Method for dispensing resin compositions, method for manufacturing electronic components, and electronic components

Abstract

The present invention provides a method for dispensing a resin composition that can effectively suppress the hardening of the resin composition within a jet dispenser. [Solution] A dispensing method using a jet dispenser 50, wherein a resin composition 20 is dispensed from a nozzle 56 of the jet dispenser 50, wherein the jet dispenser 50 is made of metal, and the material of the component that collides with the nozzle 56 when the resin composition 20 is dispensed, such as a needle 52, is metal, and the resin composition 20 contains (A) a methacrylate compound and (B) a radical polymerization initiator.

Description

[Technical Field]

[0001] The present invention relates to a method for dispensing a resin composition, a method for manufacturing an electronic component, and an electronic component. Furthermore, the present invention relates to a method for dispensing a resin composition that can effectively suppress the hardening of the resin composition in a jet dispenser, a method for manufacturing an electronic component, and an electronic component manufactured by said manufacturing method. [Background technology]

[0002] In the process of applying UV and / or thermosetting adhesives for electronic components, air dispensers are the mainstream method, but challenges remain in miniature application, miniature coating, and reducing production cycle time. Hereinafter, UV and / or thermosetting adhesives for electronic components will be collectively referred to simply as "adhesives for electronic components."

[0003] In response to the above-mentioned challenges, a technology for applying adhesives for electronic components using a jet dispenser has been investigated in recent years. For example, a resin composition that can be applied by jet dispensing using acrylate and thiol has been disclosed as such an adhesive for electronic components (see Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-203910 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, a new problem has emerged: (meth)acrylate-radical UV and / or thermosetting adhesives, such as those described in Patent Document 1, react quickly, and can gel within the jet dispenser due to impact, shear, and heat generated during application. In particular, thermosetting adhesives are prone to localized gelation due to frictional heat generated inside the jet dispenser, making continuous and stable application difficult for highly reactive adhesives like (meth)acrylate-radical adhesives. Gelation refers to the process in which the polymerization of polymers begins, forming a three-dimensional network structure and increasing viscosity and elasticity.

[0006] As mentioned above, Patent Document 1 discloses a resin composition that can be applied by jet dispensing using acrylate and thiol, but it does not disclose any actual cases that have been investigated. Furthermore, Patent Document 1 does not disclose the specific configuration of the jet dispenser (jet dispensing device) to be used, such as the material of the needle that dispenses the resin composition.

[0007] Therefore, there is a strong need to develop a method for dispensing resin compositions that effectively suppresses gelation within the jet dispenser, resulting in superior coating performance by jet dispensing and excellent curability after application. Hereafter, coating performance by jet dispensing will be referred to as "jet dispensing performance."

[0008] This invention has been made in view of the problems of the prior art. This invention provides a method for dispensing a resin composition that can effectively suppress the hardening of the resin composition in a jet dispenser. Furthermore, this invention provides a method for manufacturing an electronic component using the above-described method for dispensing a resin composition, and an electronic component manufactured by said manufacturing method. [Means for solving the problem]

[0009] According to the present invention, a method for dispensing a resin composition, a method for manufacturing an electronic component, and an electronic component are provided.

[0010] [1] A method for discharging a resin composition, which uses a jet dispenser to discharge the resin composition from a nozzle of the jet dispenser, the method comprising: using, as the jet dispenser, a jet dispenser in which a member that collides with the nozzle during discharge of the resin composition is made of metal, and the resin composition comprises (A) a methacrylate compound and (B) a radical polymerization initiator.

[0011] [2] The discharge method according to [1], wherein the resin composition further comprises, as component (C), at least one of (C1) a polyfunctional thiol compound and (C2) an acrylate compound.

[0012] [3] The discharge method according to [2], wherein the resin composition comprises both the (C1) polyfunctional thiol compound and the (C2) acrylate compound as the component (C), and a ratio of the total number of (meth)acryloyl groups in the (A) methacrylate compound and the (C2) acrylate compound to the total number of thiol groups in the (C1) polyfunctional thiol compound is 0.8 to 1.2.

[0013] [4] The discharge method according to [2], wherein the resin composition comprises only the (C1) polyfunctional thiol compound as the component (C), and a ratio of the number of methacryloyl groups in the (A) methacrylate compound to the total number of thiol groups in the (C1) polyfunctional thiol compound is 0.8 to 1.2.

[0014] [5] The discharge method according to any one of [1] to [4], wherein the resin composition further comprises (D) an anionic polymerization initiator.

[0015] [6] The discharge method according to any one of [1] to [5], wherein the resin composition further comprises (E) a polymerization inhibitor.

[0016] [7] The discharge method according to any one of [1] to [6], wherein the resin composition further comprises (F) a filler.

[0017] [8] The discharging method according to any one of the above [1] to [7], wherein the resin composition further comprises (G) a black pigment.

[0018] [9] A method for producing an electronic component, using the discharging method according to any one of the above [1] to [8].

[0019]

[10] An electronic component obtained by the method for producing an electronic component according to the above [9]. [Effects of the Invention]

[0020] The method for discharging a resin composition of the present invention is a method for discharging a resin composition that uses a jet dispenser to discharge the resin composition from a nozzle of the jet dispenser. According to the method for discharging a resin composition of the present invention, the resin composition can be continuously applied in a minute amount to a minute region using a jet dispenser. Hereinafter, the method for discharging a resin composition of the present invention may be simply referred to as the "discharging method".

[0021] Since the discharging method of the present invention uses a resin composition containing (A) a methacrylate compound, gelation of the resin composition inside the jet dispenser can be effectively suppressed. Therefore, even if frictional heat or the like is generated inside the jet dispenser, local gelation of the resin composition hardly occurs, workability and stability are high, and extremely excellent jet dispensability can be achieved. Further, in the discharging method of the present invention, as a particularly main configuration, a jet dispenser in which the material of the member that collides with the nozzle when discharging the resin composition is made of metal can be mentioned. By using such a jet dispenser, the member that collides with the nozzle (for example, a needle or the like) can be used as a heat dissipation member to effectively release the heat generated inside the jet dispenser to the outside, making local gelation of the resin composition even less likely to occur.

[0022] Furthermore, the discharge method of the present invention is suitable for bonding components that constitute a camera module together, and is particularly suitable for temporary fixing (e.g., active alignment process) and application of adhesives for fixing that primarily utilize curing by UV irradiation. It can also be applied to processes that apply adhesives that cure only by heat without UV irradiation.

[0023] Furthermore, the method for manufacturing electronic components of the present invention is a method for manufacturing electronic components using the extrusion method of the present invention described above, and in particular, it is possible to accurately apply a minute amount of adhesive for electronic components to a minute area. For this reason, the method for manufacturing electronic components of the present invention is extremely effective as a manufacturing method that requires bonding of small electronic components. Moreover, the electronic components of the present invention are electronic components manufactured by the above manufacturing method, and good bonding between electronic components is achieved. [Brief explanation of the drawing]

[0024] [Figure 1] This is a schematic cross-sectional view of an example of a jet dispensing device (jet dispenser). [Modes for carrying out the invention]

[0025] The embodiments of the present invention will be described below, but the present invention is not limited to the embodiments described below. Therefore, it should be understood that any modifications, improvements, etc., made to the embodiments described below, based on the ordinary knowledge of those skilled in the art, without departing from the spirit of the present invention, also fall within the scope of the present invention.

[0026] (1) Method for dispensing the resin composition: One embodiment of the present invention's method for dispensing a resin composition is a method for dispensing a resin composition using a jet dispenser 50, as shown in Figure 1, in which the resin composition 20 is dispensed from a nozzle 56 of the jet dispenser 50. Here, Figure 1 is a schematic cross-sectional view of an example of a jet dispensing device (jet dispenser 50). The jet dispenser 50 has a needle 52 that can reciprocate like a piston, a seal 54 (sealing member) to prevent the resin composition 20 from leaking to the outside even with the reciprocating motion of the needle 52, and a nozzle 56 for jet dispensing the resin composition 20.

[0027] As shown in Figure 1(a), the resin composition 20 is supplied to the chamber 58 in the jet dispenser 50 and jet-dispensed from the nozzle 56 by pushing out a syringe (not shown) filled with the resin composition using air pressure and by the reciprocating motion of the needle 52 over a stroke length S. The nozzle 56 has an inner diameter of 20 to 300 μm. As a result, as shown in Figure 1(b), the resin composition 20 jet-dispensed from the nozzle 56 is supplied to a predetermined object. When the resin composition 20 is discharged by the jet dispenser 50, the reciprocating needle 52 collides with the nozzle 56. In the discharge method of this embodiment, the jet dispenser 50 that discharges the resin composition 20 uses a needle 52 made of metal, which is the component that collides with the nozzle 56 when the resin composition 20 is discharged. The name of the needle 52 varies depending on the equipment manufacturer, and it may also be called a tappet, poppet, or rod. By using a jet dispenser 50 in which the needle 52 is made of metal, the needle 52 and other components can be used as heat dissipation members to release the heat generated inside the jet dispenser 50. With this configuration, localized gelation of the resin composition 20 inside the jet dispenser 50 can be effectively suppressed.

[0028] In the jet dispenser 50 used in the dispensing method of this embodiment, the material of the needle 52 that collides with the nozzle 56 is not particularly limited as long as it is metal. However, the material of the needle 52 is preferably a cemented carbide, and tungsten carbide is a particularly suitable example. By using a component made of such tungsten carbide, the heat dissipation inside the jet dispenser 50 can be improved very effectively compared to, for example, ceramic or metal components widely used as the nozzle 56 of the jet dispenser 50.

[0029] Furthermore, in the dispensing method of this embodiment, one of the main configurations is to use a resin composition 20 that contains (A) a methacrylate compound. By configuring it in this way, the hardening of the resin composition 20 inside the jet dispenser 50 can be effectively suppressed. Therefore, even if frictional heat or the like is generated inside the jet dispenser 50, localized gelation of the resin composition 20 is less likely to occur, resulting in high workability and stability, and extremely excellent continuous jet dispensing performance. For example, when applying the resin composition 20 with the jet dispenser 50, impact and heat are applied to the resin composition 20 supplied to the nozzle 56, so if the reactivity of the resin composition 20 is too high, the resin composition 20 will gel and dispensing will become difficult. By using a resin composition 20 that contains (A) a methacrylate compound, the reactivity of the resin composition 20 can be controlled, and gelation of the resin composition 20 inside the jet dispenser 50 can be made less likely. The area indicated by reference numeral 61 in Figure 1(b) is the sliding portion 61 where the needle 52 slides against the seal 54 as the needle 52 reciprocates, and stress is applied to the resin composition 20 in this sliding portion 61. The area indicated by reference numeral 62 in Figure 1(b) is the collision portion 62 where the tip of the needle 52 collides with the nozzle 56 as the needle 52 reciprocates, and stress is applied to the resin composition 20 in this collision portion 62.

[0030] The resin composition 20 may contain (A) a methacrylate compound and (B) a radical polymerization initiator. In the dispensing method of this embodiment, the resin composition 20 may or may not contain an acrylate compound. Since the resin composition 20 contains (A) a methacrylate compound, it has excellent workability and stability, even if it contains, for example, a polyfunctional thiol compound that promotes the reaction. Furthermore, the resin composition 20 used in the dispensing method of this embodiment uses acrylate compounds that are commonly used in conventional (meth)acrylate-radical resin compositions as optional components. As described above, by using a resin composition 20 that contains (A) a methacrylate compound as an essential component, stable dispensing by jet dispensing becomes possible. Hereinafter, (A) the methacrylate compound may be referred to as component (A), and (B) the radical polymerization initiator may be referred to as component (B).

[0031] According to the dispensing method of this embodiment, the resin composition 20 can be applied in minute quantities to minute areas using a jet dispenser 50. Such a dispensing method is used for bonding components that make up a camera module and is particularly suitable for temporary fixing (e.g., active alignment process) and application of fixing adhesives that utilize curing by UV irradiation. It can also be applied to processes that apply adhesives that cure only by heat without UV irradiation. When applying with a jet dispenser, the adhesive supplied to the nozzle is subjected to impact and heat, so if the resin composition used as the adhesive is highly reactive, the adhesive will gel and become impossible to dispense. The dispensing method of this embodiment improves jet dispensing performance by controlling this reactivity.

[0032] Since the dispensing method of this embodiment can be applied to adhesives that cure only by heat without UV irradiation, it can be suitably applied to, for example, engineering plastics.

[0033] In addition to (A) a methacrylate compound and (B) a radical polymerization initiator, the resin composition 20 may further contain, as component (C), at least one of (C1) a polyfunctional thiol compound and (C2) an acrylate compound. Hereinafter, the (C1) polyfunctional thiol compound may be referred to as component (C1), and the (C2) acrylate compound may be referred to as component (C2).

[0034] Furthermore, the resin composition 20 may also contain other components such as (D) anionic polymerization initiator, (E) polymerization inhibitor, (F) filler, and (G) black pigment. Each of the above-mentioned components may also be referred to as components (D) to (G) as appropriate. Below, the resin composition 20 will be described in more detail for each component.

[0035] (Component A) (A) Component is a methacrylate compound. There are no particular restrictions on component (A) as long as it has a methacryloyl group. For example, there are no particular restrictions on the number of functional groups (i.e., the number of methacryloyl groups) in the methacrylate compound of component (A). By including the methacrylate compound (A), the reactivity of the resin composition can be controlled, and gelation of the resin composition inside the jet dispenser can be made less likely.

[0036] (A) The methacrylate compound preferably has a functional group equivalent of 100 to 500, more preferably 100 to 400, and even more preferably 100 to 250, from the viewpoint of reactivity, dispersibility, and workability. Furthermore, the number of functional groups in one molecule is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 or 3. In one embodiment, it is preferable that component (A) contains a benzene ring in the molecule in order to make the physical properties of the resin composition after curing high heat resistance and high reliability. In another embodiment, it is preferable that it does not contain a benzene ring in order to make the physical properties of the resin composition after curing low elasticity.

[0037] (A)Specific examples of methacrylate compounds include, for example, 2-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 4-hydroxybutyl methacrylate, cyclohexane-1,4-dimethanol monomethacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenylpolyethoxymethacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate, o-phenylphenol monoethoxymethacrylate, o-phenylphenol polyethoxymethacrylate, p-cumylphenoxyethyl methacrylate, isovonyl methacrylate, tribromophenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Examples of monomers include methylates, 1,9-nonanediol dimethacrylate, tricyclodecanedimethanol methacrylate, bisphenol A polyethoxydimethacrylate, bisphenol A polypropoxydimethacrylate, bisphenol F polyethoxydimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tris(methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, tripentaerythritol hexamethacrylate, tripentaerythritol pentamethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane polyethoxytrimethacrylate, ditrimethylolpropane tetramethacrylate, and neopentyl glycol dimethacrylate.

[0038] ((B) component) Component (B) is a radical polymerization initiator. Since the resin composition contains a radical polymerization initiator as component (B), the resin composition can be cured by short-time heating or UV irradiation. The radical polymerization initiator of component (B) may be a thermal radical polymerization initiator alone, a photoradical polymerization initiator alone, or a combination of both. The radical polymerization initiator of component (B) is more preferably a photoradical polymerization initiator.

[0039] There are no particular limitations on the radical polymerization initiators that can be used in resin compositions, and known materials can be used. Specific examples of radical polymerization initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, or 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, and 2,2-bis(t-butylperoxy) Examples include peroxyketals such as s(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, or ethyl 3,3-(t-butylperoxy)butyrate; and alkylperoxyesters such as t-butylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, or t-butylperoxybenzoate.Other examples 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-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, and Examples include methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, camphorquinone, and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one. A single substance may be used as a radical polymerization initiator, or two or more substances may be used in combination.

[0040] There are no particular restrictions on the content of the radical polymerization initiator in component (B). For example, the radical polymerization initiator in component (B) is preferably contained in the resin composition at a concentration of 0.01 to 40% by mass, more preferably 0.03 to 30% by mass, and even more preferably 0.05 to 20% by mass.

[0041] ((C) component) Component (C) is at least one of (C1) a polyfunctional thiol compound and (C2) an acrylate compound. Thus, it is preferable that the resin composition contains at least one of (C1) a polyfunctional thiol compound and (C2) an acrylate compound in addition to components (A) and (B) described above.

[0042] ((C1) component) Component (C1) is a polyfunctional thiol compound. The polyfunctional thiol compound of component (C1) imparts elasticity to the resin composition. Component (C1) is not particularly limited as long as it has two or more functional groups. However, from the viewpoint of moisture resistance, component (C1) is preferably a non-hydrolyzable thiol that does not contain ester bonds in its molecule in order to suppress hydrolysis when exposed to moisture.

[0043] (C1) The polyfunctional thiol compound is preferably such that, from the viewpoint of dispersibility and workability, it has a molecular weight of 500 or less and is liquid at room temperature.

[0044] (C1) Component may include glycoluryl compounds represented by the following general formula (1).

[0045] [ka]

[0046] In general formula (1), R 1 , and R 2 Each of these is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. n is an integer from 0 to 10. Furthermore, component (C1) may be a compound represented by the following chemical formula (2) or chemical formula (3).

[0047] [ka]

[0048] [ka]

[0049] The compound represented by Chemical Formula (2) or Chemical Formula (3) is a more preferable compound as the component (C1).

[0050] Further, examples of the polyfunctional thiol resin having no ester bond in the molecule include the polyfunctional thiol resin represented by General Formula (4).

[0051]

Chemical Formula

[0052] In General Formula (4), R 3 , R 4 , R 5 , and R 6 each independently represent hydrogen or C n H 2n SH (n is 2 to 6). Further, at least one of R 3 , R 4 , R 5 , and R 6 is C n H 2n SH (n is 2 to 6). It is preferable that 2 to 4 of R 3 , R 4 , R 5 , and R 6 are C n H 2n SH (n is 2 to 6), and it is more preferable that 3 or 4 of R 3 , R 4 , R 5 , and R 6 are C n H 2nIt is even more preferable that SH (n is 2-6) is present. Furthermore, from the viewpoint of curability, n of the polyfunctional thiol compound of component (C1) represented by general formula (4) is preferably 2-4. Moreover, from the viewpoint of balancing the physical properties of the cured product with the curing rate, it is more preferable that this thiol compound be a mercaptopropyl group with n = 3. Component (C1) represented by general formula (4) has a sufficiently flexible skeleton itself, making it effective when it is desired to lower the elastic modulus of the cured product. By adding component (C1) represented by general formula (4), the elastic modulus of the cured product can be controlled, thereby increasing the adhesive strength (especially the peel strength) after curing.

[0053] Examples of commercially available components of (C1) include thiol glycol uryl derivatives manufactured by Shikoku Chemicals Co., Ltd. (product name: TS-G (corresponding to chemical formula (2), thiol equivalent: 100 g / eq), C3TS-G (corresponding to chemical formula (3), thiol equivalent: 114 g / eq)), and thiol compounds manufactured by SC Organic Chemicals Co., Ltd. (product name: Multhiol Y-3 (the main component of general formula (4) corresponds to a trifunctional thiol)). Component (C1) may be used alone or in combination of two or more components.

[0054] In one embodiment, it is preferable from the viewpoint of maintaining the shear strength of the resin composition after curing that component (C1) contains 50 to 100 parts by mass of a glycoluryl compound per 100 parts by mass of component (C1). The content of the glycoluryl compound in component (C1) is more preferably 60 to 100 parts by mass, and even more preferably 70 to 100 parts by mass.

[0055] In another embodiment, a polyfunctional thiol resin having ester bonds in the molecule may be used as component (C1). From the viewpoint of imparting flexibility to the cured product by the ester bonds, the content of this polyfunctional thiol resin is preferably 50 to 100 parts by mass per 100 parts by mass of component (C1). In yet another embodiment, from the viewpoint of imparting flexibility to the cured product and moisture resistance, the content of the polyfunctional thiol resin having ester bonds in the molecule is preferably less than 50 parts by mass, more preferably less than 40 parts by mass, and even more preferably less than 30 parts by mass per 100 parts by mass of component (C1).

[0056] Examples of polyfunctional thiol resins having ester bonds in their molecules include pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris-[(3-mercaptopropionyloxy)-ethyl]-isopropylmethyl Examples include anurate, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptobutyrate), and trimethylolethanetris(3-mercaptobutyrate).

[0057] ((C2) component) Component (C2) is an acrylate compound. The resin composition may further contain an acrylate compound as component (C2) in addition to the methacrylate compound as component (A).

[0058] The (C2) acrylate compound is preferably a polyfunctional acrylate compound having two or more acryloyl groups. The polyfunctional acrylate compound is more preferably bifunctional from the viewpoint of jet dispensability. If it is trifunctional or more, jet dispensability may be unfavorable.

[0059] The (C2) acrylate compound is preferably such that, from the viewpoint of reactivity, dispersibility, and workability, the functional group equivalent is 100 to 500, more preferably 100 to 400, and even more preferably 100 to 250. The number of functional groups is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 or 3. In one embodiment, (C2) is preferably contained within the molecule to improve the heat resistance and reliability of the cured resin composition. In another embodiment, it is preferable that the resin composition does not contain a benzene ring to improve its elasticity.

[0060] (C2)Specific examples of acrylate compounds include, for example, N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexane-1,4-dimethanol monoacrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenyl polyethoxyacrylate, 2-hydroxy-3-phenyloxypropyl acrylate, o-phenylphenol monoethoxyacrylate, o-phenylphenol polyethoxyacrylate, p-cumylphenoxyethyl acrylate, isovonyl acrylate, tribromophenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and Examples of monomers include lycyclodecanedimethanol acrylate, bisphenol A polyethoxydiaacrylate, bisphenol A polypropoxydiaacrylate, bisphenol F polyethoxydiaacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, tris(acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, trimethylolpropane triacrylate, trimethylolpropane polyethoxytriacrylate, ditrimethylolpropane tetraacrylate, ester diacrylates of neopentyl glycol and hydroxypivalic acid, and diacrylates of ε-caprolactone adducts of esters of neopentyl glycol and hydroxypivalic acid. Preferably, examples include N-acryloyloxyethylhexahydrophthalimide, phenoxyethyl acrylate, and dicyclopentenyloxyethyl acrylate.

[0061] When the resin composition contains both a (C1) polyfunctional thiol compound and a (C2) acrylate compound as component (C), it is more preferable that it is configured as follows: That is, the ratio of the total number of (meth)acryloyl groups in the (A) methacrylate compound and the (C2) acrylate compound to the total number of thiol groups in the (C1) polyfunctional thiol compound is preferably 0.8 to 1.2. By setting the total number of functional groups of each component to the above ratio, the reactivity of the resin composition can be improved. Here, the total number of (meth)acryloyl groups in the (A) methacrylate compound and the (C2) acrylate compound means the sum of the total number of methacryloyl groups in the (A) methacrylate compound and the total number of acryloyl groups in the (C2) acrylate compound.

[0062] Furthermore, if the resin composition contains only a (C1) polyfunctional thiol compound as component (C), it is preferable that the ratio of methacryloyl groups of the (A) methacrylate compound to the total number of thiol groups of the (C1) polyfunctional thiol compound is 0.8 to 1.2. By configuring it in this way, the reactivity of the resin composition can be improved in the same manner as described above.

[0063] Furthermore, it is preferable that the ratio of the total number of methacryloyl groups in the (A) methacrylate compound to the total number of acryloyl groups in the (C2) acrylate compound is (A):(C2) = 10:0 to 2:8. By setting the numerical range to the above, extremely excellent jet dispensing properties can be achieved. In addition, regarding the ratio of the total number of methacryloyl groups in the (A) methacrylate compound to the total number of acryloyl groups in the (C2) acrylate compound, it is preferable that the value of (A) / (C2) is (A) / (C2) = 0.8 to 1.2. By configuring it in this way, both jet dispensing properties and thermosetting properties can be achieved.

[0064] Here, we will explain the total number of methacryloyl groups in (A) methacrylate compounds, the total number of acryloyl groups in (C2) acrylate compounds, and the total number of thiol groups in (C1) polyfunctional thiol compounds. In the case of compounds having both acryloyl and methacryloyl groups in the molecule, the methacryloyl groups are counted as the total number of methacryloyl groups in (A) methacrylate compounds, and the acryloyl groups are counted as the total number of acryloyl groups in (C2) acrylate compounds. Silane coupling agents having thiol groups or (meth)acryloyl groups are not counted in the total number of components (A), (C2), and (C1).

[0065] Furthermore, the total number of methacryloyl groups in (A) methacrylate compounds, the total number of acryloyl groups in (C2) acrylate compounds, and the total number of thiol groups in (C1) polyfunctional thiol compounds can be determined by analytical methods such as NMR, gas chromatography, and liquid-phase chromatography.

[0066] ((D) component) Component (D) is an anionic polymerization initiator. The resin composition may further contain an anionic polymerization initiator as component (D) in addition to the radical polymerization initiator as component (B). Such anionic polymerization initiator is a polymerization initiator that starts polymerization when heated, and is effectively used, for example, when the resin composition is used as an adhesive for electronic components, during the main curing after temporary fixing.

[0067] There are no particular limitations on the anionic polymerization initiators that can be used in resin compositions, and known materials can be used. Specific examples of anionic polymerization initiators include imidazole compounds that are solid at room temperature, and solid-dispersible amine adduct-type latent curing accelerators, such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), and reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems). Examples of imidazole compounds that are solid at room temperature and can be used in the present invention include 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, and 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl- Examples include, but are not limited to, S-triazine isocyanuric acid adducts, 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)-adipoyldiamide.

[0068] As epoxy compounds used as raw materials for the production of solid-dispersible amine adduct-based latent curing accelerators (amine-epoxy adduct-based) that can be used in the present invention, for example, polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; lid Examples include, but are not limited to, polyglycidyl esters obtained by reacting polycarboxylic acids such as uric acid and terephthalic acid with epichlorohydrin; glycidylamine 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, as well as monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0069] The amine compound used as another raw material for the above-mentioned solid-dispersible amine adduct-type latent curing accelerator is one that has at least one active hydrogen atom capable of addition reaction with an epoxy group, and at least one functional group selected from primary, secondary, and tertiary amino groups. Examples of such amine compounds are shown below, but are not limited to these. For example, 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; heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine; and so on.

[0070] Furthermore, compounds having a tertiary amino group in the molecule are particularly useful as raw materials for providing latent curing accelerators 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 primary or secondary amines having a tertiary amino group in the molecule, such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazolin, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercapto Examples include alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in their molecule, such as pyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0071] As another raw material for the production of the above-mentioned solid-dispersible amine adduct-type latent curing accelerator, the following isocyanate compounds can be used: monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and furthermore, terminal isocyanate group-containing compounds obtained by the reaction of these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such terminal isocyanate group-containing compounds include, but are not limited to, addition compounds having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and trimethylolpropane, and addition compounds having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and pentaerythritol.

[0072] Examples of urea compounds include, but are not limited to, urea and thiourea.

[0073] A solid-disperse latent curing accelerator that can be used in the present invention can be obtained, for example, by the following method. First, the components are taken and mixed in combination of (a) an amine compound and an epoxy compound (two components), (b) these two components and an active hydrogen compound (three components), or (c) an amine compound and at least one of isocyanate compounds and urea compounds (two or three components). The resulting mixture is then reacted at a temperature from room temperature to 200°C. After that, the resulting reaction product is cooled and solidified and then pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, and after solvent removal, the solid component is pulverized to easily obtain the solid-disperse latent curing accelerator.

[0074] The following are some representative examples of commercially available solid-disperse latent curing accelerators, but they are not limited to these. Specifically, examples of amine-epoxy adduct systems (amine adduct systems) include "Amicure PN-23" (manufactured by Ajinomoto Co., Ltd., product name), "Amicure PN-40" (manufactured by Ajinomoto Co., Ltd., product name), "Amicure PN-50" (manufactured by Ajinomoto Co., Ltd., product name), "Hardener X-3661S" (manufactured by ACR Co., Ltd., product name), "Hardener X-3670S" (manufactured by ACR Co., Ltd., product name), "NovaCure HX-3742" (manufactured by Asahi Kasei Corporation, product name), "NovaCure HX-3721" (manufactured by Asahi Kasei Corporation, product name), and "NovaCure HXA9322HP" (manufactured by Asahi Kasei Corporation, product name). Examples of urea-type adduct systems include "FujiCure FXE-1000" (manufactured by T&K TOKA Corporation, product name) and "FujiCure FXR-1030" (manufactured by T&K TOKA Corporation, product name). As an anionic polymerization initiator, a single substance may be used, or two or more substances may be used in combination.

[0075] There are no particular restrictions on the content of the anionic polymerization initiator of component (D). For example, if the anionic polymerization initiator of component (D) is included, it is preferably contained in the resin composition at a ratio of 0.5 to 10% by mass, more preferably 1 to 5% by mass, and even more preferably 1 to 3% by mass.

[0076] ((E) component) Component (E) is a polymerization inhibitor. The polymerization inhibitor in component (E) is added to improve the stability of the resin composition during storage. For example, radical polymerization inhibitors can be used as polymerization inhibitors. The radical polymerization inhibitor in component (E) is added to suppress the progression of unintended radical polymerization reactions. The methacrylate compound in component (A) and the acrylate compound in component (C2) may, at a low probability, generate radicals themselves. In this case, unintended radical polymerization reactions may proceed, starting from these radicals. By adding a radical polymerization inhibitor, the progression of such unintended radical polymerization reactions of components (A) and (C2) can be suppressed.

[0077] The polymerization inhibitor for component (E) can be any known substance. Preferably, the component (E) used is at least one selected from the group consisting of, for example, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. Alternatively, known radical polymerization inhibitors disclosed in Japanese Patent Publication No. 2010-117545 and Japanese Patent Publication No. 2008-184514 can be used as component (E). Component (E) may be a single component or a combination of two or more components.

[0078] (Component F) Component (F) is a filler. By including a filler as component (F), moisture resistance and liquid cutoff during jet dispensing can be improved. There are no particular restrictions on the amount of filler, but for example, it is preferable to include 0 to 65% by mass of the filler of component (F) in the resin composition, more preferably 5 to 50% by mass, and even more preferably 10 to 30% by mass.

[0079] The filler for component (F) can be any known type. Examples of component (F) include inorganic fillers and organic fillers. Examples of inorganic fillers include glass, silica, alumina, aluminum nitride, boron nitride, titanium dioxide, calcium carbonate, talc, and silver filler. Examples of organic fillers include silicone rubber, PTFE, polystyrene, polyacrylate, polyurethane, and polydivinylbenzene filler. The average particle size of the filler is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, and even more preferably 0.5 to 5 μm.

[0080] ((G) component) Component (G) is a black pigment. The black pigment as component (G) is particularly effective when the resin composition is used as an adhesive that requires light shielding properties, such as an adhesive for camera modules. For example, when a resin composition is used as an adhesive for a camera module, light may enter the camera module from the area where the resin composition is applied. Therefore, it is preferable to include a black pigment as component (G) to provide light shielding properties in order to prevent light from entering the camera module.

[0081] The black pigment for component (G) can be any known pigment. Examples of components (G) that can be used include carbon black, graphite, titanium nitride, titanium oxide, zirconia, and titanium black.

[0082] (Component (H); anionic polymerization inhibitor) The resin composition may contain a (H) anionic polymerization inhibitor (hereinafter also referred to as "(H) component") to the extent that it does not impair the effects of the present invention. The (H) anionic polymerization inhibitor is added to enhance the storage stability of the resin composition and to suppress the occurrence of polymerization reactions due to unintended basic components.

[0083] (H) Anionic polymerization inhibitors can be any known ones, such as borate ester compounds and strong acids. Specific examples of (H) anionic polymerization inhibitors include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, barbituric acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, and dichloroacetic acid. Among these, the preferred (H) anionic polymerization inhibitor is at least one selected from tri-n-propyl borate, triisopropyl borate, and barbituric acid. Alternatively, known (H) anionic polymerization inhibitors disclosed in Japanese Patent Publication No. 2010-117545, Japanese Patent Publication No. 2008-184514, Japanese Patent Publication No. 2017-171804, etc., can also be used. Any one (H) anionic polymerization inhibitor may be used, or two or more may be used in combination.

[0084] The content of component (H) is preferably 0.1 to 10% by mass, more preferably 0.3 to 7% by mass, based on the total mass of the resin composition.

[0085] (Other combination drugs) The resin composition used in the discharge method of this embodiment may further contain components other than those described above (A) to (H), as needed. Specific examples of such components include defoaming agents, silane coupling agents, dispersants, and epoxy resins. The type and amount of each compounding agent are as per conventional methods.

[0086] (Properties of resin compositions) The resin composition used in the discharge method of this embodiment preferably has the following characteristics: The viscosity of the resin composition is preferably 0.2 to 80 Pa·s, more preferably 1 to 60 Pa·s, and even more preferably 1 to 50 Pa·s. By configuring it in this way, the resin composition is easy to handle and maintains high fluidity. The viscosity of the resin composition can be measured using a Brookfield (Type B) viscometer with an SC4-14 spindle at room temperature (25°C) and a rotation speed of 50 rpm.

[0087] The thixotropy index (TI) of the resin composition is preferably 0.7 to 7, more preferably 0.9 to 6.5, and even more preferably 1 to 6.5 at room temperature (25°C). The thixotropy index of the resin composition can be measured, for example, using a Brookfield (Type B) viscometer with an SC4-14 spindle, by dividing the value measured at a rotational speed of 5 rpm at room temperature (25°C) by the value measured at a rotational speed of 50 rpm.

[0088] (Method for manufacturing resin compositions) The resin composition used in the discharge method of this embodiment can be manufactured by conventional methods. The resin composition can be manufactured by mixing the components described above using, for example, a sieve, a pot mill, a three-roll mill, a rotary mixer, a twin-screw mixer, etc.

[0089] (Configuration and dispensing conditions of the jet dispenser) Regarding the configuration of the jet dispenser used in the dispensing method of this embodiment, as long as the material of the component that collides with the nozzle is metal, there are no particular restrictions on other configurations, and the device configuration can be similar to that of conventionally known jet dispensers. Furthermore, there are no particular restrictions on the conditions when dispensing the resin composition by the jet dispenser, and as long as the resin composition described above is being dispensed, the conditions can be similar to those of conventionally known jet dispensers. For example, the jet dispenser used in the dispensing method of this embodiment is preferably configured as follows: A metal nozzle is preferred. The nozzle temperature may be at room temperature or heated. The tip diameter of the needle is preferably 0.7 to 3 mm. The needle lifting time is preferably 0.1 to 7 msec, and the needle lowering time is preferably 0.1 to 7 msec. The needle lifting distance is preferably 0.1 to 1 mm. The nozzle inner diameter is preferably 50 to 200 μm. The syringe pressure is preferably 0.01 to 0.5 MPa.

[0090] (Applications of resin composition dispensing methods) The dispensing method of this embodiment can be used in the process of applying adhesive for electronic components. In such a process, the resin composition is used as an adhesive for electronic components. Furthermore, the resin composition can also be suitably adapted to engineering plastics. In the dispensing method of this embodiment, when the resin composition is used as an adhesive for electronic components, there are no particular restrictions on the electronic components to be bonded, and examples include ceramic substrates, organic substrates, semiconductor chips, etc. In particular, when used as an adhesive, it is useful for bonding small electronic components. The resin composition is used in the process of applying adhesive for electronic components by a jet dispenser 50 as shown in Figure 1.

[0091] The resin composition can be effectively used, for example, as an adhesive for camera modules. That is, it can be used to bond components that make up a camera module together, and is mainly used for fixing components together using UV light. For fixing components together, it can be used for temporary fixing in the active alignment process and for final fixing to secure the camera module. The resin composition used in the dispensing method of this embodiment can satisfy the fluidity requirements necessary for fixing the camera module.

[0092] Furthermore, the jet dispenser 50 shown in Figure 1 can dispense hundreds of shots per second through the reciprocating motion of the needle 52. As a result, the resin composition 20 (e.g., adhesive) used for jet dispensing is subjected to significant impact. Even after such significant impact, the resin composition 20 can maintain its fluidity.

[0093] Jet dispensing is used to supply adhesive for fixing components of camera modules. In recent years, with the miniaturization of camera modules, there has been an increasing demand for supplying adhesive to minute areas and narrow gaps. Specifically, the width of the minute areas and gaps to which adhesive is supplied is several hundred micrometers (for example, 300 micrometers). By jet dispensing the resin composition, adhesive can be supplied to areas and gaps of small dimensions.

[0094] (2) Method for manufacturing electronic components: Next, an embodiment of the method for manufacturing electronic components of the present invention will be described. The method for manufacturing electronic components of this embodiment is a method for manufacturing electronic components using the ejection method of this embodiment described above. In particular, the method for manufacturing electronic components of this embodiment, by using the ejection method described above, can accurately apply a minute amount of adhesive for electronic components to a minute area. For this reason, the method for manufacturing electronic components of this embodiment is an extremely effective manufacturing method for manufacturing small electronic components that require bonding.

[0095] (3) Electronic components: Next, embodiments of the electronic component of the present invention will be described. The electronic component of this embodiment is obtained by the manufacturing method of the electronic component described above. The electronic component of this embodiment achieves good adhesion between electronic components. For this reason, it is highly productive and reliable. [Examples]

[0096] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples. In the following examples, parts and % refer to parts by mass and mass% unless otherwise specified.

[0097] (Examples 1-23, Comparative Examples 1-2) [Preparation of resin composition] After weighing and blending each component shown in Tables 1 to 4, the resin compositions used in the dispensing methods of the examples and comparative examples were prepared by mixing them. Specifically, the resin compositions were prepared by mixing each component shown in Tables 1 to 4 in a planetary mixer, then dispersing them in a three-roll mill and forming a paste. Details of each component shown in Tables 1 to 4 are as follows.

[0098] [Component (A): Methacrylate compound] (A-1): Phenoxyethyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Ester PO, methacrylate equivalent: 206 g / eq, number of methacryloyl groups per molecule: 1). (A-2): Bisphenol A·EO 2.6 molar adduct-dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Ester BP-2EMK, methacrylate equivalent: 181 g / eq, number of methacryloyl groups per molecule: 2). (A-3): Neopentyl glycol dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Ester NP, methacrylate equivalent: 120 g / eq, number of methacryloyl groups per molecule: 2). (A-4): Trimethylolpropane trimethacrylate, manufactured by Shin Nakamura Chemical Co., Ltd. (product name: NK Ester TMPT, methacrylate equivalent: 112.8 g / eq, number of methacryloyl groups per molecule: 3). (A-5): Ditrimethylolpropanetetramethacrylate, manufactured by Shin Nakamura Chemical Co., Ltd. (product name: NK Ester D-TMP, methacrylate equivalent: 129.5 g / eq, number of methacryloyl groups per molecule: 4). (A-6): 2-Hydroxy-1,3-Dimethacryloxypropane, manufactured by Shin Nakamura Chemical Co., Ltd. (Product name: NK Ester 701, Methacrylate equivalent: 114 g / eq, Number of methacryloyl groups per molecule: 2).

[0099] [(B) Component: Radical polymerization initiator] (B-1): 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, manufactured by Nippon Oil & Fats Co., Ltd. (product name: Perocta-O, thermal radical polymerization initiator). (B-2): 1-Hydroxycyclohexyl phenyl ketone, manufactured by IGM Resins B.V. (Trade name: OMNIRAD 184, photoradical polymerization initiator). (B-3): 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, manufactured by IGM Resins B.V. (Trade name: OMNIRAD 907, photoradical polymerization initiator).

[0100] [(C) component [(C1) component: polyfunctional thiol compound] (C1-1): Tetrahydro-1,3,4,6-tetrakis(3-mercaptopropyl)-imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, manufactured by Shikoku Chemicals Co., Ltd. (product name: C3TS-G, thiol equivalent: 110 g / eq, number of thiol groups per molecule: 4). (C1-2): Pentaerythritol tetrakis(3-mercaptopropionate), manufactured by SC Organic Chemicals Co., Ltd. (product name: PEMP-LV, thiol equivalent: 122 g / eq, number of thiol groups per molecule: 4). (C1-3):3-(3-mercaptopropoxy)-2,2-bis-(3-mercaptopropoxymethyl)-propan-1-ol, manufactured by SC Organic Chemicals (product name: Multhiol Y-3, thiol equivalent: 124 g / eq, number of thiol groups per molecule: 3).

[0101] [(C) component [(C2) component: acrylate compound] (C2-1): Polyester acrylate (polyfunctional acrylic compound), manufactured by Toagosei Co., Ltd. (product name: M7100, acrylate equivalent: 188 g / eq, number of acryloyl groups per molecule: 3 or more). (C2-2): Dimethylol-tricyclodecanediaacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Acrylate DCP-A, acrylate equivalent: 152 g / eq, number of acryloyl groups per molecule: 2). (C2-3): Neopentyl glycol diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Acrylate NP-A, acrylate equivalent: 106 g / eq, number of acryloyl groups per molecule: 2).

[0102] [Component (D): Anionic polymerization initiator] (D-1): A mixture of microencapsulated amine-based curing agent and bisphenol A and F type epoxy resins, with 33% by mass being microencapsulated amine-based curing agent, manufactured by Asahi Kasei Corporation (product name: HXA9322HP). (D-2): Modified alicyclic polyamine, manufactured by T&K TOKA Corporation (product name: FXR-1121).

[0103] [(E) Ingredient: Polymerization inhibitor] (E-1): N-nitroso-N-phenylhydroxylamine aluminum, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (product name: Q-1301). (E-2): 4-tert-butylpyrocatechol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (product name: t-butylcatechol).

[0104] [(F) Ingredient: Filler] (F-1): Spherical silica, manufactured by Admatex (product name: SE5200 SEE). (F-2): Spherical silica, manufactured by Admatex (product name: SE2200 SEE). (F-3): Silicone composite powder, manufactured by Shin-Etsu Chemical Co., Ltd. (product name: KMP 600T). (F-4): Fumed silica, manufactured by Cabot (product name: TS-720).

[0105] [(G) Component: Black pigment] (G-1): Carbon black, manufactured by Evonik Degussa Japan (product name: Black 4). (G-2): Titanium nitride, titanium dioxide, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (product name: Titanium Black 13M).

[0106] [(I) Components: Other components] (I-1): Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. (product name: KBM403; 3-glycidoxypropyltrimethoxysilane).

[0107] Furthermore, for the resin compositions prepared in Examples 1 to 23 and Comparative Examples 1 to 2, the total number of methacryloyl groups in component (A), the total number of acryloyl groups in component (C2), and the total number of thiol groups in component (C1) were determined, and the ratios (1) and (2) of functional groups for each component were calculated. Here, the ratio (1) of functional groups is the ratio of the total number of methacryloyl groups in component (A) to the total number of acryloyl groups in component (C2) (i.e., the total number of methacryloyl groups in component (A) / the total number of acryloyl groups in component (C2)). The ratio (2) of functional groups is the ratio of the total number of methacryloyl groups in component (A) and the total number of acryloyl groups in component (C2) to the total number of thiol groups in component (C1) (i.e., {total number of methacryloyl groups in component (A) + total number of acryloyl groups in component (C2)} / total number of thiol groups in component (C1)). The results for the ratios (1) and (2) of functional groups for each component are shown in Tables 1 to 4.

[0108] [Table 1]

[0109] [Table 2]

[0110] [Table 3]

[0111] [Table 4]

[0112] Using a jet dispenser (trade name "Smart Stream" manufactured by ITW EAE), each of the resin compositions of Examples and Comparative Examples was continuously discharged, and the number of continuously dischargeable shots was measured. However, for Example 23 and Comparative Example 2, the jet dispensability was evaluated using the trade name "MDS3200A" manufactured by Vermes. In Examples 1 to 23 and Comparative Example 1, a jet dispenser was used in which the needle, which is the member that collides with the nozzle during discharge of the resin composition, was a metal member made of tungsten carbide. On the other hand, in Comparative Example 2, a jet dispenser was used in which the needle, which is the member that collides with the nozzle during discharge of the resin composition, was made of ceramic. Further, the resin compositions of Examples 1 to 23 and Comparative Examples 1 to 2 that were continuously discharged with the jet dispenser as described above were evaluated for curability and jet dispensability by the following methods. The results are shown in Tables 1 to 4.

[0113] [Evaluation of Curability] The resin composition discharged by the jet dispenser was subjected to UV curing or thermal curing, and the UV curing depth or the strength during thermal curing was measured. <UV Curing Depth> Two heat-resistant tapes (100 μm thick) were attached to a black resin plate A (50 mm wide x 25 mm high x 1.5 mm thick) at a 10 mm interval. Next, a resin composition was applied between the two heat-resistant tapes on resin plate A to a thickness of 100 μm, the same as the heat-resistant tapes. Then, the two heat-resistant tapes and the resin composition were sandwiched between resin plate A and another resin plate B (50 mm wide x 25 mm high x 1.5 mm thick), and the ends of the two overlapping resin plates A and B were secured with clips. The resin composition that had seeped out from the top of resin plates A and B was wiped off. UV irradiation was performed on the resin composition from the top of the jig thus prepared. More specifically, an Excelitas Technologies UV LED irradiation device "AC475 (product name)" was used, with an integrated light intensity of 2000 mJ / cm². 2 The material was then cured using UV irradiation. The cumulative light intensity was measured by connecting a UVD-365 light receiver to the UIT-250 (product name) manufactured by Ushio Inc. One of the resin plates A and B that were sandwiched together was peeled off, the uncured portion adhering to the cured resin composition was removed, and the distance of the cured portion from the UV irradiation surface was measured with a microscope. This result was defined as the UV curing depth. <Strength during heat curing> A 2mm x 3mm ceramic chip was placed on each resin composition of the example and comparative example, which were jet-dispensed onto a ceramic substrate. Next, using the AC475 UV LED irradiation device manufactured by Excelitas Technologies, an integrated light intensity of 2000 mJ / cm² was applied. 2 The material was then UV-cured by UV irradiation. The cumulative light intensity was measured by connecting a UVD-365 light receiver to a UIT-250 (product name) manufactured by Ushio Inc. The UV-cured curable resin composition was then heat-cured in a forced-air dryer at 80°C for 60 minutes. A DAGE4000 (product name) universal bond tester manufactured by Dage Inc. was used to apply a load to the ceramic chip, and the shear stress (N) at which the ceramic chip peeled off was measured. This measurement was performed 10 times for each test piece, and the average value of the 10 measurements was taken as the shear strength measurement value. A higher measured shear strength indicates better curability by ultraviolet light and / or heat. <Evaluation Criteria> The cured material prepared as described above was evaluated according to the following criteria. In the following evaluation criteria, "◎" indicates the best evaluation, followed by "〇" and then "△" indicating the lowest evaluation. ◎: UV curing depth of 450 μm or more, or thermal curing strength of 130 N or more. ○: UV curing depth is greater than 350 μm but less than 450 μm, or thermal curing strength is greater than 60 N but less than 130 N. △: UV curing depth is 350 μm or less, or thermal curing strength is 60 N or less.

[0114] [Evaluation of jet dispensing performance] In the following evaluation criteria, "◎" indicates the best rating, followed by "〇", "△", and "×" in order of decreasing quality. <Evaluation Criteria> ◎: Capable of dispensing more than 100,000 shots continuously. ○: The number of shots that can be dispensed continuously is 10,000 or more, but less than 100,000. △: The number of shots that can be dispensed continuously is 500 or more, but less than 10,000. ×: If the number of shots that can be dispensed continuously is less than 500, or if gel material is generated in the sliding part 61 or the impact part 62 (i.e., the impact part 62 where the tip of the needle collides with the nozzle) as shown in Figure 1(b), regardless of the number of shots that can be dispensed.

[0115] 〔result〕 As shown in Tables 1 to 4, the dispensing methods of Examples 1 to 23 used a resin composition containing a methacrylate compound as component (A), and the jet dispenser used had a metal component that collided with the nozzle during dispensing of the resin composition. The dispensing methods of Examples 1 to 23 showed good results in both curability and jet dispensing performance evaluations. Furthermore, the dispensing methods of Examples 1 to 23 were able to confirm curability with a radical polymerization initiator content of 20% by mass or less as component (B).

[0116] On the other hand, the dispensing method of Comparative Example 1 used a resin composition that did not contain a methacrylate compound as component (A), and therefore, in the evaluation of jet dispensing performance, the number of shots that could be dispensed continuously was less than 500. It was found that the dispensing method of Comparative Example 1 was more prone to hardening of the resin composition inside the jet dispenser compared to the dispensing methods of Examples 1 to 23, and was not suitable for application by jet dispensing. In addition, although the dispensing method of Comparative Example 2 allowed for more than 500 shots to be dispensed continuously, gelled material was observed in the sliding part 61 as shown in Figure 1(b). The presence of gelled material in the sliding part significantly reduces workability such as setup changes and cleaning, impairing productivity. In the dispensing method of Comparative Example 2, the material of the component that collides with the nozzle when the resin composition is dispensed was made of ceramic as the jet dispenser, and it is presumed that the heat generated inside the jet dispenser did not easily escape to the outside compared to the dispensing methods of Examples 1 to 23, and the resin composition partially hardened inside the jet dispenser. [Industrial applicability]

[0117] The resin composition dispensing method of the present invention can be used for coating resin compositions by jet dispensing, and in particular, can be effectively used as a method for applying adhesives, such as adhesives for electronic components. For this reason, the resin composition dispensing method of the present invention can be suitably used, for example, in the manufacture of electronic components. The electronic component manufacturing method and electronic component of the present invention can be used in the electronic component manufacturing method having an adhesive bonding step with an adhesive for electronic components, and in the electronic component manufactured by said manufacturing method. [Explanation of Symbols]

[0118] 20 Resin composition 50 Jet Dispensers 52 Needles 54 Seals (sealing components) 56 nozzles 58 Chambers 61 Sliding part 62 Collision part S Stroke

Claims

1. A method for dispensing a resin composition using a jet dispenser, wherein the resin composition is dispensed from the nozzle of the jet dispenser, As the jet dispenser, the material of the component that collides with the nozzle when the resin composition is dispensed is made of metal, and A method for dispensing a resin composition, wherein the resin composition comprises (A) a methacrylate compound and (B) a radical polymerization initiator.

2. The dispensing method according to claim 1, wherein the resin composition further comprises at least one of (C1) a polyfunctional thiol compound and (C2) an acrylate compound as component (C).

3. The discharge method according to claim 2, wherein the resin composition comprises both the (C1) polyfunctional thiol compound and the (C2) acrylate compound as component (C), and the ratio of the total number of (meth)acryloyl groups of the (A) methacrylate compound and the (C2) acrylate compound to the total number of thiol groups of the (C1) polyfunctional thiol compound is 0.8 to 1.

2.

4. The discharge method according to claim 2, wherein the resin composition comprises only the (C1) polyfunctional thiol compound as component (C), and the ratio of the methacryloyl groups of the (A) methacrylate compound to the total number of thiol groups of the (C1) polyfunctional thiol compound is 0.8 to 1.

2.

5. The dispensing method according to any one of claims 1 to 4, wherein the resin composition further comprises (D) an anionic polymerization initiator.

6. The dispensing method according to any one of claims 1 to 5, wherein the resin composition further comprises (E) a polymerization inhibitor.

7. The dispensing method according to any one of claims 1 to 6, wherein the resin composition further comprises (F) filler.

8. The dispensing method according to any one of claims 1 to 7, wherein the resin composition further comprises (G) a black pigment.

9. A method for manufacturing an electronic component using the ejection method described in any one of claims 1 to 8.

10. An electronic component obtained by the method for manufacturing an electronic component described in claim 9.

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