WO2019199032A1 - Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné et stratifié plaqué de métal - Google Patents
Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné et stratifié plaqué de métal Download PDFInfo
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- 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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- 0 N#C*c1ccc(*c(cc2)ccc2OC#N)cc1 Chemical compound N#C*c1ccc(*c(cc2)ccc2OC#N)cc1 0.000 description 2
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—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
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- 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
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- 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
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- 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. .
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Abstract
La présente invention porte sur une composition de résine thermodurcissable pour un boîtier de semi-conducteur, un préimprégné et un stratifié plaqué de métal et, plus précisément, sur une composition de résine thermodurcissable pour un boîtier de semi-conducteur, la composition de résine thermodurcissable comprenant : un composé amine contenant un groupe fonctionnel particulier ; une résine thermodurcissable ; une résine thermoplastique ; et une charge inorganique et ayant une température de transition vitreuse inférieure ou égale à 230°C, sur un préimprégné comprenant la composition et sur un stratifié plaqué de métal.
Priority Applications (4)
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CN201980007064.5A CN111601850B (zh) | 2018-04-10 | 2019-04-09 | 用于半导体封装的热固性树脂组合物、使用其的预浸料和金属包层层合体 |
US16/957,345 US12129338B2 (en) | 2018-04-10 | 2019-04-09 | Thermosetting resin composition for semiconductor package, prepreg and metal clad laminate using the same |
EP19785389.8A EP3712208B1 (fr) | 2018-04-10 | 2019-04-09 | Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné et stratifié plaqué de métal |
JP2020532729A JP7074278B2 (ja) | 2018-04-10 | 2019-04-09 | 半導体パッケージ用熱硬化性樹脂組成物、プリプレグおよび金属箔積層板 |
Applications Claiming Priority (8)
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KR10-2018-0041697 | 2018-04-10 | ||
KR20180041697 | 2018-04-10 | ||
KR20180071076 | 2018-06-20 | ||
KR10-2018-0071076 | 2018-06-20 | ||
KR10-2019-0036079 | 2019-03-28 | ||
KR1020190036078A KR102245724B1 (ko) | 2018-06-20 | 2019-03-28 | 금속박 적층판용 열경화성 수지 복합체 및 금속박 적층판 |
KR10-2019-0036078 | 2019-03-28 | ||
KR1020190036079A KR102246974B1 (ko) | 2018-04-10 | 2019-03-28 | 반도체 패키지용 열경화성 수지 조성물, 프리프레그 및 금속박 적층판 |
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PCT/KR2019/004223 WO2019199033A1 (fr) | 2018-04-10 | 2019-04-09 | Composite de résine thermodurcissable pour stratifié plaqué de métal, et stratifié plaqué de métal |
PCT/KR2019/004222 WO2019199032A1 (fr) | 2018-04-10 | 2019-04-09 | Composition de résine thermodurcissable pour boîtier de semi-conducteur, préimpregné et stratifié plaqué de métal |
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