WO2023132317A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2023132317A1
WO2023132317A1 PCT/JP2022/048510 JP2022048510W WO2023132317A1 WO 2023132317 A1 WO2023132317 A1 WO 2023132317A1 JP 2022048510 W JP2022048510 W JP 2022048510W WO 2023132317 A1 WO2023132317 A1 WO 2023132317A1
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Prior art keywords
epoxy resin
resin composition
curable resin
epoxy
epoxy resins
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PCT/JP2022/048510
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English (en)
Japanese (ja)
Inventor
智崇 野口
康代 金沢
千夏 高橋
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太陽ホールディングス株式会社
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Publication of WO2023132317A1 publication Critical patent/WO2023132317A1/fr

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    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections

Definitions

  • the present invention relates to a curable resin composition, and more particularly to a curable resin composition that can be suitably used as a filling material for filling through holes such as through holes and recesses in printed wiring boards.
  • a multi-layer substrate such as a build-up wiring board in which layers are connected and multi-layered is used.
  • thermosetting resin filler a thermosetting resin filler containing an epoxy resin as a thermosetting resin component, an epoxy resin curing agent, and an inorganic filler is generally used.
  • Patent Document 1 proposes a curable resin composition capable of forming a hole insulating layer having excellent crack resistance, adhesion, insulation reliability, heat resistance, moisture resistance, PCT resistance, and the like.
  • an object of the present invention is to provide a curable resin composition that is excellent in heat resistance, low CTE and crack resistance, as well as excellent filling properties and adhesion to copper plating.
  • the inventors focused on epoxy resins and found that the above problems can be solved by combining multiple types of epoxy resins with different functional groups.
  • the present invention is based on such findings. That is, the gist of the present invention is as follows.
  • a curable resin composition comprising The (A) epoxy resin contains at least three epoxy resins having different numbers of functional groups or different molecular skeleton structures, The three types of epoxy resins include at least an epoxy resin having a functional group number of 2 or less and an epoxy resin having a functional group number of 4 or more and an aromatic ring.
  • a curable resin composition characterized by: [2] The curable resin composition according to [1], wherein the epoxy resin having 4 or more functional groups is liquid at room temperature. [3] The curable resin composition according to [1] or [2], wherein (A) the epoxy resin further contains an epoxy resin having 3 functional groups.
  • the curable resin composition of the present invention contains (A) an epoxy resin, (B) an epoxy resin curing agent, and (C) an inorganic filler as essential components.
  • the term "liquid” means a fluid state or a semi-liquid state (paste state).
  • the curable resin composition according to the present invention contains at least three types of epoxy resins having different numbers of functional groups or different molecular skeleton structures as epoxy resins which are curable components.
  • the number of functional groups means an epoxy group (glycidyl group)
  • the molecular skeleton structure means a compound obtained by substituting a hydrogen atom for the epoxy group.
  • At least two of these three types of epoxy resins are an epoxy resin with a functional group number of 2 or less and an epoxy resin with a functional group number of 4 or more and an aromatic ring.
  • a curable resin composition mainly containing an epoxy resin as a curable component, an epoxy resin having a functional group number of 2 or less, an epoxy resin having a functional group number of 4 or more and an aromatic ring, and an epoxy having a different molecular skeleton structure from these two types
  • a resin or an epoxy resin having a functional group of 3 it is possible to obtain a curable resin composition that is excellent not only in heat resistance, low CTE, and crack resistance, but also in filling properties and adhesion to copper plating.
  • the inclusion of an epoxy resin having a polyfunctional aromatic ring with a number of functional groups of 4 or more increases the cross-linking density of the cured product, thereby improving the heat resistance of the cured product and improving the CTE. decreases. Therefore, unlike the conventional curable resin composition, it is not necessary to add a large amount of inorganic filler, so that the printability is improved and the filling property is improved. In addition, it can be inferred that the volume shrinkage at the time of curing is suppressed, the crack resistance is improved, and etching is facilitated in the desmear process, and as a result, the adhesion to the copper plating is improved due to the unevenness of the surface.
  • epoxy resin having 2 or less functional groups include, for example, bisphenol A diglycidyl ether type epoxy resin and bisphenol F diglycidyl ether type epoxy resin.
  • Resin bisphenol E type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, resorcin diglycidyl ether type epoxy resin, hydroquinone diglycidyl ether type epoxy resin, terephthalic acid diglycidyl ester type epoxy resin, bisphenoxyethanolfluorenediglycidyl ether type epoxy resin resins, bisphenol fluorenediglycidyl ether type epoxy resins, biscresol fluorenediglycidyl ether type epoxy resins, novolak glycidyl ether type epoxy resins, epoxy resins having an aromatic skeleton such as hexahydrophthalic acid glycidyl ester, cyclohexanedimethanol diglycidyl ether , butanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, and other epoxy resins having an aliphatic skeleton, but are not limited to these.
  • Epoxy resins having one functional group include aliphatic skeletons having 6 to 36 carbon atoms, such as alkyl glycidyl ethers, alkenyl glycidyl ethers, alkyl glycidyl esters, and alkenyl glycidyl esters. and epoxy resins having an aromatic skeleton such as phenylglycidyl ether and phenylglycidyl ester, but are not limited thereto.
  • the chain length of alkyl is usually about 6-18.
  • the above epoxy resins having a functional group number of 2 or less may be used alone, or two or more epoxy resins may be used in combination. Therefore, it preferably contains an epoxy resin having two functional groups.
  • the above-described epoxy resin having a functional group number of 2 or less is preferably contained in an amount of 5 to 70 parts by mass when the total solid content of the epoxy resin is 100 parts by mass. It is more preferable to contain up to 50 parts by mass.
  • epoxy resin having an aromatic ring with 4 or more functional groups include bisphenol A type epoxy resins and bisphenol F type epoxy resins.
  • resin bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, metaxylenediamine type epoxy resin, etc.
  • Liquid epoxy resin at room temperature bixylenol type Epoxy that is solid at room temperature
  • epoxy resin cresol novolac type epoxy resin
  • trisphenol type epoxy resin naphthol type epoxy resin
  • biphenyl type epoxy resin naphthylene ether type epoxy resin
  • anthracene type epoxy resin tetraphenylethane type epoxy resin, etc.
  • resins include, but are not limited to, resins.
  • epoxy resin having an aromatic ring with 5 functional groups (hereinafter also referred to as pentafunctional epoxy resin), 2,4,6-tris[(4-hydroxyphenyl)methyl]-1,3-benzenediol type epoxy Resin etc. are mentioned.
  • Examples of the epoxy resin having an aromatic ring with 6 or more functional groups include 2,3,6,7,10,11-hexaglycidyloxytriphenylene and the like. However, it is not limited to these.
  • the epoxy resin having an aromatic ring with a functional number of 4 or more may be used alone, or two or more epoxy resins may be used in combination.
  • a tetrafunctional epoxy resin is used. preferably.
  • tetrafunctional epoxy resins tetrafunctional epoxy resins that are liquid at room temperature are preferred from the viewpoint of the balance between filling properties (printability) and crack resistance.
  • tetrafunctional epoxy resins that are liquid at room temperature meta-xylene diamine type epoxy resins and the like can be preferably used from the viewpoint of heat resistance.
  • the above-mentioned epoxy resin having an aromatic ring with 4 or more functional groups is preferably contained in an amount of 5 to 50 parts by mass when the total solid content of the epoxy resin is 100 parts by mass. It is more preferable to contain up to 40 parts by mass.
  • the blending ratio of the epoxy resin having a functional group number of 2 or less and the epoxy resin having a functional group number of 4 or more and having an aromatic ring is preferably 90:10 to 10:90, preferably 90:10 to 20 in terms of solid content. :80, more preferably 90:10 to 40:60.
  • the curable resin composition according to the present invention contains an epoxy resin other than the two types of epoxy resins described above.
  • epoxy resin other than two types of epoxy resins refers to two types of epoxy resins, namely an epoxy resin having a functional group number of 2 or less and an epoxy resin having a functional group number of 4 or more and an aromatic ring.
  • the epoxy resin preferably contains one or more difunctional epoxy resins, one or more tetrafunctional aromatic ring-containing epoxy resins, and one or more trifunctional epoxy resins.
  • trifunctional epoxy resins include, but are not limited to, triazine skeleton-containing epoxy resins, aminophenol-type epoxy resins, aminocresol-type epoxy resins, triphenylglycidyl ether methane-type epoxy resins, and the like. Only one of these trifunctional epoxy resins may be used, or two or more epoxy resins may be used in combination.
  • the blending ratio is 10 to 50 parts by mass when the total solid content of the epoxy resin is 100 parts by mass, from the viewpoint of printability and heat resistance. Preferably, it is contained in an amount of 20 to 40 parts by mass.
  • the blending amount of the epoxy resin with a functional group number of 2 or less, the epoxy resin with a functional group number of 3, and the epoxy resin with a functional group number of 4 or more and an aromatic ring is 80 to 80 in terms of solid content. It is preferably 10:10-45:10-45, more preferably 70-10:15-45:15-45.
  • an epoxy resin having no aromatic ring and having a functional group number of 4 or more may be included.
  • these epoxy resins include alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, epoxy resins having a butadiene structure, dicyclopentadiene-type epoxy resins, and dipentaerythritol hexaglycidyl. ether, sorbitol hexaglycidyl ether and the like.
  • the total solid content of the epoxy resin is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, based on the total solid content of the curable resin composition.
  • the epoxy resin used in the present invention is preferably liquid rather than solid.
  • the viscosity of the epoxy resin is preferably 20 Pa ⁇ s or less, more preferably 10 Pa ⁇ s or less, and even more preferably 5 Pa ⁇ s or less.
  • the viscosity here is JIS K8803: 25 using a cone-plate viscometer (manufactured by Toki Sangyo Co., Ltd., TV-33H) in accordance with the viscosity measurement method using a 10 cone-plate rotation viscometer of 2011. It refers to the viscosity measured at ⁇ 1°C, 5 rpm, 30 seconds value.
  • the epoxy resin curing agent can be used without any particular limitation as long as it has the effect of accelerating the curing reaction of the epoxy resin.
  • Amines include dicyandiamide, diaminodiphenylmethane, and the like.
  • Examples of imidazoles include alkyl-substituted imidazoles and benzimidazoles.
  • the imidazole compound may also be an imidazole latent curing agent such as an imidazole adduct.
  • polyfunctional phenols examples include hydroquinone, resorcinol, bisphenol A and their halogen compounds, and condensates of these with aldehydes such as novolak and resole resins.
  • Acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, benzophenonetetracarboxylic acid and the like.
  • Isocyanates include tolylene diisocyanate, isophorone diisocyanate, and the like, and these isocyanates may be used after being masked with phenols or the like.
  • One type of these curing agents may be used alone, or two or more types may be used in combination.
  • amines and imidazoles can be preferably used from the viewpoint of adhesion to the conductive portion and the insulating portion, storage stability, and heat resistance.
  • Adduct compounds of aliphatic polyamines such as alkylenediamines having 2 to 6 carbon atoms, polyalkylenepolyamines having 2 to 6 carbon atoms, and aromatic ring-containing aliphatic polyamines having 8 to 15 carbon atoms, or isophoronediamine, 1,3-bis
  • the main component is an alicyclic polyamine adduct compound such as (aminomethyl)cyclohexane, or a mixture of the above aliphatic polyamine adduct compound and the above alicyclic polyamine adduct compound.
  • adduct compound of the aliphatic polyamine those obtained by subjecting the aliphatic polyamine to addition reaction with aryl glycidyl ether (especially phenyl glycidyl ether or tolyl glycidyl ether) or alkyl glycidyl ether are preferable.
  • aryl glycidyl ether especially phenyl glycidyl ether or tolyl glycidyl ether
  • alkyl glycidyl ether alkyl glycidyl ether
  • adduct compound of the alicyclic polyamine those obtained by subjecting the alicyclic polyamine to addition reaction with n-butyl glycidyl ether, bisphenol A diglycidyl ether or the like are preferable.
  • Aliphatic polyamines include alkylenediamines having 2 to 6 carbon atoms such as ethylenediamine and propylenediamine, polyalkylenepolyamines having 2 to 6 carbon atoms such as diethylenetriamine and triethylenetriamine, and aromatic ring-containing fats having 8 to 15 carbon atoms such as xylylenediamine. group polyamines.
  • Examples of commercially available modified aliphatic polyamines include Fujicure FXE-1000, Fujicure FXR-1020, Fujicure FXR-1030, Fujicure FXR-1080, Fujicure FXR-1090M2 (manufactured by T&K TOKA Co., Ltd.), Ancamine 2089K, and Sunmide P. -117, Sunmide X-4150, Ancamine 2422, Serwet R, Sunmide TX-3000, Sunmide A-100 (manufactured by Evonik Japan Co., Ltd.) and the like.
  • alicyclic polyamines examples include isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, and lalomine.
  • modified alicyclic polyamines include, for example, Ancamine 1618, Ancamine 2074, Ancamine 2596, Ancamine 2199, Sunmide IM-544, Sunmide I-544, Ancamine 2075, Ancamine 2280, Ancamine 1934, and Ancamine 2228 (Evonik Japan Co., Ltd.).
  • EH-5015S manufactured by ADEKA Co., Ltd.
  • EH-5015S can be mentioned as a polyamine-type curing agent.
  • imidazoles include reaction products of epoxy resin and imidazole.
  • Examples of commercially available imidazole compounds include imidazoles such as 2E4MZ, C11Z, C17Z, and 2PZ, imidazole AZINE compounds such as 2MZ-A and 2E4MZ-A, and imidazoles such as 2MZ-OK and 2PZ-OK. and imidazole hydroxymethyl compounds such as isocyanurate of 2PHZ and 2P4MHZ (all of which are manufactured by Shikoku Kasei Kogyo Co., Ltd.).
  • Examples of commercially available imidazole-type latent curing agents include Cure Duct P-0505 (manufactured by Shikoku Kasei Kogyo Co., Ltd.).
  • the amount of the above curing agent is preferably 1 to 100 parts by mass, more preferably 2 to 30 parts by mass, when the total solid content of the epoxy resin (A) is 100 parts by mass. It is more preferably 3 to 20 parts by mass.
  • the pre-curing speed of the resin composition generally does not slow down, and as a result, the composition in the deep part of the hole is sufficiently cured, resulting in the occurrence of cracks.
  • the amount of the (B) epoxy resin curing agent is 50 parts by mass or less, the storage stability is improved, and generally the pre-curing speed of the resin composition does not become too fast, making it difficult for voids to remain in the cured product. Therefore, it is preferable.
  • the inorganic filler includes an inorganic filler for stress relaxation due to curing shrinkage of the filler and adjustment of the coefficient of linear expansion.
  • known inorganic fillers used in ordinary resin compositions can be used. Specifically, non-metals such as silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, talc, and organic bentonite. Examples include fillers and metal fillers such as copper, gold, silver, palladium, silicon, alloys, and ferrite. One type of these inorganic fillers may be used alone, or two or more types may be used in combination.
  • silica is more preferably used.
  • Silica may be amorphous, crystalline, or a mixture thereof. Amorphous (fused) silica is particularly preferred.
  • the shape of the inorganic filler is not particularly limited, and includes spherical, needle-like, plate-like, scale-like, hollow, irregular, hexagonal, cubic, and flaky shapes.
  • a spherical shape is preferable from the point of view.
  • the average particle size of these inorganic fillers is preferably 0.1 ⁇ m to 25 ⁇ m, preferably 0.1 ⁇ m to 25 ⁇ m, taking into account the dispersibility of the inorganic filler, the ability to fill holes, and the smoothness when a wiring layer is formed in the filled portion.
  • a range of 0.1 ⁇ m to 15 ⁇ m is suitable. More preferably, it is 1 ⁇ m to 10 ⁇ m.
  • the average particle size means the average primary particle size, and the average particle size (D50) can be measured by a laser diffraction/scattering method.
  • the blending ratio of the inorganic filler is 10% with respect to the total solid content of the curable resin composition, from the viewpoint of achieving both the thermal expansion coefficient, polishability, and adhesiveness of the cured product, as well as printability and hole-filling properties. It is preferably up to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 40 to 75% by mass.
  • the curable resin composition of the present invention may contain, as a curable component, a curable resin other than the epoxy resins described above, such as isocyanate compounds, blocked isocyanate compounds, amino resins, carbodiimide resins, cyclocarbonate compounds, Oxetane compounds, episulfide resins, urea resins, resins with triazine rings such as melamine resins, unsaturated polyester resins, maleimide resins such as bismaleimide compounds, polyurethane resins, diallyl phthalate resins, benzoxazine resins, polyimide resins, polyamides Imide resin, benzocyclobutene resin, novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, cyanate ester resin such as bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin, silicone resin etc. things are mentioned. These can be used alone or in combination of two or more
  • a filler treated with a fatty acid or an amorphous filler such as organic bentonite or talc can be added to impart thixotropy.
  • the above fatty acid has the general formula: (R 1 COO) n —R 2 (substituent R 1 is a hydrocarbon having 5 or more carbon atoms, substituent R 2 is hydrogen, a metal alkoxide, or a metal, and n is 1 to 4) can be used.
  • the fatty acid can exhibit the effect of imparting thixotropy when the substituent R 1 has 5 or more carbon atoms. More preferably, n is 7 or more.
  • the fatty acid may be an unsaturated fatty acid that has a double bond or triple bond in the carbon chain, or a saturated fatty acid that does not contain them.
  • stearic acid the number of carbon atoms and the number of unsaturated bonds and the numbers in parentheses are represented by their positions. 18: 0), hexanoic acid (6: 0), oleic acid (18: 1 (9)), icosane acid (20:0), docosanoic acid (22:0), melissic acid (30:0) and the like.
  • the substituent R1 of these fatty acids preferably has 5 to 30 carbon atoms. More preferably, it has 5 to 20 carbon atoms.
  • a skeleton having a coupling agent-based structure and a long (having 5 or more carbon atoms) aliphatic chain such as a metal alkoxide in which the substituent R2 is a titanate-based substituent capped with an alkoxyl group.
  • a metal alkoxide in which the substituent R2 is a titanate-based substituent capped with an alkoxyl group there may be.
  • the product name KR-TTS manufactured by Ajinomoto Fine-Techno Co., Inc.
  • metallic soaps such as aluminum stearate and barium stearate (each manufactured by Kawamura Kasei Co., Ltd.) can be used.
  • Other metal soap elements include Ca, Zn, Li, Mg and Na.
  • the blending ratio of the fatty acid is 0.1 to 2 parts by mass with respect to 100 parts by mass of the inorganic filler from the viewpoint of thixotropy, embedding, antifoaming, etc. Proportion is appropriate.
  • the fatty acid may be incorporated by using an inorganic filler that has been surface-treated with a fatty acid in advance, making it possible to more effectively impart thixotropy to the curable resin composition.
  • the blending ratio of the fatty acid can be lower than when the untreated filler is used. It is preferably 1 to 1 part by mass.
  • the curable resin composition of the present invention may contain a silane coupling agent.
  • a silane-based coupling agent By adding a silane-based coupling agent, it is possible to improve the adhesion between the inorganic filler and the epoxy resin and suppress the occurrence of cracks in the cured product.
  • silane-based coupling agents examples include epoxysilane, vinylsilane, imidazolesilane, mercaptosilane, methacryloxysilane, aminosilane, styrylsilane, isocyanatesilane, sulfidesilane, and ureidosilane.
  • the silane coupling agent may be blended by using an inorganic filler that has been surface-treated with a silane coupling agent in advance.
  • the mixing ratio of the silane coupling agent is 100% of the inorganic filler from the viewpoint of achieving both adhesion and defoaming properties between the inorganic filler and the epoxy resin. It is preferably 0.05 to 2.5 parts by weight per part by weight.
  • the curable resin composition of the present invention may optionally contain an oxazine compound having an oxazine ring obtained by reacting a phenol compound, formalin and a primary amine.
  • an oxazine compound having an oxazine ring obtained by reacting a phenol compound, formalin and a primary amine.
  • phthalocyanine blue phthalocyanine blue
  • phthalocyanine green disazo yellow
  • titanium oxide titanium oxide
  • carbon black carbon black
  • naphthalene black naphthalene black
  • thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, and phenothiazine for imparting storage stability during storage, and clay, kaolin, and the like for viscosity adjustment.
  • known thickeners and thixotropic agents such as organic bentonite and montmorillonite can be added.
  • known additives such as silicone-based, fluorine-based, polymer-based antifoaming agents, leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agents, and other adhesive agents are added. be able to.
  • the portion protruding from the surface of the hole portion is easily formed into a protruding state that is easy to polish and remove, and is excellent in polishability, which is preferable.
  • known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc., can also be blended.
  • the curable resin composition of the present invention when a liquid epoxy resin is mainly included as the epoxy resin, it is not always necessary to use a diluent solvent, but voids are generated in order to adjust the viscosity of the curable resin composition.
  • a diluent solvent may be added to the extent that it does not
  • Diluent solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol mono Glycol ethers such as ethyl ether and triethylene glycol monoethyl ether; Esters such as ethyl acetate, butyl acetate, and acetic esters of the above glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Octane , aliphatic hydrocarbons such as decane; and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.
  • ketones such as methyl ethyl ketone
  • the curable resin composition according to the present invention can be used widely and generally, but it is preferably used for forming a cured film of a printed wiring board, more preferably for forming a permanent protective film, and is used for soldering. More preferably, it is used as a resist, an interlayer insulating layer, a coverlay, or a filler (material) for filling holes. Among these uses, it is particularly preferable to use it as a filling material for filling holes, specifically, as a filling material for filling through holes such as through holes of printed wiring boards and recesses.
  • the filling material is formed using a known patterning method such as a screen printing method, a roll coating method, a die coating method, and a vacuum printing method, for example, a multilayer printed wiring board. through-holes and recesses with bottoms.
  • the inner diameter of the hole or recess to be filled with the curable resin composition is not particularly limited, but it is 0.05 to 0.8 mm for package substrates such as IC substrates, server substrates, vehicle-mounted substrates, and the like. and the depth is 0.4 to 10 mm.
  • the curable resin composition is completely filled so as to protrude slightly from the holes and recesses.
  • the curable resin composition of the present invention preferably has a viscosity at 25 ⁇ 1° C. in the range of 100 to 1000 dPa s, more preferably 200 to 800 dPa s, more preferably 200 to 600 dPa s. s is particularly preferred. With such a range, the holes can be easily filled, and the concave portions and the through holes can be satisfactorily filled without generating voids or the like.
  • the viscosity here is based on JIS K8803: 2011 10 cone-plate type rotational viscometer viscosity measurement method, using a cone plate type viscometer (manufactured by Toki Sangyo Co., Ltd., TV-33H) It refers to the viscosity measured at 25°C, 5 rpm, 30 seconds value.
  • the curable resin composition By heating the multilayer printed wiring board in which the holes and recesses are filled with the curable resin composition, for example, at 80 to 160 ° C. for about 30 to 180 minutes, the curable resin composition is cured and a cured product is formed. .
  • the curing of the curable resin composition may be carried out in two stages from the viewpoint of easily removing unnecessary portions protruding from the surface of the substrate after filling the holes in the cured product by physical polishing. That is, the curable resin composition can be pre-cured at a lower temperature and then subjected to main curing (finish curing). Heating at 80 to 110° C. for about 30 to 180 minutes is preferable as the condition for pre-curing.
  • the hardness of the pre-cured cured product is relatively low, the unnecessary portion protruding from the substrate surface can be easily removed by physical polishing, and the surface can be flattened. After that, it is heated to be fully cured. Heating at 130 to 180° C. for about 30 to 180 minutes is preferable as the condition for main curing.
  • a hot air circulation drying oven for both pre-curing and main curing, a hot air circulation drying oven, IR oven, hot plate, convection oven, etc. (equipped with a steam air heating type heat source) is used to heat the dryer in the countercurrent direction.
  • a contact method and a method of spraying onto the material to be cured from a nozzle) can be used.
  • a hot air circulation drying furnace is particularly preferable.
  • the cured product hardly expands or contracts due to its low expansibility, and the final cured product is excellent in dimensional stability, low hygroscopicity, adhesion, electrical insulation and the like.
  • the hardness of the pre-cured product can be controlled by changing the heating time and heating temperature for pre-curing.
  • a predetermined circuit pattern is formed by patterning into a predetermined pattern. If necessary, the surface of the cured product may be roughened with an aqueous solution of potassium permanganate or the like, and then a wiring layer may be formed on the cured product by electroless plating or the like.
  • the density (D1) of the curable resin composition was measured by a pycnometer method using a 100 cm 3 capacity metal pycnometer ( Measured according to JIS K5600-2-4:2014).
  • volume shrinkage rate (%) (D2-D1)/D2 x 100
  • the calculated volumetric shrinkage was as shown in Table 1 below.
  • ⁇ Preparation of evaluation board> Screen printing from one side of a glass epoxy substrate (thickness 1.6 mm with through-holes with conductor layers formed by panel plating/through-hole diameter 0.15 mm (after plating)/pitch 1 mm glass epoxy substrate) , the curable resin compositions of Examples and Comparative Examples were filled in the through-holes under the following printing conditions. After filling, the curable resin composition was cured by heating at 110° C. for 30 minutes and then heating at 150° C. for 60 minutes in a hot air circulating drying oven to obtain an evaluation substrate.
  • the obtained measurement sample was subjected to TMA measurement using a thermomechanical analyzer (TMA Q400, manufactured by TA Instruments Japan Co., Ltd.).
  • TMA Q400 thermomechanical analyzer
  • a test load of 5 g was applied, and the temperature of the sample was increased from room temperature to 300°C at a heating rate of 10°C/min, and the measurement was continuously performed twice.
  • the intersection point of two tangent lines with different coefficients of thermal expansion in the second time was defined as the glass transition temperature (Tg).
  • Tg glass transition temperature
  • CTE coefficient of thermal expansion CTE
  • Tg glass transition temperature
  • CTE ( ⁇ 1) is less than 20 ppm ⁇ : CTE ( ⁇ 1) is 20 ppm or more and less than 30 ppm ⁇ : CTE ( ⁇ 1) is 30 ppm or more and less than 40 ppm ⁇ : CTE ( ⁇ 1) is 40 ppm or more
  • the evaluation results are shown in Table 1 below. It was true.
  • the surface of the obtained laminated substrate was subjected to roughening treatment (*1), electroless copper plating treatment (*2), and electrolytic copper plating treatment (*3) in the following order. Then, an annealing treatment was performed at 180° C. for 60 minutes in a hot air circulating drying oven to obtain a test substrate for adhesion evaluation.
  • Electroless copper plating (Thrucup PEA, manufactured by Uyemura & Co., Ltd.) was performed on the roughened resin laminated substrate.
  • the thickness of the formed electroless copper plating layer was approximately 1 ⁇ m.
  • Electrolytic copper plating treatment (*3) After heating the resin laminated substrate on which the electroless copper plating layer is formed for 30 minutes at 150° C., copper sulfate electroplating is performed in the following steps to form an electroless copper plating layer with a thickness of 25 ⁇ m on the resin layer. bottom.
  • a cut of 10 mm in width and 60 mm in length was made in the copper plating layer of the test board obtained as described above (Preparation of test board for adhesion evaluation), and one end was peeled off and pinched with a gripper, Peel strength (N/cm ) was measured.
  • the evaluation criteria for adhesion to copper plating were as follows. ⁇ : Peel strength is 5.0 or more ⁇ : Peel strength is 4.0 or more and less than 5.0 ⁇ : Peel strength is 3.0 or more and less than 4.0 ⁇ : Peel strength is less than 3.0
  • the evaluation results are shown in the table below. 1 as shown.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine durcissable qui a un CTE très faible et est excellente en termes de résistance à la chaleur et à la fissuration et de propriété de remplissage et d'adhésivité à des platine en cuivre. Cette composition de résine durcissable comprend (A) des résines époxy, (B) un durcisseur de résine époxy, et (C) une charge inorganique, les résines époxy (A) comprenant au moins trois résines époxy différentes en termes de nombre de groupes fonctionnels ou de structure squelettique moléculaire, les trois résines époxy comprenant au moins une résine époxy contenant jusqu'à deux groupes fonctionnels et une résine époxy comprenant quatre cycles aromatiques ou plus.
PCT/JP2022/048510 2022-01-07 2022-12-28 Composition de résine durcissable WO2023132317A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015007214A (ja) * 2013-05-27 2015-01-15 Dic株式会社 硬化性樹脂組成物、その硬化物および熱伝導性接着剤
JP2019038930A (ja) * 2017-08-24 2019-03-14 味の素株式会社 樹脂組成物
JP2019052278A (ja) * 2017-09-19 2019-04-04 三菱ケミカル株式会社 エポキシ樹脂、エポキシ樹脂組成物、硬化物、及び電気・電子回路用積層板
JP2021512199A (ja) * 2018-02-01 2021-05-13 ヘクセル コーポレイション 高温及び湿潤条件に耐える複合部品の製造に使用するプリプレグ
WO2021177089A1 (fr) * 2020-03-06 2021-09-10 東レ株式会社 Composition de résine epoxyde, préimprégné et matériau composite renforcé par des fibres
JP2021531389A (ja) * 2018-07-25 2021-11-18 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング 高速硬化エポキシアクリル液体シム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015007214A (ja) * 2013-05-27 2015-01-15 Dic株式会社 硬化性樹脂組成物、その硬化物および熱伝導性接着剤
JP2019038930A (ja) * 2017-08-24 2019-03-14 味の素株式会社 樹脂組成物
JP2019052278A (ja) * 2017-09-19 2019-04-04 三菱ケミカル株式会社 エポキシ樹脂、エポキシ樹脂組成物、硬化物、及び電気・電子回路用積層板
JP2021512199A (ja) * 2018-02-01 2021-05-13 ヘクセル コーポレイション 高温及び湿潤条件に耐える複合部品の製造に使用するプリプレグ
JP2021531389A (ja) * 2018-07-25 2021-11-18 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング 高速硬化エポキシアクリル液体シム
WO2021177089A1 (fr) * 2020-03-06 2021-09-10 東レ株式会社 Composition de résine epoxyde, préimprégné et matériau composite renforcé par des fibres

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