Curing agent composition, container accommodating same, thermally curable composition kit, method for producing thermally curable composition, cured product of thermally curable composition, and method for transporting and storing curing agent composition

Abstract

The present invention addresses the problem of providing: a thiol-based curing agent composition which can be used in a two-part or multi-part thermally curable composition for a semiconductor device or an electronic component; a container in which the thiol-based curing agent composition is accommodated; a thermally curable composition kit; a method for producing a thermally curable composition; a cured product of a thermally curable composition; and a method for transporting and storing a thiol-based curing agent composition.　Provided are: a curing agent composition containing (A) a thiol compound having no ester bond, (B) a thermally latent curing catalyst, and (C) water, wherein the content of the water (C) in the curing agent composition is 10-15,000 ppm; a container in which the curing agent composition is accommodated; a thermally curable composition kit; a method for producing a thermally curable composition; a cured product of a thermally curable composition; and a method for transporting and storing a curing agent composition.

Description

Curing agent composition, container containing the same, thermosetting composition kit, method for producing thermosetting composition, cured product of thermosetting composition, and method for transporting and storing curing agent composition

[0001] The present invention relates to a curing agent composition, a container containing the curing agent composition, a thermosetting composition kit, a method for producing a thermosetting composition, a cured product of the thermosetting composition, and a method for transporting and storing the curing agent composition.

[0002] BACKGROUND ART Currently, adhesives, sealants, etc. containing curable resin compositions are often used in the assembly and mounting of semiconductor devices and electronic components, such as semiconductor chips, for the purpose of maintaining reliability.

[0003] One-component adhesives or sealants for semiconductor devices or electronic components require low-temperature curing properties and moisture resistance, and it is known to use thiol-based curing agents that do not have ester bonds. Furthermore, one-component adhesives or sealants are sometimes supplied in syringes so that they can be applied to specific, minute locations on the target object. The syringe-filled adhesives or sealants may be frozen at temperatures below 0°C during storage or transportation to maintain the stability of the adhesives or sealants (see, for example, Patent Document 1).

[0004] Japanese Patent Application Laid-Open No. 2020-127919

[0005] When using an adhesive or sealant filled in a syringe and frozen, the frozen syringe filled with the adhesive or sealant is thawed, the thawed adhesive or sealant is used, and the empty syringe is discarded after use. Recently, in light of carbon neutral initiatives, environmental issues, and the like, there has been an urgent need to reduce the amount of syringe waste and the high transportation and storage energy required due to refrigeration. Furthermore, for long-distance transportation, transportation by ship or rail is being considered as an alternative to airplanes, which require high transportation energy. Based on these requirements, a two-component or multi-component thiol-based curable composition is desired that can be transported and stored for long periods at room temperature (20°C ± 15°C) and in a large-volume container.

[0006] Currently, the industrial use of two-component or multi-component thiol-based curing compositions, which can be transported and stored at room temperature for long periods of time in large-volume containers, is primarily limited to the field of civil engineering adhesives. From the standpoint of storage stability, the curing catalyst is not included in the base composition, but in the case of two-component adhesives, the curing catalyst is included in the curing agent composition. Unlike two-component or multi-component adhesives for civil engineering applications, which are applied over a wide area and cured at room temperature, two-component or multi-component thermosetting compositions for semiconductor devices or electronic components are prepared by gradually removing the base composition and the thiol-based curing agent composition from a container, mixing them, applying them to a small area, and then heating them for use. To obtain a high-quality cured product, the thiol-based curing agent composition must have a curing catalyst dispersed therein. Furthermore, two-component or multi-component thermosetting compositions for semiconductor devices or electronic components must have a long usable life after mixing with the base composition. In particular, in order to improve dischargeability by lowering the viscosity, the coating device typically heats the thermosetting composition (for example, to 30 to 50°C) when discharging, and the thermosetting composition is required to have a long usable life when heated. Furthermore, it is anticipated that the thermosetting composition may be left heated for a long period of time due to production problems, and from this perspective, a long usable life when heated is also required.

[0007] In view of the above-mentioned problems, an object of the present invention is to provide a thiol-based curing agent composition that can be used in a two-component or multi-component thermosetting composition for semiconductor devices or electronic components, a container containing the thiol-based curing agent composition, a thermosetting composition kit, a method for producing the thermosetting composition, a cured product of the thermosetting composition, and a method for transporting and storing the thiol-based curing agent composition.

[0008] Specific means for solving the above problems are as follows. Aspects of the present invention include the following curing agent composition, a container containing the curing agent composition, a thermosetting composition kit, a method for producing a thermosetting composition, a cured product of the thermosetting composition, and a method for transporting and storing the curing agent composition. [1] A curing agent composition comprising: (A) a thiol compound having no ester bond; (B) a thermally latent curing catalyst; and (C) water, wherein the content of the water (C) in the curing agent composition is 10 to 15,000 ppm. [2] The curing agent composition according to [1], wherein the rate of change in the injection distance of the curing agent composition into a 100 μm gap between glass plates after standing at 22°C for 2 hours is 10% or less before and after storing the curing agent composition in an oven set at 40°C in an environment of 22°C and 50% RH for 94 hours. [3] The curing agent composition according to [1] or [2], which is contained in a container having a volume of 3 L or more. [4] The curing agent composition according to any one of [1] to [3] above, which is to be mixed with a base composition after transportation and storage at a temperature above 0°C. [5] The curing agent composition according to any one of [1] to [4] above, wherein the base in the base composition is selected from the group consisting of epoxy compounds and compounds having a group containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule. [6] A container containing the curing agent composition according to any one of [1] to [5] above, wherein the container has a volume of 0.3 L or more. [7] A thermosetting composition kit having the curing agent composition according to any one of [1] to [5] above and a base composition, each in an independent form. [8] A method for producing a thermosetting composition, comprising mixing the curing agent composition according to any one of [1] to [5] above with a base composition. [9] A method for producing a thermosetting composition, comprising mixing the curing agent composition and the base composition in the thermosetting composition kit according to [7] above.

[10] A cured product obtained by curing a thermosetting composition containing the curing agent composition and a base composition according to any one of [1] to [5] above.

[11] A cured product obtained by curing a thermosetting composition containing the curing agent composition and the base composition in the thermosetting composition kit according to [7] above.

[12] A method for transporting and storing a curing agent composition, comprising: keeping a container containing the curing agent composition according to any one of [1] to [5] above at a temperature exceeding 0°C; and maintaining the content of the water (C) in the curing agent composition at 10 to 15,000 ppm.

[0009] According to aspects of the present invention, there are provided a curing agent composition that can be used in two-component or multi-component thermosetting compositions for semiconductor devices or electronic components, a container containing the curing agent composition, a thermosetting composition kit, a method for producing the thermosetting composition, a cured product of the thermosetting composition, and a method for transporting and storing the curing agent composition. More specifically, the following are provided: A curing agent composition is provided that can provide a thermosetting composition in which a thermal latent curing catalyst is dispersed and that has a long pot life after mixing with a base composition, particularly a long pot life when heated (e.g., 30 to 50°C). A container containing the curing agent composition and a thermosetting composition kit are provided that can be transported and stored for long periods at room temperature and are suitable for long-distance transportation by ship or the like. A method for producing a thermosetting composition and a cured product thereof that can be produced using the curing agent composition and have a long pot life, particularly a long pot life when heated (e.g., 30 to 50°C). A method for transporting and storing the curing agent composition is also provided that does not require refrigerated transportation or frozen storage and allows transportation and storage at room temperature.

[0010] In this specification, following the convention in the field of synthetic resins, the term "resin," which normally refers to a polymer (especially a synthetic polymer), may be used to refer to components constituting a thermosetting composition before heat curing, even though the components are not polymers. In this specification, "useable time" or "pot life" refers to the time during which a two-component or multi-component thermosetting composition remains usable after preparation. In this specification, "room temperature" refers to 20°C ± 15°C, as specified in JIS Z 8703. In this specification, "temperatures above 0°C" refers to the temperature range from 0°C to room temperature, and does not refer to the temperature range required for frozen transportation or frozen storage.

[0011] [Curing Agent Composition] One aspect of the present invention provides a curing agent composition comprising: (A) a thiol compound having no ester bond; (B) a thermally latent curing catalyst; and (C) water, wherein the content of the water (C) in the curing agent composition is 10 to 15,000 ppm. According to this aspect, a curing agent composition is provided that can be used in two-component or multi-component thermosetting compositions for semiconductor devices or electronic components. That is, the curing agent composition is provided in which a thermally latent curing catalyst is dispersed, thereby providing a thermosetting composition having a long pot life after mixing with a base composition, particularly a long pot life when heated (e.g., 30 to 50°C). To provide a thermosetting composition having a long pot life when mixed with a base composition, it is desirable for the curing catalyst to be dispersed in the curing agent composition. As a result of extensive research, the present inventors have surprisingly found that the inclusion of (C) water in the presence of (A) a thiol compound having no ester bond and (B) a thermal latent curing catalyst effectively suppresses aggregation of the (B) thermal latent curing catalyst and allows it to be dispersed in the curing agent composition. This is thought to be because, due to the difference in polarity between the two, the (B) thermal latent curing catalyst has low affinity for the (A) thiol compound having no ester bond, and therefore (C) water acts on the interface between the (A) thiol compound having no ester bond and the (B) thermal latent curing catalyst, improving affinity. On the other hand, it has been found that when the amount of (C) water in the curing agent composition exceeds a certain amount, the thermosetting composition after mixing with the base composition is prone to aggregate formation or gelation, especially when heated. Two-component or multi-component curable compositions for semiconductor devices or electronic components are applied to small areas, so dispensers such as jet dispensers and air dispensers are used for microapplication. From the viewpoint of the fluidity of the thermosetting composition, when the thermosetting composition is applied, the nozzle of an application device such as a dispenser is often heated to, for example, 30 to 50° C. Such aggregates and gels are likely to cause clogging in narrow areas when the thermosetting composition is applied, and deteriorate the dischargeability from the nozzle of the application device and the injection ability into narrow gaps, which ultimately shortens the usable life of the thermosetting composition, particularly the usable life when heated (for example, 30 to 50° C.).This problem was solved by setting the content of (C) water in the curing agent composition to 15,000 ppm or less.

[0012] (A) Thiol Compound Having No Ester Bond The curing agent composition of this embodiment contains (A) a thiol compound having no ester bond (hereinafter also referred to as "component (A)"). In a thiol compound having an ester bond, hydrolysis may occur due to the presence of an ester group. On the other hand, component (A) does not have an ester bond, and therefore hydrolysis can be suppressed. In this embodiment, (A) the thiol compound having no ester bond is a polyfunctional thiol compound having no ester bond and two or more thiol groups, and can react with the main component described below. In this embodiment, (A) the thiol compound having no ester bond preferably has three or more thiol groups, and more preferably has three and / or four thiol groups. In one embodiment, (A) the thiol compound having no ester bond contains a combination of a thiol compound having two thiol groups and a thiol compound having three or more thiol groups. The thiol equivalent of the (A) ester bond-free thiol compound is preferably 90 to 200 g / eq, more preferably 90 to 150 g / eq, even more preferably 90 to 140 g / eq, and particularly preferably 90 to 130 g / eq.

[0013] Examples of (A) thiol compounds having no ester bond include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, uril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol trippropanethiol, 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropyloxy)-3a,6a-diphenylglycoluril, tris(2-mercaptoethyl)isocyanurate, tris(3-mercaptopropyl)isocyanurate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol trippropanethiol, 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropyloxy)-3a,6a-diphenylglycoluril, ) propane, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, pentaerythritol tetrapropanethiol, 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-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)propane tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio) tris(4,4-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,1 2,16-Hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5 -mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethyl Examples of bifunctional thiol compounds disclosed in WO 2019 / 082962 include, but are not limited to, thiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2,2'-[cyclohexylidenebis(thio-2,1-ethanediylthio)]bis[ethanethiol], and 4,4'-[(1,3-phenylene)bis(oxy)]bis[1-butanethiol], as well as dimers, trimers, and tetramers of the above thiol compounds. These may be used alone or in combination of two or more.

[0014] The content of the thiol compound (A) having no ester bond in the curing agent composition is preferably 30 to 99% by mass relative to the total mass of the components (A) to (C) and the optional polyfunctional thiol compound having an ester bond described below in the curing agent composition. In one embodiment, the content of the thiol compound (A) having no ester bond in the curing agent composition is preferably 40 to 99% by mass, more preferably 50 to 99% by mass, and even more preferably 60 to 99% by mass relative to the total mass of the components (A) to (C) and the optional polyfunctional thiol compound having an ester bond described below in the curing agent composition.

[0015] The curing agent composition of this embodiment may contain a polyfunctional thiol compound having an ester bond, as long as the effects of the present invention are not impaired. Examples of polyfunctional thiol compounds having an ester bond include condensates of any of 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 3,3-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid, thioglycolic acid, and thiomalic acid with alcohols, and other compounds. Specific examples include trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), butanediol bisthioglycolate, hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, and pentaerythritol. Examples of suitable thiol compounds include, but are not limited to, tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. These compounds may be used alone or in combination of two or more. From the viewpoint of the hydrolysis resistance of the cured product of the thermosetting composition, the content of the polyfunctional thiol compound having an ester bond in the curing agent composition is preferably less than 100% by mass, more preferably less than 85% by mass, even more preferably less than 45% by mass, and particularly preferably less than 30% by mass, relative to 100% by mass of the thiol compound (A) not having an ester bond. In some embodiments, the curing agent composition is substantially free of a polyfunctional thiol compound having an ester bond.

[0016] (B) Thermal Latent Curing Catalyst The curing agent composition of this embodiment contains (B) a thermal latent curing catalyst (hereinafter also referred to as "component (B)"). In this specification, a "thermal latent curing catalyst" refers to a basic catalyst, a compound or substance that is inactive at room temperature but is activated by heating to function as a polymerization catalyst. Examples of thermal latent curing catalysts include amine compounds that are solid at room temperature; amine adduct-based thermal latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts) and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts); microencapsulated thermal latent curing catalysts; and solid-dispersed thermal latent curing catalysts such as inclusion-type thermal latent curing catalysts. Amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

[0017] Examples of amine compounds that are solid at room temperature include dicyandiamide, 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-methyl-1-imidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine, and 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine. Examples of the alkyl acrylate include, but are not limited to, triazine-isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.

[0018] The amine compound used as one of the raw materials for producing the amine adduct-based thermal latent curing catalyst may be any compound as long as it has one or more active hydrogen atoms in the molecule capable of addition reacting with an epoxy group or an isocyanate group, and at least one functional group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. Examples of such amine compounds include, in addition to the above-mentioned amine compounds that are solid at room temperature, 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 amine compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine. However, the present invention is not limited to these.

[0019] Among these, compounds having a tertiary amino group in the molecule and imidazole derivatives are particularly useful as raw materials that provide thermally latent curing catalysts with excellent curing acceleration capabilities.Examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, as well as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole. imidazole compounds such as phenyl-4-methylimidazole and 1-(2-aminoethyl)-2-methylimidazole; 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 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, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, benzimidazole, 2 Examples of the tertiary amino acid include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group or an imidazole skeleton in the molecule, such as N,N-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, and isonicotinic acid hydrazide.

[0020] Examples of epoxy compounds used as one of the raw materials for producing the amine-epoxy adduct thermal latent curing catalyst include, but are not limited to, polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl amine compounds obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane or m-aminophenol; and polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, various phenylphenol glycidyl ethers, and glycidyl methacrylate.

[0021] Examples of the isocyanate compound used as one of the raw materials for producing the amine-urea adduct thermal latent curing catalyst include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

[0022] Examples of urea compounds used as one of the raw materials for producing the amine-urea adduct thermal latent curing catalyst include, but are not limited to, urea and thiourea.

[0023] Amine adduct thermally latent curing catalysts are, for example, a combination of the two components (a) an amine compound and an epoxy compound, (b) a combination of the two components and an active hydrogen compound, or (c) a combination of two or three components (an amine compound and an isocyanate compound and / or a urea compound). These can be easily prepared by mixing the components, reacting them at a temperature between room temperature and 200°C, cooling them to solidify them, and then pulverizing them, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0024] A microcapsule-type thermally latent curing catalyst is a curing catalyst having a core made of an amine compound or an amine adduct compound obtained by reacting an amine compound with an epoxy compound, an isocyanate compound, or a urea compound, and coated with a shell made of a synthetic resin or an inorganic oxide. Examples of the amine compound include the amine compounds described above. Because the amine compound exhibits favorable latency, it is preferable that the amine compound be an imidazole derivative. Examples of imidazole derivatives include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Examples of synthetic resins that form the shell include phenolic resins, melamine resins, epoxy resins, urethane resins, and urea resins, and these resins can also be used in combination. Examples of inorganic oxides that form the shell include silica, alumina, titania, and magnesia.

[0025] Representative examples of commercially available thermal latent curing catalysts include, but are not limited to, the following: Amine-epoxy adduct curing catalysts include "Amicure PN-23" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (product name of ACR Co., Ltd.), "Hardener X-3670S" (product name of ACR Co., Ltd.), "Novacure HX-3742" (product name of Asahi Kasei Corporation), and "Novacure Examples of the hydroxybenzoates include, but are not limited to, "Novacure HX-3721" (product name of Asahi Kasei Corporation), "Novacure HXA9322HP" (product name of Asahi Kasei Corporation), "Novacure HXA3922HP" (product name of Asahi Kasei Corporation), "Novacure HXA3932HP" (product name of Asahi Kasei Corporation), "Novacure HXA5945HP" (product name of Asahi Kasei Corporation), "Novacure HXA5911HP" (product name of Asahi Kasei Corporation), and "Novacure HXA9382HP" (product name of Asahi Kasei Corporation). Examples of the amine-urea adduct curing catalyst include, but are not limited to, "Fujicure FXE-1000" (product name of T&K TOKA Corporation), "Fujicure FXR1020" (product name of T&K TOKA Corporation), "Fujicure FXR-1030" (product name of T&K TOKA Corporation), "Fujicure FXR1121" (product name of T&K TOKA Corporation), "Fujicure FXR1081" (product name of T&K TOKA Corporation), "Fujicure 1061" (product name of T&K TOKA Corporation), and "Fujicure 1171" (product name of T&K TOKA Corporation).

[0026] An inclusion-type thermally latent curing catalyst is a curing catalyst having a structure in which guest molecules such as amine compounds are confined at the molecular level in crystalline spaces formed by host molecules. An example of a commercially available inclusion-type thermally latent curing catalyst is "NISSOCURE TIC-188" (product name of Nippon Soda Co., Ltd.).

[0027] The thermal latent curing catalyst (B) may be used alone or in combination of two or more.

[0028] The content of the thermal latent curing catalyst (B) in the curing agent composition is preferably 0.1 to 70 mass% based on the total mass of the curing agent composition. In one embodiment, the content of the thermal latent curing catalyst (B) in the curing agent composition is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, based on the total mass of the curing agent composition excluding any solid components such as a filler described below.

[0029] (C) Water The curing agent composition of this embodiment contains (C) water (hereinafter also referred to as "component (C)"), and the content of the (C) water in the curing agent composition is 10 to 15,000 ppm, preferably 100 to 14,000 ppm, and more preferably 1,000 to 13,000 ppm.

[0030] Recently, in light of carbon neutrality efforts, environmental issues, etc., there has been a growing demand for two-component or multi-component thermosetting compositions that can be transported and stored at room temperature for long periods of time and in large-capacity containers. Currently, the industrial use of two-component or multi-component thiol-based thermosetting compositions that can be transported and stored at room temperature for long periods of time and in large-capacity containers is primarily limited to the field of civil engineering adhesives. Unlike two-component or multi-component civil engineering adhesives that are applied to large areas and cured at room temperature, two-component or multi-component thermosetting compositions for semiconductor devices or electronic components are prepared by gradually removing a base composition and a thiol-based curing agent composition from a container, mixing them, applying them to a small area, and then heating them for use. To obtain a high-quality cured product, the thiol-based thermosetting agent composition is required to have a curing catalyst dispersed therein. Furthermore, two-component or multi-component thermosetting compositions for semiconductor devices or electronic components are required to have a long usable time from mixing with the base composition until application. In particular, to improve dischargeability and injectability by reducing viscosity, coating devices typically heat the thermosetting composition (e.g., to 30 to 50°C) when discharging, and the thermosetting composition is required to have a long usable life when heated. Furthermore, it is anticipated that the thermosetting composition may be left heated for long periods of time due to production issues, and for this reason, a long usable life when heated is also required. In the curing agent composition of this embodiment, the inclusion of (C) water in the presence of (A) a thiol compound having no ester bond and (B) a thermally latent curing catalyst facilitates suppression of aggregation of the (B) thermally latent curing catalyst, and the (B) thermally latent curing catalyst is dispersed in the curing agent composition. This is thought to be because, due to the difference in polarity between the two, the (B) thermally latent curing catalyst has low affinity for the (A) thiol compound having no ester bond, and therefore (C) water acts on the interface between the (A) thiol compound having no ester bond and the (B) thermally latent curing catalyst, improving affinity. In the curing agent composition of this embodiment, the thermal latent curing catalyst (B) is dispersed. Therefore, when a thermosetting composition is produced by taking out the curing agent composition little by little from a storage container and mixing it with a base composition, a high-quality cured product can be provided.From the viewpoint of dispersibility of the (B) thermal latent curing catalyst in the curing agent composition, the content of (C) water in the curing agent composition is 10 ppm or more, preferably 100 ppm or more, and more preferably 1000 ppm or more. On the other hand, if the amount of (C) water in the curing agent composition exceeds a certain amount, the thermosetting composition after mixing with the base composition is likely to generate aggregates or gel, particularly when heated. Two-component or multi-component thermosetting compositions for semiconductor devices or electronic components are applied to minute areas, so dispensers such as jet dispensers and air dispensers are used for minute application. From the viewpoint of the flowability of the thermosetting composition, the nozzle of an application device such as a dispenser is often heated to, for example, 30 to 50°C when applying the thermosetting composition. Such aggregates and gels are likely to cause clogging in narrow areas during application of the thermosetting composition, impairing the ability to be discharged from the nozzle of the application device and to be poured into narrow gaps, ultimately shortening the usable time of the thermosetting composition, particularly when heated (e.g., 30 to 50°C). This problem is resolved by ensuring that the content of (C) water in the curing agent composition is 15,000 ppm or less. The content of (C) water in the curing agent composition is preferably 14,000 ppm or less, and more preferably 13,000 ppm or less. Furthermore, when a thiol compound having an ester bond is used as the only thiol compound in the curing agent composition, even if water is added in an amount approximately equal to that of the curing agent composition of this embodiment, the water in the system is consumed by hydrolysis, generating a carboxylic acid. Because the carboxylic acid acts as a stabilizer for the (B) thermal latent curing catalyst, the problem specific to the present application, namely, the tendency for aggregate formation or gelation to occur in the thermosetting composition after mixing with the base composition, especially when heated, is unlikely to occur.

[0031] In the curing agent composition, (C) water may be intentionally added or may be incorporated into the curing agent composition by moisture absorption. The (B) thermally latent curing catalyst has a highly polar basic group and therefore has affinity for highly polar water molecules. In particular, when the (B) thermally latent curing catalyst is an amine compound, it exhibits high hydrophilicity. Furthermore, when the (B) thermally latent curing catalyst is an amine adduct-based thermally latent polymerization catalyst, such as a reaction product of an amine compound with an epoxy compound (amine-epoxy adduct) or a reaction product of an amine compound with an isocyanate compound or a urea compound (urea adduct), hydrophilic groups such as hydroxyl groups and urea bonds in the adduct further enhance hydrophilicity. Therefore, once (C) water is incorporated into the curing agent composition by addition or moisture absorption, it is less likely to be released from the surface of the (B) thermally latent curing catalyst, even when stored for a long period of time in a low-humidity environment, and evaporation from the curing agent composition is suppressed. On the other hand, due to the hydrophilicity of the (B) thermal latent curing catalyst, the curing agent composition is prone to absorbing water from the environment (this can occur particularly during transportation in hot and humid environments such as Japan and Southeast Asia, or in regions with extreme temperature differences). Therefore, care should be taken to prevent the (C) water content from becoming too high. The moisture content can be adjusted to a desired range by maintaining a constant temperature and humidity condition for a certain period of time. Furthermore, the water (C) in the curing agent composition can be reduced by preparing the composition in a low-humidity environment, preparing the composition in a reduced-pressure environment, adding a dehydrating agent, or performing a degassing or depressurizing process. Furthermore, the amount of water (C) can be easily controlled by sealing the container after moisture adjustment, using a container made of a material that prevents moisture absorption, or using a moisture absorbent in the container.

[0032] In this specification, the content of water (C) in the curing agent composition can be measured using a moisture vaporizer for lubricating oils based on the Karl Fischer method described in JIS K 0113.

[0033] The curing agent composition of this embodiment is a curing agent composition to be mixed with a base composition. The curing agent composition of this embodiment is used in a two-component or multi-component thermosetting composition. Because it is in a state before being mixed with the base composition, it is substantially free of a base agent or has a base agent content lower than that of a one-component thermosetting composition. In this specification, "base agent" refers to an anionically polymerizable compound having a group reactive with the thiol group of a thiol compound. In this embodiment, the content of the base agent, such as an epoxy compound or a (meth)acrylate compound, in the curing agent composition is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. If it exceeds 20% by mass, the viscosity of the curing agent composition may undesirably increase. For example, some (B) thermally latent curing catalysts are provided in the form of a dispersion dispersed in an epoxy compound. When such a form of (B) thermally latent curing catalyst is used in a curing agent composition, the epoxy compound as a dispersion medium becomes the base agent contained in the curing agent composition.

[0034] If desired, the curing agent composition of this embodiment may further contain other additives, such as a filler, a stabilizer, a photoradical initiator, a thermal radical initiator, a silane coupling agent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a dehydrating agent, a solvent, etc. In addition, the curing agent composition may contain a monofunctional thiol compound to reduce the viscosity.

[0035] Fillers Fillers are broadly divided into inorganic fillers and organic fillers.

[0036] The inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added. Examples of inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. One or more inorganic fillers may be used, or two or more may be used in combination. As the inorganic filler, silica filler is preferably used because it allows for a high loading. Amorphous silica is preferred as the silica. The surface of the inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent.

[0037] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, filler having a urethane skeleton, filler having a butadiene skeleton, styrene filler, etc. The organic filler may be surface-treated.

[0038] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0039] The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. In this specification, unless otherwise specified, the average particle size refers to the volume-based median diameter (d ５０) By setting the average particle size of the filler to the upper limit or less, it is possible to suppress sedimentation of the filler, and also to suppress the formation of coarse particles, thereby suppressing wear of the jet dispenser nozzle and scattering of the thermosetting composition discharged from the jet dispenser nozzle outside the desired area. There is no particular restriction on the lower limit of the average particle size of the filler, but from the viewpoint of the viscosity of the curing agent composition, it is preferably 0.005 μm or more, and more preferably 0.1 μm or more. Fillers with different average particle sizes may be used in combination.

[0040] Various known polymerization inhibitors can be used as stabilizers. Examples of the polymerization inhibitor include acidic compounds and radical stabilizers. The acidic compound is preferably at least one selected from the group consisting of borate ester compounds, phosphoric acid compounds, alkyl phosphate ester compounds, sulfonic acid compounds, aluminum chelates, condensates of aluminum chelates and silanol compounds, and organic acids.

[0041] Examples of borate ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, trimethoxyboroxine, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate. Among borate ester compounds, those that are liquid at room temperature (25°C) are preferred because they can maintain low formulation viscosity. Examples of alkyl phosphate ester compounds include trimethyl phosphate and tributyl phosphate. Examples of sulfonic acid compounds include p-toluenesulfonic acid. Examples of aluminum chelates that can be used include Aluminum Chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.). Examples of condensates of aluminum chelates and silanol compounds include condensates of aluminum chelates and triphenylsilanol. Examples of organic acids that can be used include barbituric acid.

[0042] Examples of the radical stabilizer include phenolic compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, etc. Examples of the phenolic compounds include p-methoxyphenol, cresol, tert-butylcatechol, 3,5-di-tert-butyl-4-hydroxytoluene, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, and 4,4'-dialkoxy-2,2'-bi-1-naphthol. Examples of quinone compounds include hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, and diphenoquinone. Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyldiphenylamine, etc. Examples of thioether compounds include phenothiazine, distearyl thiodipropionate, etc.Nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, N,N-diethyl-p-nitrosoaniline, N-nitrosoethanolamine, N-nitrosodibutylamine, N-nitroso-N-butyl-4-butanolamine, 1,1′-nitrosoiminobis(2-propanol), N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, and N-nitrosomorpholine. , N-nitroso-N-phenylhydroxylamine ammonium, N-nitroso-N-phenylhydroxylamine aluminum, nitrosobenzene, 2,4,6-tri-tert-butylnitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, and the like.

[0043] The stabilizers may be used alone or in combination of two or more.

[0044] Photoradical initiators include, for example, alkylphenone compounds, acylphosphine oxide compounds, and oxime ester compounds. Examples of alkylphenone compounds include commercially available products such as benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad 651) manufactured by IGM Resins; α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (Omnirad 907); and α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone (Omnirad 184). Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Another example is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819). Examples of oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime) (Irgacure OXE01), ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (Irgacure OXE02), and the like.

[0045] Examples of other radical initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzoin methyl ether, benzoin ethyl ... diethyl benzoyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzyl, camphorquinone, and the like.

[0046] The method for producing the curing agent composition of this embodiment is not particularly limited. For example, the curing agent composition of this embodiment can be obtained by simultaneously or separately introducing components (A) to (C), and other additives as necessary, into an appropriate mixer, and stirring and mixing them while melting by heating if necessary to form a composition. The mixer is not particularly limited, but a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirring device and a heating device can be used. These devices may also be used in combination as appropriate. In the curing agent composition, water (C) may be added intentionally, or may be incorporated into the curing agent composition by moisture absorption. Possible methods for reducing the water (C) in the curing agent composition include preparing the composition in a low-humidity environment, preparing the composition in a reduced-pressure environment, adding a dehydrating agent, or performing a degassing or depressurizing process. Furthermore, the amount of water (C) can be easily controlled by sealing the container after moisture adjustment, using a container made of a material that prevents moisture absorption, or using a moisture absorbent in the container.

[0047] In this aspect, the maximum particle size of the thermal latent curing catalyst (B) in the curing agent composition is preferably 30 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, and particularly preferably 10 μm or less. Herein, the maximum particle size of the thermal latent curing catalyst in the curing agent composition can be measured using a particle gauge in accordance with JIS K5600-2-5. In some embodiments, the particle size of the thermal latent curing catalyst (B) may be 0.001 to 30 μm, 0.001 to 20 μm, 0.001 to 15 μm, or even 0.001 to 10 μm.

[0048] The manufacture of semiconductor devices and electronic components and the assembly of modules are generally carried out in clean rooms. Clean rooms are maintained at a constant temperature and humidity (e.g., 22°C and 50% RH). Two-component or multi-component thermosetting compositions for semiconductor devices or electronic components are produced by gradually removing and mixing a base composition and a curing agent composition from a storage container. Therefore, after a portion of the curing agent composition in the storage container is used, it is expected that the remaining curing agent composition will be stored in a clean room environment for a while. For this reason, the curing agent composition is required to have storage stability in a clean room environment (e.g., 22°C and 50% RH).

[0049] In this embodiment, the rate of change in the injection distance of the curing agent composition into a 100 μm gap between glass plates after standing for 2 hours at 22°C, before and after storage for 94 hours in an oven set at 40°C in a 22°C, 50% RH environment, is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. This allows the storage stability of the curing agent composition in a clean room environment to be evaluated. In this specification, "the rate of change in the injection distance of the curing agent composition into a 100 μm gap between glass plates after standing for 2 hours at 22°C, before and after storage for 94 hours in an oven set at 40°C in a 22°C, 50% RH environment" can be determined by the following method. Two glass slides are prepared, and aluminum tape is attached to both longitudinal ends of one glass slide at 10 mm intervals. The other glass slide is then placed on top of it, shifted longitudinally, and secured with a clip to prepare a test piece with a tunnel-shaped gap measuring 65 mm in length, 10 mm in width, and 100 μm in height. A curing agent composition is applied to one end of the glass slide of this test piece, and the injection distance (initial injection distance) is measured after leaving it to stand at 22 ° C for 2 hours. Next, for the curing agent composition stored in an uncovered container in an oven set at 40 ° C for 94 hours in an environment of 22 ° C and 50% RH, the injection distance after leaving it to stand at 22 ° C for 2 hours (injection distance after storage at 40 ° C for 94 hours) is similarly measured. The change (%) in the injection distance of the curing agent composition before and after storage at 40 ° C for 94 hours is calculated using the following formula: Percent change in injection distance before and after storage (%) = {| (initial injection distance) - (injection distance after 94 hours of storage at 40°C) | / (initial injection distance)} × 100 A small percentage change in injection distance means that the dispersibility of the thermal latent curing catalyst (B) in the curing agent composition remains unchanged or changes only slightly even after 94 hours of storage in an oven set at 40°C, and that the curing agent composition has good storage stability at 40°C. Good storage stability at 40°C can be said to result in better long-term storage stability in a clean room environment (e.g., a 22°C, 50% RH environment). Therefore, the percentage change in injection distance before and after 94 hours of storage in an oven set at 40°C in a 22°C, 50% RH environment is an indicator of the storage stability of the curing agent composition in a clean room environment.From this viewpoint, the content of (C) water in the curing agent composition is preferably 12,000 ppm or less, and more preferably 10,000 ppm or less.

[0050] In one embodiment, the curing agent composition of this aspect is contained in a container having a volume of 0.3 L or more, 0.5 L or more, 1 L or more, or 3 L or more. The volume of the container may be 0.3 L or more, 0.5 L or more, 1 L or more, or 3 L or more, for example, within the ranges of 0.3 to 220 L, 0.3 to 50 L, 0.3 to 20 L, 0.5 to 220 L, 0.5 to 50 L, 0.5 to 20 L, 1 to 220 L, 1 to 50 L, 1 to 20 L, 3 to 220 L, 3 to 50 L, or 3 to 20 L. (C) A moisture absorbent may be used in the container to control the amount of water. The shape of the container is not particularly limited, and examples include a pouch, a bag-in-box, a drum, a 18L can, and a pail. The material of the container is not particularly limited, and may be metallic or non-metallic, for example, steel, stainless steel, plastic, or silicone. A combination of these materials may also be used. Since the curing agent composition of this embodiment is prone to absorbing water from the environment, it is preferable that the container be one that prevents moisture absorption. After the curing agent composition is placed in the container, it is preferable that the container be sealed with a lid such as an airtight lid or a lid with a sealant. It is important that the content of water (C) in the curing agent composition is maintained at 10 to 15,000 ppm while it is placed in the container.

[0051] The curing agent composition is degassed using a vacuum degasser or the like before mixing with the base composition. If the water content in the curing agent composition is too high, exceeding 15,000 ppm, the water evaporates during degassing, forming bubbles, which takes too long to degas, and this is not preferred. Note that if the curing agent composition is not degassed before mixing with the base composition, and the two are degassed together after mixing with the base composition, this increases the amount of degassing work and takes too long to complete the degassing process, which is also not preferred.

[0052] Another aspect of the present invention is a method for transporting and storing a curing agent composition, comprising maintaining a container containing the curing agent composition of this aspect at a temperature above 0°C and maintaining the content of the water (C) in the curing agent composition at 10 to 15,000 ppm. In one embodiment, the temperature above 0°C is 5 to 35°C. The method for transporting and storing a curing agent composition of this aspect, depending on its configuration, allows the thermally latent curing catalyst in the curing agent composition to be dispersed even after long-term transportation and storage at a temperature above 0°C, for example, at room temperature. The container is as described above. Methods for maintaining the content of the water (C) in the curing agent composition at 10 to 15,000 ppm include, but are not limited to, using a container that prevents moisture absorption, sealing the container with a lid such as a hermetic lid or a lid with a sealant, using a moisture absorbent in the container, and replacing the air in the container with an inert gas such as nitrogen, carbon dioxide, or argon and sealing it.

[0053] In one embodiment, the curing agent composition of this aspect is mixed with the base composition after transportation and storage at a temperature above 0° C. In one embodiment, the temperature above 0° C. is 5 to 35° C. The curing agent composition of this aspect does not require frozen transportation or frozen storage because the content of (C) water in the curing agent composition is maintained at 10 to 15,000 ppm, and the thermally latent curing catalyst in the curing agent composition remains dispersed even after long-term transportation and storage at room temperature.

[0054] The base composition that can be mixed with the curing agent composition of this embodiment is a composition containing an anionically polymerizable compound having a group reactive with the thiol group of a thiol compound as a base. The anionically polymerizable compound is selected from the group consisting of, for example, epoxy compounds and compounds having a group containing an unsaturated double bond and an adjacent electron-withdrawing group in the molecule. Examples of compounds having an unsaturated double bond and an adjacent electron-withdrawing group in the molecule include (meth)acrylate compounds, maleimide compounds, and (meth)acrylamide compounds.

[0055] The epoxy compound contained in the base composition is preferably a polyfunctional epoxy compound having two or more epoxy groups. Polyfunctional epoxy compounds are broadly classified into epoxy compounds having an aromatic ring and polyfunctional epoxy compounds having no aromatic ring.

[0056] Specific examples of polyfunctional epoxy compounds having an aromatic ring include bisphenol A type epoxy resins (EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc., manufactured by DIC Corporation), special epoxy resins containing compounds in which a polyalkylene oxide structure is added to an epoxy resin and bisphenol A skeleton (AER9000 manufactured by Asahi Kasei Corporation, EP-4000S, EP-4003S, EP-4005, EP-4010S, EP-4088S, EP-4088L, manufactured by ADEKA Corporation, and Rikaresin BEO-60E, manufactured by New Japan Chemical Co., Ltd.), bisphenol F type epoxy resins (EPICLON (registered trademark) 830-S, EXA-830LVP, etc., manufactured by DIC Corporation), and bisphenol AD ​​type epoxy resins. epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin (EPICLON (registered trademark), HP-4032D, HP-720H, etc., manufactured by DIC Corporation), phenol novolac type epoxy resin (EPICLON (registered trademark), N-740, N-770, etc., manufactured by DIC Corporation), cresol novolac type epoxy resin (EPICLON (registered trademark), N-660, N-670, N-655-EXP-S, etc., manufactured by DIC Corporation), aminophenol type epoxy resin (630, 630LSD, manufactured by Mitsubishi Chemical Corporation), aminophenyl type epoxy resin (EP-3980, EP-3980S, manufactured by ADEKA Corporation), resorcinol type epoxy resin (Denacol EX-201, manufactured by Nagase ChemteX Corporation), and the like. Other specific examples of polyfunctional epoxy compounds having an aromatic ring include glycidyl ethers of tetra(hydroxyphenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenones, and epoxidized polyvinylphenols.

[0057] Examples of polyfunctional epoxy compounds that do not have an aromatic ring include epoxy resins having an alicyclic skeleton. The epoxy resin having an alicyclic skeleton may be any epoxy resin that has an alicyclic skeleton in one molecule. The epoxy resin having an alicyclic skeleton may contain a cycloalkylene oxide compound in which an epoxy group is formed by two adjacent carbon atoms and one oxygen atom in the alicyclic skeleton. The epoxy resin having an alicyclic skeleton may also contain an epoxy compound having an alicyclic skeleton and a glycidyl group. Examples of such epoxy compounds having an alicyclic skeleton include cyclohexane-based, cyclohexyl methyl ester-based, cyclohexyl methyl ether-based, dimer acid-based, spiro-based, and tricyclodecane-based epoxy compounds. Specific examples of epoxy resins having an alicyclic skeleton include 3',4'-epoxycyclomethyl 3,4-epoxycyclohexanecarboxylate (Celloxide (registered trademark) 2021P manufactured by Daicel Corporation, etc.), (3,3',4,4'-diepoxy)bicyclohexyl (Celloxide (registered trademark) 8010 manufactured by Daicel Corporation, etc.), 1,2:8,9-diepoxylimonene, 1,2-epoxy-4-vinylcyclohexane, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 manufactured by Daicel Corporation, etc.), and hydrogenated bisphenol A diglycidyl ether (jER manufactured by Mitsubishi Chemical Corporation, etc.). YX8000, etc.), cyclohexanedimethanol diglycidyl ether (CDMDG, etc., manufactured by Resonac Corporation), dicyclopentadiene dimethanol diglycidyl ether (EP-4088L, etc., manufactured by ADEKA Corporation), and dimer acid type epoxy resin (jER871, etc., manufactured by Mitsubishi Chemical Corporation).

[0058] Examples of polyfunctional epoxy resins that do not have an aromatic ring and do not have an alicyclic skeleton include linear aliphatic epoxy resins and linear epoxy-substituted silicone resins. Examples of linear aliphatic epoxy resins include polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts. Specific examples include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether (such as Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), pentaerythritol tetraglycidyl ether, epoxidized soybean oil, 1,3-bis(3-glycidoxypropyl)tetramethyldisiloxane, and polyethylene glycol diglycidyl ether.

[0059] The epoxy equivalent of the epoxy compound is preferably 90 g / eq to 1000 g / eq. The epoxy equivalent of the epoxy compound may be 800 g / eq or less, 600 g / eq or less, 500 g / eq or less, 400 g / eq or less, 120 g / eq or more, 130 g / eq or more, 150 g / eq or more, 180 g / eq or more, or 200 g / eq or more.

[0060] The (meth)acrylate compound contained in the base composition is preferably a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in the molecule. Examples of polyfunctional (meth)acrylate compounds include 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, and alkyl-modified dipentaerythritol polyacrylate. Examples of the (meth)acrylate compound include, but are not limited to, polyacrylate and / or polymethacrylate of caprolactone-modified dipentaerythritol; terminal acrylate of EO-modified or PO-modified bisphenol A alkylene oxide adduct and / or terminal methacrylate of bisphenol A alkylene oxide adduct; dihydrocyclopentadiethyl acrylate and / or dihydrocyclopentadiethyl methacrylate, as well as polyester acrylate and / or polyester methacrylate, dimethylol-tricyclodecane diacrylate, poly(meth)acrylate of ditrimethylolpropane, polyurethane having two or more (meth)acryloyl groups per molecule, polyester having two or more (meth)acryloyl groups per molecule, etc. The (meth)acrylate compound may be any one of the above-mentioned (meth)acrylate compounds, or two or more of them may be used in combination.Examples of commercially available (meth)acrylate compounds include polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (product name: EBECRYL140) manufactured by Daicel-Allnex Corporation, polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., neopentyl glycol-modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd., and terminal methacrylate of bisphenol A ethylene oxide adduct (product names: ABE-300, A-BPE-4, A-BPE-10, A-BPE-20) manufactured by Shin-Nakamura Chemical Co., Ltd., but are not limited thereto.

[0061] The maleimide compound contained in the base composition is preferably a polyfunctional maleimide compound having two or more maleimide groups in the molecule. In particular, maleimide compounds having two maleimide groups are sometimes called bismaleimide compounds. Examples of maleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide and bisphenol A. Examples of suitable bismaleimides include, but are not limited to, diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimidehexane, 1,2-bismaleimideethane (N,N'-ethylenedimaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, and N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide. These may be used alone or in combination of two or more.

[0062] When a low room temperature modulus is required for the cured product of the thermosetting composition, a bismaleimide compound having a hydrocarbon group derived from a dimer acid can be used as the maleimide compound. Such bismaleimide compounds are described, for example, in JP 2015-193725 A. Commercially available bismaleimide compounds having a hydrocarbon group derived from a dimer acid include, but are not limited to, products named "BMI-689," "BMI-1500," and "BMI-1700," which are liquid at 25°C, and "BMI-3000," which is solid at 25°C (all manufactured by Designer Molecules Inc.). These compounds may be used alone or in combination of two or more.

[0063] The (meth)acrylamide compound contained in the base composition is preferably a polyfunctional (meth)acrylamide compound having two or more (meth)acrylamide groups. Examples of polyfunctional (meth)acrylamide compounds include, but are not limited to, methylenebis(acrylamide), N-[tris(3-acrylamidopropoxymethyl)methyl]acrylamide, N,N-bis(2-acrylamidoethyl)acrylamide, and N,N-1,2-ethanediylbis{N-[2[(acryloylamino)ethyl]acrylamide]}. These compounds may be used alone or in combination of two or more.

[0064] The main agent in the main agent composition may be any one of an epoxy compound and a compound having a group containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule, or any combination of these.

[0065] In addition to the main component, the main component composition may further contain other additives such as reactive diluents, fillers, stabilizers, photoradical initiators, silane coupling agents, carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, antifoaming agents, viscosity modifiers, flame retardants, colorants, dehydrating agents, solvents, etc. The type and amount of each additive is as per usual.

[0066] In this specification, the reactive diluent refers to a compound that has a group reactive with the thiol group of the thiol compound and has a relatively low viscosity at room temperature. Examples of the reactive diluent include a monofunctional epoxy compound, a monofunctional (meth)acrylate compound, a monofunctional maleimide compound, and a monofunctional (meth)acrylamide compound.

[0067] A monofunctional epoxy compound is a compound having one epoxy group as a group reactive with a thiol group. Examples of the monofunctional epoxy compound include, but are not limited to, monoepoxide compounds such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, and α-pinene oxide; and monoepoxide compounds having other functional groups such as allyl glycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane.

[0068] The monofunctional (meth)acrylate compound is a compound having one (meth)acryloyl group as a group reactive with a thiol group. Examples of monofunctional (meth)acrylate compounds include ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, Esters of monohydric alcohols and (meth)acrylic acid such as phenoxypolyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and m-phenoxybenzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, 1-naphthalenemethyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, Nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1 adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2- Ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropane-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2-furanyl (meth)acrylate, 2-oxotetrahydrofuran-3-yl (meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl (meth)acrylate, (2-oxo-1,Examples of the acrylate include, but are not limited to, mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as (3-dioxolan-4-yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl(meth)acrylate.

[0069] The monofunctional maleimide compound is a compound having one maleimide group as a group reactive with a thiol group, and examples thereof include, but are not limited to, maleimide; aliphatic hydrocarbon group-containing maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; and aromatic ring-containing maleimides such as phenylmaleimide.

[0070] The monofunctional (meth)acrylamide compound is a compound having one maleimide group as a group reactive with a thiol group, and examples thereof include, but are not limited to, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-n-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-(2-hydroxyethyl)acrylamide, N-[3-(dimethylamino)]propylacrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-acryloylmorpholine, and hydroxyalkyl(meth)acrylamides such as hydroxyethylacrylamide.

[0071] The fillers and stabilizers that can be contained in the base composition can be the same as the fillers and stabilizers that can be contained in the hardener composition.

[0072] [Container Containing Curing Agent Composition] One aspect of the present invention is a container containing the curing agent composition of the above-described aspect, wherein the container has a volume of 0.3 L or more, 0.5 L or more, 1 L or more, or 3 L or more. The container containing the curing agent composition of this aspect can be transported and stored for long periods at room temperature and is suitable for long-distance transportation by ship or the like. The volume of the container may be 0.3 L or more, 0.5 L or more, 1 L or more, or 3 L or more, for example, within the ranges of 0.3 to 220 L, 0.3 to 50 L, 0.3 to 20 L, 0.5 to 220 L, 0.5 to 50 L, 0.5 to 20 L, 1 to 220 L, 1 to 50 L, 1 to 20 L, 3 to 220 L, 3 to 50 L, or 3 to 20 L. The shape of the container is not particularly limited, and examples include a pouch, a bag-in-box, a drum, a 18L can, and a pail. The material of the container is not particularly limited and may be metallic or non-metallic, for example, steel, stainless steel, plastic, silicone, etc. A combination of these materials may also be used. Because the curing agent composition of the above embodiment is prone to absorbing water from the environment, the container is preferably one that prevents moisture absorption. Furthermore, a moisture absorbent may be used in the container to control the amount of water (C). When the curing agent composition is placed in the container, it is preferable to replace the air in the container with an inert gas such as nitrogen, carbon dioxide, or argon before sealing. After placing the curing agent composition in the container, it is preferable to seal the container with a lid such as a sealing lid or a lid with a sealant.

[0073] [Thermosetting Composition Kit] One aspect of the present invention is a thermosetting composition kit having the curing agent composition of the above-described aspect and a base composition, each in a separate form. The thermosetting composition kit of this aspect preferably includes a first container containing the curing agent composition of the above-described aspect and a second container containing the base composition. The base composition is as described above. The volumes of the first container and the second container are each independently 0.3 L or more, 0.5 L or more, 1 L or more, or 3 L or more, and may be, for example, within the ranges of 0.3 to 220 L, 0.3 to 50 L, 0.3 to 20 L, 0.5 to 220 L, 0.5 to 50 L, 0.5 to 20 L, 1 to 220 L, 1 to 50 L, 1 to 20 L, 3 to 220 L, 3 to 50 L, or 3 to 20 L. The shapes of the first container and the second container are not particularly limited and may each independently be, for example, a pouch, a bag-in-box, a drum, a 18 liter can, a pail, etc. The materials of the first container and the second container are not particularly limited and each independently may be metallic or non-metallic, for example, steel, stainless steel, plastic, silicone, etc. A combination of these materials may also be used. The first container and the second container are preferably containers that prevent moisture absorption. A moisture absorbent may also be used in the container. When the curing agent composition and the base composition are respectively placed in the containers, it is preferable to replace the air in the containers with an inert gas such as nitrogen, carbon dioxide, or argon before sealing them. After the curing agent composition and the base composition are respectively placed in the containers, it is preferable to seal the containers using a lid such as a sealing lid or a lid with a sealing material.

[0074] [Method for producing a thermosetting composition] One aspect of the present invention is a method for producing a thermosetting composition, comprising mixing the curing agent composition of the above-mentioned aspect with a base composition. The base composition is as described above. Another aspect of the present invention is a method for producing a thermosetting composition, comprising mixing the curing agent composition of the above-mentioned aspect in the thermosetting composition kit with the base composition.

[0075] The method for mixing the curing agent composition and the base composition is not particularly limited. For example, the curing agent composition and the base composition can be introduced into an appropriate mixer simultaneously or separately, and then stirred and mixed while melting by heating if necessary to form a composition, thereby obtaining the thermosetting composition of this embodiment. The mixer is not particularly limited, but a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirring device and a heating device can be used. These devices may also be used in combination as appropriate. Due to the manufacturing process of mixing the curing agent composition and the base composition, bubbles are contained in the thermosetting composition. For this reason, it is preferable to degas the thermosetting composition using a vacuum degasser or the like before use. If the thermosetting composition contains too much water, the water evaporates and forms bubbles, which is undesirable because it takes too long to degas. If a thermosetting composition with a high water content is used without degassing, the water will evaporate and form bubbles during thermal curing, resulting in voids in the cured product, making it impossible to obtain the desired cured product.

[0076] In this embodiment, the mixing ratio of the curing agent composition and the base composition is preferably such that the ratio of the number of reactive group equivalents with the thiol group of the base in the base composition (and in the curing agent composition, if the curing agent composition contains a base) to the number of thiol group equivalents of the thiol compound in the curing agent composition ([number of reactive group equivalents with thiol groups of the base] / [number of thiol group equivalents of the thiol compound]) is 0.5 to 2.0, and more preferably 0.6 to 1.5. By keeping the mixing ratio within the above range, a high-quality cured product can be obtained from the thermosetting composition obtained by mixing. Note that, when a base is contained in the curing agent composition, the base in the base composition and the base in the curing agent composition are combined to calculate the "number of reactive group equivalents with the thiol group of the base."

[0077] In this specification, functional group equivalents such as thiol equivalent, epoxy equivalent, and (meth)acryloyl equivalent refer to the molecular weight of a compound per functional group, and functional group equivalents such as the number of thiol group equivalents, the number of epoxy group equivalents, and the number of (meth)acryloyl equivalents refer to the number of functional groups (number of equivalents) per mass (charged amount) of a compound.

[0078] Theoretically, the thiol equivalent of a thiol compound is the molecular weight of the thiol compound divided by the number of thiol groups in one molecule. The actual thiol equivalent can be determined, for example, by determining the thiol value by potentiometric measurement. This method is widely known and is disclosed, for example, in paragraph 0079 of JP 2012-153794 A. The thiol group equivalent of a thiol compound is the number of thiol groups (equivalents) per mass (charge amount) of the thiol compound, and is the quotient obtained by dividing the mass (g) of the thiol compound by the thiol equivalent of that thiol compound (when multiple thiol compounds are included, the sum of such quotients for each thiol compound).

[0079] Theoretically, the epoxy equivalent of an epoxy compound is the molecular weight of the epoxy compound divided by the number of epoxy groups in one molecule. The actual epoxy equivalent can be determined by the method described in JIS K7236. The epoxy group equivalent of an epoxy compound is the number of epoxy groups (equivalent number) per mass (charged amount) of the epoxy compound, and is the quotient obtained by dividing the mass (g) of the epoxy compound by the epoxy equivalent of that epoxy compound (when multiple epoxy compounds are contained, the sum of such quotients for each epoxy compound).

[0080] The (meth)acryloyl equivalent of a (meth)acrylate compound or a (meth)acrylamide compound is theoretically equal to the molecular weight of the (meth)acrylate compound or the (meth)acrylamide compound divided by the number of acryloyl groups (or methacryloyl groups) in one molecule. The actual (meth)acryloyl equivalent can be measured, for example, by NMR. The (meth)acryloyl group equivalent number of a (meth)acrylate compound and a (meth)acrylamide compound is the number of (meth)acryloyl groups (equivalent number) per mass (charge amount) of the (meth)acrylate compound and (meth)acrylamide compound, and is the quotient obtained by dividing the mass (g) of the (meth)acrylate compound and (meth)acrylamide compound by the (meth)acryloyl equivalent of the (meth)acrylate compound and (meth)acrylamide compound (when a plurality of (meth)acrylate compounds and (meth)acrylamide compounds are contained, the sum of such quotients for each of the (meth)acrylate compounds and (meth)acrylamide compounds).

[0081] Theoretically, the maleimide equivalent of a maleimide compound is equal to the molecular weight of the maleimide compound divided by the number of maleimide groups in one molecule. The actual maleimide equivalent can be measured, for example, by NMR. The maleimide group equivalent of a maleimide compound is the number of maleimide groups (equivalents) per mass (charge amount) of the maleimide compound, and is the quotient obtained by dividing the mass (g) of the maleimide compound by the maleimide equivalent of that maleimide compound (when multiple maleimide compounds are contained, the sum of such quotients for each maleimide compound).

[0082] The thermosetting composition obtained by the manufacturing method of this embodiment is thermosetting and can be cured, for example, by heat treatment at 60 to 200°C for 0.1 to 300 minutes. At a temperature of 100°C, it preferably cures within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour. When the thermosetting composition obtained by the manufacturing method of this embodiment is used in the manufacture of a semiconductor device containing components that deteriorate under high temperature conditions, it is preferably thermally cured at a temperature of 50 to 90°C for 30 to 120 minutes. Furthermore, by adding a photoradical initiator to any of the curing agent composition, the base composition, and the third composition, the thermosetting composition may be further imparted with UV curability. This allows the thermosetting composition to be thermally cured after UV curing.

[0083] The thermosetting composition obtained by the manufacturing method of this embodiment can be used, for example, as an adhesive or sealant for fixing, bonding, or protecting semiconductor devices or electronic components or components constituting them, or as a raw material thereof. This adhesive or sealant enables good fixing, bonding, or protection of general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect components constituting semiconductor devices or electronic components. Examples of semiconductor devices include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and time-of-flight sensor modules, other semiconductor modules, and integrated circuits.

[0084] [Cured Product of Thermosetting Composition] One aspect of the present invention is a cured product obtained by curing a thermosetting composition containing the curing agent composition of the above-described aspect and a base composition. The base composition is as described above. Another aspect of the present invention is a cured product obtained by curing a thermosetting composition containing the curing agent composition and the base composition in the thermosetting composition kit of the above-described aspect. The cured product of this aspect can be produced, for example, by heating the thermosetting composition produced by the thermosetting composition production method of the above-described aspect. Heating conditions can be, for example, 60 to 200°C for 0.1 to 300 minutes. At a temperature of 100°C, curing is preferably achieved within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour. When the thermosetting composition is used to manufacture a semiconductor device containing components that deteriorate under high temperature conditions, the composition is preferably thermally cured at a temperature of 50 to 90°C for 30 to 120 minutes.

[0085] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass (unit: g) and % by mass, unless otherwise specified.

[0086] [Preparation of Curing Agent Composition] The components used in preparing the curing agent compositions of the Examples and Comparative Examples are as follows.

[0087] (A) Thiol Compounds Having No Ester Bond (A-1): 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (product name: C3 TS-G, manufactured by Shikoku Chemical Industries, Ltd., thiol equivalent: 111 g / eq) (A-2): pentaerythritol tetrakis(3-mercaptopropionate) (product name: PEMP, manufactured by SC Organic Chemicals, thiol equivalent: 122 g / eq) (A-3): 1,2,3-tris(3-mercaptopropyloxy)propane (obtained from Shikoku Chemical Industries, Ltd., thiol equivalent: 106 g / eq). Note that this thiol equivalent is an average value of values ​​measured by a known method, for example, the method disclosed in paragraph 0079 of JP 2012-153794 A. (A-4): Pentaerythritol tetrapropanethiol 3-{3-(3-mercapto-propoxy)-2,2-bis-[(3-mercaptopropoxy)methyl]propoxy}-propan-1-ol (product name: Multiol Y-4, manufactured by Sakai Chemical Industry Co., Ltd., thiol equivalent: 108 g / eq). (A-5): Tris(3-mercaptopropyl)isocyanurate (thiol equivalent: 117 g / eq). This was synthesized by the method described in JP-A-56-120671 and used as is. That is, triallyl isocyanurate and thiolpropionic acid were reacted by irradiating them with ultraviolet light in a mixed solvent of acetone and acetic acid. After removing the solvent under reduced pressure, the residue of the reaction solution was boiled in concentrated hydrochloric acid and neutralized by adding anhydrous sodium carbonate. The mixture was then passed through a medium activated alumina column to remove the solvent and purified to obtain tris(3-mercaptopropyl)isocyanurate. (B) Thermal Latent Curing Catalyst (B-1): Amine-urea adduct thermal latent curing catalyst (product name: Fujicure FXR1020, manufactured by T&K TOKA Corporation). The content of (C) water in the (C) water curing agent composition was measured using a moisture vaporizer for lubricating oils based on the Karl Fischer method described in JIS K 0113.Specifically, the curing agent compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were added to dried toluene, and the mixture was heated using a moisture vaporizer for lubricating oils (manufactured by HIRANUMA Corporation, product name: EV-2000L) set to 100°C, and the amount of moisture generated was measured using a trace moisture analyzer (Karl Fischer: "MOICO-A19" manufactured by HIRANUMA Corporation). Dry N2 gas was used as the carrier gas. Then, using the moisture amount measured as above, the moisture content was calculated based on the following formula: Moisture content (ppm by mass) = measured moisture amount (g) / mass of curing agent composition (g).

[0088] Example 1 The curing agent composition of Example 1 was prepared by mixing 90 parts by mass of component (A-1) and 10 parts by mass of component (B-1) using a three-roll mill. The water content in the curing agent composition of Example 1 was 2900 ppm. The water (C) in the curing agent composition of Example 1 was not intentionally added, but was absorbed from the surrounding environment.

[0089] Example 2 89.5 parts by mass of component (A-1), 10 parts by mass of component (B-1), and 0.5 parts by mass of water (C) were mixed using a three-roll mill to prepare the curing agent composition of Example 2. The water content in the curing agent composition of Example 2 was 8,000 ppm.

[0090] Example 3 89 parts by mass of component (A-1), 10 parts by mass of component (B-1), and 1 part by mass of water (C) were mixed using a three-roll mill to prepare the curing agent composition of Example 3. The water content in the curing agent composition of Example 3 was 12,500 ppm.

[0091] Comparative Example 1 88 parts by mass of component (A-1), 10 parts by mass of component (B-1), and 2 parts by mass of water (C) were mixed using a three-roll mill to prepare a curing agent composition of Comparative Example 1. The water content in the curing agent composition of Comparative Example 1 was 22,500 ppm.

[0092] Example 4 The curing agent composition of Example 4 was prepared by mixing 63 parts by mass of component (A-1), 27 parts by mass of component (A-2), and 10 parts by mass of component (B-1) using a three-roll mill. The water content in the curing agent composition of Example 4 was 4,600 ppm. The water (C) in the curing agent composition of Example 4 was not intentionally added, but was absorbed from the surrounding environment.

[0093] Example 5 62 parts by mass of component (A-1), 27 parts by mass of component (A-2), 10 parts by mass of component (B-1), and 1 part by mass of water (C) were mixed using a three-roll mill to prepare the curing agent composition of Example 5. The water content in the curing agent composition of Example 5 was 12,500 ppm.

[0094] Comparative Example 2 61 parts by mass of component (A-1), 27 parts by mass of component (A-2), 10 parts by mass of component (B-1), and 2 parts by mass of water (C) were mixed using a three-roll mill to prepare a curing agent composition of Comparative Example 2. The water content in the curing agent composition of Comparative Example 2 was 21,100 ppm.

[0095] Example 6 The curing agent composition of Example 6 was prepared by mixing 49.5 parts by mass of component (A-1), 40.5 parts by mass of component (A-2), and 10 parts by mass of component (B-1) using a three-roll mill. The water content in the curing agent composition of Example 6 was 4,400 ppm. The water (C) in the curing agent composition of Example 6 was not intentionally added, but was absorbed from the surrounding environment.

[0096] Example 7 48.5 parts by mass of component (A-1), 40.5 parts by mass of component (A-2), 10 parts by mass of component (B-1), and 1 part by mass of water (C) were mixed using a three-roll mill to prepare the curing agent composition of Example 7. The water content in the curing agent composition of Example 7 was 13,600 ppm.

[0097] Comparative Example 3 47.5 parts by mass of component (A-1), 40.5 parts by mass of component (A-2), 10 parts by mass of component (B-1), and 2 parts by mass of water (C) were mixed using a three-roll mill to prepare the curing agent composition of Comparative Example 3. The water content in the curing agent composition of Comparative Example 3 was 21,800 ppm.

[0098] [Evaluation of Dispersibility of Curing Catalyst in Curing Agent Composition and Storage Stability of Curing Agent Composition in a Clean Room Environment] Test: To evaluate the dispersibility of the (B) thermally latent curing catalyst in the curing agent composition, the injection distance into the gap between glass plates was measured. To evaluate the storage stability of the curing agent composition in a clean room environment (e.g., an environment of 22°C and 50% RH), the curing agent composition was stored for 94 hours in an oven set at 40°C, a temperature higher than the temperature of the environment, in a 22°C and 50% RH environment, and then the injection distance was measured in the same manner. Two 76 mm x 26 mm glass slides were prepared. Aluminum tape was attached to both ends of one glass slide in the longitudinal direction at 10 mm intervals, and the other glass slide was placed on top of it with a longitudinal offset, and then inserted and fixed with clips to prepare a test piece with a tunnel-shaped gap measuring 65 mm in length, 10 mm in width, and 100 μm in height. The curing agent compositions of Examples 1 to 3 were applied to one end of the glass slide of this test piece, and the injection distance (initial injection distance) was measured after leaving the test piece standing at 22°C for 2 hours. This procedure was repeated twice, and the average of the measurements was used as the injection time measurement. Next, for the curing agent compositions of Examples 1 to 3, which were stored in lidless containers in an oven set at 40°C for 94 hours, the injection distance after leaving the test piece standing at 22°C for 2 hours (injection distance after 94 hours of storage at 40°C) was similarly measured. The percentage change in injection distance of the curing agent composition before and after 94 hours of storage at 40°C was calculated using the following formula: Percent change in injection distance before and after storage (%) = {| (initial injection distance) - (injection distance after 94 hours of storage at 40°C) | / (initial injection distance)} × 100 The results are shown in Table 1.

[0099]

[0100] Discussion: As shown in Table 1, the injection distance increased with an increase in the water content in the curing agent composition. This means that the increase in water molecules in the curing agent composition improves the dispersibility of the thermal latent curing catalyst (B) in the curing agent composition. Furthermore, even after storing the curing agent composition in an oven set at 40°C for 94 hours in a 22°C, 50% RH environment, the injection distance did not change from the initial injection distance, or the degree of change was small. This means that the dispersibility of the thermal latent curing catalyst (B) in the curing agent composition did not change, or the degree of change was small, even after 94 hours of storage in an oven set at 40°C, indicating good storage stability at 40°C. Good storage stability at 40°C means that good storage stability can be achieved for a longer period in a clean room environment (e.g., an environment at 22°C, 50% RH). Therefore, the rate of change in injection distance before and after 94 hours of storage in an oven set at 40°C in a 22°C, 50% RH environment is an indicator of the storage stability of the curing agent composition in a clean room environment.

[0101] [Evaluation of pot life of thermosetting composition] Test: Thermosetting compositions were produced by mixing the curing agent compositions of the Examples and Comparative Examples and the base composition using a three-roll mill according to the formulations shown in Table 2. The base compositions used in producing the thermosetting compositions are as follows. In Table 2, the amount of each composition is expressed as a ratio in parts by mass (unit: g). Main composition 1 (referred to as "Main composition 1" in Table 2): epoxy resin (bisphenol F type epoxy resin, product name: EPICLON EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165 g / eq) Main composition 2 (referred to as "Main composition 2" in Table 2): acrylate resin (ethoxylated bisphenol A diacrylate, product name: ABE-300, manufactured by Shin-Nakamura Chemical Co., Ltd., acryloyl equivalent: 235 g / eq) In order to evaluate the pot life of the thermosetting compositions produced as described above, the injection distance into the gap between the glass plates was measured. Two 76 mm x 26 mm glass slides were prepared. Aluminum tape was applied to both longitudinal ends of one of the glass slides at 10 mm intervals. The other glass slide was then placed on top of the tape, shifted longitudinally, and clamped in place with clips to create a test specimen with a tunnel-shaped gap measuring 65 mm in length, 10 mm in width, and 100 μm in height. An aluminum square bar was placed on a hot plate, and after one minute had passed since the test specimen's glass slide was placed in contact with the aluminum square bar, a thermosetting composition was applied to one end of the glass slide, and the injection distance was measured every 5 minutes up to 30 minutes. This procedure was repeated twice, and the average of the measurements was used as the injection time. The results are shown in Table 2.

[0102]

[0103] Discussion: As shown in Table 2, the thermosetting compositions obtained by mixing the curing agent compositions of the Examples, each containing 15,000 ppm or less of water, with the base composition continued to inject even after 15 minutes, demonstrating a long usable time when heated (50°C). On the other hand, the thermosetting compositions obtained by mixing the curing agent compositions of the Comparative Examples, each containing more than 15,000 ppm of water, with the base composition either cured immediately after mixing, resulting in no usable time, or had a usable time when heated (50°C) that was 10 minutes or more shorter than the thermosetting compositions obtained using the curing agent compositions of the Examples, each having the same composition except for the water content. The fluidity of the thermosetting composition also depends on the type of base composition. Although not shown in Table 2, a thermosetting composition containing half of main composition 1 and half of main composition 2 as main compositions in terms of functional group equivalents has an injection distance that is numerically between the injection distance of a thermosetting composition containing only main composition 1 as the main composition and the injection distance of a thermosetting composition containing only main composition 2 as the main composition. Although not shown in Table 2, a thermosetting composition (Sample 13) consisting of a curing agent composition (water content: 3,200 ppm) prepared by mixing 90 parts by mass of component (A-3) and 10 parts by mass of component (B-1) using a three-roll mill and base composition 1, and a thermosetting composition (Sample 14) consisting of a curing agent composition (water content: 2,600 ppm) prepared by mixing 90 parts by mass of component (A-4) and 10 parts by mass of component (B-1) using a three-roll mill and base composition 1 both had high fluidity, reaching 65 mm between 5 and 10 minutes after application. Measurement beyond this was not possible, but high fluidity was confirmed by visual inspection for 20 to 25 minutes. Although not shown in Table 2, a thermosetting composition (Sample 15) consisting of base composition 1 and a curing agent composition (water content: 1,800 ppm) prepared by mixing 90 parts by mass of component (A-5) and 10 parts by mass of component (B-1) using a three-roll mill showed similar trends to Sample 1, and was visually confirmed to have high fluidity up to 30 minutes. Note that, in these thermosetting compositions (Samples 13 to 15), the functional group equivalents of the base composition and the curing agent composition were adjusted to 1:1, similar to those shown in Table 2.

[0104] [Evaluation of Hygroscopicity of Curing Agent Composition] Test: The curing agent composition of Example 2 was degassed for 15 minutes to adjust the water content in the curing agent composition to 7,000 ppm, and used as a measurement sample. A container (without a lid) containing the measurement sample was left in a thermostatic chamber at 22°C and 100% RH for 48 hours, and the water content in the measurement sample was measured and found to be 17,500 ppm. The container (without a lid) containing the measurement sample was then left in a thermostatic chamber at 22°C and 50% RH for one week, and the water content in the measurement sample was measured and found to be 15,000 ppm. Discussion: The evaluation results showed that the curing agent composition, when placed in a high-humidity environment, easily absorbs water from the environment. This is because the amine compound contained as or in (B) the thermal latent curing catalyst is hydrophilic. Furthermore, when the (B) thermally latent curing catalyst is an amine adduct-based thermally latent polymerization catalyst, such as a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct) or a reaction product of an amine compound and an isocyanate compound or a urea compound (urea adduct), hydrophilic groups such as hydroxyl groups and urea bonds in the adduct further enhance hydrophilicity. Therefore, due to the hydrophilicity of the (B) thermally latent curing catalyst, the curing agent composition is likely to absorb water from the environment. This absorption of water from the environment can occur particularly during transportation in high-temperature, high-humidity environments such as Japan and Southeast Asia, or in regions with extreme temperature differences. On the other hand, when a curing agent composition that had absorbed moisture in a high-humidity environment was then left for one week in a 22°C, 50% RH environment (equivalent to a clean room environment), the water content only decreased to 15,000 ppm. This suggests that (C) water, once incorporated into the curing agent composition by addition or moisture absorption, is prevented from evaporating from the curing agent composition, even when stored for long periods in a low-humidity environment such as a clean room. For this reason, it is important to control the amount of water (C) in the curing agent composition during transportation.

[0105] The disclosure of Japanese Patent Application No. 2024-148664 (filing date: August 30, 2024) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A curing agent composition comprising: (A) a thiol compound having no ester bond; (B) a thermal latent curing catalyst; and (C) water, wherein the content of the water (C) in the curing agent composition is 10 to 15,000 ppm.

2. The hardener composition according to claim 1, wherein the hardener composition is stored in an oven set at 40°C in an environment of 22°C and 50% RH for 94 hours, and the change rate of the injection distance of the hardener composition into a 100 μm gap between glass plates after being left to stand at 22°C for 2 hours is 10% or less.

3. The curing agent composition according to claim 1 or 2, which is contained in a container having a volume of 3 L or more.

4. A hardener composition according to any one of claims 1 to 3, for mixing with a base composition after transportation and storage at temperatures above 0°C.

5. The curing agent composition according to any one of claims 1 to 4, wherein the main agent in the main agent composition is selected from the group consisting of epoxy compounds and compounds having a group containing an unsaturated double bond and an electron-withdrawing group adjacent to it in the molecule.

6. A container containing the hardener composition according to any one of claims 1 to 5, wherein the volume of the container is 0.3 L or more.

7. A thermosetting composition kit comprising the curing agent composition and the base composition according to any one of claims 1 to 5, each in an independent form.

8. A method for producing a thermosetting composition, comprising mixing the curing agent composition according to any one of claims 1 to 5 with a base composition.

9. A method for producing a thermosetting composition, comprising mixing the curing agent composition and the base composition in the thermosetting composition kit according to claim 7.

10. A cured product obtained by curing a thermosetting composition comprising the curing agent composition according to any one of claims 1 to 5 and a base composition.

11. A cured product obtained by curing a thermosetting composition comprising the curing agent composition and the base composition in the thermosetting composition kit according to claim 7.

12. A method for transporting and storing a hardener composition according to any one of claims 1 to 5, comprising maintaining a container containing the hardener composition at a temperature above 0°C, and maintaining the content of (C) water in the hardener composition at 10 to 15,000 ppm.

Images