WO2015046921A1 - Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné l'utilisant et stratifié de feuille métallique - Google Patents

Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné l'utilisant et stratifié de feuille métallique Download PDF

Info

Publication number
WO2015046921A1
WO2015046921A1 PCT/KR2014/008974 KR2014008974W WO2015046921A1 WO 2015046921 A1 WO2015046921 A1 WO 2015046921A1 KR 2014008974 W KR2014008974 W KR 2014008974W WO 2015046921 A1 WO2015046921 A1 WO 2015046921A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
resin composition
type
weight
epoxy resin
Prior art date
Application number
PCT/KR2014/008974
Other languages
English (en)
Korean (ko)
Inventor
문화연
심정진
심희용
민현성
김미선
심창보
Original Assignee
주식회사 엘지화학
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 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US14/901,895 priority Critical patent/US11535750B2/en
Priority to CN201480042067.XA priority patent/CN105408418B/zh
Priority to JP2016538868A priority patent/JP6301473B2/ja
Priority claimed from KR1020140128140A external-priority patent/KR101677736B1/ko
Publication of WO2015046921A1 publication Critical patent/WO2015046921A1/fr

Links

Classifications

    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065—Preparatory processes
    • C08G73/0655—Preparatory processes from polycyanurates
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04—Epoxynovolacs
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10—Epoxy resins modified by unsaturated compounds

Definitions

  • the present invention relates to a curable resin composition capable of improving the desmear characteristics of a printed circuit board (PCB) for a semiconductor package and a paper, and a prepreg and a metal foil laminate using the same.
  • PCB printed circuit board
  • Copper clad laminate used in the conventional printed circuit board is impregnated with the varnish of the glass fiber (glass fabric) and then semi-cured to become a prepreg, it is heated and pressurized together with the copper foil The prepreg is used again for the purpose of constructing a circuit pattern on the copper foil laminate and building up thereon.
  • thermosetting resin composition exhibiting low thermal expansion properties and facilitating a desmear process to improve workability of a printed circuit board manufacturing process.
  • the present invention is a weak desmear characteristic in the manufacturing process of the printed circuit board It is to provide a thermosetting resin composition for a semiconductor package having excellent drill and workability by improving the problem.
  • Another object of the present invention is to provide a prepreg having a high heat resistance and reliability using the thermosetting resin composition and a metal red plate including the same.
  • the present invention provides a binder comprising an epoxy resin and a bismaleimide-based resin, and a resin composition comprising benzoxazine water; And a slurry-type layer jinje; includes the benzoxazine provides a thermosetting resin composition for a semiconductor package comprising more than 10% by weight, based on the total weight of the whole, the resin composition.
  • the filler of the slurry type may be included in 160 to 350 parts by weight based on 100 parts by weight of the resin composition.
  • the benzoxazine is preferably included in 2 to 10% by weight based on the total weight of the total resin composition.
  • the binder may include 80 wt% of the inner molecular weight of the epoxy resin and 20 to 80 wt% of the bismaleimide-based resin.
  • the binder may further include a cyanate ester resin.
  • the binder is 20 to 60% by weight epoxy resin, cyanate ester It may include 30 to 70% by weight of the resin and 20 to 70% by weight of the basmaleimide-based resin.
  • the slurry type layering agent is silica, aluminum trihydrate, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, caroline, It is preferable to use a slurry containing at least one inorganic filler selected from the group consisting of talc, calcined chlorine, calcined talc, mica, short glass fiber, glass fine powder and hollow glass.
  • the epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dovolac type epoxy resin, phenol novolac epoxy resin, cresol novolac type epoxy resin, tetraphenyl ethane type epoxy resin, naphthalene type It may be at least one selected from the group consisting of an epoxy resin, a biphenyl type epoxy resin and a dicyclopentadiene type epoxy resin.
  • the bismaleimide-based resin BT (Bismaleimide-Triazine) resin, 4, 4'- bismaleimido- diphenylmethane, 1, 4-bismaleimido-2-methylbenzene and mixtures thereof; Modified mismaleimide resins containing Diels-Alder comonomers; And 4,4'-bismaleimido—diphenylmethane and allylphenyl compound; Or partially upgraded bismaleimide based on aromatic amines.
  • BT Bismaleimide-Triazine
  • the Diels-Alder comonomer is styrene And styrene derivatives, bis (propenylphenoxy) compounds, 4 4'-bis (propenylphenoxy) sulfones, 4 4'-bis (propenylphenoxy) benzophenones and 4 4'-1- (1-methyl) Ethylidene) bis (2- (2-propenyl) phenol).
  • the cyanate ester resin is at least one selected from the group consisting of bisphenol A type, bisphenol F type, bisphenol E type, bisphenol H type, bisphenol N type, phenol novolac type, dicyclopentadiene bisphenol type cyanate ester resin. Can be.
  • the thermosetting resin composition may further include at least one additive selected from the group consisting of a solvent, a curing accelerator, a dispersant, and a silane coupling agent.
  • the present invention also provides a prepreg prepared by impregnating the thermosetting resin composition on a fiber substrate.
  • the present invention also the prepreg; And a metal foil comprising integrally with the prepreg by heating and pressurizing.
  • thermosetting resin composition of the present invention exhibits high physical properties using not only epoxy resins but also cyanate resins, and provides the effect of curing bismaleimide-based resins by using benzoxazine instead of conventional phenol curing agents. . Therefore, the present invention by suppressing the smear generated by high heat during the conventional drill operation Provides excellent desmear characteristics.
  • thermosetting resin composition of the present invention unlike the conventional, using a slurry-type layering agent, while exhibiting the same physical properties as those of the conventional ' high heat resistance and reliability, and can improve the chemical resistance. Accordingly, the present invention can provide a prepreg and a metal laminate having excellent chemical resistance.
  • thermosetting resin composition according to a specific embodiment of the present invention will be described in detail.
  • a binder comprising an epoxy resin and a bismaleimide-based resin, and a resin composition comprising a benzoxazine resin; And a slurry-type layering agent; wherein the benzoxazine is provided in the thermosetting resin composition for a semiconductor package containing 10% by weight or less based on the total weight of the total resin composition.
  • the slurry-based layering agent may be included in an amount of 160 to 350 parts by weight based on 100 parts by weight of the resin composition.
  • the benzoxazine is preferably included in 2 to 10% by weight based on the total weight of the total resin composition.
  • thermosetting resin composition of the present invention instead of the conventional phenol curing agent Benzoxazine may be used to induce the curing of bismaleimide-based resins, and the slurry type may be used as a filler to increase interfacial adhesion between the resin and the filler, thereby improving chemical resistance.
  • the composition of the present invention can implement higher physical properties by using a cyanate ester resin.
  • the present invention by using less than 10% by weight of the benzoxazine used as a curing agent in the thermosetting resin composition, it is possible to implement a chemical resistance and high Tg value, it is possible to increase the content of the filler.
  • thermosetting resin composition may improve desmear characteristics by improving chemical resistance.
  • thermosetting resin composition of the present invention having such properties, a prepreg and a metal plate laminated board using the same can be applied to both the production as well as the double-sided printed circuit board ', the multi-layer printed circuit board.
  • thermosetting resin composition of this invention is demonstrated more concretely.
  • thermosetting resin composition of this invention contains the binder component containing an epoxy resin and a special resin, contains a layering agent, and may also contain a hardening
  • the present invention is characterized by using a benzoxazine of a specific content as a curing agent, using a slurry-type filler based on the content of the benzoxazine.
  • the content of the benzoxazine according to the present invention is used at 10% by weight or less based on the total weight of the total resin composition, More preferably in 2 to 10 increments 3 ⁇ 4>.
  • the content of the benzoxazine is more than 10% by weight, the physical properties are worse, it may not exhibit excellent chemical resistance and high Tg. That is, when the benzoxazine resin is included in an excessive amount, the curing reaction rate may be too high during the preparation of the prepreg, and thus the process efficiency may be reduced. In addition, if the content of benzoxazine is too low, less than 2% by weight, chemical resistance and Tg cannot be improved because the effect as a desired curing agent cannot be exhibited.
  • the benzoxazine resin used in the present invention is capable of controlling the reaction rate, thereby improving the flowability of the resin, thereby securing the flowability of the prepreg.
  • benz oxazine enables the curing of the bismaleimide resin described above.
  • the benzoxazine resin may be used as a curing agent for the bismaleimide-based resin.
  • the present invention uses the benzoxazine resin as a curing agent of the bismaleimide-based resin, thereby providing an effect of improving resin flowability and allowing full curing even under low temperature conditions. Therefore, when prepreg is manufactured using the said resin composition, it is high under low temperature pressurization. It is possible to provide a prepreg indicating the glass transition temperature.
  • the benzoxazine resin as a hardening
  • the effect which slows the rate of hardening reaction of an epoxy resin relatively can be acquired.
  • a time during which the resin composition is sufficiently impregnated into the fibrous substrate during the production of the prepreg can be ensured, and the appearance defect can be minimized.
  • the benzoxazine resin may have a weight average molecular weight of 200 to 400 in terms of securing a curing effect and mechanical properties.
  • the present invention by using a slurry-type layering agent, unlike the conventional, it is possible to improve the chemical resistance of the prepreg by increasing the interfacial adhesion between the resin and the filler compared to the case of using a conventional powder-type layering agent. That is, the slurry type filler of the present invention is advantageous in improving the resin dispersibility compared to the powder type layering agent.
  • the "slurry type filler" described in the specification of the present invention may mean a suspension dispersed in a state in which the inorganic filler is dissolved in a solvent.
  • the present invention uses the correlation that the lower the content of the benzoxazine, the higher the content of the layering agent.
  • the benzoxazine includes 2 to 10% by weight or less based on the total weight of the entire resin composition.
  • the resin flows during pressing and The separation of the filler (separat i on) may occur a lot, and if it exceeds 350 parts by weight, the filler is not filled in the glass fiber (Gl ass Fabr ic), so that the dry shape of the glass fiber (Glass Fabr ic) surface after pressing There is a problem.
  • the slurry-type inorganic filler may be prepared by a method well known in the art, and the method is not particularly limited, and preferably, the inorganic filler may be prepared by dispersing the inorganic filler in a solvent.
  • the slurry-type filler is silica, aluminum tr hydrate, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc st annate, alumina, clay And a slurry containing at least one inorganic layering agent selected from the group consisting of kaolin, talc, calcined kaline, calcined talc, mica, glass short fiber glass fine powder and hollow glass.
  • average particle diameter (D50) of the jinje layer is not particularly limited, for example, is an average particle diameter (D50) of the inorganic layer damping material is preferably 0.2 to 5 micrometers in view of dispersion.
  • these fillers may be surface treated with epoxy silanes.
  • the layering agent is surface-treated by a wet / dry method using 0.3 to 1 parts by weight of epoxy silane based on 100 parts by weight of the inorganic layering agent.
  • the epoxy silane may have a weight average molecular weight of 200 to 400.
  • the binder contains an epox resin and a bismaleimide-based resin. In this case, the binder may include 20 to 80% by weight of epoxy resin and 20 to 80% by weight of bismaleimide-based resin.
  • the binder may further include a cyanate ester resin.
  • the binder may include 20 to 60% by weight of epoxy resin, 30 to 70% by weight of cyanate ester resin, and 20 to 70% by weight of bismaleimide-based resin.
  • thermosetting resin composition for prepregs for the said epoxy resin can be used, The kind is not limited.
  • the epoxy resin is bisphenol A epoxy resin, bisphenol
  • F type epoxy resin bisphenol S type epoxy resin, novolac type epoxy resin, phenol novolac epoxy resin, cresol novolac type epoxy resin, tetraphenyl ethane type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and dicyclo
  • pentadiene type epoxy resins One or more types selected from the group consisting of pentadiene type epoxy resins can be used.
  • the special resin is characterized by using a cyanate ester resin and a bismaleimide resin.
  • the present invention can improve the resin physical properties by using the cyanate ester resin in the epoxy resin.
  • the cyanate ester resin exhibits a high glass transition temperature due to an increase in the crosslinking density, thereby providing excellent thermal and Electrical characteristics.
  • the cyanate ester resin is at least one selected from the group consisting of bisphenol A type, bisphenol F type, bisphenol E type, bisphenol H type, bisphenol N type, phenol novolak type and dicyclopentadiene bisphenol type cyanate ester resin. Can be. In addition, in consideration of flowability of the resin, it is preferable to use a cyanate ester resin having a weight average molecular weight of 200 to 400.
  • the bismaleimide-based resin is BT (Bismaleimide-Triazine) resin, 4,4'-bismaleimido-diphenylmethane, 1,4-bismaleimido-2-methylbenzene, and mixtures thereof; Modified mismaleimide resins containing Diels-Alder comonomers; And 4, 4'-bismaleimido-diphenylmethane and allylphenyl compound; Or partially upgraded bismaleimide based on aromatic amines.
  • the bismaleimide-based resin can be used that has an increased average molecular weight of 2,000 to 5,000.
  • the Diels-Alder comonomers include styrene and styrene derivatives, bis (propenylphenoxy) compounds, 4,4'-bis (propenylphenoxy) sulfones, 4,4'-bis (pros) Phenylphenoxy) benzophenone and 4,4'-1- (1-methylethylidene) bis (2- (2-propenyl) phenol).
  • the bismaleimide-based resin is bismaleimide triazine (BT), or 4,4'-bismaleimido- It may be a combination of diphenylmethane and allylphenyl compound.
  • the BT resin is a thermosetting resin that can be used as an insulating layer of an electromagnetic plate that requires high performance and high integration, and may have a weight average molecular weight of 2,000 to 5,000.
  • the binder component is a mixture of an epoxy resin and a bismaleimide resin, or a mixture of an epoxy resin, a cyanate ester resin, and a bismaleimide resin, as described above, in consideration of physical properties required as a binder. It can be used by adjusting appropriately so that the total resin mixture may be 100% by weight.
  • the thermosetting resin composition according to the embodiment of the present invention may further include at least one additive selected from the group consisting of a solvent, a curing accelerator, a dispersant, and a silane coupling agent. .
  • the present invention can be used as a solution by adding a solvent to the resin composition as needed.
  • the solvent is not particularly limited as long as it exhibits good solubility in the resin component, and alcohol, ether, ketone, amide, aromatic hydrocarbon, ester, nitrile, and the like may be used. Or you may use the combined solvent which used 2 or more types together.
  • the content of the solvent is not particularly limited as long as the resin composition may be impregnated into the glass fiber during prepreg manufacture.
  • the curing accelerator may be used for the purpose of promoting the curing of the binder described above. have.
  • the kind and compounding quantity of a hardening accelerator are not specifically limited, For example, an imidazole compound, a tertiary amine, a quaternary ammonium salt, etc. are used, 2 or more types can also be used together.
  • the present invention uses an imidazole compound as a curing accelerator.
  • the content of the curing agent may be used in an amount of about 0.1 to 1 parts by weight based on 100 parts by weight of the binder.
  • imidazole-based curing accelerator 1-methyl imidazole, 2-methyl imidazole, 2-ethyl 4-methyl imidazole (2-ethyl 4-methyl imidazole), 2-phenyl imidazole, 2-cyclonuxyl 4-methyl imidazole, 2-butyl imidazole, 4-butyl 5-ethyl imidazole 5-ethyl-imidazole), 2-methyl 5-ethyl imidazole, 2-octyl 4-nuxyl imidazole, 2,5-dichloro-4 Imidazoles such as -ethyl imidazole, 2,5-dichloro-4-ethyl imidazole, 2-butoxy 4-allyl imidazole, and the imidazole derivatives, and the like. 2-methyl imidazole or 2-phenyl imidazole is preferred because of its good reaction stability and low cost.
  • thermosetting resin composition of the present invention may further include at least one additive selected from the group consisting of a dispersing agent and a silane coupling agent which are usually added as needed.
  • resin composition of the present invention other thermosetting resins, thermoplastic resins and It may further include various high polymer compounds, other flame resistant compounds or additives such as oligomers and elastomers thereof. These are not particularly limited as long as they are selected from those commonly used.
  • Thermosetting resin composition according to an embodiment of the present invention including these components exhibits a viscosity of 20 cps to 50 cps at a temperature of 20 t to 35 ° C, providing excellent flowability compared to the existing. '
  • thermosetting resin composition prepared by impregnating the thermosetting resin composition on a fiber substrate.
  • the prepreg means that the thermosetting resin composition is impregnated into the fiber substrate in a semi-cured state.
  • polyamide-based resin fibers such as glass fiber base material, polyamide resin fiber, aromatic polyamide resin fiber, polyester resin fiber, aromatic polyester resin fiber ⁇ all aromatic polyester Synthetic fiber base composed of woven or nonwoven fabric mainly composed of polyester resin fibers such as resin fibers, polyimide resin fibers, fluorine resin fibers, kraft paper, cotton linter paper, stray paper of linter and kraft pulp, etc.
  • a paper substrate may be used, and preferably a glass fiber substrate is used.
  • the glass fiber substrate can improve the strength of the prepreg, lower the water absorption rate, and reduce the coefficient of thermal expansion.
  • the glass substrates used may be selected from glass substrates used for various printed circuit board materials.
  • glass fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, and NE glass.
  • the glass-based material may be selected according to the intended use or performance. Glass-based forms are typically woven, nonwoven, roving, chopped strand mats or surfacing mats. Although the thickness of the glass substrate is not particularly limited, about 0.01 to 0.3 mm or the like can be used. Of these materials, glass fiber materials are more preferred in terms of strength and water absorption properties.
  • the method for preparing the prepreg in the present invention is not particularly limited, and may be prepared by a method well known in the art.
  • the method of manufacturing the prepreg may be used by an impregnation method, a coating method using various coaters, a spray injection method, or the like.
  • the prepreg after preparing the varnish, may be prepared by impregnating the fiber substrate with the varnish.
  • the conditions for producing the prepreg are not particularly limited, but are preferably used in a varnish state in which a solvent is added to the thermosetting resin composition.
  • the resin varnish solvent is compatible with the resin component and is good. It will not specifically limit, if it has solubility. Examples include acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone and cyclonuxanone, aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide and dimethylacetamide, methyl cellosolve, Aliphatic alcohols such as butyl cellosolve.
  • the solvent used is volatilized by 80% by weight or more. Accordingly, also the manufacturing method and drying conditions are limited, the temperature during drying is about 80 ° C to 180 ° C, the time is not particularly limited to the balance with the varnish gelling time.
  • the impregnation amount of the varnish is preferably such that the resin solid content of the varnish is about 30 to 80% by weight relative to the total amount of the resin solid content of the varnish and the base material.
  • the prepreg On the other hand, according to another embodiment of the present invention, the prepreg; And a metal foil comprising integrally with the prepreg by heating and pressurizing.
  • the metal foil may be copper foil.
  • the copper foil included in the copper foil laminate of the present invention may be made of copper or a copper alloy.
  • the copper foil since the copper foil may be conventional in the art to which the present invention belongs, its physical properties are not particularly limited.
  • the copper foil may have a roughness Rz of Matt surface of 0.01 to 2.5 m , preferably 0.2 to 2.0, more preferably 0.2 to 1.0, and the thickness thereof is 1 or more. , Preferably 2 to 18 Can be applied.
  • the maximum temperature of the lamination (press) may be about 200 ° C or more, usually 220 ° C. have.
  • the pressure condition at the time of pressurizing the metal red plate is not particularly limited, preferably about 35 to 50 kgf / cuf.
  • the metal laminate including the prepreg thus prepared can be used for the manufacture of double-sided or multilayer printed circuit boards after laminating in one or more sheets.
  • the present invention can manufacture a double-sided or multi-layer printed circuit board by circuit processing the metal foil laminate, the circuit processing can be applied to a method performed in a general double-sided or multi-layer printed circuit board manufacturing process.
  • thermosetting resin composition As described above, according to the present invention, by using the above-mentioned resin thermosetting resin composition, it can be applied to all printed circuit boards of various fields, and can be preferably used for the manufacture of printed circuit boards for semiconductor packages.
  • thermosetting resin compositions of Examples and Comparative Examples were mixed in the following compositions and contents to prepare thermosetting resin compositions of Examples and Comparative Examples, respectively.
  • thermosetting resin composition and the filler were mixed and then mixed in a high speed stirrer to prepare a resin varnish.
  • the resin varnish was impregnated into 45 m thick glass fibers (1078, manufactured by Nittobo, T-glass), followed by hot air drying at a temperature of 140 ° C. to prepare a prepreg.
  • each component used in the preparation of the resin varnish is as follows:
  • Bismaleimide-based resins BMI-2300, DAIWA Corporation
  • BT resin Nazine 600
  • Nanokor Co. Novolac type yanate resin (PT-30S, from Lonza); Naphthalene epoxy resins (HP4710, DIC Corporation); Phenolphthalein benzoxazan resin (XU8282, Huns t man); Epoxysilane treated slurry type silica (SC2050FNC from Admatechs); Powder-type filler (SFP-30NHE, Denka); However, the content of the resin component in Tables 1 and 2 is 100% by weight (total 100 weight, and the silica content is based on 100 parts by weight of the resin).
  • the two prepregs prepared above were laminated, and copper foil (thickness 12, manufactured by Mitsui) was placed on both sides of the prepreg, and laminated at a pressure of 50 kg / cii at 2201 temperature using a press for 75 minutes. Copper foil by heating and pressurizing during A laminated plate (thickness: 100) was produced. After etching the copper foil laminate thus produced, basic physical properties and chemical resistance tests were performed.
  • Epoxy resin Naphthalene epoxy resin (HP4710, DIC Corporation)
  • BT resin (Nanozine 600, Nanokor)
  • Cyanate ester resin Novolac cyanate resin (PT-30S, Lonza)
  • BMT resin Bismaleimide resin (BMI-2300, DAIWA)
  • benzoxazine resin phenolphthalein-based benzoxazine resin (XU8282, Hunstman)
  • Phenolic Curing Agent Cresol-Novolac Curing Agent (GPX-41, Gi fu Shel lac)
  • Inorganic layering agent B powder type filler (SFP-30MHE, Denka)
  • thermosetting resin composition obtained by the Example and the comparative example the physical property was evaluated by the following method.
  • the glass transition temperature was measured at a temperature rising rate of 10 ° C / min using TMA (Thermo Mechanical Analysis).
  • DMA Dynamic Mechanical

Abstract

La présente invention porte sur une composition de résine thermodurcissable pour un boîtier de semi-conducteur, sur un préimprégné l'utilisant et sur un stratifié de feuille métallique. Plus précisément, la présente invention porte sur une composition de résine thermodurcissable pour un boîtier de semi-conducteur, sur un préimprégné l'utilisant et sur un stratifié de feuille métallique, la composition présentant de hautes résistance à la chaleur et fiabilité du fait qu'elle utilise une résine de cyanate et de la benzoxizine pour une composition de résine thermodurcissable à base de résine époxyde, ce qui améliore de cette manière des propriétés de déglaçage, et en particulier du fait qu'elle utilise une matière de charge de type suspension épaisse, ce qui améliore de cette manière les propriétés de résistance aux agents chimiques.
PCT/KR2014/008974 2013-09-30 2014-09-25 Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné l'utilisant et stratifié de feuille métallique WO2015046921A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US14/901,895 US11535750B2 (en) 2013-09-30 2014-09-25 Thermosetting resin composition for semiconductor package and prepreg and metal clad laminate using the same
CN201480042067.XA CN105408418B (zh) 2013-09-30 2014-09-25 用于半导体封装物的热固性树脂组合物以及使用其的半固化片和覆金属层压板
JP2016538868A JP6301473B2 (ja) 2013-09-30 2014-09-25 半導体パッケージ用の熱硬化性樹脂組成物とこれを用いたプリプレグおよび金属箔積層板

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20130116771 2013-09-30
KR10-2013-0116771 2013-09-30
KR1020140128140A KR101677736B1 (ko) 2013-09-30 2014-09-25 반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판
KR10-2014-0128140 2014-09-25

Publications (1)

Publication Number Publication Date
WO2015046921A1 true WO2015046921A1 (fr) 2015-04-02

Family

ID=52743949

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/008974 WO2015046921A1 (fr) 2013-09-30 2014-09-25 Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné l'utilisant et stratifié de feuille métallique

Country Status (1)

Country Link
WO (1) WO2015046921A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017165827A (ja) * 2016-03-15 2017-09-21 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板
CN107614608A (zh) * 2016-01-13 2018-01-19 株式会社Lg化学 用于半导体封装的热固性树脂组合物及使用其的预浸料
CN110573581A (zh) * 2017-12-11 2019-12-13 株式会社Lg化学 用于涂覆金属薄膜的热固性树脂组合物和使用其的金属层合体
EP3712208A4 (fr) * 2018-04-10 2020-12-30 Lg Chem, Ltd. Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné et stratifié plaqué de métal

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100121552A (ko) * 2002-06-17 2010-11-17 헨켈 코포레이션 층간 절연 물질 및 미리 도포되는 다이 부착 접착제 물질
KR101021047B1 (ko) * 2005-10-10 2011-03-15 아지노모토 가부시키가이샤 변성 폴리이미드 수지를 함유하는 열경화성 수지 조성물
KR20120012782A (ko) * 2009-03-27 2012-02-10 히다치 가세고교 가부시끼가이샤 열경화성 수지 조성물, 및 이를 이용한 프리프레그, 지지체 부착 절연 필름, 적층판 및 인쇄 배선판
WO2013015469A1 (fr) * 2011-07-28 2013-01-31 Protavic Korea Co., Ltd. Adhésif hybride souple à base de bismaléimide, de benzoxazine et de produit d'addition d'époxy-anhydride
US20130075138A1 (en) * 2011-09-22 2013-03-28 Li-Chih Yu Halogen-free resin composition and copper clad laminate and printed circuit board using same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100121552A (ko) * 2002-06-17 2010-11-17 헨켈 코포레이션 층간 절연 물질 및 미리 도포되는 다이 부착 접착제 물질
KR101021047B1 (ko) * 2005-10-10 2011-03-15 아지노모토 가부시키가이샤 변성 폴리이미드 수지를 함유하는 열경화성 수지 조성물
KR20120012782A (ko) * 2009-03-27 2012-02-10 히다치 가세고교 가부시끼가이샤 열경화성 수지 조성물, 및 이를 이용한 프리프레그, 지지체 부착 절연 필름, 적층판 및 인쇄 배선판
WO2013015469A1 (fr) * 2011-07-28 2013-01-31 Protavic Korea Co., Ltd. Adhésif hybride souple à base de bismaléimide, de benzoxazine et de produit d'addition d'époxy-anhydride
US20130075138A1 (en) * 2011-09-22 2013-03-28 Li-Chih Yu Halogen-free resin composition and copper clad laminate and printed circuit board using same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107614608A (zh) * 2016-01-13 2018-01-19 株式会社Lg化学 用于半导体封装的热固性树脂组合物及使用其的预浸料
JP2018518563A (ja) * 2016-01-13 2018-07-12 エルジー・ケム・リミテッド 半導体パッケージ用熱硬化性樹脂組成物とこれを用いたプリプレグ
US10294341B2 (en) 2016-01-13 2019-05-21 Lg Chem, Ltd. Thermosetting resin composition for semiconductor package and prepreg using the same
CN107614608B (zh) * 2016-01-13 2020-08-28 株式会社Lg化学 用于半导体封装的热固性树脂组合物及使用其的预浸料
JP2017165827A (ja) * 2016-03-15 2017-09-21 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板
CN110573581A (zh) * 2017-12-11 2019-12-13 株式会社Lg化学 用于涂覆金属薄膜的热固性树脂组合物和使用其的金属层合体
EP3712208A4 (fr) * 2018-04-10 2020-12-30 Lg Chem, Ltd. Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné et stratifié plaqué de métal
EP3750957A4 (fr) * 2018-04-10 2021-06-02 Lg Chem, Ltd. Composite de résine thermodurcissable pour stratifié plaqué de métal, et stratifié plaqué de métal

Similar Documents

Publication Publication Date Title
KR101677736B1 (ko) 반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판
KR101937994B1 (ko) 반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그
KR101668855B1 (ko) 반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판
TWI535777B (zh) A thermosetting epoxy resin composition and use thereof
US9278505B2 (en) Thermosetting resin composition and prepreg and metal clad laminate using the same
TWI605078B (zh) 樹脂組成物及使用此樹脂組成物之預浸體與疊層板
CN104379668A (zh) 树脂组合物、预浸料、覆金属箔层叠板及印刷布线板
TW201427827A (zh) 覆金屬箔疊層板之製造方法
WO2015154314A1 (fr) Composition de résine thermodurcissable
WO2015046921A1 (fr) Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné l'utilisant et stratifié de feuille métallique
JP2002194119A (ja) プリプレグ及び金属箔張り積層板
EP3156451A1 (fr) Composition de résine sans halogènes, et préimprégné et carte stratifiée pour circuit imprimé l'utilisant
KR102136861B1 (ko) 반도체 패키지용 열경화성 수지 조성물 및 이를 이용한 프리프레그
TWI401269B (zh) 環氧樹脂組成物及其製成的預浸材和印刷電路板
JP2020528471A6 (ja) 半導体パッケージ用熱硬化性樹脂組成物およびこれを用いたプリプレグ
TWI753194B (zh) 樹脂組合物、印刷電路用預浸片及覆金屬層壓板
KR101652174B1 (ko) 프리프레그 및 이를 포함하는 금속박 적층판 및 인쇄회로기판
JP2015120890A (ja) 熱硬化性樹脂組成物
WO2020133472A1 (fr) Composition de résine, préimprégné, stratifié et stratifié revêtu d'une feuille métallique
WO2013015577A1 (fr) Composition de résine thermodurcissable et plaque de préimprégné et de feuille métallique superposés l'utilisant

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480042067.X

Country of ref document: CN

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

Ref document number: 14847192

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 14901895

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2016538868

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: 14847192

Country of ref document: EP

Kind code of ref document: A1