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WO2016017751A1 - Composition de résine époxy, feuille de résine, pré-imprégné, carte stratifiée gainée de métal, carte de circuit imprimé et dispositif à semi-conducteur - Google Patents

Composition de résine époxy, feuille de résine, pré-imprégné, carte stratifiée gainée de métal, carte de circuit imprimé et dispositif à semi-conducteur Download PDF

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Publication number
WO2016017751A1
WO2016017751A1 PCT/JP2015/071632 JP2015071632W WO2016017751A1 WO 2016017751 A1 WO2016017751 A1 WO 2016017751A1 JP 2015071632 W JP2015071632 W JP 2015071632W WO 2016017751 A1 WO2016017751 A1 WO 2016017751A1
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WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
prepreg
metal
glass
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2015/071632
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English (en)
Japanese (ja)
Inventor
政隆 中西
篤彦 長谷川
一真 井上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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.)
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Priority to KR1020167032745A priority Critical patent/KR102316144B1/ko
Priority to CN201580037762.1A priority patent/CN106661200B/zh
Publication of WO2016017751A1 publication Critical patent/WO2016017751A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to an epoxy resin composition that gives a cured product excellent in heat resistance and water resistance, a prepreg impregnated with a fiber base material, a resin sheet, a metal-clad laminate, a printed wiring board, and a semiconductor device.
  • Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.
  • Patent Document 1 discloses a phenol novolac resin having a biphenyl skeleton and a phenol novolac type epoxy resin obtained by epoxidizing the phenol novolak resin, and describes its usefulness for use as a semiconductor encapsulant.
  • this epoxy resin combines high heat resistance and flame retardancy in combination with a phenol resin, there is a problem in using it for electronic materials that have high water absorption and require extremely high reliability.
  • there is no description about the characteristics of the composition containing these epoxy resins and amine-based curing agents and there is no description on the usefulness of the printed wiring board.
  • the present invention has been made as a result of studies to solve such problems.
  • the cured product has high heat resistance, water absorption, low dielectric constant, and prepreg and resin sheet using the epoxy resin composition.
  • An object is to provide a metal-clad laminate, a printed wiring board, and a semiconductor device.
  • the present invention provides (1) the following general formula (1)
  • An epoxy resin composition comprising an epoxy resin and an amine curing agent as essential components, (2) A prepreg obtained by impregnating a fiber base material with the epoxy resin composition according to item (1), (3) The prepreg according to (2) above, wherein the fiber base material is a glass fiber base material, (4) The prepreg according to (3) above, wherein the glass fiber base material includes at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass.
  • the epoxy resin composition of the present invention provides a cured product that can simultaneously achieve high heat resistance and water resistance in the cured product, it is extremely useful for producing laminated boards such as printed wiring boards and build-up boards.
  • Material According to the present invention, an epoxy resin composition whose cured product has high heat resistance, water absorption and low dielectric constant, and a prepreg, a resin sheet, a metal-clad laminate, a printed wiring board, and a semiconductor device using the epoxy resin composition. Can be provided.
  • the epoxy resin composition of the present invention comprises, as an essential component, a compound represented by the following formula (1) (hereinafter referred to as “epoxy resin of formula (1)”) and an amine curing agent as an epoxy resin.
  • the softening point (ring and ball method) of the epoxy resin used is preferably 50 to 150 ° C., more preferably 52 to 100 ° C., and particularly preferably 52 to 95 ° C. Below 50 ° C., stickiness is severe, handling is difficult, and problems may arise in productivity. Moreover, when it is 150 degreeC or more, since it is a temperature near molding temperature and the fluidity
  • the epoxy equivalent of the epoxy resin used is 180 to 350 g / eq. It is preferable that In particular, 190 to 300 g / eq. It is preferable that Epoxy equivalent is 180 g / eq. When the ratio is less than 1, since the functional group is too many, the cured product after curing tends to have a high water absorption rate and may become brittle. Epoxy equivalent is 350 g / eq. If it exceeds 1, the softening point becomes very large or epoxidation has not progressed cleanly, which is not preferable because the amount of chlorine may become very large.
  • the chlorine content of the epoxy resin used in the present invention is preferably 200 to 1500 ppm, particularly preferably 200 to 900 ppm in terms of total chlorine (hydrolysis method). From the JPCA standard, it is desired that epoxy alone does not exceed 900 ppm. Furthermore, a large amount of chlorine is not preferable because it may affect the electrical reliability. When it is less than 200 ppm, an excessive purification step is required, which may cause problems in productivity, which is not preferable.
  • the melt viscosity at 150 ° C. of the epoxy resin used in the present invention is preferably 0.05 to 5 Pa ⁇ s, particularly preferably 0.05 to 2.0 Pa ⁇ s.
  • the melt viscosity is higher than 5 Pa ⁇ s, there is a problem in fluidity, and there may be a problem in flow property and embedding property during pressing.
  • it is less than 0.05 Pa ⁇ s, the molecular weight is too small, and the heat resistance may be insufficient.
  • n is a repeating unit and is 0-5. When n does not exceed 5, the flowability and fluidity of the prepreg or resin sheet are controlled.
  • solubility in a solvent is important.
  • solvents such as methyl ethyl ketone, toluene, propylene glycol monomethyl ether and the like.
  • solubility in methyl ethyl ketone is particularly important, and it is required that crystals do not precipitate for 2 months or more at 5 ° C., room temperature or the like.
  • the epoxy resin composition of the present invention contains an amine curing agent as an essential component.
  • amine curing agents that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline and substituted biphenyls (4,4′-bis (chloromethyl) -1,1 ′).
  • Particularly preferred amine-based curing agents are bifunctional or higher amine compounds, and resins having a structure represented by the following formula are preferred.
  • n is the number of repetitions and is 1 to 10.
  • each of the amine curing agents used in the present invention exhibits a crystal or resin shape.
  • the melting point is preferably 35 to 200 ° C., particularly preferably 40 to 185 ° C.
  • the solubility in other resins is also involved, and therefore it is not always necessary that the temperature be lower than the molding temperature like a resin.
  • a softening point (ring and ball method) of 50 to 150 ° C. is preferable, and 50 to 100 ° C. is particularly preferable.
  • those with a softening point of 50 ° C. or lower are not preferable because stickiness may occur, and when the softening point exceeds 150 ° C., fluidity problems occur at the time of molding, and it cannot be molded cleanly. In addition, there may be a problem that the solvent cannot be removed.
  • the functional group equivalent of the amine compound is 60 to 600 g / eq. (Measurement by potentiometric titration) is preferred.
  • the active hydrogen equivalent is 60 or less, the cured product may have problems with water absorption and toughness. If it exceeds 600, it may be difficult to maintain heat resistance.
  • the amount of the amine curing agent used is preferably 0.2 to 0.6 equivalent in terms of amine equivalent of the amine compound with respect to 1 equivalent of epoxy group of the epoxy resin. Particularly preferred is 0.3 to 0.55 equivalent. When less than 0.2 equivalent or more than 0.6 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured physical properties may not be obtained.
  • the epoxy resin composition of the present invention may contain a curing accelerator.
  • curing accelerators that can be used include formic acid, acetic acid, lactic acid, glycolic acid, n-butyric acid, iso-butyric acid, propionic acid, caproic acid, octanoic acid, n-heptylic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, Thioglycolic acid, phenol, m-cresol, p-chlorophenol, p-nitrophenol, 2,4-dinitrophenol, o-aminophenol, p-aminophenol, 2,4,5-trichlorophenol, resorcinol, hydroquinone, Catechol, phloroglicinol, benzoic acid, p-toluic acid, p-aminobenzoic acid, p-chlorobenzoic acid, 2,4-dichlorobenzoic acid, salicylic acid,
  • epoxy resin composition of the present invention other epoxy resins can be used in combination.
  • other epoxy resins that can be used in combination with the epoxy resin of formula (1) include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl-substituted phenol, aromatic Group-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde) , Crotonaldehyde, cinnamalde
  • a conventionally known curing agent can be used in combination.
  • other curing agents that can be used in combination include acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds.
  • specific examples of curing agents that can be used include amide compounds such as polyamide resins synthesized from dimers of dicyandiamide and linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, Acid anhydride compounds such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-
  • the epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component.
  • the phosphorus-containing compound may be a reactive type or an additive type.
  • Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid ester compounds such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9- Phosphanes such as oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-
  • Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylyl) is preferable. Renyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
  • the amount of the phosphoric acid ester compound as described above is preferably phosphoric acid ester compound / epoxy resin ⁇ 0.1 (weight ratio) due to environmental problems and concerns about electrical characteristics. More preferably, it is 0.05 or less. It is particularly preferable not to add a phosphorus compound except that it is added as a curing accelerator.
  • the epoxy resin composition of the present invention may contain an inorganic filler.
  • Inorganic fillers include fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, titanium oxide, aluminum nitride, silicon nitride, and nitride Examples thereof include boron, mica, glass, quartz, and mica. Further, it is also preferable to use a metal hydroxide such as magnesium hydroxide or aluminum hydroxide in order to impart a flame retardant effect. However, it is not limited to these. Two or more kinds may be mixed and used.
  • the amount of the inorganic filler used is usually 5% to 70% by weight, preferably 10% to 60% by weight, more preferably 15% to 60% by weight. It is a range. If the amount is too small, the linear expansion increases, warping becomes a problem, and the substrate is becoming thinner, so that rigidity may not be achieved and a problem may occur during the process.
  • the shape, particle size and the like of the inorganic filler are not particularly limited, but usually the particle size is 0.01 to 50 ⁇ m, preferably 0.1 to 15 ⁇ m.
  • a release agent can be blended to improve the release from the mold during molding.
  • Any conventionally known release agent can be used, for example, ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid, and metal salts thereof, polyolefins such as polyethylene oxide and non-oxidized polyethylene And waxes. These may be used alone or in combination of two or more.
  • the compounding amount of these release agents is preferably 0.5 to 3% by weight based on the total organic components. If the amount is too small, release from the mold is poor, and if the amount is too large, adhesion to the substrate or the like may be deteriorated.
  • a coupling agent can be blended in order to enhance the adhesion between the inorganic filler and the resin component.
  • Any conventionally known coupling agent can be used.
  • examples include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more.
  • the coupling agent may be added by treating the surface of the inorganic filler with the coupling agent in advance and then kneading with the resin, or mixing the coupling agent with the resin and then kneading the inorganic filler. .
  • varnish-like composition An organic solvent can be added to the epoxy resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish).
  • the solvent used include amide solvents such as ⁇ -butyrolactone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and tetramethylene sulfone.
  • ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone
  • Aromatic solvents such as solvent, toluene, xylene and the like can be mentioned.
  • the solvent is used in the range where the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight.
  • additives can be blended in the epoxy resin composition of the present invention as necessary.
  • additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, and silicone oil.
  • colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
  • the resin sheet of the present invention will be described.
  • the resin sheet using the epoxy resin composition of the present invention has a thickness after drying the above varnish on a planar support by various coating methods such as gravure coating, screen printing, metal mask, and spin coating. Can be obtained by drying after coating so that the thickness becomes a predetermined thickness, for example, 5 to 100 ⁇ m. Which coating method is used depends on the type, shape, size, thickness of coating, support It is appropriately selected depending on the heat resistance of the body.
  • planar support examples include various types such as polyamide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetherketone, polyetherimide, polyetheretherketone, polyketone, polyethylene, polypropylene, and Teflon (registered trademark).
  • examples thereof include films made from molecules and / or copolymers thereof, and metal foils such as copper foils. After application, it can be dried to obtain a sheet-like composition (resin sheet of the present invention), but it can also be made into a sheet-like cured product by further heating the sheet. Moreover, you may serve as a solvent drying and hardening process by one heating.
  • the epoxy resin composition of the present invention can form a cured product layer on both sides or one side of the support by coating and heating on both sides or one side of the support by the above method. It is also possible to produce a laminate by bonding and adhering the adherend before curing. Moreover, the resin sheet of this invention can also be used as an adhesive sheet by peeling off from a support body, and it can also be made to contact with a to-be-adhered body and to apply pressure and heat as needed, and to make it adhere
  • the prepreg of the present invention will be described.
  • the prepreg of the present invention is obtained by impregnating a fiber base material with the epoxy resin composition of the present invention.
  • the fiber base material include glass fiber base materials such as glass woven fabric, glass non-woven fabric, and glass paper, paper, aramid, polyester, aromatic polyester, and synthetic fibers such as fluororesin, etc.
  • glass fiber base materials such as glass woven fabric, glass non-woven fabric, and glass paper, paper, aramid, polyester, aromatic polyester, and synthetic fibers such as fluororesin, etc.
  • Examples thereof include woven fabrics, nonwoven fabrics, mats and the like made of fibers, carbon fibers, mineral fibers and the like. These substrates may be used alone or in combination.
  • a glass fiber base material is preferable. Thereby, the rigidity and dimensional stability of the prepreg can be further improved.
  • As a glass fiber base material what contains at least 1 type chosen from the group which consists of T glass, S glass, E glass, NE
  • Examples of the method of impregnating the fiber base material with the epoxy resin composition of the present invention include a method of immersing the base material in a resin varnish, a method of applying with various coaters, and a method of spraying.
  • the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved.
  • a normal impregnation coating equipment can be used.
  • the epoxy resin composition of the present invention is used as it is or in the form of a varnish dissolved or dispersed in a solvent, after impregnating a substrate such as a glass cloth, usually in a drying furnace or the like, usually at 80 to 200 ° C. (however, When the solvent is used, the temperature is set to a temperature at which the solvent can be volatilized or higher), and the prepreg is obtained by drying for 2 to 30 minutes, preferably 2 to 15 minutes.
  • the metal-clad laminate of the present invention will be described.
  • the laminate used in the present invention is formed by heating and pressing the above-described prepreg of the present invention. Thereby, the metal-clad laminated board excellent in heat resistance, low expansibility, and a flame retardance can be obtained.
  • the metal foil is overlapped on both the upper and lower surfaces or one surface.
  • Two or more prepregs can be laminated.
  • a metal foil or film is laminated on the outermost upper and lower surfaces or one surface of the laminated prepreg.
  • a metal-clad laminate can be obtained by heat-pressing a laminate of a prepreg and a metal foil.
  • the heating temperature is not particularly limited, but is preferably 120 to 220 ° C, and particularly preferably 150 to 200 ° C.
  • the pressure to be pressurized is not particularly limited, but is preferably 1.5 to 5 MPa, and particularly preferably 2 to 4 MPa. If necessary, post-curing may be performed at a temperature of 150 to 300 ° C. with a high-temperature iron or the like.
  • the printed wiring board of the present invention uses the metal-clad laminate of the present invention as an inner circuit board.
  • a circuit is formed on one or both sides of the metal-clad laminate.
  • through holes can be formed by drilling or laser processing, and electrical connection on both sides can be achieved by plating or the like.
  • a commercially available or resin sheet of the present invention, or the prepreg of the present invention is superposed on the inner layer circuit board and heated and pressed to obtain a multilayer printed wiring board.
  • the insulating layer side of the resin sheet and the inner layer circuit board are combined, vacuum-pressed using a vacuum pressurizing laminator, etc., and then the insulating layer is heated and cured with a hot air dryer or the like.
  • the conditions for heat and pressure molding are not particularly limited, but as an example, it can be carried out at a temperature of 60 to 160 ° C. and a pressure of 0.2 to 3 MPa.
  • the conditions for heat curing are not particularly limited, but for example, the temperature can be 140 to 240 ° C.
  • the time can be 30 to 120 minutes.
  • it can be obtained by overlaying the prepreg of the present invention on an inner circuit board and subjecting it to hot press molding using a flat plate press or the like.
  • the conditions for heat and pressure molding are not particularly limited, but as an example, it can be carried out at a temperature of 140 to 240 ° C. and a pressure of 1 to 4 MPa.
  • the insulating layer is heat-cured simultaneously with the heat and pressure forming.
  • the method for producing a multilayer printed wiring board according to the present invention includes a step of continuously laminating the resin sheet or the prepreg of the present invention on a surface on which an inner layer circuit pattern of the inner layer circuit board is formed, and a conductor circuit Forming a layer by a semi-additive process.
  • Curing of the resin sheet or the insulating layer formed from the prepreg of the present invention may be left in a semi-cured state in order to facilitate the subsequent laser irradiation and removal of the resin residue and improve desmearability.
  • the first insulating layer is partially cured (semi-cured) by heating at a temperature lower than the normal heating temperature, and one or more insulating layers are further formed on the insulating layer to form a semi-cured insulating layer.
  • the semi-curing temperature is preferably 80 ° C.
  • the inner layer circuit board used when obtaining the multilayer printed wiring board is preferably, for example, one in which a predetermined conductor circuit is formed by etching or the like on both surfaces of a copper clad laminate and the conductor circuit portion is blackened. Can be used.
  • Resin residues after laser irradiation are preferably removed with an oxidizing agent such as permanganate or dichromate. Further, the surface of the smooth insulating layer can be simultaneously roughened, and the adhesion of the conductive wiring circuit formed by subsequent metal plating can be improved.
  • an outer layer circuit is formed.
  • the outer layer circuit is formed by connecting the insulating resin layers by metal plating and forming an outer layer circuit pattern by etching.
  • a multilayer printed wiring board can be obtained in the same manner as when a resin sheet or prepreg is used.
  • a circuit may be formed by etching for use as a conductor circuit without peeling off the metal foil.
  • an ultrathin copper foil of 1 to 5 ⁇ m, or 12 to 18 ⁇ m.
  • the copper foil is half-etched to a thickness of 1 to 5 ⁇ m by etching.
  • an insulating layer may be further laminated and a circuit may be formed in the same manner as described above.
  • a solder resist is formed on the outermost layer after the circuit is formed.
  • the method for forming the solder resist is not particularly limited. For example, a method of laminating (laminating) a dry film type solder resist, forming by exposure and development, or forming a printed liquid resist by exposure and development It is done by the method to do.
  • the electrode part for a connection is provided.
  • the connecting electrode portion can be appropriately coated with a metal film such as gold plating, nickel plating, or solder plating.
  • a multilayer printed wiring board can be manufactured by such a method.
  • a semiconductor element having solder bumps is mounted on the multilayer printed wiring board obtained as described above, and connection to the multilayer printed wiring board is attempted through the solder bumps. Then, a liquid sealing resin is filled between the multilayer printed wiring board and the semiconductor element to form a semiconductor device.
  • the solder bump is preferably made of an alloy made of tin, lead, silver, copper, bismuth or the like.
  • the semiconductor element and multilayer printed wiring board can be connected by aligning the connection electrode part on the substrate with the solder bump of the semiconductor element using a flip chip bonder, etc., and then using an IR reflow device, hot plate, etc.
  • solder bumps are heated to the melting point or higher by using a heating device, and the multilayer printed wiring board and the solder bumps are connected by fusion bonding.
  • a metal layer having a relatively low melting point such as solder paste may be formed in advance on the connection electrode portion on the multilayer printed wiring board.
  • the connection reliability can be improved by applying a flux to the solder bumps and / or the surface layer of the connection electrode portion on the multilayer printed wiring board.
  • a substrate it is used as a motherboard, a network substrate, a package substrate, etc., and used as a substrate.
  • a package substrate it is useful as a thin layer substrate for a single-sided sealing material.
  • semiconductor devices obtained from the blending include DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package). SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package), and the like.
  • the measurement conditions of each physical property value are as follows. Epoxy equivalent Measured by the method described in JIS K-7236, the unit is g / eq. It is. -Softening point Measured by a method according to JIS K-7234, the unit is ° C. -Elastic modulus (DMA) Dynamic viscoelasticity measuring instrument: TA-insRents, DMA-2980 Measurement temperature range: -30 to 280 ° C Temperature increase rate: 2 ° C./min. Test piece size: 5 mm ⁇ 50 mm cut out was used. Tg: Tan- ⁇ peak point in DMA measurement was Tg. Water absorption: disk shape with diameter 5 cm ⁇ thickness 4 mm % Increase after boiling the test piece in 100 ° C water for 24 hours
  • Example 1 The epoxy resin (EP1) obtained in Synthesis Example 1 was treated with A-1 (amine equivalent 198 g / eq, active hydrogen equivalent 97.5 g / eq, softening point 55 ° C.) as a curing agent with respect to 1 molar equivalent of epoxy equivalent.
  • the epoxy resin composition is blended at 0.5 equivalent, and salicylic acid is blended at a ratio (parts by weight) of 1 part by weight with respect to 100 parts by weight of the epoxy resin, and mixed and kneaded uniformly using a mixing roll.
  • This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C.
  • Example 1 the epoxy resin (EP1) obtained in Synthesis Example 1 and various epoxy resins were equivalent to A-1 or HA-1 (phenol novolak resin manufactured by Meiwa Kasei Kogyo Co., Ltd.) as a curing agent.
  • a test piece for evaluation for comparison was obtained by the same composition and method as in Example 1 using triphenylphosphine (TPP) or salicylic acid as a catalyst. The evaluation results are shown in Table 1.
  • Example 1 and Comparative Example 3 are compared, by using an amine curing agent as compared with using a phenol resin as a curing agent, a cured product having excellent heat resistance and water absorption characteristics can be obtained. It was confirmed that
  • FIG. 1 is a graph in which the cured physical properties obtained in Table 1 are plotted with heat resistance (Tg) on the horizontal axis and water absorption characteristics (%) on the vertical axis. From FIG. 1, it can be confirmed that the cured products of Comparative Examples 1 to 3 and Comparative Examples 4 to 7 have a correlation such that the water absorption increases as Tg increases. On the other hand, the cured product using the epoxy resin of formula (1) and the amine curing agent has high heat resistance, but has a low water absorption rate, which is different from the above correlation. It can be confirmed that it is a combination.
  • the epoxy resin composition of the present invention provides a cured product that can simultaneously achieve high heat resistance and water resistance in the cured product, and thus is extremely useful for producing laminated boards such as printed wiring boards and build-up substrates. Material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
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  • Epoxy Resins (AREA)
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Abstract

L'invention concerne une composition de résine époxy qui, lorsqu'elle est durcie, est très résistante à la chaleur, absorbe l'eau et présente une faible constante diélectrique. L'invention concerne également une feuille de résine, une carte stratifiée gainée de métal et une carte de circuit imprimé qui utilisent la composition de résine époxy, et un dispositif à semi-conducteur. La composition de résine époxy contient en tant que composants essentiels une résine époxy qui est représentée par la formule (1) et un agent de durcissement à base d'amine. (Dans la formule, le rapport ((a)/(b)) de (a) et de (b) est compris entre 1 et 3, G représente un groupe glycidyle et n représente le nombre de répétitions et est compris entre 0 et 5. )
PCT/JP2015/071632 2014-08-01 2015-07-30 Composition de résine époxy, feuille de résine, pré-imprégné, carte stratifiée gainée de métal, carte de circuit imprimé et dispositif à semi-conducteur Ceased WO2016017751A1 (fr)

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CN201580037762.1A CN106661200B (zh) 2014-08-01 2015-07-30 环氧树脂组合物、树脂片、预浸料及覆金属层叠板、印刷布线基板、半导体装置

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WO2018174446A1 (fr) * 2017-03-22 2018-09-27 주식회사 엘지화학 Composition de résine pour boîtier de semi-conducteur, préimpregné l'utilisant et plaque stratifiée de feuille métallique
KR20180107709A (ko) * 2017-03-22 2018-10-02 주식회사 엘지화학 반도체 패키지용 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판
CN109661421A (zh) * 2017-03-22 2019-04-19 株式会社Lg化学 用于半导体封装的树脂组合物、使用其的预浸料和金属包层层合体

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JP7078215B2 (ja) 2018-04-10 2022-05-31 エルジー・ケム・リミテッド 金属箔積層板用熱硬化性樹脂複合体および金属箔積層板
KR102257926B1 (ko) * 2018-09-20 2021-05-28 주식회사 엘지화학 다층인쇄회로기판, 이의 제조방법 및 이를 이용한 반도체 장치
JP6636599B2 (ja) * 2018-11-30 2020-01-29 日本化薬株式会社 エポキシ樹脂組成物、プリプレグ及び金属張積層板、プリント配線基板

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KR20170037883A (ko) 2017-04-05
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JP2016034996A (ja) 2016-03-17
CN106661200A (zh) 2017-05-10
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