Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• the present invention relates to an insulating resin composition, a cured product thereof, and an electronic component containing the cured product.
• Printed electronics in which conductive or insulating resin compositions are printed directly onto an object based on digital data to form circuits, batteries, various sensors, or insulating patterns, is a field that has been attracting attention in recent years.
• Inkjet printing is one of the printing technologies that has long been used as a representative printing technology for printed electronics.
• Piezo inkjet printing is a technology that applies pressure to ink inside a tiny nozzle with a diameter of about 20 to 50 ⁇ m to eject droplets.
• the droplets ejected from the inkjet head are 10 to 100 ⁇ m in diameter, meaning that the minimum achievable line width is 30 ⁇ m or more, limiting the line width. Also, because the printing gap between the nozzle surface and the object to be printed is narrow, this method is suitable for printing on two-dimensional flat surfaces, but presents challenges when used to print on three-dimensional curved surfaces.
• Aerosol jet printing technology is a technology in which aerosol generated is sprayed from a fine nozzle with gas (see, for example, Patent Document 1).
• minute droplets with a diameter of 10 ⁇ m or less are created, transferred to a spray section (nozzle) by gas, and spraying from the nozzle toward a substrate is digitally controlled on and off, making it possible to form fine patterns, for example with a minimum line width of 10 ⁇ m.
• the distance between the substrate and nozzle during printing is wide, and printing can be performed even with a printing gap of about 5 mm, making it possible to print on substrates with unevenness of about several mm and three-dimensional curved surfaces.
• Patent Document 2 discloses an inkjet insulating resin composition that can be applied by the inkjet method, can maintain its shape after application, and can reduce the occurrence of voids after curing.
• the inkjet insulating resin composition contains a monoacrylate with a viscosity of less than 3 mPa ⁇ s at room temperature and a filler with a maximum particle size of less than 3 ⁇ m.
• the objective of the present invention is to provide an insulating resin composition suitable for aerosol jet printing technology.
• a first embodiment of the present invention is the following insulating resin composition.
• (1) (A) inorganic particles having an average particle size (D50) of 0.02 to 0.5 ⁇ m; (B) a polyfunctional thermosetting compound; and (C) a curing agent; The viscosity measured using an E-type viscometer at 25°C and 50 rpm is 400 mPa ⁇ s or less.
• (2) The insulating resin composition according to the above (1), wherein the inorganic particles (A) are surface-treated with a (meth)acrylic surface treatment agent.
• (3) The insulating resin composition according to (1) or (2) above, wherein the polyfunctional thermosetting compound (B) includes a bifunctional thermosetting compound.
• the insulating resin composition according to any one of (1) to (6) above which is substantially free of particles having a particle diameter of more than 1.0 ⁇ m.
• a second embodiment of the present invention is (10) a cured product obtained by curing the insulating resin composition according to any one of (1) to (9) above.
• a third embodiment of the present invention is (11) an electronic component comprising the cured product described in (10) above.
• the embodiments of the present invention also include the following aspects of the printing method and use.
• (12) An aerosol jet printing method comprising a step of aerosol jet printing the insulating resin composition according to any one of (1) to (9) above onto a substrate.
• An inkjet printing method comprising a step of inkjet printing the insulating resin composition according to any one of (1) to (9) above onto a substrate.
• an insulating resin composition suitable for aerosol jet printing technology can be obtained.
• the insulating resin composition of the first embodiment is also suitable for inkjet printing technology.
• a cured product of the insulating resin composition applied by aerosol jet printing or inkjet printing can be obtained.
• an electronic component including such a cured product can be obtained.
• resin which normally refers to a polymer (especially a synthetic polymer), may be used to refer to the components that make up a curable resin composition before curing, even if the component is not a polymer, for example, a prepolymer compound before curing.
• the insulating resin composition according to the first embodiment of the present invention comprises: (A) inorganic particles having an average particle diameter (D50) of 0.02 to 0.5 ⁇ m; (B) a multifunctional thermosetting compound; and (C) a curing agent; The viscosity is 400 mPa ⁇ s or less as measured using an E-type viscometer at 25° C. and 50 rpm. According to this embodiment, an insulating resin composition suitable for aerosol jet printing technology can be obtained.
• the insulating composition of this embodiment contains (A) inorganic particles having an average particle size (D50) of 0.02 to 0.5 ⁇ m (hereinafter also referred to as "(A) inorganic particles” or “component (A)”).
• Component (A) acts as a filler, and can maintain an appropriate elastic modulus of the cured product obtained by curing the resin composition, and can also reduce the linear expansion coefficient of the cured product.
• inorganic particles include, but are not limited to, insulating inorganic particles such as silica, alumina, and magnesium oxide. In this embodiment, the inorganic particles are preferably silica particles.
• the average particle size (D50) refers to the particle size (D50) at 50% of the cumulative total of all inorganic particles, and can be determined from the results of particle size distribution measurement performed using the Microtrack method (laser diffraction scattering method).
• the inorganic particles (A) are surface-treated with a (meth)acrylic surface treatment agent.
• a (meth)acrylic surface treatment agent In the aerosol jet printing technology, minute droplets (aerosol) with a diameter of 1 to 5 ⁇ m are generated and sent to the nozzle via gas, so the particle diameter of the inorganic particles is required to be smaller than that of the minute droplets.
• the particle diameter of the inorganic particles is made small, the viscosity of the resin composition increases, causing problems such as the inability to aerosolize or eject from the nozzle.
• the viscosity of the resin composition measured at 25°C and 50 rpm using an E-type viscometer can be reduced to 400 mPa ⁇ s or less, even if the particle diameter of the inorganic particles is small.
• the surface treatment agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds with the inorganic material, and the other is a functional group that chemically bonds with the organic material.
• surface treatment agents include, but are not limited to, silane-based surface treatment agents, aluminum-based surface treatment agents, and titanium-based surface treatment agents, depending on the type of functional group that chemically bonds with the inorganic material.
• silane-based surface treatment agents aluminum-based surface treatment agents
• titanium-based surface treatment agents depending on the type of functional group that chemically bonds with the inorganic material.
• the (meth)acrylic surface treatment agent has an acryloyl group or a methacryloyl group as a functional group that chemically bonds with an organic material.
• methacryl-silane surface treatment agents include, but are not limited to, 3-methacryloxypropyltrimethoxysilane (e.g., a commercially available product, KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxysilane (e.g., a commercially available product, KBM502, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldiethoxysilane (e.g., a commercially available product, KBE502, manufactured by Shin-Etsu Chemical Co., Ltd.), and 3-methacryloxypropyltriethoxysilane (e.g., a commercially available product, KBE503, manufactured by Shin-Etsu Chemical Co., Ltd.).
• any one of the (meth)acrylic surface treatment agents may be used, or two or more of them may be used in combination.
• the average particle size (D50) of the (A) inorganic particles is 0.02 to 0.5 ⁇ m, preferably 0.03 to 0.4 ⁇ m, and more preferably 0.04 to 0.3 ⁇ m, from the viewpoint of wettability and dispersibility in resin.
• the content of the (A) inorganic particles is preferably 10 to 60 parts by mass, and more preferably 15 to 50 parts by mass, per 100 parts by mass of the resin composition, from the viewpoint of adjusting the viscosity of the resin composition and suppressing the cure shrinkage of the cured product.
• the insulating resin composition of this embodiment preferably does not substantially contain particles having a particle diameter of more than 1.0 ⁇ m.
• Particles having a particle diameter of more than 1.0 ⁇ m refer to inorganic particles such as silica, or organic particles made of resin such as fluororesin or acrylic resin, and have a particle diameter of more than 1.0 ⁇ m. This can prevent nozzle clogging when the resin composition is applied by an aerosol jet printing method.
• the insulating resin composition of the present embodiment includes (B) a multifunctional thermosetting compound (hereinafter also referred to as "component (B)").
• the (B) multifunctional thermosetting compound includes a heat- and light-curable compound.
• the (B) multifunctional thermosetting compound has two or more functional groups, and thus the resin composition can be cured by crosslinking the component (B) with the (C) curing agent described below through heat treatment, or by radical polymerization reaction of the component (B) through heat treatment and/or UV treatment, thereby imparting adhesive strength.
• the multifunctional thermosetting compound examples include, but are not limited to, a multifunctional (meth)acrylate compound having two or more (meth)acryloyloxy groups, a multifunctional epoxy compound having two or more epoxy groups, a multifunctional maleimide compound having two or more maleimide groups, and a multifunctional allyl ester compound having two or more allyl ester groups.
• the multifunctional thermosetting compound is preferably a multifunctional (meth)acrylate compound, a multifunctional epoxy compound, or a combination thereof.
• the polyfunctional (meth)acrylate compound can be cured by heat treatment and/or UV treatment.
• polyfunctional (meth)acrylate compounds include, but are not limited to, trimethylolpropane tri(meth)acrylate, 3-methyl-1.5 pentanediol di(meth)acrylate, glycidyl (meth)acrylate, 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(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, penta
• Multifunctional epoxy compounds can be cured by heat treatment.
• multifunctional epoxy compounds include, but are not limited to, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, alicyclic epoxy compounds, tetrakis(hydroxyphenyl)ethane type or tris(hydroxyphenyl)methane type epoxy compounds which are multifunctional with many benzene rings, biphenyl type epoxy compounds, triphenolmethane type epoxy compounds, polybutadiene type epoxy compounds (epoxidized polybutadiene), naphthalene type epoxy compounds, dicyclopentadiene type epoxy compounds, aminophenol type epoxy compounds, silicone epoxy compounds, etc.
• Polyglycidyl esters such as diglycidyl ether of bisphenol A ethylene oxide adduct, diglycidyl ether of bisphenol A propylene oxide adduct, reaction products of p-xylylene glycol and 1-chloro-2,3-epoxypropane, etc. can also be used as multifunctional epoxy compounds.
• the polyfunctional maleimide compound can be cured by heat treatment and/or UV treatment.
• polyfunctional maleimide compounds include, but are not limited to, bismaleimide compounds such as N,N'-(4,4'-diphenylmethane)bismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.
• Other examples of polyfunctional maleimide compounds include compounds obtained by reacting dimer acid diamine with maleic anhydride, and compounds obtained by reacting maleimide amino acids such as maleimide acetic acid and maleimide caproic acid with polyols.
• Maleimide amino acids are obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid, and the polyols are preferably polyether polyols, polyester polyols, polycarbonate polyols, and poly(meth)acrylate polyols, and those that do not contain aromatic rings are particularly preferred. Since the maleimide group can react with the allyl group, it is also preferable to use it in combination with a polyfunctional allyl ester compound.
• the polyfunctional allyl ester compound is preferably an aliphatic one, and among them, a compound obtained by transesterification of a cyclohexane diallyl ester with an aliphatic polyol is more preferable.
• the (B) polyfunctional thermosetting compound contains a bifunctional thermosetting compound. In one aspect, from the viewpoint of increasing the elastic modulus of the cured product, it is preferable that the (B) polyfunctional thermosetting compound contains a trifunctional or higher functional thermosetting compound. In one aspect, it is preferable that the (B) polyfunctional thermosetting compound contains a combination of a bifunctional thermosetting compound and a trifunctional or higher functional thermosetting compound.
• the multifunctional thermosetting compound is preferably liquid at 25°C.
• the content of the (B) polyfunctional thermosetting compound is preferably 20 to 80 parts by mass, more preferably 20 to 75 parts by mass, and more preferably 30 to 70 parts by mass, per 100 parts by mass of the resin composition, from the viewpoint of appropriately increasing the elastic modulus of the cured product.
• the insulating resin composition of this embodiment includes a curing agent (C) (hereinafter also referred to as "component (C)").
• component (C) hereinafter also referred to as "component (C)”
• the curing agent (C) includes a curing agent for crosslinking reaction (C1) and a curing agent for radical polymerization reaction (C2).
• the curing agent for crosslinking reaction (C1) a phenol-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a modified imidazole-based curing agent, a hydrazide compound, a dicyandiamide, a thiol-based curing agent, etc. can be used, but is not limited to these. From the viewpoint of adhesion of the resin composition, a phenol-based curing agent is more preferable.
• the curing agent for crosslinking reaction (C1) also includes a so-called curing accelerator that acts catalytically to promote crosslinking.
• the curing agent for the radical polymerization reaction includes a photoradical polymerization initiator and a thermal radical polymerization initiator.
• the curing agent can be appropriately selected depending on the type of component (B).
• component (B) contains a polyfunctional thermosetting compound such as a polyfunctional epoxy compound
• the resin composition of the present embodiment preferably contains (C1) a curing agent for crosslinking reaction.
• phenol-based hardener a phenol resin known as a hardener for epoxy resins can be used.
• specific examples of the phenol-based hardener include, but are not limited to, resol or novolac type phenol resins, alkyl resol type phenol resins, alkyl novolac type phenol resins, aralkyl novolac type phenol resins, xylene resins, and allyl phenol resins.
• the OH group equivalent of the phenol-based hardener is preferably 80 to 250 g/eq, and more preferably 80 to 200 g/eq.
• the alkyl group may have 1 to 18 carbon atoms, and preferably has 2 to 10 carbon atoms, such as ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl.
• phenol-based hardeners include, but are not limited to, Meiwa Kasei Co., Ltd.'s phenol resin hardener (product name: MEH8005).
• an acid anhydride known as a curing agent for epoxy resins can be used as the acid anhydride curing agent.
• acid anhydride curing agents include, but are not limited to, phthalic anhydride, maleic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
• Commercially available acid anhydride curing agents include, but are not limited to, an acid anhydride curing agent manufactured by Mitsubishi Chemical Corporation (product name: YH307).
• the amine-based curing agent includes imidazoles as well as aliphatic amines and aromatic amines. Among these, imidazoles are also used as curing accelerators that accelerate the reaction between the epoxy compound and the curing agent.
• aliphatic amines include, but are not limited to, aliphatic polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, m-xylenediamine, and 2-methylpentamethylenediamine; alicyclic polyamines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane; and piperazine-type polyamines such as N-aminoethylpiperazine and 1,4-bis(2-amino-2-methylpropyl)piperazine.
• aromatic amines include, but are not limited to, aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate, tris(dimethylaminomethyl)phenol, benzyldimethylamine, and 1,8-diazabicyclo(5,4,0)undensene-7.
• aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate, tris(dimethylaminomethyl)phenol, benzyldimethylamine, and 1,
• imidazoles include imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole, but are not limited to these.
• imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole, but are not limited to these.
• modified imidazole-based curing agents include epoxy-imidazole adduct compounds and acrylate-imidazole adduct compounds.
• epoxy-imidazole adduct compounds include, but are not limited to, curing agents manufactured by Ajinomoto Fine-Techno Co., Ltd. (product names: Amicure PN-23, Amicure PN-40), curing agents manufactured by Asahi Kasei E-Materials Corporation (product name: Novacure HX-3721), and curing agents manufactured by T&K Toka Corporation (product name: Fujicure FX-1000).
• acrylate-imidazole adduct compounds include, but are not limited to, curing agents manufactured by ADEKA Corporation (product name: EH2021).
• thiol-based curing agents include, but are not limited to, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, polysulfide polymer, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), etc.
• Thiol-based curing agents can also react with polyfunctional (meth)acrylate
• the hardener may be used alone or in combination of two or more.
• the amount of the hardener (C1) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the resin composition (excluding the solvent).
• component (B) contains a polyfunctional thermosetting compound such as a polyfunctional (meth)acrylate compound or a polyfunctional maleimide compound
• the resin composition of the present embodiment preferably contains (C2) a curing agent for radical polymerization reaction.
• the resin composition of this embodiment may contain a photoradical polymerization initiator.
• a photoradical polymerization initiator By containing a photoradical polymerization initiator, UV curing is promoted. This makes it possible to temporarily fix the resin composition by UV curing, for example.
• photoradical polymerization initiators include alkylphenone compounds and acylphosphine oxide compounds.
• alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (e.g., commercially available as Omnirad 651 from IGM Resins B.V.); ⁇ -aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (e.g., commercially available as Omnirad 907 from IGM Resins B.V.); 1-hydroxy-cyclohexyl-phenyl-ketone (e.g., commercially available as IGM Resins B.V.)
• the ⁇ -hydroxyalkylphenone include, but are not limited to, ⁇ -hydroxyalkylphenones such as Omnirad 184 manufactured by IGM Resins B.V.; 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (for example, commercially available product
• acylphosphine oxide compounds include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (e.g., a commercially available product, Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (e.g., a commercially available product, Omnirad 819, manufactured by IGM Resins B.V.), etc.
• 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide e.g., a commercially available product, Omnirad TPO H, manufactured by IGM Resins B.V.
• bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide e.g., a commercially available product, Omnirad 819, manufactured by IGM Resins B.V.
• photoradical polymerization initiator any one of them may be used, or two or more of them may be used in combination.
• the content of the photoradical polymerization initiator is preferably 0.01 to 5 mass%, more preferably 0.1 to 3 mass%, based on the total mass of the resin composition, from the viewpoint of the curing speed and pot life of the resin composition.
• the resin composition of this embodiment may contain a thermal radical polymerization initiator.
• a thermal radical polymerization initiator By including a thermal radical polymerization initiator in the resin composition, it becomes possible to cure the resin composition by heating for a short period of time.
• the thermal radical polymerization initiator There are no particular limitations on the thermal radical polymerization initiator that can be used, and known materials can be used.
• thermal radical polymerization initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, or 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)cyclohexane, and 2,2-bis(t-butylperoxy)cyclohexane.
• dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, or 2,5-di
• peroxyketals such as n-butyl 4,4-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, or ethyl 3,3-(t-butylperoxy)butyrate; and alkyl peroxyesters such as t-butylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, or t-butylperoxybenzoate, but are not limited to these.
• the thermal radical polymerization initiator any one of them may be used, or two or more of them may be used in combination.
• the content of the thermal radical polymerization initiator is preferably 0.01 to 5 mass%, more preferably 0.1 to 3 mass%, based on the total mass of the resin composition.
• the hardener may be used alone or in combination of two or more.
• the resin composition of this embodiment preferably contains (D) a monofunctional reactive diluent (hereinafter also referred to as "component (D)").
• component (D) a monofunctional reactive diluent
• the viscosity of the resin composition can be reduced.
• monofunctional reactive diluents include monofunctional (meth)acrylate compounds, monofunctional maleimide compounds, monofunctional epoxy compounds, etc.
• the (D) monofunctional reactive diluent is preferably a monofunctional (meth)acrylate compound.
• the (D) monofunctional reactive diluent preferably contains a monofunctional reactive diluent having a rigid structure such as an isobornyl structure or a dicyclopentadienyl structure.
• Examples of monofunctional (meth)acrylate compounds include ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate,
• monofunctional reactive diluents having an isobornyl structure such as isobornyl (meth)acrylate
• monofunctional reactive diluents having a dicyclopentadienyl structure such as dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate are preferred. These may be used alone or in combination of two or more.
• monofunctional maleimide compounds include, but are not limited to, maleimides; aliphatic hydrocarbon group-containing maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; aromatic ring-containing maleimides such as phenylmaleimide; and the like. These may be used alone or in combination of two or more.
• monofunctional epoxy compounds include aromatic monofunctional epoxy compounds such as phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, and N-glycidylphthalimide; and aliphatic monofunctional epoxy compounds such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, ⁇ -pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)
• the monofunctional reactive diluent may be used alone or in combination of two or more.
• the content of (D) the monofunctional reactive diluent is preferably 40 to 80 parts by mass, and more preferably 45 to 70 parts by mass, per 100 parts by mass of the total amount of (B) the polyfunctional thermosetting compound, (C) the curing agent, and (D) the monofunctional reactive diluent.
• the resin composition of the present embodiment may contain, if desired, other additives, such as carbon black, titanium black, a silane coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, or a solvent, as necessary, within a range that does not impair the properties of the resin composition of the present embodiment.
• additives such as carbon black, titanium black, a silane coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, or a solvent, as necessary, within a range that does not impair the properties of the resin composition of the present embodiment.
• the type and amount of each additive are as usual.
• the method for producing the resin composition of this embodiment is not particularly limited.
• the resin composition of this embodiment can be obtained, for example, by introducing components (A) to (C), and optionally components (D) and (E) and other additives, into an appropriate mixer either simultaneously or separately, and mixing and stirring while melting by heating if necessary to form a homogeneous composition.
• This mixer is not particularly limited, but a Raikai mixer, Henschel mixer, triple roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirrer and heater can be used. These devices may also be used in appropriate combination.
• the resin composition obtained in this manner is thermosetting and can be cured, for example, by heat treatment at 130 to 200°C for 30 to 180 minutes.
• component (B) contains a polyfunctional (meth)acrylate compound or a polyfunctional maleimide compound
• the resin composition is photocurable and thermosetting.
• it after application of the resin composition, it can be temporarily fixed by applying light of a specific wavelength, and then can be fully cured by applying heat to form a cured product.
• the specific methods for temporary fixing and fully curing are not particularly limited.
• the light to be irradiated is, for example, ultraviolet (UV) light.
• the resin composition may be only photocured.
• the viscosity of the resin composition measured using an E-type viscometer at 25°C and 50 rpm is 400 mPa ⁇ s or less, preferably 350 mPa ⁇ s or less, and more preferably 300 mPa ⁇ s or less.
• the resin composition of this embodiment is suitable for aerosol jet printing because it contains inorganic particles with a small particle size but has a low viscosity.
• the lower limit of the viscosity of the resin composition measured using an E-type viscometer at 25°C and 50 rpm is, for example, 50 mPa ⁇ s or more, preferably 100 mPa ⁇ s or more, and more preferably 200 mPa ⁇ s or more, from the viewpoint of suppressing curing shrinkage.
• the viscosity of the resin composition measured using an E-type viscometer at 25°C and 50 rpm is preferably 50 to 400 Pa ⁇ s, more preferably 100 to 350 Pa ⁇ s, and more preferably 200 to 300 Pa ⁇ s.
• the application method of the resin composition of the present embodiment is not particularly limited, and can be supplied to a desired portion of a substrate or the like by a known printing method, dispensing method, or coating method.
• printing or dispensing methods include, but are not limited to, aerosol jet printing, inkjet printing (jet dispensing printing), screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, flexographic printing, and air dispenser.
• coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, and spin coater coating.
• the method for applying the resin composition of the present embodiment is preferably aerosol jet printing or inkjet printing, more preferably aerosol jet printing. Use of the insulating resin composition of the present embodiment in aerosol jet printing or inkjet printing is also one embodiment of the present invention.
• the cured product of the second embodiment of the present invention is a cured product obtained by curing the insulating resin composition of the above-mentioned first embodiment.
• the cured product of this embodiment preferably has a modulus of elasticity of 1.0 to 9.0 GPa, more preferably 3.5 to 8.0 GPa, and even more preferably 4.0 to 7.0 GPa.
• the modulus of elasticity of the cured product can be adjusted by adjusting the types and amounts of the components of the resin composition. For example, when each component contains a rigid structure such as biphenyl, naphthalene, dicyclopentadiene, cresol novolac, isobornyl, or dicyclopentadienyl, the modulus of elasticity tends to be large. In addition, for example, the modulus of elasticity tends to be large by increasing the crosslink density by including a polyfunctional thermosetting compound having three or more functionalities.
• the cured product of this embodiment preferably has a glass transition temperature (Tg) of 60°C or higher, more preferably 70°C or higher, and even more preferably 80°C or higher.
• the Tg of the cured product can be adjusted by adjusting the type and amount of the components of the resin composition. For example, when each component contains a rigid structure such as biphenyl, naphthalene, dicyclopentadiene, cresol novolac, isobornyl, or dicyclopentadienyl, the Tg tends to be high. In addition, the Tg tends to be high by increasing the crosslink density by including a polyfunctional thermosetting compound with three or more functionalities.
• the upper limit of the Tg of the cured product is not particularly limited, but is preferably 260°C or lower.
• the electronic component of the third embodiment of the present invention includes the cured product of the second embodiment.
• the electronic component is, for example, a semiconductor package manufactured by adhering a semiconductor chip (die) such as an IC or LSI to a support member such as a substrate, bonding the die to the support member, and then sealing with a molding agent.
• a semiconductor package can be mounted on a printed circuit board or a motherboard.
• FIG. 1 Another embodiment of the present invention is an aerosol jet printing method comprising a step of aerosol jet printing the insulating resin composition of the above-mentioned first embodiment onto a substrate.
• aerosol jet printing technology minute droplets with a diameter of 10 ⁇ m or less are created, transferred to a spraying section (nozzle) by gas, and spraying from the nozzle toward a substrate is digitally controlled to form fine patterns, for example with a minimum line width of 10 ⁇ m.
• this aerosol jet printing technology allows for a wide substrate-nozzle distance during printing, and printing can be performed even with a printing gap of about 5 mm, making it possible to print on substrates with unevenness of several mm or on three-dimensional curved surfaces.
• the printed material is, for example, a component constituting an electronic component, such as, but not limited to, a semiconductor element, a substrate, etc.
• the material of the component may be any of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, metals (e.g., copper, nickel), etc.
• Yet another embodiment of the present invention comprises: This is a method for producing a cured product, comprising: a step of aerosol jet printing the insulating resin composition of the first embodiment described above onto a substrate; and a step of curing the aerosol jet printed insulating resin composition.
• Another embodiment of the present invention is an inkjet printing method comprising a step of inkjet printing the insulating resin composition of the above-mentioned first embodiment onto a substrate.
• the printed material is, for example, a component constituting an electronic component, such as, but not limited to, a semiconductor element, a substrate, etc.
• the material of the component may be any of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, metals (e.g., copper, nickel), etc.
• Yet another embodiment of the present invention comprises: The method for producing a cured product includes: a step of inkjet printing the insulating resin composition of the first embodiment described above onto a substrate; and a step of curing the inkjet-printed insulating resin composition.
• A Inorganic particles having an average particle size (D50) of 0.02 to 0.5 ⁇ m
• A-1 (meth)acrylic surface-treated silica filler 1 (product name: YC100-SM1, manufactured by Admatechs Co., Ltd., average particle size (D50): 0.1 ⁇ m
• surface treatment agent 3-methacryloxypropyltrimethoxysilane
• A-2) (meth)acrylic surface-treated silica filler 2 (product name: YA050C-SM1, manufactured by Admatechs Co., Ltd., average particle size (D50): 0.05 ⁇ m
• surface treatment agent 3-methacryloxypropyltrimethoxysilane
• A' Inorganic particles other than component (A)
• A'-1) (meth)acrylic surface-treated silica filler 3 (product name: SE2200-SME, manufactured by Admatechs Co., Ltd., average particle size (D50): greater than 1 ⁇ m
• surface treatment agent 3-
• B Multifunctional thermosetting compound
• B-1 Trifunctional (meth)acrylate compound (chemical name: trimethylolpropane triacrylate, product name: Light Acrylate TMP-A, manufactured by Kyoeisha Chemical Co., Ltd., viscosity: 80 to 120 mPa ⁇ s, Cas. No.: 15625-89-5)
• B-2) Bifunctional (meth)acrylate compound 1 (chemical name: 3-methyl-1.5 pentanediol diacrylate, product name: Light Acrylate MPD-A, manufactured by Kyoeisha Chemical Co., Ltd., viscosity: 8 mPa ⁇ s, Cas.
• B-3) Bifunctional (meth)acrylate compound 2 (chemical name: 1,9-nonanediol diacrylate, product name: Light Acrylate 1.9ND-A, manufactured by Kyoeisha Chemical Co., Ltd., viscosity: 10 mPa ⁇ s, Cas. No.: 107481-28-7)
• B-4) Trifunctional epoxy compound (chemical name: N,N-diglycidyl-4-(glycidyloxy)aniline, product name: jER-630, manufactured by Mitsubishi Chemical Corporation, viscosity: 5000 to 10000 mPa ⁇ s, Cas.
• B-5 Bifunctional epoxy compound 1 (polyoxyalkylene bisphenol A diglycidyl ether, product name: EP4000S, manufactured by ADEKA Corporation, viscosity: 1800 mPa ⁇ s, Cas. No.: 36484-54-5)
• B-6 Bifunctional epoxy compound 2 (tetramethylbiphenyl epoxy compound, product name: YX4000H, manufactured by Mitsubishi Chemical Corporation, solid (room temperature), Cas.
• B-7) Bifunctional epoxy compound 3 (polypropylene glycol type epoxy compound, product name: PG207GS, manufactured by Nippon Steel Chemical & Material Co., Ltd., viscosity: 20 to 70 mPa ⁇ s, Cas. No.: 9072-62-2)
• C Curing agent
• C-1 Phenol-based curing agent (product name: MEH8005, manufactured by Meiwa Kasei Co., Ltd., viscosity: 4500 to 7500 mPa ⁇ s, Cas. No.: 27924-97-6 or 9003-35-4)
• C-2) Imidazole-based curing agent (chemical name: 4-methyl-2-phenylimidazole, product name: 2P 4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., Cas.
• C-3) 1-hydroxy-cyclohexyl-phenyl-ketone (photoradical polymerization initiator, product name: Omnirad 184, manufactured by IGM Resins B.V., solid (room temperature), Cas. No.: 947-19-3)
• C-4) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (photoradical polymerization initiator, product name: Omnirad TPO H, manufactured by IGM Resins B.V., solid (room temperature), Cas.
• C-5) 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (thermal radical polymerization initiator, product name: Perocta O, manufactured by NOF Corporation, liquid (room temperature), Cas. No.: 22288-43-3)
• D Monofunctional reactive diluent
• D-1 Isobornyl acrylate (product name: IBXA, manufactured by Kyoeisha Chemical Co., Ltd., viscosity: 5 to 10 mPa ⁇ s, Cas. No.: 5888-33-5)
• D-2) Dicyclopentanyl acrylate (product name: FA513AS, manufactured by Showa Denko Materials Co., Ltd., viscosity: 7 to 17 mPa ⁇ s, Cas. No.: 79637-74-4)
• the properties of the resin composition and the cured product obtained by curing the resin composition were measured as follows.
• the elastic modulus of the cured product is preferably in the range of 1.0 to 9.0 GPa, more preferably 3.5 to 8.0 GPa, and even more preferably 4.0 to 7.0 GPa.
• the Tg of the cured product is preferably in the range of 60°C or higher, more preferably 70°C or higher, and even more preferably 80°C or higher. There is no particular limitation on the upper limit, but it is preferably 260°C or lower.
• the specific gravity of the resin composition at 25°C was measured using a 10cc pycnometer made of polytetrafluoroethylene (PTFE) (liquid specific gravity). Two glass plates coated with a release agent and dried were prepared. The resin composition was coated on one of the plates, and a gap was set so that the film thickness was about 300 ⁇ m, and then the plate was sandwiched between another glass plate. One side was irradiated with 500 mJ/ cm2 UV light (wavelength 365 nm) using an LED-type UV irradiation device (manufactured by Excelitas, Omnicure:AC475).
• PTFE polytetrafluoroethylene
• the plate was turned over and irradiated with 500 mJ/ cm2 UV light (wavelength 365 nm) on the other side. Then, the plate was cured under heating conditions of 175°C and 60 minutes. After measuring the weight (a, unit: g) of the cured film, the cured film was placed in pure water and thoroughly degassed. The weight (b, unit: g) of the degassed cured film was measured, and the specific gravity was calculated using formula (1) (cured product specific gravity). The shrinkage of the cured product was calculated using formula (3). The results are shown in Table 1.
• Comparative Example 3 which had a higher viscosity than the resin composition of the present invention, ejection by aerosol jet printing was not possible.
• Comparative Example 4 the viscosity of the resin composition was too high to be measured using an E-type viscometer at 25° C. and 50 rpm, and the resin composition could not be ejected by either aerosol jet printing or inkjet printing.

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• 2023
  • 2023-10-25 JP JP2024560025A patent/JPWO2024111333A1/ja active Pending
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