WO2019189458A1 - Catalyseur de durcissement latent pour résine époxy et composition de résine époxy l'utilisant - Google Patents

Catalyseur de durcissement latent pour résine époxy et composition de résine époxy l'utilisant Download PDF

Info

Publication number
WO2019189458A1
WO2019189458A1 PCT/JP2019/013355 JP2019013355W WO2019189458A1 WO 2019189458 A1 WO2019189458 A1 WO 2019189458A1 JP 2019013355 W JP2019013355 W JP 2019013355W WO 2019189458 A1 WO2019189458 A1 WO 2019189458A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl
epoxy resin
monomer
curing catalyst
vinyl monomer
Prior art date
Application number
PCT/JP2019/013355
Other languages
English (en)
Japanese (ja)
Inventor
一浩 宮内
克司 菅
Original Assignee
ナガセケムテックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ナガセケムテックス株式会社 filed Critical ナガセケムテックス株式会社
Priority to JP2020509249A priority Critical patent/JP7191936B2/ja
Publication of WO2019189458A1 publication Critical patent/WO2019189458A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a latent curing catalyst used by blending with an epoxy resin, and an epoxy resin composition comprising the same.
  • the epoxy resin is a compound having two or more highly reactive epoxy groups in the molecule, and is a curable resin that forms a crosslinked network by the reaction of the epoxy group.
  • Epoxy resin usually contains a curing agent such as acid anhydride or polyamine and a curing catalyst (also called curing accelerator) such as phosphine, tertiary amine or imidazole to form an epoxy resin composition, which is then heated. Curing proceeds with.
  • a curing agent such as acid anhydride or polyamine
  • a curing catalyst also called curing accelerator
  • phosphine phosphine
  • tertiary amine tertiary amine or imidazole
  • the epoxy resin composition since a curing catalyst easily starts curing when it comes into contact with an epoxy resin, it is widely practiced to store the epoxy resin composition as a two-pack type composition in which the main agent and the auxiliary agent are separated.
  • the two-pack type it is necessary to measure the required amounts of the main agent and the auxiliary agent immediately before use, and then mix both agents, which is complicated in work.
  • the composition is a one-pack type while avoiding complexity, it is necessary to suppress the progress of the curing reaction by storing it in a frozen or refrigerated state, which is disadvantageous in terms of cost.
  • JP-A-8-73566 JP 2012-136650 A Japanese Unexamined Patent Publication No. 2016-35056 Japanese Unexamined Patent Publication No. 2016-35057 JP 2016-153475 A
  • the encapsulated curing catalyst can be stored in a mixed state.
  • the commercially available encapsulated curing catalyst is a coarse particle having a particle size of about 50 ⁇ m, and has a very narrow gap between bumps / bumps, chips / chips, chips / substrates, etc.
  • the penetration into such a gap is poor and it is not suitable for use.
  • FO-WLP fan-out wafer level package
  • a rewiring layer is formed not only on the lower surface of the semiconductor chip but also on the lower surface of the sealing material projecting out from there, and bumps (I / O terminals) are formed. It is a structure to arrange. In order to form a thin rewiring layer, the smoothness of the lower surface of the chip and the lower surface of the sealing material, which are the coating surfaces, is important.
  • the particle size of the encapsulated curing catalyst is simply reduced, the miscibility with the epoxy resin may deteriorate, or the storage stability, which is the original purpose, may be reduced. Further, when the storage stability of the encapsulated curing catalyst is increased, the reactivity with the epoxy resin may be lowered, that is, there is a problem that good curability of the epoxy resin composition cannot be achieved.
  • the encapsulated curing catalyst is excellent in miscibility with the epoxy resin, but does not proceed with the curing reaction at a temperature lower than the predetermined curing temperature, and exhibits high storage stability, while being heated to the predetermined curing temperature. It is required that the curing reaction proceeds rapidly.
  • the present invention is an epoxy resin having a small particle size, excellent miscibility with an epoxy resin, high storage stability in a composition with the epoxy resin, and excellent curability in view of the above-mentioned present situation. It is an object of the present invention to provide a latent curing catalyst and an epoxy resin composition containing the same.
  • the first aspect of the present invention is a polymer comprising a monomer component containing a core containing a phosphorus curing catalyst and a vinyl polymer, a first vinyl monomer and a first crosslinkable vinyl monomer, or a first polymer.
  • the particle size is 0.01 to 50 ⁇ m, and the weight ratio of the second crosslinkable vinyl monomer in the second vinyl resin is greater than the weight ratio of the first crosslinkable vinyl monomer in the first vinyl resin. It is related with the latent curing catalyst for epoxy resins.
  • the first crosslinkable vinyl monomer and the second crosslinkable vinyl monomer have a (meth) acryl group.
  • the vinyl polymer contained in the core is a vinyl polymer having a crosslinked structure.
  • the weight ratio of the second crosslinkable vinyl monomer in the second vinyl resin is 50 to 100% by weight.
  • the amount of the second vinyl resin relative to 100 parts by weight of the first vinyl resin is 5 to 50 parts by weight.
  • a second aspect of the present invention is a method for producing a latent curing catalyst for an epoxy resin, in which a monomer component containing a vinyl monomer is polymerized by emulsion polymerization in the presence of a phosphorus curing catalyst to form a core.
  • a step of polymerizing a second crosslinkable vinyl monomer to form an outer shell layer covering the inner shell layer is performed in the presence of a monomer-soluble radical polymerization initiator.
  • the third invention relates to an epoxy resin composition containing an epoxy resin and the latent curing catalyst for epoxy resin according to the first invention.
  • the fourth aspect of the present invention is a cured product obtained by curing the epoxy resin composition according to the third aspect of the present invention.
  • the size of the convex part or the concave part on the surface of the cured product is 10 ⁇ m or less.
  • the fifth aspect of the present invention relates to a semiconductor device including the cured product according to the fourth aspect of the present invention as a sealing material.
  • the semiconductor device may have a gap of 100 ⁇ m or less, and the sealing material may enter the gap.
  • a rewiring layer may be formed on the surface of the sealing material.
  • the latent curing for epoxy resins has a small particle size, excellent miscibility with the epoxy resin, high storage stability in the composition with the epoxy resin, and excellent curability.
  • Catalyst, an epoxy resin composition containing the curing catalyst, an epoxy resin composition having extremely good penetration into the sandwiched gap and excellent fluidity, and surface smoothness obtained by heating the epoxy resin composition A cured product having excellent properties can be provided.
  • the epoxy resin composition of the present invention is a liquid composition
  • the viscosity immediately after preparation of the composition is low, and the viscosity hardly increases even after a lapse of time from preparation
  • the epoxy resin of the present invention When the composition is in the form of a solid sheet, the melt viscosity immediately after preparation of the composition is low, and the melt viscosity does not easily increase even after a lapse of time from preparation.
  • the melt viscosity immediately after preparation of the composition is low, and the melt viscosity does not easily increase even after a lapse of time from preparation.
  • an inorganic filler or the like there is an advantage that fluidity is good and penetration into a very narrow gap is good.
  • the latent curing catalyst for epoxy resin according to the present invention is in the form of particles having a layer structure consisting of at least three layers: a core, an inner shell layer covering the core, and an outer shell layer covering the inner shell layer. It is.
  • the core contains a phosphorus-based curing catalyst, thereby functioning as a curing catalyst for the epoxy resin.
  • the outer shell layer and the inner shell layer may be directly laminated, and it is not necessary to arrange a curing catalyst between both layers as in Patent Document 2.
  • the resin contained in the core, the inner shell layer, and the outer shell layer are all vinyl. Since the curing temperature of a general epoxy resin exceeds the glass transition temperature (Tg) of the vinyl resin, the vinyl resin is changed to a rubber state at the curing temperature, and the substance permeability of the capsule is greatly improved. Therefore, the epoxy resin flows into the capsule, and the phosphorus-based curing catalyst can be dissolved and washed out to the outside, or the phosphorus-based curing catalyst itself is spontaneously permeated through the capsule and released into the epoxy resin. . Furthermore, when the stress load on the capsule increases due to the above phenomenon or the capsule is thermally decomposed by heating, the capsule collapses, and the release rate of the phosphorus-based curing catalyst increases remarkably.
  • Tg glass transition temperature
  • the epoxy resin since the vinyl resin itself does not inhibit the curing reaction of the epoxy resin, the epoxy resin exhibits good curability at the curing temperature. On the other hand, at the storage temperature, since the vinyl resin is in a glass state, the substance permeability of the capsule is low, and the penetration of the epoxy resin into the capsule is suppressed. Furthermore, in the latent curing catalyst of the present invention, in addition to the above, the outer shell layer is composed of a highly cross-linked vinyl resin, so that the prevention of the epoxy resin from entering the capsule is extremely high. Therefore, high curability can be exhibited by heating to a predetermined temperature while exhibiting high storage stability below a predetermined temperature.
  • the outer shell layer of the latent curing catalyst of the present invention is composed of a highly crosslinked vinyl resin, only a weak cohesive force due to intermolecular force acts between the particles of the latent curing catalyst (long from the particle surface). Since there is no graft chain, aggregation due to entanglement is unlikely to occur). Therefore, in the combination of the particles and the epoxy resin, the aggregation of the particles is released and the particles are easily mixed with the epoxy resin.
  • the outer shell layer has a functional group such as an ester group
  • the miscibility is further improved by the interaction between the ester group on the particle surface and the epoxy resin. Therefore, the latent curing catalyst of the present invention is highly miscible with the epoxy resin, and can exhibit high curability when heated to a predetermined temperature while exhibiting high storage stability below a predetermined temperature.
  • the phosphorus-based curing catalyst contained in the core is not particularly limited as long as it is a curing catalyst containing phosphorus among curing catalysts that can be used as a curing catalyst for an epoxy resin.
  • Preferred are organic phosphine compounds, specifically, alkylphosphines such as ethylphosphine, propylphosphine and butylphosphine, and first phosphines such as phenylphosphine; dialkyls such as dimethylphosphine, diethylphosphine, dipropylphosphine and diamylphosphine.
  • Second phosphine such as phosphine, diphenylphosphine, methylphenylphosphine, ethylphenylphosphine; trialkylphosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenyl Phosphine, tribenzylphosphine, tolylphosphine (tri-o-tolylphosphite , Tri-p-tolylphosphine, tri-m-tolylphosphine), tri-p-styrylphosphine, tris (2,6-dimethoxyphenyl) phosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, Tertiary
  • the core contains a vinyl polymer in addition to a phosphorus curing catalyst.
  • a vinyl polymer in addition to a phosphorus curing catalyst.
  • the vinyl polymer in the core, it becomes possible to contain the phosphorus-based curing catalyst in the core, and the storage stability of the latent curing catalyst can be improved without lowering the curability. Further, the containment enables the subsequent formation of the inner shell layer.
  • the content of the vinyl polymer in the core is preferably 50 to 500 parts by weight, more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the phosphorus-based curing catalyst.
  • the content of the vinyl polymer in the core may be 50 to 5000 parts by weight with respect to 100 parts by weight of the phosphorus curing catalyst. It may be up to 4000 parts by weight.
  • the phosphorus curing catalyst cannot be dissolved in the vinyl monomer at the stage of adjusting the core component before the polymerization reaction to form the core, and the coarse phosphorus system
  • the curing catalyst may remain, and it may be difficult to contain the phosphorus-based curing catalyst in a minute core.
  • the catalyst may not be completely dissolved in the vinyl monomer at the stage of adjusting the core component before the polymerization reaction for forming the core, and a coarse catalyst may remain. In this case, a minute core cannot be formed.
  • the phosphorus-based curing catalyst is preferably dissolved in the vinyl-based monomer, but the phosphorus-based curing catalyst and the vinyl-based polymer are polymerized by the polymerization of the vinyl-based monomer.
  • the distribution state of the phosphorus-based curing catalyst is not particularly limited inside the core.
  • the core may be one in which a vinyl polymer and a phosphorus curing catalyst are compatible to form a single phase.
  • it may have a double structure in which a phosphorus-based curing catalyst is unevenly distributed in the center of the core and a vinyl polymer surrounds the periphery.
  • a so-called sea-island structure in which a discontinuous phase formed by aggregation of a phosphorus-based curing catalyst is dispersed may be formed.
  • the vinyl polymer and the phosphorus curing catalyst may form a co-continuous structure. Even before the polymerization reaction for forming the core, the phosphorus curing catalyst and the vinyl polymer are polymerized by the vinyl monomer, even if the phosphorus curing catalyst is dissolved in the vinyl monomer. Polymerization reaction induced phase separation may occur.
  • the vinyl polymer in the core is not particularly limited as long as it is a polymer obtained by polymerizing a monomer component containing a radical polymerizable vinyl monomer.
  • (meth) acrylic monomers are preferred.
  • examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, isopropyl (meth) acrylate, (meth) acrylic acid- n-butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) -N-heptyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid al
  • the vinyl polymer contained in the core is not formed by polymerizing allyl glycidyl ether or glycidyl (meth) acrylate, and may not have a glycidyl group.
  • the vinyl polymer contained in the core may be a vinyl polymer having no cross-linked structure, but is preferably a vinyl polymer having a cross-linked structure (hereinafter also referred to as a cross-linked vinyl polymer). .
  • the crosslinked structure preferably has a low density (has a loose crosslinked structure). Since the vinyl polymer in the core has a cross-linked structure, it becomes possible to contain the phosphorus-based curing catalyst more reliably in the core, and further improve the storage stability of the latent curing catalyst. By making the structure low density, the phosphorus-based curing catalyst is easily released at the curing temperature.
  • the vinyl polymer may be produced by polymerizing the vinyl monomer and the crosslinkable vinyl monomer.
  • the crosslinkable vinyl monomer referred to in the present application is a crosslinkable vinyl monomer having two or more radical polymerizable vinyl groups per molecule and capable of radical polymerization together with the vinyl monomer. Specific examples of such a crosslinkable vinyl monomer include the same specific examples as the first crosslinkable vinyl monomer described later.
  • the crosslinkable vinyl monomer used in the core the same monomer as the first crosslinkable vinyl monomer may be used, or a different monomer may be used.
  • the crosslinkable vinyl monomer used in the core is preferably a monomer having one or more (meth) acrylic groups per molecule.
  • allyl acrylate, allyl methacrylate, or di-, tri-, or tetra- (meth) acrylate esters of polyhydric alcohols or polyphenols are more preferable, and allyl acrylate or methacrylic acid is preferred. Allyl acid is particularly preferred.
  • the amount of the crosslinkable vinyl monomer used in the core is preferably small, and specifically, the crosslinkable vinyl monomer in the crosslinkable vinyl polymer forming the core is used.
  • the weight ratio (weight ratio of the cross-linked vinyl monomer in the entire cross-linked vinyl polymer) is preferably 0.01 to 10% by weight, and more preferably 0.5 to 5% by weight.
  • the inner shell layer is a resin layer that covers the core, and is formed of a first vinyl resin.
  • the first vinyl resin is a polymer of a monomer component containing a first vinyl monomer and a first crosslinkable vinyl monomer, or a polymer of a first vinyl monomer. is there. That is, the first vinyl resin is a polymer having the first vinyl monomer as an essential monomer, and may be polymerized together with the first crosslinkable vinyl monomer which is an arbitrary monomer. Good. Among these, a polymer of a first vinyl monomer and a first crosslinkable vinyl monomer is preferable.
  • the first vinyl resin may be a vinyl resin having no acidic group.
  • the first vinyl monomer is not particularly limited as long as it is a monomer having one radical polymerizable vinyl group per molecule, and specifically, a (meth) acrylic monomer, an olefinic monomer Monomer, styrene monomer (eg, metachlorostyrene, parachlorostyrene, parafluorostyrene, paramethoxystyrene, metatertiary butoxystyrene, paratertiary butoxystyrene, paravinylbenzoic acid, paramethyl- ⁇ -methylstyrene) 1-ethynyl-4-fluorobenzene), vinyl ester monomer (formula: C ⁇ C— (C ⁇ O) —O—R), maleic acid monomer (maleic anhydride monomer) Including), maleimide monomers (eg, phenylmethanemaleimide), vinyl alcohol ester monomers (formula: C ⁇ C—O— (C ⁇ O) —R) (e
  • the monomers may use only 1 type and may use 2 or more types together. Of these monomers, (meth) acrylic monomers are preferred. As the (meth) acrylic monomer, those described above (specific examples are described in the place where (core) is described in detail) can be used. These (meth) acrylic monomers may be used alone or in combination of two or more.
  • the first vinyl resin is not formed by polymerizing allyl glycidyl ether or glycidyl (meth) acrylate, and may not have a glycidyl group.
  • the first crosslinkable vinyl monomer a crosslinkable vinyl monomer having two or more radical polymerizable vinyl groups in one molecule and capable of radical polymerization with the first vinyl monomer is used.
  • the first crosslinkable vinyl monomer include, for example, allyl acrylate, allyl methacrylate; aromatic polyfunctional vinyl monomers such as divinylbenzene, divinyltoluene, and trivinylbenzene; ethylene glycol di (meth) Acrylate, diethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butane Diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate
  • the polymerizability with the first vinyl monomer is good and the first vinyl resin exhibits good capsule characteristics
  • one or more (meth) acrylic groups per molecule are more preferred.
  • Good capsule characteristics means that the capsule is in a glassy state during storage and exhibits low substance permeability, but at the curing temperature of the epoxy resin, the capsule becomes rubbery and exhibits high substance permeability, resulting in good capsule disintegration. That means.
  • a double bond having a high polymerizability with a (meth) acrylic monomer and the polymerizability is relatively low.
  • the monomer having both double bonds formed a linear polymer having the latter double bond as a graft chain by the polymerization reaction of the former double bond and the (meth) acrylic monomer.
  • the latter double bond is likely to contribute to the formation of cross-linking, and the degree of cross-linking can be achieved according to the formulation design.
  • allyl acrylate or allyl methacrylate is particularly preferable among the monomers having one or more (meth) acryl groups per molecule.
  • the weight ratio of the first crosslinkable vinyl monomer in the first vinyl resin (weight occupied by the first crosslinkable vinyl monomer in the entire first vinyl resin) The ratio is preferably 10 to 60% by weight, more preferably 15 to 40% by weight, and still more preferably 20 to 30% by weight. Further, the weight ratio of the first crosslinkable vinyl monomer in the first vinyl resin is preferably larger than the weight ratio of the crosslinkable vinyl monomer in the vinyl polymer forming the core. .
  • the outer shell layer is a resin layer that covers the inner shell layer, and is formed of a second vinyl resin.
  • the second vinyl resin is a polymer of a monomer component containing a second vinyl monomer and a second crosslinkable vinyl monomer, or is a polymer of the second crosslinkable vinyl monomer. It is a coalescence. That is, the second vinyl resin is a polymer having the second crosslinkable vinyl monomer as an essential monomer, and the second vinyl monomer is an optional monomer and the second crosslinkable vinyl It may be polymerized (copolymerized) together with the monomer or may not be polymerized (copolymerized).
  • the second vinyl resin may be a vinyl resin having no acidic group.
  • the second vinyl resin forming the outer shell layer has a cross-linked structure, it is possible to prevent the phosphorus-based curing catalyst of the core from leaking out of the particle, and the epoxy resin penetrates into the particle. Can be suppressed. Thereby, the storage stability of the latent curing catalyst can be enhanced.
  • the second vinyl monomer as long as it has one radical polymerizable vinyl group per molecule and can be radically polymerized with the second crosslinkable vinyl monomer, Specific examples include (meth) acrylic monomers, olefinic monomers, and styrene monomers (for example, metachlorostyrene, parachlorostyrene, parafluorostyrene, paramethoxystyrene, metatarsia).
  • the monomers may use only 1 type and may use 2 or more types together. Of these monomers, (meth) acrylic monomers are preferred. As the (meth) acrylic monomer, those described above can be used. These (meth) acrylic monomers may be used alone or in combination of two or more.
  • the second vinyl resin is not formed by polymerizing allyl glycidyl ether or glycidyl (meth) acrylate, and may not have a glycidyl group.
  • the second crosslinkable vinyl monomer a monomer having two or more radically polymerizable vinyl groups in one molecule can be used.
  • Specific examples of the second crosslinkable vinyl monomer include the same monomers as the first crosslinkable vinyl monomer described above, and the same monomers as the first crosslinkable vinyl monomer. May be used, or different monomers may be used.
  • the second crosslinkable vinyl monomer is preferably a monomer having one or more (meth) acryl groups per molecule.
  • Allyl acid, allyl methacrylate, or di-, tri-, or tetra- (meth) acrylic acid esters of polyhydric alcohols or polyhydric phenols are more preferred, and allyl acrylate or allyl methacrylate is particularly preferred.
  • the weight ratio of the second crosslinkable vinyl monomer in the second vinyl resin (weight occupied by the second crosslinkable vinyl monomer in the entire second vinyl resin) The ratio is preferably 60 to 100% by weight, more preferably 80 to 100% by weight, and still more preferably 90 to 99.9% by weight.
  • the weight ratio of the second crosslinkable vinyl monomer in the second vinyl resin is preferably larger than the weight ratio of the first crosslinkable vinyl monomer in the first vinyl resin.
  • the inner shell layer that uses a large amount of the crosslinkable vinyl monomer in the outer shell layer and uses a relatively small amount of the crosslinkable vinyl monomer inside or does not use the crosslinkable vinyl monomer. It is possible to form a shell layer having a high degree of cross-linking on the outermost side of the particles by suppressing the leakage of the phosphorus-based curing catalyst and the penetration of the epoxy resin as described above, and the latent curing catalyst. Can improve the storage stability.
  • the degree of crosslinking be increased in the order of the core, the inner shell layer, and the outer shell layer, that is, the crosslinkable vinyl monomer in the vinyl polymer forming the core.
  • the crosslinkable vinyl series in the order of the weight percentage of the body, the weight percentage of the first crosslinkable vinyl monomer in the first vinyl resin, and the weight percentage of the second crosslinkable vinyl monomer in the second vinyl resin.
  • the constitution is such that the weight ratio of the monomer is increased.
  • the weight ratio of the core described above, the first vinyl resin forming the inner shell layer, and the second vinyl resin forming the outer shell layer is not particularly limited.
  • the higher outer shell layer is preferably a thinner film than the inner shell layer.
  • the amount of the second vinyl resin relative to 100 parts by weight of the first vinyl resin is preferably 5 to 50 parts by weight, and more preferably 10 to 30 parts by weight.
  • the center of the particle is formed in the order of a low crosslinking density or an uncrosslinked core containing a phosphorus-based curing catalyst, a thick inner shell layer with a medium crosslinking density, and a thin outer shell layer with a high crosslinking density. It is preferable that a plurality of shell layers are formed outward from the core.
  • a structure in which gradation of the crosslinking density is provided in this way, and the inner shell layer is thick and the outer shell layer is thin is preferable. With such a structure, both excellent stability during storage and excellent curability during curing can be enhanced.
  • the phosphorus-based curing catalyst leaks out of the capsule and the epoxy resin is encapsulated by a thin outer shell layer (thin hard wall) with a high crosslinking density and a thick inner shell layer (thick wall) with a moderate crosslinking density.
  • a thin outer shell layer thin hard wall
  • a thick inner shell layer thin wall
  • the hard, brittle and thin outer shell layer collapses due to thermal shock such as pressure difference inside and outside capsule, thermal expansion difference, stress increase due to mass transfer etc. It's easy to do.
  • the outer shell layer collapses, it is induced to chain the collapse to the inner shell layer and the core. That is, the crack propagates and the whole particle collapses.
  • the inner shell layer having a medium crosslinking density exhibits physical properties that the crosslinking chain moves flexibly (rubber state) and easily releases the phosphorus-based curing catalyst.
  • the greatest feature of the latent curing catalyst according to the embodiment is that the outer shell layer has a high crosslink density and is thin. Since the mobility of the crosslinking chain due to the high crosslinking density is extremely low, the outer shell layer having a high crosslinking density is difficult to permeate the substance and exhibits very high stability during storage. On the other hand, at the curing temperature of the epoxy resin, the outer shell layer is thin and very fragile, so that it easily collapses due to thermal shock, thereby exhibiting good curability.
  • the fact that the outer shell layer has a high crosslink density and is thin contributes greatly to both storage stability and curability.
  • the inner shell layer plays a role of enhancing the function of the outer shell layer. That is, since the inner shell layer is relatively thick with a medium crosslinking density, even if the epoxy resin permeates through the thin outer shell layer during storage, the inner shell layer is a phosphorus-based material in which the epoxy resin is contained in the core. Reaching the curing catalyst can be suppressed, and this structure enhances stability during storage. Further, since the inner shell layer has a medium crosslinking density, the effect of suppressing the collapse of the outer shell layer during curing is low, and the curability is not lowered. However, if the inner shell layer has a high crosslinking density, there is a high possibility that the outer shell layer will be prevented from collapsing during curing.
  • the latent curing catalyst of the present invention is in the form of particles, and the average particle diameter (D 50 (cumulative volume 50%)) is 0.01 to 50 ⁇ m.
  • the thickness is preferably 0.05 to 5 ⁇ m, more preferably 0.1 to 3 ⁇ m, still more preferably 0.3 to 2 ⁇ m, and particularly preferably 0.3 to 1 ⁇ m. Since the average particle size is small in this way, the latent curing catalyst of the present invention has penetration into an extremely narrow gap, etc., and is used for semiconductor devices and electronic parts having such a narrow gap. It can use suitably in the sealing material to perform.
  • the latent curing catalyst for epoxy resins of the present invention can be produced by performing the following steps. First, in the presence of a phosphorus curing catalyst, a monomer component containing a vinyl monomer and optionally a crosslinkable vinyl monomer is polymerized by emulsion polymerization to form a core. Then, in the presence of the core, by emulsion polymerization, a monomer component containing the first vinyl monomer and, optionally, the first crosslinkable vinyl monomer is polymerized to coat the core Form a shell layer.
  • a monomer component containing a second crosslinkable vinyl monomer, and optionally a second vinyl monomer is polymerized, An outer shell layer covering the inner shell layer is formed.
  • Each emulsion polymerization can follow a conventional method.
  • a polymerization initiator and an emulsifier are mixed with water and stirred to form micelles.
  • a polymerization initiator and an emulsifier are mixed with water and stirred to form micelles.
  • a polymerization initiator and an emulsifier are mixed with water and stirred to form micelles.
  • the temperature is raised under an inert atmosphere, and the heat polymerization reaction is allowed to proceed at a predetermined temperature to obtain an emulsion of core particles.
  • the reaction temperature is not particularly limited, but is preferably about 60 to 100 ° C., and the reaction time is preferably about 1 to 10 hours.
  • a radical polymerization initiator such as a thermal radical polymerization initiator or a photo radical polymerization initiator that can be generally used in emulsion polymerization can be used.
  • 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride
  • 2,2′-azobis (2-methylpropionamidine) dihydrochloride 2,2′-azobis- [N- (2-carboxyethyl) -2-methylpropionamidine]
  • 2,2′-azobis- [2-methyl-N- (2-hydroxyethyl) propionamide 4,4′-azobis (4-cyanovaleric acid), etc.
  • Water-soluble azo compounds 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyrate) Nitrile), 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2 Azo compounds such as oil-soluble azo compounds such as methyl propionate), 1,1′-azobis (cyclohexane-1-carbonitrile), dimethyl 1,1′-azobis (1-cyclohexanecarboxylate); Persulfuric compounds such as potassium, sodium persulfate and ammonium persulfate; organic peroxides such as diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide (hydroperoxide) ); Organic per
  • a polymerization initiator that is easily soluble in water is preferable, and examples thereof include water-soluble azo compounds and persulfates.
  • the 10-hour half-life temperature of the thermal polymerization initiator is generally preferably 40 to 90 ° C. If it is lower than this, decomposition proceeds during charging at room temperature, and if it is higher than this, a long time is required for the polymerization reaction. . Many of the organic peroxides have a 10-hour half-life temperature exceeding the above range, and the radical generation rate at a general emulsion polymerization temperature is slow.
  • the organic peroxide redox initiator is preferable because it can be used in a general emulsion polymerization temperature range.
  • polymerization initiators may be used alone or in combination of two or more. In the case of using two or more kinds in combination, only the water-soluble radical polymerization initiator may be used, any combination of the water-soluble radical polymerization initiator and the oil-soluble radical polymerization initiator may be used, or only the oil-soluble radical polymerization initiator may be used.
  • the amount of the polymerization initiator used can be appropriately set. For example, it may be 0.01 to 1.00 parts by weight with respect to 100 parts by weight of the monomer component.
  • the total amount of the polymer is 0.01 to 100 parts by weight with respect to 100 parts by weight of the monomer component. It may be 2.00 parts by weight.
  • Emulsifiers that can be used in emulsion polymerization include alkali metal salts and ammonium salts of higher fatty acids such as disproportionated rosin acid, oleic acid and stearic acid, alkali metal salts and ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid, anions And emulsifiers and nonionic emulsifiers.
  • the anionic emulsifier is not particularly limited.
  • polyoxyethylene alkyl ether sulfate ester salts for example, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, etc.
  • alkyl examples thereof include diphenyl ether disulfonate (sodium alkyl diphenyl ether disulfonate, sodium alkyl diphenyl ether disulfonate, etc.), reactive anionic surfactant (polyoxyalkylene alkenyl ether ammonium sulfate, etc.) and the like.
  • nonionic emulsifier is not particularly limited, and polyoxyethylene alkyl ether (for example, polyoxyethylene alkyl ether), polyoxyalkylene alkyl ether (for example, polyoxyalkylene alkyl ether), reactive nonionic interface An activator (polyoxyalkylene alkenyl ether etc.) etc. are mentioned.
  • ammonium salt type anionic emulsifiers and nonionic emulsifiers that do not contain metal ions are preferred in order to reduce metal ions in the resulting polymer.
  • the ammonium salt type anionic emulsifier is preferably ammonium lauryl sulfate or ammonium di- (2-ethylhexyl) sulfosuccinate for the purpose of stability of emulsion polymerization, and the nonionic emulsifier is stable in emulsion polymerization. Therefore, polyoxyethylene monotetradecyl ether and polyoxyethylene distyrenated phenyl ether are preferable.
  • sodium salt type anionic emulsifiers are preferred from the viewpoint of industrial availability.
  • sodium salt type anionic emulsifier sodium di- (2-ethylhexyl) sulfosuccinate is preferable.
  • the amount of the emulsifier used can be appropriately set. For example, it may be 0.01 to 10.00 parts by weight with respect to 100 parts by weight of the monomer component.
  • a polymerization initiator and an emulsifier are mixed in water and stirred to form micelles.
  • the monomer components of the inner shell layer are uniformly mixed, they are added to the micelles, and both are mixed and stirred to form an emulsion for the inner shell layer.
  • the emulsion of the core particles is brought to a predetermined temperature under an inert atmosphere, the emulsion for the inner shell layer is added dropwise thereto, and the heat polymerization reaction proceeds at the predetermined temperature while mixing and stirring them.
  • the reaction temperature, reaction time, and the like can be appropriately adjusted with reference to the above-described ranges.
  • an emulsifier and water are mixed, or an emulsifier, a polymerization initiator and water are mixed and stirred to form micelles.
  • the monomer component of the outer shell layer is uniformly mixed, or the monomer component of the outer shell layer and the polymerization initiator are uniformly mixed, then added to the micelle, and both are mixed and stirred to mix the outer shell.
  • a layer emulsion is formed.
  • the emulsion of the single-shelled particles is brought to a predetermined temperature under an inert atmosphere, and then the emulsion for outer shell layer is added dropwise thereto, and these are mixed and stirred, and the heat polymerization reaction is performed at the predetermined temperature.
  • the reaction temperature, reaction time, and the like can be appropriately adjusted with reference to the above-described ranges.
  • the polymerization initiator is used by dissolving in advance only in the monomer component added to the micelle, or by dissolving in advance in the water before the formation of the micelle.
  • the monomer component added to the micelle is preferably dissolved in advance and used.
  • a monomer-soluble radical polymerization initiator it is preferable to use as the polymerization initiator, and in the latter case, a water-soluble radical polymerization initiator is used as the polymerization initiator when dissolved in water, and When dissolving with the monomer component, it is preferable to use a monomer-soluble radical polymerization initiator.
  • radical polymerization initiation reaction occurs in the monomer component in the former case, while radical polymerization initiation reaction occurs in both the monomer component and the aqueous phase in the latter case.
  • the monomer-soluble radical polymerization initiator refers to a radical polymerization initiator having a weight of 0.50 parts by weight or more uniformly dissolved at 25 ° C. with respect to 100 parts by weight of allyl methacrylate (AMA).
  • AMA allyl methacrylate
  • many oil-soluble radical polymerization initiators are applicable.
  • the polymerization initiator may be used by dissolving in advance only in water before the formation of the micelles.
  • a water-soluble radical polymerization initiator is preferably used as the polymerization initiator.
  • radical polymerization initiation reaction occurs in the aqueous phase.
  • Examples of the monomer-soluble radical polymerization initiator include the oil-soluble radical polymerization initiators described above, such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero). Nitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (4-methoxy-2,4) -Dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl 1,1'-azobis (1-cyclohexanecarboxylate) And oil-soluble azo compounds such as benzoyl peroxide; and organic peroxides (diacyl peroxide) such as benzoyl peroxide.
  • oil-soluble radical polymerization initiators such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2
  • a monomer-soluble radical polymerization initiator to promote the progress of the crosslinking reaction by the second crosslinkable vinyl monomer in the outer shell layer and to increase the degree of crosslinking of the outer shell layer.
  • the combined use of a monomer-soluble radical polymerization initiator and a water-soluble radical polymerization initiator is also preferable for increasing the degree of crosslinking of the outer shell layer.
  • a water-soluble radical polymerization initiator it is preferable to use a water-soluble radical polymerization initiator.
  • the latent curing catalyst of the present invention can be obtained by spray drying, freeze drying, or coagulation.
  • the latent curing catalyst of the present invention can also be obtained by separating particles from the emulsion by centrifugation or filtration, followed by washing with water as necessary and drying by a conventional method.
  • the water described in this specification is ion-exchanged water unless otherwise specified, but is not limited thereto.
  • the epoxy resin composition of the present invention contains at least an epoxy resin and the latent curing catalyst described above.
  • the said epoxy resin composition points out what is in the state before hardening, a liquid thing may be sufficient, and the molded object which has a gel-like and fixed shape may be sufficient as it.
  • the shape of such a molded body is not particularly limited and can be appropriately designed depending on the application, and examples thereof include a sheet shape, a film shape, and a tablet shape.
  • the epoxy resin that can be used in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule, and generally known ones can be used.
  • biphenyl type epoxy resin tetramethyl biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene phenol addition reaction type Epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol phenol co-condensed novolac type epoxy resin, naphthol cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy Resin, biphenyl novolac epoxy resin, ethylphenol novolac epoxy resin, butylphenol novolac epoxy resin Octylphenol novolac epoxy resin,
  • the epoxy resin may be selected according to desired properties and properties (liquid or solid), and is not particularly limited. For example, among the above specific examples, bis (hydroxyphenyl) alkane-based epoxy resin, naphthalene-based epoxy Resins are preferred.
  • the amount of the latent curing catalyst of the present invention to be used for the epoxy resin is not particularly limited and can be appropriately determined according to a desired curing rate and physical properties of the cured product.
  • the latent curing catalyst of the present invention is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 40 parts by weight, and still more preferably 0.5 to 100 parts by weight of the epoxy resin. -30 parts by weight, particularly preferably 1.0-20 parts by weight.
  • the phosphorus-based curing catalyst contained in the latent curing catalyst of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, and still more preferably 100 parts by weight of the epoxy resin. May be blended so as to be 0.1 to 10 parts by weight.
  • the epoxy resin composition of the present invention can further contain an epoxy resin curing agent.
  • a curing agent is not particularly limited, and those generally known as a curing agent to be blended with an epoxy resin can be used.
  • the curing agent may be selected according to desired properties and properties (liquid or solid), and is not particularly limited.
  • desired properties and properties liquid or solid
  • acid anhydrides from the viewpoint of heat resistance and chemical resistance.
  • amine-based curing agents are preferred, and from the viewpoint of low outgassing, moisture resistance, heat cycle resistance, etc. during curing, phenol-based curing agents are preferred.
  • phenol-based curing agents are preferred.
  • the amount of the curing agent used for the epoxy resin is not particularly limited, and may be a general usage amount, which can be appropriately determined according to a desired curing rate and physical properties of the cured product.
  • the curing agent is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin.
  • additives in the epoxy resin composition can be appropriately blended.
  • additives include fillers such as carbon black, adhesion imparting agents, solvents, reactive diluents, antioxidants, light stabilizers, ultraviolet absorbers, antifoaming agents, leveling agents, pigments, and the like. Is mentioned.
  • the filler is not particularly limited, and a known filler can be used. Examples thereof include fillers made of inorganic oxides, inorganic salts, glass, nitrides, metal powders, and the like.
  • the inorganic oxide include titanium oxide, silicon oxide, aluminum oxide, beryllium oxide, and zirconium oxide.
  • the inorganic salt include calcium carbonate, barium sulfate, zirconium silicate, calcium silicate, magnesium silicate, and the like.
  • Examples of the nitride include boron nitride, aluminum nitride, gallium nitride, indium nitride, and silicon nitride.
  • the metal powder include silver powder, copper powder, silver-plated copper powder, tin-plated copper powder, nickel powder, and aluminum powder. Only one type of filler may be used, or two or more types may be used in combination.
  • adhesion-imparting agent examples include a coupling agent, a phenol resin, and an organic polyisocyanate. Only one type of adhesiveness-imparting agent may be used, or two or more types may be used in combination.
  • the coupling agent examples include various coupling agents such as silane-based, aluminum-based, zircoaluminate-based, and titanium-based materials, and partial hydrolysis condensates thereof.
  • silane coupling agents and partial hydrolysis condensates thereof are preferred because of their high adhesion-imparting effect.
  • the partial hydrolysis-condensation product of a coupling agent may be a partial hydrolysis-condensation product of the same kind of coupling agent, or may be a partial hydrolysis-condensation product of two or more coupling agents.
  • silane coupling agent examples include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc.
  • the compound etc. which contain the alkoxy silyl group of these are mentioned.
  • the solvent is not particularly limited.
  • N-methylpyrrolidone N, N-dimethylformamide; dimethyl sulfoxide; ketones such as methyl ethyl ketone, cyclohexanone and cyclopentanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene
  • Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate, Such as butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers.
  • alcohols such as ethanol, propanol, methanol, ethylene glycol and propylene glycol
  • aliphatic hydrocarbons such as octane and decane
  • petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha Can be mentioned. Only one type of solvent may be used, or two or more types may be used in combination.
  • the reactive diluent is not particularly limited.
  • the latent curing catalyst for epoxy resins of the present invention can act as a sheeting agent because it itself can act to gel the epoxy resin composition. Therefore, the epoxy resin composition of the present invention can be formed into a molded article such as a sheet without adding a sheeting agent as an additional component. However, when the epoxy resin composition of the present invention is a molded article such as a sheet, a sheeting agent such as a thermoplastic resin powder may be separately added to the epoxy resin composition. The thermoplastic resin powder can absorb and swell epoxy resin or other components to make the composition gel, or can be compatible with epoxy resin or other components to make the composition gel. .
  • thermoplastic resin constituting the powder examples include polyvinyl chloride, polyethylene, polypropylene, polystyrene, and synthetic rubber (polybutadiene, butadiene-styrene copolymer, polyisoprene, polychloroprene, ethylene-propylene copolymer).
  • the epoxy resin composition of the present invention is a sheet-like molded article
  • a photopolymerizable compound and a radical generator that act as a sheeting agent can be blended in the epoxy resin composition.
  • a mixture of the epoxy resin composition and other components, a photopolymerizable compound and a radical generator is prepared, and the resulting mixture is made into a sheet shape, and then irradiated with light to give photopolymerizability.
  • a polymerized compound is used as a gel-like curable sheet.
  • Examples of the photopolymerizable compound include compounds containing one or more (meth) acryloyl groups in the molecule, specifically (meth) acrylic acid, alkyl alcohol, alkylene diol, polyhydric alcohol, and the like. And the compounds described in [0009] to [0012] of JP-A No. 11-12543.
  • the radical generator is a compound that generates radicals upon irradiation with actinic rays such as ultraviolet rays and electron beams.
  • actinic rays such as ultraviolet rays and electron beams.
  • Various conventionally used compounds can be used, for example, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, benzoin, acetophenone, and the like can be used.
  • the epoxy resin composition of the present invention can be obtained by mixing an epoxy resin and the latent curing catalyst of the present invention, and further a curing agent and other additives.
  • the method of mixing these is not particularly limited, and a conventionally known method can be used. For example, a method of stirring using a stirrer, a method of kneading using a three-roll mill, and a ball mill are used. Can do.
  • the components may be mixed as described above and then molded by a usual method such as heat molding. Further, if necessary, the epoxy resin composition heated to a liquid state is made into a coated product whose film thickness is controlled by a roll coater or the like, and it is 0.5 to 30 minutes at 60 to 150 ° C., and 1 at 80 to 120 ° C. It can also be made into a sheet by drying for ⁇ 10 minutes.
  • a cured product can be obtained by curing the epoxy resin composition.
  • the curing method may be a condition for curing a general epoxy resin composition, and is not particularly limited. For example, using a heating device, heating is performed at 100 ° C. for 1 hour, and then at 180 ° C. for 4 hours. And the like. However, specific curing conditions can be appropriately determined according to the use of the epoxy resin composition. It does not specifically limit as said heating apparatus, For example, a ventilation constant temperature dryer, a constant temperature constant temperature dryer, etc. can be used.
  • the surface shape of the cured product of the present invention is preferably such that the size of the convex portion or concave portion on the surface is 10 ⁇ m or less.
  • the surface shape was obtained by depositing gold on the surface of the cured product, and then using a scanning electron microscope (SEM) JSM-6390LV manufactured by JEOL Ltd., an acceleration voltage of 15 kV, an observation angle of 45 °, and a magnification of 400 times (observation area: 300 ⁇ m ⁇ 200 ⁇ m) or 2000 times (observation area: 60 ⁇ m ⁇ 40 ⁇ m).
  • the size of the convex portion or the concave portion can be obtained from the SEM observation image.
  • the SEM observation image can particularly evaluate the size of the concavo-convex region in an arbitrary direction within a plane.
  • the arbitrary direction in a plane is the arbitrary direction in a SEM photograph surface.
  • the surface shape can be observed using a stylus type surface shape measuring device DEKTAK 150 at a scanning speed of 1,000 ⁇ m / 60 s, a scanning distance of 1.0 mm, measurement points of five points, and measurement values of steps. .
  • the stylus type surface shape measuring instrument can particularly evaluate the size of the unevenness in the direction perpendicular to the surface.
  • the plane perpendicular direction is a direction perpendicular to the photographic plane at an arbitrary position on the SEM photographic plane.
  • the use of the epoxy resin composition of this invention is not specifically limited, It can use suitably as a sealing material or an adhesive agent.
  • the latent curing catalyst of the present invention has a small particle size and can penetrate into an extremely narrow gap, etc., so that it is particularly useful as a sealing material used for a semiconductor device or electronic component having such a narrow gap. It can be used suitably.
  • the gap include a gap between the substrate and the chip, a gap between the chip and the chip, and a gap between the solder bump and the solder bump.
  • the width of the gap may be 100 ⁇ m or less, may be 50 ⁇ m or less, and may be 30 ⁇ m or less.
  • the surface of the cured product formed from the epoxy resin composition containing the latent curing catalyst of the present invention is smooth without any unevenness, it is suitable for applications requiring smoothness.
  • a specific application as a sealing material is that a rewiring layer can be formed on the lower surface of the sealing material, so that a circuit such as a sealing material for FO-WLP applications or an antenna on the upper surface of the sealing material is used. Since it can be formed, a sealing material for antenna-on-package (AoP) use in which an antenna and a semiconductor device are integrated, or metal plating on the whole or part of the sealing is possible. It can be suitably used as a sealing material for electromagnetic wave shielding.
  • AoP antenna-on-package
  • a sealing material there is a semiconductor sealing material used when sealing a wafer level chip size package which is a large-area semiconductor package by an overmolding method.
  • the sealing material is an overmolding material that seals the terminals, the device electrodes, and the semiconductor bare chip disposed on the semiconductor wafer substrate.
  • overmold molding include transfer molding and compression molding. Of these, compression molding is preferred.
  • the overmolding is preferably performed at 50 to 200 ° C., more preferably 100 to 175 ° C. for 1 to 15 minutes. If necessary, post-cure can be performed at 100 to 200 ° C. for 30 minutes to 24 hours. By such heating, the epoxy resin composition is cured to form an overmold material.
  • the liquid epoxy resin composition of the present invention can be suitably used.
  • the sealing material is a surface acoustic wave device in which a surface acoustic wave chip is mounted on a substrate on which a wiring pattern is formed, and the electrode surface of the surface acoustic wave chip and the wiring pattern are connected by a bump.
  • the electrode surface and the wiring pattern are not in direct contact, and in a surface acoustic wave device having a hollow structure between the substrate and the chip, the sealing for sealing the surface acoustic wave chip is performed. Stop materials are mentioned.
  • the epoxy resin composition of this invention which is a molded object which has a fixed shape can be used suitably.
  • a sheet-like epoxy resin composition is disposed so as to cover the surface acoustic wave chip, and then heat pressing is performed.
  • the epoxy resin composition is cured while the hollow structure is maintained, and a protective layer for the chip can be formed.
  • the conditions for such a heat press can be appropriately determined.
  • the pressure is 100 Pa to 10 MPa, preferably 0.01 to 2 MPa
  • the temperature is 250 ° C. or less, preferably 60 to 180 ° C.
  • the time is 5 seconds to It may be 3 hours, preferably 1-15 minutes.
  • the emulsifier was dissolved in ion-exchanged water and stirred at a high speed of 1500 rpm for 5 minutes to prepare micelles. After dissolving the radical polymerization initiator in the acrylic monomer, it was added to the micelle and stirred at a high speed of 2000 rpm for 25 minutes to prepare an emulsion composed of the outer layer shell component.
  • the amount of each component is as shown in Table 1.
  • Example 2 In “Synthesis of double-shelled particles” described in Example 1, “(3) Acrylic monomer”, which is “Raw material of outer shell”, in addition to allyl methacrylate (trade name “AMA” manufactured by Mitsubishi Gas Chemical Company) Except for adding a small amount of methyl methacrylate (trade name “acrylic ester M” manufactured by Mitsubishi Chemical Corporation), double-shelled particles were synthesized according to the procedure of Example 1 and dried. The amount of each component is as shown in Table 1.
  • Examples 3 and 4 In “Preparation of emulsion comprising core component” described in Example 1, “(5) inclusion catalyst” which is “raw material of core component” is a predetermined amount (described in Table 1) of curing catalyst tri-p- Double-shelled particles were synthesized and dried according to the procedure of Example 2 except for replacing with tolylphosphine (trade name “TPTP” manufactured by Hokuko Chemical Co., Ltd.). The amount of each component is as shown in Table 1.
  • Comparative Example 1 The emulsion of “single shelled particles” obtained during the production of the double shelled particles of Example 1 was dried by spray drying to obtain single shelled particles of Comparative Example 1. Note that Comparative Example 1 is a different lot from Example 1.
  • Comparative Example 2 The emulsion of “core particles” obtained during the production of the double-shelled particles of Example 1 was dried by spray drying to obtain the core particles of Comparative Example 2. Comparative Example 2 is a different lot from Example 1 and Comparative Example 1.
  • the particles of 1 to 5 or Comparative Examples 1 and 3 were measured.
  • weight reduction due to thermal decomposition of the encapsulated catalyst in the case of TPP and TPTP, weight reduction occurs from about 150 ° C. and continues to less than 300 ° C.
  • weight reduction due to acrylic resin can be confirmed around 300 ° C.
  • the temperature at the start of viscosity increase (temperature at the minimum viscosity) was evaluated. Moreover, the viscosity (minimum viscosity) at the start of the viscosity increase was evaluated. The viscosity at 25 ° C. obtained by the measurement was evaluated as the initial viscosity. The results are shown in Table 2.
  • each obtained cured product was observed and evaluated as follows. After depositing gold on the surface of the cured product, using a scanning electron microscope (SEM) JSM-6390LV manufactured by JEOL Ltd., at an acceleration voltage of 15 kV, an observation angle of 45 °, and a magnification of 400 times (observation area: 300 ⁇ m ⁇ 200 ⁇ m) This was confirmed by SEM observation.
  • SEM scanning electron microscope
  • the maximum value of the step in each of the five measurement points was as follows. First location: 0.41 ⁇ m, second location: 0.46 ⁇ m, third location: 0.87, fourth location: 0.74 ⁇ m, and fifth location: 0.55 ⁇ m. Therefore, it was found that the unevenness in the surface perpendicular direction of the surface of the cured product of the resin composition to which the particles of Example 1 were added was 10 ⁇ m or less.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

La présente invention concerne un catalyseur de durcissement latent pour résine époxy qui présente une petite taille de particule, fait preuve d'une excellente aptitude au mélange avec la résine époxy, présente une stabilité élevée au stockage comme composition avec la résine époxy, et présente une excellente aptitude au durcissement. Le catalyseur de durcissement latent pour résine époxy comprend des particules qui ont une taille moyenne de particule de 0,01 à 50 µm, chaque particule comprenant : un cœur qui est formé d'un catalyseur de durcissement à base de phosphore et d'un polymère à base de vinyle ; une couche d'écorce interne qui recouvre le cœur et qui est formée d'une première résine de vinyle qui est un polymère de constituants monomères comprenant un premier monomère à base de vinyle et un premier monomère à base de vinyle réticulable ou un polymère du premier monomère à base de vinyle ; et une couche d'écorce externe qui recouvre la couche d'écorce interne et qui est formée d'une seconde résine de vinyle qui est un polymère de constituants monomères comprenant un second monomère à base de vinyle et un second monomère à base de vinyle réticulable ou un polymère du second monomère à base de vinyle réticulable.
PCT/JP2019/013355 2018-03-29 2019-03-27 Catalyseur de durcissement latent pour résine époxy et composition de résine époxy l'utilisant WO2019189458A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020509249A JP7191936B2 (ja) 2018-03-29 2019-03-27 エポキシ樹脂用潜在性硬化触媒、及びこれを用いたエポキシ樹脂組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-063755 2018-03-29
JP2018063755 2018-03-29

Publications (1)

Publication Number Publication Date
WO2019189458A1 true WO2019189458A1 (fr) 2019-10-03

Family

ID=68062094

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/013355 WO2019189458A1 (fr) 2018-03-29 2019-03-27 Catalyseur de durcissement latent pour résine époxy et composition de résine époxy l'utilisant

Country Status (2)

Country Link
JP (1) JP7191936B2 (fr)
WO (1) WO2019189458A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0873566A (ja) * 1994-09-06 1996-03-19 Nippon Kayaku Co Ltd マイクロカプセル型硬化促進剤、これを含むエポキシ樹脂組成物及びその硬化物
JP2014218594A (ja) * 2013-05-09 2014-11-20 京セラケミカル株式会社 封止用樹脂組成物とその製造方法、および樹脂封止型半導体装置
JP2016035056A (ja) * 2014-07-31 2016-03-17 積水化学工業株式会社 エポキシ樹脂硬化用マイクロカプセル及びエポキシ樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0873566A (ja) * 1994-09-06 1996-03-19 Nippon Kayaku Co Ltd マイクロカプセル型硬化促進剤、これを含むエポキシ樹脂組成物及びその硬化物
JP2014218594A (ja) * 2013-05-09 2014-11-20 京セラケミカル株式会社 封止用樹脂組成物とその製造方法、および樹脂封止型半導体装置
JP2016035056A (ja) * 2014-07-31 2016-03-17 積水化学工業株式会社 エポキシ樹脂硬化用マイクロカプセル及びエポキシ樹脂組成物

Also Published As

Publication number Publication date
JPWO2019189458A1 (ja) 2021-04-01
JP7191936B2 (ja) 2022-12-19

Similar Documents

Publication Publication Date Title
KR101685775B1 (ko) 중합체 분체, 경화성 수지 조성물 및 그의 경화물
TWI355720B (en) Area mount type semiconductor device, and encapsul
TWI580701B (zh) 乙烯基聚合物粉末、硬化性樹脂組成物及硬化物
KR20120024507A (ko) 전자 부품 장치의 제조 방법 및 전자 부품 밀봉용 수지 조성물 시트
JPWO2010090246A1 (ja) ビニル重合体粉体、硬化性樹脂組成物及び硬化物
WO2012086463A1 (fr) Composition de résine époxy durcissable et dispositif photo-semiconducteur l'utilisant
JP5301399B2 (ja) エポキシ樹脂組成物、及びこれを硬化したエポキシ硬化物
JP2012077129A (ja) 樹脂組成物、および、それを用いた封止材
TW201439189A (zh) 硬化性環氧樹脂組成物
TW201739867A (zh) 電子零件的製造方法、臨時固定用樹脂組成物、臨時固定用樹脂膜及臨時固定用樹脂膜片
TWI535738B (zh) （甲基）丙烯酸酯系聚合物、樹脂組成物及成形體
TWI593738B (zh) 環氧樹脂組成物、環氧硬化物及led密封材料
JP2008291152A (ja) 熱硬化性樹脂組成物、コアシェルポリマ、硬化物
JP2015172185A (ja) グラフト共重合体、樹脂組成物及び成形体
JP5845044B2 (ja) 硬化剤及び／又は硬化促進剤内包カプセル、及び、熱硬化性樹脂組成物
JP5760347B2 (ja) グラフト共重合体の製造方法、樹脂組成物及び成形体
WO2019189458A1 (fr) Catalyseur de durcissement latent pour résine époxy et composition de résine époxy l'utilisant
TW201829527A (zh) 潛在性硬化劑及其製造方法、以及熱硬化型環氧樹脂組成物
TW201109411A (en) Bonding sheet
JP5971609B2 (ja) 硬化性樹脂組成物及びこれを硬化した硬化物
JP2012092356A (ja) コアシェルポリマ及び硬化物
JP2016050221A (ja) 硬化性エポキシ樹脂組成物
KR20190103870A (ko) 반도체 몰딩용 에폭시 수지 조성물, 몰딩 필름 및 반도체 패키지
JP2013215685A (ja) 液体内包カプセルの製造方法、液体内包カプセル及びカプセル含有組成物
JP2015218317A (ja) 硬化性樹脂用応力緩和剤、硬化性樹脂組成物及び成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19776380

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020509249

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19776380

Country of ref document: EP

Kind code of ref document: A1