KR20240076415A - Method for discharging a resin composition, method for manufacturing electronic components, and electronic components - Google Patents

Abstract

A method for discharging a resin composition that can effectively suppress curing of the resin composition in a jet dispenser is provided. A discharging method of discharging a resin composition (20) from a nozzle (56) of the jet dispenser (50) using a jet dispenser (50), wherein the jet dispenser (50) dispenses a resin composition (20) such as a needle (52). The material of the member that collides with the nozzle 56 when discharging ) is made of metal, and the resin composition 20 contains (A) a methacrylate compound and (B) a radical polymerization initiator.

Description

Method for discharging a resin composition, method for manufacturing electronic components, and electronic components

The present invention relates to a method for discharging a resin composition, a method for manufacturing electronic components, and electronic components. It also relates to a method of discharging a resin composition that can effectively suppress curing of the resin composition in a jet dispenser, a method of manufacturing electronic components, and electronic components manufactured by the manufacturing method.

In the process of applying UV and/or thermosetting adhesives for electronic components, air dispensers are the mainstream, but reduction of microscopic areas, microcoating, and production tact are challenges. Hereinafter, UV and/or thermosetting adhesives for electronic components are collectively referred to as “adhesives for electronic components” in some cases.

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

Japanese Patent Publication No. 2018-203910

However, since the (meth)acrylate-radical UV and/or heat curing adhesive described in Patent Document 1 has a fast reaction, shock, shear, heat generation, etc. when applied with a jet dispenser become the cause, and the jet dispenser The task of gelling within oneself was newly discovered. In particular, thermosetting adhesives are prone to local gelation due to frictional heat generated inside the jet dispenser, so the problem of continuous stable application of highly reactive adhesives such as (meth)acrylate-radical adhesives is becoming serious. there was. Gelation refers to the beginning of the polymerization process of polymers, forming a three-dimensional network structure, and increasing viscosity and elasticity.

Patent Document 1 discloses a resin composition that can be applied by jet dispensing using acrylate and thiol as described above, but does not disclose any cases that have actually been examined. Additionally, Patent Document 1 does not disclose the specific configuration of the jet dispenser (jet dispensing device) to be used, for example, the material of the needle that discharges the resin composition.

For this reason, there is a demand for the development of a method for discharging a resin composition that effectively suppresses gelation in the jet dispenser, has excellent application performance by jet dispensing, and also has excellent curability after application. Hereinafter, the application performance by jet dispensing may be referred to as “jet dispensability.”

The present invention was made in consideration of the problems of the prior art. The present invention provides a method for discharging a resin composition that can effectively suppress curing of the resin composition in a jet dispenser. Additionally, the present invention provides a method for manufacturing an electronic component using the method for discharging the resin composition described above, and an electronic component manufactured by the method.

According to the present invention, a method for discharging a resin composition, a method for manufacturing electronic components, and electronic components shown below are provided.

[1] A method of discharging a resin composition using a jet dispenser and discharging the resin composition from a nozzle of the jet dispenser,

In the jet dispenser, a member that collides with the nozzle when discharging the resin composition is made of metal, and

A method for discharging a resin composition, wherein the resin composition contains (A) a methacrylate compound and (B) a radical polymerization initiator.

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

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

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

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

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

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

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

[9] A method of manufacturing electronic components using the ejection method according to any one of [1] to [8] above.

[10] An electronic component obtained by the electronic component manufacturing method described in [9] above.

The discharging method of the resin composition of the present invention is a method of discharging the resin composition using a jet dispenser and discharging the resin composition from the nozzle of the jet dispenser. According to the method for discharging the resin composition of the present invention, the resin composition can be continuously applied in a small amount and in a small area using a jet dispenser. Hereinafter, the discharging method of the resin composition of the present invention may simply be referred to as the “discharging method.”

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. For this reason, even when frictional heat or the like is generated inside the jet dispenser, local gelation of the resin composition is unlikely to occur, workability and stability are high, and extremely excellent jet dispensing properties can be realized. In addition, in the discharging method of the present invention, 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 cited as a particularly important configuration. By using such a jet dispenser, the heat generated inside the jet dispenser can be effectively dissipated to the outside by using the member (e.g., needle, etc.) that collides with the nozzle as a heat dissipation member, thereby preventing local gelation of the resin composition from occurring. It can be difficult.

In addition, the discharging method of the present invention is used for bonding members constituting a camera module, and mainly involves temporary fixing using curing by UV irradiation (e.g., active alignment process) and applying a fixing adhesive. It is preferably used in the process. In addition, it can also be applied to the process of applying a heat-curing adhesive without UV irradiation.

In addition, the method for manufacturing electronic components of the present invention is a method of manufacturing electronic components using the discharging method of the present invention described above, and in particular, a very small amount of adhesive for electronic components can be accurately applied to a very small area. For this reason, the electronic component manufacturing method of the present invention is very effective as a manufacturing method requiring adhesion of small electronic components. In addition, the electronic component of the present invention is an electronic component manufactured by the above manufacturing method, and excellent adhesion between electronic members is realized.

1 is a cross-sectional schematic diagram of an example of a jet dispensing device (jet dispenser).

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. Accordingly, it should be understood that appropriate changes, improvements, etc. to the following embodiments based on the common knowledge of those skilled in the art without departing from the spirit of the present invention fall within the scope of the present invention.

(1) Method of discharging the resin composition:

One embodiment of the method for discharging the resin composition of the present invention uses a jet dispenser 50 as shown in FIG. 1 to discharge the resin composition 20 from the nozzle 56 of the jet dispenser 50. This is a method of discharging a resin composition. Here, FIG. 1 is a cross-sectional schematic diagram of an example of a jet dispensing device (jet dispenser 50). The jet dispenser 50 includes a needle 52 capable of reciprocating movement like a piston, and a seal 54 (sealing member) to prevent the resin composition 20 from leaking to the outside even by the reciprocating movement of the needle 52. , has a nozzle 56 for jet dispensing the resin composition 20.

As shown in FIG. 1(a), a syringe (not shown) filled with the resin composition is extruded with pressure from air, and the needle 52 reciprocates at the length of the stroke S, thereby forming the resin composition ( 20) is supplied to a chamber 58 in the jet dispenser 50 and jet dispensed from a nozzle 56. Meanwhile, the nozzle 56 has an inner diameter of 20 to 300 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 object. When discharging the resin composition 20 by the jet dispenser 50, the needle 52 capable of the above-described reciprocating motion collides with the nozzle 56. In the discharging method of this embodiment, the jet dispenser 50 for discharging the resin composition 20 is made of metal. use what is The needle 52 has different names depending on the device manufacturer, and is sometimes called a tappet, poppet, or rod. By using the jet dispenser 50 in which the needle 52 is made of metal, heat generated inside the jet dispenser 50 can be dissipated using members such as the needle 52 as a heat dissipation member. By configuring in this way, local gelation of the resin composition 20 within the jet dispenser 50 can be effectively suppressed.

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 cemented carbide, and a particularly preferable example is tungsten carbide. By using such a member made of tungsten carbide, for example, the heat dissipation inside the jet dispenser 50 can be very effectively improved compared to the ceramic or metal member widely used as the nozzle 56 of the jet dispenser 50. You can.

In addition, in the discharge method of the present embodiment, one of the main configurations is to use a resin composition 20 containing (A) a methacrylate compound. By configuring in this way, hardening of the resin composition 20 inside the jet dispenser 50 can be effectively suppressed. For this reason, even when frictional heat or the like is generated inside the jet dispenser 50, local gelation of the resin composition 20 is unlikely to occur, workability and stability are high, and extremely excellent continuous jet dispensing performance can be realized. For example, when applying the resin composition 20 with the jet dispenser 50, shock or heat is applied to the resin composition 20 supplied to the nozzle 56, so the reactivity of the resin composition 20 may be excessive. If it is high, the resin composition 20 gels and discharge becomes difficult. By using a resin composition (20) containing (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 prevented. It can make it difficult to get up. The range indicated by symbol 61 in FIG. 1(b) is the sliding portion 61 in which the needle 52 slides relative to the yarn 54 in accordance with the reciprocating movement of the needle 52, and this sliding portion 61 In this case, stress is applied to the resin composition 20. In addition, the range indicated by symbol 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 this collision portion ( In 62), stress is applied to the resin composition (20).

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

According to the discharging method of this embodiment, the resin composition 20 can be applied in a small amount and to a small area using the jet dispenser 50. This discharge method is used to bond the members that make up the camera module, and is mainly used for temporary fixation using curing by UV irradiation (e.g., active alignment process) and is preferably used in the process of applying fixing adhesive. do. In addition, it can also be applied to the process of applying a heat-curing adhesive without UV irradiation. When applying by jet dispensing, shock or heat is applied to the adhesive supplied to the nozzle, so if the resin composition used as the adhesive has good reactivity, the adhesive gels and becomes impossible to discharge. The dispensing method of this embodiment improves jet dispensability by controlling this reactivity.

Since the discharging method of this embodiment can be applied to adhesives that only heat cure without UV irradiation, for example, it can be particularly preferably applied to engineer plastics.

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

In addition, the resin composition 20 may 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 appropriately referred to as (D) component to (G) component. Hereinafter, the resin composition 20 will be described in more detail for each component.

((A) component)

(A) The component is a methacrylate compound. (A) There are no particular restrictions on the component as long as it has a methacryloyl group. For example, there is no particular limitation on the number of functional groups (that is, the number of methacryloyl groups) in the methacrylate compound of component (A). (A) By including a methacrylate compound, the reactivity of the resin composition can be controlled and gelation of the resin composition inside the jet dispenser can be prevented from occurring.

(A) From the viewpoint of reactivity, dispersibility, and workability, the functional group equivalent weight of the methacrylate compound is preferably 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. Moreover, 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, for the reason that the physical properties of the resin composition after curing are high heat resistance and high reliability, it is preferable that component (A) contains a benzene ring in the molecule. Moreover, in another aspect, it is preferable that the resin composition does not contain a benzene ring for the reason that the physical properties after curing of the resin composition are low in elasticity.

(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, phenyl polyethoxy methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate , o-phenylphenol monoethoxy methacrylate, o-phenylphenol polyethoxy methacrylate, p-cumylphenoxyethyl methacrylate, isobornyl methacrylate, tribromophenyloxyethyl methacrylate, DC Clopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-no Nandiol dimethacrylate, tricyclodecane dimethanol methacrylate, bisphenol A polyethoxydimethacrylate, bisphenol A polypropoxydimethacrylate, bisphenol F polyethoxydimethacrylate, ethylene glycol dimethacrylate Latex, polyethylene glycol dimethacrylate, tris(methacryloxyethyl)isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, tripentaerythritol hexamethacrylate Monomers such as trimethylolpropane pentamethacrylate, tripentaerythritol pentamethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane polyethoxytrimethacrylate, ditrimethylolpropane tetramethacrylate, and neopentyl glycol dimethacrylate. I can hear it.

((B) component)

(B) Component is a radical polymerization initiator. Since the resin composition contains a radical polymerization initiator as component (B), it becomes possible to cure the resin composition by short-term heating or UV irradiation. The radical polymerization initiator of component (B) may be a thermal radical polymerization initiator alone, a photo-radical polymerization initiator alone, or these two types may be used in combination. The radical polymerization initiator of component (B) is more preferably a radical photopolymerization initiator.

There is no particular limitation on the radical polymerization initiator that can be used in the resin composition, and it is possible to use known materials. Specific examples of radical polymerization initiators include dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, or 2,5-dimethyl-2,5- dialkyl peroxides such as 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-butylperoxy)butane, n-butyl4,4-bis(t-butylperoxy)valerate, or ethyl 3,3-(t-butylperoxy)butyrate Same peroxyketal; t-butylperoxy2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, or t-butylperoxymaleate. -Alkyl peroxy esters such as butyl peroxybenzoate can be mentioned. Also, as other examples, 1-hydroxycyclohexyl-phenylketone, 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, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4- Benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone , Isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide , methylphenylglyoxylate, benzyl, camphorquinone, and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one. there is. As a radical polymerization initiator, a single substance may be used, or two or more types of substances may be used together.

There is no particular limitation on the content of the radical polymerization initiator of component (B). For example, the radical polymerization initiator of component (B) is preferably contained in the resin composition at 0.01 to 40 mass%, more preferably at 0.03 to 30 mass%, and even more preferably at 0.05 to 20 mass%. do.

((C) component)

Component (C) is at least one of (C1) a polyfunctional thiol compound and (C2) an acrylate compound. In this way, the resin composition preferably contains at least one of the polyfunctional thiol compound (C1) and the acrylate compound (C2) in addition to the above-mentioned component (A) and component (B).

((C1) component)

(C1) Component is a polyfunctional thiol compound. The polyfunctional thiol compound of component (C1) provides elasticity to the resin composition. (C1) The component is not particularly limited as long as it has two or more functional groups. However, from the viewpoint of moisture resistance, since component (C1) suppresses hydrolysis during moisture resistance, a non-hydrolyzable thiol that does not contain an ester bond in the molecule is preferred.

(C1) From the viewpoint of dispersibility and workability, the polyfunctional thiol compound preferably has a molecular weight of 500 or less and is preferably liquid at room temperature.

The (C1) component includes a glycoluril compound represented by the following formula (1).

In 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. In addition, the (C1) component may be a compound represented by the following formula (2) or formula (3).

The compound represented by formula (2) or formula (3) is a more preferable compound as the (C1) component.

In addition, examples of polyfunctional thiol resins that do not have an ester bond in the molecule include polyfunctional thiol resins represented by formula (4).

In 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). Additionally, at least one of R ³ , R ⁴ , R ⁵ , and R ⁶ is C _n H _2n SH (n is 2 to 6). 2 to 4 of R ³ , R ⁴ , R ⁵ , and R ⁶ are preferably C _n H _2n SH (n is 2 to 6), and 3 of R ³ , R ⁴ , R ⁵ , and R ⁶ Or, it is more preferable that four are C _n H _2n SH (n is 2 to 6). In addition, n of the polyfunctional thiol compound of the (C1) component represented by formula (4) is preferably 2 to 4 from the viewpoint of curability. Moreover, from the viewpoint of the balance between the physical properties of the cured product and the curing speed, this thiol compound is more preferably a mercaptopropyl group where n is 3. The (C1) component represented by formula (4) itself has a sufficiently flexible skeleton, and is therefore effective when the elastic modulus of the cured product is desired to be low. By adding the (C1) component represented by formula (4), the elastic modulus of the cured product can be controlled, and thus the adhesive strength (especially peel strength) after curing can be increased.

Commercially available products of the component (C1) include thiol glycoluril derivative manufactured by Shikoku Kasei Kogyo Co., Ltd. (product name: TS-G (equivalent to formula (2), thiol equivalent: 100 g/eq), C3TS-G (equivalent to formula (3)) , thiol equivalent weight: 114 g/eq)), and a thiol compound manufactured by SC Yuki Chemical Co., Ltd. (product name: Multhiol Y-3 (the main component in formula (4) is equivalent to trifunctional thiol)). (C1) As a component, a single component may be used, and two or more types of components may be used together.

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

In another aspect, a polyfunctional thiol resin having an ester bond in the molecule can also be used as the (C1) component. From the viewpoint of imparting flexibility to the cured product through the ester bond, the content of this polyfunctional thiol resin is preferably 50 to 100 parts by mass with respect to 100 parts by mass of component (C1). In another embodiment, from the viewpoint of providing 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 with respect to 100 parts by mass of the component (C1). , it is more preferable that it is less than 40 parts by mass, and it is still more preferable that it is less than 30 parts by mass.

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

((C2) component)

(C2) Component is an acrylate compound. In addition to the methacrylate compound as component (A), the resin composition may further contain an acrylate compound as component (C2).

(C2) The acrylate compound is preferably a multifunctional acrylate compound having two or more acryloyl groups. It is more preferable that the multifunctional acrylate compound is bifunctional from the viewpoint of jet dispensability. If it is trifunctional or more, jet dispensability may become disadvantageous.

(C2) From the viewpoint of reactivity, dispersibility, and workability, the functional group equivalent weight of the (C2) acrylate compound is preferably 100 to 500, more preferably 100 to 400, and even more preferably 100 to 250. Additionally, 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, for the reason that the physical properties after curing of the resin composition are high heat resistance and high reliability, (C2) preferably contains a benzene ring in the molecule. Moreover, in another aspect, it is preferable that the resin composition does not contain a benzene ring for the reason that the physical properties after curing of the resin composition are low in elasticity.

(C2) Specific examples of acrylate compounds include, for example, N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl acrylate, and 4-hydroxybutylacrylate. , Cyclohexane-1,4-dimethanol monoacrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenyl polyethoxy acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, o-phenyl Phenol 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, tricyclodecane dimethanol acrylate, bisphenol A polyethoxy diacrylate, bisphenol A polypropoxy diacrylate, bisphenol F polyethoxy diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, tris(acryloxyethyl)isocyanurate, penta Erythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, trimethylolpropane triacrylate, trimethylolpropane polyethoxytriacrylate, Monomers include ditrimethylolpropane tetraacrylate, ester diacrylate of neopentyl glycol and hydroxypivalic acid, and diacrylate of ε-caprolactone adduct of neopentyl glycol and hydroxypivalic acid ester. . Preferred examples include N-acryloyloxyethylhexahydrophthalimide, phenoxyethyl acrylate, and dicyclopentenyloxyethyl acrylate.

When the resin composition contains both a polyfunctional thiol compound (C1) and an acrylate compound (C2) as component (C), it is more preferable to be structured as follows. That is, it is preferable that 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 polyfunctional thiol compound (C1) is 0.8 to 1.2. do. By maintaining the total number of functional groups of each component in 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 total number of methacryloyl groups in the (A) methacrylate compound and the (C2) acrylate compound. It means the sum of the total number of acryloyl groups in the rate compound.

In addition, when the resin composition contains only the polyfunctional thiol compound (C1) as component (C), the methacrylate compound of (A) the methacrylate compound relative to the total number of thiol groups in the polyfunctional thiol compound (C1) It is preferable that the ratio of the rotyl group is 0.8 to 1.2. By configuring in this way, the reactivity of the resin composition can be improved in the same way as in the case described above.

In addition, the resin composition has a 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, (A):(C2) = It is preferably 10:0 to 2:8. By maintaining the above numerical range, very excellent jet dispensing properties can be realized. Additionally, regarding the ratio of the total number of methacryloyl groups in the (A) methacrylate compound and the total number of acryloyl groups in the (C2) acrylate compound, the value of (A)/(C2) is, It is preferable that (A)/(C2) = 0.8 to 1.2. By configuring in this way, both jet dispensing properties and thermosetting properties can be achieved.

Here, (A) the total number of methacryloyl groups in the methacrylate compound, (C2) the total number of acryloyl groups in the acrylate compound, and (C1) the total number of thiol groups in the polyfunctional thiol compound. Explain. 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 in the (A) methacrylate compound, and the acryloyl group is counted as the total number of methacryloyl groups in the (C2) acrylate compound. It is counted as the total number of acryloyl groups in the compound. In the case of a silane coupling agent having a thiol group or (meth)acryloyl group, the total number of components (A), (C2), and (C1) is not counted.

In addition, (A) the total number of methacryloyl groups in the methacrylate compound, (C2) the total number of acryloyl groups in the acrylate compound, and (C1) the total number of thiol groups in the polyfunctional thiol compound are , for example, can be obtained by analysis methods such as NMR, gas chromatography, and liquid chromatography.

((D) component)

Component (D) is an anionic polymerization initiator. In addition to the radical polymerization initiator as component (B), the resin composition may further contain an anionic polymerization initiator as component (D). This anionic polymerization initiator is a polymerization initiator that initiates polymerization upon heating, and is effectively used, for example, during main curing after temporary setting when the resin composition is used as an adhesive for electronic components.

There is no particular limitation on the anionic polymerization initiator that can be used in the resin composition, and it is possible to use known materials. Specific examples of anionic polymerization initiators include imidazole compounds that are solid at room temperature, and solid dispersed amine adduct-based latent curing accelerators, such as the reaction product of an amine compound and an epoxy compound (amine-epoxy adduct-based). , a reaction product of an amine compound and an isocyanate compound or a urea compound (urea-type adduct type), etc. Imidazole compounds that are solid at room temperature that can be used in the present invention include, for example, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-undecylimidazole. , 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazole) Zolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine·isocyanuric acid adduct , 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole Zol-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-(2-methyl Midazolyl-(1)-ethyl)-adipoyldiamide, etc. may be mentioned, but it is not limited to these.

Epoxy compounds used as one of the raw materials for producing the solid dispersed amine adduct type latent hardening accelerator (amine-epoxy adduct type) that can be used in the present invention include, for example, bisphenol A, bisphenol F, and catechol. , polyglycidyl ether obtained by reacting polyhydric phenol such as resorcinol, or polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; Glycidyl ether ester obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl ester obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; Glycidylamine compounds obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane, m-aminophenol, etc.; Furthermore, polyfunctional epoxy compounds such as epoxidized phenol novolak resin, epoxidized cresol novolac resin, and epoxidized polyolefin, and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate. epoxy compounds; These can be mentioned, but are not limited to these.

The amine compound used as another raw material for the production of the solid dispersed amine adduct-based latent curing accelerator has at least one active hydrogen capable of addition reacting with an epoxy group in the molecule, and also has a primary amino group and a secondary amino group. , and tertiary amino groups, as long as it has at least one functional group selected from among them in the molecule. Examples of such amine compounds are shown below, but are not limited to these. That is, 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 a nitrogen atom such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine; etc. can be mentioned.

In addition, among these, compounds having a tertiary amino group in the molecule are raw materials that provide a latent curing accelerator with excellent curing accelerator ability, and examples of such compounds include, for example, dimethylaminopropylamine and diethylaminopropylamine. , di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, amine compounds, 2-methylimidazole, 2-ethyl imida Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as sol, 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-mercaptopyridine, 2-benzoimidazole, 2-mercaptobenzimidazole, 2-mer Captobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid Alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide; etc. can be mentioned.

Isocyanate compounds used as another raw material for the production of the solid dispersed amine adduct-based latent curing accelerator include, for example, monofunctional ones such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate. isocyanate compounds; Hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6 -Polyfunctional isocyanate compounds such as hexamethylene triisocyanate and bicycloheptane triisocyanate; Furthermore, terminal isocyanate group-containing compounds obtained by reaction of these polyfunctional isocyanate compounds with an active hydrogen compound; etc. can also be used. Examples of such terminal isocyanate group-containing compounds include addition compounds having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, addition compounds having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and pentaerythritol, etc. may be mentioned, but are not limited to these.

In addition, examples of urea compounds include urea, thiourea, etc., but are not limited to these.

The solid dispersed latent curing accelerator that can be used in the present invention can be obtained, for example, by the following method. First, (a) the two components of an amine compound and an epoxy compound, (b) the three components of these two components and an active hydrogen compound, or (c) the two components of an amine compound and at least one of an isocyanate compound and a urea compound. Or, take each component and mix it as a combination of three components. Then, the obtained mixture is reacted at a temperature ranging from room temperature to 200°C. Thereafter, the obtained reaction product is cooled and solidified and then pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and the solid content is pulverized after removing the solvent to obtain the solid dispersed latent curing accelerator. It can be obtained easily.

Representative examples commercially available as the solid dispersed latent curing accelerator are shown below, but are not limited to these. That is, for example, the amine-epoxy adduct system (amine adduct system) includes “Amicure PN-23” (manufactured by Ajinomoto, brand name), “Amicure PN-40” (manufactured by Ajinomoto, brand name), “Amicure PN-50” (manufactured by Ajinomoto, brand name), “Hardner “Novacure HX-3742” (manufactured by Asahi Kasei, brand name), “Novacure HX-3721” (manufactured by Asahi Kasei, brand name), “Novacure HXA9322HP” (manufactured by Asahi Kasei, brand name), etc., In addition, examples of the urea-type adduct system include “Fujicure FXE-1000” (manufactured by T&K TOKA, brand name) and “Fujicure FXR-1030” (manufactured by T&K TOKA, brand name). As an anionic polymerization initiator, a single substance may be used, or two or more types of substances may be used in combination.

There is no particular limitation on the content of the anionic polymerization initiator in component (D). For example, when the anionic polymerization initiator of component (D) is contained, 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 1 to 3% by mass. It is more preferable that it is mass%.

((E) component)

(E) Component is a polymerization inhibitor. The polymerization inhibitor of component (E) is added to increase the stability of the resin composition during storage. For example, a radical polymerization inhibitor can be used as a polymerization inhibitor. The radical polymerization inhibitor of component (E) is added to suppress the progress of an unintended radical polymerization reaction. The methacrylate compound of component (A) and the acrylate compound of component (C2) may generate radicals on their own with a low probability. At this time, an unintended radical polymerization reaction may proceed starting from the radical. By adding a radical polymerization inhibitor, the progress of such unintended radical polymerization reaction of component (A) or component (C2) can be suppressed.

The polymerization inhibitor of component (E) can be a known polymerization inhibitor. The component (E) used is preferably at least one selected from the group consisting of, for example, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. . Additionally, as the component (E), a known radical polymerization inhibitor disclosed in Japanese Patent Application Laid-Open No. 2010-117545 and Japanese Patent Application Publication No. 2008-184514, etc. may be used. (E) As a component, a single component may be used, and two or more types of components may be used together.

((F) component)

(F) The ingredient is a filler. (F) By including a filler as a component, moisture resistance and liquid discharge properties during jet dispensing can be improved. There is no particular limitation on the content of the filler, but for example, the resin composition preferably contains 0 to 65% by mass of the filler of component (F), more preferably 5 to 50% by mass, and 10 to 50% by mass. It is more preferable to contain 30% by mass.

(F) A known filler for component can be used. (F) Components include, for example, inorganic fillers and organic fillers. Examples of inorganic fillers include glass, silica, alumina, aluminum nitride, boron nitride, titanium oxide, calcium carbonate, talc, and silver filler. Examples of organic fillers include silicone rubber, PTFE, polystyrene, polyacrylate, polyurethane, and polydivinylbenzene filler. The average particle diameter 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.

((G) component)

(G) The component is a black pigment. The black pigment as the component (G) is a particularly effective component when the resin composition is used as an adhesive requiring light-shielding properties, such as an adhesive for a camera module. 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. For this reason, in order to have light-shielding properties to prevent light from entering the camera module, it is preferable to include a black pigment as the (G) component.

(G) A known black pigment of component can be used. Examples of the (G) component used include carbon black, graphite, titanium nitride, titanium oxide, zirconia, and titanium black.

((H) component; 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. (H) An anionic polymerization inhibitor is added to increase the stability of the resin composition during storage and to suppress the occurrence of polymerization reaction due to unintended basic components.

(H) Known anionic polymerization inhibitors can be used, for example, boric acid 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, and difluoride. Examples include roacetic acid, trichloroacetic acid, phosphoric acid, and dichloroacetic acid. Among these, the preferred (H) anionic polymerization inhibitor is at least one selected from tri-n-propylborate, triisopropylborate, and barbituric acid. Additionally, (H) anionic polymerization inhibitors may be those known in Japanese Patent Application Laid-Open No. 2010-117545, Japanese Patent Application Laid-Open No. 2008-184514, and Japanese Patent Application Laid-Open No. 2017-171804. (H) Any one type of anionic polymerization inhibitor may be used, or two or more types may be used in combination.

The content of component (H) is preferably 0.1 to 10 mass%, more preferably 0.3 to 7 mass%, relative to the total mass of the resin composition.

(Other compounding agents)

The resin composition used in the discharge method of this embodiment may further contain components other than components (A) to (H) described so far, as needed. Specific examples of these components include antifoaming agents, silane coupling agents, dispersants, and epoxy resins. The type and mixing amount of each compounding agent are the same as the usual method.

(Characteristics of resin composition)

The resin composition used in the discharge method of this embodiment preferably has the characteristics shown below, for example. 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 in this way, the handleability of the resin composition is good and fluidity can be maintained at a high level. The viscosity of the resin composition can be measured at room temperature (25°C) using a viscometer manufactured by Brookfield (Type B) and an SC4-14 spindle at a rotation speed of 50 rpm.

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

(Method for producing resin composition)

The resin composition used in the discharge method of this embodiment can be manufactured by a common method. The resin composition can be manufactured by mixing each of the components described so far using, for example, a rotary mixer, a pot mill, a three-roll mill, a rotary mixer, or a two-axis mixer.

(Configuration and discharge conditions of jet dispenser)

Regarding the configuration of the jet dispenser used in the dispensing method of this embodiment, as long as the material of the member colliding with the nozzle is made of metal, there is no particular limitation regarding the other configuration, and the device configuration can be based on a conventionally known jet dispenser. You can. In addition, there are no particular restrictions on the conditions for discharging the resin composition by the jet dispenser, and as long as the resin composition described so far is discharged, it can be based on the discharge conditions of the conventionally known jet dispenser. For example, the jet dispenser used in the dispensing method of this embodiment is preferably configured as follows. A nozzle made of metal is preferred. The nozzle temperature may be room temperature or may be heated. The tip diameter of the needle is preferably 0.7 to 3 mm. The needle pulling time is preferably 0.1 to 7 msec, and the needle pulling time is preferably 0.1 to 7 msec. The needle pulling 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.

(Use of the discharging method of the resin composition)

The discharge method of this embodiment can be used in the process of applying the adhesive for electronic components. In this process, the resin composition is used as an adhesive for electronic components. Additionally, the resin composition can be suitably applied to engineer plastics. In the discharging method of this embodiment, when the resin composition is used as an adhesive for electronic components, there is no particular limitation on the electronic component to be adhered, and examples include ceramic substrates, organic substrates, and semiconductor chips. In particular, when used as an adhesive, it is useful for adhering small electronic components. The resin composition is used in the process of applying an adhesive for electronic components using the jet dispenser 50 shown in FIG. 1.

The resin composition can be effectively used as an adhesive for camera modules, for example. In other words, it can be used to bond the members constituting the camera module, and can mainly be used to fix the members using UV. Regarding fixation of members to each other, it can be used for temporary fixation in the active alignment process or for final fixation to finally fix the camera module. The resin composition used in the discharge method of this embodiment can satisfy the requirement of fluidity required when fixing the camera module.

On the other hand, the jet dispenser 50 shown in FIG. 1 can dispense hundreds of shots of jet in one second by reciprocating movement of the needle 52. For this reason, the resin composition 20 for jet dispensing (eg, adhesive) is subject to a large impact. Even after such a large impact is applied, the resin composition 20 can maintain fluidity.

Jet dispensing is used to supply adhesive for fixing members of the camera module. In recent years, with the miniaturization of camera modules, the demand for supplying adhesives to minute areas or narrow gaps has increased more than before. Specifically, the width of the microscopic region or gap to which the adhesive is supplied is several hundreds of micrometers (for example, 300 micrometers). If the resin composition is jet dispensed, the adhesive can be delivered to areas or gaps of small dimensions.

(2) Manufacturing method of electronic components:

Next, embodiments of the electronic component manufacturing method of the present invention will be described. The manufacturing method of the electronic component of the present embodiment is a method of manufacturing the electronic component using the ejection method of the present embodiment described so far. In particular, the electronic component manufacturing method of this embodiment uses the discharging method described so far, so that a very small amount of adhesive for electronic components can be accurately applied to a very small area. For this reason, the electronic component manufacturing method of this embodiment is a very effective manufacturing method that requires adhesion of small electronic components.

(3) Electronic components:

Next, embodiments of the electronic component of the present invention will be described. The electronic component of this embodiment is an electronic component obtained by the electronic component manufacturing method described above. The electronic component of this embodiment realizes good adhesion between electronic members. For this reason, productivity is high and reliability is high.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is in no way limited to these examples. In the following examples, parts and % represent parts by mass and % by mass, unless otherwise specified.

(Examples 1 to 23, Comparative Examples 1 to 2)

[Production of resin composition]

After measuring and blending each component shown in Tables 1 to 4, they were mixed to prepare a resin composition used in the discharging method of Examples and Comparative Examples. Specifically, the resin composition was prepared by mixing each component shown in Tables 1 to 4 with a planetary mixer, dispersing them with a three-roll mill, and forming a paste. Details of each component shown in Tables 1 to 4 are as follows.

[(A) Ingredient: Methacrylate compound]

(A-1): Phenoxyethyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (brand name: light ester PO, methacrylate equivalent weight: 206 g/eq, number of methacryloyl groups in 1 molecule: 1).

(A-2): Bisphenol A·EO 2.6 mol adduct-dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (Product name: Light Ester BP-2EMK, methacrylate equivalent weight: 181 g/eq, methacrylate in 1 molecule) Number of diaries: 2).

(A-3): Neopentyl glycol dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (brand name: Light Ester NP, methacrylate equivalent weight: 120 g/eq, number of methacryloyl groups in 1 molecule: 2).

(A-4): Trimethylolpropane trimethacrylate, manufactured by Shinnakamura Chemical (brand name: NK Ester TMPT, methacrylate equivalent: 112.8 g/eq, number of methacryloyl groups per molecule: 3).

(A-5): Ditrimethylolpropane tetramethacrylate, manufactured by Shinnakamura Chemical (Product name: NK Ester D-TMP, methacrylate equivalent weight: 129.5 g/eq, number of methacryloyl groups in 1 molecule: 4 dog).

(A-6): 2-Hydroxy-1,3-dimethacryloxypropane, manufactured by Shinnakamura Chemical (Product name: NK Ester 701, methacrylate equivalent: 114 g/eq, methacryloyl group in 1 molecule) Number: 2).

[(B) component: radical polymerization initiator]

(B-1): 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, manufactured by Nippon Yushi Co., Ltd. (trade name: Perocta O, thermal radical polymerization initiator).

(B-2): 1-hydroxycyclohexyl-phenylketone, manufactured by IGM Resins B.V. (trade name: OMNIRAD 184, radical photopolymerization initiator).

(B-3): 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, manufactured by IGM Resins B.V. (trade name: OMNIRAD 907, radical photopolymerization initiator).

[(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 Kasei Kogyo Co., Ltd. (brand name: C3TS-G, thiol equivalent weight: 110 g/eq, number of thiol groups per molecule: 4).

(C1-2): Pentaerythritol tetrakis (3-mercaptopropionate), manufactured by SC Yuki Chemical Company (brand name: PEMP-LV, thiol equivalent weight: 122 g/eq, number of thiol groups in 1 molecule: 4) .

(C1-3): 3-(3-Mercapto-propoxy)-2,2-bis-(3-mercapto-propoxymethyl)-propan-1-ol, manufactured by SC Yuki Chemical Co., Ltd. (Product name: Multhiol Y-3, thiol equivalent weight: 124 g/eq, number of thiol groups in 1 molecule: 3).

[(C) component [(C2) component]: acrylate compound]

(C2-1): Polyester acrylate (multifunctional acrylic compound), manufactured by Toagosei Corporation (brand name: M7100, acrylate equivalent weight: 188 g/eq, number of acryloyl groups per molecule: 3 or more).

(C2-2): Dimethylol-tricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (Product name: Light Acrylate DCP-A, acrylate equivalent weight: 152 g/eq, number of acryloyl groups in 1 molecule: 2 dog).

(C2-3): Neopentyl glycol diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. (brand name: Light Acrylate NP-A, acrylate equivalent weight: 106 g/eq, number of acryloyl groups per molecule: 2).

[(D) Component: Anionic polymerization initiator]

(D-1): It is a mixture of a microencapsulated amine-based curing agent and a bisphenol A type and F-type epoxy resin, and 33 mass% of the amine-based curing agent is microencapsulated, manufactured by Asahi Kasei Corporation (brand name: HXA9322HP).

(D-2): Modified alicyclic polyamine, manufactured by T&K TOKA (brand name: FXR-1121).

[(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. (trade name: t-butylcatechol).

[(F) Ingredient: Filler]

(F-1): Globular silica, manufactured by Admatex (brand name: SE5200 SEE).

(F-2): Globular silica, manufactured by Admatex (brand 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 Corporation (Product name: TS-720).

[(G) Ingredient: 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 Denshi Kasei (Product name: Titanium Black 13M).

[(I) Ingredients: Other ingredients]

(I-1): Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. (brand name: KBM403; 3-glycidoxypropyltrimethoxysilane).

In addition, 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 acryloyl groups in component (C1) The total number of thiol groups was determined, and the ratio (1) and ratio (2) of functional groups for each component were determined. Here, the ratio of functional groups (1) 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) /(C2) is the total number of acryloyl groups in the component). The ratio of functional groups (2) 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., {(A ) Total number of methacryloyl groups in component + Total number of acryloyl groups in (C2) component}/Total number of thiol groups in (C1) component). The results of ratio (1) and ratio (2) of functional groups for each component are shown in Tables 1 to 4.

Using a jet dispenser (brand name "Smart Stream" manufactured by ITW EAE), each resin composition of the examples and comparative examples was continuously discharged, and the number of shots that could be continuously discharged was measured. However, in Example 23 and Comparative Example 2, jet dispensability was evaluated using the product 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 a member that collides with the nozzle when discharging the resin composition, is made of a metal member made of tungsten carbide. Meanwhile, in Comparative Example 2, a jet dispenser was used in which the needle, which is a member that collides with the nozzle when discharging the resin composition, is made of ceramic. In addition, as described above, the resin compositions of Examples 1 to 23 and Comparative Examples 1 to 2, which were continuously discharged with a jet dispenser, were evaluated for curability and jet dispensability by the following methods. The results are shown in Tables 1 to 4.

[Evaluation of hardenability]

The resin composition discharged from the jet dispenser was subjected to UV curing or heat curing, and the UV curing depth or intensity during heat curing was measured.

＜UV curing depth＞

On the black resin plate A (width 50 mm Next, the resin composition was applied between the two heat-resistant tapes on the resin plate A to a thickness of 100 μm, which is the same thickness as the heat-resistant tape. Next, on the resin plate A and another resin plate B (width 50 mm was fixed with a clip. The resin composition protruding from the top of resin plates A and B was removed. UV irradiation was performed on the resin composition from the upper part of the jig manufactured in this way. More specifically, UV curing was carried out by UV irradiation at an integrated light amount of 2000 mJ/cm2 using a UV LED irradiation device "AC475 (brand name)" manufactured by Excelitas Technologies. The integrated light amount was measured by connecting the light receiver "UVD-365 (brand name)" to "UIT-250 (brand name)" manufactured by Ushio Denki. Peel off one side of the resin plates A and B placed in between, remove the uncured portion adhering to the cured resin composition, measure the distance of the cured portion from the UV irradiated surface with a microscope, and measure the result as UV curing depth. I did it.

＜Strength during heat curing＞

A 2 mm x 3 mm ceramic chip was placed on each resin composition of the examples and comparative examples that were jet dispensed onto a ceramic substrate. Next, UV curing was carried out by UV irradiation at an accumulated light amount of 2000 mJ/cm 2 using a UV LED irradiation device “AC475 (brand name)” manufactured by Excelitas Technologies. The integrated light amount was measured by connecting the light receiver "UVD-365 (brand name)" to the "UIT-250 (brand name)" manufactured by Ushio Denki. The UV-cured curable resin composition was heat-cured at 80°C for 60 minutes in a blow dryer. Using the universal bond tester "DAGE4000 (brand name)" manufactured by Dage, a load was applied to the ceramic chip, and the shear stress (N) when the ceramic chip peeled was measured. This measurement was performed 10 times for one test piece, and the average value of the 10 measurements was taken as the measured value of the shear strength. The higher the measured shear strength, the better the curability by ultraviolet rays and/or heat.

＜Evaluation criteria＞

The cured product cured as described above was evaluated using the following evaluation criteria. In the following evaluation criteria, the evaluation of "◎" is the best, and the evaluation of "○" and "△" in that order is poor.

◎: UV curing depth of 450 μm or more, or strength during heat curing of 130 N or more.

○: UV curing depth is greater than 350 μm and less than 450 μm, or strength during heat curing is greater than 60 N and less than 130 N.

Δ: UV curing depth is 350 μm or less, or strength during heat curing is 60 N or less.

[Evaluation of jet dispensability]

In the following evaluation criteria, the evaluation of "◎" is the best, and the evaluations of "○", "△", and "×" are poor in that order.

＜Evaluation criteria＞

◎: The number of shots that can be discharged continuously is 100,000 or more.

○: The number of shots that can be discharged continuously is 10,000 or more and less than 100,000.

△: The number of shots that can be discharged continuously is 500 or more and less than 10,000.

×: The number of shots that can be discharged continuously is less than 500, or the sliding portion 61 or the collision portion 62 shown in FIG. 1(b) (i.e., the tip of the needle collides with the nozzle) regardless of the number of shots that can be discharged. When gelation occurs in the collision section (62).

[result]

As shown in Tables 1 to 4, in the discharge methods of Examples 1 to 23, a resin composition containing a methacrylate compound as component (A) is used, and as a jet dispenser, a nozzle is used when discharging the resin composition. The material of the colliding member was made of metal. The ejection methods of Examples 1 to 23 showed good results in both evaluations of curability and jet dispensability. In addition, the discharge methods of Examples 1 to 23 confirmed curability when the content of the radical polymerization initiator as component (B) was 20% by mass or less.

On the other hand, since the ejection method of Comparative Example 1 used a resin composition that did not contain a methacrylate compound as component (A), the number of shots that could be continuously ejected was less than 500 in the evaluation of jet dispensability. It was found that the discharging method of Comparative Example 1, compared to the discharging method of Examples 1 to 23, was more likely to cause curing of the resin composition in the jet dispenser and was not suitable for application by jet dispensing. In addition, in the discharge method of Comparative Example 2, the number of shots that could be continuously discharged was 500 or more, but gelled matter was observed in the sliding portion 61 shown in FIG. 1(b). If a gelled product is present in the sliding portion, workability such as change of order and cleaning is significantly reduced, and productivity is hindered. The discharge method of Comparative Example 2 uses a jet dispenser in which the material of the member that collides with the nozzle when discharging the resin composition is made of ceramic, and therefore, compared to the discharge method of Examples 1 to 23, the heat generated inside the jet dispenser It is difficult to discharge to the outside, and it is presumed that the resin composition has partially hardened inside the jet dispenser.

The method for discharging the resin composition of the present invention can be used to apply a resin composition by jet dispensing, and can be particularly effectively used as a method for applying an adhesive, for example, an adhesive for electronic components. For this reason, the method for discharging the resin composition 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 for the electronic component manufacturing method having an adhesion process using an electronic component adhesive and the electronic component manufactured by the manufacturing method.

20 Resin composition
50 jet dispenser
52 Needle
54 Seal (sealing member)
56 nozzle
58 chamber
61 sliding part
62 collision section
S stroke

Claims (10)

A method of discharging a resin composition using a jet dispenser, discharging the resin composition from a nozzle of the jet dispenser,
In the jet dispenser, a member that collides with the nozzle when discharging the resin composition is made of metal, and
A method for discharging a resin composition, wherein the resin composition contains (A) a methacrylate compound and (B) a radical polymerization initiator. According to claim 1,
A discharge method wherein the resin composition further contains at least one of a polyfunctional thiol compound (C1) and an acrylate compound (C2) as component (C). According to claim 2,
The resin composition contains, as the (C) component, both the (C1) polyfunctional thiol compound and the (C2) acrylate compound, and relative to the total number of thiol groups of the (C1) polyfunctional thiol compound, A discharge method wherein the ratio of the total number of (meth)acryloyl groups of the (A) methacrylate compound and the (C2) acrylate compound is 0.8 to 1.2. According to claim 2,
The resin composition contains only the polyfunctional thiol compound (C1) as the component (C), and the ratio of the methacrylate compound (A) to the total number of thiol groups in the polyfunctional thiol compound (C1) is A discharge method in which the ratio of the cryloyl group is 0.8 to 1.2. The method according to any one of claims 1 to 4,
A discharging method wherein the resin composition further contains (D) an anionic polymerization initiator. The method according to any one of claims 1 to 5,
A discharging method wherein the resin composition further contains (E) a polymerization inhibitor. The method according to any one of claims 1 to 6,
A discharging method wherein the resin composition further contains (F) a filler. The method according to any one of claims 1 to 7,
A discharging method wherein the resin composition further contains (G) a black pigment. A method of manufacturing electronic components using the ejection method of any one of claims 1 to 8. An electronic component obtained by the electronic component manufacturing method of claim 9.

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