TW201827512A - Resin composition for inkjet printing, electronic components, and method for manufacturing electronic component having an acrylic monoester as a main content and reducing the occurrence of voids after being hardened - Google Patents

Abstract

Provided is a resin composition for inkjet printing, which can be applied as a coating by an inkjet printing method, can maintain the shape after being applied, and can reduce the occurrence of voids after being hardened. The resin composition for inkjet printing contains an acrylic monoester having a viscosity at room temperature of less than 3 mPa.s, and a filler material having a maximum particle diameter of less than 3 [mu]m. The method for manufacturing electronic components includes steps of a coating step, an illumination step and a thermal hardening step.

Description

 Resin composition for inkjet, electronic component, and method of manufacturing electronic component  

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

The manufacture of electronic components such as semiconductor packages is carried out by bonding a semiconductor wafer (die) such as an IC or an LSI to a supporting member such as a substrate, and wire bonding the support member from the die. (molding agent) seal. The adhesive material used at this time (adhesive material for bonding the crystal grains to the supporting member) is known as a resin-based die attach paste. The adhesion of the die to the support member is performed by, for example, the following steps. First, the adhesive member is coated on the supporting member, and the adhesive is temporarily fixed to the supporting member by irradiating light of a predetermined wavelength. Thereafter, a crystal grain (adhesive crystal) is mounted on the temporarily fixed adhesive, and the adhesive is completely hardened by heating to adhere the die and the supporting member. Moreover, the temporary fixing is to temporarily cure the adhesive to position the die. The complete hardening is to harden the entire adhesive to fix the crystal grains to the supporting member.

In order to apply the adhesive to the support member in an efficient manner, for example, an inkjet method can be used (see Patent Document 1: JP-A-2015-185807). Further, Patent Document 1 discloses that a solvent may be added in order to improve the fluidity of the adhesive. The solvent is used to adjust the viscosity of the adhesive, but it does not participate in the chemical reaction during hardening.

Further, as the adhesive, there is 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 ceria is dispersed. Examples of the insulating adhesive colloid include those described in Japanese Laid-Open Patent Publication No. 2002-285104. Further, the adhesive of Patent Document 2 contains a reactive diluent (having a volatile acrylate). The reactive diluent is used in the same manner as the solvent to adjust the viscosity of the adhesive, and is combined into the resin by a chemical reaction at the time of curing, thereby suppressing the deterioration of the performance of the adhesive. Further, Patent Document 2 describes that a reactive diluent is used to suppress bleed of the adhesive. Further, Patent Document 2 discloses that the reactive diluent volatilizes when it is completely cured to take away heat, and reduces the molecular motion of the adhesive to suppress the progress of the bleed.

Here, in the ink jet method, the adhesive is discharged from the fine nozzle (tens of μm) of the ink jet head, so that the viscosity of the adhesive is desired to be low.

However, when the viscosity of the adhesive is low, it is easy to expand on the support member after coating, and it is difficult to maintain the shape at the time of coating. Therefore, for example, in the case where a plurality of crystal grains are mounted on the same supporting member, it is necessary to separate the crystal grains from each other, so that it is difficult to achieve high integration.

Further, since the adhesive of Patent Document 1 contains a solvent, voids (air bubbles) are likely to be generated by the influence of heat when the adhesive is hardened.

Further, the insulating adhesive gel described in Patent Document 2 contains a reactive diluent, but the viscosity of the gel is high and it is difficult to use it for an inkjet method.

An object of the present invention is to provide a resin composition for inkjet, an electronic component having a cured product of the inkjet resin composition, and a method for producing an electronic component, which can be applied by an inkjet method. The shape after coating is maintained, and the generation of voids after hardening can be reduced.

In order to achieve the above object, the main invention is a resin composition for inkjet, comprising a viscosity at room temperature of less than 3 mPa. Acrylic monoester of s and a filler material having a maximum particle diameter of less than 3 μm. Other features of the present invention will be apparent from the description of the specification.

The resin composition for inkjet according to the present invention can be applied by an inkjet method, and the shape after coating can be maintained, and the generation of voids after hardening can be reduced.

The above and other objects, features and advantages of the present invention will become more <RTIgt; The record is not only the above-mentioned main invention, but at least the following matters are clear.

That is, in the resin composition for inkjet (hereinafter may be referred to as "composition"), the acrylic monoester is selected from the group consisting of methoxyethyl acrylate, isobutyl acrylate, cyclohexyl acrylate, and acrylic acid. At least one of methylaminoethyl esters. These acrylic monoesters have a low viscosity at normal temperature. Therefore, the resin composition containing the acrylic monoesters has a low viscosity and can be applied by an inkjet method. Further, since these acrylic monoesters have high volatility, they are easily volatilized after coating. Since the viscosity of the resin composition is increased by volatilization of the acrylic monoester, the shape after coating can be maintained.

Moreover, it is clear that the average particle diameter of the filler in the resin composition for inkjet is 0.1 μm to 2 μm. Such a resin composition can be applied by an inkjet method.

Further, it was found that the elastic modulus of the resin composition for inkjet after curing was less than 4 GPa. By making the elastic modulus at room temperature after hardening less than 4 GPa, even if the temperature is lowered to room temperature by the high temperature at the time of reflow (for example, 260 ° C), the stress caused by the temperature drop in the electronic component can be alleviated. Therefore, peeling of the cured product of the resin composition from the crystal grains or the support member can be prevented.

In addition, it is clear that the resin composition for inkjet further contains a thermosetting resin, and the ratio of the acrylic monoester in the total amount of the inkjet resin composition excluding the filler is 50 to 79% by mass. By setting the ratio of the acrylic monoester to this range, it can be applied by an inkjet method, the shape after coating can be maintained, and the generation of voids after hardening can be reduced.

Further, it is clear that the electronic component has a cured product of the inkjet resin composition as an adhesive layer, and the thickness of the adhesive layer is 10 μm or more and less than 50 μm. By setting the thickness of the adhesive layer to this range, the resin composition can be temporarily fixed to the supporting member, and voids generated in the adhesive layer can be reduced.

Further, it is clear that the method of manufacturing an electronic component includes a coating step, an illuminating step, and a thermosetting step of applying the inkjet resin composition to a supporting member by an inkjet method, and the illuminating step is performed The inkjet resin composition applied to the support member is irradiated with light of a predetermined wavelength, and the inkjet resin composition is temporarily fixed to the support member, and the thermal curing step is performed by inkjet for temporarily fixing the support member. An adherend is attached to the resin composition, and the inkjet resin composition is completely cured by heating to form an adhesive layer. By this method, the resin composition can be applied by an inkjet method, and the shape of the resin composition after coating can be maintained. Moreover, voids in the adhesive layer after the thermosetting step can be reduced.

<Examples> (Composition of resin composition for inkjet) The resin composition for inkjet according to the present embodiment can be applied to a supporting member such as a substrate by an inkjet method. The resin composition contains at least an acrylic monoester and a filler. The resin composition of this example is insulative. The resin composition is used as a die bond. The adhesive is used for, for example, an adhesive in which a die such as an IC wafer is adhered to a supporting member. Further, since the ink jet method can be a general ink jet mechanism, detailed description thereof will be omitted.

(Acrylic Monoester) The acrylic monoester of the present embodiment functions as a reactive diluent. The reactive diluent reacts with a thermosetting resin or a radical polymerization initiator described later, and lowers the viscosity of the inkjet resin composition.

The viscosity of the acrylic monoester of this embodiment at room temperature is less than 3 mPa. s. "Room temperature" is 20 °C ± 5 °C. As the acrylic acid monoester, for example, methoxyethyl acrylate (having a viscosity of 1.5 mPa·s at room temperature), isobutyl acrylate (viscosity at room temperature of 0.8 mPa·s), cyclohexyl acrylate (in The viscosity at room temperature is at least one of 2.5 mPa·s) and dimethylaminoethyl acrylate (viscosity at room temperature of 1.3 mPa·s). In the case of using several reactive diluents, the overall viscosity of the reactive diluent is preferably less than 3 mPa at room temperature. s.

The viscosity of the acrylic monoester is at 3mPa. When s or more, the viscosity of the inkjet resin composition containing an acrylic monoester cannot be sufficiently lowered. For example, the viscosity of hydroxyethyl acrylate at room temperature is 6.0 mPa. s. A resin composition containing such a highly viscous acrylic monoester is not suitable for use in an ink jet method. Further, the reactive diluent also has vinyl alcohols. However, the resin composition containing a vinyl alcohol has low reactivity, and it is easy to generate voids at the time of hardening.

On the other hand, the resin composition of the present embodiment has a viscosity of less than 3 mPa by inclusion at room temperature. s acrylic monoester, so the viscosity is reduced. Therefore, the resin composition of the present embodiment can be applied by an inkjet method. Further, since the acrylic monoester of the present embodiment has high volatility, it is easily volatilized after coating. Thereby, the viscosity of the resin composition to be applied is increased, so that the shape after coating can be maintained.

(Filling Material) The filler of the present embodiment is added in order to ensure that the elastic modulus at the time of wire bonding is 50 MPa or more. When the cured product containing the filler has a thermoelastic modulus at 200 ° C of 50 MPa or more, chip shift at the time of wire bonding can be prevented, which is preferable. As the filler, for example, insulation such as cerium oxide, aluminum oxide, or magnesium oxide can be used.

The maximum particle diameter of the filler of this embodiment was less than 3 μm. When the maximum particle diameter exceeds 3 μm, the discharge property of the inkjet is deteriorated, or the filler is likely to settle. In the present specification, the maximum particle diameter is the largest particle size in the particle size distribution based on the volume measurement by laser diffraction or scattering. The maximum particle size is measured by, for example, a laser scattering diffraction particle size analyzer: LS13320 (manufactured by Beckman Coulter, wet type).

Further, the average particle diameter of the filler is preferably from 0.1 μm to 2 μm. When the average particle diameter of the filler is less than 0.1 μm, the viscosity of the resin composition increases, and it cannot be used for the inkjet method. Further, when the average particle diameter of the filler is more than 2 μm, the filler sinks in the resin composition, and the filler and the resin component are easily separated in the groove in which the resin composition is housed or in the ink jet head. Therefore, it is impossible to apply a homogeneous resin composition. In the present specification, the average particle diameter is measured by a laser diffraction or scattering method, and the particle size of 50% is accumulated in the particle size distribution based on the volume. The average particle diameter is measured by, for example, a laser diffraction scattering particle size analyzer: LS13320 (manufactured by Beckman Coulter Co., Ltd., wet type).

(Other components) In the resin composition for inkjet, in addition to the acrylic monoester and the filler, a radical polymerization such as a thermosetting resin, a curing agent, a curing accelerator, a photoinitiator or an organic peroxide may be added. Starting agent, coupling agent, defoaming agent, and the like.

In the present specification, the thermosetting resin is a resin having two or more functional groups which contribute to thermosetting in one molecule. As the thermosetting resin, di(meth)acrylate or tri(meth)acrylate which is reacted with an acrylic monoester may be used, or an epoxy resin may be used in order to improve the adhesion strength. Further, maleimide or thiol may be added as necessary.

Examples of the di(meth)acrylate or the tri(meth)acrylate include trimethylolpropane tri(meth)acrylate, zinc di(meth)acrylate, and ethylene glycol di(meth)acrylate. Propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(methyl) Acrylate, 1,3-butanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, butanediol di(meth)acrylate, glycerol II (Meth) acrylate, trimethylolpropane di(meth) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, and the like.

A commercially available product of the di(meth)acrylate may, for example, be a methacrylic resin (product name: LIGHT ESTER NP) manufactured by Kyoeisha Chemical Co., Ltd., or an acrylate resin manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (product name: A-HD- N) and so on. A commercially available product of tris (meth) acrylate may, for example, be an acrylate resin (product name: LIGHT ACRYLATE TMP-A) manufactured by Kyoei Kogyo Co., Ltd., or a methacrylate resin manufactured by Shin-Nakamura Chemical Co., Ltd. (product name: TMPT) )Wait.

A maleic imine is a compound containing more than one maleimine group in one molecule, and can be hardened by heating to react a maleimine group to form a three-dimensional network structure. For example, N,N'-(4,4'-diphenylmethane) bismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2 , a double-maleimide resin such as 2-bis[4-(4-maleimidophenoxy)phenyl]propane. Preferred maleimides are compounds obtained by reacting dimer acid diamine with maleic anhydride; maleic imidized amino acids such as maleic imine acetate, maleimide caproic acid and the like A compound obtained by the reaction of a polyol. The maleated aminated amino acid is obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid, and the polyhydric alcohol is preferably a polyether polyol, a polyester polyol, a polycarbonate polyol, or a poly(polyhydric alcohol). A methyl acrylate polyol, more preferably an aromatic ring. The maleimine group can be reacted with an allyl group, so that an allyl ester resin can also be used in combination. The allyl ester resin is preferably aliphatic, and particularly preferably a compound obtained by transesterification of a cyclohexane diallyl ester with an aliphatic polyol.

A thiol is a compound containing one or more mercapto groups in one molecule, and can be hardened 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 ginseng (3- Mercaptopropionate, ginseng-[(3-mercaptopropyloxy)-ethyl]-isocyanate, polysulfide polymer. Preferred thiols are 1,4-bis(3-mercaptobutyloxy)butane, 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-triazine-2 4,6(1H,3H,5H)-trione, trimethylolpropane ginseng (3-mercaptobutyrate), trimethylolethane ginate (3-mercaptobutyrate).

The epoxy resin may, for example, be a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenolic (Novolac type) epoxy resin, an alicyclic epoxy resin, or a polyfunctional type having a plurality of benzene rings. (Hydroxyphenyl)ethane type or ginseng (hydroxyphenyl)methane type epoxy resin, biphenyl type epoxy resin, trisphenol methane type epoxy resin, polybutadiene type epoxy resin (epoxidized polybutylene) Alkene type, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, aminophenol type epoxy resin, oxime epoxy resin, and the like. It is also possible to use a diglycidyl ether of a bisphenol A ethylene oxide adduct, a polyepoxypropyl ether such as a diglycidyl ether of a bisphenol A propylene oxide adduct, and p-xylylene. a reaction product of a diol and 1-chloro-2,3-epoxypropane, and the like.

Among them, from the viewpoint of low viscosity, the epoxy resin is preferably liquid. Commercially available products include DIC bisphenol A type/bisphenol F type epoxy resin (product name: EXA835LV), Momentive Performance oxirane type epoxy resin (product name: TSL9906), and Nippon Steel & Sumitomo Chemical Co., Ltd. , 4-cyclohexanedimethanol diepoxypropyl ether (product name: ZX1658GS), ADEKA epoxy resin (product name: EP-4000S), ADEKA bisphenol A propylene oxide adduct diethylene oxide propyl Ether (BPA-PO4000S) and the like. The epoxy resins may be used singly 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, an anthraquinone compound, dicyandiamide or the like can be used. From the viewpoint of the adhesiveness of the resin composition, a phenol-based curing agent is preferred.

As the phenol resin-based curing agent, a phenol resin which is conventionally used as a curing agent for an epoxy resin can be used. Specific examples thereof include a Resole type or a Novolac type phenol resin; an alkyl Resole type, an alkyl Novolac type, an aralkyl Novolac type phenol resin; a xylene resin, an allyl phenol resin, and the like. The phenol resin-based curing agent preferably has an OH group equivalent of from 80 to 250 g/eq, more preferably from 80 to 200 g/eq. In the case of an alkyl Resole type or an alkyl Novolac type phenol resin, an alkyl group may be used in an amount of from 1 to 18, preferably an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a fluorene group. The base carbon number is 2~10. A commercially available product of a phenol resin-based curing agent is, for example, a phenol resin-based curing agent (product name: MEH8005) manufactured by Minghe Chemical Co., Ltd.

As the acid anhydride-based curing agent, an acid anhydride which is conventionally used as a curing agent for an epoxy resin can be used. Specific examples thereof include phthalic anhydride, maleic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, tetrahydroxy phthalic anhydride, and hexahydroxy neighbor Phthalic anhydride and the like. The commercially available product of the acid anhydride-based curing agent is, for example, an acid anhydride-based curing agent (product name: YH307) manufactured by Mitsubishi Chemical Corporation.

The amine-based curing agent contains an aliphatic amine, an aromatic amine, and an imidazole. Among them, imidazoles also act as hardening accelerators for promoting the reaction of epoxy resins with hardeners.

The aliphatic amine may, for example, be diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylhexamethylenediamine, m-xylylenediamine or 2-methylpentamethylenediamine. Alicyclic polyamine; isophorone diamine, 1,3-diaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornene diamine, 1,2-diamine An alicyclic polyamine such as cyclohexane; a piperazine-type polyamine such as N-aminoethylpiperazine or 1,4-bis(2-amino-2-methylpropyl)piperazine; and the like. The aromatic amine may, for example, be diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylphosphonium, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), poly An aromatic polyamine such as tetramethylene-di-p-aminobenzoate is oxidized. A tertiary amine such as dimethylaminomethyl phenol, benzyldimethylamine or 1,8-diazabicyclo(5,4,0)undecane-7 can also be used.

Further, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, An imidazole compound such as 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole or 2-phenyl-4,5-dihydroxymethylimidazole.

Further, a modified imidazole-based hardener can also be used. Specific examples thereof include an epoxy-imidazole adduct compound or an acrylate-imidazole adduct compound. The commercially available product of the epoxy-imidazole adduct-based compound may, for example, be a hardener (product name: Amicure PN-23, Amicure PN-40) manufactured by Ajinomoto Fine-Techno Co., Ltd., or a hardener made by Asahi Kasei E-materials Co., Ltd. ( Product name: Novacure HX-3721), a curing agent made by Fuji Chemical Industry Co., Ltd. (product name: Fujicure FX-1000). Further, as a commercial product of the acrylate-imidazole adduct-based compound, for example, a curing agent (product name: EH2021) manufactured by ADEKA Co., Ltd., or the like can be mentioned. Hardeners are not limited to these product names. The hardeners may be used singly or in combination of two or more.

The curing agent is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition for inkjet (excluding solvent) from the viewpoint of storage stability and hardenability.

The radical polymerization initiator may, for example, be a photopolymerization initiator or a thermal polymerization initiator. The photopolymerization initiator is preferably a fluorenylphosphine oxide-based photopolymerization initiator, and a commercial product such as bis(2,4,6-trimethylbenzylidene)-phenyl oxide produced by BASF Japan Co., Ltd. Phosphine (product name: IRGACURE 819). The thermal polymerization initiator is preferably an organic peroxide. The commercially available product of the radical polymerization initiator may, for example, be a radical polymerization initiator, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (product name) manufactured by Nippon Oil Co., Ltd. : PEROCTA O), tert-butyl peroxybenzoate (product name: PERBUTYL Z). The commercially available product of the coupling material is, for example, 3-glycidoxypropyltrimethoxydecane (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd., and 3-methacryl oxime manufactured by Shin-Etsu Chemical Co., Ltd. Oxypropyl trimethoxy decane (product name: KBM-503) and the like.

In the resin composition for inkjet according to the present embodiment, the ratio of the acrylic monoester (100 × (acrylic monoester) / (resin composition - filler)) is preferably 50 in the total amount of the resin composition excluding the filler. ~79% by mass. When the ratio of the acrylic monoester is less than 50% by mass, the viscosity at room temperature is likely to increase. When it exceeds 79% by mass, the unreacted acrylic monoester remains in the resin composition when temporarily fixed. On the other hand, the resin composition containing 50 to 79% by mass can be applied by an inkjet method, and the shape after coating can be maintained, and the generation of voids after hardening can be reduced.

(Manufacturing Method of Resin Composition for Inkjet) The method for producing the resin composition for inkjet according to the present embodiment is not particularly limited as long as it can uniformly mix the acrylic monoester, the filler, and other additives. The apparatus for dispersing the raw materials is not particularly limited, and a stirrer, a three-roll mill, a planetary mixer, a bead mill, or the like can be used. Moreover, these apparatuses can also be combined and used suitably.

(Cured Product) The resin composition for inkjet according to the present embodiment is temporarily fixed by irradiation with light of a predetermined wavelength after application, and then completely cured by heating to form a cured product. The specific method of temporarily fixing or completely hardening is not particularly limited. For example, after the resin composition is applied, temporary fixation can be performed by irradiating light of an ultraviolet band. In addition to the ultraviolet curable acrylic monoester, the resin composition for inkjet may contain an ultraviolet curable resin such as a polyfunctional (meth)acrylate resin. Further, it is possible to perform complete hardening by attaching crystal grains to the resin composition after temporary hardening and applying heat of about 180 °C.

The elastic modulus of the resin composition for inkjet after curing is preferably less than 4 GPa. The acrylic monoester of the present embodiment has a lower glass transition temperature of the cured product than the polyfunctional acrylate. Therefore, even when the temperature is lowered to room temperature by the high temperature (for example, 260 ° C) at the time of reflow, the stress caused by the temperature drop in the electronic component can be alleviated. Therefore, peeling of the cured product of the resin composition from the crystal grains or the support member can be prevented.

(Electronic component) The electronic component is a semiconductor package manufactured by bonding a semiconductor wafer (die) such as an IC or an LSI to a support member such as a substrate, and bonding the support member from the die, and then sealing it with a sealant. Such a semiconductor package can be mounted on a printed circuit board or a motherboard.

A cured product of a resin composition is formed as an adhesive layer between the crystal grains and the supporting member. The bond line thickness (BLT) is preferably 10 μm or more and less than 50 μm.

(Method of Manufacturing Electronic Component) The electronic component of the present embodiment can be manufactured by the following steps.

First, in the coating step, the resin composition for inkjet is applied onto a support member by a thickness of 10 to 100 μm by an inkjet method. When the thickness is less than 10 μm, even if light of a predetermined wavelength is irradiated, the resin composition may not be temporarily fixed. On the other hand, when the thickness exceeds 100 μm, the acrylic monoester in the resin composition is difficult to volatilize after coating, and voids may occur in the adhesive layer. Then, in the illuminating step, the ink composition for inkjet coating applied to the supporting member is irradiated with light of a predetermined wavelength to temporarily fix the resin composition for inkjet in the supporting member. Thereafter, in the thermal curing step, an adherend (grain) is attached to the inkjet resin composition temporarily fixed to the supporting member, and the inkjet resin composition is completely cured by heating to form an adhesive layer. Thereafter, wire bonding is performed as needed or sealed with a sealant to obtain an electronic component.

<Examples> With respect to the resin compositions for inkjet obtained in the following Examples 1 to 6 and Comparative Examples 1 to 3, the viscosity, the normal temperature elastic modulus, the thermoelastic modulus at 200 ° C, and the presence or absence of voids were measured.

The reactive diluent is any of the following.

‧ "2-MTA" (methoxyethyl acrylate. Viscosity at room temperature: 1.5 mP.s. Osaka Organic Chemical Industry Co., Ltd.)

‧ "AIB" (isobutyl acrylate. Viscosity at room temperature: 0.8mP.s. Osaka Organic Chemical Industry Co., Ltd.)

‧"LIGHT ESTER HOA(N)" (2-hydroxyethyl acrylate. Viscosity at room temperature: 6.0 mP.s. Co., Ltd.)

‧"NBVE" (n-butyl vinyl ether. Viscosity at room temperature: 0.5mP.s. manufactured by Japan Carbide Industrial Co., Ltd.)

The filling material is any of the following.

‧ "SEAHOSTAR KE-S30" (cerium oxide filling material. The average particle size is 0.3 μm, and the maximum particle size is less than 0.6 μm. manufactured by Nippon Shokubai Co., Ltd.)

‧ "SEAHOSTAR KE-S100" (cerium oxide filling material. The average particle size is 1.0 μm, and the maximum particle size is less than 2.0 μm. manufactured by Nippon Shokubai Co., Ltd.)

The other ingredients used are the following materials. Specifically, the thermosetting resin is a triacrylate "LIGHT ACRYLATE TMP-A" (manufactured by Kyoeisha Chemical Co., Ltd.) and an epoxy resin "EXA835LV" (manufactured by DIC Corporation). A phenol resin "MEH8005" (made by Showa Chemical Co., Ltd.) was used for the hardener. For the hardening accelerator, "Igly-based "Fujicure 7000" (manufactured by T&K TOKA Co., Ltd.) is used as a radical polymerization initiator (IRGACURE 819) using a photoinitiator (radical polymerization initiator) (BASF Japan Co., Ltd.) And "PEROCTA O" (manufactured by Nippon Oil Co., Ltd.) of an organic peroxide (radical polymerization initiator).

(Example 1) 30 parts by mass of "SEAHOSTAR KE-S30" (vol.%: 16%) and "thermosetting resin (including curing agent, curing accelerator)" were dispersed in a three-roll mill. 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") were added and stirred to prepare a resin composition a.

(Example 2) An example of reducing the amount of the acrylic monoester relative to Example 1. 30 parts by mass (vol.%: 16%) of "SEAHOSTAR KE-S30" and 33.9 parts by mass of "thermosetting resin (including curing agent and curing accelerator)" were dispersed in a three-roll mill, and then "2-MTA" was added. 35 parts by mass and 1.2 parts by mass of a radical polymerization initiator ("IRGACURE 819" 0.6 parts by mass and "PEROCTA O" 0.6 parts by mass) were stirred to prepare a resin composition b.

(Example 3) An example in which the amount of the acrylic monoester was increased with respect to Example 1. 30 parts by mass (vol.%: 16%) of "SEAHOSTAR KE-S30" and 14.6 parts by mass of "thermosetting resin (including curing agent and curing accelerator)" were dispersed in a three-roll mill, and then "2-MTA" was added. 55 parts by mass of 0.6 parts by mass of a radical polymerization initiator ("0.3 parts by mass of IRGACURE 819" and 0.3 parts by mass of "PEROCTA O") were stirred to prepare a resin composition c.

(Example 4) An example of reducing the amount of the filler material with respect to Example 1. 20 parts by mass of "SEAHOSTAR KE-S30" (vol.%: 10%) and "thermosetting resin (including curing agent, curing accelerator)" were dispersed in a three-roll mill, and then "2-MTA" was added. 50 parts by mass of a radical polymerization initiator 1 part by mass ("IRGACURE 819" 0.5 parts by mass and "PEROCTA O" 0.5 parts by mass) was stirred to prepare a resin composition d.

(Example 5) An example of changing the kind of the acrylic monoester. 30 parts by mass of "SEAHOSTAR KE-S30" (vol.%: 16%) and "thermosetting resin (including curing agent, curing accelerator)" were dispersed in a three-roll mill, and then "AIB" 40 was added. 1 part by mass of the radical polymerization initiator (0.5 parts by mass of "IRGACURE 819" and 0.5 part by mass of "PEROCTA O") was stirred to prepare a resin composition e.

(Example 6) An example of changing the kind of the filling material. 30 parts by mass of "SEAHOSTAR KE-S100" (vol.%: 16%) and "thermosetting resin (including curing agent, curing accelerator)" were dispersed in a three-roll mill, and then "2-MTA" was added. 40 parts by mass of a radical polymerization initiator 1 part by mass ("IRGACURE 819" 0.5 parts by mass and "PEROCTA O" 0.5 parts by mass) was stirred to prepare a resin composition f.

(Comparative Example 1) No filler material. 57 parts by mass of "2-MTA", 41.5 parts by mass of "thermosetting resin (including curing agent and curing accelerator)", and 1.4 parts by mass of radical polymerization initiator ("IRGACURE 819" 0.7 parts by mass and "PEROCTA O" 0.7 parts by mass) was mixed and stirred to prepare a resin composition g.

(Comparative Example 2) An example of changing the kind of the acrylic monoester. 30 parts by mass of "SEAHOSTAR KE-S30" (vol.%: 16%) and "thermosetting resin (including curing agent, curing accelerator)" were dispersed in a three-roll mill, and then "LIGHT ESTER HOA" was added. (N) "40 parts by mass of a radical polymerization initiator 1 part by mass ("IRGACURE 819" 0.5 parts by mass and "PEROCTA O" 0.5 parts by mass) was stirred to prepare a resin composition h.

(Comparative Example 3) An example of changing the kind of the acrylic monoester. 30 parts by mass of "SEAHOSTAR KE-S30" (vol.%: 16%) and "thermosetting resin (including curing agent, curing accelerator)" were dispersed in a three-roll mill, and then "NBVE" 40 was added. 1 part by mass of the radical polymerization initiator (0.5 parts by mass of "IRGACURE 819" and 0.5 part by mass of "PEROCTA O") was stirred to prepare a resin composition i.

(measuring viscosity)

The viscosity of the produced resin composition for inkjet was measured at 25 ° C and 30 rpm using a cone-and-plate viscometer TV-22 (cone plate: 1° 34' × R24) manufactured by Toki Sangyo Co., Ltd. In the examples and comparative examples, the viscosity is 30 mPa. The following cases are marked as "○". Viscosity is higher than 30mPa. The case of s is written as "X".

(Measurement of room temperature elastic modulus and thermoelastic modulus at 200 ° C) In a container coated with a release agent and dried, the inkjet resin composition was applied and the film thickness was about 300 μm at 175 ° C. Hardened into flakes under 60 minutes. This was processed into a size of 40 mm × 5 mm to prepare a test piece for DMA measurement. Using a viscoelasticity measuring apparatus (DMS6100, manufactured by Seiko Instruments Co., Ltd.), DMA measurement was carried out under the conditions of a tensile measurement mode, a temperature increase rate of 3 ° C/min, and a measurement frequency of 10 Hz, and the elastic modulus at room temperature and 200 ° C was determined.

In the examples and the comparative examples, the case where the room temperature elastic modulus was less than 4 GPa was indicated as "○" indicating that it was acceptable. In the case where the thermoelastic modulus at 200 ° C is 50 MPa or more, "○" indicates that it is acceptable, and when the modulus of elasticity is less than 50 MPa, "X" indicates that it is unacceptable.

(The presence or absence of voids) After the inkjet resin composition was dropped onto a glass slide, it was subjected to UV irradiation at 300 mW/cm ² to be gelled (to the extent that the shape did not collapse). Thereafter, another glass slide was placed on the gelled composition, and the test piece sandwiched between the two slides was heated from 25 ° C to 175 ° C for 30 minutes, and the temperature was maintained for 1 hour to confirm the hardening. The hollow of the test piece.

As shown in the first table, the resin composition for inkjet of any of the examples was obtained as a result of low viscosity. On the other hand, it is clearly known that the viscosity at room temperature is 6.0 mPa. In the case of the acrylic monoester of s (Comparative Example 2), the viscosity of the resin composition was increased.

Further, as shown in the first table, the resin composition for inkjet of the examples was obtained as a result of maintaining a high thermoelastic modulus. On the other hand, it is clear that when the filler is not used (Comparative Example 1), the thermoelastic modulus is lowered.

Further, as shown in the first table, the resin composition for inkjet according to the example was obtained as a result of no voiding after curing. On the other hand, in the case where a reactive diluent other than the acrylic monoester was used (Comparative Example 3), voids were formed after hardening.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

Claims (7)

 A resin composition for inkjet comprising: a viscosity at room temperature of less than 3 mPa. Acrylic monoester of s; and a filler material having a maximum particle diameter of less than 3 μm.    The resin composition for inkjet according to claim 1, wherein the acrylic monoester is selected from the group consisting of methoxyethyl acrylate, isobutyl acrylate, cyclohexyl, and dimethylaminoethyl. At least one of acrylates.    The resin composition for inkjet according to the first or second aspect of the invention, wherein the filler has an average particle diameter of 0.1 μm to 2 μm.    The resin composition for inkjet according to any one of claims 1 to 3, wherein the elastic modulus after curing is less than 4 GPa.    The resin composition for inkjet according to any one of claims 1 to 4, further comprising a thermosetting resin, and the acrylic resin is the total amount of the inkjet resin composition excluding the filler. The ratio of the monoester is 50 to 79% by mass.    An electronic component having a cured product of the inkjet resin composition according to any one of claims 1 to 5, wherein the adhesive layer has a thickness of 10 μm or more and less than 50 μm.    A method of producing an electronic component, comprising: a coating step of applying a resin composition for inkjet according to any one of claims 1 to 5 to a support member by an inkjet method; a step of irradiating light of a predetermined wavelength with respect to the inkjet resin composition applied to the support member, temporarily fixing the inkjet resin composition to the support member, and a thermal curing step temporarily fixing the resin composition The adherend is attached to the resin composition for inkjet of the supporting member, and the inkjet resin composition is completely cured by heating to form an adhesive layer.