WO2019199032A1 - Thermosetting resin composition for semiconductor package, prepreg, and metal-clad laminate - Google Patents

Thermosetting resin composition for semiconductor package, prepreg, and metal-clad laminate Download PDF

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Publication number
WO2019199032A1
WO2019199032A1 PCT/KR2019/004222 KR2019004222W WO2019199032A1 WO 2019199032 A1 WO2019199032 A1 WO 2019199032A1 KR 2019004222 W KR2019004222 W KR 2019004222W WO 2019199032 A1 WO2019199032 A1 WO 2019199032A1
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WO
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Prior art keywords
group
thermosetting resin
resin composition
semiconductor package
weight
Prior art date
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PCT/KR2019/004222
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French (fr)
Korean (ko)
Inventor
심창보
송승현
문화연
민현성
심희용
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020190036079A external-priority patent/KR102246974B1/en
Priority claimed from KR1020190036078A external-priority patent/KR102245724B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19785389.8A priority Critical patent/EP3712208B1/en
Priority to JP2020532729A priority patent/JP7074278B2/en
Priority to US16/957,345 priority patent/US20200332056A1/en
Priority to CN201980007064.5A priority patent/CN111601850B/en
Publication of WO2019199032A1 publication Critical patent/WO2019199032A1/en

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    • 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
    • C08G59/40—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
    • 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
    • C08G59/56—Amines together with other curing agents
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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 a thermosetting resin composition, a prepreg and a metal foil laminate for a semiconductor package, and more particularly, excellent flowability, low glass transition temperature and modulus, low thermal expansion coefficient, and warpage page)
  • the present invention relates to a thermosetting resin composition for semiconductor packages capable of minimizing phenomena, and to prepreg and metal foil laminates including the same.
  • Copper cl ad laminate used in the conventional printed circuit board is a prepreg by impregnating the substrate of the glass fiber (Glass Fabr ic) in the varnish of the thermosetting resin and then semi-cured, it is heated together with the copper foil It is prepared by pressing.
  • the prepreg is used again to construct a circuit pattern on the copper foil laminate and to build up thereon.
  • the present invention can ensure excellent flowability, low glass transition temperature and modulus, low thermal expansion coefficient, and can provide a thermosetting resin composition for a semiconductor package that can minimize the warpage 3 ⁇ 3 ⁇ 6 ) phenomenon.
  • this invention is providing the prepreg containing the said thermosetting resin composition for semiconductor packages.
  • the present invention is to provide a metal foil laminate comprising the prepreg.
  • thermosetting resin composition for semiconductor packagers which has the following glass transition temperature is provided.
  • thermosetting resin composition for semiconductor packages to a fiber base material.
  • the prepreg; And by heating and pressurization It provides a metal foil laminate comprising a; metal foil containing integral with the prepreg.
  • thermosetting resin composition for a semiconductor package and a prepreg and a metal foil laminate using the same will be described in detail.
  • thermosetting resin composition for a semiconductor package having a glass transition temperature of 230 ° C. or less, may be provided.
  • the present inventors have conducted research on materials for semiconductor packages, and the composition having the above-described characteristics can ensure excellent flowability, can realize low glass transition temperature and modulus, low thermal expansion rate, and warpage phenomenon. Experiment confirmed that it can be minimized and completed the invention.
  • the resin composition for a semiconductor package of the embodiment is a sulfone group; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; C2-C30 heteroaryl group substituted or unsubstituted by the nitro group, cyano group, or halogen group; And an amine compound containing at least one functional group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group;
  • the above-described amine compound exhibits relatively low reactivity, including a strong electron withdrawing group (Molester), thereby curing the thermosetting resin composition. Make the reaction easy to control.
  • the resin composition for a semiconductor package of the embodiment includes the thermosetting resin content in an amount of 400 parts by weight or less with respect to 100 parts by weight of the amine compound, so that the thermosetting resin to a more sufficient level without the effect of the filler injected in a high content
  • the reliability of the final product can be improved, mechanical properties such as toughness (Toughness) can also be increased, and the glass transition temperature can be lowered to below 230 ° C.
  • thermosetting resin content in an amount of 400 parts by weight or less with respect to 100 parts by weight of the amine curing agent, when the amine curing agent is added in a relatively excessive amount, the flowability and moldability due to excessive curing of the thermosetting resin decreases There was.
  • an excessive amount of a specific amine curing agent having reduced reactivity including an electron withdrawing group (EWG) is added as described above, a rapid increase in the curing rate of the thermosetting resin is suppressed due to a decrease in the reactivity of the curing agent. It is possible to exhibit high flowability even in long-term storage in the resin composition for semiconductor package or the prepreg state obtained therefrom, and can have excellent moldability.
  • EWG electron withdrawing group
  • thermosetting resin 400 weight of the said thermosetting resin with respect to 100 weight part of said amine hardening
  • the thermosetting resin mixture content is also 400 parts by weight or less, or 150 parts by weight to 400 parts by weight, or 180 parts by weight to 300 parts by weight, based on 100 parts by weight of the amine curing agent mixture, Or 180 parts by weight to 290 parts by weight, or 190 parts by weight to 290 parts by weight.
  • thermosetting resin content based on 100 parts by weight of the amine curing agent
  • thermosetting resin When it is excessively increased to more than 400 parts by weight, it is difficult to uniformly cure the thermosetting resin to a more sufficient level due to the increase of the curing density and the filler injected at a high content, and the reliability of the final product may be reduced, and the toughness Mechanical properties such as) may also be reduced.
  • the resin composition for a semiconductor package is represented by the following equation 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • the equivalent ratio calculated may be at least 1.4, or 1.4 to 2.5, or 1.45 to 2.5, or 1.45 to 2. 1, or 1.45 to 1.8, or 1.49 to 1.75.
  • Equivalence ratio total active hydrogen equivalents contained in the amine curing agent / 5 , total curable functional group equivalents contained in the thermosetting resin More specifically, in the formula (1), the total active contained in the amine curing agent .
  • the hydrogen hydrogen equivalent means the value obtained by dividing the total weight (unit: dragon) of the amine curing agent by the unit equivalent of active hydrogen of the amine curing agent (yong).
  • the weight of each compound (unit: obtained by dividing the unit equivalent of the active hydrogen by the use amount of eight ⁇ ) and the sum of the total amount contained in the amine curing agent of Equation 1
  • the active hydrogen equivalent can be obtained.
  • the active hydrogen contained in the amine curing agent means a hydrogen atom contained in the 15 amino group (-) present in the amine curing agent, and the active hydrogen may form a cured structure through reaction with the curable functional group of the thermosetting resin.
  • the total curable functional group equivalent contained in the thermosetting resin means a value obtained by dividing the total weight (unit: yaw) of the thermosetting resin by the curable wearable unit equivalent of the thermosetting resin (yoh).
  • thermosetting resin is a mixture of two or more kinds
  • the weight (unit: use) of each compound is calculated by dividing the unit equivalent of the curable functional group by the urine (total value), and the sum of the total amounts contained in the thermosetting resin of Equation 1 Curable functional group equivalents can be obtained.
  • the curable functional group contained in the thermosetting resin means a functional group that forms a cured structure through reaction with 5 active hydrogens of the amine curing agent, and the type of the curable functional group may also vary according to the thermosetting resin type.
  • the curable functional group contained in the epoxy resin may be an epoxy group
  • the curable functional group contained in the epoxy resin when using a bismaleimide resin as the thermosetting resin, it is contained in the bismaleimide 0 resin
  • Curable functional groups can be maleimide groups. 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • the resin composition for a semiconductor package satisfies that the equivalent ratio calculated by Equation 1 above 1.4 means that a sufficient amount of amine curing agent is contained so that the curable functional groups contained in all the thermosetting resins can cause a curing reaction. Means. Therefore, when the equivalent ratio calculated by Equation 1 in the resin composition for semiconductor package is reduced to less than 1.4, it is difficult to uniformly cure the thermosetting resin to a more sufficient level under the influence of the filler added in a high content, the final product Reliability can be reduced, and mechanical properties can also be reduced.
  • the amine compound may be a sulfone group; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; A heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; And an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with a nitro group, cyano group or halogen group; and at least one functional group selected from the group consisting of 2 to 5 amine groups. have.
  • the amine compound may include at least one compound selected from the group consisting of the following Chemical Formulas 1 to 3.
  • Formula 1 is a sulfone group, a carbonyl group, or an alkylene group having 1 to 10 carbon atoms
  • 3 ⁇ 4 to 3 ⁇ 4 are each independently a nitro group, cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, 6 carbon atoms Is a 3 ⁇ 4 group of 15 to 15, or a heteroaryl group having 2 to 20 carbon atoms, and 3 ⁇ 4 'is 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • the alkyl group having 1 to 10 carbon atoms, the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each independently selected from the group consisting of nitro, cyano and halogen groups It may be substituted with the above functional groups.
  • to 3 ⁇ 4 are each independently a nitro group, cyano group, hydrogen atom, halogen group, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 15 carbon atoms, heteroaryl group of 2 to 20 carbon atoms
  • And IV are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, an integer of 1 to 10, and the above 1 to 6 carbon atoms
  • An alkyl group, an aryl group having 6 to 15 carbon atoms, and a heteroaryl group having 2 to 20 carbon atoms may be independently substituted with one or more functional groups selected from the group consisting of nitro groups, cyano groups, and halogen groups, respectively.
  • 1 to ⁇ 4 are each independently a nitro group, 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • 3 ⁇ 4 ' are each independently a hydrogen atom, a halogen group, an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms, or a heteroaryl group of 2 to 20 carbon atoms, the alkyl group of 1 to 6 carbon atoms, 6 to 15 carbon atoms
  • the aryl group and the heteroaryl group having 2 to 20 carbon atoms may be independently substituted with one or more functional groups selected from the group consisting of a nitro group, a cyano group and a halogen group.
  • the alkyl group is a monovalent functional group derived from alkane (1 «11 ⁇ 2), and is, for example, linear, branched or cyclic, methyl, ethyl, propyl, isobutyl, 16-butyl, pentyl, nuclear chamber and the like. At least one hydrogen atom included in the alkyl group may be substituted with each substituent.
  • the alkylten group is a divalent functional group derived from alkane (1 «11 ⁇ 2), and is, for example, a linear, branched or cyclic group, and is a methylene group, ethylene group, propylten group, isobutylene group, 3 (It may be a -butylene group, a labutylene group, a pentylene group, a nuclear styrene group, etc.).
  • One or more hydrogen atoms contained in the alkylten group may be substituted with the same substituents as in the case of the alkyl group, respectively.
  • the aryl group is a monovalent functional group derived from arene (611 ⁇ 2), and may be, for example, monocyclic or polycyclic.
  • the monocyclic aryl group may be a phenyl group, biphenyl group, terphenyl group, stilbenyl group and the like, but is not limited thereto.
  • the polycyclic aryl group may be naphthyl group, anthryl group, phenanthryl group, ' pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. At least one hydrogen atom of such an aryl group may be each substituted with the same substituent as in the alkyl group.
  • the heteroaryl group is a hetero atom 0, Or as a heterocyclic group containing £, carbon number is not particularly limited but may be 2 to 30 carbon atoms.
  • the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • Dibenzothiophene group benzofuranyl group, dibenzofuran group and the like, but are not limited thereto.
  • At least one hydrogen atom of such a heteroaryl group may be each substituted with the same substituent as in the alkyl group.
  • substituted means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent may be substituted.
  • the substituents may be the same or different from one another.
  • Chemical Formula 1 may include a compound represented by Chemical Formula 1-1.
  • Chemical Formula 2 may include a compound represented by the following Chemical Formula 2-1. 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • Chemical Formula 3 may include a compound represented by Chemical Formula 3-1.
  • the content includes the above-mentioned content in the formula (3).
  • thermosetting resin composition for a semiconductor package is 2019/199032 1 »(1 ⁇ 1 ⁇ 2019/004222
  • And may include a glass transition temperature of 230 or less, or 170 to 230 ° 0, or 180 to 220 ° (:) after thermosetting.
  • the storage modulus at 30 ⁇ and 180 ° (:) measured after curing of the thermosetting resin composition for a semiconductor package was 16, respectively. It may be: In addition, the storage modulus at 260 ° (: measured after curing of the thermosetting resin composition for a semiconductor package is It may be: The thermosetting resin composition for the semiconductor package is 16 at a relatively low temperature range, such as 30 ⁇ and 180 ° (:) after curing. It has a low storage modulus of less than that, it can exhibit a relatively deformable force at the same coefficient of thermal expansion, and thus can exhibit a relatively low warpage of the semiconductor package at low temperature ranges such as 30 ° [and 180 ° (: have.
  • thermosetting resin composition for a semiconductor package after curing
  • thermosetting resin composition for a semiconductor package is 12? / 1 or less, or may have a coefficient of thermal expansion of 5 to 12 ⁇ / ⁇ or 4 to 13 ⁇ 4 p 111 kon ( 0.
  • the thermosetting resin composition for a semiconductor package of the embodiment is an amine compound, thermosetting resin, thermoplastic resin, and inorganic May contain fillers.
  • the content of the components is not particularly limited, the above-mentioned components may be included in consideration of the physical properties of the final product manufactured from the thermosetting resin composition for a semiconductor package of the above embodiment, and the content ratio between these components is described below. As shown.
  • the thermosetting resin may include an epoxy resin.
  • an epoxy resin what is normally used for the thermosetting resin composition for semiconductor packages 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • bisphenol show epoxy resin phenol novolak epoxy resin, phenyl aralkyl epoxy resin, tetraphenyl ethane epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, It may be at least one selected from the group consisting of a dicyclopentadiene epoxy resin, and a mixture of a dicyclopentadiene epoxy resin and a naphthalene epoxy resin.
  • the epoxy resin is a bisphenol-type epoxy resin represented by the formula (5), a novolak-type epoxy resin represented by the formula (6), a phenyl aralkyl epoxy resin represented by the formula (7), tetraphenyl represented by the formula (8) 1 selected from the group consisting of an ethane type epoxy resin, a naphthalene type epoxy resin represented by Formulas 9 and 10, a biphenyl type epoxy resin represented by Formula 11, and a dicyclopentadiene type epoxy resin represented by Formula 12: More than one species can be used.
  • II is 0 or an integer from 1 to 50.
  • the epoxy resin of Formula 5 may be a bisphenol show type epoxy resin, a bisphenol type epoxy resin, a bisphenol type epoxy resin, or a bisphenol £ type epoxy resin, respectively, according to the type of urine. 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • II is 0 or an integer from 1 to 50.
  • the novolak-type epoxy resin of Formula 6 may be a phenol novolak-type epoxy resin or cresol novolak-type epoxy resin, respectively, depending on the type of seedlings.
  • thermosetting resin may further include at least one resin selected from the group consisting of bismaleimide resin, cyanate ester resin and bismaleimide-triazine resin. 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • the bismaleimide resin can be used without limitation usually used in the thermosetting resin composition for semiconductor packages, the type is not limited.
  • the bismaleimide resin is a diphenylmethane bismaleimide resin represented by the following formula (13), a phenylene type bismaleimide resin represented by the following formula (14), and a bisphenol show diphenyl ether represented by the following formula (15). It may be at least one selected from the group consisting of a bismaleimide resin, and a bismaleimide resin composed of an oligomer of diphenylmethane bismaleimide and phenylmethane type maleimide resin represented by the following formula (16).
  • 3 ⁇ 4 and 3 ⁇ 4 are each independently (: 3 ⁇ 4 or 3 ⁇ 43 ⁇ 4).
  • II is 0 or an integer from 1 to 50.
  • the cyanate-based resin may be cyanate ester resin, and can be used without limitation, usually used in the thermosetting resin composition for semiconductor packages, the type is not limited.
  • the cyanate ester resin is a novolac cyanate resin represented by the following formula (17), a dicyclopentadiene type cyanate resin represented by the following formula (18), and a bisphenol type cyanate resin represented by the following formula (19). And some triazineylated prepolymers thereof, and these may be used alone or in combination of two or more thereof.
  • II is 0 or an integer from 1 to 50.
  • II is 0 or an integer from 1 to 50.
  • the cyanate resin of the formula (19) is bisphenol show type cyanate resin, bisphenol five type cyanate resin, bisphenol I ? It may be a type cyanate resin, or a bisphenol type cyanate resin.
  • the bismaleimide-triazine resin may be exemplified as the bismaleimide resin, and the bismaleimide-triazine resin may be used without limitation in the thermosetting resin composition for a semiconductor package. kind is not limited.
  • the thermoplastic resin is, after curing the prepreg, 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • thermoplastic resin a (meth) acrylate type polymer is mentioned.
  • Examples of the (meth) acrylate-based polymer are not particularly limited, and examples thereof include an acrylic ester copolymer including a repeating unit derived from a (meth) acrylate monomer and a repeating unit derived from (meth) acrylonitrile; Or it may be an acrylic ester copolymer containing a repeating unit derived from butadiene.
  • the (meth) acrylate polymer may be a monomer such as butyl acrylate, ethyl acrylate, acrylonitrile, methyl methacrylate, glycidyl methacrylate in the range of 1 to 40% by weight, respectively. (Compared to the total weight of the entire monomer), which may be a copolymer copolymer.
  • the (meth) acrylate-based polymer may have a weight average molecular weight of 500, 000 to 1,000, 000. If the weight average molecular weight of the (meth) acrylate-based polymer is too small, it may be technically disadvantageous after curing because the effect is decreased to increase the toughness 0 'or 63) of the prepreg or to decrease the coefficient of thermal expansion and elastic modulus. In addition, when the weight average molecular weight of the (meth) acrylate-based polymer is too large, the flowability of the prepreg can be reduced.
  • thermoplastic resin may determine the content used in consideration of the use and properties of the final product, for example, the thermosetting resin composition for the semiconductor package includes 10 to 200 parts by weight of the thermoplastic resin relative to 100 parts by weight of the thermosetting resin. can do.
  • thermosetting resin composition for a semiconductor package according to the embodiment may include the amine compound described above, and may further include an additional curing agent other than the amine compound.
  • thermosetting resin composition for a semiconductor package of the embodiment is a second amine compound, acid anhydride resin, bismaleimide resin, cyanate resin, phenol novolak resin and benzoxazine different from the amine compound 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • thermosetting resin composition for a semiconductor package of the embodiment may include an inorganic filler.
  • the inorganic fillers can be used in the thermosetting resin composition for the semiconductor package is usually used without limitation, specific examples include silica, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate , Zinc stannate, alumina, clay, kaolin, talc, calcined kaolin, calcined talc, mica, short glass fiber, glass fine powder and hollow glass, and may be one or more selected from the group consisting of these.
  • the thermosetting resin composition for a semiconductor package may include 30 to 300 parts by weight, or 30 to 200 parts by weight, or 50 to 150 parts by weight of the inorganic filler relative to a total of 100 parts by weight of the thermosetting resin, the thermoplastic resin, and the amine compound. If the content of the inorganic filler is too small, the coefficient of thermal expansion increases, the whip phenomenon intensifies during the reflow process (in silver 1), and the rigidity of the printed circuit board is reduced.
  • the packing density by using a small size of the nano particle size and a large size of the micro particle size together (The filling rate can be increased by increasing the amount.
  • the inorganic filler may include two or more inorganic fillers having different average particle diameters. Specifically, at least one of the two or more inorganic fillers may be an inorganic filler having an average particle size of 0.01 im to 100 / pack, and the other one may be an inorganic filler having an average particle diameter of 1 11111 to 90.
  • the average particle diameter is 1 11111 to 100 parts by weight of the inorganic filler having an average particle diameter of 0.1 to 100.
  • the inorganic filler content may be 1 part by weight to 30 parts by weight.
  • the inorganic filler may use silica surface-treated with a silane coupling agent from the viewpoint of improving moisture resistance and dispersibility.
  • Dry or wet treatment of silica particles using the treatment agent may be used.
  • the silica may be surface treated by a wet method using 0.01 to 1 part by weight of the silane coupling agent based on 100 parts by weight of the silica particles.
  • the silane coupling agent includes aminosilanes such as 3-aminopropyltriethoxysilane, phenyl-3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane.
  • Coupling agent epoxy silane coupling agent such as 3-glycidoxypropyltrimethoxysilane, vinyl silane coupling agent such as 3-methacryloxypropyl trimethoxysilane, ⁇ 2-( ⁇ vinylbenzylaminoethyl) -3- Cationic silane coupling agents such as aminopropyltrimethoxysilane hydrochloride and phenyl silane coupling agents, and silane coupling agents may be used alone or in combination of at least two silane coupling agents, if necessary. .
  • the silane compound may include aromatic amino silane or (meth) acrylsilane
  • the inorganic filler having an average particle diameter of 0.01 to 100 ⁇ 1 may use silica treated with aromatic amino silane.
  • silica treated with (meth) acryl silane can be used as the inorganic filler having an average particle diameter of 1 to 90 ⁇ .
  • the aromatic amino silane-treated silica examples include ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Co., Ltd., and the specific example of the (meth) acrylic silane-treated silica is shown in the show 0413 ( ⁇ (1 33 ()))
  • the said (meth) acryl was used by the meaning containing all acryl or methacryl.
  • the thermosetting resin composition for a semiconductor package according to the embodiment may be used as a solution by adding a solvent as necessary.
  • the solvent is not particularly limited as long as it shows 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 mixed solvent which used 2 or more types together.
  • the content of the solvent is enough to impregnate the resin composition in the glass fiber during prepreg production 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • thermosetting resin composition for a semiconductor package may further include various high molecular compounds such as other thermosetting resins, thermoplastic resins, and oligomers and elastomers thereof, and other flame retardant compounds or additives, so long as the properties of the resin composition are not impaired. . They are not particularly limited as long as they are selected from those commonly used.
  • additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, pigments, dyes, thickeners, lubricants, antifoaming agents, dispersants, Leveling agents, varnishes and the like, it is also possible to use a mixture to meet the purpose.
  • a prepreg including the thermosetting resin composition for the semiconductor package and the fiber substrate may be provided.
  • the prepreg means that the thermosetting resin composition for the semiconductor package is impregnated into the fiber base material 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, kraft paper, cotton linter paper, linter and kraft pulp composed of woven or non-woven fabric mainly composed of polyester resin fibers such as resin fibers, polyimide resin fibers, polybenzoxazole fibers, and fluororesin fibers
  • polyester resin fibers such as resin fibers, polyimide resin fibers, polybenzoxazole fibers, and fluororesin fibers
  • Paper substrates based on honcho paper and the like may be used, and glass fiber substrates are preferably 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 fiber substrate can be selected from glass substrates used for various printed circuit board materials. Examples of meals are £ glass, 0 glass, 3 glass, I glass, Glass fibers such as glass and no glass and zero glass include, but are not limited to. Depending on the intended use or performance as required, and the glass can select a base material. Glass-based forms are typically woven, non-woven, rovings (for ⁇ 11), chopped strand mats 0 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222 versus 111) or surfacing mat (US). Although the thickness of the said glass base material is not specifically limited, About 0.01-0.3ä etc. 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 is not particularly limited, and may be prepared by a method well known in the art.
  • the method of manufacturing the prepreg may be an impregnation method, a coating method using various coaters, a spray injection method, or the like.
  • the prepreg may be manufactured by joining the fiber substrate to the varnish.
  • the solvent for the resin varnish is not particularly limited as long as it can be mixed with the resin component and has good solubility. Specific examples thereof 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, methylcello Aliphatic alcohols such as sorb and butyl cellosolve.
  • the solvent used is volatilized by 80% by weight or more.
  • the temperature at the time of drying is about 80 To 200 ° (1, time is not particularly limited in balance with the gelation time of the varnish).
  • the varnish impregnation amount is preferably such that the resin solid content of the varnish is about 30 to 80% by weight based on the total amount of the resin solid content of the varnish and the base material.
  • the above-described prepreg having a sheet shape; And a metal foil formed on at least one surface of the prepreg. 2019/199032 1 »(: 1 ⁇ 1 ⁇ 2019/004222
  • the metal foil is copper foil; Aluminum foil; A composite foil having a three-layer structure including nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy as an intermediate layer, and including copper layers having different thicknesses on both surfaces thereof; Or the composite foil of the two-layered structure which combined aluminum and copper foil.
  • the metal foil may be a copper foil or an aluminum foil, and a metal having a thickness of about 2 to 200 sun rays may be used, but the thickness thereof is preferably about 2 to 35.
  • copper foil is used as said metal foil.
  • nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy is used as an intermediate layer, and 0.5 to 15 copper layers and 10 to 300 III copper on both surfaces thereof. It is also possible to use a three-layered composite foil having layers, or a two-layer composite foil composed of aluminum and copper foil.
  • the metal laminated plate containing 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 metal foil laminate may be circuit processed to manufacture a double-sided or multilayer printed circuit board, and the circuit processing may be applied to a method performed in a general double-sided or multilayer printed circuit board manufacturing process.
  • thermosetting resin composition for a semiconductor package capable of minimizing a phenomenon per large bulk the thermosetting resin composition for a semiconductor package capable of minimizing a phenomenon per large bulk
  • the semiconductor package A prepreg provided using the thermosetting resin composition for metal, and a metal foil laminate including the prepreg may be provided.
  • each component was added to methyl ethyl ketone according to the solid content of 40% and mixed, and then stirred at room temperature at 400 rpm for one day to prepare the resin compositions for semiconductor packages of Examples and Comparative Examples (resin Varnish) was prepared.
  • the specific composition of the resin composition prepared in Example is as shown in Table 1 below
  • the specific composition of the resin composition prepared in Comparative Example is as shown in Table 2 below.
  • Hot air was dried at a temperature of 170 ° C. for 2 to 5 minutes to prepare a prepreg of 18_.
  • Two sheets of the prepregs prepared above were laminated, and copper foil (12 m thick) was placed on both sides thereof.
  • the laminate was laminated and cured for 100 minutes under conditions of 220 ° C. and 35 kg / oif to prepare a copper foil laminate.
  • thermosetting resin composition for a semiconductor package, the prepreg, and the copper foil laminated sheet obtained in the said Example and the comparative example were measured by the following method, The result is shown in Table 3.
  • test piece was prepared in the MD direction, and using a DMA (TA Instruments, Q800) in a tensile mode at a temperature of 5 ° C./min 25
  • the peak temperature of tan delta was measured as the glass transition temperature by measuring from ° C to 300 ° C.
  • the prepreg obtained by the said Example and the comparative example is located in both surfaces of a circuit pattern (pattern height 7um 'residual ratio 50%), and copper foil (thickness) on it Mitsui Co., Ltd.) was placed, pressed for 100 minutes under conditions of 220 ° C. and 35 kg / cuf, and then the copper foils on both sides were etched, and the circuit pattern fillability was evaluated under the following criteria.
  • PS100 PS100 was used to measure the warpage based on Shadow Moi re measurement theory.
  • the warpage was determined by measuring the semiconductor package from 30 ° C. to 260 ° C. and then cooling to 30 ° C. as a difference between the maximum and minimum values of the warpage.
  • the warpage of the semiconductor package was evaluated based on the following criteria. It was.
  • thermosetting resin composition for semiconductor packages of Examples and physical properties of prepreg (unit: g)
  • thermosetting resin composition for semiconductor package of comparative example Composition of thermosetting resin composition for semiconductor package of comparative example and physical properties of prepreg (unit: g)
  • Acrylic rubber B (Mw 800,000): PARACRON KG_3015P (Negami chemical industrial Co. , LTD company)
  • Equation 1 (Total active hydrogen equivalent of DDS + total active hydrogen equivalent of TFB + total active hydrogen equivalent of DDM) / ⁇ (total epoxy equivalent of XD-1000 + total epoxy equivalent of NC-3000H + total epoxy equivalent of HP-6000) + (Total maleimide equivalent of BMI-2300) ⁇
  • the total activity , hydrogen equivalent weight of DDS is the total weight (g) of DDS divided by the unit equivalent weight of active hydrogen (62 g / eq) of DDS,
  • the total active hydrogen equivalent of seedlings is the total weight (g) of TFB divided by the unit equivalent of TFB (80 g / eq),
  • the total active hydrogen equivalent of DDM is the total weight of DDM divided by the unit equivalent of active hydrogen of DDM (49.5 g / eq),
  • the total epoxy equivalent of XD-1000 is the total weight (g) of XD-1000 divided by the epoxy unit equivalent (253 g / eq) of XD-1000,
  • the total epoxy equivalent of NC-3000H is the total weight (g) of NC-3000H divided by the epoxy unit equivalent (290 g / eq) of NC-3000H,
  • the total epoxy equivalent of HP-6000 is the total weight of HP-6000 divided by the epoxy equivalent of HP-6000 (250 g / eq),
  • the total maleimide equivalent of BMI-2300 is the total weight (g) of BMI-230 divided by the male equivalent of BMI-2300 (179 g / eq).
  • the prepreg containing the amine compound having an electron withdraw (Electron Withdrawing Group, EWG) as in the embodiment has a glass transition temperature of 230 ° C or less, low thermal expansion coefficient of 10 ppm / ° C It has been confirmed that it has a good circuit pattern fillability while having.
  • the equivalent ratio of the amine compound equivalent ratio based on the thermosetting resin equivalent ratio is 1.4 or more, including 290 parts by weight or less of the thermosetting resin with respect to 100 parts by weight of the amine compound having an elektron drawing (EWG).
  • EWG elektron drawing
  • the amount of the inorganic additive added is 150 parts by weight in an amount of 50 parts by weight based on 100 parts by weight of the total amount of the thermosetting resin, the thermoplastic resin and the amine compound, the thermal properties bonded to the semiconductor packaging, excellent low thermal expansion characteristics, flowability And it was confirmed that the mechanical properties can be secured.
  • the thermal stress factor for each prepreg obtained in the examples is less than 21 Mpa.
  • a semiconductor package manufactured using the prepreg having such a thermal stress factor has a relatively low level of warpage. It was confirmed to represent only. In contrast, it was confirmed that the thermal stress factor for each prepreg obtained in the comparative examples is more than 25 Mpa, and the semiconductor package manufactured using the prepreg having such a high thermal stress factor generates relatively high warpage. .

Abstract

The present invention relates to a thermosetting resin composition for a semiconductor package, a prepreg, and a metal-clad laminate and, more specifically, to a thermosetting resin composition for a semiconductor package, the thermosetting resin composition comprising: an amine compound containing a particular functional group; a thermosetting resin; a thermoplastic resin, and an inorganic filler, and having a glass transition temperature of 230°C or lower, to a prepreg comprising the composition, and to a metal-clad laminate.

Description

【발명의 설명】  [Explanation of invention]
【발명의 명칭】  [Name of invention]
반도체 패키지용 열경화성 수지 조성물， 프리프레그 및 금속박 적층판  Thermosetting resin composition, prepreg and metal foil laminate for semiconductor package
【기술분야】  Technical Field
관란 출원 (들)과의 상호 인용  Cross Citation with Controversial Application (s)
본 출원은 2018년 4월 10일자 한국특허출원 제 10-2018-0041抑 7호， 2018년 6월 20일자 한국특허출원 제 10-2018-0071076 호， 2019년 3월 28일자 한국특허출원 제 10-2019-0036079호， 및 2019년 3월 28일자 한국특허출원 제 10-2019-0036078호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.  The present application is filed with Korean Patent Application No. 10-2018-0041 # 7 of April 10, 2018, Korean Patent Application No. 10-2018-0071076 of June 20, 2018, and Korean Patent Application No. 10 of March 28, 2019. -2019-0036079, and the benefit of priority based on Korean Patent Application No. 10-2019-0036078 dated March 28, 2019, all the contents disclosed in the documents of the relevant Korean patent applications are incorporated as part of this specification. .
본 발명은 반도체 패키지용 열경화성 수지 조성물, 프리프레그 및 금속박 적층판에 관한 것으로， 보다 상세하게는 우수한 흐름성을 확보할 수 있고， 낮은 유리전이온도 및 모듈러스， 낮은 열팽창률을 구현할 수 있으며 , 휨 (war page)현상을 최소화 할 수 있는 반도체 패키지용 열경화성 수지 조성물과 이를 포함한 프리프레그 및 금속박 적층판에 관한 것이다.  The present invention relates to a thermosetting resin composition, a prepreg and a metal foil laminate for a semiconductor package, and more particularly, excellent flowability, low glass transition temperature and modulus, low thermal expansion coefficient, and warpage page) The present invention relates to a thermosetting resin composition for semiconductor packages capable of minimizing phenomena, and to prepreg and metal foil laminates including the same.
【발명의 배경이 되는 기술】  [Technique to become background of invention]
종래의 인쇄회로기판에 사용되는 동박적층판 (copper cl ad laminate)은 유리 섬유 (Glass Fabr i c)의 기재를 상기 열경화성 수지의 바니시에 함침한 후 반경화시키면 프리프레그가 되고， 이를 다시 동박과 함께 가열 가압하여 제조한다. 이러한 동박 적층판에 회로 패턴을 구성하고 이 위에 빌드업 (bui ld-up)을 하는 용도로 프리프레그가 다시 사용되게 된다. 최근 전자 기기, 통신기기， 개인용 컴퓨터, 스마트폰 등의 고성능화, 박형화, 경량화가 가속되면서 반도체 패키지 또한 박형화가 요구됨에 따라， 동시에 반도체 패키지용 안쇄회로기판도 박형화의 필요성이 커지고 있다. 그러나, 박형화 과정에서 인쇄회로기판의 강성이 감소하는 문제가 발생함과 동시에, 칩과 인쇄회로기판간 열팽창률 차이로 인해 반도체 패키지의 휨 (Warpage) 문제가 발생하고 있다. 이러한 휨 현상은 리플로우와 같은 고온 공정을 거치면서 인쇄회로기판이 원복이 되지 않는 현상으로 더 2019/199032 1»（：1^1{2019/004222 Copper cl ad laminate used in the conventional printed circuit board is a prepreg by impregnating the substrate of the glass fiber (Glass Fabr ic) in the varnish of the thermosetting resin and then semi-cured, it is heated together with the copper foil It is prepared by pressing. The prepreg is used again to construct a circuit pattern on the copper foil laminate and to build up thereon. Recently, as the performance, thickness, and weight of electronic devices, communication devices, personal computers, and smart phones are accelerated, the semiconductor packages are also required to be thin, and at the same time, the necessity of thinning the printed circuit boards for semiconductor packages is increasing. However, in the thinning process, the rigidity of the printed circuit board is reduced, and the warpage problem of the semiconductor package is generated due to the difference in thermal expansion coefficient between the chip and the printed circuit board. This warpage phenomenon is a phenomenon in which the printed circuit board is not rolled back through a high temperature process such as reflow. 2019/199032 1 »（： 1 ^ 1 {2019/004222
심화된다. Deepen.
이에, 휨 현상을 개선하기 위해 기판의 열팽창률을 낮추는 기술에 대한 연구가 진행되고 있으며, 예를 들어 프리프레그에 필러를 고함량으로 충진하는 기술이 제안되고 있으나， 단순히 프리프레그에 필러를 고함량으로 충진하기만하는 경우프리프레그의 흐름성이 감소하는 한계가 있었다.  In order to improve the warpage phenomenon, research on lowering the coefficient of thermal expansion of the substrate is being conducted. For example, a technique of filling a filler with a high content of a prepreg has been proposed, but simply a high content of a filler with the prepreg is proposed. There was a limit to decrease the flow of prepreg when only filling with.
따라서， 흐름성이 확보되면서도 낮은 열팽창률을 구현할 수 있으며 휨 크대크용 발생을 줄일 수 있는 프리프레그 및 금속박 적층판의 개발이 요구되고 있다.  Accordingly, there is a demand for development of prepreg and metal foil laminates that can achieve low thermal expansion rate while reducing flowability and can reduce occurrence of warp bulk.
【발명의 내용】  [Content of invention]
【해결하고자 하는 과제】  Problem to be solved
본 발명은 우수한 흐름성을 확보할 수 있고， 낮은 유리전이온도 및 모듈러스， 낮은 열팽창률을 구현할 수 있으며， 휨 3印3§6）현상을 최소화 할 수 있는 반도체 패키지용 열경화성 수지 조성물을 제공하기 위한 것이다. 또한 , 본 발명은 상기 반도체 패키지용 열경화성 수지 조성물을 포함하는프리프레그를 제공하기 위한 것이다. The present invention can ensure excellent flowability, low glass transition temperature and modulus, low thermal expansion coefficient, and can provide a thermosetting resin composition for a semiconductor package that can minimize the warpage 3 印 3 §6 ) phenomenon. will be. Moreover, this invention is providing the prepreg containing the said thermosetting resin composition for semiconductor packages.
또한, 본 발명은 상기 프리프레그를 포함하는 금속박 적층판을 제공하기 위한 것이다.  In addition, the present invention is to provide a metal foil laminate comprising the prepreg.
【과제의 해결 수단】  [Measures of problem]
본 명세서에서는， 술폰기; 카보닐기; 할로겐기; 니트로기, 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 니트로기, 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴기; 및 니트로기， 시아노가 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기;로 이루어진 군에서 선택된 1종 이상의 작용기를 1이상 포함한 아민 화합물， 열경화성 수지， 열가소성 수지， 및 무기 충진제를 포함하고, 230
Figure imgf000003_0001
이하의 유리 전이 온도를 갖는, 반도체 패키자용 열경화성 수지 조성물이 제공된다. In the present specification, a sulfone group; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; A heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; And an amine compound including at least one functional group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms or unsubstituted or substituted with a nitro group, cyano or halogen group, a thermosetting resin, a thermoplastic resin, and an inorganic filler. , 230
Figure imgf000003_0001
The thermosetting resin composition for semiconductor packagers which has the following glass transition temperature is provided.
본 명세서에서는 또한， 상기 반도체 패키지용 열경화성 수지 조성물을섬유 기재에 함침시켜 얻어진 프리프레그를 제공한다.  This specification also provides the prepreg obtained by impregnating the said thermosetting resin composition for semiconductor packages to a fiber base material.
본 명세서에서는 또한， 상기 프리프레그; 및 가열 및 가압에 의해 상기 프리프레그와 일체화된 포함하는 금속박 ;을 포함하는 금속박 적층판을 제공한다. In the present specification, the prepreg; And by heating and pressurization It provides a metal foil laminate comprising a; metal foil containing integral with the prepreg.
이하 발명의 구체적인 구현예에 따른 반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판에 대하여 보다 상세하게 설명하기로 한다.. 발명의 일 구현예에 따르면, 술폰기; 카보닐기; 할로겐기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴기; 및 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기;로 이루어진 군에서 선택된 1종 이상의 작용기를 1이상 포함한 아민 화합물， 열경화성 수지, 열가소성 수지, 및 무기 충진제를 포함하고, 230 °C 이하의 유리 전이 온도를 갖는, 반도체 패키지용 열경화성 수지 조성물이 제공될 수 있다. 본 발명자들은 반도체 패키지용 재료에 관한 연구를 진행하여， 상술한 특징을 갖는 조성물이 우수한 흐름성을 확보할 수 있고， 낮은 유리전이온도 및 모듈러스， 낮은 열팽창률을 구현할 수 있으며 휨 (Warpage) 현상을 최소화할 수 있다는 점을 실험을 통해서 확인하고 발명을 완성하였다. Hereinafter, a thermosetting resin composition for a semiconductor package and a prepreg and a metal foil laminate using the same according to a specific embodiment of the present invention will be described in detail. . According to one embodiment of the invention, a sulfone group; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; A heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; And an amine compound containing at least one functional group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms or unsubstituted or substituted with a nitro group, cyano group, or halogen group, a thermosetting resin, a thermoplastic resin, and an inorganic filler. A thermosetting resin composition for a semiconductor package, having a glass transition temperature of 230 ° C. or less, may be provided. The present inventors have conducted research on materials for semiconductor packages, and the composition having the above-described characteristics can ensure excellent flowability, can realize low glass transition temperature and modulus, low thermal expansion rate, and warpage phenomenon. Experiment confirmed that it can be minimized and completed the invention.
보다 구체적으로， 상기 일 구현예의 반도체 패키지용 수지 조성물은 술폰기; 카보닐기; 할로겐기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비차환된 탄소수 2 내지 30의 헤테로아릴기 ; 및 니트로기 , 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기;로 이루어진 군에서 선택된 1종 이상의 작용기를 1이상 포함한 아민 화합물을 포함하는데; 상술한 아민 화합물은 강력한 전자 끌개 작용기 (Electron Wi thdrawing Group , 묘이를 포함하여 상대적으로 낮아진 반응성을 나타내어 상기 열경화성 수지 조성물의 경화 반응을 용이하게 제어할수 있게 한다. More specifically, the resin composition for a semiconductor package of the embodiment is a sulfone group; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; C2-C30 heteroaryl group substituted or unsubstituted by the nitro group, cyano group, or halogen group; And an amine compound containing at least one functional group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; The above-described amine compound exhibits relatively low reactivity, including a strong electron withdrawing group (Molester), thereby curing the thermosetting resin composition. Make the reaction easy to control.
특히, 상기 일 구현예의 반도체 패키지용 수지 조성물은 상기 아민 화합물 100 중량부에 대하여 상기 열경화성 수지 함량을 400 중량부 이하， 로 포함하여， 높은 함량으로 투입된 필러에 의한 영향없이 열경화성 수지가 보다 충분한 수준으로 균일하게 경화 가능하도록 유도하여, 최종 제조되는 제품의 신뢰성이 향상될 수 있고， 인성 (Toughness)와 같은 기계적 물성 또한증가시킬 수 있으며， 유리전이온도 230°C로 이하로 낮출 수 있다. In particular, the resin composition for a semiconductor package of the embodiment includes the thermosetting resin content in an amount of 400 parts by weight or less with respect to 100 parts by weight of the amine compound, so that the thermosetting resin to a more sufficient level without the effect of the filler injected in a high content By inducing to be uniformly curable, the reliability of the final product can be improved, mechanical properties such as toughness (Toughness) can also be increased, and the glass transition temperature can be lowered to below 230 ° C.
종래에는 상기 아민 경화제 100 중량부에 대하여 상기 열경화성 수지 함량을 400 중량부 이하로 포함시키는 것과 같이， 아민 경화제를 상대적으로 과량으로 첨가시 열경화성 수지의 과도한 경화로 인해 흐름성 및 성형성이 감소하는 한계가 있었다. 그러나, 상술한 바와 같이 전자 끌개 작용기 (Electron Wi thdrawing Group , EWG)를 포함하여 반응성이 감소한 특정 아민 경화제를 과량으로 첨가하더라도, 경화제의 반응성 감소로 인해, 열경화성 수지의 경화속도가 급격히 상승하는 것을 억제할 수 있어， 반도체 패키지용 수지 조성물이나 이로부터 얻어지는 프리프레그 상태에서의 장기간보관시에도높은 흐름성을 나타내어 우수한성형성을 가질 수 있다. 상기 아민 경화제 100 중량부에 대하여 상기 열경화성 수지 함량을 400 중량.부 이하， 또는 150 중량부 내자 400 중량부， 또는 180 중량부 내지 300 중량부， 또는 180 중량부 내지 290 중량부, 또는 190 중량부 내지 290 중량부일 수 있다. 상기 아민 경화제 또는 열경화성 수지가 2 종 이상의 혼합물인 경우， 아민 경화제 혼합물 100 중량부에 대하여 열경화성 수지 혼합물 함량 또한 400 중량부 이하， 또는 150 중량부 내지 400 중량부， 또는 180 중량부 내지 300 중량부， 또는 180 중량부 내지 290 중、량부， 또는 190중량부 내지 290 중량부일 수 있다. Conventionally, as including the thermosetting resin content in an amount of 400 parts by weight or less with respect to 100 parts by weight of the amine curing agent, when the amine curing agent is added in a relatively excessive amount, the flowability and moldability due to excessive curing of the thermosetting resin decreases There was. However, even when an excessive amount of a specific amine curing agent having reduced reactivity including an electron withdrawing group (EWG) is added as described above, a rapid increase in the curing rate of the thermosetting resin is suppressed due to a decrease in the reactivity of the curing agent. It is possible to exhibit high flowability even in long-term storage in the resin composition for semiconductor package or the prepreg state obtained therefrom, and can have excellent moldability. 400 weight of the said thermosetting resin with respect to 100 weight part of said amine hardening | curing agents . Or less, or 150 parts by weight of 400 parts by weight, or 180 parts by weight to 300 parts by weight, or 180 parts by weight to 290 parts by weight, or 190 parts by weight to 290 parts by weight. When the amine curing agent or the thermosetting resin is a mixture of two or more kinds, the thermosetting resin mixture content is also 400 parts by weight or less, or 150 parts by weight to 400 parts by weight, or 180 parts by weight to 300 parts by weight, based on 100 parts by weight of the amine curing agent mixture, Or 180 parts by weight to 290 parts by weight, or 190 parts by weight to 290 parts by weight.
상기 아민 경화제 100 중량부에 대하여 상기 열경화성 수지 함량을 The thermosetting resin content based on 100 parts by weight of the amine curing agent
400 중량부 초과로 지나치게 증가할 경우， 경화밀도 증가 및 고함량으로 투입된 필러의 영향으로 열경화성 수지가 보다 충분한 수준까지 균일하게 경화되기 어려워， 최종 제조되는 제품의 신뢰성이 감소할 수 있고, 인성 (Toughness)와 같은 기계적 물성 또한 감소될 수 있다. When it is excessively increased to more than 400 parts by weight, it is difficult to uniformly cure the thermosetting resin to a more sufficient level due to the increase of the curing density and the filler injected at a high content, and the reliability of the final product may be reduced, and the toughness Mechanical properties such as) may also be reduced.
한편， 상기 반도체 패키지용 수지 조성물은 하기 수학식 1 로 2019/199032 1»（：1^1{2019/004222 On the other hand, the resin composition for a semiconductor package is represented by the following equation 2019/199032 1 »（： 1 ^ 1 {2019/004222
계산되는 당량비가 1.4 이상, 또는 1.4 내지 2.5， 또는 1.45 내지 2.5 , 또는 1.45내지 2. 1， 또는 1.45 내지 1.8 , 또는 1.49 내지 1.75일 수 있다. The equivalent ratio calculated may be at least 1.4, or 1.4 to 2.5, or 1.45 to 2.5, or 1.45 to 2. 1, or 1.45 to 1.8, or 1.49 to 1.75.
[수학식 1]  [Equation 1]
당량비 = 상기 아민 경화제에 함유된 총 활성수소 당량 / 상기 , 5 열경화성 수지에 함유된 총 경화성 작용기 당량 보다구체적으로, 상기 수학식 1에서 , 상기 아민 경화제에 함유된 총 활.성수소 당량은, 상기 아민 경화제의 총 중량（단위: 용）을 상기 아민 경화제의 활성수소 단위당량（용 로 나눈 값을 의미한다. Equivalence ratio = total active hydrogen equivalents contained in the amine curing agent / 5 , total curable functional group equivalents contained in the thermosetting resin More specifically, in the formula (1), the total active contained in the amine curing agent . The hydrogen hydrogen equivalent means the value obtained by dividing the total weight (unit: dragon) of the amine curing agent by the unit equivalent of active hydrogen of the amine curing agent (yong).
10 상기 아민 경화제가 2 종 이상의 혼합물인 경우， 각각의 화합물 별로 중량（단위: 을 활성수소 단위당량（용八ᅬ로 나눈 값을 구하고， 이를 합한 값으로상기 수학식 1의 아민 경화제에 함유된 총 활성수소 당량을 구할수 있다.  10 In the case where the amine curing agent is a mixture of two or more kinds, the weight of each compound (unit: obtained by dividing the unit equivalent of the active hydrogen by the use amount of eight ᅬ) and the sum of the total amount contained in the amine curing agent of Equation 1 The active hydrogen equivalent can be obtained.
상기 아민 경화제에 함유된 활성수소는, 아민 경화제에 존재하는 15 아미노기（- ）에 포함된 수소원자를 의미하며 , 상기 활성수소가 열경화성 수지의 경화성 작용기와의 반응을 통해 경화구조를 형성할수 있다.  The active hydrogen contained in the amine curing agent means a hydrogen atom contained in the 15 amino group (-) present in the amine curing agent, and the active hydrogen may form a cured structure through reaction with the curable functional group of the thermosetting resin.
또한， 상기 수학식 1 에서, 상기 열경화성 수지에 함유된 총 경화성 작용기 당량은， 상기 열경화성 수지의 총 중량（단위: 요）을 상기 열경화성 수지의 경화성 착용가단위당량（요八 로 나눈 값을 의미한다. In addition, in Equation 1, the total curable functional group equivalent contained in the thermosetting resin means a value obtained by dividing the total weight (unit: yaw) of the thermosetting resin by the curable wearable unit equivalent of the thermosetting resin (yoh).
0 상기 열경화성 수지가 2 종 이상의 혼합물인 경우， 각각의 화합물 별로 중량（단위:용）을 경화성 작용기 단위당량（요 로 나눈 값을 구하고, 이를 합한 값으로 상기 수학식 1 의 열경화성 수지에 함유된 총 경화성 작용기 당량을 구할수 있다.  0 In the case where the thermosetting resin is a mixture of two or more kinds, the weight (unit: use) of each compound is calculated by dividing the unit equivalent of the curable functional group by the urine (total value), and the sum of the total amounts contained in the thermosetting resin of Equation 1 Curable functional group equivalents can be obtained.
상기 열경화성 수지에 함유된 경화성 작용기는， 상기 아민 경화제의 5 활성수소와의 반응을 통해 경화구조를 형성하는 작용기를 의미하며, 상기 열경화성 수지 종류에 따라 경화성 작용기의 종류 또한달라질 수 있다 . 예를 들어， 상기 열경화성 수지로 에폭시 수지를 사용할 경우, 상기 에폭시 수지에 함유된 경화성 작용기는 에폭시기가 될 수 있고， 상기 열경화성 수지로 비스말레이미드수지를 사용할 경우， 상기 비스말레이미드 0 수지에 함유된 경화성 작용기는 말레이미드기가 될 수 있다 . 2019/199032 1»（：1^1{2019/004222 The curable functional group contained in the thermosetting resin means a functional group that forms a cured structure through reaction with 5 active hydrogens of the amine curing agent, and the type of the curable functional group may also vary according to the thermosetting resin type. For example, when using an epoxy resin as the thermosetting resin, the curable functional group contained in the epoxy resin may be an epoxy group, when using a bismaleimide resin as the thermosetting resin, it is contained in the bismaleimide 0 resin Curable functional groups can be maleimide groups. 2019/199032 1 »（： 1 ^ 1 {2019/004222
즉， 상기 반도체 패키지용 수지 조성물이 상기 수학식 1 로 계산되는 당량비가 1.4 이상을 만족한다는 것은, 모든 열경화성 수지에 함유된 경화성 작용기가 경화반응을 일으킬 수 있을 정도로 충분한 수준의 아민 경화제가 함유되어있음을 의미한다. 따라서， 상기 반도체 패키지용 수지 조성물에서 상기 수학식 1 로 계산되는 당량비가 1.4 미만으로 감소하는 경우, 고함량으로 투입된 필러의 영향으로 열경화성 수지가 보다 충분한 수준까지 균일하게 경화되기 어려워， 최종 제조되는 제품의 신뢰성이 감소할수 있고， 기계적 물성 또한 감소할수 있는 단점이 있다. 상기 아민 화합물은 술폰기; 카보닐기; 할로겐기; 니트로기, 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 니트로기, 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴기; 및 니트로기, 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기;로 이루어진 군에서 선택된 1종 이상의 작용기를 1 이상 포함하고， 2 내지 5개의 아민기를 포함하는 방향족 아민 화합물일 수 있다. That is, the resin composition for a semiconductor package satisfies that the equivalent ratio calculated by Equation 1 above 1.4 means that a sufficient amount of amine curing agent is contained so that the curable functional groups contained in all the thermosetting resins can cause a curing reaction. Means. Therefore, when the equivalent ratio calculated by Equation 1 in the resin composition for semiconductor package is reduced to less than 1.4, it is difficult to uniformly cure the thermosetting resin to a more sufficient level under the influence of the filler added in a high content, the final product Reliability can be reduced, and mechanical properties can also be reduced. The amine compound may be a sulfone group; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; A heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; And an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with a nitro group, cyano group or halogen group; and at least one functional group selected from the group consisting of 2 to 5 amine groups. have.
보다 구체적으로, 상기 아민 화합물은 하기 화학식 1 내지 3 으로 이루어진 군에서 선택된 1종 이상의 화합물을포함할수 있다. More specifically, the amine compound may include at least one compound selected from the group consisting of the following Chemical Formulas 1 to 3.
[화학식 1]  [Formula 1]
Figure imgf000007_0001
Figure imgf000007_0001
상기 화학식 1 에서, 는 술폰기, 카보닐기, 또는 탄소수 1 내지 10 의 알킬렌기이며， ¾ 내지 ¾는 각각 독립적으로 니트로기， 시아노기， 수소원자， 할로겐기, 탄소수 1 내지 6 의 알킬기， 탄소수 6 내지 15 의 아 ¾기， 또는 탄소수 2 내지 20 의 헤테로아릴기이고, 및 ¾’는 2019/199032 1»（：1^1{2019/004222 In Formula 1, is a sulfone group, a carbonyl group, or an alkylene group having 1 to 10 carbon atoms, ¾ to ¾ are each independently a nitro group, cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, 6 carbon atoms Is a ¾ group of 15 to 15, or a heteroaryl group having 2 to 20 carbon atoms, and ¾ 'is 2019/199032 1 »（： 1 ^ 1 {2019/004222
각각독립적으로 수소원자, 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15 의 아릴기， 또는 탄소수 2 내지 20 의 헤테로아릴기이며， II 은 1 내지 10의 정수일 수 있다. Each independently represents a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and II may be an integer of 1 to 10.
상기 탄소수 1 내지 10 의 알킬텐기, 탄소수 1 내지 6 의 알킬기， 탄소수 6 내지 15 의 아릴기， 및 탄소수 2 내지 20 의 헤테로아릴기는 각각 독립적으로 니트로기, 시아노기 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 작용기로 치환될 수 있다.  The alkyl group having 1 to 10 carbon atoms, the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each independently selected from the group consisting of nitro, cyano and halogen groups It may be substituted with the above functional groups.
[화학식 2]  [Formula 2]
Figure imgf000008_0001
Figure imgf000008_0001
상기 화학식 2 에서， 내지 ¾ 는 각각 독립적으로 니트로기, 시아노기, 수소원자， 할로겐기, 탄소수 1 내지 6 의 알킬기， 탄소수 6 내지 15 의 아릴기， 또는 탄소수 2 내지 20 의 헤테로아릴기이고，
Figure imgf000008_0002
및 IV는 각각 독립적으로 수소원자， 할로겐기, 탄소수 1 내지 6 의 알킬기， 탄소수 6 내지 15 의 아릴기, 또는 탄소수 2 내지 20 의 헤테로아릴기이며， 1 내지 10 의 정수이고, 상기 탄소수 1 내지 6 의 알킬기， 탄소수 6 내지 15 의 아릴기， 및 탄소수 2 내지 20 의 헤테로아릴기는 각각독립적으로 니트로기, 시아노기 및 할로겐기로 이루아진 군에서 선택된 1종 이상의 작용기로 치환될 수 있다. In Chemical Formula 2, to ¾ are each independently a nitro group, cyano group, hydrogen atom, halogen group, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 15 carbon atoms, heteroaryl group of 2 to 20 carbon atoms,
Figure imgf000008_0002
And IV are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, an integer of 1 to 10, and the above 1 to 6 carbon atoms An alkyl group, an aryl group having 6 to 15 carbon atoms, and a heteroaryl group having 2 to 20 carbon atoms may be independently substituted with one or more functional groups selected from the group consisting of nitro groups, cyano groups, and halogen groups, respectively.
[화학식 3]  [Formula 3]
Figure imgf000008_0003
Figure imgf000008_0003
상기 화학식 3 에서， 1 내지 å4 는 각각 독립적으로 니트로기, 2019/199032 1»（：1^1{2019/004222 In Formula 3, 1 to å 4 are each independently a nitro group, 2019/199032 1 »（： 1 ^ 1 {2019/004222
시아노기， 수소원자， 할로겐기, 탄소수 1 내지 6 의 알킬기, 탄소수 6 내지 15 의 아릴기， 또는 탄소수 2 내지 20 의 헤테로아릴기이고,
Figure imgf000009_0001
및A cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
Figure imgf000009_0001
And
¾’는 각각 독립적으로 수소원자, 할로겐기， 탄소수 1 내지 6 의 알킬기， 탄소수 6 내지 15 의 아릴기， 또는 탄소수 2 내지 20 의 헤테로아릴기이며， 상기 탄소수 1 내지 6 의 알킬기 , 탄소수 6 내지 15 의 아릴기， 및 탄소수 2 내지 20 의 헤테로아릴기는 각각 독립적으로 니트로기， 시아노기 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 작용기로 치환될 수 있다. 상기 알킬기는， 알케인（ 1«1½）으로부터 유래한 1 가의 작용기로, 예를 들어, 직쇄형， 분지형 또는 고리형으로서， 메틸， 에틸， 프로필, 이소부틸，
Figure imgf000009_0002
16 _부틸, 펜틸， 핵실 등이 될 수 있다. 상기 알킬기에 포함되어 있는 하나 이상의 수소 원자는 각각 치환기로 치환가능하다. ¾ 'are each independently a hydrogen atom, a halogen group, an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms, or a heteroaryl group of 2 to 20 carbon atoms, the alkyl group of 1 to 6 carbon atoms, 6 to 15 carbon atoms The aryl group and the heteroaryl group having 2 to 20 carbon atoms may be independently substituted with one or more functional groups selected from the group consisting of a nitro group, a cyano group and a halogen group. The alkyl group is a monovalent functional group derived from alkane (1 «1½), and is, for example, linear, branched or cyclic, methyl, ethyl, propyl, isobutyl,
Figure imgf000009_0002
16-butyl, pentyl, nuclear chamber and the like. At least one hydrogen atom included in the alkyl group may be substituted with each substituent.
상기 알킬텐기는, 알케인（ 1«1½）으로부터 유래한 2 가의 작용기로， 예를 들어, 직쇄형, 분지형 또는 고리형으로서, 메틸렌기， 에틸렌기， 프로필텐기， 이소부틸렌기， 3（3（： -부틸렌기， 라 부틸텐기， 펜틸렌기， 핵실렌기 등이 될 수 있다. 상기 알킬텐기에 포함되어 있는 하나 이상의 수소 원자는 각각 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다 . 상기 아릴기는 아렌（ 61½）으로부터 유래한 1 가의 작용기로, 예를 들어， 단환식 또는 다환식일 수 있다. 구체적으로, 단환식 아릴기로는 페닐기， 바이페닐기， 터페닐기, 스틸베닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 다환식 아릴기로는 나프틸기, 안트릴기， 페난트릴기， ' 파이레닐기, 페릴레닐기， 크라이세닐기, 플루오레닐，기 등이 될 수 있으나， 이에 한정되는 것은 아니다. 이러한 아릴기 중 하나 이상의 수소 원자는 각각 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다 . The alkylten group is a divalent functional group derived from alkane (1 «1½), and is, for example, a linear, branched or cyclic group, and is a methylene group, ethylene group, propylten group, isobutylene group, 3 (It may be a -butylene group, a labutylene group, a pentylene group, a nuclear styrene group, etc.). One or more hydrogen atoms contained in the alkylten group may be substituted with the same substituents as in the case of the alkyl group, respectively. The aryl group is a monovalent functional group derived from arene (61½), and may be, for example, monocyclic or polycyclic. Specifically, the monocyclic aryl group may be a phenyl group, biphenyl group, terphenyl group, stilbenyl group and the like, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthryl group, phenanthryl group, ' pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. At least one hydrogen atom of such an aryl group may be each substituted with the same substituent as in the alkyl group.
상기 헤테로아릴기는 이종원자로 0，
Figure imgf000009_0003
또는 £ 를 포함하는 헤테로 고리기로서, 탄소수는 특별히 한정되지 않으나 탄소수 2 내지 30 일 수 있다. 헤테로 고리기의 예로는 티오펜기, 퓨란기， 피롤기， 이미다졸기 , 티아졸기 , 옥사졸기， 옥사디아졸기， 트리아졸기 , 피리딜기， 비피리딜기 , 트리아진기， 아크리딜기， 피리다진기， 퀴놀리닐기， 이소퀴놀린기 , 인돌기 , 카바졸기， 벤조옥사졸기， 벤조이미다졸기， 벤조티아졸기 , 벤조카바졸기， 벤조티오펜기 , 2019/199032 1»（：1^1{2019/004222 The heteroaryl group is a hetero atom 0,
Figure imgf000009_0003
Or as a heterocyclic group containing £, carbon number is not particularly limited but may be 2 to 30 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, 2019/199032 1 »（： 1 ^ 1 {2019/004222
디벤조티오펜기, 벤조퓨라닐기 및 디벤조퓨란기 등이 있으나， 이들에만 한정되는 것은 아니다. 이러한 헤테로아릴기 중 하나 이상의 수소 원자는 각각 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다 . Dibenzothiophene group, benzofuranyl group, dibenzofuran group and the like, but are not limited thereto. At least one hydrogen atom of such a heteroaryl group may be each substituted with the same substituent as in the alkyl group.
상기 "치환"이라는 용어는 화합물 내의 수소 원자 대신 다른 작용기가 결합하는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉， 치환기가 치환 가능한 위치라면 한정되지 않으며 , 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.  The term "substituted" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent may be substituted. The substituents may be the same or different from one another.
보다 구체적으로， 상기 화학식 1 은 하기 화학식 1-1 로 표시되는 화합물을 포함할 수 있다.  More specifically, Chemical Formula 1 may include a compound represented by Chemical Formula 1-1.
[화학식 1-1]  [Formula 1-1]
Figure imgf000010_0001
Figure imgf000010_0001
이다.） 등을 들 수 있다.  Etc.).
또한 , 상기 화학식 2는 하기 화학식 2-1로 표시되는 화합물을 포함할 수 있다. 2019/199032 1»（：1^1{2019/004222 In addition, Chemical Formula 2 may include a compound represented by the following Chemical Formula 2-1. 2019/199032 1 »（： 1 ^ 1 {2019/004222
[화학식 2-1] [Formula 2-1]
Figure imgf000011_0004
Figure imgf000011_0004
¾’는 각각 독립적으로 수소원자이며， !11은 1 이다.） 등을 들 수 있다. ¾ 'are each independently a hydrogen atom,! 11 is 1).
또한， 상기 화학식 3는 하기 화학식 3-1로 표시되는 화합물을 포함할 수 있다.  In addition, Chemical Formula 3 may include a compound represented by Chemical Formula 3-1.
[화학식 3-1]  [Formula 3-1]
Figure imgf000011_0001
대한 내용은 상가화학식 3에서 상술한 내용을 포함한다.
Figure imgf000011_0001
The content includes the above-mentioned content in the formula (3).
상기 화학식 3-1 의 구체적인 예로는 2/3,5,6 6 3!11101"（ 61  116- 1，4-（ 꽤比6 （화학식
Figure imgf000011_0002
¾는 할로겐으로 플루오르기
Figure imgf000011_0003
Specific examples of the chemical formula 3-1 include 2 / 3,5,6 6 3! 11101 "(61 116-1,4- (fairly ratio 6
Figure imgf000011_0002
¾ is halogenated fluorine
Figure imgf000011_0003
¾ 및 ¾’는 각각 독립적으로 수소원자이다.）등을 들 수 있다. 한편， 상기 반도체 패키지용 열경화성 수지 조성물은 상술한 성분을 2019/199032 1»（그1^1{2019/004222 ¾ and ¾ 'are each independently a hydrogen atom.) On the other hand, the thermosetting resin composition for a semiconductor package is 2019/199032 1 »（1 ^ 1 {2019/004222
포함함에 따라서 열경화 이후 230 이하， 또는 170 내지 230 °0 , 또는 180 내지 220°(：의 유리 전이 온도를 가질 수 있다. And may include a glass transition temperature of 230 or less, or 170 to 230 ° 0, or 180 to 220 ° (:) after thermosetting.
또한， 상기 반도체 패키지용 열경화성 수지 조성물의 경화 이후 측정한 30^ 및 180° (:에서의 저장 탄성율이 각각 16
Figure imgf000012_0001
이하일 수 있다. 또한, 상기 반도체 패키지용 열경화성 수지 조성물의 경화 이후 측정한 260° (:에서의 저장 탄성율이
Figure imgf000012_0002
이하일 수 있다. 상기 반도체 패키지용 열경화성 수지 조성물은 경화 이후에 30^ 및 180° (:와 같이 상대적으로 낮은 온도 범위에서 16
Figure imgf000012_0003
이하의 낮은 저장 탄성율을 갖는데， 이에 따라 동일 열팽창계수에서 상대적으로 변형력을 나타낼 수 있고 이에 따라 30ᄋ〔 및 180° (:와 같이 낮은 온도 범위에사 반도체패키지의 휨이 상대적으로 낮은 특징을 가질 수 있다. In addition, the storage modulus at 30 ^ and 180 ° (:) measured after curing of the thermosetting resin composition for a semiconductor package was 16, respectively.
Figure imgf000012_0001
It may be: In addition, the storage modulus at 260 ° (: measured after curing of the thermosetting resin composition for a semiconductor package is
Figure imgf000012_0002
It may be: The thermosetting resin composition for the semiconductor package is 16 at a relatively low temperature range, such as 30 ^ and 180 ° (:) after curing.
Figure imgf000012_0003
It has a low storage modulus of less than that, it can exhibit a relatively deformable force at the same coefficient of thermal expansion, and thus can exhibit a relatively low warpage of the semiconductor package at low temperature ranges such as 30 ° [and 180 ° (: have.
상기 반도체 패키지용 열경화성 수지 조성물은 경화 이후에 The thermosetting resin composition for a semiconductor package after curing
260° (:에서 상술한 저장 탄성율을 가짐에 따라서, 이에 따라 동일 열팽창계수에서 상대적으로 변형력을 나타낼 수 있고 이에 따라 260° (:에서 반도체패키지의 휨이 상대적으로 낮은 특징을 가질 수 있다. As a result of the storage modulus described above at 260 ° ( :), it is possible to exhibit a relatively deformable force at the same coefficient of thermal expansion, and thus the warpage of the semiconductor package at 260 ° ( :) may be relatively low.
상기 반도체 패키지용 열경화성 수지 조성물은 경화 이후 12 ? / 1：이하， 또는 5 내지 12^/^ 또는 4 내지 1¾피111广 (0의 열팽창계수를 가질 수 있다. 상기 구현예의 반도체 패키지용 열경화성 수지 조성물은 아민 화합물, 열경화성 수지， 열가소성 수지， 및 무기 충진제를 포함할수 있다. The thermosetting resin composition for a semiconductor package is 12? / 1 or less, or may have a coefficient of thermal expansion of 5 to 12 ^ / ^ or 4 to 1¾ p 111 kon ( 0. The thermosetting resin composition for a semiconductor package of the embodiment is an amine compound, thermosetting resin, thermoplastic resin, and inorganic May contain fillers.
상기 성분의 함량이 크게 한정되는 것은 아니나， 상기 상기 구현예의 반도체 패키지용 열경화성 수지 조성물로부터 제조되는 최종 제품의 물성 등을 고려하여 상술한 성분들을 포함할 수 있으며, 이들 성분간의 함량 비율 등은후술하는 바와 같다.  Although the content of the components is not particularly limited, the above-mentioned components may be included in consideration of the physical properties of the final product manufactured from the thermosetting resin composition for a semiconductor package of the above embodiment, and the content ratio between these components is described below. As shown.
상기 열경화성 수지는 에폭시 수지를 포함할 수 있다. 상기 에폭시 수지로는 통상 반도체 패키지용 열경화성 수지 조성물에 사용되는 것을 2019/199032 1»（：1^1{2019/004222 The thermosetting resin may include an epoxy resin. As said epoxy resin, what is normally used for the thermosetting resin composition for semiconductor packages 2019/199032 1 »（： 1 ^ 1 {2019/004222
제한 없이 사용 할 수 있으며， 그 종류가 한정되지는 않으며， 비스페놀 쇼 형 에폭시 수지， 페놀 노볼락 에폭시 수지， 페닐 아랄킬계 에폭시 수지, 테트라페닐 에탄 에폭시 수지 , 나프탈렌계 에폭시 수지 , 바이페닐계 에폭시 수지， 디시클로펜타디엔 에폭시 수지， 및 디시클로펜타디엔계 에폭시 수지와 나프탈렌계 에폭시 수지의 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다. It can be used without limitation, but the type is not limited, bisphenol show epoxy resin, phenol novolak epoxy resin, phenyl aralkyl epoxy resin, tetraphenyl ethane epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, It may be at least one selected from the group consisting of a dicyclopentadiene epoxy resin, and a mixture of a dicyclopentadiene epoxy resin and a naphthalene epoxy resin.
구체적으로， 상기 에폭시 수지는 하기 화학식 5로 표시되는 비스페놀형 에폭시 수지, 하기 화학식 6로 표시되는 노볼락형 에폭시 수지， 하기 화학식 7로 표시되는 페닐 아랄킬계 에폭시 수지， 하기 화학식 8로 표시되는 테트라페닐에탄형 에폭시 수지， 하기 화학식 9과 10으로 표시되는 나프탈렌형 에폭시 수지, 하기 화학식 11로 표시되는 바이페닐형 에폭시 수지， 및 하기 화학식 12로 표시되는 디시클로펜타디엔형 에폭시 수지로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.  Specifically, the epoxy resin is a bisphenol-type epoxy resin represented by the formula (5), a novolak-type epoxy resin represented by the formula (6), a phenyl aralkyl epoxy resin represented by the formula (7), tetraphenyl represented by the formula (8) 1 selected from the group consisting of an ethane type epoxy resin, a naphthalene type epoxy resin represented by Formulas 9 and 10, a biphenyl type epoxy resin represented by Formula 11, and a dicyclopentadiene type epoxy resin represented by Formula 12: More than one species can be used.
[화학식 5]  [Formula 5]
Figure imgf000013_0001
Figure imgf000013_0001
II은 0 또는 1 내지 50의 정수이다.  II is 0 or an integer from 1 to 50.
보다 구체적으로, 상기 화학식 5의 에폭시 수지는 요의 종류에 따라， 각각 비스페놀 쇼형 에폭시 수지， 비스페놀 형 에폭시 수지 , 비스페놀 형 에폭시 수지 , 또는 비스페놀 £형 에폭시 수지일 수 있다 . 2019/199032 1»（：1^1{2019/004222 More specifically, the epoxy resin of Formula 5 may be a bisphenol show type epoxy resin, a bisphenol type epoxy resin, a bisphenol type epoxy resin, or a bisphenol £ type epoxy resin, respectively, according to the type of urine. 2019/199032 1 »（： 1 ^ 1 {2019/004222
[화학식 6] [Formula 6]
Figure imgf000014_0001
Figure imgf000014_0001
II은 0 또는 1 내지 50의 정수이다.  II is 0 or an integer from 1 to 50.
보다 구체적으로, 상기 화학식 6의 노볼락형 에폭시 수지는 묘의 종류에 따라， 각각 페놀 노볼락형 에폭시 수지 또는 크레졸 노볼락형 에폭시 수지일 수 있다 .  More specifically, the novolak-type epoxy resin of Formula 6 may be a phenol novolak-type epoxy resin or cresol novolak-type epoxy resin, respectively, depending on the type of seedlings.
[화학식 7]  [Formula 7]
Figure imgf000014_0002
Figure imgf000014_0002
[화학식 9] 2019/199032 1»（：1^1{2019/004222 [Formula 9] 2019/199032 1 » （： 1 ^ 1 {2019/004222
Figure imgf000015_0001
Figure imgf000015_0001
상기 화학식 12에서 , II은 0 또는 1 내지 50의 정수이다. 한편， 상기 열경화성 수지는 비스말레이미드 수지， 시아네이트 에스터 수지 및 비스말레이미드-트리아진 수지로 이루어진 군으로부터 선택되는 1종 이상의 수지를 더 포함할 수 있다. 2019/199032 1»（：1^1{2019/004222 In Formula 12, II is 0 or an integer of 1 to 50. On the other hand, the thermosetting resin may further include at least one resin selected from the group consisting of bismaleimide resin, cyanate ester resin and bismaleimide-triazine resin. 2019/199032 1 »（： 1 ^ 1 {2019/004222
상기 비스말레이미드 수지는 통상 반도체 패키지용 열경화성 수지 조성물에 사용되는 것을 제한 없이 사용 할 수 있으며， 그 종류가 한정되지는 않는다. 바람직한 일례를 들면 , 상기 비스말레이미드 수지는 하기 화학식 13으로 표시되는 디페닐메탄형 비스말레이미드 수지， 하기 화학식 14로 표시되는 페닐렌형 비스말레이미드 수지， 하기 화학식 15로 표시되는 비스페놀 쇼형 디페닐 에테르 비스말레이미드 수지， 및 하기 화학식 16으로 표시되는 디페닐메탄형 비스말레이미드 및 페닐메탄형 말레이미드 수지의 올리고머로 구성된 비스말레이미드 수지로 이루어진 군에서 선택된 1종 이상일 수 있다. The bismaleimide resin can be used without limitation usually used in the thermosetting resin composition for semiconductor packages, the type is not limited. As a preferable example, the bismaleimide resin is a diphenylmethane bismaleimide resin represented by the following formula (13), a phenylene type bismaleimide resin represented by the following formula (14), and a bisphenol show diphenyl ether represented by the following formula (15). It may be at least one selected from the group consisting of a bismaleimide resin, and a bismaleimide resin composed of an oligomer of diphenylmethane bismaleimide and phenylmethane type maleimide resin represented by the following formula (16).
[화학식 13]  [Formula 13]
Figure imgf000016_0001
Figure imgf000016_0001
상기 화학식 13에서,  In Chemical Formula 13,
¾ 및 ¾는 각각 독립적으로， （：¾ 또는 ¾¾이다.  ¾ and ¾ are each independently (： ¾ or ¾¾).
[화학식 14]  [Formula 14]
Figure imgf000016_0002
Figure imgf000016_0002
[화학식 16] 2019/199032 1»（：1^1{2019/004222
Figure imgf000017_0001
[Formula 16] 2019/199032 1 »（： 1 ^ 1 {2019/004222
Figure imgf000017_0001
상기 화학식 16에서，  In Chemical Formula 16,
II은 0또는 1 내지 50의 정수이다.  II is 0 or an integer from 1 to 50.
또한， 상기 시아네이트계 수지의 구체적인 예로 시아네이트 에스터 수지를 들 수 있으며， 통상 반도체 패키지용 열경화성 수지 조성물에 사용되는것을 제한 없이 사용 할 수 있으며， 그 종류가 한정되지는 않는다. 바람직한 일례를 들면， 상기 시아네이트 에스터 수지는 하기 화학식 17로 표시되는 노볼락형 시아네이트 수지， 하기 화학식 18로 표시되는 디시클로펜타디엔형 시아네이트 수지， 하기 화학식 19로 표시되는 비스페놀형 시아네이트 수지 및 이들의 일부 트리아진화된 프리폴리머를 들 수 있고， 이들은 단독 혹은 2종 이상혼합하여 사용할 수 있다.  In addition, a specific example of the cyanate-based resin may be cyanate ester resin, and can be used without limitation, usually used in the thermosetting resin composition for semiconductor packages, the type is not limited. As a preferred example, the cyanate ester resin is a novolac cyanate resin represented by the following formula (17), a dicyclopentadiene type cyanate resin represented by the following formula (18), and a bisphenol type cyanate resin represented by the following formula (19). And some triazineylated prepolymers thereof, and these may be used alone or in combination of two or more thereof.
[화학식 17]  [Formula 17]
Figure imgf000017_0002
Figure imgf000017_0002
상기 화학식 17에서，  In Chemical Formula 17,
II은 0또는 1 내지 50의 정수이다.  II is 0 or an integer from 1 to 50.
[화학식 18] 2019/199032 1»（：1^1{2019/004222 [Formula 18] 2019/199032 1 »（： 1 ^ 1 {2019/004222
Figure imgf000018_0001
Figure imgf000018_0001
상기 화학식 18에서，  In Chemical Formula 18,
II은 0 또는 1 내지 50의 정수이다.  II is 0 or an integer from 1 to 50.
[화학식 19]  [Formula 19]
Figure imgf000018_0002
Figure imgf000018_0002
보다 구체적으로, 상기 화학식 19의 시아네이트 수지는 묘의 종류에 따라， 각각 비스페놀 쇼형 시아네이트 수지， 비스페놀 五형 시아네이트 수지， 비스페놀 I?형 시아네이트 수지, 또는 비스페놀 형 시아네이트 수지일 수 있다. More specifically, the cyanate resin of the formula (19) is bisphenol show type cyanate resin, bisphenol five type cyanate resin, bisphenol I ? It may be a type cyanate resin, or a bisphenol type cyanate resin.
그리고 , 상기 비스말레이미드 수지로는 비스말레이미드-트리아진 수지 등을 들 수 있고 , 상기 비스말레이미드-트리아진 수지는 통상 반도체 패키지용 열경화성 수지 조성물에 사용되는 것을 제한 없이 사용 할 수 있으며， 그 종류가 한정되지는 않는다. 한편， 상기 열가소성 수지는 프리프레그의 경화 후, 2019/199032 1»（：1^1{2019/004222 The bismaleimide-triazine resin may be exemplified as the bismaleimide resin, and the bismaleimide-triazine resin may be used without limitation in the thermosetting resin composition for a semiconductor package. Kind is not limited. On the other hand, the thermoplastic resin is, after curing the prepreg, 2019/199032 1 »（： 1 ^ 1 {2019/004222
인성 0'아 ）11½33）을 증가시키는 효과가 있으며， 열팽창계수 및 탄성률을 낮게 하여 반도체 패키지의 휨（\ 대3당6）를 완화시키는 역할을 할 수 있다. 상기 열가소성 수지의 구체적인 예로는 （메트）아크릴레이트계 고분자를 들 수 있다. It has the effect of increasing the toughness 0 ' a) 11½33) and lowers the coefficient of thermal expansion and modulus of elasticity, thereby reducing the warpage (\ 6 per 3) of the semiconductor package. As a specific example of the said thermoplastic resin, a (meth) acrylate type polymer is mentioned.
상기 （메트）아크릴레이트계 고분자의 예가 크게 한정되는 것은 아니며， 예를 들어 （메트）아크릴레이트계 단량체 유래의 반복단위와 （메트）아크릴로니트릴 유래의 반복 단위가 포함되는 아크릴산 에스테르 공중합체; 또는 부타디엔 유래의 반복 단위가 포함되는 아크릴산 에스테르 공중합체일 수 있다. 예를 들어, 상기 （메트）아크릴레아트계 고분자는 부틸아크릴레이트 , 에틸아크릴레이트， 아크릴로니트릴， 메틸메타크릴레이트 , 글리시딜메타크릴레이트 등의 단량체를 각각 1 내지 40중량%의 범위내（단량체 전체의 총 중량 대비）에서 사용하여 공중한 공중합체 일 수 있다.  Examples of the (meth) acrylate-based polymer are not particularly limited, and examples thereof include an acrylic ester copolymer including a repeating unit derived from a (meth) acrylate monomer and a repeating unit derived from (meth) acrylonitrile; Or it may be an acrylic ester copolymer containing a repeating unit derived from butadiene. For example, the (meth) acrylate polymer may be a monomer such as butyl acrylate, ethyl acrylate, acrylonitrile, methyl methacrylate, glycidyl methacrylate in the range of 1 to 40% by weight, respectively. (Compared to the total weight of the entire monomer), which may be a copolymer copolymer.
상기 （메트）아크릴레이트계 고분자는 500 , 000 내지 1 , 000 , 000의 중량평균분자량을 가질 수 있다. 상기 （메트）아크릴레이트계 고분자의 중량평균분자량이 너무 작으면, 경화 후， 프리프레그의 인성 0'아 63）증가나 열팽창률 및 탄성률 감소에 효과가 감소하여 기술적으로 불리할 수 있다. 또한, 상기 （메트）아크릴레이트계 고분자의 중량평균분자량이 너무 크면， 프리프레그의 흐름성을 감소시킬 수 있다.  The (meth) acrylate-based polymer may have a weight average molecular weight of 500, 000 to 1,000, 000. If the weight average molecular weight of the (meth) acrylate-based polymer is too small, it may be technically disadvantageous after curing because the effect is decreased to increase the toughness 0 'or 63) of the prepreg or to decrease the coefficient of thermal expansion and elastic modulus. In addition, when the weight average molecular weight of the (meth) acrylate-based polymer is too large, the flowability of the prepreg can be reduced.
상기 열가소성 수지는 최종 제품의 용도 및 특성 등을 고려하여 사용되는 함량을 결정할 수 있으며， 예를 블어 상기 반도체 패키지용 열경화성 수지 조성물은 상기 열경화성 수지 100 중량부에 대하여 상기 열가소성 수지 10 내지 200 중량부를 포함할 수 있다. 한편, 상기 구현예의 반도체 패키지용 열경화성 수지 조성물은 상술한 아민 화합물을 포함할 수 있으며， 상기 아민 화합물 이외의 추가적인 경화제를 더 포함할 수도 있다.  The thermoplastic resin may determine the content used in consideration of the use and properties of the final product, for example, the thermosetting resin composition for the semiconductor package includes 10 to 200 parts by weight of the thermoplastic resin relative to 100 parts by weight of the thermosetting resin. can do. Meanwhile, the thermosetting resin composition for a semiconductor package according to the embodiment may include the amine compound described above, and may further include an additional curing agent other than the amine compound.
보다 구체적으로, 상기 구현예의 반도체 패키지용 열경화성 수지 조성물은 상기 아민 화합물과 상이한 제 2의 아민 화합물, 산무수물계 수지, 비스말레이미드 수지, 시아네이트계 수지， 페놀 노볼락 수지 및 벤즈옥사진 2019/199032 1»（：1^1{2019/004222 More specifically, the thermosetting resin composition for a semiconductor package of the embodiment is a second amine compound, acid anhydride resin, bismaleimide resin, cyanate resin, phenol novolak resin and benzoxazine different from the amine compound 2019/199032 1 »（： 1 ^ 1 {2019/004222
수지로 이루어진 군에서 선택되는 1종 이상와경화제를 더 포함할수 있다. 또한， 상기 일 구현예의 반도체 패키지용 열경화성 수지 조성물은 무기 충진제를 포함할수 있다. It may further include one or more selected from the group consisting of a resin and a curing agent. In addition, the thermosetting resin composition for a semiconductor package of the embodiment may include an inorganic filler.
상기 무기 충진제는 통상 반도체 패키지용 열경화성 수지 조성물에 사용되는 것을 제한 없이 사용 할 수 있으며, 구체적인 예로는 실리카, 알루미늄 트리하이드록사이드， 마그네슘 하이드록사이드， 몰리브데늄 옥사이드, 징크 몰리브데이트, 징크 보레이트， 징크 스타네이트， 알루미나， 클레이， 카올린， 탈크， 소성 카올린， 소성 탈크， 마이카， 유리 단섬유, 글라스 미세 파우더 및 중공 글라스를 들 수 있으며 이들로 이루어진 군에서 선택된 1종 이상일 수 있다.  The inorganic fillers can be used in the thermosetting resin composition for the semiconductor package is usually used without limitation, specific examples include silica, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate , Zinc stannate, alumina, clay, kaolin, talc, calcined kaolin, calcined talc, mica, short glass fiber, glass fine powder and hollow glass, and may be one or more selected from the group consisting of these.
상기 반도체 패키지용 열경화성 수지 조성물은 상기 열경화성 수지 , 열가소성 수지 및 아민 화합물의 총합 100중량부 대비 무기 충진제 30 내지 300중량부, 또는 30 내지 200중량부， 또는 50 내지 150중량부를 포함할 수 있다. 상기 무기 충진제의 함량이 너무 작으면 열팽창계수가 증가하여 리플로우（: 은 1에） 공정시 휩 현상이 심화되며， 인쇄회로기판의 강성이 감소하는 문제가 있다.  The thermosetting resin composition for a semiconductor package may include 30 to 300 parts by weight, or 30 to 200 parts by weight, or 50 to 150 parts by weight of the inorganic filler relative to a total of 100 parts by weight of the thermosetting resin, the thermoplastic resin, and the amine compound. If the content of the inorganic filler is too small, the coefficient of thermal expansion increases, the whip phenomenon intensifies during the reflow process (in silver 1), and the rigidity of the printed circuit board is reduced.
또한， 상기 표면 처리된 충진제를 사용시， 나노 입경의 작은 사이즈와 마이크로 입경의 큰 사이즈를 함께 사용하여 팩킹 밀도
Figure imgf000020_0001
（ 매 를 높여 충진률을높일 수 있다. In addition, when using the surface-treated filler, the packing density by using a small size of the nano particle size and a large size of the micro particle size together
Figure imgf000020_0001
(The filling rate can be increased by increasing the amount.
상기 무기 충진제는 평균 입경이 상이한 2종 이상의 무기 충진제를 포함할 수 있다. 구체적으로， 상기 2종 이상의 무기 충진제 중 적어도 1종이 평균 입경이 0. 1 im 내지 100 /패인 무기 충진제이고， 다른 1종이 평균 입경이 1 11111 내지 90때인 무기 충진제일 수 있다.  The inorganic filler may include two or more inorganic fillers having different average particle diameters. Specifically, at least one of the two or more inorganic fillers may be an inorganic filler having an average particle size of 0.01 im to 100 / pack, and the other one may be an inorganic filler having an average particle diameter of 1 11111 to 90.
상기 평균 입경이 0. 1 _ 내지 100 인 무기 충진제 100 중량부에 대하여 상기 평균 입경이 1 11111 내지
Figure imgf000020_0002
무기 충진제 함량이 1 중량부 내지 30 중량부일 수 있다. The average particle diameter is 1 11111 to 100 parts by weight of the inorganic filler having an average particle diameter of 0.1 to 100.
Figure imgf000020_0002
The inorganic filler content may be 1 part by weight to 30 parts by weight.
상기 무기 충진제는 내습성, 분산성을 향상시키는 관점에서 실란 커플링제로 표면 처리된 실리카를사용할수 있다.  The inorganic filler may use silica surface-treated with a silane coupling agent from the viewpoint of improving moisture resistance and dispersibility.
상기 무기 충진제를 표면 처리하는 방법은， 실란 커플링제를 표면 2019/199032 1»（：1^1{2019/004222 The method for surface treatment of the inorganic filler, the surface of the silane coupling agent 2019/199032 1 »（： 1 ^ 1 {2019/004222
처리제로 이용하여 실리카 입자를 건식 또는 습식으로 처리하는 방법이 사용될 수 있다. 예를 들어, 실리카 입자 100 중량부를 기준으로 0.01 내지 1 중량부의 실란 커플링제를 사용하여 습식방법으로 실리카를 표면처리하여 사용할 수 있다. Dry or wet treatment of silica particles using the treatment agent may be used. For example, the silica may be surface treated by a wet method using 0.01 to 1 part by weight of the silane coupling agent based on 100 parts by weight of the silica particles.
구체적으로， 상기 실란 커플링제로는 3 -아미노프로필트리에톡시실란， 페닐- 3 -아미노프로필트리메톡시실란 및 N-2-（아미노에틸）- 3- 아미노프로필트리메톡시실란과 같은 아미노실란 커플링제， 3 - 글리시독시프로필트리메톡시실란과 같은 에폭시 실란커플링제， 3 - 메타크릴옥시프로필 트리메톡시실란과 같은 비닐 실란커플링제， ^2-（^ 비닐벤질아미노에틸）- 3 -아미노프로필트리메톡시실란 하이드로클로라이드와 같은 양이온 실란커플링제 및 페닐 실란커플링제를 들 수 있으며， 실란 커플링제는 단독으로 사용될 수 있으며， 또는 필요에 따라 적어도 두 개의 실란 커플링제를 조합하여 사용할 수 있다.  Specifically, the silane coupling agent includes aminosilanes such as 3-aminopropyltriethoxysilane, phenyl-3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. Coupling agent, epoxy silane coupling agent such as 3-glycidoxypropyltrimethoxysilane, vinyl silane coupling agent such as 3-methacryloxypropyl trimethoxysilane, ^ 2-(^ vinylbenzylaminoethyl) -3- Cationic silane coupling agents such as aminopropyltrimethoxysilane hydrochloride and phenyl silane coupling agents, and silane coupling agents may be used alone or in combination of at least two silane coupling agents, if necessary. .
보다 구체적으로， 상기 실란 화합물은 방향족 아미노 실란 또는 （메트）아크릴실란을 포함할 수 있으며, 상기 평균 입경이 0. 1 _ 내지 100 쎈 1인 무기 충진제로는 방향족 아미노 실란이 처리된 실리카를 사용할 수 있고， 상기 평균 입경이 1 내지 90 ■인 무기 충진제로는 （메트）아크릴 실란이 처리된 실리카를 사용할 수 있다. 상기 방향족 아미노 실란아 처리된 실리카의 구체적인 예로는 就 볘附 如크삵군산 사）를 들 수 있고， 상기 （메트）아크릴실란이 처리된 실리카의 구체적인 예로는 쇼0413（凡 （1 33 （ 사）를 들 수 있다 상기 （메트）아크릴은 아크릴 또는 메타크릴을 모두 포함하는 의미로 사용되었다. 그리고, 상기 일 구현예의 반도체 패키지용 열경화성 수지 조성물은 필요에 따라 용제를 첨가하여 용액으로 사용할 수 있다. 상기 용제로는 수지 성분에 대해 양호한 용해성을 나타내는 것이면 그 종류가 특별히 한정되지 않으며， 알코올계， 에테르계， 케톤계， 아미드계， 방향족 탄화수소계， 에스테르계， 니트릴계 등을 사용할 수 있고, 이들은 단독 또는 2종 이상 병용한 혼합 용제를 이용할 수도 있다. 또한 상기 용매의 함량은 프리프레그 제조시 유리섬유에 수지 조성물을 함침할 수 있는 정도면 2019/199032 1»（：1^1{2019/004222 More specifically, the silane compound may include aromatic amino silane or (meth) acrylsilane, and the inorganic filler having an average particle diameter of 0.01 to 100 쎈 1 may use silica treated with aromatic amino silane. In addition, as the inorganic filler having an average particle diameter of 1 to 90 ■, silica treated with (meth) acryl silane can be used. Specific examples of the aromatic amino silane-treated silica include 就 볘 附 삵 삵 삵 삵 삵 삵 삵 삵 삵 삵 산 Co., Ltd., and the specific example of the (meth) acrylic silane-treated silica is shown in the show 0413 (凡 (1 33 (）)) The said (meth) acryl was used by the meaning containing all acryl or methacryl. In addition, the thermosetting resin composition for a semiconductor package according to the embodiment may be used as a solution by adding a solvent as necessary. The solvent is not particularly limited as long as it shows 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 mixed solvent which used 2 or more types together. In addition, the content of the solvent is enough to impregnate the resin composition in the glass fiber during prepreg production 2019/199032 1 »（： 1 ^ 1 {2019/004222
특별히 한정되지 않는다. It is not specifically limited.
또한 상기 반도체 패키지용 열경화성 수지 조성물은, 수지 조성물 고유의 특성을 손상시키지 않는 한, 기타 열경화성 수지, 열가소성 수지 및 이들의 올리고머 및 엘라스토머와 같은 다양한 고분자 화합물， 기타 난연성 화합물 또는 첨가제를 더 포함할 수도 있다. 이들은 통상적으로 사용되는 것으로부터 선택되는 것이라면 특별히 한정하지 않는다.예를 들어 첨가제로는 자외선흡수제 , 산화방지제， 광중합개시제 , 형광증백제 , 광증감제, 안료， 염료, 증점제， 활제, 소포제， 분산제， 레벨링제， 광택제 등이 있고， 목적에 부합되도록 혼합하여 사용하는 것도 가능하다. 한편， 발명의 다른 구현예에 따르면, 상기 반도체 패키지용 열경화성 수지 조성물 및 섬유 기재를 포함하는, 프리프레그가 제공 될 수 있다.  In addition, the thermosetting resin composition for a semiconductor package may further include various high molecular compounds such as other thermosetting resins, thermoplastic resins, and oligomers and elastomers thereof, and other flame retardant compounds or additives, so long as the properties of the resin composition are not impaired. . They are not particularly limited as long as they are selected from those commonly used. For example, additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, pigments, dyes, thickeners, lubricants, antifoaming agents, dispersants, Leveling agents, varnishes and the like, it is also possible to use a mixture to meet the purpose. Meanwhile, according to another embodiment of the present invention, a prepreg including the thermosetting resin composition for the semiconductor package and the fiber substrate may be provided.
상기 프리프레그는 상기 반도체 패키지용 열경화성 수지 조성물이 반경화상태로 섬유 기재에 함침되어 있는 것을 의미한다.  The prepreg means that the thermosetting resin composition for the semiconductor package is impregnated into the fiber base material in a semi-cured state.
상기 섬유 기재는 그 종류가 특별히 한정되지는 않으나， 유리 섬유 기재, 폴리아미드 수지 섬유, 방향족 폴리아미드 수지 섬유 등의 폴리아미드계 수지 섬유, 폴리에스테르 수지 섬유， 방향족 폴리에스테르 수지 섬유， 전 방향족 폴리에스테르 수지 섬유 등의 폴리에스테르계 수지 섬유, 폴리이미드 수지 섬유, 폴리벤족사졸 섬유, 불소 수지 섬유 등을 주성분으로 하는 직포 또는 부직포로 구성되는 합성 섬유 기재, 크래프트지, 코튼 린터지, 린터와 크래프트 펄프의 혼초지 등을 주성분으로 하는 종이 기재 등이 사용될 수 있으며, 바람직하게 유리 섬유 기재를 사용한다. 상기 유리 섬유 기재는 프리프레그의 강도가 향상되고 흡수율을 내릴 수 있으며, 또 열팽창 계수를 작게 할수 있다.  Although the kind of the fiber base material is not particularly limited, 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, kraft paper, cotton linter paper, linter and kraft pulp composed of woven or non-woven fabric mainly composed of polyester resin fibers such as resin fibers, polyimide resin fibers, polybenzoxazole fibers, and fluororesin fibers Paper substrates based on honcho paper and the like may be used, and glass fiber substrates are preferably used. The glass fiber substrate can improve the strength of the prepreg, lower the water absorption rate, and reduce the coefficient of thermal expansion.
상기 유리 섬유 기재는 다양한 인쇄회로가판 물질용으로 사용되는 유리기재로부터 선택될 수 있다. 끼들의 예로서는， £ 글라스， 0 글라스， 3 글라스， I 글라스，
Figure imgf000022_0001
글라스 및 느 글라스， 0 글라스와 같은 유리 섬유를 포함하나 이에 한정되는 것은 아니다. 필요에 따라서 의도된 용도 또는 성능에 따라， 상기 유리기재 물질을 선택할 수 '있다. 유리기재 형태는 전형적으로 직포, 부직포 , 로빙（］： ^11용）， 잘개 다진 스트랜드 매트 0 2019/199032 1»（：1^1{2019/004222 대 111 ） 또는 서페이싱 매트（ 미 ）이다. 상기 유리기재 기재의 두께는 특별히 한정되지 않지만, 약 0.01 내지 0.3ä 등을 사용할 수 있다. 상기 물질 중， 유리 섬유 물질이 강도 및 수분 흡수 특성 면에서 더욱 바람직하다. The glass fiber substrate can be selected from glass substrates used for various printed circuit board materials. Examples of meals are £ glass, 0 glass, 3 glass, I glass,
Figure imgf000022_0001
Glass fibers such as glass and no glass and zero glass include, but are not limited to. Depending on the intended use or performance as required, and the glass can select a base material. Glass-based forms are typically woven, non-woven, rovings (for ^ 11), chopped strand mats 0 2019/199032 1 »（： 1 ^ 1 {2019/004222 versus 111） or surfacing mat (US). Although the thickness of the said glass base material is not specifically limited, About 0.01-0.3ä etc. can be used. Of these materials, glass fiber materials are more preferred in terms of strength and water absorption properties.
또한 상기 프리프레그를 제조하는 방법은 특별히 한정되지 않으며, 이 분야에 잘 알려진 방법에 의해 제조될 수 있다. 예를 들면, 상기 프리프레그의 제조방법은 함침법， 각종 코터를 이용하는 코팅법, 스프레이 분사법 등을 이용할수 있다.  In addition, the method for preparing the prepreg is not particularly limited, and may be prepared by a method well known in the art. For example, the method of manufacturing the prepreg may be an impregnation method, a coating method using various coaters, a spray injection method, or the like.
상기 함침법의 경우 바니시를 제조한후， 상기 섬유 기재를 바니시에 함참하는 방법으로 프리프레그를 제조할수 있다.  In the case of the impregnation method, after the varnish is manufactured, the prepreg may be manufactured by joining the fiber substrate to the varnish.
즉， 상기 프리프레그의 제조 조건 등은 특별히 제한하는 것은 아니지만， 상기 반도체 패키지용 열경화성 수지 조성물에 용제를 첨가한 바니시 상태로 사용하는 것이 바람직하다. 상기 수지 바니시용 용제는 상기 수지 성분과 혼합 가능하고 양호한 용해성을 갖는 것이라면 특별히 한정하지 않는다. 이들의 구체적인 예로는， 아세톤， 메틸 에틸 케톤, 메틸이소부틸 케톤 및 시클로핵사논과 같은 케톤， 벤젠, 톨루엔 및 자일렌과 같은 방향족 하이드로카본， 및 디메틸포름아미드 및 디메틸아세트아미드와 같은 아미드, 메틸셀로솔브 , 부틸셀로솔브 같은 알리파틱 알코올등이 있다 .  That is, although the manufacturing conditions, etc. of the said prepreg are not specifically limited, It is preferable to use it in the varnish state which added the solvent to the said thermosetting resin composition for semiconductor packages. The solvent for the resin varnish is not particularly limited as long as it can be mixed with the resin component and has good solubility. Specific examples thereof 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, methylcello Aliphatic alcohols such as sorb and butyl cellosolve.
또한, 상기 프리프레그로 제조시， 사용된 용제가 80 중량% 이상 휘발하는 것이 바람직하다. 이 때문에， 제조 방법이나 건조 조건 등도 제한은 없고， 건조시의 온도는 약 80
Figure imgf000023_0001
내지 200 °（1， 시간은 바니시의 겔화 시간과의 균형으로 특별히 제한은 없다. 또한， 바니시의 함침량은 바니시의 수지 고형분과 기재의 총량에 대하여 바니시의 수지 고형분이 약 30 내지 80중량%가 되도록 하는 것이 바람직하다. In the preparation of the prepreg, it is preferable that the solvent used is volatilized by 80% by weight or more. For this reason, there is no restriction | limiting in manufacturing method, drying conditions, etc., The temperature at the time of drying is about 80
Figure imgf000023_0001
To 200 ° (1, time is not particularly limited in balance with the gelation time of the varnish). The varnish impregnation amount is preferably such that the resin solid content of the varnish is about 30 to 80% by weight based on the total amount of the resin solid content of the varnish and the base material.
, 또한， 발명의 또 다른 구현예에 따르면， 시트 형상을 갖는 상술한 프리프레그; 및 상기 프리프레그의 적어도 일면에 형성된 금속박;을 포함하는 금속박 적층판이 제공될 수 있다. 2019/199032 1»（：1^1{2019/004222 In addition, according to another embodiment of the invention, the above-described prepreg having a sheet shape; And a metal foil formed on at least one surface of the prepreg. 2019/199032 1 »（： 1 ^ 1 {2019/004222
상기 금속박은 동박; 알루미늄박; 니켈， 니켈-인, 니켈-주석 합금， 니켈-철 합금， 납 또는 납-주석 합금을 중간층으로 하고, 이 양면에 서로 다른 두께의 구리층을 포함하는 3층 구조의 복합박; 또는 알루미늄과 동박을 복합한 2층 구조의 복합박을 포함한다. The metal foil is copper foil; Aluminum foil; A composite foil having a three-layer structure including nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy as an intermediate layer, and including copper layers having different thicknesses on both surfaces thereof; Or the composite foil of the two-layered structure which combined aluminum and copper foil.
바람직한 일예에 따르면 , 상기 금속박은 동박이나 알루미늄박이 이용되고, 약 2 내지 200 썬 !의 두께를 갖는 것을 사용할 수 있지만, 그 두께가 약 2 내지 35 이인 것이 바람직하다. 바람직하게， 상기 금속박으로는 동박을 사용한다. 또한, 상기 금속박으로서 니켈， 니켈-인, 니켈-주석 합금， 니켈-철 합금， 납, 또는 납-주석 합금 등을 중간층으로 하고, 이의 양면에 0.5 내지 15 의 구리층과 10 내지 300 III의 구리층을 설치한， 3층 구조의 복합박 또는 알루미늄과 동박을 복합한 2층 구조 복합박을사용할수도 있다.  According to a preferred example, the metal foil may be a copper foil or an aluminum foil, and a metal having a thickness of about 2 to 200 sun rays may be used, but the thickness thereof is preferably about 2 to 35. Preferably, copper foil is used as said metal foil. Further, as the metal foil, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy is used as an intermediate layer, and 0.5 to 15 copper layers and 10 to 300 III copper on both surfaces thereof. It is also possible to use a three-layered composite foil having layers, or a two-layer composite foil composed of aluminum and copper foil.
이렇게 제조된 프리프레그를 포함하는 금속 적층판은 1매 이상으로 적층한 후， 양면 또는 다층 인쇄 회로 기판의 제조에 사용할 수 있다. 상기 금속박 적층판을 회로 가공하여 양면 또는 다층 인쇄회로기판을 제조할 수 있으며， 상기 회로 가공은 일반적인 양면 또는 다층 인쇄 회로 기판 제조 공정에서 행해지는 방법을 적용할수 있다.  The metal laminated plate containing 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 metal foil laminate may be circuit processed to manufacture a double-sided or multilayer printed circuit board, and the circuit processing may be applied to a method performed in a general double-sided or multilayer printed circuit board manufacturing process.
【발명의 효과】  【Effects of the Invention】
본 발명에 따르면， 우수한 흐름성을 확보할 수 있고， 낮은 유리전이온도 및 모듈러스， 낮은 열팽창률을 구현할 수 있으며， 휨（ 크대크당 현상을 최소화 할 수 있는 반도체 패키지용 열경화성 수지 조성물과, 상기 반도체 패키지용 열경화성 수지 조성물을 이용하여 제공되는 프리프레그와， 상기 프리프레그를 포함하는 금속박 적층판이 제공될 수 있다.  According to the present invention, excellent flowability can be ensured, low glass transition temperature and modulus, low thermal expansion rate can be achieved, and warpage (the thermosetting resin composition for a semiconductor package capable of minimizing a phenomenon per large bulk), and the semiconductor package A prepreg provided using the thermosetting resin composition for metal, and a metal foil laminate including the prepreg may be provided.
【발명을실시하기 위한구체적인 내용】  [Specific contents for carrying out invention]
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단， 하기의 실시예는 본 발명을 예시하는 것일 뿐， 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다. ＜실시예 및 비교예 : 반도체 패키지용 열경화성 수지 조성물, 프리프레그 및 동박적층판＞ The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. <Example and Comparative Example: Thermosetting resin composition for semiconductor package, Prepreg and Copper Clad Laminates ＞
(1) 반도체 패키지용 열경화성 수지 조성물의 제조  (1) Preparation of thermosetting resin composition for semiconductor package
하기 표 1 및 표 2의 조성에 따라， 각성분을 메틸에틸케톤에 고형분 40%에 맞추어 투입하여 혼합한 후, 400 rpm 속도로 하루동안 상온 교반하여 실시예 및 비교예의 반도체 패키지용 수지 조성물 (수지 바니시 )를 제조하였다. 구체적으로 상기 실시예에서 제조된 수지 조성물의 구체적인 조성은 하기 표 1에 기재된 바와 같고, 상기 비교예에서 제조된 수지 조성물의 구체적인 조성은 하기 표 2에 기재된 바와 같다.  According to the composition of Table 1 and Table 2, each component was added to methyl ethyl ketone according to the solid content of 40% and mixed, and then stirred at room temperature at 400 rpm for one day to prepare the resin compositions for semiconductor packages of Examples and Comparative Examples (resin Varnish) was prepared. Specifically, the specific composition of the resin composition prepared in Example is as shown in Table 1 below, and the specific composition of the resin composition prepared in Comparative Example is as shown in Table 2 below.
(2) 프리프레그 및 동박 적층판의 제조  (2) Preparation of prepreg and copper foil laminate
상기 제조된 반도체 패키지용 수지 조성물 (수지 바니시)을 두께 Thickness of the resin composition (resin varnish) for the semiconductor package prepared above
13이의 유리 섬유 (Ni t tobo사 제조, T-gl ass #1010)에 함침시킨 후,After impregnating 13 glass fibers (manufactured by Ni t tobo, T-gl ass # 1010),
170 。(:의 온도에서 2~5분간 열풍 건조하여 18_의 프리프레그를 제조하였다. 상기에서 제조된 프리프레그 2매를 적층한후, 그 양면에 동박 (두께 12m Mi tsui사 제조)을 위치시켜 적층하고， 220 °C 및 35 kg/oif의 조건으로 100분간 경화시켜 동박 적층판을 제조하였다. Hot air was dried at a temperature of 170 ° C. for 2 to 5 minutes to prepare a prepreg of 18_. Two sheets of the prepregs prepared above were laminated, and copper foil (12 m thick) was placed on both sides thereof. The laminate was laminated and cured for 100 minutes under conditions of 220 ° C. and 35 kg / oif to prepare a copper foil laminate.
＜실험예: 실시예 및 비교예에서 얻어진 반도체 패키지용 열경화성 수지 조성물, 프리프레그 및 동박 적층판의 물성 측정＞ <Experimental example: Measurement of the physical properties of the thermosetting resin composition for semiconductor packages, the prepreg, and the copper foil laminated sheet obtained by the Example and the comparative example>
상기 실시예 및 비교예에서 얻어진 반도체 패키지용 열경화성 수지 조성물， 프리프레그 및 동박 적층판의 물성을 하기 방법으로 측정하였으며， 그 결과를 표 3에 나타내었다.  The physical properties of the thermosetting resin composition for a semiconductor package, the prepreg, and the copper foil laminated sheet obtained in the said Example and the comparative example were measured by the following method, The result is shown in Table 3.
1. 열팽창계수 (CTE) 1.Coefficient of Thermal Expansion (CTE)
상기 실시예 및 비교예에서 얻어진 동박 적층판의 동박층을 에칭하여 제거한 후， MD방향으로 시험편을 제작하여, TMA(TA Instruments , Q400)를 이용하여， 30 °C에서 260 °C까지 , 승온 속도 10 °C /min 조건으로 측정한후， 50 °C 에서 150 °C 범위의 측정값을 열팽창계수로 기록하였다. After etching and removing the copper foil layer of the copper foil laminate obtained in the above Examples and Comparative Examples, to prepare a test piece in the MD direction, using a TMA (TA Instruments, Q400), from 30 ° C to 260 ° C, heating rate 10 After the measurement in ° C / min, the measured value in the range of 50 ° C to 150 ° C was recorded as the coefficient of thermal expansion.
2. 유리전이온도 0¾) 2019/199032 1＞（그1'/표1¾2019/004222 2. Glass transition temperature 0¾) 2019/199032 1 ＞ （1 '/ Table 1¾2019 / 004222
상기 실시예 및 비교예에서 얻어진 동박 적층판의 동박층을 에칭하여 제거한 후， MD방향으로 시험편을 제작하고, DMA(TA Instruments, Q800)를 이용하여 인장모드로 5°C/분의 승온조건으로 25°C부터 300°C까지 측정하여 tan delta의 피크 온도를 유리전이온도로 하였다. After etching and removing the copper foil layer of the copper foil laminate obtained in the above Examples and Comparative Examples, a test piece was prepared in the MD direction, and using a DMA (TA Instruments, Q800) in a tensile mode at a temperature of 5 ° C./min 25 The peak temperature of tan delta was measured as the glass transition temperature by measuring from ° C to 300 ° C.
3. 저장탄성률측정 (Storage Modulus) 3. Storage Modulus
상기 실시예 및 비교예에서 얻어진 동박 적층판의 동박층을 에칭하여 제거한 후, MD방향으로 시험편을 제작하고, DMATA Instruments, Q800)를 이용하여 인장모드로 5°C/분의 승온조건으로 25°C부터 30CTC까지 저장탄성률을 즉정하였다. After etching and removing the copper foil layer of the copper foil laminate obtained in the above Examples and Comparative Examples, to prepare a test piece in the MD direction, using a DMATA Instruments, Q800) 25 ° C. at a temperature rising condition of 5 ° C / min in tensile mode The storage modulus from 30CTC was immediately determined.
4. 회로패턴 채움성 4. Filling of circuit pattern
상기 실시예 및 비교예에서 얻어진 프리프레그를, 회로패턴 (패턴높이 7um„ 잔동률 50%)의 양면에 위치시키고， 그 위에 동박 (두께
Figure imgf000026_0001
Mitsui사 제조)을 위치시켜, 220 °C 및 35 kg/cuf의 조건으로 100분간 프레스한 후， 양면의 동박을 에칭하여， 다음 기준 하에 회로패턴 채움성을 평가하였다. The prepreg obtained by the said Example and the comparative example is located in both surfaces of a circuit pattern (pattern height 7um 'residual ratio 50%), and copper foil (thickness) on it
Figure imgf000026_0001
Mitsui Co., Ltd.) was placed, pressed for 100 minutes under conditions of 220 ° C. and 35 kg / cuf, and then the copper foils on both sides were etched, and the circuit pattern fillability was evaluated under the following criteria.
◦ : Void발생 없음  ◦: No void
X : Void발생  X: Void occurrence
5. 인장신율(Tensile Elongation)측정 5. Tensile Elongation Measurement
상기 실시예 및 비교예에서 얻어진 프리프레그를 유리섬유의 MD 및 TD방향이 일치하도록 15매를 적층하여, 220 °C 및 35 kg/cm2의 조건으로 100분간 프레스 한 후, IPC-TM-650 (2.4.18.3)에 따라， Universal Testing MachineClnstron 3365)장비를 이용하여 MD방향의 인장신율을 측정하였다. 15 sheets of the prepreg obtained in the above Examples and Comparative Examples were laminated so as to match the MD and TD directions of the glass fibers, and pressed for 100 minutes at 220 ° C and 35 kg / cm 2 , followed by IPC-TM-650 In accordance with (2.4.18.3), tensile elongation in the MD direction was measured using a Universal Testing Machine Clnstron 3365 instrument.
6. 반도체 패키지의 휨 (ffarpage측정) 6. Deflection of semiconductor package (ffarpage measurement)
상기 실시예 및 비교예에서 얻어진 동박 적층판에서 동박의 일부를 통상의 에칭법을 통해 배선을 가공하여 프린트배선판을 제조하였다 (두께 90·) . 제조된 프린트배선판에 반도체칩 (11.5_ X 11.5mm x 두께 80um)을 탑재하여 반도체 패키지 ( 14.5mm x 14.5mm x 두께 390um)를 제조하였다. 제조된 반도체 패키지에 대하여 휨측정장치 (AKR0METRIX사 THERMO IREIn the copper foil laminated sheet obtained by the said Example and the comparative example, a part of copper foil was processed through the normal etching method, and the printed wiring board was manufactured (thickness 90 *). Semiconductor chip (11.5_ X 11.5mm x Thickness 80um) It was mounted to prepare a semiconductor package (14.5mm x 14.5mm x thickness 390um). Bending measuring device for manufactured semiconductor packages (AKR0METRIX company THERMO IRE
PS100)을 이용하여 Shadow Moi re측정이론에 근거하여 휨을 측정하였다. 휨은 상기의 반도체 패키지를 30°C에서 260°C까지 측정하고， 그 이후 30°C까지 냉각하였을 때， 휨의 최대값과 최소값의 차이로 구하였고, 다음과 같은 기준하에 반도체 패키지의 휨을 평가하였다. PS100) was used to measure the warpage based on Shadow Moi re measurement theory. The warpage was determined by measuring the semiconductor package from 30 ° C. to 260 ° C. and then cooling to 30 ° C. as a difference between the maximum and minimum values of the warpage. The warpage of the semiconductor package was evaluated based on the following criteria. It was.
◦ : 휨의 최대값과 최소값차이가 170um 이하  ◦: The difference between the maximum and minimum value of warpage is less than 170um
X : 휨의 최대값과 최소값차이가 170um 이상 7. 열 응력 인자 (Thermal Stress Factor) 계산  X: The difference between the maximum and minimum value of warpage is over 170um 7. Calculation of Thermal Stress Factor
상기 얻어진 열팽창계수와 저장탄성율을 바탕으로 3CTC에서 260°C까지 TC단위로 각 온도에서의 열팽창계수와 저장탄성률을 곱한 후， 모두 합하여 하기 일반식 1의 열 응력 인자 (Thermal St ress Factor )을 측정 (계산)하였다. Based on the coefficient of thermal expansion and storage modulus obtained, multiply the coefficient of thermal expansion and storage modulus at each temperature by TC unit from 3CTC to 260 ° C., and then add all together to measure the thermal stress factor of the following general formula (1). (Calculated).
［일반식 1］  [General formula 1]
열 응력 인자 (Thermal Stress Factor , 단위 : MPa)  Thermal Stress Factor (Unit: MPa)
= J［저장탄성률 (Storage Modulus) * 열팽창계수］ dT  = J [Storage Modulus * Thermal expansion coefficient] dT
［표 1］ 실시예의 반도체 패키지용 열경화성 수지 조성물의 조성 및 프리프레그의 물성 확인 (단위: g) TABLE 1 Composition of thermosetting resin composition for semiconductor packages of Examples and physical properties of prepreg (unit: g)
Figure imgf000027_0001
2019/199032 1»(：1/10公019/004222
Figure imgf000028_0001
Figure imgf000027_0001
2019/199032 1 »(： 1/10 公 019/004222
Figure imgf000028_0001
[표 2] 비교예의 반도체 패키지용 열경화성 수지 조성물의 조성 및 프리프레그의 물성 확인 （단위: g）[Table 2] Composition of thermosetting resin composition for semiconductor package of comparative example and physical properties of prepreg (unit: g)
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000028_0002
Figure imgf000029_0001
* : 4,4’ - 31 110(1：［1)11611：71 3111군0!½ *: 4,4 '-31 110 (1 ： [1) 11611 ： 71 3111 group 0! ½
* TFB: 2,2'-bis(trifluoromethyl )benzidine； 2,2'- * TFB: 2,2'-bis (trifluoromethyl) benzidine; 2,2'-
Bis(tri fluoromethyl )-4,4’-biphenyldiamine Bis (tri fluoromethyl) -4,4′-biphenyldiamine
* DDM: 4,4'-diaminodiphenyl methane  * DDM: 4,4'-diaminodiphenyl methane
* XD-1000： 에폭시 수지 (Nippon kayaku사)  * XD-1000: epoxy resin (Nippon kayaku)
* NC-3000H: 에폭시 수지 (Nippon kayaku사)  * NC-3000H: epoxy resin (Nippon kayaku)
* HP-6000： 에폭시 수지 (DIC사) * BMI-2300: 비스말레이미드계 수지 (DAIWA KASEI사)* HP-6000 ： Epoxy Resin (DIC Corporation) * BMI-2300: Bismaleimide Resin (DAIWA KASEI Co., Ltd.)
* Acrylic rubber B(Mw 800,000): PARACRON KG_3015P(Negami chemical industrial Co.，LTD사) * Acrylic rubber B (Mw 800,000): PARACRON KG_3015P (Negami chemical industrial Co. ， LTD company)
* Acrylic rubber C(Mw 600,000): PARACRON KG_3113(Negami chemical industrial Co., LTD사)  * Acrylic rubber C (Mw 600,000): PARACRON KG_3113 (Negami chemical industrial Co., LTD)
* 당량비 : 하기 수학식 1을통해 계산됨 ·  * Equivalence Ratio: Calculated Through Equation 1
[수학식 1]  [Equation 1]
열경화성 수지 대비 아민 화합물 당량비  Equivalent compound ratio of amine compound to thermosetting resin
= (DDS 의 총 활성수소 당량 + TFB의 총 활성수소 당량 + DDM의 총 활성수소 당량) / {(XD-1000의 총 에폭시 당량 + NC-3000H의 총 에폭시 당량 + HP-6000의 총 에폭시 당량) + (BMI-2300의 총 말레이미드 당량)} 상기 수학식 1에서, DDS의 총 활성,수소 당량은 DDS의 총 중량 (g)을 DDS의 활성수소 단위당량 (62g/eq)으로 나눈 값이고，= (Total active hydrogen equivalent of DDS + total active hydrogen equivalent of TFB + total active hydrogen equivalent of DDM) / {(total epoxy equivalent of XD-1000 + total epoxy equivalent of NC-3000H + total epoxy equivalent of HP-6000) + (Total maleimide equivalent of BMI-2300)} In Equation 1, the total activity , hydrogen equivalent weight of DDS is the total weight (g) of DDS divided by the unit equivalent weight of active hydrogen (62 g / eq) of DDS,
묘의 총 활성수소 당량은 TFB의 총 중량 (g)을 TFB의 활성수소 단위당량 (80g/eq)으로 나눈 값이고，  The total active hydrogen equivalent of seedlings is the total weight (g) of TFB divided by the unit equivalent of TFB (80 g / eq),
DDM의 총 활성수소 당량은 DDM의 총 중량 (g)을 DDM의 활성수소 단위당량 (49.5g/eq)으로 나눈 값이고，  The total active hydrogen equivalent of DDM is the total weight of DDM divided by the unit equivalent of active hydrogen of DDM (49.5 g / eq),
XD-1000의 총 에폭시 당량은 XD-1000의 총 중량 (g)을 XD-1000의 에폭시 단위당량 (253g/eq)으로 나눈 값이고，  The total epoxy equivalent of XD-1000 is the total weight (g) of XD-1000 divided by the epoxy unit equivalent (253 g / eq) of XD-1000,
NC-3000H의 총 에폭시 당량은 NC-3000H의 총 중량 (g)을 NC-3000H의 에폭시 단위당량 (290g/eq)으로 나눈 값이고,  The total epoxy equivalent of NC-3000H is the total weight (g) of NC-3000H divided by the epoxy unit equivalent (290 g / eq) of NC-3000H,
HP-6000의 총 에폭시 당량은 HP-6000의 총 중량 (g)을 HP-6000의 에폭시 단위당량 (250g/eq)으로 나눈 값이고,  The total epoxy equivalent of HP-6000 is the total weight of HP-6000 divided by the epoxy equivalent of HP-6000 (250 g / eq),
BMI-2300의 총 말레이미드 당량은 BMI-230◦의 총 중량 (g)을 BMI- 2300의 말레이미드 단위당량 (179g/eq)으로 나눈 값이다. 상기 표 1에 나타난 바와 같이 , 실시예와 같이 전자끌기 (Electron Withdrawing Group, EWG)를 갖는 아민 화합물을 포함한 프리프레그는 230 °C 이하의 유리 전이 온도를 가지고， 10 ppm/°C 의 낮은 열팽창률을 가지면서도 우수한회로패턴 채움성을 갖는다는 점이 확인되었다. 즉, 실시예와 같이 전자끌기 (El ectron Wi thdrawing Group , EWG)를 갖는 아민 화합물 100 중량부 대비 290 중량부 이하의 열경화성 수지를 포함하고， 열경화성 수지 당량 기준 아민 화합물 당량비율인 당량비가 1.4 이상을 만족하면서， 무기 첨가제의 첨가량을 열경화성 수지, 열가소성 수지 및 아민 화합물의 총합 100중량부 대비 50 중량비에서 150 중량부의 무기 첨가제를 포함하는 경우, 반도체 패키징에 접합한 열적 특성， 우수한 저열팽창 특성, 흐름성 및 기계적 물성을 확보할 수 있음을 확인하였다. 한편, 실시예들에서 얻어진 각각의 프리프레그에 대한 열 응력 인자가 21 Mpa 아하라는 점이 확인되는데, 이러한 열 응력 인자를 갖는 프리프레그를 이용하여 제조된 반도체 패키지는 상대적으로 낮은 수준의 휨 (Warpage)만을 나타내는 것으로 확인되었다. 이에 반해서 , 비교예들에서 얻어진 각각의 프리프레그에 대한 열 응력 인자가 25 Mpa 초과이며， 이러한 높은 열 응력 인자를 갖는 프리프레그를 이용하여 제조된 반도체 패키지는 상대적으로 높은 휨이 발생한다는 점이 확인되었다. The total maleimide equivalent of BMI-2300 is the total weight (g) of BMI-230 divided by the male equivalent of BMI-2300 (179 g / eq). As shown in Table 1, the prepreg containing the amine compound having an electron withdraw (Electron Withdrawing Group, EWG) as in the embodiment has a glass transition temperature of 230 ° C or less, low thermal expansion coefficient of 10 ppm / ° C It has been confirmed that it has a good circuit pattern fillability while having. That is, as shown in Example, the equivalent ratio of the amine compound equivalent ratio based on the thermosetting resin equivalent ratio is 1.4 or more, including 290 parts by weight or less of the thermosetting resin with respect to 100 parts by weight of the amine compound having an elektron drawing (EWG). When satisfactory, the amount of the inorganic additive added is 150 parts by weight in an amount of 50 parts by weight based on 100 parts by weight of the total amount of the thermosetting resin, the thermoplastic resin and the amine compound, the thermal properties bonded to the semiconductor packaging, excellent low thermal expansion characteristics, flowability And it was confirmed that the mechanical properties can be secured. On the other hand, it is confirmed that the thermal stress factor for each prepreg obtained in the examples is less than 21 Mpa. A semiconductor package manufactured using the prepreg having such a thermal stress factor has a relatively low level of warpage. It was confirmed to represent only. In contrast, it was confirmed that the thermal stress factor for each prepreg obtained in the comparative examples is more than 25 Mpa, and the semiconductor package manufactured using the prepreg having such a high thermal stress factor generates relatively high warpage. .

Claims

2019/199032 1»（：1^1{2019/004222 2019/199032 1 »（： 1 ^ 1 {2019/004222
【청구범위】 [Claim]
【청구항 11  [Claim 11
술폰기; 카보닐기; 할로겐기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 니트로기, 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기; 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴기; 및 니트로기， 시아노기 또는 할로겐기로 치환 또는 비치환된 탄소수 1 내지 20의 알킬텐기 ;로 이루어진 군에서 선택된 1종 이상의 작용기를 1이상 포함한 아민 화합물，  Sulfone groups; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; A heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; And an amine compound containing at least one functional group selected from the group consisting of an alkylten group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group,
열경화성 수지,  Thermosetting resin,
열가소성 수지, 및  Thermoplastic resins, and
무기 충진제를 포함하고,  Contains inorganic fillers,
230 X： 이하의 유리 전이 온도를 갖는, 반도체 패키지용 열경화성 수지 조성물.  230X: The thermosetting resin composition for semiconductor packages which has a glass transition temperature of the following.
【청구항 2] [Claim 2]
제 1항에 있어서，  The method of claim 1,
상기 아민 화합물 100중량부 대비 상기 열경화성 수지 400중량부 이하로 포함하는,  It comprises less than 400 parts by weight of the thermosetting resin relative to 100 parts by weight of the amine compound,
반도체 패키지용 열경화성 수지 조성물.  Thermosetting resin composition for semiconductor packages.
【청구항 3】 [Claim 3]
제 1항에 있어서,  The method of claim 1,
하기 수학식 1로 계산되는 당량비가 1 . The equivalent ratio calculated by Equation 1 is 1.
4 이상인， 반도체 패키지용 수자 조성물: A water composition for semiconductor packages of 4 or more:
[수학식 1]  [Equation 1]
당량비 = 상기 아민 화합물에 함유된 총 활성수소 당량 / 상기 열경화성 수지에 함유된 총 경화성 작용기 당량. 【청구항 4] 0 2019/199032 1＞（그1'/1 ?2019/004222 Equivalence ratio = total active hydrogen equivalents contained in said amine compound / total curable functional group equivalents contained in said thermosetting resin. [Claim 4] 0 2019/199032 1 ＞ （1 '/ 1? 2019/004222
저 항에 있어서, In that claim,
상기 아민 화합물은 2 내지 5개의 아민기를 포함하는 방향족 아민 화합물을 포함하는， 반도체 패키지용 열경화성 수지 조성물.  Said amine compound contains the aromatic amine compound containing 2-5 amine groups, The thermosetting resin composition for semiconductor packages.
【청구항 5] [Claim 5]
제 1항에 있어서，  The method of claim 1,
상기 반도체 패키지용 열경화성 수지 조성물은 상기 열경화성 수지, 열가소성 수지 및 아민 화합물의 총합 100 중량부에 대하여 상기 무기 충진제 50 중량부 내지 150 중량부를 포함하는， 반도체 패키지용 열경화성 수지 조성물 .  The thermosetting resin composition for a semiconductor package comprises 50 parts by weight to 150 parts by weight of the inorganic filler based on 100 parts by weight of the total of the thermosetting resin, thermoplastic resin and amine compound.
【청구항 6】 [Claim 6]
제 1항에 있어서,  The method of claim 1,
상기 반도체 패키지용 열경화성 수지 조성물은 경화 이후 12
Figure imgf000033_0001
열팽창계수를 갖는， 반도체 패키지용 열경화성 수지 조성물 . The thermosetting resin composition for the semiconductor package after curing 12
Figure imgf000033_0001
Thermosetting resin composition for semiconductor packages having a coefficient of thermal expansion.
【청구항 7】 [Claim 7]
제 1항에 있어서，  The method of claim 1,
상기 반도체 패키지용 열경화성 수지 조성물의 경화 이후 측정한 30°〔 및 180° (:에서의 저장 탄성율이 각각 16
Figure imgf000033_0002
이하인， 반도체 패키지용 열경화성 수지 조성물 . The storage modulus at 30 [deg.] And 180 [deg.] Measured after curing of the thermosetting resin composition for semiconductor packages was 16, respectively.
Figure imgf000033_0002
The following is a thermosetting resin composition for semiconductor packages.
【청구항 8] 제 7항에 있어서， [Claim 8] The method of claim 7,
상기 반도체 패키지용 열경화성 수지 조성물의 경화 이후 측정한 260° (:에서의 저장 탄성율이 이하인, 반도체 패키지용 열경화성 수지 조성물. 2019/199032 1»（：1^1{2019/004222 The thermosetting resin composition for semiconductor packages whose storage elastic modulus in 260 degrees (:) measured after hardening of the said thermosetting resin composition for semiconductor packages is below. 2019/199032 1 »（： 1 ^ 1 {2019/004222
【청구항 9] [Claim 9]
제 1항에 있어서,  The method of claim 1,
상기 열경화성 수지는 비스페놀 요 형 에폭시 수지, 페놀 노볼락 에폭시 수지 , 테트라페닐 에탄 에폭시 수지， 나프탈렌계 에폭시 수지， 바이페닐계 에폭시 수지, 디시클로펜타디엔 에폭시 수지, 및 디시클로펜타디엔계 에폭시 수지와 나프탈렌계 에폭시 수지의 혼합물로 이루어진 군에서 선택된 1종 이상의 에폭시 수지를 포함하는, 반도체 패키지용 열경화성 수지 조성물.  The thermosetting resins include bisphenol-type epoxy resins, phenol novolac epoxy resins, tetraphenyl ethane epoxy resins, naphthalene epoxy resins, biphenyl epoxy resins, dicyclopentadiene epoxy resins, and dicyclopentadiene epoxy resins and naphthalenes. A thermosetting resin composition for a semiconductor package comprising at least one epoxy resin selected from the group consisting of a mixture of epoxy resins.
【청구항 10】 [Claim 10]
제 9 항에 있어서,  The method of claim 9,
상기 열경화성 수지는 비스말레이미드 수지 , 시아네이트 에스터 수지 및 비스말레이미드-트리아진 수지로 이루어진 군으로부타 선택되는 1종 이상의 수지를 더 포함하는, 반도체 패키지용 열경화성 수지 조성물.  The thermosetting resin further comprises at least one resin selected from the group consisting of a bismaleimide resin, a cyanate ester resin and a bismaleimide-triazine resin, the thermosetting resin composition for a semiconductor package.
【청구항 11】 [Claim 11]
제 1항에 있어서,  The method of claim 1,
상기 아민 화합물과 상이한 제 2의 아민 화합물, 산무수물계 수지， 페놀 노볼락 수지 및 벤즈옥사진 수지로 이루어진 군에서 선택되는 1종 이상의 경화제를 더 포함하는， 반도체 패키지용 열경화성 수지 조성물.  A thermosetting resin composition for a semiconductor package further comprising at least one curing agent selected from the group consisting of a second amine compound different from the amine compound, an acid anhydride resin, a phenol novolak resin and a benzoxazine resin.
【청구항 12】 [Claim 12]
제 1항에 있어서,  The method of claim 1,
상기 열가소성 수지는 （메트）아크릴레이트계 고분자를 포담하는， 반도체 패키지용 열경화성 수지 조성물.  The thermoplastic resin is a thermosetting resin composition for a semiconductor package containing (meth) acrylate polymer.
【청구항 13】 [Claim 13]
제 12항에 있어서,  The method of claim 12,
상기 （메트）아크릴레이트계 고분자는 （메트）아크릴레이트계 단량체 유래의 반복단위와 （메트）아크릴로니트릴 유래의 반복 단위가 포함되는 2019/199032 1»（：1^1{2019/004222 The (meth) acrylate polymer includes a repeating unit derived from a (meth) acrylate monomer and a repeating unit derived from a (meth) acrylonitrile. 2019/199032 1 »（： 1 ^ 1 {2019/004222
아크릴산 에스테르 공중합체 ; 또는 부타디엔 유래의 반복 단위가 포함되는 아크릴산 에스테르 공중합체인， 반도체 패키지용 열경화성 수지 조성물 . Acrylic ester copolymers; Or a thermosetting resin composition for semiconductor packages which is an acrylic ester copolymer containing the repeating unit derived from butadiene.
【청구항 14】 [Claim 14]
제 12항에 있어서,  The method of claim 12,
상기 （메트）아크릴레이트계 고분자는 500 , 000 내지 1 , 000 , 000의 중량평균분자량을 갖는， 반도체 패키지용 열경화성 수지 조성물.  The said (meth) acrylate type polymer has a weight average molecular weight of 500, 000-1, 000, 000, The thermosetting resin composition for semiconductor packages.
【청구항 15】 [Claim 15]
제 1항에 있어서,  The method of claim 1,
상기 무기 충진제는 평균 입경이 상이한 2종 이상의 무기 충진제를 포함할수 있으며，  The inorganic filler may include two or more inorganic fillers having different average particle diameters,
상기 2종 이상의 무기 충진제 중 적어도 1종이 평균 입경이 0. 1 11 내지 100 인 무기 충진제이고, 다른 1종이 평균 입경이 1 11111 내지 90 인 무기 충진제인， 반도체 패키지용 열경화성 수지 조성물.  At least one of the two or more inorganic fillers is an inorganic filler having an average particle diameter of 0.01 1 to 100, and the other one is an inorganic filler having an average particle diameter of 1 11111 to 90, wherein the thermosetting resin composition for a semiconductor package.
【청구항 16】 [Claim 16]
제 1항의 반도체 패키지용 열경화성 수지 조성물 및 섬유 기재를 포함하는， 프리프레그.  The prepreg containing the thermosetting resin composition for semiconductor packages of Claim 1, and a fiber base material.
【청구항 17】 [Claim 17]
시트 형상을 갖는 제 16항의 프리프레그; 및 상기 프리프레그의 적어도 일면에 형성된 금속박;을 포함하는 금속박 적층판.  A prepreg of claim 16 having a sheet shape; And a metal foil formed on at least one surface of the prepreg.
PCT/KR2019/004222 2018-04-10 2019-04-09 Thermosetting resin composition for semiconductor package, prepreg, and metal-clad laminate WO2019199032A1 (en)

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