WO2019117624A1 - Thermosetting resin composition for coating thin metal film, and metal laminate using same - Google Patents

Thermosetting resin composition for coating thin metal film, and metal laminate using same Download PDF

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Publication number
WO2019117624A1
WO2019117624A1 PCT/KR2018/015776 KR2018015776W WO2019117624A1 WO 2019117624 A1 WO2019117624 A1 WO 2019117624A1 KR 2018015776 W KR2018015776 W KR 2018015776W WO 2019117624 A1 WO2019117624 A1 WO 2019117624A1
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Prior art keywords
group
carbon atoms
rubber
resin
resin composition
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PCT/KR2018/015776
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French (fr)
Korean (ko)
Inventor
윤민혁
민현성
김영찬
심희용
심창보
손길상
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180157085A external-priority patent/KR102187162B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880028267.8A priority Critical patent/CN110573585B/en
Priority to US16/606,108 priority patent/US11459449B2/en
Priority to JP2019566895A priority patent/JP6891380B2/en
Publication of WO2019117624A1 publication Critical patent/WO2019117624A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a thermosetting resin composition for metal thin film coating which is excellent in crack resistance and a metal laminate using the same.
  • a copper clad laminate used in a conventional printed circuit board is made by impregnating a base of a glass fabric into a varnish of the thermosetting resin and then semi-curing the prepreg, which is then heated and pressed together with the copper foil .
  • the prepreg is used again to build circuit patterns on these copper-clad laminates and build-up on them.
  • the thickness of the semiconductor package has also become thinner.
  • the prepreg which is a laminated material among the package components, conventionally includes a woven glass fabric It is difficult to reduce the thickness by more than a certain amount.
  • resin-coated copper which is an alternative prepreg material, can be made thinner than prepregs because it does not contain glass fibers.
  • the most important characteristic of the laminated material is the pattern filling property (landfillability). That is, since the resin-coated copper foil as a laminated material must be filled with a pattern, the flowability of the resin is an important characteristic. Particularly, as the thickness of the resinous copper foil laminate becomes thinner, the amount of the resin becomes smaller and it is difficult to fill the pattern. If the pattern is not properly filled, an empty space (> 0 < 1 >) is generated and the reliability and performance of the semiconductor substrate become poor. When the thickness of the resin-coated copper foil is reduced, the amount of the resin is reduced, so that the pattern can not be filled and the possibility of voids after lamination increases. That is, if the thickness of the resin is reduced to reduce the thickness of the substrate, the pattern filling property is deteriorated.
  • a commonly used method is to use a monomolecular resin.
  • a resin having a low molecular weight since the viscosity before curing is low in the temperature range of the lamination process, flowability and pattern filling property are excellent.
  • monomolecular resin has a disadvantage that it is vulnerable to changes over time because a protective film is required since the surface of the resin is cured 15 times and the curing reaction proceeds slowly at room temperature. In addition, the resin has insufficient crack resistance and causes a reduction in the overall yield.
  • An object of the present invention is to provide a thermosetting resin composition for metal thin film coating which is excellent in flowability and pattern filling property by widening a temperature range maintaining minimum viscosity and capable of improving crack resistance of a metal thin film.
  • Another object of the present invention is to provide a metal laminate including a resin coating layer which is a cured product of the thermosetting resin composition having excellent mechanical properties, and a method for producing the same.
  • alkyl group having 1 to 20 carbon atoms aryl group having 6 to 20 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, 2019/117624 1 »(: 1 ⁇ 1 ⁇ 2018/015776
  • the rubber component includes at least one member selected from the group consisting of styrene butadiene rubber, neoprene rubber, 5 nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, silicone rubber, urethane rubber and acrylic rubber ,
  • the rubber component comprises at least 5 parts by weight and less than 40 parts by weight based on 100 parts by weight of the total of the amine compound and the binder resin,
  • the present specification also includes a resin coating layer in which the thermosetting resin composition is cured on at least one surface of the metal thin film,
  • the present invention also provides a method for producing a metal laminate, which comprises coating the thermosetting resin composition on at least one surface of a metal thin film.
  • the present invention also provides a metal-clad laminate in which one or more metal laminate layers are laminated.
  • thermosetting resin 30 composition for metal thin film coating according to a specific embodiment of the present invention and a resin-coated metal laminate and a metal foil laminate using the composition 2019/117624 1 » (: 1 ⁇ 1 ⁇ 2018/015776
  • the metal laminate may include a thermosetting resin composition coated on a metal thin film to a predetermined thickness.
  • the metal thin film is a substrate for coating a resin composition, and may be in the form of a thin film containing a single or composite metal component as described later.
  • the metal-clad laminate may include a structure in which one or more metal laminate layers are stacked.
  • the present invention relates to a thermosetting resin composition and a metal thin film for metal thin film coating, which have sufficient flowability to improve pattern filling and crack resistance.
  • metal foil laminates have been produced mainly by using a 25 prepreg impregnated with a woven glass fiber.
  • the resin flowability during the laminating process of copper foil is reduced, There was a problem with poor sex.
  • the copper foil coated with the resin thinner, there are many disadvantages in terms of storage stability and stability when a monomolecular resin is used.
  • thermosetting resin composition after curing is higher modulus 2019/117624 1> (1 '/ 1? 2018/015776
  • the present invention not only the flowability of resin is ensured by introducing a small amount of a resin system and a rubber component constituted of epoxy and amine curing agent and the like, but also crack resistance of the metal laminate coated with the thermosetting resin composition is 5 . Further, the composition of the present invention is characterized by optimizing the type of resin and the mixing ratio .
  • the curing reaction of the resin can be easily controlled by using a specific amine curing agent. More specifically, the modulus can be lowered by controlling the functional groups of the amine curing agent to control the number of bonds generated during the curing reaction of the resin. This increases the crack resistance and makes it more stable against the same tensile force or impact.
  • thermosetting resin composition for metal thin film coating used in the present invention controls flowability by adding a specific rubber component to the composition together with controlling the curing reaction. Accordingly rheometer minimum viscosity region (11 (1 03 ⁇ 4 0 15 is so spread is advantageous flowability and gender fill pattern.
  • the present invention as in the temperature region of the metal foil lamination process, the widening section (11 (10 ⁇ maintaining a minimum viscosity, there is an effect of improving the flowability of the resin.
  • the temperature range satisfying the viscosity condition 20 is 90 to 180 DEG (very wide). That is, the flowability in the laminating process section is high and the pattern filling property is excellent, and the crack resistance of the metal thin film coated with the thermosetting resin composition can be improved. That, however, the complex viscosity conditions of the thermosetting resin composition becomes too high, the flowability dropped to the ground than the above range, a pattern may be poor filling property. Also, even if the complex viscosity condition is satisfied, the conventional thermosetting resin composition can have a relatively narrow working temperature range.
  • thermosetting resin composition for metal thin film coating which comprises a sulfone group, a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An amine compound including an electron donating group (EWG) such as at least one functional group selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms and an alkylene group having 1 to 20 carbon atoms, It was confirmed that the curing reaction of the resin composition can be easily controlled by reducing the reactivity.
  • EWG electron donating group
  • thermosetting resin composition of this embodiment is a thermosetting resin composition comprising a sulfone group, a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, And an amine compound including at least one functional group selected from the group consisting of a halogen atom and a halogen atom.
  • the amine compound may be used as an amine curing agent.
  • the amine compound may include one or more compounds selected from the group consisting of the following chemical formulas (1) to (3).
  • X I to 3 ⁇ 4 each independently represent a nitro group, a cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms , heteroaryl Kii 0 and C 6 -C 15 aryl group, or 2 to 20 carbon atoms of, 3 ⁇ 4 and 3 ⁇ 4 'each independently represent a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15, or A heteroaryl group having 2 to 20 carbon atoms, II is an integer of 1 to 10 ,
  • the alkylene group having 1 to 10 carbon atoms, the alkyl group having 1 to 6 carbon atoms, the aryl group 0 of 2 to 6 carbon atoms having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each independently a nitro group, a cyano group and a halogen group is substituted with at least one member selected from the group consisting of functional groups,
  • Each heteroaryl group having 2 to 20 carbon atoms is independently substituted with one or more functional groups selected from the group consisting of a nitro group, a cyano group and a halogen group,
  • 1 'to 3 each independently represent a nitro group, a 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
  • 3 ⁇ 4 , 3 ⁇ 4 ' , 3 ⁇ 4 and 3 ⁇ 4' each independently represent 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 2 carbon atoms
  • the alkyl group having 6 to 15 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each 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 above- Derived monovalent functional group for example, linear, branched or cyclic, such as methyl, ethyl, propyl, isobutyl, 16 - can be a butyl, pentyl, haeksil.
  • the alkylene group is a divalent functional group derived from an alkene (1 3 ⁇ 41 1 ⁇ 2 ), for example, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, such as methylene, ethylene, propylene, isobutylene, Pentylene, heptylene, heptene, heptene, heptene, heptene, heptene, heptene, heptene, heptene, heptene, heptene, The at least one hydrogen atom contained in the alkylene group may each be substituted with the same substituent as the alkyl group.
  • the aryl group is a monovalent functional group derived from arenes ( 3 11 ⁇ 2 ), for example, monocyclic or polycyclic.
  • the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like.
  • the polycyclic aryl group include a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group, It is not.
  • These hydrogen atoms of at least one of the aryl groups may be substituted with the same substituents as those in the alkyl group.
  • the heteroaryl group is a heterocyclic group containing 0, N or a hetero atom, and the number of carbon atoms is not particularly limited, but may be 2 to 30 carbon atoms.
  • the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, , A quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group and a dibenzofuran And the like,
  • " substituted " means that another functional group is bonded in place of the hydrogen atom in the compound, and the position to be substituted is not limited as far as the position where the hydrogen atom is substituted, that is, The two or more substituents may be the same or different from each other.
  • the compound represented by Formula 1 may include a compound represented by Formula 1-1.
  • the contents of A, Xi to 3 ⁇ 4, Ri , Ri ' , R 2 and 3 ⁇ 4', n include the above-mentioned contents in Formula 1.
  • formula 1-1 examples include 4,4'-diaminodiphenylsul fone (in formula 1-1, A is a sulfone group, 3 ⁇ 4 to X 8, Ri , 3 ⁇ 4 ' , 3 ⁇ 4 and 3 ⁇ 4' atom, and, n is 1.) in bi s (4_aminophenyl) methanone (formula a is a carbonyl group 1_1, 3 ⁇ 4, X Ri, Ri ', 3 ⁇ 4 2019/117624 1 »(: 1 ⁇ 1 ⁇ 2018/015776
  • Ke 6 -2,2- (1 1, 3 ⁇ 4 to 8, 3 ⁇ 4, 3 ⁇ 4 ', I 2 and 3 ⁇ 4' are each independently a hydrogen atom, - 1 is a 1), 4 , 4 '- (2,2,2 (1 1, group 11 is 06 3116-1, 1- (1 1 1 1 ⁇ 2 standing (formula , 13 ⁇ 4 and
  • the formula (2) may include a compound represented by the following formula (2-1).
  • 2,2 ', 3,3', 5,5 ', 6,6'_ 0 (interstitial 3 £ 1 or 01 _ 0 1 ) 1 1613 ⁇ 4 1-4,4'- 3 11 11 ⁇ 2 to a halogen group is fluorine
  • 3 ⁇ 4, 3 ⁇ 4 ', 3 ⁇ 4 and 3 ⁇ 4' are each independently a hydrogen atom, a 111: 1), 2,2'-3 (1 or 0, US 1 3 ⁇ 4, 1) 1 1) 1 16] 3 ⁇ 4 1-4,4 '- (1 111 1 ⁇ 2
  • 3 ⁇ 4 ' , 3 ⁇ 4 and 3 ⁇ 4' are each independently a hydrogen atom, and 111 is 1).
  • the formula 3 may include a compound represented by the following formula 3-1.
  • Halogen, fluorine group , 3 ⁇ 4 , 3 ⁇ 4 ' , 3 ⁇ 4 and 3 ⁇ 4' each independently represents a hydrogen atom).
  • the content of the amine compound may be from 15 to 60% by weight based on the total weight of the amine compound and the binder resin. Preferably, the content of the amine compound may be 20 to 55% by weight based on 100 parts by weight of the total of the amine compound and the binder resin. If the content of the amine compound is excessively reduced to less than 15% by weight, un-curing may occur. If the content of the amine compound is excessively increased to more than 80% by weight, the curing rate is increased and the fluidity of the thermosetting resin composition is decreased In addition, the mechanical properties of the metal thin film using the thermosetting resin composition may be deteriorated by the unreacted amine compound.
  • the thermosetting resin composition for metal thin film coating in one embodiment may include a binder resin.
  • the transition metal binder resin may include one or more resins selected from the group consisting of an epoxy resin and a bismaleimide resin.
  • epoxy resin there may be used any of those used in the thermosetting resin composition without limitation, and examples thereof include bisphenol-type epoxy resins, phenol novolac epoxy resins, phenyl aralkyl-type epoxy resins, Epoxy resin, naphthalene-based epoxy resin, biphenyl-based epoxy resin, dicyclopentadiene epoxy resin, and a mixture of dicyclopentadiene-based epoxy resin and naphthalene-based epoxy resin 2019/117624 1 » (: 1/10/01 018/015776.
  • the epoxy resin is to tetraphenyl ethane epoxy represented the formula resin bisphenol epoxy represented by the 5 to resin novolak epoxy represented by the formula (6) to phenyl aralkyl kilgye epoxy resin represented by the following formula (7) in formula (8) resin to the naphthalene type epoxy resin, to at least one selected from the group consisting of a dicyclopentadiene type epoxy resin represented by the biphenyl type epoxy resin, and the following formula (12) represented by the formula (11) represented by the following formulas 9 and 10 Can be used.
  • the epoxy resin of formula ( 5) may be a bisphenol-type epoxy resin, a bisphenol-type epoxy resin, or a bisphenol epoxy resin, depending on the type of seedlings.
  • the novolak type epoxy resin of Formula 3 may be a phenol novolak type epoxy resin or a cresol novolak type epoxy resin, respectively, depending on the type of urine.
  • 0 is an integer of 1 to 50 .
  • the content of the epoxy resin may be 30 to 80 wt % and the content of the bismaleimide resin may be 1 to 20 wt % based on the total weight of the amine compound and the binder resin.
  • the content of the epoxy resin is
  • the content of the bismaleimide resin may be 1 to 10 % by weight based on 100 parts by weight of the total amount of the amine compound and the binder resin.
  • the amount of the epoxy resin contained in the binder resin is less than 30 % by weight, it is difficult to realize high solubility.
  • the amount exceeds 80 % by weight
  • the bismaleimide resin is usually heat-treated .
  • Those used in the curable resin composition can be used without limitation, and the kind thereof is not limited.
  • the bismaleimide resin is represented by the type diphenylmethane bismaleimide resin, to the formula 14 of the formula 13
  • the bisphenol-type diphenyl ether bismaleimide resin represented by the following formula ( 15 ) and the bismaleimide resin composed of the diphenylmethane type bismaleimide and the oligomer of the phenylmethane type maleimide resin represented by the following formula ( 16 ) one member selected from the group consisting of resins may be at least. 2019/117624 1 »(: 1 ⁇ 1 ⁇ 2018/015776
  • thermosetting resin composition of one embodiment may include a rubber component together with the binder component.
  • thermosetting composition 5 rheometer minimum viscosity range is from 90 to 180X with the binder containing the amine compound: complex viscosity under the following conditions 3500 sukeu in the range of And the lower limit of the complex viscosity condition is largely limited
  • the compound that satisfies the above complex viscosity criteria is styrene butadiene rubber, neoprene-based rubber nitrile rubber, butyl-based rubber butadiene 10 rubber ethylene propylene-based rubber, silicone rubber polyurethane rubber and selected from the group consisting of acrylic rubber 1 May be a rubber-based component or more. More preferably , the rubber component may be at least one member selected from the group consisting of butadiene-based rubber, silicone rubber and acrylic rubber.
  • the binder resin 1 00 15 parts by weight of styrene-butadiene-based rubber for the neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene pro NW-based rubber, silicone rubber, one or more rubber components selected from the group consisting of urethane rubber and an acrylic rubber can also contain 5 parts by weight or more and less than 40 parts by weight.
  • the flowability and the filling pattern 20 optimum rubber component for improving the sex ratio of the rubber component may comprise 5 to 20 parts by weight parts by weight for 100 parts by weight of the total of the amine compound and a binder resin. If the content of the rubber component is less than 5 parts by weight, the flowability of the resin is excessively increased to increase the thickness variation. If the content of the rubber component is more than 40 parts by weight, the flowability is too small.
  • the butadiene-based rubber is a butadiene repeating unit in which a terminal group is substituted with a hydroxy group;
  • butadiene repeat units containing an epoxy group and having a weight average molecular weight can also contain a copolymer of I X10 to 5X10.
  • the silicone rubber may be a silicone repeating unit in which an epoxy group or polyether-modified silicone 30 repeating unit: or a repeating unit in which a terminal group is substituted with an amine group or an epoxy group 2019/117624 1 »(: 1 ⁇ 1 ⁇ 2018/015776
  • the acrylic rubber is contained in the resin composition and can exhibit a low curing shrinkage ratio.
  • the acrylic rubber can further enhance the effect of the expansion relaxation action.
  • Such an acrylic rubber uses an acrylic ester copolymer having a molecular structure having rubber elasticity.
  • the acrylic rubber is an acrylic acid ester copolymer containing a repeating unit derived from butyl acrylate and a repeating unit derived from acrylonitrile; Or an acrylic acid ester copolymer containing a repeating unit derived from butadiene; or a repeating unit derived from a linear or branched alkyl group-containing acrylic acid alkyl group having 2 to 10 carbon atoms.
  • the weight-average molecular weight of the acrylic rubber is 30 ⁇ 10 4 to 65 ⁇ 10 4 , and if it is out of the above range, the flowability may be insufficient or excessive.
  • styrene butadiene rubber neoprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, and urethane rubber are not particularly limited, and materials well known in the art can be used.
  • the rubber component may be at least one selected from the group consisting of butadiene rubber, silicone rubber and acrylic rubber.
  • thermosetting resin composition of one embodiment may include an inorganic filler.
  • the inorganic filler can be used without any particular limitation as long as it is well known in the art to which the present invention belongs.
  • the inorganic filler may be selected from the group consisting of silica, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, fired kaolin, Talc, mica, short glass fiber, glass fine powder, and hollow glass.
  • the content of the inorganic filler may be 200 parts by weight or more, 200 parts by weight to 500 parts by weight, or 250 parts by weight to 400 parts by weight based on 100 parts by weight of the total amount of the amine compound and the binder resin.
  • the content of the filler is about 200 2019/117624 1 »(: 1 ⁇ 1 ⁇ 2018/015776
  • the average particle diameter of the inorganic filler is preferably 0.1 lM to 100 l.
  • the inorganic filler may be a substance whose surface has been subjected to silane treatment if necessary.
  • the inorganic filler is preferably mixed with small particles of nanoscale and large particles of microscale to increase the packing density.
  • the inorganic filler may be dispersed in the binder resin.
  • the fact that the inorganic filler is dispersed in the binder resin means that the inorganic filler and the binder resin are not separately separated and mixed. That is, the thermosetting resin composition for metal thin film coating according to one embodiment of the present invention can form a dispersed phase by mixing the inorganic filler and the resin evenly without forming a separation phase such as an inorganic filler separation phase or a resin separation phase made of a resin. Accordingly, even when the inorganic filler is filled in a high content, it is possible to achieve an appropriate level of flowability and high thermal stability and mechanical properties when coating the metal foil.
  • thermosetting resin composition according to one embodiment of the present invention can be used in a wide variety of applications such as a solvent, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitener, a photosensitizer, a pigment, a dye, a thickener, a lubricant, a defoamer, And one or more additives selected from the group consisting of
  • thermosetting resin composition for metal thin film coating of the embodiment can be used as a solution by adding a solvent as needed.
  • the solvent is not particularly limited as long as it exhibits good solubility with respect to the resin component, and alcohol, ether, ketone, amide, aromatic hydrocarbon, ester, nitrile and the like can be used. Or a mixed solvent of two or more of them may be used.
  • the content of the solvent is not particularly limited, as it can be suitably used for viscosity control in the production of the thermosetting resin composition for metal thin film coating.
  • the present invention may further include various other polymer compounds such as other thermosetting resins, thermoplastic resins and oligomers and elastomers thereof, and other flame retardant compounds or additives, as long as the inherent characteristics of the thermosetting resin composition are not impaired. These are particularly preferred if they are selected from those commonly used 2019/117624 1 » (: 1 ⁇ 1 ⁇ 2018/015776
  • the additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, pigment dye thickeners, lubricant defoamers, dispersants, leveling agent brighteners, and the like.
  • thermosetting resin composition according to one embodiment of the invention having 5 This configuration rheometer the minimum viscosity range in the range of 90 to 1 80 ⁇
  • the temperature interval 10 satisfying the above viscosity condition of 90 to 180 (: very wide with. Therefore, the flowability in the laminating process section is high, so that void space is not generated after the resin lamination, and the pattern filling property is excellent.
  • thermosetting resin composition of the present invention has the above resin flow property, it is possible to make a metal laminate by using a metal thin film or to secure the flow property 15 in a build-up process, so that it is possible to easily fill a fine pattern, You can improve your sex.
  • thermosetting resin composition of the present invention exhibits a minimum complex viscosity condition of a specific value due to curing which can broaden a section maintaining the minimum viscosity, and does not cause voids in pattern filling), thereby providing an effect of improving pattern filling 20 . Also, by using the thermosetting resin composition of the present invention, it is possible to provide a metal laminate having a reduced thickness and improved stability and storage through at least one surface of a metal thin film.
  • thermosetting resin composition on at least one surface the cured resin coating layer of the metal thin film, the resin coating layer, a sulfone group a carbonyl group, a halogen group having 1 to 20 carbon atoms an alkyl group having 6 to 20 of the aryl group and the binder resin containing a heteroaryl group, and an amine compound and an epoxy resin and 30 bismaleimide resin including at least one functional group selected from the group consisting of a polyalkylene group having 1 to 20 carbon atoms having 2 to 30, and styrene butadiene-based Rubber, 2019/117624 1 »(: 1 ⁇ 1 ⁇ 2018/015776
  • thermosetting resin composition on at least one surface of a metal thin film.
  • a metal-clad laminate in which one or more of the metal laminates are stacked may be provided.
  • the present invention provides a metal thin film including a cured product of the thermosetting resin composition.
  • the present invention can provide a metal laminate which exhibits excellent thermal and mechanical properties by preparing a resin composition having excellent flowability and pattern filling property of a resin in the form of a varnish and directly coating it on a metal thin film 15.
  • a thermosetting resin including a filler may be formed on at least one surface of the metal thin film, and the filler may be uniformly dispersed in the cured product.
  • thermosetting resin composition may include coating the thermosetting resin composition on at least one surface of the metal thin film.
  • thermosetting resin composition coated on at least one side of the metal thin film.
  • a well-known drying step may be further performed if necessary.
  • the curing reaction of the resin is deliberately delayed to lengthen the section in which the minimum viscosity within the temperature range of the lamination step 25 is maintained.
  • the curing condition may be carried out at a temperature of 180 to 250 for 1 to 4 hours.
  • the method of coating the thermosetting resin composition on the metal thin film is not particularly limited, and a coating method well known in the art can be used.
  • thermosetting resin composition of the present invention is placed in a coater apparatus, 2019/117624 1 » (: 1 ⁇ 1 ⁇ 2018/015776
  • the coater apparatus may be a comma coater blade coater lip coater rod coater, a squeeze coater, a reverse coater transfer roll coater gravure coater or a spray coater
  • a carrier film can be used for flowability evaluation, and plastic films such as polyethylene terephthalate), polyester film, polyimide film, polyamideimide film, polypropylene film and polystyrene film can be used .
  • the varnish used for the coating may be a state in which the solvent is added to the thermosetting resin composition 10.
  • the solvent for resin varnish is not particularly limited as long as it is miscible with the resin component and has good solubility. Specific examples thereof include ketones such as acetone methyl ethyl ketone methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene toluene and xylene, amides such as dimethylformamide and dimethylacetamide, 15 methyl cellosolve butyl cell And alopecic alcohols such as rosolv.
  • ketones such as acetone methyl ethyl ketone methyl isobutyl ketone and cyclohexanone
  • aromatic hydrocarbons such as benzene toluene and xylene
  • amides such as dimethylformamide and dimethylacetamide
  • 15 methyl cellosolve butyl cell And alopecic alcohols such as
  • the metal thin film may have a three- layer structure comprising a copper foil, an aluminum foil, an intermediate layer of nickel, a nickel-nickel-tin alloy, a nickel-iron alloy, a lead or a lead-tin alloy, A composite foil or a composite foil of a two-layer structure in which aluminum and a copper foil are combined.
  • the metal thin film used in the present invention may be a copper foil or an aluminum foil, having a thickness of about 2 to 200 , but preferably has a thickness of about 2 to 35. More preferably, A copper foil is used as the metal thin film .
  • the minimum complex viscosity condition can be satisfied over a wide 30 temperature range as compared with the conventional method, 2019/117624 1 »(: 1 ⁇ 1 ⁇ 2018/015776
  • the thickness of the resin coating layer in the metal laminate may be from 5 to 90 _, preferably from 5 / ⁇ 1 to 30 days. Even if such a cured product is formed thin on the metal thin film, excellent thermal and mechanical properties of the metal thin film can be exhibited.
  • the glass transition temperature of the resin after curing 0) is 220 to 2401 :.
  • the dielectric properties of the metal thin films are 3.4 eq.
  • the elongation ( 6101 3 011 ) of the cured after-treatment support can be 1.5 to 2% or 1.6% lower than the tensile test results.
  • the present invention is superior to conventional resin-coated copper foils made of monomolecular system in crack resistance at the time of comparison, thereby contributing to improvement of the performance of semiconductor devices.
  • a metal-clad laminate in which one or more of the metal laminates are stacked can be provided.
  • the metal plate laminates may further include a metal thin film.
  • the metal foil may be a resin layer of a metal laminate.
  • the metal thin film may be used for lamination after etching and patterning are performed.
  • the metal thin film (mainly & 1 ) as the first layer is patterned through complete etching or 25 partial etching, The resin coating layer of the first metal layer is brought into contact with the metal thin film, and the second layer is laminated.
  • the metal laminate thus produced can be provided in the form of a metal laminate laminated one or more times.
  • the metal laminates may include two metal laminates stacked such that the resin layers formed on the metal laminates face each other. 2019/117624 1 » (: 1 ⁇ 1 ⁇ 2018/015776
  • the present invention can be used to manufacture double-sided or multi-layer printed circuit boards after stacking more than one piece using the metal laminate.
  • the metal-clad laminate can be processed by circuit processing to produce a double-sided or multi-layer printed circuit board, and the circuit processing can be performed in a general double-sided or multi-layer printed circuit board manufacturing process.
  • thermosetting resin composition As described above, according to the present invention, by using the above-mentioned thermosetting resin composition, it is possible to provide a resin-coated metal thin film which can be applied to various printed circuit boards in various fields.
  • thermosetting resin composition for metal thin film coating of the present invention can optimize the type of resin constituting the binder and the mixing ratio thereof and adjust the curing reaction of the resin by using a certain amount of the amine curing agent and the rubber component, this high flow properties within the pattern filling Republic 15 can provide an effect that good.
  • the present invention even if the thickness of the laminated material is thin, since the rheometer minimum viscosity section is wider than the conventional one, the pattern filling property can be improved to improve the reliability and performance of the semiconductor device as well as the thickness of the substrate. Therefore, the present invention can improve the crack resistance as compared with the conventional metal thin film.
  • the invention also has the effect of excellent thermal and mechanical properties of the resin layer after curing and provides excellent metal thin film 20 dielectric properties. That is, when the thermosetting resin composition of the present invention is used, the resin composition can be directly coated on the metal foil by a simple method without using a method of preparing a prepreg using glass fiber to provide a thin metal laminate . Further, the present invention can provide a metal laminate excellent in glass transition temperature of the resin after curing and having a dielectric property of 25 .
  • the metal thin film can provide a metal-clad laminate used for the thinning of an electronic apparatus by stacking more than one piece.
  • Fig. 1 shows a rheometer curve for confirming the flowability and pattern filling property 30 of Example 1 and Comparative Example 1 of the present invention.
  • 2 is a graph showing a comparison between the elongation measurement results of Example 1 and Comparative Example 1 of the present invention.
  • thermosetting resin composition (1) Production of thermosetting resin composition
  • an amine compound, an epoxy resin, and a bismaleimide resin were dissolved in a cyclohexanone solvent to prepare a varnish.
  • a silica inorganic filler was added to the varnish.
  • the varnish containing the above components was stirred for at least 24 hours to prepare a coating solution.
  • the viscosity of the coating solution was adjusted and defoamed using a rotary evaporator.
  • thermosetting resin composition (resin-coated copper-clad laminate)
  • the coating solution was coated (coating thickness: 16 ⁇ m) on one side of a copper foil (thickness 2 [ m, Mi tsui]) with a comma coater and then cured for 100 minutes under conditions of 220 ° C and 35 kg / cuf. Subsequently, the sample was cut to a size of 17 x 15 cm to prepare a resin-coated copper-clad laminate sample.
  • thermosetting resin composition (1) Production of thermosetting resin composition
  • Varnishes were prepared using the components of the following Table 2 and cyclohexanone solvents. At this time, when the acrylic rubber A or the acrylic rubber seedling is not used Was the case with Comparative Example 1 was a case where the content is outside the range of the present range in Comparative Examples 2 to 4.
  • the varnish containing the above components was stirred for at least 24 hours to prepare a coating solution.
  • the coating solution was coated on a copper foil (thickness: 2 m, manufactured by Mitsui) with a comma coater (coating thickness: 16 ⁇ m), and then cured for 10 minutes at 220 ° C and 35 kg / cuf for 100 minutes. Subsequently, the sample was cut into a size of 17 x 15 cm to prepare a resin-coated copper foil sample.
  • the resin composition was laminated with the copper foil 15 integrated with the prepreg impregnated in the fiber substrate
  • thermosetting resin composition ( 1 ) Production of thermosetting resin composition
  • the resin was dissolved in an organic solvent to give a varnish as shown in Table 2 , followed by stirring for 2 4 hours or more.
  • Epoxy resin naphthalene-based epoxy resin (HP4710, DIC)
  • Bismaleimide-triazine resin BMI-2300, DAIWA Inc.
  • Cyanate ester resin novolak cyanate resin (PT-30S, Lonza) ⁇ SG-P3-PT197 (Mw 65X10 4 , Tg: 12 ° C), Nagase Cheratex Coporate ion
  • Acrylic rubber B SG-P3-MW1 (Mw 30X10 4 , Tg: 12 ° C), Nagase Chemtex Coporate ion
  • Silicone rubber AM2-119, Dow Corning
  • Butadiene rubber A B-1000, Nippon Soda
  • Butadiene rubber B RIC0N181, Cray Valley
  • Filler A Phenylaminosilane treated slurry type filler, average particle diameter 0.5um (SC2050MTO, Admatechs)
  • Example 1 and Comparative Example 1 were coated on a PET substrate and laminated through a laminator to make a sample of a proper thickness to measure the rheometer viscosity Temperature measurement conditions, rate of temperature rise: 5 degrees / min, frequency: 1 case z). 2019/117624 1 »(: 1 ⁇ 1 ⁇ 2018/015776
  • Viscosity and flowability were also confirmed by the presence of empty space in the pattern stacking test.
  • a copper-clad laminate 01: 0 having a pattern in which a copper foil thickness of 10 11111 and a total area of about 60% of the total area was etched was used, and a resin-coated copper-clad coating sample (or a prepreg Leg) were stacked. If void ( 0 8 1) or delamination ((1 61 1 1 ) does not occur Voids ((!) Or delamination ( ⁇ 1 6131 11 : 1 011 ) occurred. As a result of observing the presence or absence of void formation, voids were not generated in Example 1 but voids were generated in Comparative Example 1.
  • Fig. 1 shows a rheometer curve for confirming the flowability and pattern fillability of Example 1 and Comparative Example 1 of the present invention.
  • Dielectric properties were calculated by measuring the dielectric constant (Dk) and dielectric loss (Df) at 1 GHz using the Agilent E5071B ENA instrument using splitter post dielectric resonance (SPDR) method.
  • the copper foil layers of the copper clad laminate obtained in the above Examples and Comparative Examples were removed by etching and then measured using TEA. (50 ° C to 150 ° C, table direction)

Abstract

The present invention relates to a superbly crack-resistant thermosetting resin composition for coating thin metal film, and a metal laminate using the composition.

Description

【발명의 명칭】  Title of the Invention
금속 박막코팅용 열경화성 수지 조성물 및 이를 이용한금속 적층체 【기술분야】  Thermosetting resin composition for metal thin film coating and metal laminate using the same
관련 출원(들)과의 상호 인용  Cross-reference with related application (s)
본 출원은 2017년 12월 14일자 한국 특허 출원 제 10-2017-0172270호 및 2018년 12월 7일자한국특허 출원 제 10-2018-0157085호에 기초한우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0172270, dated December 14, 2017, and Korean Patent Application No. 10-2018-0157085, dated December 7, 2018, The entire contents of which are incorporated herein by reference.
본 발명은 내크랙성이 우수한금속 박막코팅용 열경화성 수지 조성물 및 이를이용한금속적층체에 관한것이다.  The present invention relates to a thermosetting resin composition for metal thin film coating which is excellent in crack resistance and a metal laminate using the same.
【발명의 배경이 되는기술】  TECHNICAL BACKGROUND OF THE INVENTION
종래의 인쇄회로기판에 사용되는 동박적층판(copper clad laminate)은 유리 섬유(Glass Fabric)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(build-up)을하는용도로프리프레그가다시 사용되게 된다. A copper clad laminate used in a conventional printed circuit board is made by impregnating a base of a glass fabric into a varnish of the thermosetting resin and then semi-curing the prepreg, which is then heated and pressed together with the copper foil . The prepreg is used again to build circuit patterns on these copper-clad laminates and build-up on them.
최근 전자 기기， 통신기기， 개인용 컴퓨터， 스마트폰 등의 고성능화， 박형화,경량화가 가속되면서 반도체 패키지 또한 박형화가 요구됨에 따라， 동시에 반도체 패키지용 인쇄회로기판도 박형화의 필요성이 커지고 있다.  In recent years, as the performance of electronic devices, communication devices, personal computers, smart phones, and the like have been accelerated, thinning of semiconductor packages has been required, and at the same time, there is a growing need for thinner printed circuit boards for semiconductor packages.
다시 말해, 최근 전자기기의 폼팩터가 줄어들면서 반도체 패키지의 두께도 점점 얇아지고 있다.그런데,종래 패키지 구성 성분 중 적층 소재인 프리프레그 (prepreg)는 직조된 유리 섬유(glass fabric)를 포함하고 있기 때문에 두께를 일정 이상줄이기가어렵다.  In other words, since the form factor of electronic devices has recently been reduced, the thickness of the semiconductor package has also become thinner. However, since the prepreg, which is a laminated material among the package components, conventionally includes a woven glass fabric It is difficult to reduce the thickness by more than a certain amount.
한편, 프리프레그 대안 소재인 수지 코팅 동박 (RCC， resin coated copper)은 유리섬유를 포함하지 않기 때문에 프리프레그에 비해 두께를 더 얇게 만들수있다.  On the other hand, resin-coated copper (RCC), which is an alternative prepreg material, can be made thinner than prepregs because it does not contain glass fibers.
그러나， 기존 프리프레그 보다 얇은 소재인 수지가코팅된 동박은 보강 기재로 유리섬유가 들어가지 않으므로 패키지 공정 과정에서 크랙이 발생하기 쉽다. 공정 과정에서 크랙이 발생하면 전체 수율 감소로 이어지게 되며, 신뢰성에도 악영향을 미칠 수 있다.따라서,수지 코팅 동박 내 수지 층의 2019/117624 1»（그1^1{2018/015776 However, since copper foil coated with a resin, which is thinner than conventional prepregs, does not contain glass fiber as a reinforcing base material, cracks tend to occur during the packaging process. If cracks are generated during the process, the overall yield is reduced, and reliability may be adversely affected. Therefore, the resin layer in the resin-coated copper foil 2019/117624 1 »(1 ^ 1 {2018/015776
내크랙성 향상이 필요하다. It is necessary to improve the crack resistance.
또한， 적층 소재의 특성 중 가장 중요한 것은 패턴 채움성 （매립성）이다. 즉, 적층 소재로서 수지 코팅 동박은 패턴을 채워야 하므로 수지의 흐름성은중요한특성이다. 특히， 수지 동박적층의 두께가얇아질수록 5 수지량이 적어져 패턴을 채우기 어렵다. 패턴이 제대로 채워지지 않는 경우， 빈 공간 （＞0 1）가 발생하게 되고 반도체 기판의 신뢰성, 성능 등이 떨어지게 된다. 수지 코팅 동박의 두께가얇아지면수지의 양도줄어들기 때문에 패턴을 채우지 못하고 적층 후 빈 공간이 발생할 가능성이 높아진다. 즉, 기판의 박막화를위해수지 두께를얇게 하면패턴 채움성이 떨어지게 되는것이다.The most important characteristic of the laminated material is the pattern filling property (landfillability). That is, since the resin-coated copper foil as a laminated material must be filled with a pattern, the flowability of the resin is an important characteristic. Particularly, as the thickness of the resinous copper foil laminate becomes thinner, the amount of the resin becomes smaller and it is difficult to fill the pattern. If the pattern is not properly filled, an empty space (> 0 < 1 >) is generated and the reliability and performance of the semiconductor substrate become poor. When the thickness of the resin-coated copper foil is reduced, the amount of the resin is reduced, so that the pattern can not be filled and the possibility of voids after lamination increases. That is, if the thickness of the resin is reduced to reduce the thickness of the substrate, the pattern filling property is deteriorated.
10 따라서, 두께를 얇게 하면서도 동시에 패턴 채움성을 높이고 크랙을 방지하기 위해서는수지의 흐름성과내크랙성을동시에 높이는것이 필요하다. 통상적으로 사용되는 방법은 단분자 계열의 수지를 사용하는 것이다. 분자량이 낮은수지의 경우， 적층공정 온도구간내에서 경화전 점도가낮기 때문에 흐름성 및 패턴 채움성이 우수하다. 하지만단분자계열의 수지는경화 15 전표면 끈적임이 있으므로보호 필름이 필요하며， 상온보관시 경화반응이 서서히 진행되므로 경시 변화에 취약한 단점을 가지고 있다. 또한, 상기 수지는내크랙성이 충분치 못하여, 전체 수율감소를야기하는문제가있다. 10 Therefore, it is necessary to simultaneously increase the flowability and crack resistance of the resin in order to increase the pattern filling property and to prevent the cracks while reducing the thickness. A commonly used method is to use a monomolecular resin. In the case of a resin having a low molecular weight, since the viscosity before curing is low in the temperature range of the lamination process, flowability and pattern filling property are excellent. However, monomolecular resin has a disadvantage that it is vulnerable to changes over time because a protective film is required since the surface of the resin is cured 15 times and the curing reaction proceeds slowly at room temperature. In addition, the resin has insufficient crack resistance and causes a reduction in the overall yield.
【발명의 내용】 DISCLOSURE OF THE INVENTION
20 【해결하고자하는과제】  20 [Problem to be solved]
본 발명의 목적은 최소 점도를 유지하는 온도 구간을 넓혀 흐름성 및 패턴 채움성이 우수하고금속박막의 내크랙성을향상시킬 수 있는금속박막 코팅용열경화성 수지 조성물을제공하는것이다.  An object of the present invention is to provide a thermosetting resin composition for metal thin film coating which is excellent in flowability and pattern filling property by widening a temperature range maintaining minimum viscosity and capable of improving crack resistance of a metal thin film.
본 발명의 다른 목적은 기계적 물성이 우수한 상기 열경화성 수지 25 조성물의 경화물인 수지 코팅층을 포함한 금속 적층체 및 그 제조방법을 제공하는것이다.  Another object of the present invention is to provide a metal laminate including a resin coating layer which is a cured product of the thermosetting resin composition having excellent mechanical properties, and a method for producing the same.
【과제의 해결수단】 MEANS FOR SOLVING THE PROBLEMS
본 명세서에서는， 술폰기， 카보닐기， 할로겐기, 탄소수 1 내지 20의 30 알킬기， 탄소수 6 내지 20의 아릴기， 탄소수 2 내지 30의 헤테로아릴기 및 2019/117624 1»（：1^1{2018/015776 In the present specification, the term " alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 2 to 30 carbon atoms, 2019/117624 1 »(: 1 ^ 1 {2018/015776
탄소수 1내지 20의 알킬렌기로 이루어진 군에서 선택된 1종 이상의 작용기를 포함한 아민 화합물; 에폭시 수지 및 비스말레이미드 수지를 포함한 바인더 수지; 무기 충진제; 및 고무계성분을포함하고， An amine compound containing at least one functional group selected from the group consisting of alkylene groups having 1 to 20 carbon atoms; A binder resin including an epoxy resin and a bismaleimide resin; Inorganic fillers; And a rubber-based component,
상기 고무계 성분은 스티렌 부타디엔계 고무， 네오프렌계 고무 , 5 니트릴계 고무， 부틸계 고무， 부타디엔계 고무， 에틸렌프로필렌계 고무， 실리콘계 고무， 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종이상을포함하며，  The rubber component includes at least one member selected from the group consisting of styrene butadiene rubber, neoprene rubber, 5 nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, silicone rubber, urethane rubber and acrylic rubber ,
상기 아민 화합물 및 바인더 수지의 총합 100 중량부에 대해, 상기 고무계성분은 5중량부이상 40중량부미만으로포함하고,  Wherein the rubber component comprises at least 5 parts by weight and less than 40 parts by weight based on 100 parts by weight of the total of the amine compound and the binder resin,
10 레오미터 최저 점도구간이 90내지 180 X：의 범위에서 350 3.3 이하의 복소점도조건을만족하는, 금속박막코팅용열경화성 조성물을제공한다. 본명세서에서는또한， 금속박막의 적어도 일면에 상기 열경화성 수지 조성물이 경화된수지 코팅층을포함하며, Wherein the 10 rheometer minimum viscosity section satisfies the complex viscosity condition of 350 3.3 or less in the range of 90 to 180 X :. The present specification also includes a resin coating layer in which the thermosetting resin composition is cured on at least one surface of the metal thin film,
상기 수지 코팅층은，  The resin coating layer
15 술폰기， 카보닐기, 할로겐기, 탄소수 1 내지 20의 알킬기， 탄소수 6 내지 20의 아릴기， 탄소수 2 내지 30의 헤테로아릴기 및 탄소수 1 내지 20의 알킬텐기로 이루어진 군에서 선택된 1종 이상의 작용기를 포함한 아민 화합물과, 에폭시 수지 및 비스말레이미드 수지를 포함한 바인더 수지와， 스티렌 부타디엔계 고무， 네오프렌계 고무, 니트릴계 고무, 부틸계 고무， 20 부타디엔계 고무， 에틸렌프로필렌계 고무， 실리콘계 고무, 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종 이상의 고무계 성분 간의 경화물; 및  At least one functional group selected from the group consisting of a sulfone group, a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, and an alkylene group having 1 to 20 carbon atoms A binder resin containing an epoxy resin and a bismaleimide resin, and a binder resin including a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a 20 butadiene rubber, an ethylene propylene rubber, a silicone rubber, A cured product of at least one rubber component selected from the group consisting of rubber and acrylic rubber; And
상기 경화물사이에 분산되어 있는 충진제;를 포함하는 금속 적층체를 제공한다.  And a filler dispersed among the cured products.
25 본 명세서에서는 또한, 상기 열경화성 수지 조성물을 금속 박막의 적어도일면에 코팅하는단계를포함하는금속적층체의 제조방법을제공한다. 본 명세서에서는 또한， 상기 금속 적층체가 1매 이상 적층된 금속박 적층판을제공한다.  25 The present invention also provides a method for producing a metal laminate, which comprises coating the thermosetting resin composition on at least one surface of a metal thin film. The present invention also provides a metal-clad laminate in which one or more metal laminate layers are laminated.
이하발명의 구체적인 구현예에 따른금속 박막코팅용 열경화성 수지 30 조성물과이를이용한수지 코팅 금속적층체 및 금속박적층판에 대하여 보다 2019/117624 1»（：1^1{2018/015776 A thermosetting resin 30 composition for metal thin film coating according to a specific embodiment of the present invention and a resin-coated metal laminate and a metal foil laminate using the composition 2019/117624 1 » (: 1 ^ 1 {2018/015776
상세하게 설명하기로 한다. 먼저， 본 발명에서 금속 적층체는 열경화성 수지 조성물이 금속 박막 상에 일정 두께로코팅된 형태를포함할수 있다. Will be described in detail. First, in the present invention, the metal laminate may include a thermosetting resin composition coated on a metal thin film to a predetermined thickness.
5 상기 금속 박막은 수지 조성물을 코팅하기 위한 기재로서， 후술하는 바와 같이 단일 또는 복합금속성분을포함하는 박막 형태일 수 있다. 또한， 금속박적층판은상기 금속 적층체가 1종 이상 적층된 구조를포함할수 있다. 발명의 일 구현예에 따르면 술폰기， 카보닐기， 할로겐기 탄소수 1 10 내지 20의 알킬기， 탄소수 6 내지 20의 아릴기， 탄소수 2 내지 30의 헤테로아릴기 및 탄소수 1내지 20의 알킬텐기로 이루어진 군에서 선택된 1종 이상의 작용기를 포함한 아민 화합물;에폭시 수지 및 비스말레이미드 수지를 포함한 바인더 수지;무기 충진제;및 고무계 성분을 포함하고， 상기 고무계 성분은 스티렌 부타디엔계 고무， 네오프렌계 고무， 니트릴계 고무， 부틸계 15 고무 부타디엔계 고무 에틸렌프로필렌계 고무 실리콘계 고무， 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종 이상을 포함하며， 상기 아민 화합물 및 바인더 수지의 총합 100중량부에 대해， 상기 고무계 성분은 5 중량부 이상 40 중량부 미만으로 포함하고 레오미터 최저 점도 구간이 90 내지 1801：의 범위에서 3500Pa.s 이하의 복소 점도 조건을 만족하는 금속 20 박막코팅용 열경화성 조성물이 제공된다. 5 The metal thin film is a substrate for coating a resin composition, and may be in the form of a thin film containing a single or composite metal component as described later. In addition, the metal-clad laminate may include a structure in which one or more metal laminate layers are stacked. According to one embodiment of the invention, a sulfone group, a carbonyl group, a halogen group having 1 10 to 20 alkyl group, having 6 to 20 carbon atoms in the aryl group, a heteroaryl group having a carbon number of 2 to 30 and the group consisting alkyl, X having 1 to 20 carbon atoms An epoxy resin and a bismaleimide resin, an inorganic filler, and a rubber component, wherein the rubber component is at least one selected from the group consisting of a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, butyl series 15 of rubber of butadiene-based rubber ethylene propylene-based rubber silicone rubber, urethane rubber and comprises at least one selected from the group consisting of acrylic rubber, the above amine compound and a total based on 100 parts by weight of the rubber component of the binder resin has 5 including the parts by weight or more and less than 40 parts by weight, and rheometer minimum viscosity range 90 to 1801: The thermosetting composition is provided for coating a metal thin film 20 that satisfies the condition of the complex viscosity in the range of less than 3500Pa.s.
본 발명은 흐름성이 충분하여 패턴 채움성도 좋고 내크랙성을 향상시킨 금속 박막 코팅용 열경화성 수지 조성물 및 금속 박막에 관한 것이다.  The present invention relates to a thermosetting resin composition and a metal thin film for metal thin film coating, which have sufficient flowability to improve pattern filling and crack resistance.
기존에는 주로 수지 조성물을 직조된 유리 섬유에 함침한 25 프리프레그를 이용하여 금속박 적층판을 제조하여 왔지만， 두께를 줄이는데 한계가 있을뿐 아니라두께가줄어들면 동박의 적층공정 중에 수지 흐름성이 떨어져 패턴 채움성이 불량한 문제가 있었다. 또한 수지가 코팅된 형태의 동박의 박막화가 가능해도， 단분자 계열의 수지가 사용되는 경우 보관성 및 안정성의 측면에서 불리한점이 많았다. Conventionally, metal foil laminates have been produced mainly by using a 25 prepreg impregnated with a woven glass fiber. However, when the thickness is reduced, the resin flowability during the laminating process of copper foil is reduced, There was a problem with poor sex. In addition, although it is possible to make the copper foil coated with the resin thinner, there are many disadvantages in terms of storage stability and stability when a monomolecular resin is used.
30 한편， 기존 열경화성 수지 조성물에서는 경화 후 모듈러스가 높아 2019/117624 1＞（그1'/1 ?2018/015776 30 On the other hand, in the conventional thermosetting resin composition after curing is higher modulus 2019/117624 1> (1 '/ 1? 2018/015776
깨지기 쉽고이에 따라내크랙성은떨어진다는단점이 있었다. It is fragile and thus the crack resistance is deteriorated.
따라서, 본 발명에서는 에폭시와 아민 경화제 등으로 구성된 수지 시스템 및 고무계 성분을소량도입하여 수지의 흐름성이 확보할뿐 아니라, 금속 박막에 상기 열경화성 수지 조성물이 코팅된 금속 적층체의 내크랙성을 5 향상시키고자 한다. 또한, 본 발명의 조성물은 수지 종류 및 혼합 비율을 최적화하는특징이 있다. Therefore, in the present invention, not only the flowability of resin is ensured by introducing a small amount of a resin system and a rubber component constituted of epoxy and amine curing agent and the like, but also crack resistance of the metal laminate coated with the thermosetting resin composition is 5 . Further, the composition of the present invention is characterized by optimizing the type of resin and the mixing ratio .
본 발명에 따르면， 특정 아민 경화제를사용해서, 수지의 경화 반응을 용이하게 제어할 수 있다. 좀 더 구체적으로는 아민 경화제의 작용기를 조절하여 수지의 경화 반응 시 생기는 결합의 수를 조절함으로써 모듈러스를 10 낮출수 있다. 이를통해 내크랙성은증가하게 되며 같은 인장력 또는충격에 대해보다안정성을가질수 있게 된다.  According to the present invention, the curing reaction of the resin can be easily controlled by using a specific amine curing agent. More specifically, the modulus can be lowered by controlling the functional groups of the amine curing agent to control the number of bonds generated during the curing reaction of the resin. This increases the crack resistance and makes it more stable against the same tensile force or impact.
또한， 본 발명에 사용된 금속 박막 코팅용 열경화성 수지 조성물은 경화 반응의 제어와 함께, 상기 조성물에 특정 고무계 성분을 첨가하여 흐름성을 조절하게 된다. 이에 따라 레오미터 최저 점도 구간（ 11（10¾0이 15 넓어져서 흐름성 및 패턴 채움성에 유리하게 된다. 바람직하게, 본 발명은 금속박적층공정의 온도구간내에서， 최소점도를유지하는구간（ 11（10的을 넓힘으로써 , 수지의 흐름성을향상시키는효과가있다.In addition, the thermosetting resin composition for metal thin film coating used in the present invention controls flowability by adding a specific rubber component to the composition together with controlling the curing reaction. Accordingly rheometer minimum viscosity region (11 (1 0¾ 0 15 is so spread is advantageous flowability and gender fill pattern. Preferably, the present invention as in the temperature region of the metal foil lamination process, the widening section (11 (10的maintaining a minimum viscosity, there is an effect of improving the flowability of the resin.
Figure imgf000007_0001
Figure imgf000007_0001
가정할 때， 본 발명에서 제시하는 수지 조성물의 경우, 상기 점도 조건을 20 만족하는 온도 구간이 90 내지 180°（：로 매우 넓다. 즉， 적층 공정 구간 내 흐름성이 높고 패턴 채움성이 우수해져서, 열경화성 수지 조성물이 코팅된 금속 박막의 내크랙성을 향상시킬 수 있다. 그·러나， 상기 열경화성 수지 조성물의 복소 점도 조건이 상기 범위 이상으로 너무 높아지면 흐름성이 떨어지므로， 패턴 채움성이 불량해질 수 있다. 또한, 상기 복소 점도조건을 25 만족하더라도, 종래 열경화성 수지 조성물은 상대적으로 작업 온도 구간이 좁아질수 있다. 그러면， 본 발명의 바람직한 일 구현예에 따른 금속 박막 코팅용 열경화성 수지 조성물의 구성 성분과상기 수지 조성물을이용한금속박막및 30 금속박적층판에 대하여 보다구체적으로설명한다. 본 발명자들은, 상기 일 구현예의 금속 박막 코팅용 열경화성 수지 조성물을 사용할 경우, 술폰기， 카보닐기, 할로겐기， 치환된 탄소수 1 내지 20의 알킬기, 치환된 탄소수 6내지 20의 아릴기, 치환된 탄소수 2내지 30의 헤테로아릴기 및 치환된 탄소수 1 내지 20의 알킬렌기로 이루어진 군에서 선택된 1종 이상의 작용기와 같이 강력한 전자 끌개 작용가 (Electron Wi thdrawing Group , EWG)를 포함한 아민 화합물을 통해， 아민 화합물의 반응성을 줄여 수지 조성물의 경화 반응을 용이하게 제어할 수 있음을 확인하였다. Assuming, in the case of the resin composition proposed in the present invention, the temperature range satisfying the viscosity condition 20 is 90 to 180 DEG (very wide). That is, the flowability in the laminating process section is high and the pattern filling property is excellent, and the crack resistance of the metal thin film coated with the thermosetting resin composition can be improved. That, however, the complex viscosity conditions of the thermosetting resin composition becomes too high, the flowability dropped to the ground than the above range, a pattern may be poor filling property. Also, even if the complex viscosity condition is satisfied, the conventional thermosetting resin composition can have a relatively narrow working temperature range. Hereinafter, the components of the thermosetting resin composition for metal thin film coating, the metal thin film using the resin composition and the 30 metal foil laminate according to a preferred embodiment of the present invention will be described in more detail. The present inventors have found that when the thermosetting resin composition for metal thin film coating according to the above embodiment is used, it is possible to use a thermosetting resin composition for a metal thin film coating, which comprises a sulfone group, a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An amine compound including an electron donating group (EWG) such as at least one functional group selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms and an alkylene group having 1 to 20 carbon atoms, It was confirmed that the curing reaction of the resin composition can be easily controlled by reducing the reactivity.
구체적으로， 상기 일 구현예의 열경화성 수지 조성물은 술폰기， 카보닐기， 할로겐기， 탄소수 1내지 20의 알킬기 , 탄소수 6내지 20의 아릴기， 탄소수 2내지 30의 헤테로아릴기 및 탄소수 1내지 20의 알킬렌기로이루어진 군에서 선택된 1종 이상의 작용기를 포함한 아민 화합물을 포함할 수 있다. 상기 아민화합물은아민 경화제로사용될수있다.  Specifically, the thermosetting resin composition of this embodiment is a thermosetting resin composition comprising a sulfone group, a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, And an amine compound including at least one functional group selected from the group consisting of a halogen atom and a halogen atom. The amine compound may be used as an amine curing agent.
이때， 상기 아민 화합물에 포함된 탄소수 1 내지 20의 알킬기, 탄소수 6내지 20의 아릴기， 탄소수 2내지 30의 헤테로아릴기 및 탄소수 1내지 20의 알킬렌기는 각각 독립적으로 니트로기, 시아노기 및 할로겐기로 이루어진 군에서 선택된 1종이상의 작용기로치환될수 있다.  The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the heteroaryl group having 2 to 30 carbon atoms, and the alkylene group having 1 to 20 carbon atoms contained in the amine compound are each independently a nitro group, a cyano group and a halogen Gt; may be substituted with one or more functional groups selected from the group consisting of < RTI ID = 0.0 >
상기 아민 화합물에 포함된 술폰기， 카보닐기, 할로겐기, 치환된 탄소수 1 내지 20의 알킬기， 치환된 탄소수 6 내지 20의 아릴기， 치환된 탄소수 2 내지 30의 헤테로아릴기 및 치환된 탄소수 1 내지 20의 알킬텐기로 이루어진 군에서 선택된 1종 이상의 작용기는 강력한 전자 끌개 작용기 (Electron Wi thdrawing Group, EWG)로서， 상기 전자 끌개 작용기를 포함한 아민 화합물은 전자끌개 작용기를 포함지 않은 아민 화합물에 비해 반응성이 감소하여 이로부터 수지 조성물의 경화 반응을 용이하게 제어할 수 있다.  A substituted or unsubstituted C1-C20 alkyl group, a substituted C6-C20 aryl group, a substituted C2-C30 hetero aryl group, and a substituted C1-C20 alkyl group, which are contained in the amine compound, (EWG), and the amine compound including the electron-withdrawing group is more reactive than the amine compound not including the electron-withdrawing group Whereby the curing reaction of the resin composition can be easily controlled.
따라서， 상기 아민 화합물에 의해 조성물의 경화반응 정도를 조절하여 유동성을향상시켜 회로패턴 채움성이 향상될수 있다.  Therefore, by controlling the curing reaction degree of the composition by the amine compound, fluidity can be improved and filling of the circuit pattern can be improved.
구체적으로， 상기 아민 화합물은 하기 화학식 1 내지 3으로 이루어진 군에서 선택된 1종이상의 화합물을포함할수있다.  Specifically, the amine compound may include one or more compounds selected from the group consisting of the following chemical formulas (1) to (3).
[화학식 1] 2019/117624 1»（：1^1{2018/015776 [Chemical Formula 1] 2019/117624 1 » (: 1 ^ 1 {2018/015776
지  G
/  /
X?  X?
5  5
상기 화학식 1에서， 쇼는 술폰기 카보 X닐I기， 또는 탄소수 1 내지 10의 알킬렌기이며， XI 내지 ¾는 각각 독립적으로 니트로기， 시아노기， 수소원자 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기， 또는 탄소수 2내지 20의 헤테로아릴기이 0고， ¾및 ¾’ 는각각독립적으로 수소원자， 할로겐기 탄소수 1내지 6의 알킬기， 탄소수 6내지 15의 아릴기， 또는탄소수 2내지 20의 헤테로아릴기이며， II은 1내지 10의 정수이고， In the general formula (1), show a sulfone group carbonyl X carbonyl I group, or an alkylene group having 1 to 10, X I to ¾ each independently represent a nitro group, a cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms , heteroaryl Kii 0 and C 6 -C 15 aryl group, or 2 to 20 carbon atoms of, ¾ and ¾ 'each independently represent a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15, or A heteroaryl group having 2 to 20 carbon atoms, II is an integer of 1 to 10 ,
상기 탄소수 1내지 10의 알킬렌기， 탄소수 1내지 6의 알킬기， 탄소수 6내지 15의 아릴 0기 2— /， =및 탄소수 2내지 20의 헤테로아릴기는각각독릴적으로 니트로기， 시아노기 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 작용기로치환되며， The alkylene group having 1 to 10 carbon atoms, the alkyl group having 1 to 6 carbon atoms, the aryl group 0 of 2 to 6 carbon atoms having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each independently a nitro group, a cyano group and a halogen group is substituted with at least one member selected from the group consisting of functional groups,
[화학식 2]  (2)
Figure imgf000009_0001
Figure imgf000009_0001
상기 화학식 2에서， 내지 는각각독립적으로니트로기 시아노기， 수소원자， 할로겐기， 탄소수 1내지 6의 알킬기， 탄소수 6내지 15의 아릴기， 또는 탄소수 2 내지 20의 헤테로아릴기는 이고， ¾ ¾’ ¾ 및 ¾’ 는 각각 독립적으로 수소원자 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기 또는 탄소수 2 내지 20의 헤테로아릴기이며 은 1 내지 10의 정수이고， 상기 탄소수 1 내지 6의 알킬기 탄소수 6 내지 15의 아릴기 및 \¥0 2019/117624 1＞（：17 1技018/015776 In the above formula (2), to are each independently a nitro group a cyano group, a hydrogen atom, a halogen group, an aryl group, the alkyl group, having 6 to 15 having from 1 to 6 carbon atoms, or a heteroaryl group having 2 to 20, ¾ ¾ ' ¾ and ¾ 'are independently a hydrogen atom a halogen group, and a heteroaryl group is an integer from 1 to 10 C 1 -C 6 alkyl group, a C 6 -C 15 aryl group, or 2 to 20 carbon atoms of the group having 1 to 6 carbon atoms, respectively An alkyl group having 6 to 15 carbon atoms, \ \ 0 2019/117624 1> (: 17 1 technique 018/015776
탄소수 2 내지 20의 헤테로아릴기는 각각 독립적으로 니트로기， 시아노기 및 할로겐기로이루어진군에서 선택된 1종이상의 작용기로치환되며， Each heteroaryl group having 2 to 20 carbon atoms is independently substituted with one or more functional groups selected from the group consisting of a nitro group, a cyano group and a halogen group,
[화학식 3]  (3)
Figure imgf000010_0001
Figure imgf000010_0001
상기 화학식 3에서, 1'내지 ¾는각각독립적으로니트로기， 시아노기, 수소원자, 할로겐기 , 탄소수 1내지 6의 알킬기， 탄소수 6내지 15의 아릴기 , 또는 탄소수 2 내지 20의 헤테로아릴기이고， ¾, ¾’ , ¾ 및 ¾’ 는 각각 독립적으로 수소원자, 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기， 또는탄소수 2내지 2◦의 헤테로아릴기이며， 상기 탄소수 1내지 6의 알킬기， 탄소수 6 내지 15의 아릴기, 및 탄소수 2 내지 20의 헤테로아릴기는 각각독립적으로 니트로기， 시아노기 및 할로겐기로 이루어진 군에서 선택된 1종이상의 작용기로치환된다. In Formula 3, 1 'to 3 each independently represent a nitro group, a 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 , ¾ , ¾ ' , ¾ and ¾' each independently represent 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 2 carbon atoms, The alkyl group having 6 to 15 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each independently substituted with one or more functional groups selected from the group consisting of a nitro group, a cyano group and a halogen group.
상기 알킬기는,
Figure imgf000010_0002
유래한 1가의 작용기로, 예를 들어， 직쇄형， 분지형 또는 고리형으로서, 메틸， 에틸， 프로필， 이소부틸，
Figure imgf000010_0003
16 -부틸, 펜틸, 핵실등이 될수 있다. The above-
Figure imgf000010_0002
Derived monovalent functional group, for example, linear, branched or cyclic, such as methyl, ethyl, propyl, isobutyl,
Figure imgf000010_0003
16 - can be a butyl, pentyl, haeksil.
상기 알킬텐기는, 알케인（ 1¾1½）으로부터 유래한 2가의 작용기로, 예를 들어， 직쇄형， 분지형 또는 고리형으로서, 메틸렌기, 에틸렌기, 프로필렌기, 이소부틸렌기, 드% -부틸텐기, 七라卜부틸렌기, 펜틸렌기， 핵실렌가 등이 될 수 있다. 상기 알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 각각상기 알킬기의 경우와마찬가지의 치환기로치환가능하다. The alkylene group is a divalent functional group derived from an alkene (1 ¾1 ½ ), for example, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, such as methylene, ethylene, propylene, isobutylene, Pentylene, heptylene, heptene, heptene, heptene, heptene, heptene, heptene, The at least one hydrogen atom contained in the alkylene group may each be substituted with the same substituent as the alkyl group.
상기 아릴기는아렌（3 1½）으로부터 유래한 1가의 작용기로, 예를들어, 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, 플루오레닐기 등이 될 수 있으나， 이에 한정되는 것은아니다. 이러한아릴기 중하나 이상의 수소 원자는각각상기 알킬기의 경우와마찬가지의 치환기로치환가능하다. The aryl group is a monovalent functional group derived from arenes ( 3 1½ ), for example, monocyclic or polycyclic. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like. Examples of the polycyclic aryl group include a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group, It is not. These hydrogen atoms of at least one of the aryl groups may be substituted with the same substituents as those in the alkyl group.
상기 헤테로아릴기는 이종원자로 0， N 또는 를 포함하는 헤테로 고리기로서, 탄소수는 특별히 한정되지 않으나 탄소수 2 내지 30일 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 , 디벤조티오펜기， 벤조퓨라닐기 및 디벤조퓨란기 등이 있으나， 이들에만 한정되는것은아니다. 이러한헤테로아릴기 중하나이상의 수소원자는각각 상기 알킬기의 경우와마찬가지의 치환기로치환가능하다.  The heteroaryl group is a heterocyclic group containing 0, N or a hetero atom, and the number of carbon atoms is not particularly limited, but may be 2 to 30 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, , A quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group and a dibenzofuran And the like, but the present invention is not limited thereto. The hydrogen atoms of one or more of these heteroaryl groups may each be substituted with the same substituent as in the case of 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 치환기는서로동일하거나상이할수있다.  The term " substituted " means that another functional group is bonded in place of the hydrogen atom in the compound, and the position to be substituted is not limited as far as the position where the hydrogen atom is substituted, that is, The two or more substituents may be the same or different from each other.
보다구체적으로, 상기 화학식 1은하기 화학식 1-1로표시되는화합물을 포함할수있다.  More specifically, the compound represented by Formula 1 may include a compound represented by Formula 1-1.
[화학식 1-1]  [Formula 1-1]
Figure imgf000011_0001
상기 화학식 1-1에서， A， Xi내지 ¾， Ri, Ri' , R2및 ¾’ , n에 대한내용은 상기 화학식 1에서 상술한내용을포함한다.
Figure imgf000011_0001
In Formula 1-1, the contents of A, Xi to ¾, Ri , Ri ' , R 2 and ¾', n include the above-mentioned contents in Formula 1.
상기 화학식 1-1의 구체적인 예로는 4,4’ -di ami nodi phenyl sul fone（화학식 1-1에서 A는 술폰기, ¾ 내지 X8, Ri, ¾’ , ¾ 및 ¾’ 는 각각 독립적으로 수소원자이며， n은 1 이다.）， bi s（4_aminophenyl）methanone（화학식 1_1에서 A는카보닐기 , ¾, X Ri, Ri’ , ¾ 2019/117624 1»（：1^1{2018/015776 Specific examples of the formula 1-1 include 4,4'-diaminodiphenylsul fone (in formula 1-1, A is a sulfone group, ¾ to X 8, Ri , ¾ ' , ¾ and ¾' atom, and, n is 1.) in bi s (4_aminophenyl) methanone (formula a is a carbonyl group 1_1, ¾, X Ri, Ri ', ¾ 2019/117624 1 »(: 1 ^ 1 {2018/015776
및 ¾’ 는 각각 독립적으로 수소원자이며， II은 1 이다.）,And ¾ 'are each independently a hydrogen atom, and II is 1),
4,4’ - 111아01）1，（피3]16-2,2-（｝ 1）（1131111오 （화학식 1-1에서 쇼는4, 1 ', 11 , 01 ) 1 , (P 3] 16 -2,2- (1) (1 13111 1
?6 11!0101）1애 6-2,2-（1 1， ¾내지 8, ¾, ¾’ ，요2및 ¾’ 는각각독립적으로 수소원자이며, ]1은 1이다.）， 4,4’-（2,2,2-（:1· 군 111이06 3116-1， 1-（1 1서 1 ½ （화학식
Figure imgf000012_0001
, 1¾및 ? 61 1? 0101) 1 Ke 6 -2,2- (1 1, ¾ to 8, ¾, ¾ ', I 2 and ¾' are each independently a hydrogen atom, - 1 is a 1), 4 , 4 '- (2,2,2 (1 1, group 11 is 06 3116-1, 1- (1 1 1 ½ standing (formula
Figure imgf000012_0001
, 1¾ and
¾’ 는각각독립적으로수소원자이며, II은 1이다.）등을들수있다. Is a hydrogen atom, and II is 1), and the like.
또한， 상기 화학식 2는 하기 화학식 2-1로 표시되는 화합물을 포함할 수 있다.  The formula (2) may include a compound represented by the following formula (2-1).
[화학식 2-1]  [Formula 2-1]
Figure imgf000012_0002
대한내용은 상기 화학식 2에서 상술한내용을포함한다.
Figure imgf000012_0002
The above-mentioned contents in the above formula (2) are included.
상기 화학식 2-1의 구체적인 예로는 Specific examples of the formula (2-1) include
2,2' ,3,3' ,5,5' ,6,6’_0（介3£ 1나01_0 1）1161¾1-4,4’- 311 1½（화학식 2-1에서 내지 은 할로겐으로 플루오르기, ¾, ¾’ , ¾ 및 ¾’ 는 각각 독립적으로 수소원자이며, 111은 1이다.）, 2,2'- 3（ 1나0 미 1¾，1）1 1）116]¾1-4,4’-（1 111 ½
Figure imgf000012_0003
2,2 ', 3,3', 5,5 ', 6,6'_ 0 (interstitial 3 £ 1 or 01 _ 0 1 ) 1 161¾ 1-4,4'- 3 11 1½ to a halogen group is fluorine, ¾, ¾ ', ¾ and ¾' are each independently a hydrogen atom, a 111: 1), 2,2'-3 (1 or 0, US 1 ¾, 1) 1 1) 1 16] ¾ 1-4,4 '- (1 111 ½
Figure imgf000012_0003
¾’ , ¾및 ¾’ 는 각각 독립적으로 수소원자이며， 111은 1 이다.） 등을 들 수 있다. ¾ ' , ¾ and ¾' are each independently a hydrogen atom, and 111 is 1).
또한， 상기 화학식 3는 하기 화학식 3-1로 표시되는 화합물을 포함할수 있다.  The formula 3 may include a compound represented by the following formula 3-1.
[화학식 3-1] 2019/117624 1»（：1^1{2018/015776 [Formula 3-1] 2019/117624 1 »(: 1 ^ 1 {2018/015776
Figure imgf000013_0001
Figure imgf000013_0001
화학식 3에서 상술한내용을포함한다. (3).
상기 화학식 3-1의 구체적인 예로는
Figure imgf000013_0002
Specific examples of the formula (3-1) include
Figure imgf000013_0002
할로겐으로 플루오르기, ¾, ¾’ , ¾ 및 ¾’ 는 각각 독립적으로 수소원자이다.）등을들수있다. Halogen, fluorine group , ¾ , ¾ ' , ¾ and ¾' each independently represents a hydrogen atom).
상기 아민 화합물및 바인더 수지의 전체 중량에 대하여 아민 화합물의 함량이 15내지 60중량%일수있다. 바람직하게, 상기 아민화합물의 함량은 상기 아민 화합물 및 바인더 수지의 총합 100 중량부에 대하여 20 내지 55 중량%일 수 있다. 상기 아민 화합물의 함량이 15 중량% 미만으로 지나치게 감소할 경우， 미경화가 발생할 수 있으며， 상기 아민 화합물의 함량이 80 중량부 초과로 지나치게 증가할 경우, 경화속도가 증가되어 열경화성 수지 조성물의 유동성이 감소될 수 있으며, 또한， 미반응된 아민 화합물에 의해 열경화성 수지 조성물을이용한금속박막의 기계적 물성이 저하될수 있다. 또한， 상기 일 구현예의 금속 박막 코팅용 열경화성 수지 조성물은 바인더 수지를포함할수있다.  The content of the amine compound may be from 15 to 60% by weight based on the total weight of the amine compound and the binder resin. Preferably, the content of the amine compound may be 20 to 55% by weight based on 100 parts by weight of the total of the amine compound and the binder resin. If the content of the amine compound is excessively reduced to less than 15% by weight, un-curing may occur. If the content of the amine compound is excessively increased to more than 80% by weight, the curing rate is increased and the fluidity of the thermosetting resin composition is decreased In addition, the mechanical properties of the metal thin film using the thermosetting resin composition may be deteriorated by the unreacted amine compound. In addition, the thermosetting resin composition for metal thin film coating in one embodiment may include a binder resin.
상가 바인더 수지는 에폭시 수지 및 비스말레이미드 수지로 이루어진 군으로부터 선택되는 1종이상의 수지를포함할수 있다.  The transition metal binder resin may include one or more resins selected from the group consisting of an epoxy resin and a bismaleimide resin.
이 때， 상기 에폭시 수지로는 열경화성 수지 조성물에 사용되는 것을 제한 없이 사용할 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 2019/117624 1»（：1/10公018/015776 있다. As the epoxy resin, there may be used any of those used in the thermosetting resin composition without limitation, and examples thereof include bisphenol-type epoxy resins, phenol novolac epoxy resins, phenyl aralkyl-type epoxy resins, Epoxy resin, naphthalene-based epoxy resin, biphenyl-based epoxy resin, dicyclopentadiene epoxy resin, and a mixture of dicyclopentadiene-based epoxy resin and naphthalene-based epoxy resin 2019/117624 1 » (: 1/10/01 018/015776.
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 9및 10으로 표시되는 나프탈렌형 에폭시 수지, 하기 화학식 11로 표시되는 바이페닐형 에폭시 수지， 및 하기 화학식 12로 표시되는 디시클로펜타디엔형 에폭시 수지로 이루어진 군에서 선택된 1종 이상을사용할수 있다. Specifically, the epoxy resin is to tetraphenyl ethane epoxy represented the formula resin bisphenol epoxy represented by the 5 to resin novolak epoxy represented by the formula (6) to phenyl aralkyl kilgye epoxy resin represented by the following formula (7) in formula (8) resin to the naphthalene type epoxy resin, to at least one selected from the group consisting of a dicyclopentadiene type epoxy resin represented by the biphenyl type epoxy resin, and the following formula (12) represented by the formula (11) represented by the following formulas 9 and 10 Can be used.
[화학식 5]  [Chemical Formula 5]
Figure imgf000014_0001
Figure imgf000014_0001
II은 0또는 1내지 50의 정수이다. II is 0 or an integer from 1 to 50;
보다 구체적으로 상기 화학식 5의 에폭시 수지는 묘의 종류에 따라 각각 비스페놀 쇼형 에폭시 수지 비스페놀 형 에폭시 수지 비스페놀 형 에폭시 수지， 또는비스페놀 £형 에폭시 수지일수 있다. More specifically, the epoxy resin of formula ( 5) may be a bisphenol-type epoxy resin, a bisphenol-type epoxy resin, or a bisphenol epoxy resin, depending on the type of seedlings.
[화학식 6]  [Chemical Formula 6]
Figure imgf000014_0002
2019/117624 1»（：1^1{2018/015776
Figure imgf000014_0002
2019/117624 1 »(: 1 ^ 1 {2018/015776
II은 0또는 1내지 50의 정수이다. II is 0 or an integer from 1 to 50;
보다구체적으로, 상기 화학식 3의 노볼락형 에폭시 수지는요의 종류에 따라, 각각 페놀 노볼락형 에폭시 수지 또는 크레졸 노볼락형 에폭시 수지일 수있다.  More specifically, the novolak type epoxy resin of Formula 3 may be a phenol novolak type epoxy resin or a cresol novolak type epoxy resin, respectively, depending on the type of urine.
[화학식 7]  (7)
Figure imgf000015_0001
Figure imgf000015_0001
[화학식 11] 2019/117624 1»（：1^1{2018/015776 (11) 2019/117624 1 » (: 1 ^ 1 {2018/015776
Figure imgf000016_0001
Figure imgf000016_0001
상기 화학식 11에서  In the above formula (11)
은 0또는 1내지 50의 정수이다. Is an integer of 0 or 1 to 50. [
［화학식 1到 [Formula 1]
5
Figure imgf000016_0002
5
Figure imgf000016_0002
상기 화학식 12에서， 은 0또는 1내지 50의 정수이다. In the above formula ( 12 ), 0 is an integer of 1 to 50 ,
또한, 본 발명에서 상기 아민 화합물 및 바인더 수지의 전체 중량에 대하여 에폭시 수지의 함량이 30 내지 80 중량%이고 비스말레이미드 수지의 함량이 1내지 20중량%일 수 있다. 바람직하게 상기 에폭시 수지의 함량은In the present invention, the content of the epoxy resin may be 30 to 80 wt % and the content of the bismaleimide resin may be 1 to 20 wt % based on the total weight of the amine compound and the binder resin. Preferably, the content of the epoxy resin is
10 상기 아민 화합물 및 바인더 수지의 총합 100 중량부에 대하여 35 내지 70 중량%일수 있다. 또한， 상기 비스말레이미드수지의 함량은상기 아민화합물 및 바인더 수지의 총합 100중량부에 대하여 1내지 10중량%일수있다. 10 may be 35 to 70 % by weight based on 100 parts by weight of the total of the amine compound and the binder resin. The content of the bismaleimide resin may be 1 to 10 % by weight based on 100 parts by weight of the total amount of the amine compound and the binder resin.
상기 바인더 수지 중에 포함되는 에폭시 수지의 사용량이 30 중량% 미만이면 높은 용의 구현이 어려운 문제가 있고， 80 중량%를 초과하면When the amount of the epoxy resin contained in the binder resin is less than 30 % by weight, it is difficult to realize high solubility. When the amount exceeds 80 % by weight
15 흐름성이 나빠지는문제가있다. 15 There is a problem of poor flowability.
그리고 상기 비스말레이미드 수지는 통상 열.경화성 수지 조성물에 사용되는것을제한없이 사용할수있으며， 그종류가한정되지는않는다. 일 구현예에 따르면， 상기 비스말레이미드 수지는 하기 화학식 13로 표시되는 디페닐메탄형 비스말레이미드 수지， 하기 화학식 14로 표시되는And the bismaleimide resin is usually heat-treated . Those used in the curable resin composition can be used without limitation, and the kind thereof is not limited. According to one embodiment, the bismaleimide resin is represented by the type diphenylmethane bismaleimide resin, to the formula 14 of the formula 13
20 페닐렌형 비스말레이미드 수지 하기 화학식 15로 표시되는 비스페놀 쇼형 디페닐 에테르 비스말레이미드 수지， 및 하기 화학식 16로 표시되는 디페닐메탄형 비스말레이미드 및 페닐메탄형 말레이미드 수지의 올리고머로 구성된비스말레이미드수지로이루어진군에서 선택된 1종이상일수 있다. 2019/117624 1»（：1^1{2018/015776 20 Phenylene Type Bismaleimide Resin The bisphenol-type diphenyl ether bismaleimide resin represented by the following formula ( 15 ) and the bismaleimide resin composed of the diphenylmethane type bismaleimide and the oligomer of the phenylmethane type maleimide resin represented by the following formula ( 16 ) one member selected from the group consisting of resins may be at least. 2019/117624 1 »(: 1 ^ 1 {2018/015776
[화학식 13] [Chemical Formula 13]
Figure imgf000017_0001
Figure imgf000017_0001
상기 화학식 13에서,  In Formula 13,
및 ¾는각각독립적으로,比 抑 3또는 ¾¾이다. And? Are independent of each other, and are 3 or more.
[화학식 14]  [Chemical Formula 14]
Figure imgf000017_0002
Figure imgf000017_0002
상기 화학식 16에서，  In Formula 16,
II은 0또는 1내지 50의 정수이다.  II is 0 or an integer from 1 to 50;
상기 바인더 수지 중에 포함되는 비스말레이미드 수지의 사용량이 1 중량%미만이면원하는물성 구현이 안되는문제가있고, 20중량%를초과하면 미반응기가많아내화학성 등의 특성에 악영향을끼칠수 있다. 2019/117624 1»（：1^1{2018/015776 When the amount of the bismaleimide resin contained in the binder resin is less than 1 wt%, there is a problem in that desired physical properties can not be realized. When the amount exceeds 20 wt%, unreacted groups are abundant, which may adversely affect chemical properties such as chemical resistance. 2019/117624 1 » (: 1 ^ 1 {2018/015776
한편， 상기 일 구현예의 열경화성 수지 조성물은 상기 바인더 성분과 함께 고무계 성분을포함할수 있다. Meanwhile, the thermosetting resin composition of one embodiment may include a rubber component together with the binder component.
본 발명은 아민 화합물이 함유된 바인더와 함께 특정 고무계 성분을 일정 비율로 포함함으로써， 상기 금속 박막 코팅용 열경화성 조성물은 5 레오미터 최저 점도 구간이 90내지 180X：의 범위에서 3500므크 이하의 복소 점도 조건을 만족하며 상기 복소 점도 조건의 하한은 크게 한정되는 것은
Figure imgf000018_0001
The present invention, by containing specific rubber components at a predetermined ratio, wherein the thin metal film coating the thermosetting composition is 5 rheometer minimum viscosity range is from 90 to 180X with the binder containing the amine compound: complex viscosity under the following conditions 3500 meukeu in the range of And the lower limit of the complex viscosity condition is largely limited
Figure imgf000018_0001
구체적으로， 상기 복소 점도 조건을 만족하게 하는 화합물은 스티렌 부타디엔계 고무， 네오프렌계 고무 니트릴계 고무， 부틸계 고무 부타디엔계 10 고무 에틸렌프로필렌계 고무， 실리콘계 고무 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종 이상의 고무계 성분일 수 있다. 더 바람직하게, 상기 고무계 성분은부타디인계 고무， 실리콘계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종 이상일 수 있다. Specifically, the compound that satisfies the above complex viscosity criteria is styrene butadiene rubber, neoprene-based rubber nitrile rubber, butyl-based rubber butadiene 10 rubber ethylene propylene-based rubber, silicone rubber polyurethane rubber and selected from the group consisting of acrylic rubber 1 May be a rubber-based component or more. More preferably , the rubber component may be at least one member selected from the group consisting of butadiene-based rubber, silicone rubber and acrylic rubber.
또한， 본 발명에서 특징으로 하는 고무계 성분은 상기 바인더 수지 100 15 중량부에 대해 스티렌 부타디엔계 고무 네오프렌계 고무， 니트릴계 고무， 부틸계 고무， 부타디엔계 고무， 에틸렌프로팔렌계 고무， 실리콘계 고무， 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종 이상의 고무계 성분 5중량부 이상 40중량부 미만을포함할수 있다. Further, the rubber-based composition which is characterized in the present invention, the binder resin 1 00 15 parts by weight of styrene-butadiene-based rubber for the neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene pro NW-based rubber, silicone rubber, one or more rubber components selected from the group consisting of urethane rubber and an acrylic rubber can also contain 5 parts by weight or more and less than 40 parts by weight.
바람직하게， 흐름성 및 패턴 채움성을 향상시키기 위한 고무계 성분의 20 최적비는 상기 고무계 성분은 아민 화합물 및 바인더 수지의 총합 100 중량부에 대해 5 중량부 내지 20 중량부를 포함할 수 있다. 상기 고무계 성분의 함량이 5 중량부 미만이면 수지의 흐름성이 너무 많아 두께 편차가 증가되는문제가 있고， 40중량부 이상이면 흐름성이 너무 적어 패턴 채움성이 떨어지는문제가 있다. Preferably, the flowability and the filling pattern 20 optimum rubber component for improving the sex ratio of the rubber component may comprise 5 to 20 parts by weight parts by weight for 100 parts by weight of the total of the amine compound and a binder resin. If the content of the rubber component is less than 5 parts by weight, the flowability of the resin is excessively increased to increase the thickness variation. If the content of the rubber component is more than 40 parts by weight, the flowability is too small.
25 상기 고무계 성분 중， 상기 부타디엔계 고무는 말단기가 히드록시기로 치환된 부타디엔 반복단위; 또는 아크릴기를 포함하는 부타디엔 반복단위; 또는 에폭시기를 포함하는 부타디엔 반복단위를 포함하고 중량평균분자량이 IX10 내지 5X10 인 공중합체를포함할수 있다. 25 Among the rubber-based components, the butadiene-based rubber is a butadiene repeating unit in which a terminal group is substituted with a hydroxy group; A butadiene repeat unit comprising an acrylic group; Or butadiene repeat units containing an epoxy group and having a weight average molecular weight can also contain a copolymer of I X10 to 5X10.
또한， 상기 실리콘계 고무는 에폭시기 또는 폴리에테르 변성 실리콘 30 반복단위:또는 말단기가 아민기 또는 에폭시기로 치환된 실리콘 반복단위를 2019/117624 1»（：1^1{2018/015776 Further, the silicone rubber may be a silicone repeating unit in which an epoxy group or polyether-modified silicone 30 repeating unit: or a repeating unit in which a terminal group is substituted with an amine group or an epoxy group 2019/117624 1 »(: 1 ^ 1 {2018/015776
포함하고 중량평균분자량이 1>< 103 내지 5>< 104 인 공중합체를 포함할 수 있다. And a weight average molecular weight of 1 &lt; 10 3 to 5 &gt; 10 4 .
상기 아크릴계 고무는， 수지 조성물에 포함되어 낮은 경화 수축율 특성을나타낼수 있다. 또한, 상기 아크릴계 고무는팽창완화작용의 효과를 한층더 높일수있다.  The acrylic rubber is contained in the resin composition and can exhibit a low curing shrinkage ratio. In addition, the acrylic rubber can further enhance the effect of the expansion relaxation action.
이러한 상기 아크릴계 고무는 아크릴산 에스테르 공중합체가 고무 탄성을가지는분자구조를가지고 있는것을사용한다.  Such an acrylic rubber uses an acrylic ester copolymer having a molecular structure having rubber elasticity.
구체적으로， 상기 아크릴계 고무는 아크릴산부틸 유래의 반복 단위와 아크릴로니트릴 유래의 반복 단위가 포함되는 아크릴산 에스테르 공중합체; 또는 부타디엔 유래의 반복 단위가 포함되는 아크릴산 에스테르 공중합체: 또는 탄소수 2 내지 10의 직쇄 또는 분지쇄의 알킬기 포함 아크릴산 알킬 유래의 반복단위를 포함할 수 있다. 한편 상기 아크릴계 고무의 중량평분자량은 30 X 104 내지 65>< 104이며， 상기 범위를 벗어나면 흐름성이 부족하거나과다할수 있다. Specifically, the acrylic rubber is an acrylic acid ester copolymer containing a repeating unit derived from butyl acrylate and a repeating unit derived from acrylonitrile; Or an acrylic acid ester copolymer containing a repeating unit derived from butadiene; or a repeating unit derived from a linear or branched alkyl group-containing acrylic acid alkyl group having 2 to 10 carbon atoms. On the other hand, the weight-average molecular weight of the acrylic rubber is 30 × 10 4 to 65 ≦ 10 4 , and if it is out of the above range, the flowability may be insufficient or excessive.
또한， 상기 스티렌 부타디엔계 고무， 네오프렌계 고무, 니트릴계 고무, 부틸계 고무, 에틸렌프로필렌계 고무， 우레탄계 고무의 종류는크게 제한되지 않으며， 이 분야에 잘알려진물질이 사용될수있다.  The types of the styrene butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, and urethane rubber are not particularly limited, and materials well known in the art can be used.
바람직하게， 상기 고무계 성분은 부타디엔계 고무, 실리콘계 고무 및 아크릴계 고무로이루어진군에서 선택된 1종이상을사용할수있다.  Preferably, the rubber component may be at least one selected from the group consisting of butadiene rubber, silicone rubber and acrylic rubber.
또한， 상기 일 구현예의 열경화성 수지 조성물은무기 충진제를포함할 수 있다. 상기 무기 충진제는 본 발명이 속하는 기술분야에 잘 알려진 것이 특별한 제한 없이 사용될 수 있다. 예를 들어， 상기 무기 충진제는 실리카, 알루미늄트리하이드록사이드， 마그네슘하이드록사이드， 몰리브데늄옥사이드， 징크 몰리브데이트, 징크 보레이트， 징크 스타네이트, 알루미나， 클레이, 카올린， 탈크, 소성 카올린, 소성 탈크， 마이카， 유리 단섬유， 글라스 미세 파우더， 및 중공 글라스로 이루어진 군에서 선택된 1종 이상의 화합물일 수 있다.  In addition, the thermosetting resin composition of one embodiment may include an inorganic filler. The inorganic filler can be used without any particular limitation as long as it is well known in the art to which the present invention belongs. For example, the inorganic filler may be selected from the group consisting of silica, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, fired kaolin, Talc, mica, short glass fiber, glass fine powder, and hollow glass.
한편， 상기 무기 충진제의 함량은상기 아민 화합물 및 바인더 수지의 총합 100중량부에 대하여 200중량부이상， 또는 200중량부내지 500중량부, 또는 250 중량부 내지 400 중량부일 수 있다. 상기 충진제의 함량이 약 200 2019/117624 1»（：1^1{2018/015776 Meanwhile, the content of the inorganic filler may be 200 parts by weight or more, 200 parts by weight to 500 parts by weight, or 250 parts by weight to 400 parts by weight based on 100 parts by weight of the total amount of the amine compound and the binder resin. When the content of the filler is about 200 2019/117624 1 »(: 1 ^ 1 {2018/015776
중량부 미만이면 열팽창계수가 증가하여 리플로우（ 0\0 공정시 뒤틀림 현상이 심화되며， 인쇄회로기판의 강성이 감소하는문제가있다. If the parts by weight is less than the thermal expansion coefficient increases, and the reflow (0 \ 0 process when distortion depth, there is a problem that the rigidity of the printed circuit board decreases.
상기 무기 충진제의 평균 입경은 0.1 lM 내지 100 _인 것이 바람직하다. 그리고 상기 무기 충진제는 필요에 따라 표면이 실란 처리된 물질일 수 있다. 또, 무기 충진제는 나노 스케일의 작은 입자와 마이크로 스케일의 큰입자를혼합사용하여 팩킹 밀도를높이는것이 바람직하다.  The average particle diameter of the inorganic filler is preferably 0.1 lM to 100 l. The inorganic filler may be a substance whose surface has been subjected to silane treatment if necessary. The inorganic filler is preferably mixed with small particles of nanoscale and large particles of microscale to increase the packing density.
상기 무기 충진제는 상기 바인더 수지에 분산될 수 있다. 상기 무기 충진제가바인더 수지에 분산되었다는것은상기 무기 충진제와바인더 수지가 각각분리되지 않고혼화된상태를의미한다. 즉, 상기 일구현예의 금속박막 코팅용열경화성 수지 조성물은무기 충진제 분리상이나수지로이루어진수지 분리상과 같은 분리상을 형성하지 않고, 무기 충진제와 수지가 골고루 혼합되어 분산상을 형성할 수 있다. 이에 따라， 상기 무기 충진제가 고함량으로 충진된 상태에서도 금속박에 코팅시 적정 수준의 흐름성과 높은 열안전성 및 기계적 물성을구현할수있다.  The inorganic filler may be dispersed in the binder resin. The fact that the inorganic filler is dispersed in the binder resin means that the inorganic filler and the binder resin are not separately separated and mixed. That is, the thermosetting resin composition for metal thin film coating according to one embodiment of the present invention can form a dispersed phase by mixing the inorganic filler and the resin evenly without forming a separation phase such as an inorganic filler separation phase or a resin separation phase made of a resin. Accordingly, even when the inorganic filler is filled in a high content, it is possible to achieve an appropriate level of flowability and high thermal stability and mechanical properties when coating the metal foil.
한편， 본 발명의 일 구현예에 따른 열경화성 수지 조성물은 용제, 자외선흡수제, 산화방지제, 광중합개시제， 형광증백제, 광증감제， 안료, 염료， 증점제， 활제， 소포제， 분산제, 레벨링제 및 광택제로 이루어지는 군에서 선택된 1종이상의 첨가제를더 포함할수 있다.  Meanwhile, the thermosetting resin composition according to one embodiment of the present invention can be used in a wide variety of applications such as a solvent, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitener, a photosensitizer, a pigment, a dye, a thickener, a lubricant, a defoamer, And one or more additives selected from the group consisting of
구체적으로， 상기 일 구현예의 금속 박막 코팅용 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 금속박막코팅용 열경화성 수지 조성물의 제조시 점도조절을위해 적절하게 사용할수있는바, 크게 제한되지 않는다.  Specifically, the thermosetting resin composition for metal thin film coating of the embodiment can be used as a solution by adding a solvent as needed. The solvent is not particularly limited as long as it exhibits good solubility with respect to the resin component, and alcohol, ether, ketone, amide, aromatic hydrocarbon, ester, nitrile and the like can be used. Or a mixed solvent of two or more of them may be used. The content of the solvent is not particularly limited, as it can be suitably used for viscosity control in the production of the thermosetting resin composition for metal thin film coating.
또한본 발명은 열경화성 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. 이들은통상적으로사용되는것으로부터 선택되는것이라면특별히 2019/117624 1»（：1^1{2018/015776 The present invention may further include various other polymer compounds such as other thermosetting resins, thermoplastic resins and oligomers and elastomers thereof, and other flame retardant compounds or additives, as long as the inherent characteristics of the thermosetting resin composition are not impaired. These are particularly preferred if they are selected from those commonly used 2019/117624 1 » (: 1 ^ 1 {2018/015776
한정하지 않는다. 예를 들어 첨가제로는 자외선흡수제， 산화방지제 광중합개시제 형광증백제， 광증감제， 안료 염료 증점제， 활제 소포제， 분산제， 레벨링제 광택제 등이 있고 목적에 부합되도록 혼합하여 사용하는 것도가능하다. Not limited. For example, the additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, pigment dye thickeners, lubricant defoamers, dispersants, leveling agent brighteners, and the like.
5 이러한 구성을 갖는 본 발명의 일 구현예에 따른 금속 박막 코팅용 열경화성 수지 조성물은레오미터 최저 점도구간이 90내지 180公의 범위에서
Figure imgf000021_0001
A thin metal film coating the thermosetting resin composition according to one embodiment of the invention having 5 This configuration rheometer the minimum viscosity range in the range of 90 to 1 80公
Figure imgf000021_0001
본 발명에서 제시하는 수지 조성물의 경우， 상기 점도 조건을 만족하는 온도 10 구간이 90 내지 180（:로 매우 넓다. 따라서， 적층 공정 구간 내 흐름성이 높아서 수지 적층 후 빈 공간이 발생되지 않아 패턴 채움성이 우수해지는 것이다. For the resin composition proposed in this invention, the temperature interval 10 satisfying the above viscosity condition of 90 to 180 (: very wide with. Therefore, the flowability in the laminating process section is high, so that void space is not generated after the resin lamination, and the pattern filling property is excellent.
본 발명의 열경화성 수지 조성물은 상기 수지 흐름성을 가짐에 따라， 금속 박막을 이용해서 금속적층판을 만들거나 빌드업 과정에서 흐름성을 15 확보할수 있어 미세 패턴을 용이하게 채울 수 있고 또한 박막의 내크랙성을 향상시킬수있다. Since the thermosetting resin composition of the present invention has the above resin flow property, it is possible to make a metal laminate by using a metal thin film or to secure the flow property 15 in a build-up process, so that it is possible to easily fill a fine pattern, You can improve your sex.
즉， 본 발명의 열경화성 수지 조성물은 최소 점도를유지하는구간을 넓힐 수 있는 경화에 따른특정 값의 최소복소 점도조건을 나타내어， 패턴 매립시 보이드 ）가 생기지 않아패턴 채움성을 향상시키는 효과를 제공할 20 수 있다. 또한， 본 발명의 열경화성 수지 조성물을 이용하면 금속 박막의 적어도 어느 일면에 코팅하는 공정을 통해， 두께를 줄일 수 있고 안정성 및 보관성이 개선된금속적층체를제공할수있다. That is, the thermosetting resin composition of the present invention exhibits a minimum complex viscosity condition of a specific value due to curing which can broaden a section maintaining the minimum viscosity, and does not cause voids in pattern filling), thereby providing an effect of improving pattern filling 20 . Also, by using the thermosetting resin composition of the present invention, it is possible to provide a metal laminate having a reduced thickness and improved stability and storage through at least one surface of a metal thin film.
＜금속적층체＞ &Lt; Metal laminate &
25 다른구현예에 따르면， 금속박막의 적어도 일면에 상기 열경화성 수지 조성물이 경화된 수지 코팅층을 포함하며， 상기 수지 코팅층은， 술폰기 카보닐기， 할로겐기 탄소수 1내지 20의 알킬기 탄소수 6내지 20의 아릴기 탄소수 2내지 30의 헤테로아릴기 및 탄소수 1내지 20의 알킬렌기로이루어진 군에서 선택된 1종 이상의 작용기를 포함한 아민 화합물과， 에폭시 수지 및 30 비스말레이미드 수지를 포함한 바인더 수지와， 스티렌 부타디엔계 고무， 2019/117624 1»（：1^1{2018/015776 25 According to another embodiment, it comprises the two above-mentioned thermosetting resin composition on at least one surface the cured resin coating layer of the metal thin film, the resin coating layer, a sulfone group a carbonyl group, a halogen group having 1 to 20 carbon atoms an alkyl group having 6 to 20 of the aryl group and the binder resin containing a heteroaryl group, and an amine compound and an epoxy resin and 30 bismaleimide resin including at least one functional group selected from the group consisting of a polyalkylene group having 1 to 20 carbon atoms having 2 to 30, and styrene butadiene-based Rubber, 2019/117624 1 »(: 1 ^ 1 {2018/015776
네오프렌계 고무， 니트릴계 고무, 부틸계 고무, 부타디엔계 고무, 에틸렌프로필렌계 고무, 실리콘계 고무, 우레탄계 고무 및 아크릴계 고무로 이루어진군에서 선택된 1종이상의 고무계 성분간의 경화물; 및 상기 경화물 사이에 분산되어 있는충진제;를포함하는금속적층체가제공될수 있다. A cured product of at least one rubber component selected from the group consisting of neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, silicone rubber, urethane rubber and acrylic rubber; And a filler dispersed between the cured products.
5 또, 본발명의 다른구현예 따르면, 상기 열경화성 수지 조성물을금속 박막의 적어도 일면에 코팅하는 단계를 포함하는 금속 적층체의 제조방법이 제공될수있다.  According to another embodiment of the present invention, there is provided a method of manufacturing a metal laminate including the step of coating the thermosetting resin composition on at least one surface of a metal thin film.
부가하여, 또 다른 구현예에 따르면， 상기 금속 적층체가 1매 이상 적층된금속박적층판이 제공될수있다.  In addition, according to another embodiment, a metal-clad laminate in which one or more of the metal laminates are stacked may be provided.
10 구체적으로， 본 발명에서는 상기 열경화성 수지 조성물의 경화물을 포함하는금속박막이 제공된다.  More specifically, the present invention provides a metal thin film including a cured product of the thermosetting resin composition.
상술한바대로, 본발명은수지의 흐름성과패턴 채움성이 우수한수지 조성물을 바니시 형태로 제조하고, 이를 금속박막에 직접 코팅하는 간단한 방법으로, 우수한 열적 및 기계적 물성을 나타내는 금속 적층체를 제공할 수 15 있다. 상기 과정에 따라충진제를포함한열경화성 수지가금속박막의 적어도 일면에 경화물로형성될수 있고, 상기 경화물내에는충진제가고르게 분산된 형태가될수 있다.  As described above, the present invention can provide a metal laminate which exhibits excellent thermal and mechanical properties by preparing a resin composition having excellent flowability and pattern filling property of a resin in the form of a varnish and directly coating it on a metal thin film 15. According to the above process, a thermosetting resin including a filler may be formed on at least one surface of the metal thin film, and the filler may be uniformly dispersed in the cured product.
따라서， 본 발명의 일 구현예에 따르면, 상기 열경화성 수지 조성물을 금속박막의 적어도일면에 코팅하는단계를포함할수있다.  Therefore, according to an embodiment of the present invention, it may include coating the thermosetting resin composition on at least one surface of the metal thin film.
20 또한， 상기 금속적층체의 제조방법은상기 금속박막의 적어도 일면에 코팅된 열경화성 수지 조성물을경화하는단계 ;를더 포함할수있다. 그리고， 상기 열경화성 수지 조성물의 경화 단계 후에는 필요에 따라 잘 알려진 건조 공정이 더 수행될수있다.  20. The method for manufacturing a metal laminate according to any one of the preceding claims, further comprising curing the thermosetting resin composition coated on at least one side of the metal thin film. After the curing step of the thermosetting resin composition, a well-known drying step may be further performed if necessary.
본 발명에서는 수지의 경화 반응을 의도적으로 지연시켜 적층 공정 25 온도구간내 최소점도가유지되는구간을길게한다.  In the present invention, the curing reaction of the resin is deliberately delayed to lengthen the section in which the minimum viscosity within the temperature range of the lamination step 25 is maintained.
바람직하게, 열경화성 수지 조성물을 경화하는 단계에서, 상기 경화조건은 180내지 250 의 온도에서 1내지 4시간동안진행될수 있다. 또한， 상기 열경화성 수지 조성물을 금속박막에 코팅하는 방법은 크게 제한되지 않으며， 이 분야에 잘알려진코팅 방법이 사용될수 있다.  Preferably, in the step of curing the thermosetting resin composition, the curing condition may be carried out at a temperature of 180 to 250 for 1 to 4 hours. The method of coating the thermosetting resin composition on the metal thin film is not particularly limited, and a coating method well known in the art can be used.
30 일례로， 본 발명의 열경화성 수지 조성물을 코터 장치에 넣고， 금속 2019/117624 1»（：1^1{2018/015776 30, the thermosetting resin composition of the present invention is placed in a coater apparatus, 2019/117624 1 » (: 1 ^ 1 {2018/015776
박막의 적어도 일면에 일정 두께로 코팅하는 방법이 사용될 수 있다. 상기 코터 장치는 콤마 코터 블레이드 코터 립 코터 로드 코터， 스퀴즈 코터， 리버스 코터 트랜스퍼 롤 코터 그라비아 코터 또는 분무 코터 등을 이용할 수 있다 A method of coating at least one surface of the thin film with a predetermined thickness may be used . The coater apparatus may be a comma coater blade coater lip coater rod coater, a squeeze coater, a reverse coater transfer roll coater gravure coater or a spray coater
5 또한， 흐름성 평가를 위해 캐리어 필름을 사용할 수 있으며， 상기 캐리어 필름으로는 폴리에틸렌테레프탈레이트 ）， 폴리에스테르 필름， 폴리이미드 필름， 폴리아미드이미드 필름， 폴리프로필렌 필름， 폴리스티렌 필름등의 플라스틱 필름을사용할수 있다. 5 Also, a carrier film can be used for flowability evaluation, and plastic films such as polyethylene terephthalate), polyester film, polyimide film, polyamideimide film, polypropylene film and polystyrene film can be used .
한편 상기 코팅에 사용되는 바니시는 열경화성 수지 조성물에 용제를 10 첨가한 상태일 수 있다.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， 15 메틸셀로솔브 부틸셀로솔브 같은 알리파틱 알코올등이 있다. On the other hand, the varnish used for the coating may be a state in which the solvent is added to the thermosetting resin composition 10. The solvent for resin varnish is not particularly limited as long as it is miscible with the resin component and has good solubility. Specific examples thereof include ketones such as acetone methyl ethyl ketone methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene toluene and xylene, amides such as dimethylformamide and dimethylacetamide, 15 methyl cellosolve butyl cell And alopecic alcohols such as rosolv.
상기 금속박막은 동박;알루미늄박;니켈， 니켈-인 니켈-주석 합금， 니켈-철 합금， 납또는납-주석 합금을 중간층으로 하고 이 양면에 서로 다른 두께의 구리층을포함하는 3층구조의 복합박;또는 알루미늄과 동박을 복합한 2층구조의 복합박을포함할수 있다. The metal thin film may have a three- layer structure comprising a copper foil, an aluminum foil, an intermediate layer of nickel, a nickel-nickel-tin alloy, a nickel-iron alloy, a lead or a lead-tin alloy, A composite foil or a composite foil of a two-layer structure in which aluminum and a copper foil are combined.
20 바람직한 일 구현예에 따르면 본 발명에 이용되는 금속박막은 동박 또는 알루미늄박이 이용되고 약 2내지 200 _의 두께를 갖는 것을사용할수 있지만， 그 두께가 약 2 내지 35 인 것이 바람직하다.보다 바람직하게 상기 금속박막으로는 동박을 사용한다. 또한, 본 발명에 따르면 금속박막으로서 니켈 니켈-인 니켈-주석 합금 니켈-철 합금， 납， 또는 25 납-주석 합금 등을 중간층으로 하고 이의 양면에 0.5내지 15 의 구리층과 10 내지 300 /패의 구리층을 설치한， 3층 구조의 복합박 또는 알루미늄과 동박을복합한 2층구조복합박을사용할수도 있다. 20 According to a preferred embodiment, the metal thin film used in the present invention may be a copper foil or an aluminum foil, having a thickness of about 2 to 200 , but preferably has a thickness of about 2 to 35. More preferably, A copper foil is used as the metal thin film . Further, according to the present invention as a metallic thin film of nickel the nickel-nickel-tin alloy, nickel-iron alloy, lead, or 25-lead-tin alloy or the like to the intermediate layer and the copper layer of 0.5 on its both sides to 15 and 10 to 300 / It is also possible to use a composite foil of a three- layer structure in which a copper layer of a foil is provided, or a two- layer composite foil in which aluminum and a copper foil are combined.
상술한 방법에 따라 본 발명은 금속 박막의 적어도 일면에 상기 열경화성 수지 조성물이 경화된 수지 코팅층을 포함함으로써， 종래 대비 넓은 30 온도 구간에서 최소 복소 점도 조건을 만족할 수 있고， 특히 흐름성 및 패턴 2019/117624 1»（：1^1{2018/015776 According to the above-mentioned method, since the resin coating layer in which the thermosetting resin composition is cured is formed on at least one surface of the metal thin film, the minimum complex viscosity condition can be satisfied over a wide 30 temperature range as compared with the conventional method, 2019/117624 1 »(: 1 ^ 1 {2018/015776
채움성이 우수한금속적층체를제공할수있다. It is possible to provide a metal laminate excellent in filling property.
이때, 상기 금속 적층체에서 수지 코팅층의 두께는 5 내지 90 _， 바람직 하게는 5/^1 내지 30 일 수 있다. 이러한 경화물은 금속박막 상에 두께가 얇게 형성되어도， 금속박막에 대하여 우수한 열적， 기계적 물성을 5 나타내도록할수있다. At this time, the thickness of the resin coating layer in the metal laminate may be from 5 to 90 _, preferably from 5 / ^ 1 to 30 days. Even if such a cured product is formed thin on the metal thin film, excellent thermal and mechanical properties of the metal thin film can be exhibited.
또한, 본 발명의 금속 적층체는 경화 후 수지의 유리전이온도 0 ）는 220내지 2401：를가지게 된다. Further, in the metal laminate of the present invention, the glass transition temperature of the resin after curing 0) is 220 to 2401 :.
Figure imgf000024_0001
Figure imgf000024_0001
금속박막의 유전특성 （ /아）은 3.4八）.007로우수하다.  The dielectric properties of the metal thin films are 3.4 eq.
10 또한, 본원의 수지 조성물을이용한경우, 경화후수지지의 인장실험 결과신율（6101¾3 011）이 1.5내지 2 %혹은 1.6%로우수하다. 10 Further, when the resin composition of the present invention is used, the elongation ( 6101 3 011 ) of the cured after-treatment support can be 1.5 to 2% or 1.6% lower than the tensile test results.
즉, 단분자계열로 이루어진 수지 조성물과함께 인장테스트를한결과, 동일 두께에서 비교 시 파단 시까지 신율（61011용 1011）이 더 우수한 것을 관찰할수있고, 이를통해 내크랙성이 우수함을확인할수 있다. In other words, as a result of performing a tensile test together with a resin composition composed of a single molecular series, it was observed that the elongation (1 011 for 61011 ) was superior from the same thickness to the breaking at the time of comparison. have.
15 그러므로， 본 발명은 기존 단분자 계열로 이루어진 수지 코팅 동박에 비해 동일두께에서 비교시 내크랙성이 우수하여 , 반도체 소자의 성능향상에 기여할수있다.  15 Therefore, the present invention is superior to conventional resin-coated copper foils made of monomolecular system in crack resistance at the time of comparison, thereby contributing to improvement of the performance of semiconductor devices.
상술한 바대로, 다른 구현예에 따르면, 상기 금속 적층체가 1매 이상 적층된금속박적층판이 제공될수 있다.  As described above, according to another embodiment, a metal-clad laminate in which one or more of the metal laminates are stacked can be provided.
20 이러한 경우 금속판 적층판은 금속 박막을 더 포함할 수 있다. 예를 들어， 금속박막은금속적층체의 수지층이 맞다을수 있다.  20 In this case, the metal plate laminates may further include a metal thin film. For example, the metal foil may be a resin layer of a metal laminate.
또， 상기 금속판 적층판을 제공시， 상기 금속 박막은 에칭 및 패턴을 제작한 후 적층에 사용될 수 있다. 예를 들어, 금속 박막인 제 1층 위에 제 2층을 적층한다고 할 때， 제 1층인 금속 박막（주로 &1）을 완전 에칭 또는 25 부분에칭을통한패턴화를시킨 후， 그위에 금속관적층체의 수지 코팅층이 금속박막에 맞닿게 하여, 제 2층을적층하는방법으로진행될수 있다. When the metal plate laminate is provided, the metal thin film may be used for lamination after etching and patterning are performed. For example, when the second layer is laminated on the first layer as the metal thin film, the metal thin film (mainly & 1 ) as the first layer is patterned through complete etching or 25 partial etching, The resin coating layer of the first metal layer is brought into contact with the metal thin film, and the second layer is laminated.
따라서， 이렇게 제조된 금속 적층체는 1매 이상 적층된 금속 적층판 형태로 제공될 수 있다. 바람직하게， 상기 금속 적층판은 금속 적층체에 형성된상기 수지층이 서로마주하도록적층된 2매의 금속적층체를포함할수 30 있다. 2019/117624 1»（：1^1{2018/015776 Thus, the metal laminate thus produced can be provided in the form of a metal laminate laminated one or more times. Preferably, the metal laminates may include two metal laminates stacked such that the resin layers formed on the metal laminates face each other. 2019/117624 1 » (: 1 ^ 1 {2018/015776
더욱이， 본 발명은 상기 금속 적층체를 이용하여 매 이상으로 적층한 후， 양면 또는 다층 인쇄 회로 기판의 제조에 사용할 수 있다. 본 발명은 상기 금속박 적층판을 회로 가공하여 양면 또는 다층 인쇄회로기판을 제조할 수 있으며， 상기 회로 가공은 일반적인 양면 또는 다층 인쇄 회로 기판 제조 5 공정에서 행해지는 방법을 적용할수 있다. Furthermore, the present invention can be used to manufacture double-sided or multi-layer printed circuit boards after stacking more than one piece using the metal laminate. In the present invention, the metal-clad laminate can be processed by circuit processing to produce a double-sided or multi-layer printed circuit board, and the circuit processing can be performed in a general double-sided or multi-layer printed circuit board manufacturing process.
이와 같이， 본 발명에 따르면 상술한 열경화성 수지 조성물을 이용함으로써， 다양한분야의 인쇄회로기판에 모두 적용 가능한수지가코팅된 금속 박막을 제공할수 있다.  As described above, according to the present invention, by using the above-mentioned thermosetting resin composition, it is possible to provide a resin-coated metal thin film which can be applied to various printed circuit boards in various fields.
10 【발명의 효과】 10 EFFECT OF THE INVENTION
본 발명의 금속 박막 코팅용 열경화성 수지 조성물은 바인더를 구성하는 수지 종류와 이들의 혼합 비율을 최적화하고， 아민계 경화제 및 고무계 성분을 일정량 사용함으로써， 수지의 경화 반응을 조절하여 종래보다 적증 공정 온도 구간내 흐름성이 높고 패턴 채움성이 우수하게 하는 효과를 15 제공할 수 있다. 특히 본 발명에 따르면 적층 소재의 두께가 얇아도 레오미터 최저 점도 구간이 기존보다 넓기 때문에， 패턴 채움성이 향상되어 기판의 박막화는 물론 반도체 소자의 신뢰성 및 성능을 향상시킬 수 있다. 따라서 본 발명은 기존금속 박막에 비해 내크랙성을 향상시킬 수 있다. INDUSTRIAL APPLICABILITY The thermosetting resin composition for metal thin film coating of the present invention can optimize the type of resin constituting the binder and the mixing ratio thereof and adjust the curing reaction of the resin by using a certain amount of the amine curing agent and the rubber component, this high flow properties within the pattern filling Province 15 can provide an effect that good. Particularly, according to the present invention, even if the thickness of the laminated material is thin, since the rheometer minimum viscosity section is wider than the conventional one, the pattern filling property can be improved to improve the reliability and performance of the semiconductor device as well as the thickness of the substrate. Therefore, the present invention can improve the crack resistance as compared with the conventional metal thin film.
또한, 본 발명은 경화 후 수지층의 열적 및 기계적 물성이 우수하고 20 유전 특성도 우수한 금속 박막을 제공하는 효과가 있다. 즉 본 발명의 열경화성 수지 조성물을 이용하면 유리 섬유를 사용해서 프리프레그를 제조해야 하는 방법을 사용하지 않아도， 간단한 방법으로 금속박에 직접 수지 조성물의 코팅을 진행하여 두께가 얇은금속 적층체를 제공할수 있다.더욱이， 본 발명은 경화 후 수지의 유리전이온도가 상대적으로 높으며， 유전특성도 25 우수한 금속 적층체를 제공할 수 있다. 상기 금속 박막은 1매 이상으로 적층하여 전자기기의 박막화에 사용하는 금속 적층판을 제공할수 있다. The invention also has the effect of excellent thermal and mechanical properties of the resin layer after curing and provides excellent metal thin film 20 dielectric properties. That is, when the thermosetting resin composition of the present invention is used, the resin composition can be directly coated on the metal foil by a simple method without using a method of preparing a prepreg using glass fiber to provide a thin metal laminate . Further, the present invention can provide a metal laminate excellent in glass transition temperature of the resin after curing and having a dielectric property of 25 . The metal thin film can provide a metal-clad laminate used for the thinning of an electronic apparatus by stacking more than one piece.
【도면의 간단한설명】 BRIEF DESCRIPTION OF THE DRAWINGS
도 1은 본 발명의 실시예 1 및 비교예 1의 흐름성 및 패턴 채움성을 30 확인하기 위한 레오미터 커브를 나타낸 것이다. 도 2는본발명의 실시예 1 및 비교예 1의 신율측정 결과를 비교하여 나타낸그래프이다. Fig. 1 shows a rheometer curve for confirming the flowability and pattern filling property 30 of Example 1 and Comparative Example 1 of the present invention. 2 is a graph showing a comparison between the elongation measurement results of Example 1 and Comparative Example 1 of the present invention.
【발명을실시하기 위한구체적인내용】 DETAILED DESCRIPTION OF THE INVENTION
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단， 하기의 실시예는 본 발명을 예시하는 것일 뿐， 본 발명의 내용이 하기의 실시예에 의하여 한정되는것은아니다.  The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
<실시예 1내지 6> &Lt; Examples 1 to 6 >
수지 조성물이 코팅된동박적층체 제조  Production of copper-clad laminate coated with resin composition
(1) 열경화성 수지 조성물의 제조  (1) Production of thermosetting resin composition
다음표 1과 같이, 아민 화합물， 에폭시 수지， 비스말레이미드수지를 시클로핵사논 용매에 녹여 바니시를 제작하였다. 기계적 강도 향상을 위해， 상기 바니시에 실리카무기 충진제를첨가했다.  As shown in the following Table 1, an amine compound, an epoxy resin, and a bismaleimide resin were dissolved in a cyclohexanone solvent to prepare a varnish. To improve the mechanical strength, a silica inorganic filler was added to the varnish.
상기 성분들을 포함한 바니쉬를 24시간 이상 교반하여, 코팅 용액을 준비하였다.  The varnish containing the above components was stirred for at least 24 hours to prepare a coating solution.
회전 증발 농축기 (rotary evaporator)를 사용해서 상기 코팅 용액의 점도조절 및 탈포를진행했다.  The viscosity of the coating solution was adjusted and defoamed using a rotary evaporator.
(2) 열경화성 수지 조성물이 코팅된금속박막 (수지 코팅 동박적층체) 제조  (2) Production of metal thin film coated with thermosetting resin composition (resin-coated copper-clad laminate)
콤마코터로상기 코팅 용액을동박 (두께 2[m, Mi tsui사제조)의 일면에 코팅 (코팅 두께 : 16um )한 후 , 220 °C 및 35 kg/cuf의 조건으로 100 분간 경화시켰다. 이어서， 17 x 15cm 크기로 재단하여 수지 코팅된 동박 적층체 샘플을제작하였다. The coating solution was coated (coating thickness: 16 袖 m) on one side of a copper foil (thickness 2 [ m, Mi tsui]) with a comma coater and then cured for 100 minutes under conditions of 220 ° C and 35 kg / cuf. Subsequently, the sample was cut to a size of 17 x 15 cm to prepare a resin-coated copper-clad laminate sample.
<비교예 1내지 3> &Lt; Comparative Examples 1 to 3 >
수지 조성물이 코팅된동박제조  Copper foil coated with resin composition
(1) 열경화성 수지 조성물의 제조  (1) Production of thermosetting resin composition
다음 표 2의 성분과 시클로핵사논 용매를 이용하여 바니시를 제조하였다. 이때, 아크릴계 고무 A 또는 아크릴계 고무묘를 사용하지 않는 경우를 비교예 1로 하였고 그 함량 범위가 본원 범위를 벗어나는 경우를 비교예 2내지 4로 하였다. Varnishes were prepared using the components of the following Table 2 and cyclohexanone solvents. At this time, when the acrylic rubber A or the acrylic rubber seedling is not used Was the case with Comparative Example 1 was a case where the content is outside the range of the present range in Comparative Examples 2 to 4.
상기 성분들을 포함한 바니시를 24시간 이상 교반하여， 코팅 용액을 준비하였다.  The varnish containing the above components was stirred for at least 24 hours to prepare a coating solution.
5 회전 증발 농축기 （rotary evaporator）를 사용해서 상기 코팅 용액의 점도조절 및 탈포를진행했다. 5 rotary evaporator using (rotar y eva porator) proceeded the viscosity control and the deaeration of the coating solution.
（2） 열경화성 수지 조성물이 코팅된금속박막제조  (2) Production of metal thin film coated with thermosetting resin composition
콤마코터로 상기 코팅 용액을 동박 （두께 2m, Mitsui사 제조）에 코팅（코팅 두께 : 16um ）한 후， 220 C 및 35 kg/cuf의 조건으로 100 분간 10 경화시켰다. 이어서， 17 x 15cm크기로 재단하여 수지 코팅 동박 샘플을 제작하였다. The coating solution was coated on a copper foil (thickness: 2 m, manufactured by Mitsui) with a comma coater (coating thickness: 16 袖 m), and then cured for 10 minutes at 220 ° C and 35 kg / cuf for 100 minutes. Subsequently, the sample was cut into a size of 17 x 15 cm to prepare a resin-coated copper foil sample.
<비교예 4> & Lt; Comparative Example 4 &
수지 조성물이 섬유 기재에 함침된 프리프레그와 일체화된 동박을 15 포함한 적층판제조 The resin composition was laminated with the copper foil 15 integrated with the prepreg impregnated in the fiber substrate
（1） 열경화성 수지 조성물의 제조 ( 1 ) Production of thermosetting resin composition
하기 표 2와 같은 비율로 수지를 유기 용매에 녹여 바니쉬로 만든 후 24시간 이상교반하였다. The resin was dissolved in an organic solvent to give a varnish as shown in Table 2 , followed by stirring for 2 4 hours or more.
（2） 프리프레그 및 동박 적층판의 제조 ( 2 ) Preparation of prepreg and copper-clad laminate
20 상기 교반한 바니쉬를 직조된 유리 섬유 （01388 ? 1 （：）（두께 12；·, 쇼33 이333사제조）에 함침시킨후， 180ᄃ의 온도에서 2~5분간열풍건조하여 16 /해의 프리프레그를제조하였다. 20 The agitated varnish was applied to woven glass fiber (01 388? 1 (:); was impregnated in (thickness, 12, 33 show the 333 Corporation), by hot-air drying 2-5 minutes at a temperature of 180 d 16 / year prepreg was prepared him.
이후， 동박을 위 아래로 적층하여 동박적층판을 제작하였다. 즉，
Figure imgf000027_0001
Thereafter, the copper foil was stacked up and down to produce a copper clad laminate. In other words,
Figure imgf000027_0001
적층판을제조하였다.  To prepare a laminate.
【표 11[Table 11
Figure imgf000027_0002
2019/117624 1»（：1/10公018/015776
Figure imgf000028_0001
Figure imgf000027_0002
2019/117624 1 » (: 1/10 public 018/015776
Figure imgf000028_0001
【표 2] [Table 2]
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000028_0002
Figure imgf000029_0001
주) week)
* DDS: 4,4'-diaminodiphenyl sulfone  * DDS: 4,4'-diaminodiphenyl sulfone
에폭시 수지: 나프탈렌계 에폭시 수지 (HP4710, DIC사)  Epoxy resin: naphthalene-based epoxy resin (HP4710, DIC)
비스말레이미드-트리아진수지: BMI-2300, DAIWA사  Bismaleimide-triazine resin: BMI-2300, DAIWA Inc.
시아네이트에스터 수지 : 노볼락형 시아네이트수지 (PT-30S, Lonza乂｝) 아크릴계 고무 SG-P3-PT197 (Mw 65X104, Tg： 12°C), Nagase Cheratex Coporat ion Cyanate ester resin: novolak cyanate resin (PT-30S, Lonza)} SG-P3-PT197 (Mw 65X10 4 , Tg: 12 ° C), Nagase Cheratex Coporate ion
아크릴계 고무B: SG-P3-MW1 (Mw 30X104, Tg： 12°C), Nagase Chemtex Coporat ion Acrylic rubber B: SG-P3-MW1 (Mw 30X10 4 , Tg: 12 ° C), Nagase Chemtex Coporate ion
실리콘계 고무: AM2-119, Dow Corning  Silicone rubber: AM2-119, Dow Corning
부타디엔고무A: B-1000, Nippon Soda  Butadiene rubber A: B-1000, Nippon Soda
부타디엔고무B: RIC0N181, Cray Valley  Butadiene rubber B: RIC0N181, Cray Valley
Filler A: 페닐아미노실란처리된 슬러리 타입의 필러， 평균입경 0.5um (SC2050MTO, Admatechs사)  Filler A: Phenylaminosilane treated slurry type filler, average particle diameter 0.5um (SC2050MTO, Admatechs)
＜실험예＞ <Experimental Example>
실시예 및 비교예에서 제조한 동박 적층판에 대해 다음의 방법으로 물성을측정하였다: 1. 점도및흐름성 분석  The physical properties of the copper clad laminates prepared in Examples and Comparative Examples were measured by the following methods: 1. Viscosity and flowability analysis
온도에 따른수지 층의 점도 및 흐름성을 관찰하기 위해， 실시예 1 및 비교예 1의 코팅액을 PET기재에 코팅한후, 라미네이터를통해적층하여 적정 두께의 샘플을 만들어서 레오미터 점도를 측정했다 (온도에 따른 점도 측정 조건, 승온속도 5도/min, 주파수: 1예z). 2019/117624 1»（：1^1{2018/015776 In order to observe the viscosity and flowability of the resin layer according to the temperature, the coating solution of Example 1 and Comparative Example 1 was coated on a PET substrate and laminated through a laminator to make a sample of a proper thickness to measure the rheometer viscosity Temperature measurement conditions, rate of temperature rise: 5 degrees / min, frequency: 1 case z). 2019/117624 1 »(: 1 ^ 1 {2018/015776
또한, 점도 및 흐름성은 패턴 적층 테스트에서 빈 공간 생성 유무를 통해 확인하였다. 패턴 적층 테스트를 위해, 동박 두께 1011111, 전체 면적의 약 60%가에칭되어 있는 패턴을가진 동박적층판 01：0을사용하여 그 위에 상기 실시예 또는 비교예를 통해 얻은 수지 동박 코팅 샘플 （또는 프리프레그）을 적층하였다. 보이드（ 0八1）나 디라미네이션（（161抑1 이1）이 발생하지 않은 경우
Figure imgf000030_0001
보이드（ （ （!）나 디라미네이션（＜16131 11 ：1011）이 발생한 경우 ’ 로 평가하였다. 보이드 생성 유무 관찰 결과, 실시예 1은 빈공간생성이 발생하지 않았으나， 비교예 1은보이드가발생되었다. Viscosity and flowability were also confirmed by the presence of empty space in the pattern stacking test. For the pattern stacking test, a copper-clad laminate 01: 0 having a pattern in which a copper foil thickness of 10 11111 and a total area of about 60% of the total area was etched was used, and a resin-coated copper-clad coating sample (or a prepreg Leg) were stacked. If void ( 0 8 1) or delamination ((1 61 1 1 ) does not occur
Figure imgf000030_0001
Voids ((!) Or delamination (<1 6131 11 : 1 011 ) occurred. As a result of observing the presence or absence of void formation, voids were not generated in Example 1 but voids were generated in Comparative Example 1.
도 1은 본 발명의 실시예 1 및 비교예 1의 흐름성 및 패턴 채움성을 확인하기 위한레오미터 커브를나타낸것이다.  Fig. 1 shows a rheometer curve for confirming the flowability and pattern fillability of Example 1 and Comparative Example 1 of the present invention.
도 1의 결과에서 보면, 패턴을채우는데 적합한복소점도를 3500 ?3.3 이하라고 가정할 때， 본 발명의 실시예 1 및 6은 비교예 1에 비해， 레오미터 최저 점도 구간（ 이 이
Figure imgf000030_0002
내지 180°（:로서， 상기 350이 .3 이하의 복소점도 범위를만족하고 매우 넓어져 흐름성 및 패턴 채움성이 더 유리함을 확인할수있다. . 1, the complex viscosity suitable for filling the pattern is 3500? 3.3 or less, Examples 1 and 6 of the present invention are compared with Comparative Example 1 in that the rheometer minimum viscosity interval
Figure imgf000030_0002
To &lt; RTI ID = 0.0 &gt; 180, &lt; / RTI &gt; 3 &gt; or less, and it is possible to confirm that the flowability and pattern filling are more advantageous. .
2. 경화후수지 물성 2. Resin properties after curing
경화후수지의 물성을분석하기 위해， 상기 실시예의 수지 코팅 동박 2매를 이용해서 수지층이 마주하도록 적층하고, 진공 열프레스를통해 220 X: 및 35 1¾/011 2의 조건으로 100분간 경화를 진행하였다. 또한, 비교예 4는 상술한프리프레그를이용한동박적층판을이용하여 실험에 사용하였다. In order to analyze the physical properties of the post-curing resin, the embodiment of the resin coating, and laminated to the opposite to the resin layer using a copper foil having two vacuum heat through the press 220 X: and 35 1 ¾ / 0 11 2 100 minutes at the conditions of the Curing was carried out. In addition, Comparative Example 4 was used in the experiment using the above-mentioned prepreg-coated copper-clad laminate.
실험 진행시， 동박을 에칭하여 제거한후, 다음과 같은 방법으로 수지 층의 열적 0 ）, 기계적 «0（1111115）, 유전 특성 （¾/야） 등을 측정하여 그 결과를표 3및 4에 나타내었다. 열적, 기계적 특성은 쇼 0·， 11^등의 분석 장비를이용하여 측정하였다. 유전특성 측정은
Figure imgf000030_0003
방식으로 1抑2에서의 ¾， 야를구하였다. Experiment was removed by the etching of the copper foil during progress by measuring the following way thermally 0) of the resin layer, the mechanical «0 (1 111 115), the dielectric properties (¾ / I) including the same and the results are shown in Table 3 and 4 Respectively. The thermal and mechanical properties were measured using the analytical equipment such as show 0, 11. Measurement of dielectric properties
Figure imgf000030_0003
In a way it obtains ¾, be at 1抑2.
（1）유리전이온도 0 ） (1) Glass transition temperature 0)
를이용하여 유리전이온도를측정하였다. 2019/117624 1»(：1^1{2018/015776 Was used to measure the glass transition temperature. 2019/117624 1 » (: 1 ^ 1 {2018/015776
(2)모듈러스 (Gpa) (2) Modulus (Gpa)
DMA를 이용하여 모듈러스를측정하였다. DMA was used to measure the modulus.
(3)유전특성 (Dk/Df) (3) Dielectric properties (Dk / Df)
유전특성 측정 장비는 Agi lent E5071B ENA 장비로, SPDR (spl it post dielectric resonance) 방법으로 1GHz에서의 유전 상수 (Dk) 및 유전 손실 (Df )을측정하여 유전특성 (Dk/Dg)를계산하였다.  Dielectric properties (Dk / Dg) were calculated by measuring the dielectric constant (Dk) and dielectric loss (Df) at 1 GHz using the Agilent E5071B ENA instrument using splitter post dielectric resonance (SPDR) method.
(4) 열팽창계수 (CTE) (4) Coefficient of thermal expansion (CTE)
상기 실시예 및 비교예에서 얻어진 동박 적층판의 동박층을 에칭하여 제거한후, TEA를이용하여 측정하였다. (50 °C ~ 150 °C , 표 방향)  The copper foil layers of the copper clad laminate obtained in the above Examples and Comparative Examples were removed by etching and then measured using TEA. (50 ° C to 150 ° C, table direction)
(5)신율 (elongation) (5) elongation
UTM을 통해 인장실험을 진행하였다. 인장력 (Tensi le Stress) 을 가하면서 끊어질 때의 인장율 (Tensi le Strain at Break) , 즉， 신율 (Elongat ion)을측정하였다. (도 2)  Tensile tests were carried out through UTM. Tensi le Strain at Break was measured while the tensile stress was applied, and elongation was measured. (Fig. 2)
【표 3】 [Table 3]
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000031_0001
Figure imgf000032_0001
【표 4】 [Table 4]
Figure imgf000032_0002
상기 실시예 및 비교예를 통해 본원 실시예의 유리전이 온도 奸용는 220도， 열팽창계수 (0å)는 16? 으로 측정되었다. 또한， 비교예에 비하여， 본원 실시예들이 최소 점도 구간 및 흐름성이 우수한 것을 레오미터를 통해 확인하였다. 2019/117624 1»（：1^1{2018/015776
Figure imgf000032_0002
Examples and Comparative Examples to the present embodiment, the glass transition temperature奸yongneun through 220 degrees, the coefficient of thermal expansion (0å) is 16? Respectively. Compared with the comparative example, the rheometer confirmed that the embodiments of the present invention are excellent in minimum viscosity interval and flowability. 2019/117624 1 »(: 1 ^ 1 {2018/015776
그리고， 인장실험 결과에서도 본원 실시예는 비교예에 비해 신율이 1.6%로길어 내크랙성이 우수함을확인하였다. As a result of the tensile test, it was confirmed that the examples of the present invention had an excellent elongation at break of 1.6% as compared with the comparative example.

Claims

2019/117624 1»（：1^1{2018/015776 【청구범위】 2019/117624 1 (: 1 ^ {2018/015776)
【청구항 1] [Claim 1]
술폰기, 카보닐기, 할로겐기, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 2내지 30의 헤테로아릴기 및 탄소수 1 내지 20의 5 알킬렌기로이루어진 군에서 선택된 1종이상의 작용기를포함한아민화합물; 에폭시 수지 및 비스말레이미드수지를포함한바인더 수지; 무기 충진제; 및 고무계성분을포함하고 ,  At least one functional group selected from the group consisting of a sulfone group, a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, and a 5 alkylene group having 1 to 20 carbon atoms ; A binder resin including an epoxy resin and a bismaleimide resin; Inorganic fillers; And a rubber-based component,
상기 고무계 성분은 스티렌 부타디엔계 고무 , 네오프렌계 고무 , 니트릴계 고무， 부틸계 고무， 부타디엔계 고무， 에틸렌프로필렌계 고무， 10 실리콘계 고무， 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종이상을포함하며，  The rubber component includes at least one member selected from the group consisting of styrene butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, 10 silicone rubber, urethane rubber and acrylic rubber ,
상기 아민 화합물 및 바인더 수지의 총합 100 중량부에 대해， 상기 고무계 성분은 5중량부이상 40중량부미만으로포함하고，  Wherein the rubber component comprises at least 5 parts by weight and less than 40 parts by weight based on 100 parts by weight of the total of the amine compound and the binder resin,
레오미터 최저 점도구간이 90내지 180 의 범위에서 350아¾.3 이하의 15 복소점도조건을만족하는, 금속박막코팅용열경화성 조성물. The rheometer minimum viscosity ranges from 350 to 350 in the range of 90 to 180. 3 &lt; / RTI &gt; of the total weight of the thermosetting composition.
【청구항 2] [Claim 2]
제 1항에 있어서, 상기 고무계 성분은 부타디인계 고무, 실리콘계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종 이상인 금속 박막 코팅용 20 열경화성 수지 조성물.  The 20 thermosetting resin composition according to claim 1, wherein the rubber component is at least one member selected from the group consisting of butadiene-based rubber, silicone rubber and acrylic rubber.
【청구항 3】 [Claim 3]
저 11항에 있어서, 상기 고무계 성분은 상기 바인더 수지 100 중량부에 대해 상기 고무계 성분은 5 내지 15 중량부를 포함하는 금속 박막 코팅용 25 열경화성 수지 조성물.  11. The thermosetting resin composition according to claim 11, wherein the rubber-based component comprises 5 to 15 parts by weight of the rubber-based component relative to 100 parts by weight of the binder resin.
【청구항 4] [4]
제 1항에 었어서, 상기 아크릴계 고무는 중량평분자량 30>< 104 내지 65>< 104이며 아크릴산 부틸 유래의 반복 단위와 아크릴로니트릴 유래의 반복 30 단위; 또는 부타디엔 유래의 반복 단위가 포함되는 아크릴산 에스테르 2019/117624 1»（：1^1{2018/015776 The acrylic rubber according to claim 1, wherein the acrylic rubber has a weight average molecular weight of 30 &lt; 10 4 to 65 &gt; 10 4, and repeating units derived from butyl acrylate and repeating units derived from acrylonitrile; Or an acrylic acid ester containing a repeating unit derived from butadiene 2019/117624 1 » (: 1 ^ 1 {2018/015776
공중합체; 또는탄소수 2내지 10의 직쇄 또는분지쇄의 알킬기 포함아크릴산 알킬 유래의 반복단위를 포함하는 혼합물인 금속 박막 코팅용 열경화성 수지 조성물. Copolymer; Or a mixture of recurring units derived from an alkyl acrylate including alkyl groups of straight or branched chain having 2 to 10 carbon atoms.
【청구항 5] [Claim 5]
제 1항에 있어서， 상기 실리콘계 고무는에폭시기 또는폴리에테르 변성 실리콘 반복단위: 또는 말단기가 아민기 또는 에폭시기로 치환된 실리콘 반복단위를 포함하고 중량평균분자량이 1>< 10 내지 5>< 10 인 공중합체를 포함하는금속박막코팅용열경화성 수지 조성물. The method of claim 1, wherein the silicone rubber is an epoxy group or a polyether-modified silicone repeating unit: or a public terminal groups is above the silicon repeating units and having a weight average molecular weight 1><10 - 5><10 substituted with an amine group or an epoxy group A thermosetting resin composition for metal thin film coating.
【청구항 6] [Claim 6]
제1항에 있어서 상기 부타디엔계 고무는 말단기가 히드록시기로 치환된 부타디엔 반복단위 또는 아크릴기를 포함하는 부타디엔 반복단위 또는 에폭시기를 포함하는 부타디엔 반복단위를 포함하고 중량평균분자량이 IX10 3 내지 5X10"인 공중합체를 포함하는 금속 박막 코팅용 열경화성 수지 조성물. The butadiene-based rubber according to claim 1 , wherein the butadiene-based rubber comprises a butadiene repeating unit in which a terminal group is substituted with a hydroxy group, or a butadiene repeating unit having an acrylic group or a butadiene repeating unit having an epoxy group and having a weight average molecular weight of IX10 3 to 5X10 & And a thermosetting resin composition for a metal thin film coating.
【청구항 7] [ 7]
제 1항에 있어서，  The method according to claim 1,
상기 아민화합물은하기 화학식 1내지 3으로 이루어진 군에서 선택된The amine compound is selected from the group consisting of the following formulas ( 1) to ( 3)
1종이상의 화합물을포함하는， 금속박막코팅용열경화성 수지 조성물: A thermosetting resin composition for metal thin film coating comprising one or more compounds:
[화학식 1]  [Chemical Formula 1]
Figure imgf000035_0001
Figure imgf000035_0001
상기 화학식 1에서, In Formula 1 ,
쇼는술폰기 카보닐기 또는탄소수 1내지 10의 알킬렌기이며 2019/117624 1»（：1^1{2018/015776 Show is a sulfone carbonyl group or an alkylene group having 1 to 10 carbon atoms 2019/117624 1 »(: 1 ^ 1 {2018/015776
¾내지 ¾는각각독립적으로니트로기， 시아노기， 수소원자, 할로겐기， 탄소수 1 내지 6의 알킬기, 탄소수 6 내지 15의 아릴기 , 또는 탄소수 2내지 20의 헤테로아릴기이고,Each of ¾ and ¾ is independently a nitro group, a 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 imgf000036_0001
Figure imgf000036_0001
5 내지 6의 알킬기, 탄소수 6 내지 15의 아릴기， 또는 탄소수 2 내지 20의 헤테로아릴기이며，  An alkyl group having 5 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
II은 1내지 10의 정수이고,  II is an integer of 1 to 10,
상기 탄소수 1내지 10의 알킬렌기， 탄소수 1내지 6의 알킬기， 탄소수 6내지 15의 아릴기， 및 탄소수 2내지 20의 헤테로아릴기는각각독립적으로 10 니트로기， 시아노기 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 작용기로치환되며，  The alkylene 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 10 nitro groups, cyano groups, Lt; RTI ID = 0.0 &gt;
Figure imgf000036_0002
Figure imgf000036_0002
상기 화학식 2에서，  In Formula 2,
15 내지 ¾는각각독립적으至니트로기， 시아노기， 수소원자， 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기， 또는 탄소수 2 내지 20의 헤테로아릴기이고，  Each independently represent a nitro group, a 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,
¾, ¾’ , ¾ 및 ¾， 는 각각 독립적으로 수소원자， 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기， 또는 탄소수 2 내지 20의 20 헤테로아릴기이며， , ¾ , ¾ ' , ¾ and ¾' 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 20 to 20 heteroaryl group having 2 to 20 carbon atoms,
미은 1내지 10의 정수이고，  Wherein R 1 is an integer from 1 to 10,
상기 탄소수 1 내지 6의 알킬기, 탄소수 6 내지 15의 아릴기， 및 탄소수 2 내지 20의 헤테로아릴기는 각각 독립적으로 니트로기, 시아노기 및 할로겐기로이루어진군에서 선택된 1종이상의 작용기로치환되며，  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 substituted with one or more functional groups selected from the group consisting of a nitro group, a cyano group and a halogen group,
25 [화학식 3] 2019/117624 1»（：1/10公018/015776 25 [Formula 3] 2019/117624 1 » (: 1/10 public 018/015776
Figure imgf000037_0001
Figure imgf000037_0001
상기 화학식 3에서 In the above formula ( 3 )
IX내지 ¾는각각독립적으로니트로기， 시아노기， 수소원자 할로겐기， 탄소수 1 내지 6의 알킬기 탄소수 6내지 15의 아릴기 또는 탄소수 2 내지 20의 헤테로아릴기이고 I X to ¾ each independently represents a nitro group, a cyano group, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms in an alkyl group, or a heteroaryl group having 2 to 20 carbon atoms
¾ ¾’ ¾ 및 ¾’ 는 각각 독립적으로 수소원자， 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기 또는 탄소수 2 내지 20의 헤테로아릴기이며， Each of ¾ ¾ ' and ¾' 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,
상기 탄소수 1 내지 6의 알킬기 탄소수 6 내지 15의 아릴기， 및 탄소수 2 내지 20의 헤테로아릴기는 각각 독립적으로 니트로기， 시아노기 및 할로겐기로이루어진군에서 선택된 1종이상의 작용기로치환된다. The aryl group having 6 to 15 carbon atoms in the alkyl group and the heteroaryl group having 2 to 20 carbon atoms in the alkyl group having 1 to 6 carbon atoms are each independently substituted with one or more functional groups selected from the group consisting of a nitro group, a cyano group and a halogen group.
【청구항 8] [ 8]
제 1항에 있어서，  The method according to claim 1,
상기 아민 화합물 및 바인더 수지의 총합 100 중량부에 대하여 상기 무기 충진제 함량이 200 중량부 이상인， 금속 박막 코팅용 열경화성 수지 조성물. Wherein the content of the inorganic filler is 200 parts by weight or more based on 100 parts by weight of the total of the amine compound and the binder resin.
【청구항 9】 [Claim 9 ]
제 1항에 있어서， The method according to claim 1 ,
상기 아민 화합물 및 바인더 수지의 전체 중량에 대하여 아민 화합물의 함량이 15내지 60중량%인 박막코팅용 열경화성 수지 조성물. Wherein the amine compound and the binder resin have an amine compound content of 15 to 60 % by weight based on the total weight of the thermosetting resin composition.
【청구항 10】 Claim 10
제 1항에 있어서 2019/117624 1»（：1^1{2018/015776 The method of claim 1, wherein 2019/117624 1 »(: 1 ^ 1 {2018/015776
상기 아민화합물및 바인더 수지의 전체 중량에 대하여 에폭시 수지의 함량이 30 내지 80 중량%이고, 비스말레이미드 수지의 함량이 1 내지 20 중량%인금속박막코팅용열경화성 수지 조성물. Wherein the amine compound and the binder resin have an epoxy resin content of 30 to 80 wt% and a bismaleimide resin content of 1 to 20 wt% based on the total weight of the amine compound and the binder resin.
5 5
【청구항 11】 Claim 11
제 1항에 있어서,  The method according to claim 1,
상기 무기 충진제는 실리카， 알루미늄 트리하이드록사이드， 마그네슘 하이드록사이드, 몰리브데늄 옥사이드, 징크 몰리브데이트， 징크 보레이트, 징크스타네이트， 알루미나, 클레이， 카올린， 탈크, 소성 카올린, 소성 탈크， 10 마이카, 유리 단섬유， 글라스미세 파우더, 및 중공글라스로이루어진군에서 선택된 1종이상의 화합물인, 금속박막코팅용열경화성 수지 조성물.  The inorganic filler may be selected from the group consisting of silica, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, fired kaolin, , A glass short fiber, a glass fine powder, and a hollow glass.
【청구항 12】 Claim 12
제 1항에 있어서，  The method according to claim 1,
15 용제， 자외선흡수제， 산화방지제， 광중합개시제， 형광증백제， 광증감제, 안료, 염료, 증점제， 활제, 소포제， 분산제， 레벨링제 및 광택제로이루어지는 군에서 선택된 1종 이상의 첨가제를더 포함하는， 금속박막코팅용 열경화성 수지 조성물.  15. The composition of claim 1, further comprising at least one additive selected from the group consisting of a solvent, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, a photosensitizer, a pigment, a dye, a thickener, a lubricant, a defoaming agent, A thermosetting resin composition for metal thin film coating.
20 20
【청구항 13】 Claim 13
금속 박막의 적어도 일면에 제 1항의 열경화성 수지 조성물이 경화된 수지 코팅층을포함하며，  A thermosetting resin composition according to claim 1, wherein at least one surface of the metal thin film comprises a resin coating layer cured,
상기 수지 코팅층은,  The resin coating layer
술폰기, 카보닐기, 할로겐기, 탄소수 1 내지 20의 알킬기, 탄소수 6 25 내지 20의 아릴기， 탄소수 2 내지 30의 헤테로아릴기 및 탄소수 1 내지 20의 알킬렌기로 이루어진 군에서 선택된 1종 이상의 작용기를 포함한 아민 화합물과， 에폭시 수지 및 비스말레이미드 수지를 포함한 바인더 수지와， 스티렌 부타디엔계 고무, 네오프렌계 고무， 니트릴계 고무， 부틸계 고무, 부타디엔계 고무， 에틸렌프로필렌계 고무， 실리콘계 고무, 우레탄계 고무 및 30 아크릴계 고무로 이루어진 군에서 선택된 1종 이상의 고무계 성분 간의 0 2019/117624 1»（：1^1{2018/015776 At least one functional group selected from the group consisting of a sulfone group, a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms and an alkylene group having 1 to 20 carbon atoms A binder resin containing an epoxy resin and a bismaleimide resin, and a binder resin including an epoxy resin and a bismaleimide resin, and a binder resin including a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a butadiene rubber, an ethylene propylene rubber, And 30 acrylic rubbers. 0 2019/117624 1 »(: 1 ^ 1 {2018/015776
경화물; 및 - 상기 경화물사이에 분산되어 있는충진제 ; Cured goods; And - a filler dispersed between the cured products;
를포함하는금속적층체.  &Lt; / RTI &gt;
【청구항 14】 14.
제 13항에 있어서, 상기 수지 코팅층의 두께가 5 내지 30 이고, 유리전이온도 0 ）는 210내지 2301：인금속적층체.  14. The metal laminate according to claim 13, wherein the resin coating layer has a thickness of 5 to 30 and a glass transition temperature of 0 to 210 to 2301 :.
【청구항 15】 15.
제 1항의 열경화성 수지 조성물을 금속 박막의 적어도 일면에 코팅하는 단계를포함하는금속적층체의 제조방법 .  A method for producing a metal laminate, comprising the step of coating the thermosetting resin composition of claim 1 on at least one surface of a metal thin film.
【청구항 16】 Claim 16
제 13항의 금속적층체가 1매 이상적층된금속박적층판.  14. A metal-clad laminate comprising at least one metal laminate according to claim 13.
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