Resin composition for jet dispensing, adhesive for electronic component, cured products thereof, and electronic component

Abstract

Provided is a resin composition for jet dispensing having excellent jet dispensability and curability. The resin composition includes (A) a methacrylate compound, (B) a polyfunctional thiol compound, and (C) a radical polymerization initiator.

Description

Jet-dispensing resin composition, adhesive for electronic components, and cured product thereof, and electronic component

[0001] The present invention relates to a jet-dispensable resin composition, an adhesive for electronic components, and a cured product thereof, as well as an electronic component.

[0002] In the process of applying UV and / or thermosetting adhesives for electronic components, air dispensers are the mainstream, but there are challenges in applying them to small areas, applying them in small amounts, and reducing production takt time. Hereinafter, UV and / or thermosetting adhesives for electronic components may be collectively referred to simply as "adhesives for electronic components."

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

[0004] Japanese Patent Application Laid-Open No. 2018-203910

[0005] However, a new problem has been found in that the (meth)acrylate-radical UV- and / or thermosetting adhesive as described in Patent Document 1 reacts quickly, and gelation occurs in the jet dispenser due to impact, shear, heat generation, and the like during application by the jet dispenser.

[0006] For example, Patent Document 1 discloses a resin composition that uses an acrylate and a thiol and can be applied by jet dispensing, as described above, but does not disclose any examples in which this has actually been investigated.

[0007] For this reason, there is a strong demand for the development of a resin composition that can actually be applied by jet dispensing, and in particular, a resin composition that has excellent continuous jet dispensing performance by effectively suppressing gelation in a jet dispenser and also has excellent curing properties after application. Hereinafter, the continuous jet dispensing performance may be referred to as "jet dispensability."

[0008] The present invention has been made in view of the problems associated with the prior art, and provides a jet-dispensable resin composition having excellent jet-dispensability and curability, an adhesive for electronic components, and a cured product thereof, as well as an electronic component.

[0009] According to the present invention, there are provided a jet-dispensable resin composition, an adhesive for electronic components, and cured products thereof, as well as electronic components, as shown below.

[0010] [1] A resin composition for jet dispensing, comprising: (A) a methacrylate compound; (B) a polyfunctional thiol compound; and (C) a radical polymerization initiator.

[0011] [2] The resin composition for jet dispensing according to [1] above, further comprising (D) an acrylate compound.

[0012] [3] The resin composition for jet dispensing according to [2] above, wherein the ratio of the total number of methacryloyl groups in the (A) methacrylate compound and the total number of acryloyl groups in the (D) acrylate compound to the total number of thiol groups in the (B) polyfunctional thiol compound is 0.8 to 1.2.

[0013] [4] The resin composition for jet dispensing according to any one of [1] to [3] above, further comprising (E) an anionic polymerization initiator.

[0014] [5] The resin composition for jet dispensing according to any one of [1] to [4] above, further comprising (F) a polymerization inhibitor.

[0015] [6] The resin composition for jet dispensing according to any one of [1] to [5] above, further comprising (G) a filler.

[0016] [7] The resin composition for jet dispensing according to any one of [1] to [6] above, further comprising (H) a black pigment.

[0017] [8] An adhesive for electronic components using the jet-dispensable resin composition according to any one of [1] to [7] above.

[0018] [9] A cured product comprising the jet-dispensable resin composition according to any one of [1] to [7] above, or the adhesive for electronic components according to [8] above.

[0019]

[10] An electronic component using the jet-dispensable resin composition according to any one of [1] to [7] above, or the adhesive for electronic components according to [8] above.

[0020]

[11] An electronic component comprising the cured product according to [9].

[0021] The jet-dispensing resin composition and adhesive for electronic components of the present invention contain a methacrylate compound as component (A), and therefore have excellent workability and stability, even when they contain a thiol compound with a fast reaction rate, and can be effectively used in a jet dispenser. In particular, it is particularly important in the present invention that the essential component is a methacrylate compound, rather than an acrylate compound that is commonly used in (meth)acrylate-radical resin compositions.

[0022] The jet-dispensable resin composition and adhesive for electronic components of the present invention can also be used as an adhesive that cures only by heat without UV irradiation. The jet-dispensable resin composition of the present invention is not limited to applications for electronic components.

[0023] The jet-dispensing resin composition and adhesive for electronic components of the present invention are also suitable for use in bonding components constituting a camera module, and are primarily used as adhesives for temporary fixing (e.g., active alignment processes) and fixing that utilize UV ​​irradiation for curing. They can also be used as adhesives that are only thermally cured without UV irradiation.

[0024] FIG. 1 is a cross-sectional schematic view of an example of a jet dispenser.

[0025] While the present invention will be described below with reference to exemplary embodiments, it should be understood that the present invention is not limited to the following exemplary embodiments. Therefore, it should be understood that modifications and improvements to the following exemplary embodiments, based on the ordinary knowledge of those skilled in the art, are also within the scope of the present invention, provided that they do not deviate from the spirit of the present invention.

[0026] (1) Jet-dispensing resin composition: One embodiment of the jet-dispensing resin composition of the present invention is a jet-dispensing resin composition containing (A) a methacrylate compound, (B) a polyfunctional thiol compound, and (C) a radical polymerization initiator. Hereinafter, the (A) methacrylate compound may be referred to as component (A). Similarly, the (B) polyfunctional thiol compound may be referred to as component (B), and the (C) radical polymerization initiator may be referred to as component (C).

[0027] The jet-dispense resin composition of this embodiment (hereinafter sometimes simply referred to as the "resin composition") contains the (A) methacrylate compound, and therefore has excellent workability and stability, even when it contains the (B) multifunctional thiol compound, which has a fast reaction rate, and can be effectively used in a jet dispenser. It is particularly important that the jet-dispense resin composition of this embodiment does not contain an acrylate compound, which is commonly used in (meth)acrylate-radical resin compositions, as an essential component, but instead contains a methacrylate compound as an essential component. That is, by containing the (A) methacrylate compound as an essential component, continuous discharge by jet dispensing becomes possible.

[0028] The jet-dispensing resin composition of this embodiment is used to bond components constituting a camera module together, and is preferably used primarily as a UV-based temporary fixation (e.g., active alignment process) and fixation adhesive. It can also be used as an adhesive that only cures thermally without UV irradiation. When applied by jet dispensing, the adhesive supplied to the nozzle is subjected to impact and heat, and if the resin composition used as the adhesive has high reactivity, the adhesive will gel and become impossible to dispense. The jet-dispensing resin composition of this embodiment has improved jet-dispensability by controlling this reactivity.

[0029] The jet-dispensable resin composition of this embodiment can also be used as an adhesive that is cured only by heat without UV irradiation.

[0030] The jet dispensing resin composition of this embodiment may contain, in addition to the above-described components (A), (B), and (C), other components such as (D) an acrylate compound, (E) an anionic polymerization initiator, (F) a polymerization inhibitor, (G) a filler, and (H) a black pigment. Hereinafter, the above-described components may be appropriately referred to as components (D) to (H).

[0031] 1 shows a schematic cross-sectional view of an example of a jet dispenser (jet dispenser 50). The jet dispenser 50 has a needle 52 that can reciprocate like a piston, a seal 54 (sealing member) that prevents the resin composition 20 from leaking to the outside even when the needle 52 reciprocates, and a nozzle 56 for jet-dispensing the resin composition 20.

[0032] As shown in FIG. 1( a), a syringe (not shown) filled with the resin composition is pushed out by air pressure, and a needle 52 reciprocates through a stroke S. As a result, the resin composition 20 is supplied to a chamber 58 in a jet dispenser 50 and jet-dispensed from a nozzle 56. The nozzle 56 has an inner diameter of 50 to 200 μm. As a result, as shown in FIG. 1( b), the resin composition 20 jet-dispensed from the nozzle 56 is supplied to a predetermined target. The jet-dispensable resin composition of this embodiment effectively suppresses gelation in the chamber 58 in the jet dispenser 50, thereby providing excellent jet dispensability and curing properties after jet dispensing. In particular, even when the resin composition 20 is subjected to impact or heat generation due to shear caused by the reciprocating motion of the needle 52, gelation of the resin composition 20 in the chamber 58 in the jet dispenser 50 can be extremely effectively suppressed. The area indicated by reference numeral 61 in Fig. 1(b) is a 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 at this sliding portion 61. The area indicated by reference numeral 62 in Fig. 1(b) is a 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 at this collision portion 62.

[0033] (Component (A)) The component (A) is a methacrylate compound. There are no particular restrictions on the 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 the component (A).

[0034] From the viewpoints of reactivity, dispersibility, and workability, the (A) methacrylate compound preferably has a functional group equivalent of 100 or more and 500 or less, more preferably 100 or more and 400 or less, and even more preferably 100 or more and 250 or less. 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 aspect, the component (A) preferably contains a benzene ring in the molecule in order to provide high heat resistance and high reliability in the physical properties of the resin composition after curing. In another aspect, the component (A) preferably does not contain a benzene ring in order to provide low elasticity in the physical properties of the resin composition after curing.

[0035] Specific examples of the methacrylate compound (A) include 2-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 4-hydroxybutyl methacrylate, cyclohexane-1,4-dimethanol monomethacrylate, tetrahydrofurofuryl methacrylate, phenoxyethyl methacrylate, phenyl polyethoxy methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate, o-phenylphenol monoethoxy methacrylate, o-phenylphenol polyethoxy methacrylate, p-cumylphenoxyethyl methacrylate, isobornyl methacrylate, tribromophenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, Examples of monomers that can be used include acrylate, 1,9-nonanediol dimethacrylate, tricyclodecane dimethanol 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.

[0036] (Component (B)) The component (B) is a polyfunctional thiol compound. The polyfunctional thiol compound of the component (B) imparts thermosetting properties to the resin composition for jet dispensing of this embodiment and also has the effect of improving UV curability. The component (B) is not particularly limited as long as it has two or more functional groups. However, from the viewpoint of moisture resistance, the component (B) is preferably a non-hydrolyzable thiol that does not contain an ester bond in the molecule in order to suppress hydrolysis.

[0037] From the viewpoints of dispersibility and workability, it is particularly preferred that the polyfunctional thiol compound (B) has a molecular weight of 500 or less and is liquid at room temperature.

[0038] Examples of component (B) include glycoluril compounds represented by the following general formula (1):

[0039]

[0040] In general formula (1), R １ , and R ２ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. n is an integer from 0 to 10. Component (B) may also be a compound represented by the following chemical formula (2) or (3).

[0041]

[0042]

[0043] The compounds represented by chemical formula (2) or chemical formula (3) are more preferred compounds as component (B).

[0044] Furthermore, examples of polyfunctional thiol resins that do not have an ester bond in the molecule include polyfunctional thiol resins represented by general formula (4).

[0045]

[0046] In general formula (4), R ３ , R ４ , R ５ , and R ６ are each independently hydrogen or C ｎ H ２ｎ SH (n is 2 to 6).３ , R ４、 R ５ , and R ６ At least one of ｎ H ２ｎ SH (n is 2 to 6). ３ , R ４、 R ５ , and R ６ 2 to 4 of these are C ｎ H ２ｎ SH (n is 2 to 6) is preferred, and R ３ , R ４、 R ５ , and R ６ Three or four of these are C ｎ H ２ｎ SH (n is 2 to 6) is more preferred. Furthermore, in terms of curability, n in the thiol compound of component (B) represented by general formula (4) is preferably 2 to 4. Furthermore, in terms of the balance between the physical properties of the cured product and the curing rate, this thiol compound is more preferably a mercaptopropyl group where n is 3. Because component (B) represented by general formula (4) itself has a sufficiently flexible skeleton, it is effective when it is desired to lower the modulus of elasticity of the cured product. By adding component (B) represented by general formula (4), the modulus of elasticity of the cured product can be controlled, thereby increasing the adhesive strength (particularly peel strength) after curing.

[0047] Commercially available products of the component (B) include a thiol glycoluril derivative manufactured by Shikoku Chemical Industry 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 a thiol compound manufactured by SC Organic Chemical Industry Co., Ltd. (product name: Multiol Y-3 (the main component of general formula (4) corresponds to a trifunctional thiol)). As the component (B), a single component may be used, or two or more components may be used in combination.

[0048] In one embodiment, component (B) preferably contains 50 to 100 parts by mass of glycoluril compound per 100 parts by mass of component (B), from the viewpoint of maintaining the shear strength of the resin composition after curing. The content of glycoluril compound in component (B) is more preferably 60 to 100 parts by mass, and even more preferably 70 to 100 parts by mass.

[0049] In another embodiment, a polyfunctional thiol resin having an ester bond in the molecule can also be used as component (B). From the viewpoint of imparting flexibility to the cured product by the ester bond, the content of this polyfunctional thiol resin is preferably 50 to 100 parts by mass per 100 parts by mass of component (B). In yet another embodiment, from the viewpoint of imparting flexibility and moisture resistance to the cured product, the content of the polyfunctional thiol resin having an ester bond 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 (B).

[0050] Examples of polyfunctional thiol resins having an ester bond in the molecule include pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 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, trimethylolpropane tris(3-mercaptobutyrate), and trimethylolethane tris(3-mercaptobutyrate).

[0051] (Component (C)) The component (C) is a radical polymerization initiator. The resin composition for jet dispensing of this embodiment contains a radical polymerization initiator as the component (C), and therefore the resin composition for jet dispensing can be cured by short-term heating or UV irradiation. The radical polymerization initiator of the component (C) may be a thermal radical polymerization initiator alone, or a photoradical polymerization initiator alone, or two of these may be used in combination. The radical polymerization initiator of the component (C) is more preferably a photoradical polymerization initiator.

[0052] The radical polymerization initiator that can be used in the resin composition for jet dispensing of this embodiment is not particularly limited, and known materials can be used. Specific examples of the radical polymerization initiator include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, and 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, 2,2-bis(t-amylperoxy)cyclohexane, and 2,2-bis(t-butylperoxy)cyclohexane. peroxyketals such as bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, or ethyl 3,3-(t-butylperoxy)butyrate; alkyl peroxyesters 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, benzil dimethyl ketal, benzophenone, benzoylbenzoic acid ... Examples of the radical polymerization initiator include methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzyl, camphorquinone, and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one. As the radical polymerization initiator, a single substance may be used, or two or more substances may be used in combination.

[0053] There are no particular restrictions on the content of the radical polymerization initiator of component (C). For example, the radical polymerization initiator of component (C) is preferably contained in the jet dispensing resin composition at a ratio of 0.01 to 20 mass%, more preferably 0.03 to 10 mass%, and even more preferably 0.05 to 5 mass%. In particular, in the jet dispensing resin composition of this embodiment, good curability was confirmed even when the content of component (C) in the jet dispensing resin composition was 2 mass% or less.

[0054] (Component (D)) The component (D) is an acrylate compound. The resin composition for jet dispensing of this embodiment may further contain an acrylate compound as component (D), in addition to the methacrylate compound as component (A).

[0055] The acrylate compound (D) is preferably a polyfunctional acrylate compound having two or more acryloyl groups. From the viewpoint of jet dispensability, the polyfunctional acrylate compound is preferably bifunctional. If the polyfunctional acrylate compound is trifunctional or higher, jet dispensability may be impaired.

[0056] From the viewpoints of reactivity, dispersibility, and workability, the (D) acrylate compound preferably has a functional group equivalent of 100 or more and 500 or less, more preferably 100 or more and 400 or less, and even more preferably 100 or more and 250 or less. The number of functional groups is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 or 3. In one aspect, the component (D) preferably contains a benzene ring in the molecule in order to provide high heat resistance and high reliability in the physical properties of the resin composition after curing. In another aspect, the component (D) preferably does not contain a benzene ring in order to provide low elasticity in the physical properties of the resin composition after curing.

[0057] Specific examples of the acrylate compound (D) include N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexane-1,4-dimethanol monoacrylate, tetrahydrofurofuryl acrylate, phenoxyethyl acrylate, phenyl polyethoxy acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, o-phenylphenol monoethoxy acrylate, o-phenylphenol polyethoxy acrylate, p-cumylphenoxyethyl acrylate, isobornyl acrylate, tribromophenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, tribromophenyloxyethyl acrylate, dicyclopentan ... Examples of suitable monomers include cyclodecane dimethanol acrylate, bisphenol A polyethoxydiacrylate, bisphenol A polypropoxydiacrylate, bisphenol F polyethoxydiacrylate, 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 diacrylate of neopentyl glycol and hydroxypivalic acid, and diacrylate of an ε-caprolactone adduct of an ester of neopentyl glycol and hydroxypivalic acid. Preferred examples include N-acryloyloxyethylhexahydrophthalimide, phenoxyethyl acrylate, and dicyclopentenyloxyethyl acrylate.

[0058] In the jet dispensing resin composition of this embodiment, the ratio of the total number of methacryloyl groups in the (A) methacrylate compound and the total number of acryloyl groups in the (D) acrylate compound to the total number of thiol groups in the (B) polyfunctional thiol compound is preferably 0.8 to 1.2. By setting the total number of functional groups in each component to such a ratio, the reactivity of the resin composition can be improved.

[0059] It is preferable that the ratio of the total number of methacryloyl groups in the methacrylate compound of component (A) to the total number of acryloyl groups in the acrylate compound of component (D) is (A):(D) = 10:0 to 2:8. The compounding ratio of components (A) and (D) is controlled by the total number of (meth)acryloyl groups in both components, and by keeping the ratio within the above numerical range, extremely excellent jet dispensability can be achieved. In consideration of continuous jet dispensing performance, the (A):(D) ratio is preferably 10:0 to 5:5. On the other hand, in certain embodiments where high UV and / or heat reactivity is required, a higher amount of acrylate compound is desirable, and therefore the (A):(D) ratio is preferably 5:5 to 2:8.

[0060] Here, the total number of thiol groups for (B) polyfunctional thiol compounds, the total number of methacryloyl groups for (A) methacrylate compounds, and the total number of acryloyl groups for (D) acrylate compounds will be explained. In the case of a compound having an acryloyl group and a methacryloyl group in the molecule, the methacryloyl group is counted as the total number of methacryloyl groups for (A) methacrylate compounds, and the acryloyl group is counted as the total number of acryloyl groups for (D) acrylate compounds. In the case of a silane coupling agent having a thiol group or a (meth)acryloyl group, it is not counted in the total number of components (A), (B), and (D).

[0061] Furthermore, the total number of thiol groups in the (B) polyfunctional thiol compound, the total number of methacryloyl groups in the (A) methacrylate compound, and the total number of acryloyl groups in the (D) acrylate compound can be determined by analytical methods such as NMR, gas chromatography, and liquid phase chromatography.

[0062] In addition, the ratio of the total number of methacryloyl groups in the methacrylate compound (A) to the total number of thiol groups in the polyfunctional thiol compound (B) may be 0.1 to 1.2. By configuring in this manner, the reactivity of the resin composition can be improved in the same way as in the case described above.

[0063] (Component (E)) The component (E) is an anionic polymerization initiator. The jet-dispense resin composition of this embodiment contains a radical polymerization initiator as the component (C) as an essential component, but may further contain an anionic polymerization initiator as the component (E). Such an anionic polymerization initiator is a polymerization initiator that initiates polymerization when heated, and is effectively used during main curing after temporary fixing when the jet-dispense resin composition of this embodiment is used as an adhesive for electronic components.

[0064] The anionic polymerization initiator that can be used in the jet dispensing resin composition of this embodiment is not particularly limited, and known materials can be used. Specific examples of the anionic polymerization initiator include imidazole compounds that are solid at room temperature, and solid-dispersion amine adduct latent curing accelerators, such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts), and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts). 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, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl- Examples of the methylimidazole include, but are not limited to, S-triazine-isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.

[0065] Examples of epoxy compounds that can be used as one of the raw materials for producing the solid dispersion type amine adduct latent curing accelerator (amine-epoxy adduct) that can be used in the present invention include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; Examples of epoxy compounds include, but are not limited to, polyglycidyl esters obtained by reacting polycarboxylic acids such as carboxylic acid and terephthalic acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane, m-aminophenol, or the like with epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0066] The amine compound used as another raw material for producing the solid dispersion-type amine adduct latent curing accelerator may be any compound as long as it has one or more active hydrogen atoms in the molecule capable of addition reacting with an epoxy group and at least one functional group selected from a primary amino group, a secondary amino group, and a tertiary amino group. Examples of such amine compounds are shown below, but are not limited to these. Examples include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0067] Among these, 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 primary or secondary amines having a tertiary amino group in the molecule, such as amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, and imidazole compounds 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-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercapto Examples thereof include alcohols, phenols, thiols, carboxylic acids and hydrazides having a tertiary amino group in the 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; and the like.

[0068] Examples of the isocyanate compound used as another production raw material for the solid dispersion-type amine adduct latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

[0069] Examples of urea compounds include, but are not limited to, urea and thiourea.

[0070] The solid-dispersed latent curing accelerator that can be used in the present invention can be obtained, for example, by the following method. First, the components of the above-mentioned two-component combination (a) of an amine compound and an epoxy compound, (b) of these two components and an active hydrogen compound, or (c) of a two-component or three-component combination of an amine compound and at least one of an isocyanate compound and a urea compound are taken and mixed. The resulting mixture is then reacted at a temperature of from room temperature to 200°C. The resulting reaction product is then cooled and solidified and pulverized, or the reaction product is reacted in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, and the solvent is removed, followed by pulverization of the solid content, thereby easily obtaining the solid-dispersed latent curing accelerator.

[0071] Representative examples of the solid dispersion-type latent curing accelerators that are commercially available are shown below, but are not limited to these. That is, for example, examples of amine-epoxy adducts (amine adducts) include "Amicure PN-23" (trade name, manufactured by Ajinomoto Co., Inc.), "Amicure PN-40" (trade name, manufactured by Ajinomoto Co., Inc.), "Amicure PN-50" (trade name, manufactured by Ajinomoto Co., Inc.), "Hardener X-3661S" (trade name, manufactured by ACR Co., Ltd.), "Hardener X-3670S" (trade name, manufactured by ACR Co., Ltd.), and "No Examples of suitable urea adducts include "Vacure HX-3742" (trade name, manufactured by Asahi Kasei Corporation), "Novacure HX-3721" (trade name, manufactured by Asahi Kasei Corporation), "Novacure HXA9322HP" (trade name, manufactured by Asahi Kasei Corporation), "Novacure HXA5945HP" (trade name, manufactured by Asahi Kasei Corporation), and "Novacure HXA5911HP" (trade name, manufactured by Asahi Kasei Corporation). Examples of suitable urea adducts include "Fujicure FXE-1000" (trade name, manufactured by T&K TOKA Corporation) and "Fujicure FXR-1030" (trade name, manufactured by T&K TOKA Corporation). These are selected according to the application, but Novacure manufactured by Asahi Kasei Corporation has a latent curing accelerator dispersed in the epoxy resin, HXA9322HP has low viscosity and is therefore excellent for compounding design of resin compositions, and HXA5945HP and HXA5911HP have fast reactivity and are therefore suitable for applications requiring low-temperature or short-time curing of adhesives. As the anionic polymerization initiator, a single substance may be used, or two or more substances may be used in combination.

[0072] There are no particular restrictions on the content of the anionic polymerization initiator of component (E). For example, the content of the anionic polymerization initiator of component (E) in the resin composition is preferably 0.5 to 10 mass %, more preferably 1 to 5 mass %, and even more preferably 1 to 3 mass %.

[0073] (Component (F)) Component (F) is a polymerization inhibitor. The polymerization inhibitor of component (F) is added to increase the stability of the resin composition during storage. For example, a radical polymerization inhibitor can be used as the polymerization inhibitor. The radical polymerization inhibitor of component (F) is added to suppress the progress of unintended radical polymerization reactions. There is a low probability that the methacrylate compound of component (A) and the acrylate compound of component (D) may generate radicals themselves. In such cases, an unintended radical polymerization reaction may proceed with the radical as the starting point. By adding a radical polymerization inhibitor, the progress of such unintended radical polymerization reactions of component (A) and component (D) can be suppressed.

[0074] Known polymerization inhibitors can be used for component (F). The component (F) used is preferably at least one selected from the group consisting of, for example, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. Also, known radical polymerization inhibitors disclosed in, for example, JP-A Nos. 2010-117545 and 2008-184514 can be used as component (F). A single component may be used as component (F), or two or more components may be used in combination.

[0075] (Component (G)) Component (G) is a filler. By including a filler as component (G), it is possible to improve moisture resistance and liquid drainage during jet dispensing. There are no particular restrictions on the content of the filler, but, for example, the resin composition for jet dispensing of this embodiment preferably contains 0 to 65 mass % of the filler of component (G), more preferably 5 to 50 mass %, and even more preferably 10 to 30 mass %.

[0076] Known fillers can be used for the component (G). Examples of the component (G) used include inorganic fillers and organic fillers. Examples of inorganic fillers include glass, silica, alumina, aluminum nitride, boron nitride, titanium oxide, calcium carbonate, talc, and silver fillers. 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.

[0077] (Component (H)) Component (H) is a black pigment. The black pigment as component (H) is a particularly effective component when the jet dispensing resin composition of this embodiment is used as an adhesive that requires light-blocking properties, such as an adhesive for a camera module. For example, when the 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. For this reason, it is preferable to include a black pigment as component (H) to impart light-blocking properties that prevent light from entering the camera module.

[0078] Known black pigments can be used as the component (H), and examples of the component (H) that can be used include carbon black, graphite, titanium nitride, titanium oxide, zirconia, and titanium black.

[0079] (Component (I): Anionic Polymerization Inhibitor) The resin composition for jet dispensing of this embodiment may contain (I) anionic polymerization inhibitor (hereinafter also referred to as "component (I)") to the extent that the effects of the present invention are not impaired. The anionic polymerization inhibitor (I) is added to increase the stability of the resin composition for jet dispensing during storage and to inhibit the occurrence of an unintended polymerization reaction due to a basic component.

[0080] As the (I) anionic polymerization inhibitor, known inhibitors can be used, such as boric acid ester compounds and strong acids. Specific examples of the (I) anionic polymerization inhibitor 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, preferred (I) anionic polymerization inhibitors are at least one selected from tri-n-propyl borate, triisopropyl borate, and barbituric acid. Furthermore, known (I) anionic polymerization inhibitors disclosed in JP 2010-117545 A, JP 2008-184514 A, JP 2017-171804 A, and the like can also be used. As the (I) anionic polymerization inhibitor, any one type may be used, or two or more types may be used in combination.

[0081] The content of component (I) is preferably 0.1 to 10% by mass, and more preferably 0.3 to 7% by mass, based on the total mass of the resin composition.

[0082] (Other Compounding Agents) The resin composition of this embodiment may further contain components other than the components (A) to (I) described above, as necessary. Specific examples of such components include an antifoaming agent, a silane coupling agent, a dispersant, a thixotropic agent, and an epoxy resin. The type and amount of each compounding agent are the same as in conventional methods.

[0083] (Characteristics of Jet Dispense Resin Composition) The jet dispensing resin composition of this embodiment preferably has, for example, the following characteristics. The viscosity of the jet dispensing resin composition of this embodiment is preferably 0.2 to 80 Pa·s, more preferably 1 to 60 Pa·s, even more preferably 1 to 50 Pa·s, and particularly preferably 1 to 20 Pa·s. By configuring in this manner, the product has good handleability and can maintain high and satisfactory workability. The viscosity of the jet dispensing resin composition can be measured, for example, using a Brookfield (Type B) viscometer at room temperature (25°C) and a rotation speed of 50 rpm.

[0084] The thixotropy index (TI) of the resin composition for jet dispensing according to this embodiment 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 for jet dispensing can be measured, for example, by dividing the value measured at room temperature (25°C) at a rotational speed of 5 rpm using a Brookfield (B-type) viscometer by the value measured at a rotational speed of 50 rpm.

[0085] (Method for Producing Resin Composition for Jet Dispense) The resin composition for jet dispensing of this embodiment can be produced by a conventional method. The resin composition for jet dispensing of this embodiment can be produced by mixing the components described above using, for example, a Raikai mixer, a pot mill, a three-roll mill, a rotary mixer, a twin-screw mixer, or the like.

[0086] (Uses of Jet-Dispense Resin Composition) The jet-dispense resin composition of this embodiment can be used as an adhesive for electronic components. The resin composition of this embodiment can also be suitably applied to engineering plastics. When the jet-dispense resin composition of this embodiment 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, and semiconductor chips. In particular, when used as an adhesive, the jet-dispense resin composition is useful for bonding small electronic components. The jet-dispense resin composition is used in a process of applying an adhesive for electronic components using a jet dispenser 50 such as that shown in FIG. 1.

[0087] The jet-dispensing resin composition of this embodiment can be effectively used, for example, as an adhesive for a camera module. That is, it can be used to bond components constituting a camera module together, and can be used mainly for fixing the components together using UV. The fixing of the components together can be used for temporary fixing in an active alignment process, or for final fixing of the camera module. The jet-dispensing resin composition of this embodiment can satisfy the fluidity requirements necessary for fixing the camera module.

[0088] 1 can perform several hundred jet dispensing shots per second by the reciprocating motion of the needle 52. Therefore, a large impact is applied to the resin composition 20 for jet dispensing (e.g., adhesive). Even after such a large impact is applied, the resin composition for jet dispensing (resin composition 20) of this embodiment can maintain its fluidity.

[0089] Jet dispensing is used to supply adhesive for fixing camera module components. In recent years, with the miniaturization of camera modules, there has been an increasing demand for supplying adhesive to minute regions and narrow gaps. Specifically, the width of the minute regions and gaps to which adhesive is supplied is several hundred μm (e.g., 300 μm). If the resin composition of this embodiment is jet dispensed, adhesive can be supplied to small regions and gaps.

[0090] (2) Adhesive for Electronic Components: Next, an embodiment of the adhesive for electronic components of the present invention will be described. The adhesive for electronic components of this embodiment is an adhesive for electronic components that uses the resin composition for jet dispensing of this embodiment that has been described so far.

[0091] (3) Cured Product of Resin Composition and Cured Product of Adhesive for Electronic Components: Next, an embodiment of the cured product of the present invention will be described. The cured product of the embodiment is a cured product made from the resin composition for jet dispensing of the present embodiment described above. Furthermore, the cured product of the embodiment may be a cured product made from an adhesive for electronic components using the resin composition for jet dispensing of the present embodiment described above.

[0092] (4) Electronic Components: The electronic components of the present invention include a cured product of the above-described jet-dispensable resin composition or a cured product of an adhesive for electronic components using the jet-dispensable resin composition, and therefore have high productivity and high reliability.

[0093] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0094] (Examples 1 to 27, Comparative Examples 1 to 3) [Sample Preparation] The components shown in Tables 1 to 5 were weighed and blended, and then mixed to prepare jet-dispensing resin compositions of the Examples and Comparative Examples. Specifically, the components shown in Tables 1 to 5 were dispersed in a three-roll mill to form a paste, thereby preparing the resin compositions. Details of each component shown in Tables 1 to 5 are as follows.

[0095] [Component (A); Methacrylate Compound] (A1): Phenoxyethyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (trade name: Light Ester PO, methacrylate equivalent: 206 g / eq, number of methacryloyl groups per molecule: 1). (A2): Bisphenol A·EO 2.6 mole adduct-dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (trade name: Light Ester BP-2EMK, methacrylate equivalent: 181 g / eq, number of methacryloyl groups per molecule: 2). (A3): Neopentyl glycol dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (trade name: Light Ester NP, methacrylate equivalent: 120 g / eq, number of methacryloyl groups per molecule: 2). (A4): Trimethylolpropane trimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. (trade name: NK Ester TMPT, methacrylate equivalent: 112.8 g / eq, number of methacryloyl groups per molecule: 3). (A5): Ditrimethylolpropane tetramethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. (trade name: NK Ester D-TMP, methacrylate equivalent: 129.5 g / eq, number of methacryloyl groups per molecule: 4). (A6): 2-hydroxy-1,3-dimethacryloxypropane, manufactured by Shin-Nakamura Chemical Co., Ltd. (trade name: NK Ester 701, methacrylate equivalent: 114 g / eq, number of methacryloyl groups per molecule: 2).

[0096] [Component (B); Polyfunctional Thiol Compound] (B1): 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, manufactured by Shikoku Chemical Industry Co., Ltd. (trade name: TS-G, thiol equivalent: 94 g / eq, number of thiol groups per molecule: 4). (B2): tetrahydro-1,3,4,6-tetrakis(3-mercaptopropyl)-imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, manufactured by Shikoku Chemical Industry Co., Ltd. (trade name: C3TS-G, thiol equivalent: 110 g / eq, number of thiol groups per molecule: 4). (B3): pentaerythritol tetrakis(3-mercaptopropionate), manufactured by SC Organic Chemical Industry Co., Ltd. (trade name: PEMP-LV, thiol equivalent: 122 g / eq, number of thiol groups per molecule: 4). (B4): 3-(3-mercapto-propoxy)-2,2-bis-(3-mercapto-propoxymethyl)-propan-1-ol, manufactured by SC Organic Chemical Industry Co., Ltd. (trade name: Multiol Y-3, thiol equivalent: 124 g / eq, number of thiol groups per molecule: 3). (B5): Pentaerythritol tetrakis(3-mercaptobutyrate), manufactured by Showa Denko K.K. (trade name: Karenz MT PE1, thiol equivalent: 136.2 g / eq, number of thiol groups per molecule: 4).

[0097] [Component (C): Radical Polymerization Initiator] (C1): 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, manufactured by NOF Corporation (trade name: Perocta O, thermal radical polymerization initiator). (C2): 1-hydroxycyclohexyl-phenyl ketone, manufactured by IGM Resins B.V. (trade name: OMNIRAD 184, photoradical polymerization initiator). (C3): 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, manufactured by IGM Resins B.V. (trade name: OMNIRAD 907, photoradical polymerization initiator).

[0098] [Component (D); Acrylate Compound] (D1): Polyester acrylate (polyfunctional acrylic compound), manufactured by Toagosei Co., Ltd. (trade name: M7100, acrylate equivalent: 188 g / eq, number of acryloyl groups per molecule: 3 or more). (D2): Dimethylol-tricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (trade name: Light Acrylate DCP-A, acrylate equivalent: 152 g / eq, number of acryloyl groups per molecule: 2). (D3): Neopentyl glycol diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (trade name: Light Acrylate NP-A, acrylate equivalent: 106 g / eq, number of acryloyl groups per molecule: 2).

[0099] [Component (E); Anionic Polymerization Initiator] (E1): A mixture of a microencapsulated amine curing agent and bisphenol A-type and F-type epoxy resins, 33% by mass of which is microencapsulated, manufactured by Asahi Kasei Corporation (trade name: HXA9322HP). (E2): A modified alicyclic polyamine, manufactured by T&K Toka Corporation (trade name: FXR-1121). (E3): A mixture of a microencapsulated amine curing agent and bisphenol A-type and F-type epoxy resins, 33% by mass of which is microencapsulated, manufactured by Asahi Kasei Corporation (trade name: HXA5945HP). (E4): A mixture of a microencapsulated amine curing agent and bisphenol A-type and F-type epoxy resins, 50% by mass of which is microencapsulated, manufactured by Asahi Kasei Corporation (trade name: HXA5911HP).

[0100] [Component (F): Polymerization inhibitor] (F1): N-nitroso-N-phenylhydroxylamine aluminum, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (trade name: Q-1301). (F2): 4-tert-butylpyrocatechol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (trade name: t-butylcatechol).

[0101] [Component (G); Filler] (G1): Spherical silica, manufactured by Admatechs Co., Ltd. (trade name: SE5200 SEE). (G2): Spherical silica, manufactured by Admatechs Co., Ltd. (trade name: SE2200 SEE). (G3): Silicone composite powder, manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: KMP-600T). (G4): Fumed silica, manufactured by Cabot Corporation (trade name: TS-720).

[0102] [Component (H): Black pigment] (H1): Carbon black, manufactured by Evonik Degussa Japan (trade name: Black 4). (H2): Titanium nitride, titanium dioxide, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (trade name: Titanium Black 13M).

[0103] [Component (J): Other Components] (J-1): Bisphenol F epoxy resin / bisphenol A epoxy resin mixture, manufactured by DIC Corporation (trade name: EXA-835LV). (J-2): Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: KBM403; 3-glycidoxypropyltrimethoxysilane).

[0104] Furthermore, for the jet-dispense resin compositions of Examples 1 to 27 and Comparative Examples 1 to 3, the total number of methacryloyl groups in component (A), the total number of thiol groups in component (B), and the total number of acryloyl groups in component (D) were determined, and functional group ratios (1) and (2) for each component were calculated. Here, functional group ratio (1) is the ratio of the total number of methacryloyl groups in component (A) to the total number of acryloyl groups in component (D) (i.e., total number of methacryloyl groups in component (A) / total number of acryloyl groups in component (D)). Functional group ratio (2) is the ratio of the total number of methacryloyl groups in component (A) and the total number of acryloyl groups in component (D) to the total number of thiol groups in component (B) (i.e., {total number of methacryloyl groups in component (A) + total number of acryloyl groups in component (D)} / total number of thiol groups in component (B)). The results of the ratio (1) and ratio (2) of functional groups for each component are shown in Tables 1 to 5.

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] The curability and jet dispensability of the jet-dispensable resin compositions of Examples 1 to 27 and Comparative Examples 1 to 3 were evaluated by the following methods. The results are shown in Tables 1 to 5.

[0111] [Curability Evaluation] The jet-dispensed resin composition was UV-cured or heat-cured, and the UV cure depth or strength upon heat curing was measured. <UV Cure Depth> Two pieces of heat-resistant tape (100 μm thick) were attached 10 mm apart to a black resin plate A (50 mm wide x 25 mm long x 1.5 mm thick). Next, the resin composition was applied between the two pieces of heat-resistant tape on resin plate A to a thickness of 100 μm, the same as the heat-resistant tape. Next, the two pieces of heat-resistant tape and the resin composition were sandwiched between resin plate A and another resin plate B (50 mm wide x 25 mm long x 1.5 mm thick), and both ends of the two overlapping resin plates A and B were fastened with clips. Any resin composition that protruded from the top of resin plates A and B was wiped off. The resin composition was irradiated with UV from above the jig prepared in this way. More specifically, a UV LED irradiation device "AC475 (product name)" manufactured by Excelitas Technologies was used, and the cumulative light amount was 2000 mJ / cm. ２ The resin compositions were cured by UV irradiation at 1000 W. The cumulative light dose was measured by connecting a light receiver "UVD-365 (trade name)" to a "UIT-250 (trade name)" manufactured by Ushio Inc. One of the sandwiched resin plates A and B was peeled off, and uncured portions adhering to the cured resin composition were removed. The distance from the UV-irradiated surface to the cured portion was measured using a microscope, and the result was taken as the UV cure depth. <Intensity> A 2 mm x 3 mm ceramic chip was placed on each of the resin compositions of the Examples and Comparative Examples that had been jet dispensed onto a ceramic substrate. Next, a UV LED irradiation device "AC475 (trade name)" manufactured by Excelitas Technologies was used to measure the cumulative light dose of 2000 mJ / cm. ２The specimens were UV-cured by UV irradiation. The integrated light intensity was measured by connecting a UVD-365 (product name) receiver to a Ushio Inc. UIT-250 (product name). The UV-cured curable resin composition was thermally cured in a blower dryer at 80°C for 60 minutes. A load was applied to the ceramic chip using a DAGE 4000 (product name) universal bond tester manufactured by DAGE Corporation, and the shear stress (N) at which the ceramic chip peeled was measured. This measurement was performed 10 times per test piece, and the average of the 10 measurements was used as the measured shear strength. A higher measured shear strength indicates better UV and / or thermal curing properties. <Evaluation Criteria> The cured products cured as described above were evaluated according to the following evaluation criteria. In the following evaluation criteria, a rating of "◎" indicates the best rating, followed by "◯", "△", and "×" indicates the worst ratings. ◎: UV curing depth of 450 μm or more, or strength upon thermal curing of 130 N or more. Good: UV curing depth is greater than 350 μm and less than 450 μm, or strength upon heat curing is greater than 60 N and less than 130 N. Fair: UV curing depth is 350 μm or less, or strength upon heat curing is 60 N or less.

[0112] [Evaluation of Jet Dispensability] Each resin composition of the Examples and Comparative Examples was continuously discharged using a jet dispenser (trade name "Smart Stream" manufactured by ITW EAE), and the number of shots that could be continuously discharged was measured. In the evaluation criteria below, "continuously dischargeable" refers to a state in which the resin composition can be continuously discharged without falling into the "discharge impossible" state described below. "Discharge impossible" refers to a state in which the operation of the jet dispenser stops due to a gelation reaction of the resin composition. <Evaluation Criteria> ⊚: The number of shots that can be continuously discharged is 100,000 or more. ◯: The number of shots that can be continuously discharged is 10,000 or more but less than 100,000. Δ: The number of shots that can be continuously discharged is 500 or more but less than 10,000. ×: The number of shots that can be continuously discharged is less than 500.

[0113] [Results] As shown in Tables 1 to 5, the jet-dispensing resin compositions of Examples 1 to 27 containing a methacrylate compound as component (A) showed good results in the evaluations of both curability and jet-dispensability. Furthermore, for the jet-dispensing resin compositions of Examples 1 to 27, it was confirmed that they were curable when the content of the radical polymerization initiator as component (C) was 2% by mass or less.

[0114] On the other hand, since the jet-dispensing resin compositions of Comparative Examples 1 to 3 did not contain a methacrylate compound as component (A), the number of shots that could be continuously discharged in the jet-dispensing evaluation was less than 500. It was found that the jet-dispensing resin compositions of Comparative Examples 1 to 3 were more susceptible to gelation in the jet dispenser than the jet-dispensing resin compositions of Examples 1 to 27, and were therefore unsuitable for application by jet dispensing.

[0115] The resin compositions of Examples 25 to 27, which used HXA5945HP or HXA5911HP as the anionic polymerization initiator (component (E)), respectively, had a faster thermal reaction rate than the other examples. This reaction rate was compared by measuring the gelation time at 80°C.

[0116] The jet-dispensing resin composition of the present invention can be used as a resin composition that can be applied by jet dispensing, and can be effectively used in particular as an adhesive, for example, an adhesive for electronic components. Furthermore, the jet-dispensing resin composition of the present invention, the adhesive for electronic components, and their cured products can be used in the production of electronic components. Furthermore, the jet-dispensing resin composition of the present invention can also be suitably used for engineering plastics.

[0117] 20 Resin composition 50 Jet dispenser 52 Needle 54 Seal (sealing member) 56 Nozzle 58 Chamber 61 Sliding part 62 Collision part S Stroke

Claims

1. (A) a methacrylate compound; (B) a polyfunctional thiol compound; (C) a radical polymerization initiator.

2. The resin composition for jet dispensing described in claim 1, further comprising (F) a polymerization inhibitor.

3. The resin composition for jet dispensing according to claim 2 , further comprising (D) an acrylate compound.

4. The resin composition for jet dispensing according to any one of claims 1 to 3, further comprising (E) an anionic polymerization initiator.

5. The resin composition for jet dispensing according to any one of claims 1 to 3, further comprising (G) a filler.

6. The resin composition for jet dispensing described in claim 4, further comprising (G) a filler.

7. The resin composition for jet dispensing according to any one of claims 1 to 3, further comprising (H) a black pigment.

8. The resin composition for jet dispensing described in claim 4, further comprising (H) a black pigment.

9. The resin composition for jet dispensing described in claim 5, further comprising (H) a black pigment.

10. The resin composition for jet dispensing described in claim 6, further comprising (H) a black pigment.

11. An adhesive for electronic components, comprising the jet-dispense resin composition according to any one of claims 1 to 3.

12. A cured product comprising the jet-dispense resin composition according to any one of claims 1 to 3, or an adhesive for electronic components using the jet-dispense resin composition.

13. An electronic component using the jet-dispense resin composition according to any one of claims 1 to 3, or an adhesive for electronic components using the jet-dispense resin composition.

14. An electronic part comprising the cured product according to claim 12.