Resin composition and curable resin composition using same

Abstract

The purpose of the present invention is to provide a resin composition containing a 2-methylene-1,3-dicarbonyl compound and having improved workability.　The resin composition contains: (A) a 2-methylene-1,3-dicarbonyl compound having at least one structural unit represented by formula (I) and having a molecular weight of 230 to 1000; and (B) fumed silica having an average primary particle diameter of 1 to 50 nm and a specific surface area of 50 m2 / g to 250 m2 / g.

Description

Resin composition and curable resin composition using the same

[0001] The present invention relates to a resin composition, a curable resin composition or kit containing the same, a cured product thereof, and an electronic component containing the cured product.

[0002] Currently, adhesives, sealants, etc. containing curable resin compositions are often used to assemble and mount electronic components used in semiconductor devices, with the aim of maintaining reliability, etc. Semiconductor devices, such as electronic devices such as smartphones, are composed of various electronic modules. The components that make up these electronic modules often contain materials whose mechanical and electronic properties deteriorate due to heat. For this reason, the assembly of the electronic modules and the assembly and sealing of electronic devices are preferably carried out at relatively low temperatures, for example, 100°C or lower. Therefore, adhesives and sealants used in the manufacture of the electronic devices and electronic modules are required to exhibit sufficient curability even under such low-temperature conditions (Patent Document 1).

[0003] In recent years, the use of curable resin compositions containing 2-methylene-1,3-dicarbonyl compounds such as methylene malonate as adhesives, etc. has been studied in the production of such electronic components. Patent Document 2 discloses a resin composition containing one or more 2-methylene-1,3-dicarbonyl compounds as a resin composition suitable as a one-component adhesive used in the production of image sensor modules and electronic components, which can be cured at low temperatures of 80°C or less, preferably at room temperature, and which contains few components that volatilize during use (application) or curing.

[0004] JP 2016-021033 A JP 2018-193530 A

[0005] The manufacture of such electronic components may require particularly high precision in the positioning of the components. In particular, as electronic components become smaller and more highly integrated, the importance of positional precision in bonding or sealing these components is increasing. The curable resin composition used in such cases may need to exhibit a certain level of viscosity (especially measured at a low shear rate). Use of such a curable resin composition not only prevents misalignment of components during bonding, but also prevents dripping from the discharge device and contamination of other components (due to bleeding, flow, etc.), thereby improving workability.

[0006] In contrast, many of the currently known 2-methylene-1,3-dicarbonyl compounds, particularly methylene malonate, exhibit low viscosities of less than 100 mPa·s. Accordingly, curable resin compositions containing 2-methylene-1,3-dicarbonyl compounds exhibit relatively low viscosities, which may hinder improvements in workability in the manufacture of electronic components. Therefore, with regard to curable resin compositions containing 2-methylene-1,3-dicarbonyl compounds, it may be necessary to appropriately increase their viscosity in order to further improve workability in the manufacture of electronic components.

[0007] Another characteristic required of curable resin compositions used in the manufacture of electronic components for semiconductor devices is a suitable pot life. Because the pot life allows for tasks such as component positioning and alignment, this is an important characteristic for the manufacture of electronic components, which require particularly high precision. The pot life of a curable resin composition can be evaluated, for example, by its gelation time. Herein, gelation refers to the phenomenon in which a resin composition loses fluidity as the resin component (in this invention, the 2-methylene-1,3-dicarbonyl compound) undergoes a chemical reaction to increase its molecular weight. Gelation time refers to the time from when the curable resin composition reaches a state in which it can begin to cure under specified conditions until the curable resin composition loses fluidity. Meanwhile, herein, curing and curing time refer to the phenomenon and time required for the composition to solidify as polymerization progresses, regardless of whether a crosslinked structure is formed, to a degree that allows it to hold and adhere objects. These terms are defined differently from gelation and gelation time (pot life).

[0008] However, since 2-methylene-1,3-dicarbonyl compounds such as methylene malonate are highly reactive as described above, it has been difficult for curable resin compositions containing them to have a workable time (gelation time) suitable for work. For this reason, there have been limitations on the processes in which curable resin compositions containing 2-methylene-1,3-dicarbonyl compounds can be applied in the production of electronic components.

[0009] One possible way to adjust the usable life (gelation time) of a curable resin composition is to increase the amount of stabilizer and / or polymerization inhibitor added. However, when this method is applied to a curable resin composition containing a 2-methylene-1,3-dicarbonyl compound, the occurrence of the polymerization reaction is excessively suppressed, which may result in variations in curability.

[0010] Therefore, an object of the present invention is to provide a resin composition containing a 2-methylene-1,3-dicarbonyl compound, which has improved workability.

[0011] As a result of extensive research to solve the above problems, the present inventors discovered that by incorporating a 2-methylene-1,3-dicarbonyl compound having a specific molecular weight and fumed silica having a specific average primary particle size and specific surface area into a resin composition, it is possible to simultaneously impart a pot life (gelation time) and viscosity suitable for work without causing variation in curability, and thus arrived at the present invention.

[0012] That is, the present invention includes, but is not limited to, the following inventions: (1) (A) a compound represented by the following formula (I): and a molecular weight of 230 to 1000; and (B) a 2-methylene-1,3-dicarbonyl compound having an average primary particle size of 1 nm to 50 nm and a specific surface area of ​​50 m ２ / g~250m ２ / g. (2) The resin composition according to (1) above, wherein the content of (B) fumed silica per 1 part by mass of the resin composition is 0.01 to 0.3 parts by mass. (3) The resin composition according to (1) above, wherein the gel time (GT) of the resin composition, which is the time from mixing 0.01 to 0.1 part by mass of N,N-dimethylbenzylamine with 1 part by mass of the resin composition at 25°C until the resin composition loses fluidity, is 1 minute to 60 minutes. (4) The gel time (GT) of the (A) 2-methylene-1,3-dicarbonyl compound, which is the time from mixing 0.01 to 0.1 part by mass of N,N-dimethylbenzylamine with 1 part by mass of the (A) 2-methylene-1,3-dicarbonyl compound contained in the resin composition at 25°C until the (A) 2-methylene-1,3-dicarbonyl compound loses fluidity, is 1 minute to 60 minutes. Ａ ) to the gel time (GT) of the resin composition (wherein the ratio of the mass of N,N-dimethylbenzylamine to the mass of the resin composition in the measurement of GT is Ａ(5) The resin composition according to any one of (1) to (4) above, having a viscosity of 100 to 100,000 mPa·s as measured at 1 rpm using an E-type viscometer. (6) The resin composition according to any one of (1) to (5) above, which can be cured by the action of a basic compound as a curing agent or curing catalyst. (7) The resin composition according to any one of (1) to (6) above, further comprising a polymer compound. (8) The resin composition according to any one of (1) to (7) above, which is substantially free of a Lewis acid compound capable of coordinating to the carbonyl oxygen of the (A) 2-methylene-1,3-dicarbonyl compound. (9) The resin composition according to any one of (1) to (8) above, which is substantially inert to water in the atmosphere. (10) A one-component curable resin composition comprising the resin composition according to any one of (1) to (9) above, and a latent basic compound or a photobase generator. (11) A kit of two-component curable resin compositions, comprising: (A) the resin composition according to any one of (1) to (9) above; and (B) a curing agent or curing catalyst containing a basic compound. (12) The resin composition according to any one of (1) to (9) above, the one-component curable resin composition according to (10) above, or the kit according to (11) above, which are used in the production of electronic components. (13) A cured product obtained by curing the resin composition according to any one of (1) to (9) above, the one-component curable resin composition according to (10) above, or the kit according to (11) above. (4) An electronic component comprising the cured product according to (13) above.

[0013] According to the present invention, it is possible to obtain a kit of a resin composition containing a 2-methylene-1,3-dicarbonyl compound, a one-component curable resin composition, and a two-component curable resin composition, all of which have a pot life (gelation time) and viscosity suitable for work. The resin composition, one-component curable resin composition, and two-component curable resin composition kit of the present invention are useful for producing various electronic components.

[0014] Hereinafter, embodiments of the present invention will be described in detail. Various numerical ranges are indicated using the symbol "to". Each of these numerical ranges includes the numerical values ​​immediately before and after the symbol "to" as the lower and upper limits, respectively.

[0015] The present invention relates to a resin composition, the composition comprising: (A) a compound represented by the following formula (I): and a molecular weight of 230 to 1000; and (B) a 2-methylene-1,3-dicarbonyl compound having an average primary particle size of 1 nm to 50 nm and a specific surface area of ​​50 m ２ / g~250m ２ The resin composition of the present invention contains fumed silica having a molecular weight of 1.001 to 1.001 g. The components contained in the resin composition of the present invention will be described below.

[0016] (A) 2-Methylene-1,3-dicarbonyl Compound The resin composition of the present invention contains (A) a 2-methylene-1,3-dicarbonyl compound. In the present invention, the (A) 2-methylene-1,3-dicarbonyl compound is represented by the following formula (I): The (A) 2-methylene-1,3-dicarbonyl compound contains one or more structural units of formula (I). In one embodiment, the (A) 2-methylene-1,3-dicarbonyl compound contains two to six, preferably two, structural units of formula (I). The structural unit of formula (I) consists of a vinyl group having two carbonyl groups covalently bonded to one π-bonded carbon and no substituent covalently bonded to the other π-bonded carbon. In such a structure, due to the influence of the carbonyl group, the π-bonded carbon in the vinyl group not bonded to the carbonyl group is susceptible to attack by nucleophiles (i.e., the vinyl group is activated). This provides the (A) 2-methylene-1,3-dicarbonyl compound with high polymerizability.

[0017] The 2-methylene-1,3-dicarbonyl compound (A) contains the structural unit of formula (I) above, and therefore undergoes polymerization of the structural units in the presence of a polymerization initiator, typically a basic compound.

[0018] The molecular weight of the (A) 2-methylene-1,3-dicarbonyl compound is 230 to 1,000, preferably 230 to 800, more preferably 240 to 800, even more preferably 240 to 700, particularly preferably 250 to 700, and most preferably 250 to 550. The molecular weight of the (A) 2-methylene-1,3-dicarbonyl compound, the mass content of the (A) 2-methylene-1,3-dicarbonyl compound when the entire composition is defined as 1, and, when the resin composition contains multiple (A) 2-methylene-1,3-dicarbonyl compounds, the mass content of each 2-methylene-1,3-dicarbonyl compound when the entire (A) 2-methylene-1,3-dicarbonyl compound in the composition is defined as 1 can be determined, for example, by calibration using a reversed-phase high-performance liquid chromatography (reverse-phase HPLC) technique, using an ODS column as the column and a mass spectrometer (MS) and PDA (detection wavelength: 190 to 800 nm) or ELSD as the detector. If the molecular weight of the (A) 2-methylene-1,3-dicarbonyl compound is less than 230, the vapor pressure at 25°C will be too high, and various problems due to volatile substances may occur. In particular, if volatile substances adhere to surrounding components, they will harden due to the base on the surface, which may lead to contamination of the surrounding components. Furthermore, such 2-methylene-1,3-dicarbonyl compounds (A) are highly reactive, making it difficult to ensure the desired gel time. On the other hand, 2-methylene-1,3-dicarbonyl compounds (A) having a molecular weight of more than 1,000 may cause adverse effects such as excessively high viscosity of compositions containing the compounds, reducing workability and limiting the amount of filler that can be added.

[0019] The 2-methylene-1,3-dicarbonyl compound (A) may contain a polyfunctional component. "Polyfunctional" refers to the 2-methylene-1,3-dicarbonyl compound containing two or more structural units of formula (I). In this specification, the number of structural units of formula (I) contained in a 2-methylene-1,3-dicarbonyl compound is referred to as the "number of functional groups" of the 2-methylene-1,3-dicarbonyl compound. Among 2-methylene-1,3-dicarbonyl compounds, those with one functionality are referred to as "monofunctional," those with two functionality groups as "bifunctional," and those with three functionality groups as "trifunctional." Because a cured product obtained using the 2-methylene-1,3-dicarbonyl compound (A) containing a polyfunctional component is crosslinked, the physical properties of the cured product, such as heat resistance and mechanical properties at high temperatures, are improved.

[0020] When the 2-methylene-1,3-dicarbonyl compound (A) contains a polyfunctional component, the cured product forms a network-like crosslinked structure, and therefore does not flow at high temperatures, particularly at temperatures above the glass transition temperature, and maintains a constant storage modulus. The storage modulus of the cured product at high temperatures can be evaluated, for example, by dynamic mechanical analysis (DMA). Generally, when a cured product that has formed a crosslinked structure is evaluated by DMA, a region in which the temperature change in the storage modulus is relatively small, called a plateau, is observed over a wide range in the temperature range above the glass transition temperature. The storage modulus in this plateau region is evaluated as a quantity related to the crosslink density, i.e., the content of the polyfunctional component in the 2-methylene-1,3-dicarbonyl compound (A).

[0021] In one embodiment, when the entire resin composition of the present invention is taken as 1, the mass proportion of the (A) 2-methylene-1,3-dicarbonyl compound is preferably 0.05 to 0.99, more preferably 0.10 to 0.98, even more preferably 0.20 to 0.97, and particularly preferably 0.50 to 0.95.

[0022] In one embodiment, the 2-methylene-1,3-dicarbonyl compound has the following formula (II): (In the formula, X １ and X ２ are each independently a single bond, O, or NR ３ (In the formula, R ３represents hydrogen or a monovalent hydrocarbon group, R １ and R ２ are each independently hydrogen, a monovalent hydrocarbon group, or a group represented by the following formula (III): (In the formula, X ３ and X ４ are each independently a single bond, O, or NR ５ (In the formula, R ５ represents hydrogen or a monovalent hydrocarbon group), W represents a spacer, R ４ represents hydrogen or a monovalent hydrocarbon group).

[0023] In one embodiment, the 2-methylene-1,3-dicarbonyl compound has the following formula (IV): (In the formula, R １ and R ２ are each independently hydrogen, a monovalent hydrocarbon group, or a group represented by the following formula (V): (Wherein, W represents a spacer, R ４ represents hydrogen or a monovalent hydrocarbon group).

[0024] In another embodiment, the 2-methylene-1,3-dicarbonyl compound has the following formula (VI): (In the formula, R １１ is represented by the following formula (VII): Each R represents a 1,1-dicarbonylethylene unit represented by the formula: １２ each independently represents a spacer; １３ and R １４ each independently represents hydrogen or a monovalent hydrocarbon group; １１ and each X １２ and X １３ are each independently a single bond, O, or NR １５ (In the formula, R １５ represents hydrogen or a monovalent hydrocarbon group, each m independently represents 0 or 1, and n represents an integer of 1 to 20.

[0025] In this specification, the term "monovalent hydrocarbon group" refers to a group generated by removing one hydrogen atom from a carbon atom of a hydrocarbon. Examples of such monovalent hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, alkyl-substituted cycloalkyl groups, aryl groups, aralkyl groups, and alkaryl groups, and these groups may partially contain heteroatoms such as N, O, S, P, and Si. The monovalent hydrocarbon group partially containing a heteroatom may have, for example, a polyether structure or a polyester structure.

[0026] The monovalent hydrocarbon group may be substituted with an alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, allyl, alkoxy, alkylthio, hydroxyl, nitro, amido, azido, cyano, acyloxy, carboxy, sulfoxy, acryloxy, siloxy, epoxy, or ester. The monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group, or an alkyl group substituted with a cycloalkyl group, more preferably an alkyl group, a cycloalkyl group, or an alkyl group substituted with a cycloalkyl group.

[0027] The number of carbon atoms in the alkyl group, alkenyl group, and alkynyl group (hereinafter collectively referred to as "alkyl group, etc.") is not particularly limited. The number of carbon atoms in the alkyl group is usually 1 to 18, preferably 1 to 16, more preferably 2 to 12, more preferably 3 to 10, and particularly preferably 4 to 8. The number of carbon atoms in the alkenyl group and alkynyl group is usually 2 to 12, preferably 2 to 10, more preferably 3 to 8, more preferably 3 to 7, and particularly preferably 3 to 6. When the alkyl group, etc. has a cyclic structure, the number of carbon atoms in the alkyl group, etc. is usually 5 to 16, preferably 5 to 14, more preferably 6 to 12, and more preferably 6 to 10. The number of carbon atoms in the alkyl group, etc. can be determined, for example, by reverse phase HPLC or nuclear magnetic resonance (NMR) spectroscopy.

[0028] The structure of the alkyl group, etc. is not particularly limited. The alkyl group, etc. may be linear or may have a side chain. The alkyl group, etc. may have a chain structure or a cyclic structure (cycloalkyl group, cycloalkenyl group, and cycloalkynyl group). The alkyl group, etc. may have one or more other substituents. For example, the alkyl group, etc. may have a substituent containing an atom other than carbon atoms and hydrogen atoms as a substituent. Furthermore, the alkyl group, etc. may contain one or more atoms other than carbon atoms and hydrogen atoms in the chain structure or cyclic structure. Examples of the atoms other than carbon atoms and hydrogen atoms include one or more of oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and silicon atoms.

[0029] Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a 2-methylcyclohexyl group. Specific examples of the alkenyl group include a vinyl group, an allyl group, and an isopropenyl group. Specific examples of the cycloalkenyl group include a cyclohexenyl group.

[0030] The 2-methylene-1,3-dicarbonyl compound is represented by the formula (II) or (IV), and R １ and R ２ are both monovalent hydrocarbon groups, R １ and R ２ is particularly preferably an alkyl group, cycloalkyl group, alkyl-substituted cycloalkyl group, aryl group, aralkyl group or alkaryl group each having 2 to 8 carbon atoms.

[0031] In this specification, the term "spacer" refers to a divalent hydrocarbon group, and more specifically, a cyclic, straight-chain, or branched, substituted or unsubstituted alkylene group. There is no particular limitation on the number of carbon atoms in the alkylene group. The number of carbon atoms in the alkylene group is usually 1 to 12, preferably 2 to 10, more preferably 3 to 8, and even more preferably 4 to 8. Here, the alkylene group may contain, as desired, a group containing a heteroatom selected from N, O, S, P, and Si. Furthermore, the alkylene group may have an unsaturated bond. In one aspect, the spacer is an unsubstituted alkylene group having 4 to 8 carbon atoms. Preferably, the spacer is a straight-chain substituted or unsubstituted alkylene group, more preferably a group represented by the formula -(CH ２ ) ｎ - (where n is an integer of 2 to 10, preferably 4 to 8), and the carbon atoms at both ends of the alkylene group bond to the remainder of the 2-methylene-1,3-dicarbonyl compound. Specific examples of the divalent hydrocarbon group as the spacer include, but are not limited to, a 1,4-n-butylene group and a 1,4-cyclohexylenedimethylene group.

[0032] When the 2-methylene-1,3-dicarbonyl compound has a spacer, the number of carbon atoms in the terminal monovalent hydrocarbon group is preferably 6 or less. That is, when the 2-methylene-1,3-dicarbonyl compound is represented by the formula (II) or (IV), R ４ is preferably an alkyl group having 1 to 6 carbon atoms, provided that R １ and R ２ When one of the formulas is represented by formula (III) or (V), R １ and R ２ The other is preferably an alkyl group having 1 to 6 carbon atoms. In this case, in the formula (II) or (IV), R １ and R ２ may be represented by the formula (III) or (V), but preferably, R １ and R ２Only one of the above is represented by the formula (III) or the formula (V). Preferably, the 2-methylene-1,3-dicarbonyl compound is represented by the formula (IV).

[0033] Particularly preferred compounds having a spacer include those represented by the formula (IV) １ or R ２ one of which is an ethyl group, an n-hexyl group, or a cyclohexyl group, and the other is represented by the formula (V), W is a 1,4-n-butylene group or a 1,4-cyclohexylenedimethylene group, and R ４ is an ethyl group, an n-hexyl group, or a cyclohexyl group. １ and R ２ is represented by the formula (V), W is either a 1,4-n-butylene group or a 1,4-cyclohexylenedimethylene group, and R ４ is an ethyl group, an n-hexyl group, or a cyclohexyl group.

[0034] Various 2-methylene-1,3-dicarbonyl compounds can be synthesized by methods disclosed in published patent publications such as WO2012 / 054616, WO2012 / 054633, and WO2016 / 040261. When both ends of the structural unit represented by formula (I) contained in the 2-methylene-1,3-dicarbonyl compound are bonded to oxygen atoms, a known method such as transesterification with a diol or polyol disclosed in JP-A-2015-518503 can be used to produce a 2-methylene-1,3-dicarbonyl compound having a higher molecular weight in which a plurality of structural units represented by formula (I) are bonded via ester bonds and the spacer. The 2-methylene-1,3-dicarbonyl compound thus produced is a compound represented by formula (II) or formula (IV), wherein R １ and R ２ , R in the formula (III) or the formula (V) ４ and R in the formula (VI) １４ and R １３In particular, polyfunctional components (i.e., 2-methylene-1,3-dicarbonyl compounds having two or more structural units of formula (I)) can be synthesized by the method disclosed in JP-A-2015-517973, for example.

[0035] Specific examples of preferred compounds as the (A) 2-methylene-1,3-dicarbonyl compound include dipentyl methylene malonate, dihexyl methylene malonate, dicyclohexyl methylene malonate, ethyl octyl methylene malonate, propyl hexyl methylene malonate, 2-ethylhexyl-ethyl methylene malonate, and ethyl phenyl-ethyl methylene malonate. These are preferred because of their low volatility and high reactivity. From the viewpoint of ease of handling, dihexyl methylene malonate and dicyclohexyl methylene malonate are particularly preferred.

[0036] As the 2-methylene-1,3-dicarbonyl compound (A), one of the above-mentioned 2-methylene-1,3-dicarbonyl compounds may be used, or two or more of them may be used in combination.

[0037] (B) Fumed Silica The resin composition of the present invention contains (B) fumed silica having an average primary particle size of 1 nm to 50 nm and a specific surface area of ​​50 m ２ / g~250m ２ / g of fumed silica, which prevents variations in curability and simultaneously provides the resin composition containing the 2-methylene-1,3-dicarbonyl compound (A) with a pot life (gelation time) and viscosity suitable for work.

[0038] Fumed silica is a finely divided, synthetic amorphous silica obtained by hydrolyzing a halogenated silane such as silicon tetrachloride in an oxyhydrogen flame (dry process). Fumed silica contains aggregates formed by the fusion of primary particles (average primary particle size of approximately 1 to 200 nm) through relatively strong interactions. Some of these aggregates further fuse through relatively weak interactions to form agglomerates. The agglomerates can be easily de-agglomerated by dispersing them in an appropriate medium, but de-aggregating the agglomerates back to primary particles is considered difficult using conventional methods.

[0039] In the present invention, the average primary particle size of the (B) fumed silica is 1 nm to 50 nm. In one embodiment, from the viewpoint of increasing the viscosity in a low shear rate range (e.g., 1 rpm) and obtaining a usable time (gelation time) suitable for work, the average primary particle size of the (B) fumed silica is preferably 1 to 40 nm, more preferably 1 to 20 nm. In one embodiment, from the viewpoint of ensuring a longer usable time (gelation time), the average primary particle size of the (B) fumed silica is preferably 3 to 50 nm, more preferably 5 to 30 nm. In one embodiment, from the viewpoint of shortening the curing time, the average primary particle size of the (B) fumed silica is preferably 5 to 20 nm, more preferably 5 to 15 nm. Herein, the gelation time is the time from the time when the curable resin composition reaches a state where it can start curing under specified conditions until the curable resin composition loses fluidity. On the other hand, in this specification, the curing time refers to the time required for the polymerization to proceed and solidify to a degree that makes the silica harder and stronger and that enables it to hold and adhere objects, regardless of whether a crosslinked structure is formed. In this specification, unless otherwise specified, the average primary particle size of (B) fumed silica is measured by analyzing a transmission electron microscope photograph taken of a sample of (B) fumed silica using image processing software, and quantifying and statistically processing the sizes of all or some of the particles in the photograph.

[0040] In the present invention, the specific surface area of ​​(B) fumed silica is 50 m ２ / g~250m ２ In one embodiment, from the viewpoint of ensuring a longer usable time (gelation time), the specific surface area of ​​the (B) fumed silica is preferably 50 m ２ / g~240m ２ In one embodiment, from the viewpoint of shortening the curing time, the specific surface area of ​​the (B) fumed silica is preferably 80 to 250 m ２ / g, more preferably 100 to 250m ２ / g, and more preferably 110 to 250m ２ In this specification, the specific surface area of ​​(B) fumed silica is measured by the BET method unless otherwise specified.

[0041] The surface of (B) fumed silica may be hydrophobized with a surface treatment agent. In the present invention, it is preferable that at least a portion of the surface of (B) fumed silica is hydrophobized with a surface treatment agent. Examples of the surface treatment agent include silicone oil (e.g., polydimethylsiloxane), silane coupling agents (e.g., n-octyltrialkoxysilane), silylating agents (e.g., hexamethyldisilazane and dimethyldichlorosilane), and the like. The surface treatment agent is preferably any of silicone oil, silane coupling agents, and silylating agents, and more preferably any of silicone oil, hexamethyldisilazane, and dimethyldichlorosilane. The surface treatment agents used for hydrophobization may be used alone or in combination of two or more. Furthermore, multiple fumed silicas, each having a hydrophobized surface with a different surface treatment agent, may be used in combination.

[0042] The content of (B) fumed silica in the resin composition of the present invention is not particularly limited, and the content of (B) fumed silica per part by mass of the resin composition of the present invention is preferably 0.01 to 0.3 parts by mass, more preferably 0.02 to 0.24 parts by mass, and particularly preferably 0.03 to 0.19 parts by mass.

[0043] The resin composition of the present invention may contain the following components as needed, in addition to the (A) 2-methylene-1,3-dicarbonyl compound and (B) fumed silica.

[0044] Inorganic Filler: If desired, the resin composition of the present invention may further contain (B) an inorganic filler other than fumed silica. Examples of inorganic fillers include silica produced by methods other than dry processes, such as the melting method, the deflagration method (VMC (Vaporized Metal Combustion) method), and the sol-gel method; metal oxides such as calcium carbonate, alumina, and zinc oxide; metals such as nickel, copper, and silver; glass beads; bentonite; acetylene black; and ketjen black. The inorganic filler may be surface-treated with a silane coupling agent or the like. The use of a surface-treated inorganic filler is expected to prevent aggregation of the inorganic filler. The inorganic filler may be used alone or in combination of two or more types.

[0045] The average particle size of the inorganic filler (or the average maximum diameter if the filler is not spherical) is not particularly limited, but is preferably 0.005 to 50 μm in order to uniformly disperse the filler in the resin composition and also because it provides excellent injectability when the resin composition is used as an adhesive, an underfill, or other liquid sealing material. Here, the average particle size of the inorganic filler is measured using a laser diffraction / scattering particle size distribution analyzer or a dynamic light scattering Nanotrac particle size analyzer.

[0046] The inorganic filler may be insulating or conductive. When the inorganic filler is insulating, the content of the inorganic filler is preferably 0 to 95 parts by mass, more preferably 0 to 85 parts by mass, and even more preferably 0 to 50 parts by mass, per 100 parts by mass of all components of the resin composition. In one embodiment, when the resin composition is used as a liquid encapsulant such as an underfill, the content of the inorganic filler is preferably 0 to 50 parts by mass, per 100 parts by mass of all components of the resin composition, from the viewpoint of avoiding deterioration of the injectability of the resin composition. In one embodiment, the content of the inorganic filler is preferably 10 to 95 parts by mass, per 100 parts by mass of all components of the resin composition, from the viewpoint of reducing the linear expansion coefficient of the resin composition. Furthermore, when the inorganic filler is conductive, the content of the inorganic filler is preferably 50 to 95 parts by mass, per 100 parts by mass of all components of the resin composition, from the viewpoint of electrical conductivity, so that the resin composition can be used as a conductive paste.

[0047] Stabilizer: The resin composition of the present invention may further contain a stabilizer, if desired. The stabilizer is added to enhance the storage stability of the resin composition and to suppress the occurrence of polymerization reactions caused by unintended radicals or basic components. 2-methylene 1,3-dicarbonyl compounds may generate radicals themselves with a low probability, and unintended radical polymerization reactions may occur using these radicals as the starting point. Furthermore, 2-methylene 1,3-dicarbonyl compounds may undergo anionic polymerization reactions when very small amounts of basic components are mixed in. The addition of a stabilizer can suppress the occurrence of such polymerization reactions caused by unintended radicals or basic components.

[0048] Known stabilizers can be used, such as strong acids and radical scavengers. Specific examples of stabilizers include trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, 4-methoxyphenol, and hydroquinone. Among these, preferred stabilizers are at least one selected from maleic acid, methanesulfonic acid, N-nitroso-N-phenylhydroxylamine aluminum, and 4-methoxyphenol. Furthermore, known stabilizers disclosed in JP 2010-117545 A, JP 2008-184514 A, and the like can also be used. The stabilizers may be used alone or in combination of two or more.

[0049] Interfacial Treatment Agent The resin composition of the present invention may further contain an interfacial treatment agent, if desired. The interfacial treatment agent is not particularly limited, but a coupling agent can typically be used. The coupling agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds with an inorganic material, and the other is a functional group that chemically bonds with an organic material. When the resin composition contains a coupling agent, the adhesion of the resin composition to a substrate or the like is improved.

[0050] Examples of coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, titanium coupling agents, etc. One type of coupling agent may be used, or two or more types may be used in combination.

[0051] Examples of functional groups possessed by coupling agents that chemically bond with organic materials include vinyl groups, epoxy groups, styryl groups, methacrylic groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, sulfide groups, and isocyanate groups.

[0052] Pigment: The resin composition of the present invention may further contain a pigment if desired. The inclusion of a pigment allows for the adjustment of the chromaticity of the resin composition of the present invention. Pigments are not particularly limited, but examples include carbon black, titanium black (e.g., titanium nitride), black organic pigments, mixed-color organic pigments, and inorganic pigments. Examples of black organic pigments include perylene black and aniline black. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, magenta, cyan, etc. Examples of inorganic pigments include graphite and fine particles of metals and their oxides, composite oxides, sulfides, nitrides, etc. Examples of metals include titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, etc. Pigments may be used alone or in combination. The pigment is preferably carbon black or titanium black.

[0053] Plasticizer: The resin composition of the present invention may further contain a plasticizer, if desired. Any known plasticizer can be blended as the plasticizer. The plasticizer can improve moldability and adjust the glass transition temperature. Plasticizers that have good compatibility and are unlikely to bleed can be used. Examples of plasticizers include phthalates such as di-n-butyl phthalate, di-n-octyl phthalate, bis(2-ethylhexyl) phthalate, di-n-decyl phthalate, and diisodecyl phthalate; adipates such as bis(2-ethylhexyl) adipate and di-n-octyl adipate; sebacates such as bis(2-ethylhexyl) sebacate and di-n-butyl sebacate; azelaates such as bis(2-ethylhexyl) azelate; and paraffins such as chlorinated paraffins. Examples of suitable plasticizers include glycols such as polypropylene glycol, epoxy-modified vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, phosphate esters such as trioctyl phosphate and triphenyl phosphate, phosphites such as triphenyl phosphite, ester oligomers such as esters of adipic acid and 1,3-butylene glycol, low-molecular-weight polymers such as low-molecular-weight polybutene, low-molecular-weight polyisobutylene, and low-molecular-weight polyisoprene, and oils such as process oil and naphthenic oil. These plasticizers may be used alone or in combination of two or more.

[0054] Polymer Compound The resin composition of the present invention may further contain a polymer compound if desired. In one embodiment, the resin composition of the present invention further contains a polymer compound. The polymer compound is usually used for the purpose of adjusting the viscosity of the resin composition. In the resin composition of the present invention, the polymer compound may be dissolved or dispersed as a particulate solid, but is preferably dissolved.

[0055] In the resin composition of the present invention, when the polymer compound is dissolved, the polymer compound preferably has a weight-average molecular weight of 10,000 to 1,000,000. From the viewpoint of solubility, the polymer compound is preferably a (meth)acrylate polymer. The term "(meth)acrylate polymer" is a general term for "acrylate polymer" and "methacrylate polymer." An acrylate polymer is a polymer obtained by polymerizing one or more alkyl acrylates (alkyl esters of acrylic acid), and a methacrylate polymer is a polymer obtained by polymerizing one or more alkyl methacrylates (alkyl esters of methacrylic acid). The term "(meth)acrylate polymer" also includes copolymers obtained by copolymerizing alkyl acrylates and alkyl methacrylates.

[0056] On the other hand, when the polymer compound is dispersed as a particulate solid in the resin composition of the present invention, the particulate solid preferably has an average primary particle diameter of 100 μm or less. Furthermore, the particulate solid may be formed of a crystal of the polymer compound or an amorphous polymer compound.

[0057] When the resin composition of the present invention further contains a polymer compound, the content of the polymer compound is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the total of all components of the resin composition.

[0058] The resin composition of the present invention may further contain components other than the above-described components, such as a flame retardant, an ion trapping agent, an antifoaming agent, a leveling agent, a foam breaker, a solvent, etc., within the range that does not impair the effects of the present invention. When considering the impact on the environment, it is preferable that the resin composition does not contain an organic solvent.

[0059] The resin composition of the present invention contains the above-mentioned components as needed, in addition to the (A) 2-methylene-1,3-dicarbonyl compound and (B) fumed silica. The resin composition of the present invention can be prepared by mixing these components. A known device can be used for mixing. For example, mixing can be performed using a known device such as a Henschel mixer or a roll mill. These components may be mixed simultaneously, or some of the components may be mixed first and the rest may be mixed later.

[0060] The resin composition of the present invention may have various physical and / or chemical properties as needed, taking into consideration the workability during assembly and installation of electronic components used in semiconductor devices. For example, in one embodiment, the resin composition of the present invention has a viscosity measured at 1 rpm using an E-type viscometer of preferably 100 to 100,000 mPa·s, more preferably 200 to 80,000 mPa·s, even more preferably 500 to 50,000 mPa·s, and particularly preferably 1,000 to 10,000 mPa·s. By having the viscosity of the resin composition (measured at a low shear rate) within the above range, it is possible to suppress misalignment during assembly / installation, dripping from the discharge device, and contamination of other components (due to bleeding, flow, etc.), thereby improving workability.

[0061] Basic Compound When the resin composition of the present invention containing the above components is brought into contact with a basic compound, it can be cured by the action of the basic compound as a curing agent or curing catalyst. Therefore, a curable resin composition can be produced by combining the resin composition of the present invention with a curing agent or curing catalyst containing a basic compound. The basic compound is expected to contribute to the polymerization initiation reaction when the curable resin composition is cured by a Michael addition reaction. The basic compounds used in the present invention may be used alone or in combination of two or more. The present invention also provides a curable resin composition, particularly a one-component curable resin composition, containing the resin composition of the present invention and one or more basic compounds.

[0062] The method for contacting the resin composition of the present invention with a basic compound is not particularly limited. Examples of such a method include a method of mixing the resin composition of the present invention with a basic compound, a method of applying the resin composition of the present invention onto a basic compound that has been applied in advance to the surface of an adherend, and a method of applying the resin composition of the present invention to the surface of an adherend made of a solid having basic sites on its surface.

[0063] The basic compound used in the present invention is not particularly limited as long as it exhibits sufficient basicity to function as a curing agent or curing catalyst for the resin composition of the present invention, but typically includes an organic base, an inorganic base, or an organometallic material. Examples of organic bases include the amine compounds described below. Examples of inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali or alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate; and metal bicarbonates such as potassium bicarbonate and sodium bicarbonate. Examples of organometallic materials include organic alkali metal compounds such as butyllithium, t-butyllithium, and phenyllithium, and organocopper reagents prepared therefrom; organic alkaline earth metal compounds such as methylmagnesium bromide, dimethylmagnesium, and phenylmagnesium chloride, and organocopper reagents prepared therefrom; alkoxides such as sodium methoxide and t-butylmethoxide; and carboxylates such as sodium benzoate.

[0064] When a curable resin composition using the resin composition of the present invention is used for electronic material applications, if the composition contains an inorganic base or an organometallic material, there is a concern that the composition may have an unintended effect on the electrical properties of peripheral electrical and electronic circuits. Therefore, the basic compound used in the present invention is preferably one that does not contain an alkali metal, an alkaline earth metal, a transition metal element, or a halogen element. In another aspect, the basic compound used in the present invention is nonionic. Basic compounds are broadly classified into ionic and nonionic compounds, and it is preferable that the basic compound is nonionic, particularly when the basic compound is mixed with the resin composition of the present invention.

[0065] The basic compound used in the present invention is preferably an organic base, more preferably an amine compound. The amine compound is an organic compound having at least one primary amino group, one secondary amino group, or one tertiary amino group in the molecule, and may have two or more different types of amino groups of these classes simultaneously in the same molecule.

[0066] Examples of compounds having a primary amino group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, and diaminodiphenylsulfone.

[0067] Examples of compounds having a secondary amino group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, and phenylethylamine.

[0068] Examples of compounds having a tertiary amino group include triethylamine, tributylamine, trihexylamine, triallylamine, 3-diethylaminopropylamine, dibutylaminopropylamine, tetramethylethylenediamine, tri-n-octylamine, dimethylaminopropylamine, N,N-dimethylethanolamine, triethanolamine, N,N-diethylethanolamine, N-methyl-N,N-diethanolamine, N,N-dibutylethanolamine, triphenylamine, 4-methyltriphenylamine, Examples of such an amine include 4,4-dimethyltriphenylamine, diphenylethylamine, diphenylbenzylamine, N,N-diphenyl-p-anisidine, 1,1,3,3-tetramethylguanidine, N,N-dicyclohexylmethylamine, 1,4-diazabicyclo[2,2,2]octane, 2,6,10-trimethyl-2,6,10-triazaundecane, 1-benzylpiperidine, N,N-dimethylbenzylamine, N,N-dimethyldodecylamine, N-ethyl-N-methylbenzylamine, and N,N-diethylbenzylamine.

[0069] Furthermore, the compound having two or more different amino groups simultaneously in the same molecule is not particularly limited, but examples thereof include guanidine compounds, imidazole compounds, etc. Examples of guanidine compounds include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluoylguanidine, 1,1,3,3-tetramethylguanidine, etc. Examples of the imidazole compound include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1))-ethyl-S-triazine, and 2,4-diamino-6-(2'-methylimidazolyl-(1))-ethyl-S-triazine. Examples of imidazole compounds include N,N'-(2-methylimidazolyl-1-ethyl)-(2-methylimidazolyl-(1)-ethyl)-adipoyldiamide, N ...adipoyldiamide, N-(2-methylimidazolyl-1-ethyl)-adipoyldiamide, N-

[0070] From the viewpoint of smooth progress of the curing reaction, the amine compound preferably contains a secondary or tertiary amino group. When the amino group contained in the amine compound is primary, there is a high possibility that active hydrogen generated from the amino group will inhibit the polymerization reaction. The amine compound more preferably contains a tertiary amino group. In other words, the amine compound is more preferably a tertiary amine compound. The amine compound preferably does not contain alkali metal, alkaline earth metal, or transition metal elements or halogen elements. The amine compound preferably does not contain a group having active hydrogen, such as a hydroxy group or a sulfhydryl group.

[0071] In a curable resin composition using the resin composition of the present invention, if the basic compound is solid during curing, the reaction will proceed on the surface of the basic compound and will not spread throughout the composition, resulting in uneven curing. For this reason, it is preferable that the basic compound is not solid during curing, i.e., is liquid or soluble in the resin composition.

[0072] The molecular weight of the amine compound is preferably 100 to 1,000, more preferably 100 to 500, and even more preferably 110 to 300. If the molecular weight of the amine compound is less than 100, it will be highly volatile, raising concerns about its effect on surrounding components and fluctuations in the physical properties of the cured product. If the molecular weight of the amine compound exceeds 1,000, it will raise concerns about an increase in the viscosity of the amine compound and a decrease in its dispersibility in the composition. In the present invention, the basic compounds may be used alone or in combination of two or more types.

[0073] Specific examples of preferred amine compounds include triethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,1,3,3-tetramethylguanidine, N,N-dimethylbenzylamine, N-ethyl-N-methylbenzylamine, 2,6,10-trimethyl-2,6,10-triazaundecane, N,N-dimethyloctylamine, N,N-dimethyloctadecylamine, and N,N-dimethyldodecylamine, N,N-diisopropylethylamine, and N,N-dicyclohexylmethylamine, but are not limited to these.

[0074] In the present invention, the basic compound may be inactive by separation or latentization and may be activated by any stimulus such as heat, light, mechanical shear, etc. More specifically, the basic compound may be a latent basic compound such as a microcapsule, ion dissociation type, or inclusion type, or may be in a form that generates a base when exposed to heat, light, electromagnetic waves, ultrasound, or physical shear.

[0075] In one embodiment, the basic compound is a photobase generator. The photobase generator is a compound capable of generating a basic compound through a chemical reaction in which light energy directly or indirectly participates. The photobase generators may be used alone or in combination of two or more. In the present invention, the photobase generator is not particularly limited, but it is preferable that the photobase generator is excited by absorption of ultraviolet light (preferably ultraviolet light with a wavelength of 365 nm) and undergoes a chemical reaction to generate a basic compound, or that the photobase generator undergoes a chemical reaction by energy transferred from a photosensitizer excited by absorption of ultraviolet light and generates a basic compound. Furthermore, it is preferable that the photobase generator has a structure that does not generate outgassing in principle. The photobase generator may be ionic or nonionic.

[0076] In one embodiment, the basic compound is activated by heat. In this case, the basic compound is either (i) physically separated from the 2-methylene-1,3-dicarbonyl compound (A) before heating and becomes able to come into contact with the 2-methylene-1,3-dicarbonyl compound (A) upon heating, or (ii) latent and not basic before heating (and therefore does not act as a curing agent or curing catalyst) and becomes basic upon heating. Although such a basic compound is not particularly limited, it is preferable that the basic compound is activated by heating at 40 to 100°C.

[0077] The present invention also provides a curable resin composition, particularly a one-component curable resin composition, containing the resin composition of the present invention and a latent basic compound or a photobase generator.

[0078] The resin composition of the present invention can also be used as a base agent in combination with a curing agent or curing catalyst containing one or more basic compounds to form a two-part curable resin composition (adhesive) kit. That is, the present invention also relates to a two-part curable resin composition kit comprising (A) the resin composition described above; and (B) a curing agent or curing catalyst containing a basic compound. The two-part curable resin composition kit of the present invention can be cured by contacting the base agent with the curing agent.

[0079] In the present invention, the amount of the basic compound used is preferably 0.01 mol % to 30 mol %, more preferably 0.01 mol % to 10 mol %, based on the total amount (100 mol %) of the 2-methylene-1,3-dicarbonyl compound (A) in the resin composition. If the amount of the basic compound is less than 0.01 mol %, curing becomes unstable. Conversely, if the amount of the basic compound is more than 30 mol %, a large amount of the basic compound that does not form a chemical bond with the resin matrix remains in the cured product, causing a decrease in the physical properties of the cured product and bleeding, etc.

[0080] As described above, the resin composition of the present invention cures through the action of a nucleophilic reagent, such as an amine compound. While water can also act as a nucleophilic reagent in some cases, the nucleophilicity (reactivity with electrophiles) of water is not as high as that of amine compounds. Therefore, the resin composition of the present invention typically does not cure when in contact with water and can be stored in contact with an atmosphere containing water vapor. This property of the resin composition of the present invention is based on the fact that the electrophilicity (reactivity with nucleophiles) of the 2-methylene-1,3-dicarbonyl compound (A) is high enough to allow direct reaction with an amine compound, but not high enough to allow direct reaction with water. However, if the resin composition of the present invention contains a substance that increases the electrophilicity of the 2-methylene-1,3-dicarbonyl compound (A), it may become impossible to store the resin composition in contact with an atmosphere containing water vapor. Examples of such substances include Lewis acid compounds. Lewis acidic compounds coordinate to the carbonyl oxygen of the 2-methylene-1,3-dicarbonyl compound (A) and thereby withdraw electrons, thereby enhancing the electrophilicity of the 2-methylene-1,3-dicarbonyl compound (A). Among these, Lewis acidic compounds containing monovalent to tetravalent metal cations have a particularly high effect. Therefore, it is preferable that the resin composition of the present invention does not contain any Lewis acidic compounds, particularly Lewis acidic compounds containing monovalent to tetravalent metal cations. In one embodiment, the resin composition of the present invention is substantially free of any Lewis acidic compounds capable of coordinating to the carbonyl oxygen of the 2-methylene-1,3-dicarbonyl compound (A). In such cases, the resin composition of the present invention is substantially inert to water in the atmosphere and can be stored in contact with an atmosphere containing water vapor.

[0081] An example of a characteristic required for a curable resin composition used in the manufacture of electronic components for semiconductor devices is a suitable pot life. Because the pot life allows tasks such as component positioning and alignment to be performed, this is an important characteristic for the manufacture of electronic components, which require particularly high precision. The pot life of a curable resin composition can be evaluated, for example, by its gelation time. Herein, gelation refers to the phenomenon in which a resin composition loses fluidity as the resin components undergo a chemical reaction to increase their molecular weight. Gelation time refers to the time from when the curable resin composition reaches a state in which it can begin curing under specified conditions until the curable resin composition loses fluidity. Meanwhile, herein, curing and curing time refer to the phenomenon and time during which the composition solidifies as polymerization progresses, regardless of whether a crosslinked structure is formed, to a degree that allows it to hold and adhere objects. These terms are defined differently from gelation and gelation time. The resin composition of the present invention has a pot life (gelation time) suitable for use in applications. In this specification, the gel time (GT) of a resin composition refers to the time from mixing 0.01 to 0.1 parts by mass of N,N-dimethylbenzylamine with 1 part by mass of the resin composition at 25° C. until the resin composition loses fluidity. The gel time (GT) of the resin composition of the present invention is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, particularly preferably 3 to 15 minutes, and even more preferably 4 to 10 minutes.

[0082] The gel time of the 2-methylene-1,3-dicarbonyl compound (A) can be measured in the same manner as the gel time (GT) of the resin composition. That is, in this specification, the gel time (GT) of the 2-methylene-1,3-dicarbonyl compound (A) Ａ ) is the time from mixing 0.01 to 0.1 parts by mass of N,N-dimethylbenzylamine with 1 part by mass of the 2-methylene-1,3-dicarbonyl compound (A) contained in the resin composition at 25°C until the 2-methylene-1,3-dicarbonyl compound (A) loses fluidity. In the present invention, the GT Ａis compared with the GT of the resin composition of the present invention containing the 2-methylene-1,3-dicarbonyl compound (A) measured under the same conditions, Ａ That is, the resin composition of the present invention has a gel time (GT Ａ ) exhibits an extended gel time (GT).

[0083] Regarding the resin composition of the present invention having a certain gel time (GT), the gel time (GT) of the 2-methylene-1,3-dicarbonyl compound (A) is Ａ ) to the gel time (GT) of the resin composition (wherein the ratio of the mass of N,N-dimethylbenzylamine to the mass of the resin composition in the measurement of GT is Ａ (Equivalent to the ratio of the mass of N,N-dimethylbenzylamine to the mass of the 2-methylene-1,3-dicarbonyl compound (A) in the measurement of (A)) is preferably 1.1 to 3, more preferably 1.5 to 2.5, and particularly preferably 1.7 to 2.1.

[0084] The resin composition of the present invention, as well as the curable resin composition and kit using the resin composition of the present invention, can be used as an adhesive or sealant. In particular, they can be used as a one-component resin composition, a one-component adhesive, or a sealant. Furthermore, they can be used as a solventless one-component resin composition, a solventless one-component adhesive, or a sealant. Specifically, the resin composition, curable resin composition, and kit are suitable as adhesives or sealants for manufacturing electronic components. More specifically, the resin composition, curable resin composition, and kit can be used for bonding and sealing components for camera modules, and are particularly suitable for bonding sensor modules such as image sensor modules. The present invention also provides electronic components bonded using the resin composition or a curable resin composition or kit using the resin composition. Furthermore, electronic components sealed using the resin composition, curable resin composition, or kit are also provided. The resin composition and curable resin composition can also be used as both an insulating composition and a conductive composition. The present invention also provides a cured product obtained by curing the resin composition of the present invention or the curable resin composition or kit using the resin composition of the present invention as described above. Electronic components containing this cured product are also provided.

[0085] The curable resin composition can be supplied to the surface to be adhered using, for example, a jet dispenser or an air dispenser. The curable resin composition can be cured at room temperature without heating. The curable resin composition can also be cured by heating at a temperature of, for example, 25 to 80°C. The heating temperature is preferably 50 to 80°C. The heating time is, for example, 0.01 to 4 hours.

[0086] Examples and comparative examples of the present invention will be described below, but the present invention is not limited to these. In the following examples and comparative examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0087] [Preparation of Resin Composition] The raw materials for the resin compositions used in the Examples and Comparative Examples are as follows: (A) 2-methylene-1,3-dicarbonyl compound The compounds used as the (A) 2-methylene-1,3-dicarbonyl compound in the Examples and Comparative Examples are as follows: (A-1): Dihexylmethylenemalonate (DHMM) (manufactured by SIRRUS, Chemilian (registered trademark) L3000 XP) (A-2): Dicyclohexylmethylenemalonate (DCHMM) (manufactured by SIRRUS, Chemilian (registered trademark) H4000 XP) The specific structures of the above 2-methylene-1,3-dicarbonyl compounds are as shown in the chemical formulas in Table 1 below.

[0088] (B) Fumed Silica In the examples and comparative examples, the compounds used as (B) fumed silica are as follows: (B-1): Surface-treated fumed silica (trade name: AEROSIL (registered trademark) NX90G, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 20 nm, specific surface area 64 m ２ / g, surface-treated with hexamethyldisilazane) (B-2): Surface-treated fumed silica (trade name: AEROSIL (registered trademark) R202, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 14 nm, specific surface area 98 m ２ / g, surface-treated with silicone oil) (B-3): Surface-treated fumed silica (trade name: AEROSIL (registered trademark) R972, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 16 nm, specific surface area 105 m ２ / g, surface-treated with dimethyldichlorosilane) (B-4): Surface-treated fumed silica (trade name: AEROSIL (registered trademark) RY200, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 12 nm, specific surface area 107 m ２ / g, surface-treated with silicone oil) (B-5): Surface-treated fumed silica (trade name: CAB-O-SIL (registered trademark) TS-720, manufactured by Cabot Corporation, average primary particle diameter 15 nm, specific surface area 120 m ２ / g, surface-treated with silicone oil) (B-6): Surface-treated fumed silica (trade name: AEROSIL (registered trademark) RX200, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 12 nm, specific surface area 145 m ２ / g, surface-treated with hexamethyldisilazane) (B-7): Non-surface-treated fumed silica (trade name: AEROSIL (registered trademark) 200, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 12 nm, specific surface area 207 m ２ / g, not surface-treated) (B-8): Surface-treated fumed silica (trade name: AEROSIL (registered trademark) R976S, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 7 nm, specific surface area 238 m ２ / g, surface treated with dimethyldichlorosilane)

[0089] (B') Fumed silica other than the above (B) (B'-1): Surface-treated fumed silica (trade name: AEROSIL (registered trademark) RX50, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 40 nm, specific surface area 33 m ２ / g, surface treated with hexamethyldisilazane)

[0090] (C) Basic Compound In the examples and comparative examples, the compounds used as (C) basic compound are as follows: (C-1): N,N-dimethylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 135.21)

[0091] [Examples 1 to 12, Comparative Examples 1 to 3] Resin compositions were prepared by dispersing (A) a 2-methylene-1,3-dicarbonyl compound and (B) fumed silica (or (B') fumed silica other than (B)) in the mass ratio shown in Table 2 using a hybrid mixer. Note that Comparative Examples 1 and 2 are single compounds (unless unintentionally mixed impurities are taken into consideration), but for convenience they will be referred to as "resin compositions" here.

[0092] In the examples and comparative examples, the properties of the resin compositions were measured as follows.

[0093] [Evaluation of viscosity of resin composition] The viscosity (unit: mPa s) of the produced resin composition was measured using an E-type viscometer (TVE-25H: manufactured by Toki Sangyo Co., Ltd., rotor: 3° × R9.7 or 1°34' × R24) set to the appropriate measurement range (H, R, or U) under conditions of 25°C ± 2°C and 50% RH ± 10% RH at a rotor rotation speed of 1 rpm. The results are shown in Table 2. Note that measured values ​​of less than 640 mPa s are below the calibration limit of the viscometer and are therefore used as reference values.

[0094] [Evaluation of gelation time of resin composition] 1 g of the resin composition of each Example and Comparative Example was weighed into a screw cap bottle made of borosilicate glass, and (C-1) (0.02 parts by mass per 1 part by mass of DHMM when the resin composition contains DHMM, and 0.04 parts by mass per 1 part by mass of DCHMM when the resin composition contains DCHMM) was added to this at room temperature and mixed quickly, and the time until the resulting mixture generated heat and essentially lost fluidity (gelation time (GT), unit: minutes) was measured. In addition, the gelation time (GT) of component (A) was Ａ ) (i.e., the gelation time of the resin composition of Comparative Example 1 or Comparative Example 2) (wherein the ratio of the mass of N,N-dimethylbenzylamine to the mass of the resin composition in the measurement of GT is the ratio of the mass of N,N-dimethylbenzylamine to the mass of the resin composition in the measurement of GT). Ａ The viscosity of the component (A) was calculated (this is equal to the ratio of the mass of N,N-dimethylbenzylamine to the mass of component (A) in the measurement of the viscosity of the component (A)). The results are shown in Table 2. The phrase "substantially loses fluidity" means that the content in the screw cap bottle becomes so viscous that it cannot be stirred with a polypropylene stick.

[0095]

[0096]

[0097] (Discussion of Results) The resin compositions of the present invention, which contain (B) fumed silica having an average primary particle size and specific surface area within a predetermined range in combination with (A) a 2-methylene-1,3-dicarbonyl compound, have a viscosity (measured at a low shear rate) suitable for work (Examples 1 to 12). In addition, the gel time (GT) of the resin compositions of the present invention was measured at a low shear rate and the gel time (GT) of the 2-methylene-1,3-dicarbonyl compound (A) contained in the composition. Ａ ) (Comparative Examples 1 and 2) were able to be extended to a moderate extent.

[0098] In contrast, a resin composition containing fumed silica whose average primary particle size and / or specific surface area are not within the predetermined range has a very low viscosity, and its gel time (GT) is shorter than the gel time (GT) of the 2-methylene-1,3-dicarbonyl compound (A) contained in the composition. Ａ ) (Comparative Examples 1 and 2), the extension was not sufficient (Comparative Example 3).

[0099] The resin composition containing the 2-methylene-1,3-dicarbonyl compound of the present invention has a pot life (gelation time) and viscosity suitable for work, and is therefore useful for the production of various electronic components, particularly those requiring high positional accuracy.

[0100] The disclosure of Japanese Patent Application No. 2022-017009 (filing date: February 7, 2022) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described 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) Formula (I): 【Chemistry 1】 and a molecular weight of 230 to 1000; and (B) The average primary particle size is 1 nm to 50 nm and the specific surface area is 50 m ２ / g~250m ２ / g of fumed silica.

2. The resin composition according to claim 1, wherein the content of (B) fumed silica per 1 part by mass of the resin composition is 0.01 to 0.3 parts by mass.

3. 3. The resin composition according to claim 1, wherein the gel time (GT) of the resin composition, which is the time from mixing 0.01 to 0.1 parts by mass of N,N-dimethylbenzylamine with 1 part by mass of the resin composition at 25°C until the resin composition loses fluidity, is 1 minute to 60 minutes.

4. The gel time (GT) of the 2-methylene-1,3-dicarbonyl compound (A) is the time from mixing 0.01 to 0.1 parts by mass of N,N-dimethylbenzylamine with 1 part by mass of the 2-methylene-1,3-dicarbonyl compound (A) contained in the resin composition at 25°C until the 2-methylene-1,3-dicarbonyl compound (A) loses fluidity. Ａ ) to the gel time (GT) of the resin composition (wherein the ratio of the mass of N,N-dimethylbenzylamine to the mass of the resin composition in the measurement of GT is Ａ The resin composition according to claim 3, wherein the mass ratio (equal to the ratio of the mass of N,N-dimethylbenzylamine to the mass of the 2-methylene-1,3-dicarbonyl compound (A) in the measurement

5. 3. The resin composition according to claim 1, wherein the viscosity measured at 1 rpm using an E-type viscometer is 100 to 100,000 mPa·s.

6. 3. The resin composition according to claim 1, which can be cured by the action of a basic compound as a curing agent or curing catalyst.

7. The resin composition according to claim 1 or 2, further comprising a polymer compound.

8. 3. The resin composition according to claim 1, which is substantially free of a Lewis acid compound capable of coordinating to the carbonyl oxygen of the 2-methylene-1,3-dicarbonyl compound (A).

9. 3. The resin composition according to claim 1, which is substantially inert to water in the atmosphere.

10. A one-component curable resin composition comprising the resin composition according to claim 1 or 2, and a latent basic compound or a photobase generator.

11. A kit of a two-component mixed curable resin composition, (A) the resin composition according to claim 1 or 2; and (B) A curing agent or curing catalyst containing a basic compound Includes a kit.

12. The resin composition according to claim 1 or 2, which is used in the production of electronic parts.

13. A one-component curable resin composition according to claim 10, which is used in the manufacture of electronic components.

14. A kit as described in claim 11, used in manufacturing electronic components.

15. A cured product obtained by curing the resin composition according to claim 1 or 2.

16. A cured product obtained by curing the one-component curable resin composition according to claim 10.

17. A cured product obtained by curing the kit described in claim 11.

18. An electronic part comprising the cured product according to claim 15.

19. An electronic component comprising the cured product described in claim 16.

20. An electronic component comprising the cured product described in claim 17.

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