JP6973768B2 - Inkjet resin composition, electronic components, manufacturing method of electronic components - Google Patents

Description

The present invention relates to an inkjet resin composition, an electronic component having a cured product of the inkjet resin composition, and a method for manufacturing the electronic component.

For electronic components such as semiconductor packages, for example, semiconductor chips (dies) such as ICs and LSIs are bonded to support members such as substrates, wire bonding is performed from the die to the support members, and then the components are sealed with a molding agent. Manufactured by As an adhesive material (adhesive material for adhering a die and a support member) used at this time, a paste (diatouch paste) using a resin as a main raw material is known. Adhesion between the die and the support member is performed, for example, by the following procedure. First, the die attach paste is applied to the support member, and the die attach paste is temporarily fixed to the support member by irradiating the support member with light having a predetermined wavelength. Then, the die is placed on the temporarily fixed die attach paste (diatouch), and the die attach paste is finally cured by applying heat, and the die and the support member are adhered to each other. Temporary fixing refers to temporarily curing the die attach paste for positioning on which the die is placed. This curing means that the entire die attach paste is cured in order to fix the die to the support member.

In order to efficiently apply the die attach paste to the support member, for example, an inkjet method can be used (see Patent Document 1). In addition, Patent Document 1 describes that a solvent may be contained in order to improve the fluidity of the die attach paste. The solvent is used to adjust the viscosity of the die attach paste, but does not participate in the chemical reaction during curing.

Further, as the die attach paste, there are a conductive paste in which a conductive filler such as silver powder is dispersed and an insulating paste in which an insulating filler such as silica is dispersed. The insulating die attach paste is described in, for example, Patent Document 2. The die attach paste of Patent Document 2 contains a reactive diluent (volatile acrylate). Like the solvent, the reactive diluent is used for adjusting the viscosity of the paste, and by incorporating it into the resin by a chemical reaction during curing, the deterioration of the paste performance can be suppressed to a low level. Further, Patent Document 2 describes that a reactive diluent is used for suppressing bleeding of the die attach paste. Further, Patent Document 2 describes that this reactive diluent takes heat by volatilizing during the main curing, reduces the molecular motion of the die attach paste, and suppresses the progress of bleeding.

Japanese Unexamined Patent Publication No. 2015-185807 Japanese Unexamined Patent Publication No. 2002-285104

Here, since the inkjet method ejects the die attach paste from a thin nozzle (several tens of μm) of the inkjet head, it is desired that the viscosity of the die attach paste is low.

However, when the viscosity of the die attach paste is low, it easily spreads on the support member after coating, and it is difficult to maintain the shape at the time of coating. Therefore, for example, when mounting a plurality of dies on the same support member, it is necessary to keep a distance between the dies, and it is difficult to achieve high integration.

Further, since the die attach paste of Patent Document 1 contains a solvent, voids (bubbles) are likely to be generated due to the influence of heat when the die attach paste is cured.

Further, although the insulating die attach paste described in Patent Document 2 contains a reactive diluent, the viscosity of the paste is high and it is difficult to use it in an inkjet method.

An object of the present invention is an inkjet resin composition that can be coated by an inkjet method, can maintain its shape after coating, and can reduce the generation of voids after curing, and a cured product of the inkjet resin composition. It is an object of the present invention to provide an electronic component having the above, and a method for manufacturing the electronic component.

The main invention for achieving the above object is an inkjet resin composition containing a monoacrylate having a viscosity of less than 3 mPa · s at room temperature and a filler having a maximum particle size of less than 3 μm. Other features of the invention will be clarified by the description herein.

The resin composition for inkjet of the present invention can be applied by an inkjet method, can maintain the shape after application, and can reduce the generation of voids after curing.

== Outline of Disclosure ==
In addition to the above-mentioned main inventions, at least the following matters will be clarified by the description of the present specification.

That is, a resin composition for inkjet (hereinafter, may be referred to as "resin composition") in which the monoacrylate is at least one selected from methoxyethyl acrylate, isobutyl acrylate, cyclohexyl acrylate, and dimethylaminoethyl acrylate. It will be clear. These monoacrylates have a low viscosity at room temperature. Therefore, the resin composition containing these monoacrylates also has a low viscosity and can be applied by an inkjet method. Moreover, since these monoacrylates are highly volatile, they tend to volatilize after coating. Since the viscosity of the resin composition increases due to the volatilization of the monoacrylate, the shape after coating can be maintained.

Further, an inkjet resin composition having an average particle size of the filler of 0.1 μm to 2 μm becomes clear. Such a resin composition can be applied by an inkjet method.

Further, it becomes clear that the resin composition for inkjet has an elastic modulus of less than 4 GPa after curing. By setting the elastic modulus at room temperature after curing to less than 4 GPa, it is possible to relieve the stress generated in electronic components due to the temperature drop even when the temperature drops from the high temperature during solder reflow (for example, 260 ° C) to room temperature. can. Therefore, it is possible to prevent the cured product of the resin composition from peeling off from the die or the support member.

Further, it becomes clear that the inkjet resin composition further contains a thermosetting resin and the proportion of the monoacrylate in the total amount of the inkjet resin composition excluding the filler is 50 to 79% by mass. By setting the ratio of the monoacrylate in this range, the resin composition can be applied by an inkjet method, the shape after application can be maintained, and the generation of voids after curing can be reduced. ..

Further, an electronic component having a cured product of the above-mentioned inkjet resin composition as an adhesive layer and having a thickness of the adhesive layer of 10 μm or more and less than 50 μm becomes clear. By setting the thickness of the adhesive layer within this range, the resin composition can be temporarily fixed to the support member, and voids generated in the adhesive layer can be reduced.

Further, in the coating step of applying the above-mentioned inkjet resin composition to the support member by an inkjet method, the inkjet resin composition coated on the support member is irradiated with light of a predetermined wavelength, and the support member is subjected to the above-mentioned. The inkjet resin composition is subjected to a light irradiation step of temporarily fixing the inkjet resin composition and a heat applied by placing an object to be adhered on the inkjet resin composition temporarily fixed to the support member. A method for manufacturing an electronic component having a thermosetting step of curing and forming an adhesive layer is clarified. In this method, the resin composition can be applied by an inkjet method, and the shape of the resin composition after application can be maintained. In addition, it is possible to reduce the generation of voids in the adhesive layer after the heat curing step.

== Embodiment ==
[Composition of resin composition for inkjet]
The inkjet resin composition according to the present embodiment can be applied to a support member such as a substrate by an inkjet method. The resin composition comprises at least a monoacrylate and a filler. The resin composition according to this embodiment is insulating. The resin composition is used as a die attach paste. The die attach paste is an adhesive for adhering a die such as an IC chip to a support member, for example. Since a general inkjet mechanism can be used in the inkjet method, detailed description thereof will be omitted.

(Monoacrylate)
The monoacrylate according to this embodiment acts as a reactive diluent. The reactive diluent reacts with the thermosetting resin and the radical polymerization initiator described later, and lowers the viscosity of the resin composition for inkjet.

The monoacrylate according to this embodiment has a viscosity at room temperature of less than 3 mPa · s. “Room temperature” is 20 ° C. ± 5 ° C. Examples of the monoacrylate include methoxyethyl acrylate (viscosity at room temperature: 1.5 mPa · s), isobutyl acrylate (viscosity at room temperature: 0.8 mPa · s), cyclohexyl acrylate (viscosity at room temperature: 2.5 mPa · s). s) At least one selected from dimethylaminoethyl acrylate (viscosity at room temperature: 1.3 mPa · s) can be used. When a plurality of reactive diluents are used, it is preferable that the viscosity of the entire reactive diluent is less than 3 mPa · s at room temperature.

When the viscosity of the monoacrylate becomes 3 mPa · s or more, the viscosity of the ink jet resin composition containing the monoacrylate cannot be sufficiently lowered. For example, hydroxyethyl acrylate has a viscosity of 6.0 mPa · s at room temperature. Such a resin composition containing a highly viscous monoacrylate is not suitable for use in an inkjet method. In addition, vinyl ethers also exist as the reactive diluent. However, the resin composition containing vinyl ethers has low reactivity, and voids are likely to be generated at the time of curing.

On the other hand, the resin composition according to the present embodiment has a low viscosity by containing a monoacrylate having a viscosity of less than 3 mPa · s at room temperature. Therefore, the resin composition according to the present embodiment can be applied by an inkjet method. Further, since the monoacrylate according to the present embodiment is highly volatile, it easily volatilizes after coating. Therefore, since the applied resin composition has a high viscosity, it becomes easy to maintain the shape after application.

(Filler)
The filler according to the present embodiment is added in order to secure the elastic modulus at the time of wire bonding at 50 MPa or more. When the elastic modulus of the cured product containing the filler at 200 ° C. is 50 MPa or more, chip shift during wire bonding can be prevented, which is preferable. As the filler, for example, an insulating filler such as silica, alumina, or magnesium oxide is used.

The filler according to this embodiment has a maximum particle size of less than 3 μm. If the maximum particle size exceeds 3 μm, the ejection property of the inkjet is deteriorated or the filler is likely to settle. In the present specification, the maximum particle size is the maximum particle size in the particle size distribution on a volume basis measured by a laser diffraction / scattering method. The maximum particle size can be measured by, for example, a laser scattering diffraction method particle size distribution measuring device: LS13320 (manufactured by Beckman Coulter, wet).

The average particle size of the filler is preferably 0.1 μm to 2 μm. If the average particle size of the filler is smaller than 0.1 μm, the viscosity of the resin composition becomes high and it cannot be used in the inkjet method. Further, when the average particle size of the filler is larger than 2 μm, the filler is settled in the resin composition, and the filler and the resin component are easily separated in the tank accommodating the resin composition or in the inkjet head. Therefore, it is not possible to apply a homogeneous resin composition. In the present specification, the average particle size is the particle size at an integrated value of 50% in the particle size distribution on a volume basis, which is measured by a laser diffraction / scattering method. The average particle size can be measured by, for example, a laser scattering diffraction method particle size distribution measuring device: LS13320 (manufactured by Beckman Coulter, wet).

(Other ingredients)
In addition to monoacrylates and fillers, the resin compositions for inkjet include thermosetting resins, curing agents, curing accelerators, radical polymerization initiators such as photoinitiators and organic peroxides, coupling agents, defoaming agents and the like. Can be added.

As used herein, the thermosetting resin is a resin having two or more functional groups that contribute to thermosetting in one molecule. As the thermosetting resin, di (meth) acrylate and tri (meth) acrylate that react with monoacrylate, and epoxy resin for improving the adhesive strength can be used. Moreover, maleimides and thiols may be added as needed.

Examples of the di (meth) acrylate and tri (meth) acrylate include trimethyl propanthry (meth) acrylate, zinc di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1,4-butane. Didioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonandiol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,10-decanediol di Examples thereof include (meth) acrylate, tetramethylene glycol di (meth) acrylate, glycerindi (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, and pentaerythritol tri (meth) acrylate.

Examples of commercially available di (meth) acrylate products include methacrylic resins manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Ester NP) and acrylate resins manufactured by Shin-Nakamura Chemical Co., Ltd. (product name: A-HD-N). Examples of commercially available tri (meth) acrylate products include acrylate resins manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Acrylate TMP-A) and methacrylate resins manufactured by Shin-Nakamura Chemical Co., Ltd. (product name: TMPT).

Maleimides are compounds containing one or more maleimide groups in one molecule, and can be cured by forming a three-dimensional network structure by reacting the maleimide groups by heating. For example, N, N'-(4,4'-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, 2,2-bis [4- (4-maleimidephenoxy) phenyl. ] Examples include bismaleimide resins such as propane. More preferable maleimides are compounds obtained by the reaction of diamine dimerate with maleic anhydride, and compounds obtained by the reaction of maleimided amino acids such as maleimide acetic acid and maleimide caproic acid with polyols. The maleimided amino acid is obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid, and the polyol is preferably a polyether polyol, a polyester polyol, a polycarbonate polyol, or a poly (meth) acrylate polyol, and has an aromatic ring. Those that do not contain are particularly preferable. Since the maleimide group can react with the allyl group, it is also preferable to use it in combination with the allyl ester resin. As the allyl ester resin, an aliphatic one is preferable, and a compound obtained by transesterification of cyclohexanedialyl ester and an aliphatic polyol is particularly preferable.

Thiols are compounds having one or more sulfanyl groups in one molecule, and can be cured by reacting with an epoxy group or a vinyl group to form a three-dimensional network structure. For example, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, polysulfide polymer can be mentioned. More preferred thiols include 1,4-bis (3-mercaptobutylyloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4, 6 (1H, 3H, 5H)-Trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane ethanetris (3-mercaptobutyrate).

Examples of the epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin, and a polyfunctional tetrakis (hydroxyphenyl) ethane type or tris (hydroxyphenyl) ethane type having a large number of benzene rings. Hydroxyphenyl) methane type epoxy resin, biphenyl type epoxy resin, triphenol methane type epoxy resin, polybutadiene type epoxy resin (epoxidized polybutadiene), naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, aminophenol type epoxy resin, silicone epoxy Examples include resin. Diglycidyl ether of bisphenol A ethylene oxide adduct, polyglycidyl ester such as diglycidyl ether of bisphenol A propylene oxide adduct, reaction product of p-xylylene glycol and 1-chloro-2,3-epoxypropane, etc. are also used. be able to.

Above all, from the viewpoint of reducing the viscosity, the epoxy resin is preferably liquid. Commercially available products include DIC bisphenol A type / bisphenol F type mixed epoxy resin (product name: EXA835LV), momentary performance siloxane resin (product name: TSL9906), and Nippon Steel & Sumitomo Metal Corporation 1,4-cyclohexanedimethanol di. Examples thereof include glycidyl ether (product name: ZX1658GS), ADEKA epoxy resin (product name: EP-4000S), and ADEKA bisphenol A propylene oxide adduct diglycidyl ether (product name: BPA-PO4000S). The epoxy resin may be used alone or in combination of two or more.

As the curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a hydrazide compound, a dicyandiamide, or the like can be used. From the viewpoint of the adhesiveness of the resin composition, a phenolic curing agent is more preferable.

As the phenol resin-based curing agent, a known phenol resin can be used as the curing agent for the epoxy resin. Specific examples thereof include a resol type or novolak type phenol resin, an alkyl resol type, an alkyl novolak type, an aralkyl novolak type phenol resin, a xylene resin, an allyl phenol resin and the like. The OH group equivalent of the phenolic resin-based curing agent is preferably 80 to 250 g / eq, and more preferably 80 to 200 g / eq. In the case of an alkylresole type or an alkylnovolac type phenol resin, an alkyl group having 1 to 18 carbon atoms can be used, and the number of carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl and decyl can be used. 2 to 10 are preferable. Examples of commercially available phenol resin-based curing agents include phenol resin-based curing agents manufactured by Meiwa Kasei Co., Ltd. (product name: MEH8005).

As the acid anhydride-based curing agent, an acid anhydride known as a curing agent for an epoxy resin can be used. Specific examples include phthalic anhydride, maleic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and the like. Examples of commercially available acid anhydride-based curing agents include acid anhydride-based curing agents manufactured by Mitsubishi Chemical Corporation (product name: YH307).

The amine-based curing agent includes imidazoles as well as aliphatic amines and aromatic amines. Of these, imidazoles are also used as a curing accelerator that promotes the reaction between the epoxy resin and the curing agent.

Examples of the aliphatic amine include aliphatic polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, m-xylenediamine and 2-methylpentamethylenediamine, isophoronediamine and 1,3-bisamino. Alicyclic polyamines such as methylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine Examples thereof include piperazine-type polyamines such as. Examples of the aromatic amine include aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), and polytetramethylene oxide-di-p-aminobenzoate. Can be mentioned. Tris (dimethylaminomethyl) phenol, benzyldimethylamine, tertiary amines such as 1,8-diazabicyclo (5,4,0) undensen-7 can also be used.

In addition, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2 Imidazole compounds such as −phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole can also be used.

Furthermore, a modified imidazole-based curing agent can also be used. Specific examples include an epoxy-imidazole adduct compound and an acrylate-imidazole adduct compound. Commercially available epoxy-imidazole adduct-based compounds include Ajinomoto Fine-Techno's curing agent (product name: Amicure PN-23, Amicure PN-40) and Asahi Kasei E-Materials' curing agent (product name: NovaCure HX-). 3721), a curing agent manufactured by Fuji Kasei Kogyo Co., Ltd. (product name: Fujicure FX-1000) and the like can be mentioned. Examples of commercially available acrylate-imidazole adduct-based compounds include a curing agent manufactured by ADEKA (product name: EH2021). The curing agent is not limited to these product names. The curing agent may be used alone or in combination of two or more.

From the viewpoint of storage stability and curability, the curing agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the ink jet resin composition (excluding the solvent).

Examples of the radical polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. As the photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator is preferable, and as a commercially available product, BASF Japan Ltd.'s bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (product name: IRGACURE 819) is used. can give. Organic peroxides are preferred as the thermal polymerization initiator. Commercially available products of the radical polymerization initiator include NOF Corporation's radical polymerization initiator 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (product name: Perocta O) and t-butylper. Oxybenzoate (product name: perbutyl Z), and the like. Commercially available coupling materials include 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. (product name: KBM-403) and 3-methacryloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. (product name: KBM). -503) and the like.

In the inkjet resin composition according to the present embodiment, the ratio of monoacrylate (100 × (monoacrylate) / (resin composition-filler)) in the total amount of the resin composition without the filler is 50 to 79% by mass. Is preferable. If the proportion of monoacrylate is less than 50% by mass, the viscosity at room temperature tends to be high, and if it exceeds 79% by mass, unreacted monoacrylate remains in the resin composition during temporary fixing. On the other hand, the resin composition containing monoacrylate in the range of 50 to 79% by mass can be applied by an inkjet method, can maintain the shape after application, and can reduce the generation of voids after curing. ..

[Manufacturing method of resin composition for inkjet]
The method for producing the resin composition according to the present embodiment is not particularly limited as long as the monoacrylate, the filler, and other additives can be uniformly mixed. The device for dispersing these raw materials is not particularly limited, but a stirring, three-roll mill, a planetary mixer, a bead mill and the like can be used. Further, these devices may be used in combination as appropriate.

[Cursed product]
The inkjet resin composition according to the present embodiment can be temporarily fixed by irradiating it with light having a predetermined wavelength after coating, and then being main-cured by applying heat to obtain a cured product. The specific method of temporary fixing and main curing is not particularly limited. For example, temporary fixing can be performed by applying the resin composition and then irradiating it with light in the ultraviolet band. Inkjet resin compositions may contain UV curable resins such as polyfunctional (meth) acrylate resins, in addition to UV curable monoacrylates. Further, the main curing can be performed by placing a die on the temporarily cured resin composition and applying heat at about 180 ° C.

The elastic modulus of the ink jet resin composition after curing is preferably less than 4 GPa. The monoacrylate according to the present embodiment has a lower glass transition temperature of the cured product than the polyfunctional acrylate. Therefore, even when the temperature drops from the high temperature (for example, 260 ° C.) during solder reflow to room temperature, the stress generated in the electronic component due to the temperature drop can be relieved. Therefore, it is possible to prevent the cured product of the resin composition from peeling off from the die or the support member.

[Electronic components]
Electronic components are semiconductors manufactured by bonding semiconductor chips (dies) such as ICs and LSIs to support members such as substrates, wire bonding from the dies to the support members, and then sealing them with a molding agent. Package etc. Such a semiconductor package can be mounted on a printed circuit board or a motherboard.

A cured product of the resin composition is formed as an adhesive layer between the die and the support member. The thickness (Bondo Line Stickness; BLT) of this adhesive layer is preferably 10 μm or more and less than 50 μm.

[Manufacturing method of electronic parts]
The electronic component according to this embodiment can be manufactured by the following process.

First, in the coating step, the inkjet resin composition is coated on the support member by an inkjet method to a thickness of 10 to 100 μm. If the thickness is less than 10 μm, the resin composition may not be temporarily fixed even if it is irradiated with light having a predetermined wavelength. On the other hand, when the thickness exceeds 100 μm, the monoacrylate in the resin composition is less likely to volatilize after coating, and voids may occur in the adhesive layer. Next, in the light irradiation step, the inkjet resin composition coated on the support member is irradiated with light having a predetermined wavelength, and the inkjet resin composition is temporarily fixed to the support member. Then, in the thermosetting step, the adherend (die) is placed on the inkjet resin composition temporarily fixed to the support member, and heat is applied to mainly cure the inkjet resin composition to form an adhesive layer. Form. After that, electronic components can be obtained by performing wire bonding or sealing with a molding agent, if necessary.

== Example ==
The viscosity, normal temperature elastic modulus, thermal elastic modulus at 200 ° C., and the presence or absence of void generation were measured with respect to the ink jet resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 below.

As the reactive diluent, one of the following was used.
-"2-MTA" (methoxyethyl acrylate. Viscosity at room temperature: 1.5 mP · s. Manufactured by Osaka Organic Chemical Industry Co., Ltd.)
-"AIB" (isobutyl acrylate. Viscosity at room temperature: 0.8 mP · s. Manufactured by Osaka Organic Chemical Industry Co., Ltd.)
-"Light Ester HOA (N)" (2-hydroxyethyl acrylate. Viscosity at room temperature: 6.0 mP · s. Kyoeisha Chemical Co., Ltd.)
-"NBVE" (normal butyl vinyl ether. Viscosity at room temperature: 0.5 mP · s manufactured by Nippon Carbide Industries Co., Ltd.)

As the filler, one of the following was used.
-"Sea Hoster KE-S30" (Silica filler. Average particle size 0.3 μm, maximum particle size less than 0.6 μm. Made by Nippon Shokubai Co., Ltd.)
-"Sea Hoster KE-S100" (Silica filler. Average particle size 1.0 μm, maximum particle size less than 2.0 μm. Made by Nippon Shokubai Co., Ltd.)

The following materials were used as other components. Specifically, as the thermosetting resin, triacrylate "light acrylate TMP-A" (manufactured by Kyoeisha Chemical Co., Ltd.) and epoxy resin "EXA835LV" (manufactured by DIC Corporation) were used. As the curing agent, a phenol resin "MEH8005" (manufactured by Showa Kasei Co., Ltd.) was used. As the curing accelerator, imidazole "Fujicure 7000" (manufactured by T & K TOKA Co., Ltd.) was used. The radical polymerization initiators are "IRGACURE 819" (manufactured by BASF Japan Co., Ltd.) which is a photoinitiator (radical polymerization initiator) and "Perocta O" (Nichiyu Co., Ltd.) which is an organic peroxide (radical polymerization initiator). Made) was used.

(Example 1)
After dispersing 30 parts by mass (vol.%: 16%) of "Seahoster KE-S30" and 29 parts by mass of "thermosetting resin (including curing agent and curing accelerator)" with 3 rolls, "2- 40 parts by mass of "MTA" and 1 part by mass of a radical polymerization initiator (0.5 parts by mass of "IRGACURE 819" and 0.5 parts by mass of "Perocta O") were added and stirred to prepare a resin composition a.

(Example 2) An example in which the amount of monoacrylate was reduced with respect to Example 1 30 parts by mass (vol.%: 16%) of "Seahoster KE-S30", "thermosetting resin (curing agent, curing accelerator) (Including) ”33.9 parts by mass with 3 rolls, then 35 parts by mass of“ 2-MTA ”, 1.2 parts by mass of radical polymerization initiator (“IRGACURE 819” 0.6 parts by mass, and “Per Octa”. O "0.6 parts by mass) was added and stirred to prepare a resin composition b.

(Example 3) An example in which the amount of monoacrylate is increased as compared with Example 1.

After dispersing 30 parts by mass (vol.%: 16%) of "Seahoster KE-S30" and 14.6 parts by mass of "thermosetting resin (including curing agent and curing accelerator)" with three rolls, " Add 55 parts by mass of "2-MTA" and 0.6 parts by mass of the radical polymerization initiator (0.3 parts by mass of "IRGACURE 819" and 0.3 parts by mass of "Perocta O") and stir to obtain the resin composition c. Made.

(Example 4) Example in which the amount of filler is reduced with respect to Example 1 20 parts by mass (vol.%: 10%) of "Seahoster KE-S30", "thermosetting resin (including curing agent and curing accelerator) ) ”29 parts by mass with 3 rolls, then 50 parts by mass of“ 2-MTA ”, 1 part by mass of radical polymerization initiator (“IRGACURE 819” 0.5 part by mass, and “Per Octa O” 0.5 part. By mass) was added and stirred to prepare a resin composition d.

(Example 5) Example of changing the type of monoacrylate "Seahoster KE-S30" 30 parts by mass (vol.%: 16%), "thermosetting resin (including curing agent and curing accelerator)" 29 parts by mass Is dispersed in 3 rolls, 40 parts by mass of "AIB", 1 part by mass of a radical polymerization initiator (0.5 part by mass of "IRGACURE 819", and 0.5 part by mass of "Perocta O") are added and stirred. Then, the resin composition e was prepared.

(Example 6) Example of changing the type of filler 30 parts by mass (vol.%: 16%) of "Seahoster KE-S100" and 29 parts by mass of "thermosetting resin (including curing agent and curing accelerator)" After dispersing in 3 rolls, 40 parts by mass of "2-MTA" and 1 part by mass of a radical polymerization initiator (0.5 parts by mass of "IRGACURE 819" and 0.5 parts by mass of "Perocta O") are added. The mixture was stirred to prepare a resin composition f.

(Comparative Example 1) 57 parts by mass of "2-MTA" without filler, 41.5 parts by mass of "thermosetting resin (including curing agent and curing accelerator)", 1.4 parts by mass of radical polymerization initiator ("IRGACURE") 819 ”0.7 parts by mass and“ Per Octa O ”0.7 parts by mass) were mixed and stirred to prepare a resin composition g.

(Comparative Example 2) Example of changing the type of monoacrylate "Seahoster KE-S30" 30 parts by mass (vol.%: 16%), "heat curable resin (including curing agent and curing accelerator)" 29 parts by mass Is dispersed in 3 rolls, then 40 parts by mass of "light ester HOA (N)", 1 part by mass of a radical polymerization initiator (0.5 parts by mass of "IRGACURE 819", and 0.5 parts by mass of "Perocta O". ) Was added and stirred to prepare a resin composition h.

(Comparative Example 3) Example of changing the type of monoacrylate "Seahoster KE-S30" 30 parts by mass (vol.%: 16%), "thermosetting resin (including curing agent and curing accelerator)" 29 parts by mass Is dispersed in 3 rolls, 40 parts by mass of "NBVE", 1 part by mass of a radical polymerization initiator (0.5 part by mass of "IRGACURE 819", and 0.5 part by mass of "Perocta O") are added and stirred. Then, the resin composition i was prepared.

(Measurement of viscosity)
The viscosity of the produced ink jet resin composition was measured at 25 ° C. and 30 rpm using a cone plate type viscometer TV-22 (cone plate: 1 ° 34'× R24) manufactured by Toki Sangyo Co., Ltd. In Examples and Comparative Examples, the case where the viscosity was 30 mPa · s or less was designated as “◯”, and the case where the viscosity was higher than 30 mPa · s was designated as “x”.

(Measurement of normal temperature elastic modulus and thermal elastic modulus at 200 ° C)
An inkjet resin composition was applied to a container to which a mold release agent was applied and dried so that the film thickness was about 300 μm, and the mixture was cured into a sheet at 175 ° C. × 60 minutes. This was processed into a size of 40 mm × 5 mm and used as a test piece for DMA measurement. Using a viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.), perform DMA measurement under the conditions of tension in measurement mode, temperature rise rate of 3 ° C / min, and measurement frequency of 10 Hz, and obtain elastic modulus at room temperature and 200 ° C. rice field.

In the examples and comparative examples, the case where the normal temperature elastic modulus was less than 4 GPa was designated as “◯”, which means pass. Further, the case where the elastic modulus at heat at 200 ° C. is 50 MPa or more is designated as “◯”, which means “pass”, and the case where the elastic modulus is lower than 50 MPa is designated as “x”, which means reject.

(Presence / absence of voids)
The ink-jet resin composition was dropped onto a slide glass ^{and then irradiated with UV at 300 mW / cm 2} to gelate (thicken to the extent that the shape does not collapse). Then, another slide glass was placed on the gelled composition, and the test piece sandwiched between the two slide glasses was heated from 25 ° C. to 175 ° C. for 30 minutes, held for 1 hour, and cured. The void of the test piece was confirmed.

As shown in Table 1, the results showed that all of the inkjet resin compositions of Examples had low viscosities. On the other hand, when a monoacrylate having a viscosity at room temperature of 6.0 mPa · s was used (Comparative Example 2), it was clarified that the viscosity of the resin composition was high.

Further, as shown in Table 1, it was obtained that the inkjet resin composition of the example was able to maintain a high thermal elastic modulus. On the other hand, it was clarified that when the filler was not used (Comparative Example 1), the elastic modulus at the time was low.

Further, as shown in Table 1, the results showed that the inkjet resin composition of the example did not generate voids after curing. On the other hand, when a non-monoacrylate was used as the reactive diluent (Comparative Example 3), it was clarified that voids were generated after curing.

Although embodiments and examples of the present invention have been described, they are presented as examples and are not intended to limit the scope of the invention. The embodiment can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. The embodiments and variations thereof are included in the scope of the invention described in the claims and the equivalent scope thereof, as are included in the scope and gist of the invention.

Claims (6)

Monoacrylate with a viscosity of less than 3 mPa · s at room temperature,
With a filler with a maximum particle size of less than 3 μm,
Thermosetting resin and
The A including inkjet resin composition,
The proportion of the monoacrylate in the total amount of the inkjet resin composition excluding the filler is 50 to 79% by mass.
A resin composition for inkjet having a viscosity of 30 mPa · s or less. The resin composition for inkjet according to claim 1, wherein the monoacrylate is at least one selected from methoxyethyl acrylate, isobutyl acrylate, cyclohexyl acrylate, and dimethylaminoethyl acrylate. The inkjet resin composition according to claim 1 or 2, wherein the average particle size of the filler is 0.1 μm to 2 μm. The inkjet resin composition according to any one of claims 1 to 3, wherein the elastic modulus after curing is less than 4 GPa. The cured product of the inkjet resin composition according to any one of claims 1 to 4 is provided as an adhesive layer.
An electronic component having an adhesive layer having a thickness of 10 μm or more and less than 50 μm. A coating step of applying the inkjet resin composition according to any one of claims 1 to 4 to a support member by an inkjet method.
A light irradiation step of irradiating the inkjet resin composition coated on the support member with light having a predetermined wavelength and temporarily fixing the inkjet resin composition to the support member.
A thermosetting step of placing an object to be adhered on an inkjet resin composition temporarily fixed to the support member and applying heat to the main curing of the inkjet resin composition to form an adhesive layer.
A method of manufacturing an electronic component having.