardener available from AsahiKASHI. Speedcure TPO-L is a photoradical generator available from IGM Resin. TS 720 is a fumed silica available from Cabot Corporation. 12S is a pigment available from Mitsubishi Materials Corporation.

[0133] [Manufacturing method:] Example 1 (Ex. 1) 3 g of Speedcure TPO-L and 0.4 g of 12S were mixed with 57.01 g of BMI4 in a covered container. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (FlackTek, Inc.). Then, 27.67 g of KARENZ MT NR1 was added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. Then, 5.00 g of EH-5057P and 4.30 g of HX-3722 were added, and the mixture was mixed at 1000 rpm for 5 minutes. Then, 2.62 g of TS 720 was added, and the mixture was mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer, and a curable adhesive composition was obtained. The equivalent ratio of maleimide groups to mercapto groups was 1.26:1.00.

[0134] Example 2 (Ex.2) 29.25 g of Ebecryl 3700 and 24.44 g of BMI4 were mixed in a covered container, and then 3 g of Speedcure TPO-L and 0.4 g of 12S were added. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (manufactured by FlackTek, Inc.). Then, 31.96 g of KARENZ MTNR1 was added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. Then, 5.00 g of EH-5057P and 3.91 g of HX-3722 were added and mixed at 1000 rpm for 5 minutes. Then, 2.04 g of TS 720 was added and mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer to obtain a curable adhesive composition. The equivalent ratio of maleimide groups and -C=C- carbon bonds to mercapto groups was 1.17:1.00.

[0135] Example 3 (Ex. 3) 44.70 g of BMI4 and 12.28 g of CM1016 were mixed in a covered container, and then 3 g of Speedcure TPO-L and 0.4 g of 12S were added. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (manufactured by FlackTek, Inc.). Then, 29.33 g of KARENZ MT NR1 was added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. Then, 4.00 g of EH-5057P and 2.99 g of HX-3722 were added, and the mixture was mixed at 1000 rpm for 5 minutes. Then, 3.30 g of TS 720 was added, and the mixture was mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer, and a curable adhesive composition was obtained. The equivalent ratio of maleimide groups to mercapto groups was 1.20:1.00.

[0136] Example 4 (Ex. 4) 44.94 g of BMI4 and 10.55 g of TrisMI-1 were mixed in a covered container, and 3 g of Speedcure TPO-L and 0.4 g of 12S were added. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (manufactured by FlackTek, Inc.). Then, 29.51 g of KARENZ MTNR1 was added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. Then, 4.00 g of EH-5057P and 3.39 g of HX-3722 were added and mixed at 1000 rpm for 5 minutes, followed by 4.21 g of TS 720 and mixing at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer, resulting in a curable adhesive composition. The equivalent ratio of maleimide groups to mercapto groups was 1.20:1.00.

[0137] Example 5 (Ex. 5) 9.73 g of SR 833S, 24.75 g of Ebecryl 3700, and 28.01 g of BMI4 were mixed in a covered container, and 0.4 g of 12S was added. The mixture was stirred at room temperature for 10 minutes at 2000 rpm in a Speedmixer DAC 150.1 FVZ-K (FlackTek, Inc.). 21.73 g of C3TS-G was then added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. 6.00 g of EH-5057P and 4.93 g of HX-3722 were then added, and the mixture was mixed at 1000 rpm for 5 minutes. 4.45 g of TS 720 was then added, and the mixture was mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer, resulting in a curable adhesive composition. The equivalent ratio of maleimide groups and -C=C- carbon bonds to mercapto groups was 1.30:1.00.

[0138] Example 6 (Ex. 6) 69.73 g of BMI4 was mixed with 0.4 g of 12S in a covered container. The mixture was stirred at room temperature for 10 minutes at 2000 rpm in a Speedmixer DAC 150.1 FVZ-K (FlackTek, Inc.). 19.71 g of C3TS-G was then added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. 4.00 g of EH-5057P and 3.00 g of HX-3722 were then added, and the mixture was mixed at 1000 rpm for 5 minutes. 3.16 g of TS 720 was then added, and the mixture was mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer, and a curable adhesive composition was obtained. The equivalent ratio of maleimide groups to mercapto groups was 1.30:1.00.

[0139] Example 7 (Ex. 7) 65.86 g of BMI4 was mixed with 0.4 g of 12S in a covered container. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (FlackTek, Inc.). 20.23 g of Multhiol Y4 was then added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. 5.00 g of EH-5057P and 3.36 g of HX-3722 were then added, and the mixture was mixed at 1000 rpm for 5 minutes. 5.15 g of TS 720 was then added, and the mixture was mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer, and a curable adhesive composition was obtained. The equivalent ratio of maleimide groups to mercapto groups was 1.30:1.00.

[0140] Example 8 (Ex. 8) 4.02 g of SR525 and 57.22 g of BMI4 were mixed in a covered container, and 0.4 g of 12S was added. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (manufactured by FlackTek, Inc.). Then, 27.82 g of KARENZ MTNR1 was added to the container and the mixture was mixed at 1000 rpm for 5 minutes. Then, 9.07 g of EH-5057P was added and mixed at 1000 rpm for 5 minutes, followed by 1.47 g of TS 720 and mixing at 1000 rpm for an additional 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer to obtain the curable adhesive composition of the present invention. The equivalent ratio of maleimide groups to mercapto groups was 1.50:1.00.

[0141] Example 9 (Ex. 9) 60.86 g of TrisMI-1 was mixed with 0.4 g of 12S in a covered container. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (manufactured by FlackTek, Inc.). Then, 24.99 g of KARENZ MT BD1 was added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. Then, 5.00 g of EH-5057P and 5.00 g of HX-3722 were added and mixed at 1000 rpm for 5 minutes, followed by 3.75 g of TS 720 and mixing at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer, resulting in a curable adhesive composition of the present invention. The equivalent ratio of maleimide groups to mercapto groups was 1.22:1.00.

[0142] Comparative example 1 (CE.1) 37.54 g of SR 833S and 0.4 g of 12S were added to a covered container. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (manufactured by FlackTek, Inc.). Then, 35.72 g of KARENZ MTNR1 was added to the container and the mixture was mixed at 1000 rpm for 5 minutes. Then, 10.00 g of EH-5057P and 6.90 g of HX-3722 were added and mixed at 1000 rpm for 5 minutes, followed by the addition of 6.44 g of TS 720 and mixing at 1000 rpm for an additional 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer to obtain a curable adhesive composition.

[0143] Comparative example 2 (CE.2) 52.65 g of Ebecryl 3700 and 0.4 g of 12S were added to a covered container. The mixture was stirred at 2000 rpm for 10 minutes at room temperature in a Speedmixer DAC 150.1 FVZ-K (manufactured by FlackTek, Inc.). Then, 33.84 g of KARENZ MT NR1 was added to the container and the mixture was mixed at 1000 rpm for 5 minutes. Then, 5.00 g of EH-5057P and 3.91 g of HX-3722 were added and mixed at 1000 rpm for 5 minutes, followed by 1.20 g of TS 720 and mixing at 1000 rpm for an additional 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer to obtain a curable adhesive composition.

[0144] Comparative example 3 (CE.3) 19.46 g of SR 833S, 39.50 g of Ebecryl 3700, and 0.4 g of 12S were added to a covered container. The mixture was stirred at room temperature for 10 minutes at 2000 rpm in a Speedmixer DAC 150.1 FVZ-K (FlackTek, Inc.). 26.18 g of Multhiol Y4 was then added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. 7.00 g of EH-5057P and 3.30 g of HX-3722 were then added, and the mixture was mixed at 1000 rpm for 5 minutes. 4.16 g of TS 720 was then added, and the mixture was mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed from the homogeneous mixture using a Thinky ARV-310 mixer, resulting in a curable adhesive composition.

[0145] Comparative example 4 (CE.4) 46.46 g of BMI4 was mixed with 0.4 g of 12S in a covered container. The mixture was stirred at room temperature for 10 minutes at 2000 rpm in a Speedmixer DAC 150.1 FVZ-K (FlackTek, Inc.). 42.22 g of SMS-0421 was then added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. 5.00 g of EH-5057P and 3.50 g of HX-3722 were then added, and the mixture was mixed at 1000 rpm for 5 minutes. 2.42 g of TS 720 was then added, and the mixture was mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed using a Thinky ARV-310 mixer, and a curable adhesive composition was obtained. However, phase separation of the adhesive composition mixture was observed immediately after production.

[0146] Comparative example 5 (CE.5) 35.98 g of BMI4 was mixed with 11.98 g of TrisMI-1 in a covered container, and then 0.4 g of 12S was added. The mixture was stirred at room temperature for 10 minutes at 2000 rpm in a Speedmixer DAC 150.1 FVZ-K (FlackTek, Inc.). 44.21 g of SMS-042 was then added to the container, and the mixture was mixed at 1000 rpm for 5 minutes. 6.30 g of HX-3722 was then added, and the mixture was mixed at 1000 rpm for 5 minutes. 1.13 g of TS 720 was then added, and the mixture was mixed at 1000 rpm for another 5 minutes. Finally, air bubbles were removed using a Thinky ARV-310 mixer, and a curable adhesive composition was obtained. However, phase separation of the adhesive composition mixture was observed immediately after production.

[0147] [Test method:] (Die shear strength of adhesion to LCP substrate before hydrothermal aging:) From Ex.1 to Ex.4 and CE.1 and CE.2, the composition was obtained by measuring 3×3 mm 2The laminate was coated onto a glass top adherend at a thickness of 0.8 mm. The glass top adherend was then placed on an LCP substrate. Ten laminated samples were prepared for each composition. All laminated samples for each composition were cured under UV irradiation at a wavelength of 365 nm for 2 seconds, followed by heat curing in an oven at 70°C for 1 hour. No pressure was used. After curing, the die shear strength of five of the ten laminated samples for each composition was measured at 25°C using a DAGE4000 (Nordson Corporation). The five test values ​​were then averaged to determine the final die shear strength.

[0148] From Ex.5 to Ex.9 and CE.3 to CE.5, the composition is 2 The adhesive was coated onto an LCP (liquid crystal polymer) substrate at a thickness of 2 mm. Another LCP substrate was then completely covered with the curable adhesive layer. Ten laminated samples were prepared for each composition. All laminated samples were thermally cured in an oven at 70°C for 1 hour. No pressure was used. After curing, the die shear strength of five of the ten laminated samples for each composition was measured at 25°C using a DAGE4000 (Nordson Corporation). The five test values ​​were then averaged to determine the final die shear strength.

[0149] [Hydrothermal aging test:] After curing, another five laminated samples of each composition were placed in a temperature and humidity chamber SH-642 Benchtop (manufactured by ESPEC) at 85°C and 85% humidity for 120 hours.

[0150] [Die shear strength of adhesion to LCP substrate after hydrothermal aging:] After hydrothermal aging, the die shear strength of each sample was measured using a DAGE4000 (manufactured by Nordson Corporation) at 25° C. The five test values ​​were then averaged to obtain the final die shear strength.

[0151] [Retention rate calculated according to the following formula:] Retention rate = (die shear strength after hydrothermal aging - die shear strength before hydrothermal aging) / die shear strength before hydrothermal aging) × 100%

[0152] A retention rate of 0 or more is acceptable for Ex.1 to Ex.4 and CE.1 and CE.2, and a retention rate of 0 or more is acceptable for Ex.5 to Ex.9 and CE.3 to CE.5, preferably greater than 40%, more preferably greater than 70%, which means that the adhesive composition can withstand a hydrothermal environment.

[0153] The test results of the performance evaluation of the curable adhesive compositions of the present invention and the comparative examples are shown in Tables 1 and 2, respectively.

[0154] [Table 1]

[0155] The results in Table 1 showed that the curable adhesive composition containing the combination of the maleimide compound and the thiol compound exhibited excellent hydrothermal resistance properties, but without the maleimide compound, the curable adhesive composition could not withstand the hydrothermal test.

[0156] [Table 2]

[0157] The components of CE.4 and CE.5 cannot form a homogeneous adhesive composition that can be applied to a substrate, and therefore die shear strength cannot be measured.

[0158] The results in Table 2 showed that the thermosetting adhesive composition containing the combination of the maleimide compound (A) and the thiol compound (B) of the present invention exhibited excellent hydrothermal resistance properties, but without the maleimide compound, the thermosetting adhesive composition could not withstand the hydrothermal test.

[0159] While several preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims. The initial disclosure of this specification encompasses at least the following aspects. [1] (A) at least one maleimide compound; (B) at least one thiol compound having at least two mercapto groups and no siloxane group in the molecule; (C) at least one latent hardener; and (D) optionally, at least one photoradical polymerization initiator 1. A curable adhesive composition comprising: [2] The maleimide compound has the general formula (I): TIFF0007784439000013.tif4444 [wherein n is an integer of 2 or more, and X is an aromatic group or an aliphatic group] The composition according to [1], [3] The maleimide compound has the formula (II): TIFF0007784439000014.tif4460 [where, X 1 is selected from linear or branched alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, cycloalkenylene, cycloalkylarylene, biphenylene, heterocycloalkylene, or heterocycloarylene having 1 to 36 carbon atoms and optionally containing at least one carbonyl group, carboxyl group, amide group, carbamate group, urea group, ester group, ether group, and combinations thereof. The composition according to [1] or [2], wherein the bismaleimide has the formula: [4] The composition according to any one of [1] to [3], wherein at least one thiol compound has at least three mercapto groups, more preferably at least four mercapto groups, in the molecule. [5] At least one thiol compound is C 1- C 36 aliphatic group, C 4- C 36 Alicyclic group, C 6- C 40 The composition according to any one of [1] to [4], comprising at least two mercapto groups bonded to a divalent linking unit selected from an aromatic group, a urethane group, an imide group, a carbonyl group, a carboxyl group, an amide group, a carbamate group, a urea group, an ester group, an ether group, a poly(butadiene) group, a polycarbonate group, a polyurethane group, a polyether group, a polyester group, and combinations thereof. [6] The divalent linking unit is a C containing one or more ether groups. 12- C 36 The composition according to [5], wherein the group is an aliphatic group. [7] Thiol compounds include 3,3'-[[2,2-bis[(3-mercaptopropoxy)methyl]propane-1,3-diyl]dioxy]bis(propane-1-thiol), 1-[3-(2-sulfanylpropoxy)-2,2-bis(2-sulfanylpropoxymethyl)propoxy]propane-2-thiol, 3-[2-(methoxymethyl)-3-(3-sulfanylpropoxy)-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol, 2-(sulfanylmethyl)-2-[[3- Sulfanyl-2-[[3-sulfanyl-2,2-bis(sulfanylmethyl)propoxy]methyl]-2-(sulfanylmethyl)propoxy]methyl]propane-1,3-dithiol, 2-[3-(2-sulfanylethoxy)-2,2-bis(2-sulfanylethoxymethyl)propoxy]ethanethiol, 2-[2-[3-[2-(2-sulfanylethoxy)ethoxy]-2,2-bis[2-(2-sulfanylethoxy)ethoxymethyl]propoxy]ethoxy]ethanethiol, 3-[2-(butanoic acid) 3-[2-[2-(2-sulfanylethoxy)ethoxymethyl]-2-(2-sulfanylethylperoxymethyl)-3-(3-sulfanylpropoxy)propoxy]propane-1-thiol, 3-[2-(2-sulfanylethoxy)ethoxymethyl]-2-(2-sulfanylethylperoxymethyl)-3-(3-sulfanylpropoxy)propoxy]propane-1-thiol, 3-[2-(2-sulfanylethylperoxymethyl)-3-(3-sulfanylpropoxy)-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol ol, 3-[3-(3-sulfanylpropoxy)-2-[[3-(3-sulfanylpropoxy)-2,2-bis(3-sulfanylpropoxymethyl)propoxy]methyl]-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol, 2-[3-(2-sulfanylethoxy)-2-[[3-(2-sulfanylethoxy)-2,2-bis(2-sulfanylethoxymethyl)propoxy]methyl]-2-(2-sulfanylethoxymethyl)propoxy]ethanethiol, 3-[2,The composition according to [6], wherein the hydroxyl group is selected from 2-bis[2-(2-sulfanylethoxy)ethoxymethyl]-3-(2-sulfanylethylperoxy)propoxy]propane-1-thiol, 3-[2-[3-[2-(3-sulfanylpropoxy)ethoxy]-2,2-bis[2-(3-sulfanylpropoxy)ethoxymethyl]propoxy]ethoxy]propane-1-thiol, O-[3-(3-sulfanylpropanethioyloxy)-2-[[3-(3-sulfanylpropanethioyloxy)-2,2-bis(3-sulfanylpropanethioyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanethioyloxymethyl)propyl]3-sulfanylpropanethioate, and combinations thereof. [8] The bivalent linking unit is C 4- C 36 C is selected from cycloalkylene, bicycloalkylene, tricycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, cycloalkenylene, cycloalkylarylene, biphenylene, heterocycloalkylene, heterocycloarylene, and combinations thereof. 4- C 36 Alicyclic group or C 6- C 40 The composition according to [5], wherein the group is an aromatic group. [9] Thiol compounds include 1,3,4,6-tetra(2-mercaptoethyl)octahydroimidazo[4,5-d]imidazole-2,5-dione, 1,3,4,6-tetrakis(3-sulfanylpropyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione, 3a-methyl-1,3,4,6-tetrakis(2-sulfanylethyl)-6aH-imidazo[4,5-d]imidazole-2,5-dione, and 1,3,4,6-tetrakis(2- The composition according to [8], wherein the hydroxybenzoate is selected from the group consisting of 1,6-dipropyl-3,4-bis(2-sulfanylethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione, 1,6-dipropyl-3,4-bis(2-sulfanylethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione, 6-propyl-1,3,4-tris(2-sulfanylethyl)-3a,6a-dihydro-2H-imidazo[4,5-d]imidazol-5-one, and combinations thereof.

[10] The composition according to any one of [1] to [9], wherein the ratio of the maleimide equivalent in component (A) to the mercapto equivalent in component (B) is 0.2 to 1.8, preferably 1.0 to 1.5.

[11] The composition according to any one of [1] to

[10] , wherein the latent curing agent is selected from an imidazole compound, an amine adduct obtained by a reaction product of an amine compound with an epoxy compound, an isocyanate compound, and / or a urea compound, a core-shell type latent curing agent, a masterbatch type latent curing agent, and a combination thereof.

[12] The composition according to any one of [1] to

[11] , wherein the photoradical polymerization initiator is selected from hydrogen abstraction photoradical polymerization initiators, including benzil dimethyl ketal, benzoin ether, hydroxyalkyl phenyl ketone, benzoylcyclohexanol, dialkoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, trimethylbenzoylphosphine oxide, methylthiophenyl morpholinoketone, and morpholinophenyl aminoketone; and “alpha-cleavage type” photoradical polymerization initiators, including coinitiators based on benzophenone, thioxanthone, benzil, camphorquinone, ketocoumarin, and combinations thereof.

[13] The composition according to any one of [1] to

[12] , further comprising component (E): at least one acrylic resin selected from acrylic acid ester monomers, methacrylic acid ester monomers, or oligomers thereof.

[14] The composition according to any one of [1] to

[13] , wherein component (A) is present in an amount of 10 to 80% by weight, preferably 20 to 70% by weight, based on the total weight of the composition.

[15] The composition according to any one of [1] to

[14] , wherein component (B) is present in an amount of 15% by weight to 70% by weight, preferably 15% by weight to 40% by weight, based on the total weight of the composition.

[16] The composition according to any one of [1] to

[15] , wherein component (C) is present in an amount of 5% by weight to 20% by weight, preferably 5% by weight to 15% by weight, based on the total weight of the composition.

[17] The composition according to any one of [1] to

[16] , wherein component (D) is present in an amount of 0 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the composition.

[18] The composition according to any one of [1] to

[17] , wherein component (E) is present in an amount of 0 to 35% by weight, preferably 15 to 25% by weight, based on the total weight of the composition.

[19] First base material, Cured adhesive, and A second substrate bonded to a first substrate via a cured adhesive obtained from the curable adhesive composition according to any one of [1] to

[18] . Including, goods.

[20] An electronic device comprising an article according to

[19] or an article manufactured using the curable adhesive composition according to any one of [1] to

[18] .

[21] Use of the curable adhesive composition according to any one of [1] to

[18] or the article according to

[19] in the manufacture of an electronic device.

Claims

1. (A) at least one maleimide compound; (B) at least one thiol compound having at least two mercapto groups and no siloxane group in the molecule; (C) at least one latent curing agent; and (D) optionally, at least one photoradical polymerization initiator 1. A curable adhesive composition comprising: the at least one thiol compound comprises at least two mercapto groups bonded to a divalent linking unit, the divalent linking unit being a C 12 -C 36 aliphatic group containing one or more ether groups; A curable adhesive composition.

2. Maleimide compounds have the general formula (I): 【Chemistry 1】 [wherein n is an integer of 2 or more, and X is an aromatic group or an aliphatic group] 10. The composition of claim 1, wherein

3. The maleimide compound has the formula structure (II): 【Chemistry 2】 [In the formula, X １ is selected from linear or branched alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, cycloalkenylene, cycloalkylarylene, biphenylene, heterocycloalkylene, or heterocycloarylene having 1 to 36 carbon atoms and optionally containing at least one carbonyl group, carboxyl group, amide group, carbamate group, urea group, ester group, ether group, and combinations thereof.

3. The composition of claim 1, wherein the bismaleimide is a bismaleimide having the formula:

4. The composition according to any one of claims 1 to 3, wherein at least one thiol compound has at least three mercapto groups in the molecule.

5. The thiol compounds include 3,3'-[[2,2-bis[(3-mercaptopropoxy)methyl]propane-1,3-diyl]dioxy]bis(propane-1-thiol), 1-[3-(2-sulfanylpropoxy)-2,2-bis(2-sulfanylpropoxymethyl)propoxy]propane-2-thiol, 3-[2-(methoxymethyl)-3-(3-sulfanylpropoxy)-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol, 2-(sulfanylmethyl)-2-[[3-sulfanyl 2-[[3-sulfanyl-2,2-bis(sulfanylmethyl)propoxy]methyl]-2-(sulfanylmethyl)propoxy]methyl]propane-1,3-dithiol, 2-[3-(2-sulfanylethoxy)-2,2-bis(2-sulfanylethoxymethyl)propoxy]ethanethiol, 2-[2-[3-[2-(2-sulfanylethoxy)ethoxy]-2,2-bis[2-(2-sulfanylethoxy)ethoxymethyl]propoxy]ethoxy]ethanethiol, 3-[2-(butoxy) Methyl)-3-(3-sulfanylpropoxy)-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol, 3-[2-[2-(2-sulfanylethoxy)ethoxymethyl]-2-(2-sulfanylethylperoxymethyl)-3-(3-sulfanylpropoxy)propoxy]propane-1-thiol, 3-[2-(2-sulfanylethylperoxymethyl)-3-(3-sulfanylpropoxy)-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol 3-[3-(3-sulfanylpropoxy)-2-[[3-(3-sulfanylpropoxy)-2,2-bis(3-sulfanylpropoxymethyl)propoxy]methyl]-2-(3-sulfanylpropoxymethyl)propoxy]propane-1-thiol, 2-[3-(2-sulfanylethoxy)-2-[[3-(2-sulfanylethoxy)-2,2-bis(2-sulfanylethoxymethyl)propoxy]methyl]-2-(2-sulfanylethoxymethyl)propoxy]ethanethiol, 3-[2,The composition of any one of claims 1 to 4, wherein the hydroxyl group is selected from 2-bis[2-(2-sulfanylethoxy)ethoxymethyl]-3-(2-sulfanylethylperoxy)propoxy]propane-1-thiol, 3-[2-[3-[2-(3-sulfanylpropoxy)ethoxy]-2,2-bis[2-(3-sulfanylpropoxy)ethoxymethyl]propoxy]ethoxy]propane-1-thiol, O-[3-(3-sulfanylpropanethioyloxy)-2-[[3-(3-sulfanylpropanethioyloxy)-2,2-bis(3-sulfanylpropanethioyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanethioyloxymethyl)propyl]3-sulfanylpropanethioate, and combinations thereof.

6. 6. The composition according to claim 1, wherein the ratio of the maleimide equivalents in component (A) to the mercapto equivalents in component (B) is 0.2 to 1.

8.

7. The composition according to any one of claims 1 to 6, wherein the latent curing agent is selected from an imidazole compound, an amine adduct obtained by a reaction product of an amine compound with an epoxy compound, an isocyanate compound, and / or a urea compound, a core-shell type latent curing agent, a masterbatch type latent curing agent, and a combination thereof.

8. 8. The composition of claim 1, wherein the photoradical polymerization initiator is selected from hydrogen abstraction photoradical polymerization initiators, including benzil dimethyl ketal, benzoin ether, hydroxyalkyl phenyl ketone, benzoylcyclohexanol, dialkoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, trimethylbenzoylphosphine oxide, methylthiophenyl morpholinoketone, and morpholinophenyl aminoketone; photoradical polymerization initiators, and "alpha-cleavage type" photoradical polymerization initiators, including coinitiators based on benzophenone, thioxanthone, benzil, camphorquinone, ketocoumarin, and combinations thereof.

9. The composition of any one of claims 1 to 8, wherein the composition further comprises component (E): at least one acrylic resin selected from acrylate ester monomers, methacrylate ester monomers, or oligomers thereof.

10. The composition of any of claims 1 to 9, wherein component (A) is present in an amount of 10 to 80 wt%, based on the total weight of the composition.

11. The composition of any of claims 1 to 10, wherein component (B) is present in an amount of 15% to 70% by weight based on the total weight of the composition.

12. The composition of any of claims 1 to 11, wherein component (C) is present in an amount of 5 wt% to 20 wt%, based on the total weight of the composition.

13. The composition of any of claims 1 to 12, wherein component (D) is present in an amount of 0 to 5 wt%, based on the total weight of the composition.

14. 14. The composition according to any one of claims 1 to 13, wherein the content of component (E): at least one acrylic resin selected from an acrylic acid ester monomer, a methacrylic acid ester monomer, or an oligomer thereof is 0 to 35 wt% based on the total weight of the composition.

15. first base material, Cured adhesive, and A second substrate bonded to a first substrate via a cured adhesive obtained from the curable adhesive composition of any one of claims 1 to 14. Including, goods.

16. An electronic device comprising an article according to claim 15 or an article manufactured using the curable adhesive composition according to any one of claims 1 to 14.

17. Use of the curable adhesive composition according to any one of claims 1 to 14 or the article according to claim 15 in the manufacture of an electronic device.

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