WO2019117574A1 - Thermosetting resin composition for metal thin film coating and metal laminate using same - Google Patents

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

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Publication number
WO2019117574A1
WO2019117574A1 PCT/KR2018/015649 KR2018015649W WO2019117574A1 WO 2019117574 A1 WO2019117574 A1 WO 2019117574A1 KR 2018015649 W KR2018015649 W KR 2018015649W WO 2019117574 A1 WO2019117574 A1 WO 2019117574A1
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WO
WIPO (PCT)
Prior art keywords
rubber
resin
weight
resin composition
group
Prior art date
Application number
PCT/KR2018/015649
Other languages
French (fr)
Korean (ko)
Inventor
윤민혁
김영찬
민현성
심창보
심희용
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180157084A external-priority patent/KR102196881B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/606,652 priority Critical patent/US11274218B2/en
Priority to JP2019566968A priority patent/JP6938833B2/en
Priority to CN201880026892.9A priority patent/CN110573581B/en
Publication of WO2019117574A1 publication Critical patent/WO2019117574A1/en

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention relates to a thermosetting resin composition for metal thin film coating which is excellent in flowability and pattern filling property, and a metal laminate using the same.
  • a copper clad laminate used in a conventional printed circuit board is made by impregnating a base material of a glass fiber into a varnish of the thermosetting resin and semi-curing it to become a prepreg, And pressurized.
  • the prepreg is used again for the purpose of constructing a circuit pattern on the copper-clad laminate and building up on it.
  • the thickness of semiconductor packages is getting thinner with the recent decrease in electronics and form factor.
  • the prepreg which is a laminated material among the package components includes woven glass fiber (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 above-mentioned 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. In particular, the thinner the resinous copper foil laminate is, the smaller the amount of resin is, and it is difficult to fill the pattern. If the pattern is not filled properly, 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • the empty space ( ⁇ ) is generated, and the reliability and performance of the semiconductor substrate are deteriorated.
  • 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. Therefore, it is necessary to increase the flowability of the resin in order to increase the pattern filling while reducing the thickness.
  • 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.
  • a monomolecular resin has a surface stickiness before curing, a protective film is required, and since the curing reaction proceeds slowly at room temperature, it is vulnerable to changes in aging and storage stability.
  • 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 by widening a temperature range maintaining minimum viscosity.
  • Another object of the present invention is to provide a metal laminate for a semiconductor package and a method for manufacturing the same, which comprises a resin coating, which is a cured product of the thermosetting resin composition, which is excellent in thermal characteristics and mechanical properties at a high glass transition temperature.
  • a binder resin containing an epoxy resin, a cyanate ester resin, a bismaleimide resin and a benzoxazine resin Rubber system components; And an inorganic filler,
  • the rubber component comprises at least one member selected from the group consisting of a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a butadiene rubber, an ethylene propylene rubber, a silicone rubber, a urethane rubber,
  • the rheometer minimum viscosity range is 350 in the range of 90 to 18010. 3 > or less, wherein the thermosetting resin composition for metal thin film coating is a thermosetting resin composition for metal thin film coating.
  • 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.
  • a thermosetting resin composition according to a specific embodiment of the present invention a resin-coated metal laminate and a metal foil laminate using the same will be described in detail.
  • the metal laminate may include a thermosetting resin composition coated on a metal thin film to a predetermined thickness.
  • the metal thin film may be in the form of a thin film containing a single or composite metal component, as described below, as a substrate for coating the resin composition.
  • 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, an epoxy resin, a cyanate ester resin, 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • the rubber component is selected from the group consisting of styrene butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, silicone rubber, urethan
  • the present invention relates to a thermally decomposable resin composition in which flowability and pattern filling properties are improved by intentionally delaying the curing reaction and a metal thin film coated with such a thermosetting resin composition.
  • metal foil laminates have been manufactured mainly by using a prepreg impregnated with a woven glass fiber.
  • the thickness of the foil laminate is limited.
  • the thickness of the foil laminates is reduced, There was a problem with poor sex.
  • it is possible to make the copper foil coated with resin thinner there are many disadvantages in terms of storage stability and stability when a monomolecular resin is used.
  • thermosetting resin composition of the present invention is characterized by deliberately delaying the curing reaction and optimizing the type of resin and mixing ratio for viscosity control.
  • thermosetting resin composition of the present invention is prepared by adding an epoxy, a cyanate ester resin and a benzoxazine or bismaleimide resin for controlling the curing reaction in an appropriate ratio, adding an inorganic filler to improve the mechanical strength, By adding a rubber component, flowability can be ensured.
  • the present invention shows a, rheometer minimum viscosity interval ( ⁇ ⁇ 1 (1 0) is widened flowability and gender pattern fill advantageous effects according to the intended retardation of the curing reaction.
  • the present invention as in the temperature region of the metal foil lamination process, the widening section (11 (1 03 ⁇ 4 0 to maintain a minimum viscosity, can improve the flowability and the filling pattern of the resin.
  • a complex viscosity suitable for filling a pattern is less than 3500 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • thermosetting resin composition proposed in the present invention the temperature range satisfying the above viscosity condition is very wide, such as 90 to 180 ° C or about 115 to 180 °. That is, the flowability in the firing process section is high and the pattern filling property is excellent.
  • the complex viscosity condition of the above-mentioned thermosetting resin composition is too high above the above range, the flowability is lowered, so that the pattern filling property may become poor.
  • the conventional thermosetting resin composition can be relatively narrowed in the working temperature range.
  • thermosetting resin composition of one embodiment may include a binder resin.
  • the binder resin may include at least one resin selected from the group consisting of an epoxy resin, a bismaleimide resin, a cyanate ester resin, and a bismaleimide resin.
  • the epoxy resin may be any of those conventionally used in thermosetting resin compositions, and the type thereof is not limited.
  • the epoxy resin include bisphenol-type epoxy resins, phenol novolac epoxy resins, phenyl aralkyl type epoxy resins, Epoxy resins, naphthalene-based epoxy resins, biphenyl-based epoxy resins, dicyclopentadiene epoxy resins, and mixtures of dicyclopentadiene-based epoxy resins and naphthalene-based epoxy resins.
  • the epoxy resin includes a bisphenol-type epoxy resin represented by the following general formula (1), a novolak-type epoxy resin represented by the following general formula (2), a phenyl aralcohol-based epoxy resin represented by the following general formula (3) Selected from the group consisting of a naphthalene type epoxy resin represented by the following Chemical Formulas 5 and 6, a biphenyl type epoxy resin represented by the following Chemical Formula 7, and a dicyclopentadiene type epoxy resin represented by the following Chemical Formula 8 More than species can be used. 2019/117574 1 »(: 1/10 ⁇ 018/015649
  • the epoxy resin of formula (5) may be a bisphenol type epoxy resin, a bisphenol type epoxy resin, a bisphenol type epoxy resin or a bisphenol type epoxy resin, respectively, depending on the kind of seedling.
  • the urine is II or (: 3 ⁇ 4,
  • 11 is 0 or an integer from 1 to 50;
  • 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.
  • II is 0 or an integer of 1 to 50.
  • the epoxy resins can be used as a 10 to 60% by weight, based on the total weight of the entire binder. If the amount of the epoxy resin is less than 10% by weight, there is a problem that it is difficult to realize high solubility. When the amount exceeds 60% by weight, the flowability is deteriorated.
  • the cyanate ester resin used in the thermosetting resin composition can be used without limitation, and the kind thereof is not limited.
  • the cyanate ester resin may be at least one selected from the group consisting of a novolac cyanate resin, a dicyclopentadiene-type cyanate resin, a bisphenol-type cyanate resin, and a partially triarylated prepolymer thereof .
  • the cyanate ester resin may include a novolak type cyanate resin represented by the following formula (9), a dicyclopentadiene type cyanate resin represented by the following formula (10), a bisphenol type cyanate resin represented by the following formula And some triarylated prepolymers thereof. These may be used singly or in combination of two or more.
  • the cyanate resin of Formula 11 may be a bisphenol-type cyanate resin, a bisphenol-capped cyanate resin, a bisphenol I? -Type cyanate resin, or a bisphenol-type cyanate resin, respectively.
  • the cyanate resin may be used in an amount of 20 to 70% by weight based on the total weight of the binder.
  • amount of the cyanate resin is less than 20% by weight, it is difficult to realize high solubility.
  • amount of the cyanate resin is more than 70% by weight, it adversely affects chemical resistance such as dismear There is a problem that the occurrence is increased.
  • the bismaleimide resin is usually added to a thermosetting resin composition 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • the bismaleimide resin may be a diphenylmethane type bismaleimide resin represented by the following formula (12), a phenylene type resin represented by the following formula (13)
  • the bismaleimide resin may be used in an amount of 5 to 60% by weight based on the total weight of the binder. When the amount of the bismaleimide resin is less than 5% by weight, there is a problem that desired physical properties can not be achieved. When the amount of the bismaleimide resin is more than 60% by weight, there are many unreacted groups, which may adversely affect characteristics such as chemical resistance.
  • the binder of one embodiment may comprise a benzoxazine resin.
  • the reaction rate can be controlled by changing phenol novolak used as a conventional curing agent to benzoylphosgene resin. That is, the phenol novolac curing agent, which has been mainly used in the past, generally has a hydroxyl group in its structure and reacts with epoxy resin and the like at room temperature, and thus the initial reaction rate is fast.
  • the benzoxazine resin used in the present invention shows a role as a curing agent and has a property of generating a hydroxyl group at a temperature of 15010 or higher. As a result, the reaction occurs slowly at room temperature or at an early stage, It is possible to adjust.
  • reaction rate can be controlled and the flowability of the resin can be ensured.
  • benzoxazine enables curing of the above-mentioned epoxy resin and bismaleimide resin.
  • the benzoxazine resin can be used as a curing agent for the epoxy resin and the bismaleimide resin. Since the benzoxazine resin is used as a curing agent for the bismaleimide resin, the curing reaction of the resins, which can be carried out at a low temperature such as the drying process, is small unlike the conventional phenol novolak resin, So that the flowability can be secured. This is not only the case when the resin-coated single metal foil and the metal laminate are manufactured 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • Such a benzoxazine resin may be at least one selected from the group consisting of a bisphenol-type benzoxazine resin, a bisphenol I-type benzoxazine resin, a phenolphthalein benzoxazine resin, and a mixture of benzoxazine resin and some curing accelerator have.
  • the benzoxazine resin may be used in an amount of 2 to 15% by weight based on the total weight of the entire binder so that sufficient curing of the bismaleimide resin contained in the binder can be induced. At this time, if the benzoxazine resin is contained in an excessive amount, the curing reaction rate of the resin composition may be delayed more than necessary and the process efficiency may be lowered. Accordingly, it is preferable that the benzoxazine resin is contained in an amount of 15% by weight or less based on the total weight of the binder. However, if the content is too small, the effect as a desired curing agent can not be exhibited, so that the chemical resistance and the solubility can not be improved.
  • thermosetting resin composition of one embodiment may include a rubber component together with the binder component.
  • thermosetting composition for a metal thin film coating comprises a binder and a specific rubber component in a predetermined ratio so that the rheometer minimum viscosity range satisfies the complex viscosity condition of from 90 to 180 ° (: Although the lower limit of the complex viscosity condition is not particularly limited, for example, 100 500 Or more.
  • the compound that satisfies the above-mentioned complex viscosity condition is a compound composed of a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a butadiene rubber, an ethylene propylene rubber, a silicone rubber, a urethane rubber and an acrylic rubber Based rubber component. 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 rubber-based component according to the present invention may further contain at least one member selected from the group consisting of styrene butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • the rubber component may include 5 to 15 parts by weight or 5 to 10 parts by weight based on 100 parts by weight of the binder resin. If the content of the rubber component is less than 5 parts by weight, there is a problem that the flowability of the resin is too large to increase the thickness variation. If the content is more than 20 parts by weight, the flowability is too small and the pattern filling property is poor. At this time, the optimum ratio of the rubber component for improving flowability and pattern filling property may be 5 to 10 parts by weight based on 100 parts by weight of the binder resin.
  • 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 an butadiene repeating unit containing an epoxy group and having a weight average molecular weight of IX 10 3 to 5 ⁇ 10 4 .
  • the silicone rubber has an epoxy group or a polyether-modified silicone repeating unit: or terminal groups comprise a copolymer comprising a silicone repeating units substituted, and having a weight average molecular weight of IX 10 3 to 5> ⁇ 4 of 10 with an amine group or an epoxy group Can ⁇ ⁇
  • 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 in the range of 30 < 10 4 to 65 ⁇ 10 4 , and if it is out of the above range, the flowability may be insufficient or excessive.
  • 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 heavy stabilizer.
  • 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 160 to 350 parts by weight based on 100 parts by weight of the binder resin. Specifically, the inorganic filler may be 200 to 250 parts by weight based on 100 parts by weight of the resin.
  • the average particle diameter of the inorganic filler is preferably 0.1 to 100 .
  • 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 of the embodiment can form a dispersed phase by mixing the inorganic filler and the resin evenly without forming a separation phase such as an inorganic fine powder 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 coated on the copper 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, In the army 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • thermosetting resin composition of one 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 or the like can be used. Mixed solvents used in combination of two or more kinds may also be used. Further, the content of the solvent is not limited so long as it can be suitably used for viscosity control in the production of the thermosetting resin composition.
  • 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 not particularly limited as long as they are selected from commonly used ones.
  • the additive include UV assistant agents, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, pigments, dyes, thickeners, lubricants, defoamers, dispersants, leveling agents and brighteners. It is also possible to use.
  • thermosetting resin composition according to one embodiment of the present invention having such a constitution has a rheometer minimum viscosity range of 350 to 350 in the range of 90 to 180. Less than 3 or 2000 The following complex viscosity conditions can be satisfied.
  • the complex viscosity suitable for filling the pattern is 3500 Or less, the temperature range satisfying the above viscosity condition is very wide in the range of 90 to 1801: in the case of the resin composition proposed in the present invention. 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 using a metal thin film or to ensure flowability during a build-up process, thereby easily filling a fine pattern.
  • 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 ( ⁇ 3 ⁇ 4) during pattern embedding, To provide the effect 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • 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 the metal thin film. ≪ Metal laminate &
  • the metal thin film includes a resin coating layer in which the thermosetting resin composition is cured on at least one side of the metal thin film, and the resin coating layer is composed of a binder including an epoxy resin, a cyanate ester resin, a bismaleimide resin, A cured product of at least one rubber component selected from the group consisting of a resin and a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a butadiene rubber, an ethylene propylene rubber, a silicone rubber, a urethane rubber and an acrylic rubber; And a filler dispersed between the cured products.
  • a binder including an epoxy resin, a cyanate ester resin, a bismaleimide resin
  • 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 may be provided.
  • a metal-clad laminate in which one or more of the metal laminates are stacked may be provided.
  • thermosetting resin composition a resin-coated metal laminate comprising a cured product of the thermosetting resin composition.
  • the present invention can provide a metal laminate which exhibits excellent thermal and mechanical properties by a simple method of 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 .
  • 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.
  • the method for manufacturing the metal laminate may include curing the thermosetting resin composition coated on at least one surface of the metal thin film.
  • thermosetting resin composition After the curing step of the thermosetting resin composition, a well-known drying process can be further performed if necessary.
  • the curing reaction of the resin is intentionally delayed to lengthen the section in which the minimum viscosity in the temperature range of the lamination process 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 may be put into a coater apparatus and coated on at least one surface of the metal thin film to a predetermined thickness.
  • the above-mentioned coater apparatus may be a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater or a spray coater.
  • a carrier film can be used for the flowability evaluation, and as the carrier film, a plastic film such as a polyethylene terephthalate liver), a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film can be used .
  • the varnish used for the coating may be a state in which a solvent is added to the thermosetting resin composition.
  • 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, And aliphatic alcohols such as sorb and butyl cellosolve.
  • the metal thin film comprises: a copper foil; Aluminum foil; A three-layered composite foil having an intermediate layer of nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead or lead-tin alloy and having copper layers of different thicknesses on both sides; 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 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • the thickness is preferably about 2 to 35 / pane. More preferably, a copper foil is used as the metal thin film . According to the present invention, an intermediate layer of nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead or lead-tin alloy is used as the metal thin film. A composite foil of a three-layer structure in which 10 to 300 copper layers are provided, or a two-layer composite foil in which aluminum and a copper foil are combined.
  • 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 temperature range, It is possible to provide a metal laminate having excellent properties.
  • the thickness of the resin coating layer in the metal laminate may be 5 to 90, preferably 5 to 30.
  • Such a cured product can exhibit excellent thermal and mechanical properties for a metal thin film even if it is formed thin on the metal foil.
  • the glass transition temperature of the resin after curing is 0 &lt
  • the dielectric properties of the metal thin films are 3.3.
  • the present invention is more excellent in pattern filling at a comparable thickness of 20 than the conventional monomolecular resin-coated copper foil, and is more stable at room temperature in the aging test.
  • a metal-clad laminate in which one or more of the metal laminates are stacked can be provided.
  • the metal plate laminate may further include a metal thin film.
  • the metal thin film may be a resin layer of a metal laminate.
  • the metal thin film can be used in the production after the etching pattern and stacked.
  • the metal thin film (mainly the first layer) is patterned through complete etching or partial etching, and then the resin The coating layer is brought into contact with the metal thin film 30, and the second layer is laminated. 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • 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, wherein the resin layers formed on the metal laminates are stacked so as to face each other.
  • the present invention can be used for manufacturing a double-sided or multi-layer printed circuit board after stacking one or more sheets by using the metal laminate.
  • the metal-clad laminate may be subjected to a circuit processing to produce a double-sided or multi-layer printed circuit board.
  • the circuit processing may 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 metal foil film coated with a resin applicable 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 use a small amount of the rubber component to intentionally retard the curing reaction of the resin, It is possible to provide an effect that flowability is high and pattern filling property is excellent .
  • 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.
  • the present invention has the effect of providing a metal thin film having excellent thermal and mechanical properties of the resin layer after curing and excellent dielectric properties. That is, when the 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 producing a prepreg using glass fiber, so that a thin metal laminate can be provided. Moreover, the present invention has a glass transition temperature of the resin is relatively high, after hardening, the dielectric properties can be provided an excellent metal laminate.
  • the metal thin film may be laminated by one or more sheets to provide a metal laminate used for thinning an electronic device. ⁇ ⁇ 0 2019/117574 1 »(Jiang / 10 ⁇ 2018/015649
  • Fig. 1 shows a rheometer curve for confirming flowability and pattern fillability of Example 1 of the present invention and Comparative Examples 1 and 2.
  • thermosetting resin composition (1) Production of thermosetting resin composition
  • varnishes were prepared by dissolving a resin such as an epoxy resin or a cyanate ester in a cyclohexanone solvent. To adjust the curing reaction, benzoxazine and bismaleimide resin were added to the varnish. Further, in order to improve the mechanical strength, a silica inorganic filler was added to the varnish.
  • a resin such as an epoxy resin or a cyanate ester
  • benzoxazine and bismaleimide resin were added to the 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 ⁇ ⁇ ) on one side of a copper foil (thickness 2, manufactured by Mi Tsui) with a comma coater and then cured for 200 minutes at 230 ⁇ ⁇ and 35 kg / cin. Subsequently, samples were made of resin-coated copper-clad laminate samples by cutting to size of 17 cm in height of 17 feet.
  • Varnishes were prepared using the components of the following Table 2 and cyclohexanone solvents.
  • the case where the acrylic rubber A or the acrylic rubber B was not used was designated as Comparative Example 1
  • Comparative Examples 2 to 4 the case where the content of the acrylic rubber A or the acrylic rubber B deviated from the present invention was designated as Comparative Examples 2 to 4.
  • 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.
  • the coating solution was coated on a copper foil (thickness: 2 pm, manufactured by Mi-sui) with a comma coater (coating thickness: 16 ⁇ m) and cured for 200 minutes at 230 ° C and 35 kg / cuf. Subsequently, the sample was cut into a size of 17 x 15 cm to prepare a resin-coated copper foil sample. ≪ Comparative Example 4 &
  • thermosetting resin composition (1) Production of thermosetting resin composition
  • the resin was dissolved in an organic solvent at a ratio shown in Table 2 below to make a varnish, which was then stirred for more than 24 hours.
  • Said a stirring varnish glass fabric 1 ⁇ 21 greater than 33 greater ⁇ thickness 13 ⁇ 4 ® shows 33 was impregnated in (greater deusa, Ltd.), 1701: 16 ⁇ and dried 2-5 minutes hot air at a temperature of prepreg manufacture him of ⁇ Respectively.
  • Comparative Example 4 shows the composition ratio of only the resin excluding the weight of the glass fiber substrate
  • Epoxy resin naphthalene-based epoxy resin 4710, 1) 1 (g)
  • Benzoxazine resin phenolphthalein benzoxazine resin (XU8282, Hunstman) BT resin: Nanozine 600, Nanokor company
  • Acrylic rubber SG-P3-PT197 (Mw 65X 10 4, Tg: 12 ° C), Nagase Chemtex Coporat ion
  • Acrylic rubber B SG-P3-MW1 (Mw 30 ⁇ 10 4 , Tg: 12 ° C), Nagase Chemtex
  • Silicone rubber AY42-119, Dow Corning
  • Buda diene rubber A B-1000, Nippon Soda
  • Butadiene rubber B RIC0N181, Cray Valey
  • Fi l ler A a slurry type filler with methacryl silane treatment, average particle diameter 0.5um
  • Example 1 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-dependent viscosity measurement conditions, rate of temperature rise: 5 degrees / min, frequency: 10 Hz).
  • Viscosity and flowability were also confirmed by the presence or absence of void formation in the pattern stacking test.
  • a copper-clad laminate (CCL) having a pattern in which a copper foil thickness of 10 mu m and a total area of about 60% of the total area was etched was used and the resin-coated copper clad samples (or prepreg ). 'OK' when no void or delamination occurred, and a case where void or delaminat ion occurred.
  • voids were not generated in Example 1 but voids were generated in Comparative Examples 1 and 2.
  • 1 shows the flowability and pattern filling properties of Example 1 of the present invention and Comparative Examples 1 and 2 2019/117574 1 »(: 1 ⁇ ⁇ 2018/015649
  • the complex viscosity suitable for filling the pattern is 3500 Pa.
  • the first embodiment of the present invention has a rheometer minimum viscosity window of 90 ° C to 180 ° C, which is much wider than those of Comparative Examples 1 and 2, You can see the advantage.
  • the resin compositions of Examples and Comparative Examples for 3 months were subjected to pattern test after storage at room temperature / refrigeration to observe the change over time. If the curing rate of the resin increases with the passage of time, and the flowability is reduced, the possibility of occurrence of voids increases. As a result of the pattern test after 3 months of storage at room temperature / refrigeration, it was observed that there was no void in the examples.
  • Comparative Example 4 was used in the experiment using the above-mentioned prepreg-coated copper-clad laminate.
  • Tg thermal and mechanical properties were measured using DSC, TGA DMA, and TMA.
  • the dielectric properties were measured by SPDR method at 1 GHz.
  • the glass transition temperature was measured using DMA.
  • Dielectric properties were measured by measuring the dielectric constant (Dk) and dielectric loss (Df) at 1 GHz using the Agi lent E5071B ENA instrument. Respectively.
  • the glass transition temperature was found to be 290 deg., The dielectric constant was 3.3 and the dielectric loss tangent was 0.006.
  • Examples 1 to 6 of the present invention compared to Comparative Examples 1 to 4, the range of the minimum viscosity range was wide and the flowability was excellent was confirmed through the presence or absence of empty space 0 in the pattern lamination test.

Abstract

The present invention relates to: a thermosetting resin composition for a metal thin film coating having high flowability and a pattern-filling property; and a metal laminate using the same.

Description

2019/117574 1»（：1^1{2018/015649  2019/117574 1 »(: 1 ^ {2018/015649
【발명의 명칭】 Title of the Invention
금속박막코팅용열경화성 수지 조성물및 이를이용한금속적층체 【기술분야】  Thermosetting resin composition for metal thin film coating and metal laminate using the same
관련출원 (들)과의상호인용  Cross-reference with related application (s)
본 출원은 2017년 12월 11일자 한국 특허 출원 제 10-2017-0169493호 및 2018년 12월 7일자한국특허 출원제 10-2018-0157084호에 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. 10-2017-0169493, dated December 11, 2017, and Korean Patent Application No. 10-2018-0157084, dated December 7, 2018, The entire contents of which are incorporated herein by reference.
본발명은흐름성 및 패턴 채움성이 우수한금속박막코팅용열경화성 수지 조성물및 이를이용한금속적층체에 관한것이다.  The present invention relates to a thermosetting resin composition for metal thin film coating which is excellent in flowability and pattern filling property, and a metal laminate using the same.
【발명의 배경이 되는기술】  TECHNICAL BACKGROUND OF THE INVENTION
종래의 인쇄회로기판에 사용되는 동박적층판 (copper cl ad laminate)은 유리 섬유 (Glass Fabri c)의 기재를상기 열경화성 수지의 바니시에 함침한후 반경화시키면 프리프레그가 되고, 이를 다시 동박과 함께 가열 가압하여 제조한다. 이러한 동박 적층판에 회로 패턴을 구성하고 이 위에 빌드업 (bui ld-up)을하는용도로프리프레그가다시사용되게된다.  A copper clad laminate used in a conventional printed circuit board is made by impregnating a base material of a glass fiber into a varnish of the thermosetting resin and semi-curing it to become a prepreg, And pressurized. The prepreg is used again for the purpose of constructing a circuit pattern on the copper-clad laminate and building up on it.
최근 전자 기기， 통신기기， 개인용 컴퓨터, 스마트폰 등의 고성능화, 박형화， 경량화가 가속되면서 반도체 패키지 또한 박형화가 요구됨에 따라, 동시에 반도체 패키지용인쇄회로기판도박형화의 필요성이 커지고있다.  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 전자기기와 폼팩터가 줄어들면서 반도체 패키지의 두께도 점점 얇아지고 있다. 그런데， 종래 패키지 구성 성분 중 적층소재인 프리프레그 (prepreg)는 직조된 유리 섬유 (gl ass fabr i c)를 포함하고 있기 때문에 두께를일정 이상줄이기가어렵다.  In other words, the thickness of semiconductor packages is getting thinner with the recent decrease in electronics and form factor. However, since the prepreg which is a laminated material among the package components includes woven glass fiber (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.
상기 언급된 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 수지량이 적어져 패턴을 채우기 어렵다. 패턴이 제대로 채워지지 않는 경우, 2019/117574 1»（：1^1{2018/015649 The most important characteristic of the above-mentioned 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. In particular, the thinner the resinous copper foil laminate is, the smaller the amount of resin is, and it is difficult to fill the pattern. If the pattern is not filled properly, 2019/117574 1 »(: 1 ^ {2018/015649
빈 공간 （\ ）가발생하게 되고 반도체 기판의 신뢰성， 성능등이 떨어지게 된다. 수지 코팅 동박의 두께가얇아지면수지의 양도줄어들기 때문에 패턴을 채우지 못하고 적층 후 빈 공간이 발생할 가능성이 높아진다. 즉, 기판의 박막화를위해수지 두께를얇게하면패턴채움성이 떨어지게 되는것이다. 따라서， 두께를 얇게 하면서도동시에 패턴 채움성을높이기 위해서는 수지의흐름성을높이는것이 필요하다. The empty space ( \ ) is generated, and the reliability and performance of the semiconductor substrate are deteriorated. 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. Therefore, it is necessary to increase the flowability of the resin in order to increase the pattern filling while reducing the thickness.
통상적으로 사용되는 방법은 단분자 계열의 수지를 사용하는 것이다. 분자량이 낮은수지의 경우, 적층공정 온도구간내에서 경화전점도가낮기 때문에 흐름성 및 패턴 채움성이 우수하다. 하지만단분자계열의 수지는경화 전표면 끈적임이 있으므로보호필름이 필요하며， 상온보관시 경화반응이 서서히 진행되므로경시 변화및보관안정성에 취약한단점을가지고있다.  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, since a monomolecular resin has a surface stickiness before curing, a protective film is required, and since the curing reaction proceeds slowly at room temperature, it is vulnerable to changes in aging and storage stability.
【발명의 내용】 DISCLOSURE OF THE INVENTION
【해결하고자하는과제】  [Problem to be solved]
본 발명의 목적은 최소 점도를 유지하는 온도 구간을 넓혀 흐름성 및 패턴 채움성이 우수한 금속 박막 코팅용 열경화성 수지 조성물을 제공하는 것이다.  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 by widening a temperature range maintaining minimum viscosity.
본 발명의 다른 목적은 높은 유리 전이온도의 열적 특성과 기계적 물성도 우수한상기 열경화성 수지 조성물의 경화물인 수지 코팅증을 포함한 반도체 패키지용금속적층체 및그제조방법을제공하는것이다.  Another object of the present invention is to provide a metal laminate for a semiconductor package and a method for manufacturing the same, which comprises a resin coating, which is a cured product of the thermosetting resin composition, which is excellent in thermal characteristics and mechanical properties at a high glass transition temperature.
【과제의 해결수단】 MEANS FOR SOLVING THE PROBLEMS
본 명세서에서는, 에폭시 수지， 시아네이트 에스터 수지, 비스말레이미드수지 및 벤즈옥사진수지를포함한바인더 수지; 고무계성분; 및무기 충진제를포함하고，  In the present specification, a binder resin containing an epoxy resin, a cyanate ester resin, a bismaleimide resin and a benzoxazine resin; Rubber system components; And an inorganic filler,
상기 고무계 성분은 스티렌 부타디엔계 고무， 네오프렌계 고무， 니트릴계 고무, 부틸계 고무， 부타디엔계 고무， 에틸렌프로필렌계 고무, 실리콘계 고무, 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종이상을포함하며，  Wherein the rubber component comprises at least one member selected from the group consisting of a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a butadiene rubber, an ethylene propylene rubber, a silicone rubber, a urethane rubber,
상기 바인더 수지 100 중량부에 대해 상기 고무계 성분은 5 중량부 2019/117574 1»（：1^1{2018/015649 Based on 100 parts by weight of the binder resin, 5 parts by weight of the rubber- 2019/117574 1 »(: 1 ^ {2018/015649
이상 20중량부이하로포함하고， By weight or more and 20 parts by weight or less,
레오미터 최저 점도구간이 90내지 18010의 범위에서 350아¾.3 이하의 복소 점도 조건을 만족하는， 금속 박막 코팅용 열경화성 수지 조성물을 제공한다. The rheometer minimum viscosity range is 350 in the range of 90 to 18010. 3 > or less, wherein the thermosetting resin composition for metal thin film coating is a thermosetting resin composition for metal thin film coating.
본명세서에서는또한， 금속박막의 적어도일면에 상기 열경화성 수지 조성물이 경화된수지 코팅층을포함하며，  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 수지코팅층은,  The resin coating layer
에폭시 수지， 시아네이트 에스터 수지， 비스말레이미드 수지 및 벤즈옥사진수지를포함한바인더 수지와스티렌부타디엔계고무 , 네오프렌계 고무， 니트릴계 고무， 부틸계고무, 부타디엔계고무, 에틸렌프로필렌계 고무， 실리콘계 고무, 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종이상의 고무계성분간의 경화물; 및  Butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, silicone rubber, epoxy resin, cyanate ester resin, bismaleimide resin and benzoxazine resin, , A cured product of at least one rubber-based component selected from the group consisting of urethane rubber and acrylic rubber; And
상기 경화물사이에 분산되어 있는 충진제;를포함하는금속 적층체를 제공한다.  And a filler dispersed among the cured products.
본 명세서에서는 또한， 상기 열경화성 수지 조성물을 금속 박막의 적어도일면에 코팅하는단계를포함하는금속적층체의 제조방법을제공한다. 본 명세서에서는 또한, 상기 금속 적층체가 1매 이상 적층된 금속박 적층판을제공한다. 이하 발명의 구체적인 구현예에 따른 열경화성 수지 조성물과 이를 이용한 수지 코팅 금속 적층체 및 금속박 적층판에 대하여 보다 상세하게 설명하기로한다. 먼저, 본 발명에서 금속 적층체는 열경화성 수지 조성물이 금속 박막 상에 일정 두께로코팅된형태를포함할수있다.  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. Hereinafter, a thermosetting resin composition according to a specific embodiment of the present invention, a resin-coated metal laminate and a metal foil laminate using the same 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.
상기 금속 박막은， 수지 조성물을 코팅하기 위한 기재로서， 후술하는 바와같이 단일또는복합금속성분을포함하는박막형태일수있다. 또한， 금속박적층판은상기 금속적층체가 1종이상적층된구조를포함할수있다. 발명의 일 구현예에 따르면, 에폭시 수지, 시아네이트 에스터 수지， 2019/117574 1»（：1^1{2018/015649 The metal thin film may be in the form of a thin film containing a single or composite metal component, as described below, as a substrate for coating the resin composition. 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, an epoxy resin, a cyanate ester resin, 2019/117574 1 »(: 1 ^ {2018/015649
비스말레이미드수지 및 벤즈옥사진수지를포함한바인더 수지; 고무계성분; 및 무기 충진제를 포함하고, 상기 고무계 성분은 스티렌 부타디엔계 고무， 네오프렌계 고무, 니트릴계 고무, 부틸계 고무, 부타디엔계 고무， 에틸렌프로필렌계 고무， 실리콘계 고무, 우레탄계 고무 및 아크릴계 고무로 이루어진군에서 선택된 1종이상을포함하며， 상기 바인더 수지 100중량부에 대해 상기 고무계 성분은 5중량부 이상 20중량부 이하로포함하고, 레오미터 최저 점도 구간이 90 내지 1801：의 범위에서 3500?3.8 이하의 복소 점도 조건을만족하는， 금속박막코팅용열경화성 수지 조성물이 제공된다. A binder resin including a bismaleimide resin and a benzoxazine resin; Rubber system components; And an inorganic filler, wherein the rubber component is selected from the group consisting of styrene butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, silicone rubber, urethane rubber and acrylic rubber Wherein the rubber component is contained in an amount of 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the binder resin, and the rheometer minimum viscosity range is 3500? And satisfies the complex viscosity condition of not more than 3.8 , as a thermosetting resin composition for metal thin film coating.
본발명은 경화반응을의도적으로지연시켜 흐름성 및 패턴 채움성을 향상시킨 열화성 수지 조성물및 이러한 열경화성 수지 조성물이 코팅된 금속 박막에 관한것이다.  The present invention relates to a thermally decomposable resin composition in which flowability and pattern filling properties are improved by intentionally delaying the curing reaction and a metal thin film coated with such a thermosetting resin composition.
기존에는 주로, 수지 조성물을 직조된 유리 섬유에 함침한 프리프레그를 이용하여 금속박 적층판을 제조하여 왔지만， 두께를 줄이는데 한계가있을뿐아니라두께가줄어들면동박의 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 manufactured mainly by using a prepreg impregnated with a woven glass fiber. However, the thickness of the foil laminate is limited. In addition, when the thickness of the foil laminates is reduced, There was a problem with poor sex. In addition, although it is possible to make the copper foil coated with resin thinner, there are many disadvantages in terms of storage stability and stability when a monomolecular resin is used.
이에 따라, 본발명의 열경화성 수지 조성물은경화반응을의도적으로 지연시키고， 또한 점도 조절를 위해, 수지 종류 및 혼합 비율 최적화하는 특징이 있다.  Accordingly, the thermosetting resin composition of the present invention is characterized by deliberately delaying the curing reaction and optimizing the type of resin and mixing ratio for viscosity control.
구체적으로， 본 발명의 열경화성 수지 조성물은 에폭시, 시아네이트 에스터 수지와경화반응을조절하기 위한벤즈옥사진， 비스말레이미드수지를 적정 비율로 첨가하고 여기에 기계적 강도 향상을 위해 무기 충진제를 첨가하며， 또한 고무계 성분을 추가함으로써， 흐름성을 확보할 수 있다. 따라서， 본 발명은 경화 반응의 의도적 지연에 따라， 레오미터 최저 점도 구간（\¥ 1（10）이 넓어져서 흐름성 및 패턴 채움성에 유리한 효과를 나타낸다. 바람직하게， 본 발명은 금속박 적층 공정의 온도 구간 내에서, 최소 점도를 유지하는 구간 （ 11（10¾0을 넓힘으로써， 수지의 흐름성 및 패턴 채움성을 향상시킬수있다. Specifically, the thermosetting resin composition of the present invention is prepared by adding an epoxy, a cyanate ester resin and a benzoxazine or bismaleimide resin for controlling the curing reaction in an appropriate ratio, adding an inorganic filler to improve the mechanical strength, By adding a rubber component, flowability can be ensured. Accordingly, the present invention shows a, rheometer minimum viscosity interval (\ ¥ 1 (1 0) is widened flowability and gender pattern fill advantageous effects according to the intended retardation of the curing reaction. Preferably, the present invention as in the temperature region of the metal foil lamination process, the widening section (11 (1 0¾ 0 to maintain a minimum viscosity, can improve the flowability and the filling pattern of the resin.
예를 들어， 패턴을 채우는데 적합한 복소 점도를 3500 이하라고 2019/117574 1»（：1^1{2018/015649 For example, a complex viscosity suitable for filling a pattern is less than 3500 2019/117574 1 »(: 1 ^ {2018/015649
가정할 때， 본 발명에서 제시하는 열경화성 수지 조성물의 경우， 상기 점도 조건을만족하는온도구간이 90내지 180ᄃ 혹은 약 115내지 180°（：로 매우 넓다. 즉, 적증공정 구간내흐름성이 높고패턴채움성이 우수해지는것이다. 그러나, 상기 열경화성 수지 조성물의 복소 점도조건이 상기 범위 이상으로 너무높아지면흐름성이 떨어지므로, 패턴채움성이 불량해질수있다. 또한, 상기 복소 점도 조건을 만족하더라도， 종래 열경화성 수지 조성물은 상대적으로작업 온도구간이좁아질수있다. 그러면, 본발명의 바람직한일구현예에 따른열경화성 수지 조성물의 구성 성분과상기 수지 조성물을이용한금속박막및금속박적층판에 대하여 보다구체적으로설명한다. In the case of the thermosetting resin composition proposed in the present invention, the temperature range satisfying the above viscosity condition is very wide, such as 90 to 180 ° C or about 115 to 180 °. That is, the flowability in the firing process section is high and the pattern filling property is excellent. However, if the complex viscosity condition of the above-mentioned thermosetting resin composition is too high above the above range, the flowability is lowered, so that the pattern filling property may become poor. Also, even if the complex viscosity condition is satisfied, the conventional thermosetting resin composition can be relatively narrowed in the working temperature range. Hereinafter, the constituent components of the thermosetting resin composition according to a preferred embodiment of the present invention and the metal thin film and the metal foil laminate using the resin composition will be described in more detail.
상기 일 구현예의 열경화성 수지 조성물은 바인더 수지를 포함할 수 있다.  The thermosetting resin composition of one embodiment may include a binder resin.
상기 바인더 수지는 에폭시 수지, 비스말레이미드 수지， 시아네이트 에스터 수지 및 비스말레이미드 수지로 이루어진 군으로부터 선택되는 1종 이상의 수지를포함할수있다.  The binder resin may include at least one resin selected from the group consisting of an epoxy resin, a bismaleimide resin, a cyanate ester resin, and a bismaleimide resin.
이 때, 상기 에폭시 수지로는 통상 열경화성 수지 조성물에 사용되는 것을제한없이 사용할수 있으며, 그종류가한정되지는않으며, 비스페놀쇼 형 에폭시 수지, 페놀 노볼락 에폭시 수지， 페닐 아랄킬계 에폭시 수지， 테트라페닐 에탄 에폭시 수지, 나프탈렌계 에폭시 수지, 바이페닐계 에폭시 수지， 디시클로펜타디엔 에폭시 수지, 및 디시클로펜타디엔계 에폭시 수지와 나프탈렌계 에폭시 수지의 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다.  In this case, the epoxy resin may be any of those conventionally used in thermosetting resin compositions, and the type thereof is not limited. Examples of the epoxy resin include bisphenol-type epoxy resins, phenol novolac epoxy resins, phenyl aralkyl type epoxy resins, Epoxy resins, naphthalene-based epoxy resins, biphenyl-based epoxy resins, dicyclopentadiene epoxy resins, and mixtures of dicyclopentadiene-based epoxy resins and naphthalene-based epoxy resins.
구체적으로， 상기 에폭시 수지는하기 화학식 1로표시되는비스페놀형 에폭시 수지, 하기 화학식 2로 표시되는노볼락형 에폭시 수지， 하기 화학식 3로 표시되는 페닐 아랄킬계 에폭시 수지, 하기 화학식 4로 표시되는 테트라페닐에탄형 에폭시 수지， 하기 화학식 5및 6으로표시되는나프탈렌형 에폭시 수지， 하기 화학식 7로 표시되는 바이페닐형 에폭시 수지, 및 하기 화학식 8로 표시되는 디시클로펜타디엔형 에폭시 수지로 이루어진 군에서 선택된 1종이상을사용할수있다. 2019/117574 1»(：1/10公018/015649 Specifically, the epoxy resin includes a bisphenol-type epoxy resin represented by the following general formula (1), a novolak-type epoxy resin represented by the following general formula (2), a phenyl aralcohol-based epoxy resin represented by the following general formula (3) Selected from the group consisting of a naphthalene type epoxy resin represented by the following Chemical Formulas 5 and 6, a biphenyl type epoxy resin represented by the following Chemical Formula 7, and a dicyclopentadiene type epoxy resin represented by the following Chemical Formula 8 More than species can be used. 2019/117574 1 »(: 1/10 公 018/015649
［화학식 1］ [Chemical Formula 1]
Figure imgf000008_0001
Figure imgf000008_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 요형 에폭시 수지， 비스페놀 형 에폭시 수지， 비스페놀 형 에폭시 수지， 또는비스페놀 형 에폭시 수지일수있다.  More specifically, the epoxy resin of formula (5) may be a bisphenol type epoxy resin, a bisphenol type epoxy resin, a bisphenol type epoxy resin or a bisphenol type epoxy resin, respectively, depending on the kind of seedling.
［화학식到  [Formula
Figure imgf000008_0002
Figure imgf000008_0002
상기 화학식 2에서，  In Formula 2,
요은 II또는（：¾이고,  The urine is II or (: ¾,
11은 0또는 1내지 50의 정수이다. 11 is 0 or an integer from 1 to 50;
보다구체적으로， 상기 화학식 3의 노볼락형 에폭시 수지는요의 종류에 따라， 각각페놀 노볼락형 에폭시 수지 또는크레졸 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 3］ 2019/117574 1»（：1/10公018/015649 (3) 2019/117574 1 »(: 1/10 公 018/015649
Figure imgf000009_0001
상기 화학식 7에서，
Figure imgf000009_0001
In Formula 7,
은 0또는 1내지 50의 정수이다. 2019/117574 1»（：1^1{2018/015649 Is an integer of 0 or 1 to 50. [ 2019/117574 1 »(: 1 ^ {2018/015649
[화학식 8] [Chemical Formula 8]
Figure imgf000010_0001
Figure imgf000010_0001
상기 화학식 8에서， II은 0또는 1내지 50의 정수이다.  In the formula (8), II is 0 or an integer of 1 to 50.
상기 에폭시 수지는 전체 바인더의 총 중량을 기준으로 10 내지 60 중량%로 사용할 수 있다. 상기 에폭시 수지의 사용량이 10 중량% 미만이면 높은 용의 구현이 어려운 문제가 있고， 60 중량%를 초과하면 흐름성이 나빠지는문제가있다. The epoxy resins can be used as a 10 to 60% by weight, based on the total weight of the entire binder. If the amount of the epoxy resin is less than 10% by weight, there is a problem that it is difficult to realize high solubility. When the amount exceeds 60% by weight, the flowability is deteriorated.
상기 시아네이트에스터 수지는통상열경화성 수지 조성물에 사용되는 것을제한없이 사용할수있으며, 그종류가한정되지는않는다.  The cyanate ester resin used in the thermosetting resin composition can be used without limitation, and the kind thereof is not limited.
바람직한 일례를 들면， 상기 시아네이트 에스터 수지는 노볼락형 시아네이트 수지， 디시클로펜타디엔형 시아네이트 수지 , 비스페놀형 시아네이트수지 및 이들의 부분트리아진화된 프리폴리머로 이루어진 군에서 선택된 1종 이상일 수 있다. 더 구체적으로， 상기 시아네이트 에스터 수지는 하기 화학식 9로 표시되는 노볼락형 시아네이트 수지， 하기 화학식 10로 표시되는 디시클로펜타디엔형 시아네이트 수지， 하기 화학식 11로 표시되는 비스페놀형 시아네이트수지 및 이들의 일부트리아진화된프리폴리머를들수 있고, 이들은단독혹은 2종이상혼합하여사용할수있다.  For example, the cyanate ester resin may be at least one selected from the group consisting of a novolac cyanate resin, a dicyclopentadiene-type cyanate resin, a bisphenol-type cyanate resin, and a partially triarylated prepolymer thereof . More specifically, the cyanate ester resin may include a novolak type cyanate resin represented by the following formula (9), a dicyclopentadiene type cyanate resin represented by the following formula (10), a bisphenol type cyanate resin represented by the following formula And some triarylated prepolymers thereof. These may be used singly or in combination of two or more.
[화학식 9]  [Chemical Formula 9]
Figure imgf000010_0002
Figure imgf000010_0002
상기 화학식 9에서,  In the above formula (9)
II은 0또는 1내지 5◦의 정수이다. 2019/117574 1»（：1^1{2018/015649 II is an integer of 0 or 1 to 5; 2019/117574 1 »(: 1 ^ {2018/015649
[화학식 10] [Chemical formula 10]
Figure imgf000011_0001
Figure imgf000011_0001
상기 화학식 10에서，  In Formula 10,
II은 0또는 1내지 50의 정수이다.  II is 0 or an integer from 1 to 50;
[화학식 11]  (11)
Figure imgf000011_0002
Figure imgf000011_0002
보다 구체적으로， 상기 화학식 11의 시아네이트 수지는 요의 종류에 따라， 각각 비스페놀 쇼형 시아네이트 수지, 비스페놀 묘형 시아네이트 수지, 비스페놀 I?형 시아네이트 수지, 또는 비스페놀 형 시아네이트 수지일 수 있다.  More specifically, the cyanate resin of Formula 11 may be a bisphenol-type cyanate resin, a bisphenol-capped cyanate resin, a bisphenol I? -Type cyanate resin, or a bisphenol-type cyanate resin, respectively.
상기 시아네이트 수지는 전체 바인더의 총 중량을 기준으로 20 내지 70중량%로 사용할 수 있다. 상기 시아네이트 수지의 사용량이 20 중량% 미만이면 높은 용의 구현이 어려운 문제가 있고， 70 중량%를 초과하면 디스미어 등의 내화학성에 안좋은 영향을끼치며
Figure imgf000011_0003
발생이 많아지는문제가 있다. The cyanate resin may be used in an amount of 20 to 70% by weight based on the total weight of the binder. When the amount of the cyanate resin is less than 20% by weight, it is difficult to realize high solubility. When the amount of the cyanate resin is more than 70% by weight, it adversely affects chemical resistance such as dismear
Figure imgf000011_0003
There is a problem that the occurrence is increased.
그리고， 상기 비스말레이미드 수지는 통상 열경화성 수지 조성물에 2019/117574 1»（：1^1{2018/015649 The bismaleimide resin is usually added to a thermosetting resin composition 2019/117574 1 »(: 1 ^ {2018/015649
사용되는것을제한없이 사용할수있으며， 그종류가한정되지는않는다 일 구현예에 따르면， 상기 비스말레이미드 수지는 하기 화학식 12로 표시되는 디페닐메탄형 비스말레이미드 수지， 하기 화학식 13으로 표시되는 페닐렌형 비스말레이미드 수지, 하기 화학식 14로 표시되는 비스페놀 쇼형 디페닐 에테르 비스말레이미드 수지， 및 하기 화학식 15으로 표시되는 디페닐메탄형 비스말레이미드 및 페닐메탄형 말레이미드 수지의 올리고머로 구성된비스말레이미드수지로이루어진군에서 선택된 1종이상일수있다. The bismaleimide resin may be a diphenylmethane type bismaleimide resin represented by the following formula (12), a phenylene type resin represented by the following formula (13) A bismaleimide resin composed of a bismaleimide resin, a bisphenol-type diphenyl ether bismaleimide resin represented by the following formula (14), and an oligomer of a diphenylmethane type bismaleimide and a phenylmethane type maleimide resin represented by the following formula (15) And the like.
[화학식 12]  [Chemical Formula 12]
Figure imgf000012_0001
Figure imgf000012_0001
상기 화학식 12에서，  In Formula 12,
¾및 ¾는각각독립적으로， II，（：¾또는 ¾¾이다.  (I), (III) and (III) each independently represent II, (III or IV).
[화학식 13]  [Chemical Formula 13]
Figure imgf000012_0002
Figure imgf000012_0002
[화학식 14] 2019/117574 1»（：1^1{2018/015649 [Chemical Formula 14] 2019/117574 1 »(: 1 ^ {2018/015649
Figure imgf000013_0001
Figure imgf000013_0001
상기 화학식 15에서，  In Formula 15,
II은 0또는 1내지 50의 정수이다.  II is 0 or an integer from 1 to 50;
상기 비스말레이미드수지는전체 바인더의 총중량을기준으로 5내지 60중량%로사용할수 있다. 상기 비스말레이미드수지의 사용량이 5중량% 미만이면 원하는 물성 구현이 안되는 문제가 있고， 60 중량%를 초과하면 미반응기가많아내화학성 등의 특성에 악영향을끼칠수있다.  The bismaleimide resin may be used in an amount of 5 to 60% by weight based on the total weight of the binder. When the amount of the bismaleimide resin is less than 5% by weight, there is a problem that desired physical properties can not be achieved. When the amount of the bismaleimide resin is more than 60% by weight, there are many unreacted groups, which may adversely affect characteristics such as chemical resistance.
또한， 상기 일 구현예의 바인더는 벤즈옥사진 수지를포함할수 있다. 본발명은기존경화제로사용하던페놀노볼락을벤즈옥사진수지로변경하여 사용함으로써， 반응속도를제어할수있다. 즉， 기존에 주로사용되오던페놀 노볼락경화제는일반적으로히드록시기가자체구조에 포함되어 상온에서부터 에폭시 수지 등과 반응하여 초기 반응 속도가 빠르다. 반면， 본 발명에서 사용하는 벤즈옥사진 수지는 경화제로서의 역할을 나타내어 15010 이상의 온도에서 히드록시기가 생기는 특성이 있고， 이로 인해 상온 또는 초기에는 반응이 천천히 일어나지만 일정온도 이상에서 반응에 참여하여 반응속도를 조절하는것이 가능하다.  In addition, the binder of one embodiment may comprise a benzoxazine resin. In the present invention, the reaction rate can be controlled by changing phenol novolak used as a conventional curing agent to benzoylphosgene resin. That is, the phenol novolac curing agent, which has been mainly used in the past, generally has a hydroxyl group in its structure and reacts with epoxy resin and the like at room temperature, and thus the initial reaction rate is fast. On the other hand, the benzoxazine resin used in the present invention shows a role as a curing agent and has a property of generating a hydroxyl group at a temperature of 15010 or higher. As a result, the reaction occurs slowly at room temperature or at an early stage, It is possible to adjust.
따라서 , 본 발명에서 사용하는 벤즈옥사진
Figure imgf000013_0002
Therefore, the benzoxazine used in the present invention
Figure imgf000013_0002
반응속도 조절이 가능하아 수지의 흐름성을 확보할 수 있게 한다. 또한, 벤즈옥사진은상술한에폭시 수지 및 ·비스말레이미드수지의 경화를가능하게 한다. The reaction rate can be controlled and the flowability of the resin can be ensured. In addition, benzoxazine enables curing of the above-mentioned epoxy resin and bismaleimide resin.
즉 , 상기 벤즈옥사진 수지는 상기 에폭시 수지 및 비스말레이미드 수지에 대한경화제의 용도로사용될수 있다. 상기 벤즈옥사진수지를상기 비스말레이미드 수지의 경화제로 사용함에 따라， 기존의 페놀 노볼락 수지와 달리 건조공정과같은낮은온도에서도진행될 수 있는수지들의 경화반응이 적어， 적층 공정에서 수지 조성물의 경화정도를 낮추어 흐름성을 확보할 수있다. 이는 수지 코팅된 단일 금속박과 금속 적층판을 제조할 때 뿐만 2019/117574 1»（：1^1{2018/015649 That is, the benzoxazine resin can be used as a curing agent for the epoxy resin and the bismaleimide resin. Since the benzoxazine resin is used as a curing agent for the bismaleimide resin, the curing reaction of the resins, which can be carried out at a low temperature such as the drying process, is small unlike the conventional phenol novolak resin, So that the flowability can be secured. This is not only the case when the resin-coated single metal foil and the metal laminate are manufactured 2019/117574 1 »(: 1 ^ {2018/015649
아니라， 빌드업 공정에서 이용되는 프레스 공정에서 발생하는 외관 불량을 최소화할수있는효과도제공한다. But also provides an effect of minimizing appearance defects occurring in the press process used in the build-up process.
이러한 벤즈옥사진 수지는 비스페놀 쇼형 벤즈옥사진 수지, 비스페놀 I?형 벤즈옥사진 수지， 페놀프탈레인 벤즈옥사진 수지， 및 이들의 벤즈옥사진 수지와 일부 경화촉진제의 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다.  Such a benzoxazine resin may be at least one selected from the group consisting of a bisphenol-type benzoxazine resin, a bisphenol I-type benzoxazine resin, a phenolphthalein benzoxazine resin, and a mixture of benzoxazine resin and some curing accelerator have.
상기 바인더에 포함되는 비스말레이미드수지의 충분한 경화가유도될 수있도록, 상기 벤즈옥사진수지는전체 바인더의 총중량을기준으로 2내지 15중량%로사용할수 있다. 이때, 상기 벤즈옥사진수지가과량으로포함될 경우 수지 조성물의 경화 반응 속도가 필요 이상으로 지연되어 공정 효율이 저하될 수 있다. 따라서, 상기 벤즈옥사진 수지는 상기 바인더의 총 중량을 기준으로 15중량%이하로포함되는 것이 바람직하다. 다만， 그함량이 너무 적으면 원하는경화제로서의 효과를나타낼수 없기 때문에 내화학성 및 용를 향상시킬수없으므로， 상술한범위내로사용하는것이 좋다.  The benzoxazine resin may be used in an amount of 2 to 15% by weight based on the total weight of the entire binder so that sufficient curing of the bismaleimide resin contained in the binder can be induced. At this time, if the benzoxazine resin is contained in an excessive amount, the curing reaction rate of the resin composition may be delayed more than necessary and the process efficiency may be lowered. Accordingly, it is preferable that the benzoxazine resin is contained in an amount of 15% by weight or less based on the total weight of the binder. However, if the content is too small, the effect as a desired curing agent can not be exhibited, so that the chemical resistance and the solubility can not be improved.
한편, 상기 일 구현예의 열경화성 수지 조성물은 상기 바인더 성분과 함께고무계성분을포함할수있다.  Meanwhile, the thermosetting resin composition of one embodiment may include a rubber component together with the binder component.
본 발명은 바인더와 함께 특정 고무계 성분을 일정 비율로 포함함으로써， 상기 금속박막코팅용 열경화성 조성물은 레오미터 최저 점도 구간이 90 내지 180° (:의 범위에서 3500 크 이하의 복소 점도 조건을 만족하며， 상기 복소 점도 조건의 하한은 크게 한정되는 것은 아니나, 예를 들어 100
Figure imgf000014_0001
500
Figure imgf000014_0002
이상일수있다. The thermosetting composition for a metal thin film coating according to the present invention comprises a binder and a specific rubber component in a predetermined ratio so that the rheometer minimum viscosity range satisfies the complex viscosity condition of from 90 to 180 ° (: Although the lower limit of the complex viscosity condition is not particularly limited, for example, 100
Figure imgf000014_0001
500
Figure imgf000014_0002
Or more.
구체적으로， 상기 복소 점도 조건을 만족하게 하는 화합물은 스티렌 부타디엔계 고무， 네오프렌계 고무, 니트릴계 고무, 부틸계 고무, 부타디엔계 고무， 에틸렌프로필렌계 고무, 실리콘계 고무， 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종 이상의 고무계 성분일 수 있다. 더 바람직하게 , 상기 고무계성분은부타디인계 고무, 실리콘계 고무및 아크릴계 고무로이루어진군에서 선택된 1종이상일수있다.  Specifically, the compound that satisfies the above-mentioned complex viscosity condition is a compound composed of a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a butadiene rubber, an ethylene propylene rubber, a silicone rubber, a urethane rubber and an acrylic rubber Based rubber component. 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 100중량부에 대해스티렌부타디엔계 고무， 네오프렌계 고무， 니트릴계고무， 부틸계 고무， 부타디엔계 고무， 에틸렌프로필렌계 고무， 실리콘계 고무， 2019/117574 1»（：1^1{2018/015649 The rubber-based component according to the present invention may further contain at least one member selected from the group consisting of styrene butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, 2019/117574 1 »(: 1 ^ {2018/015649
우레탄계 고무및 아크릴계 고무로이루어진군에서 선택된 1종이상의 고무계 성분 5내지 20중량부이하로포함할수있다. Based rubber component and 5 to 20 parts by weight of a rubber-based component selected from the group consisting of urethane rubber and acrylic rubber.
바람직하게, 상기 고무계성분은상기 바인더 수지 100중량부에 대해， 5 내지 15 중량부 혹은 5 내지 10 중량부를 포함할 수 있다. 상기 고무계 성분의 함량이 5 중량부 미만이면 수지의 흐름성이 너무 많아 두께 편차가 증가되는 문제가 있고， 20 중량부를 초과하면 흐름성이 너무 적어 패턴 채움성이 떨어지는 문제가 있다. 이때， 흐름성 및 패턴 채움성을 향상시키기 위한고무계성분의 최적비는， 상기 바인더 수지 100중량부에 대해 5내지 10 중량부일수있다.  Preferably, the rubber component may include 5 to 15 parts by weight or 5 to 10 parts by weight based on 100 parts by weight of the binder resin. If the content of the rubber component is less than 5 parts by weight, there is a problem that the flowability of the resin is too large to increase the thickness variation. If the content is more than 20 parts by weight, the flowability is too small and the pattern filling property is poor. At this time, the optimum ratio of the rubber component for improving flowability and pattern filling property may be 5 to 10 parts by weight based on 100 parts by weight of the binder resin.
상기 고무계 성분중， 상기 부타디엔계 고무는 말단기가히드록시기로 치환된 부타디엔 반복단위; 또는 아크릴기를 포함하는 부타디엔 반복단위; 또는 에폭시기를 포함하는 부타디엔 반복단위를 포함하고 중량평균분자량이 I X 103내지 5 ñ< 104인공중합체를포함할수있다. 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 an butadiene repeating unit containing an epoxy group and having a weight average molecular weight of IX 10 3 to 5 <<10 4 .
또한， 상기 실리콘계 고무는 에폭시기 또는 폴리에테르 변성 실리콘 반복단위: 또는 말단기가 아민기 또는 에폭시기로 치환된 실리콘 반복단위를 포함하고 중량평균분자량이 I X 103 내지 5>< 104 인 공중합체를 포함할 수 있^^ In addition, the silicone rubber has an epoxy group or a polyether-modified silicone repeating unit: or terminal groups comprise a copolymer comprising a silicone repeating units substituted, and having a weight average molecular weight of IX 10 3 to 5><4 of 10 with an amine group or an epoxy group Can ^ ^
상기 아크릴계 고무는， 수지 조성물에 포함되어 낮은 경화 수축율 특성을나타낼수있다. 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 탄성을가지는분자구조를가지고있는것을사용한다.  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>< 104 내지 65>< 104이며, 상기 범위를 벗어나면 흐름성이 부족하거나과다할수있다. 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 in the range of 30 &lt; 10 4 to 65 < 10 4 , and if it is out of the above range, the flowability may be insufficient or excessive.
또한， 상기 스티렌부타디엔계 고무， 네오프렌계 고무， 니트릴계 고무, 2019/117574 1»（：1^1{2018/015649 The styrene-butadiene rubber, neoprene rubber, nitrile rubber, 2019/117574 1 »(: 1 ^ {2018/015649
부틸계 고무， 에틸렌프로필렌계 고무, 우레탄계 고무의 종류는크게 제한되지 않으며, 이 분야에 잘알려진물질이사용될수있다. The types of 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 중진제를포함할 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 heavy stabilizer. 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.
상기 무기 충진제의 함량은바인더 수지 100중량부에 대하여 160내지 350 중량부일 수 있다. 구체적으로， 상기 무기 충진제는 바인수 수지 100 중량부에 대하여 200내지 250중량부일수있다.  The content of the inorganic filler may be 160 to 350 parts by weight based on 100 parts by weight of the binder resin. Specifically, the inorganic filler may be 200 to 250 parts by weight based on 100 parts by weight of the resin.
상기 무기 충진제의 평균 입경은 0.1 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 to 100 . 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 일 구현예의 열경화성 수지 조성물은무기 중진제 분리상이나 수지로 이루어진 수지 분리상과 같은 분리상을 형성하지 않고， 무기 충진제와 수지가 골고루 혼합되어 분산상을 형성할 수 있다. 이에 따라， 상기 무기 충진제가 고함량으로 충진된 상태에서도 동박에 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 of the embodiment can form a dispersed phase by mixing the inorganic filler and the resin evenly without forming a separation phase such as an inorganic fine powder 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 coated on the copper 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 2019/117574 1»（：1^1{2018/015649 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, In the army 2019/117574 1 »(: 1 ^ {2018/015649
선택된 1종이상의 첨가제를더 포함할수있다. And may further include one or more selected additives.
구체적으로， 상기 일 구현예의 열경화성 수지 조성물은 필요에 따라 용제를 첨가하여 용액으로사용할수 있다. 상기 용제로는수지 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 이용할수도 있다. 또한상기 용매의 함량은 열경화성 수지 조성물의 제조시 점도조절을위해 적절하게사용할수있는바， 크게 제한되지 않는다. 또한본 발명은 열경화성 수지 조성물고유의 특성을손상시키지 않는 한, 기타열경화성 수지, 열가소성 수지 및 이들의 올리고머 및 엘라스토머와 같은 다양한 고분자 화합물, 기타 난연성 화합물 또는 첨가제를 더 포함할 수도있다. 이들은통상적으로사용되는것으로부터 선택되는것이라면특별히 한정하지 않는다. 예를 들어 첨가제로는 자외선돕수제, 산화방지제, 광중합개시제， 형광증백제， 광증감제， 안료, 염료， 증점제， 활제， 소포제， 분산제， 레벨링제， 광택제 등이 있고, 목적에 부합되도록 혼합하여 사용하는 것도가능하다.  Specifically, the thermosetting resin composition of one 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 or the like can be used. Mixed solvents used in combination of two or more kinds may also be used. Further, the content of the solvent is not limited so long as it can be suitably used for viscosity control in the production of the thermosetting resin composition. 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 not particularly limited as long as they are selected from commonly used ones. Examples of the additive include UV assistant agents, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, pigments, dyes, thickeners, lubricants, defoamers, dispersants, leveling agents and brighteners. It is also possible to use.
이러한 구성을 갖는 본 발명의 일 구현예에 따른 열경화성 수지 조성물은레오미터 최저 점도구간이 90내지 180 의 범위에서 350아¾.3이하 혹은 2000
Figure imgf000017_0001
이하의 복소점도조건을만족할수있다. The thermosetting resin composition according to one embodiment of the present invention having such a constitution has a rheometer minimum viscosity range of 350 to 350 in the range of 90 to 180. Less than 3 or 2000
Figure imgf000017_0001
The following complex viscosity conditions can be satisfied.
즉， 패턴을채우는데 적합한복소점도를 3500
Figure imgf000017_0002
이하라고가정할때， 본 발명에서 제시하는수지 조성물의 경우, 상기 점도조건을 만족하는온도 구간이 90 내지 1801：로 매우 넓다. 따라서， 적층 공정 구간 내 흐름성이 높아서 수지 적층 후 빈 공간이 발생되지 않아 패턴 채움성이 우수해지는 것이다. That is, the complex viscosity suitable for filling the pattern is 3500
Figure imgf000017_0002
Or less, the temperature range satisfying the above viscosity condition is very wide in the range of 90 to 1801: in the case of the resin composition proposed in the present invention. 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 확보할수있어 미세 패턴을용이하게 채울수있다.  Since the thermosetting resin composition of the present invention has the above resin flow property, it is possible to make a metal laminate using a metal thin film or to ensure flowability during a build-up process, thereby easily filling a fine pattern.
즉， 본발명의 열경화성 수지 조성물은， 최소 점도를유지하는구간을 넓힐 수 있는 경화에 따른특정 값의 최소복소 점도조건을 나타내어， 패턴 매립시 보이드（\¾ ）가생기지 않아패턴 채움성을향상시키는효과를 제공할 2019/117574 1»（：1^1{2018/015649 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 (\ ¾) during pattern embedding, To provide the effect 2019/117574 1 »(: 1 ^ {2018/015649
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. ＜금속적층체＞ . Further, when the thermosetting resin composition of the present invention is used, it is possible to provide a metal laminate having a reduced thickness and improved stability and storage through at least one surface of the metal thin film. &Lt; Metal laminate &
다른구현예에 따르면， 금속박막의 적어도일면에 상기 열경화성 수지 조성물이 경화된 수지 코팅층을포함하며， 상기 수지 코팅층은, 에폭시 수지, 시아네이트 에스터 수지， 비스말레이미드 수지 및 벤즈옥사진 수지를 포함한 바인더 수지와 스티렌 부타디엔계 고무, 네오프렌계 고무， 니트릴계 고무, 부틸계 고무， 부타디엔계 고무， 에틸렌프로필렌계 고무, 실리콘계 고무， 우레탄계 고무및 아크릴계고무로이루어진군에서 선택된 1종이상의 고무계 성분간의 경화물; 및 상기 경화물사이에 분산되어 있는충진제;를포함하는 금속적층체가제공될수있다.  According to another embodiment, the metal thin film includes a resin coating layer in which the thermosetting resin composition is cured on at least one side of the metal thin film, and the resin coating layer is composed of a binder including an epoxy resin, a cyanate ester resin, a bismaleimide resin, A cured product of at least one rubber component selected from the group consisting of a resin and a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a butadiene rubber, an ethylene propylene rubber, a silicone rubber, a urethane rubber and an acrylic rubber; And a filler dispersed between the cured products.
또， 다른 구현예 따르면， 상기 열경화성 수지 조성물을 금속 박막의 적어도일면에 코팅하는단계를포함하는금속적층체의 제조방법이 제공될수 있다.  According to another embodiment, 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 may be provided.
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.
구체적으로, 본 발명에서는 상기 열경화성 수지 조성물의 경화물을 포함하는수지 코팅 금속적층체가제공된다.  Specifically, in the present invention, a resin-coated metal laminate comprising a cured product of the thermosetting resin composition is provided.
상술한바대로, 본발명은수지의 흐름성과패턴 채움성이 우수한수지 조성물을 바니시 형태로 제조하고， 이를 금속 박막에 직접 코팅하는 간단한 방법으로， 우수한 열적 및 기계적 물성을 나타내는 금속 적층체를 제공할수 있다. 상기 과정에 따라충진제를포함한열경화성 수지가금속박막의 적어도 일면에 경화물로형성될수있고， 상기 경화물내에는충진제가고르게분산된 형태가될수있다.  As described above, the present invention can provide a metal laminate which exhibits excellent thermal and mechanical properties by a simple method of 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 . 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.
또한, 상기 금속적층체의 제조방법은상기 금속박막의 적어도일면에 코팅된열경화성 수지 조성물을경화하는단계;를더 포함할수있다. 그리고， 2019/117574 1»（：1^1{2018/015649 In addition, the method for manufacturing the metal laminate may include curing the thermosetting resin composition coated on at least one surface of the metal thin film. And, 2019/117574 1 »(: 1 ^ {2018/015649
상기 열경화성 수지 조성물의 경화단계 후에는 필요에 따라잘 알려진 건조 공정이 더 수행될수있다. After the curing step of the thermosetting resin composition, a well-known drying process can be further performed if necessary.
본 발명에서는 수지의 경화 반응을 의도적으로 지연시켜 적층 공정 온도구간내최소점도가유지되는구간을길게한다.  In the present invention, the curing reaction of the resin is intentionally delayed to lengthen the section in which the minimum viscosity in the temperature range of the lamination process is maintained.
바람직하게， 열경화성 수지 조성물을 경화하는 단계에서， 상기 경화조건은 180내지 250 의 온도에서 1내지 4시간동안진행될수있다. 또한， 상기 열경화성 수지 조성물을금속박막에 코팅하는 방법은크게 제한되지 않으며, 이 분야에 잘알려진코팅 방법이사용될수있다.  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.
일례로, 본 발명의 열경화성 수지 조성물을 코터 장치에 넣고， 금속 박막의 적어도 일면에 일정 두께로 코팅하는 방법이 사용될 수 있다. 상기 코터 장치는 콤마 코터， 블레이드 코터， 립 코터， 로드 코터， 스퀴즈 코터, 리버스코터, 트랜스퍼 롤코터， 그라비아코터 또는분무코터 등을 이용할 수있다.  For example, the thermosetting resin composition of the present invention may be put into a coater apparatus and coated on at least one surface of the metal thin film to a predetermined thickness. The above-mentioned coater apparatus may be a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater or a spray coater.
또한， 흐름성 평가를 위해 캐리어 필름을 사용할 수 있으며， 상기 캐리어 필름으로는 폴리에틸렌테레프탈레이트 肝）， 폴리에스테르 필름， 폴리이미드 필름， 폴리아미드이미드 필름, 폴리프로필렌 필름, 폴리스티렌 필름등의 플라스틱 필름을사용할수있다.  Further, a carrier film can be used for the flowability evaluation, and as the carrier film, a plastic film such as a polyethylene terephthalate liver), a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film can be used .
한편, 상기 코팅에 사용되는 바니시는 열경화성 수지 조성물에 용제를 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， 메틸셀로솔브， 부틸셀로솔브같은알리파틱 알코올등이 있다.  On the other hand, the varnish used for the coating may be a state in which a solvent is added to the thermosetting resin composition. 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, And aliphatic alcohols such as sorb and butyl cellosolve.
상기 금속박막은 동박; 알루미늄박; 니켈, 니켈-인， 니켈-주석 합금, 니켈-철합금， 납또는납-주석 합금을중간층으로하고, 이 양면에 서로다른 두께의 구리층을포함하는 3층구조의 복합박; 또는알루미늄과동박을복합한 2층구조의 복합박을포함할수있다.  Wherein the metal thin film comprises: a copper foil; Aluminum foil; A three-layered composite foil having an intermediate layer of nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead or lead-tin alloy and having copper layers of different thicknesses on both sides; Or a composite foil of a two-layer structure in which aluminum and a copper foil are combined.
바람직한 일 구현예에 따르면, 본 발명에 이용되는 금속박막은 동박 또는알루미늄박이 이용되고， 약 2내지 200 _의 두께를갖는것을사용할수 2019/117574 1»（：1^1{2018/015649 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 2019/117574 1 »(: 1 ^ {2018/015649
있지만, 그 두께가 약 2 내지 35 /페인 것이 바람직하다. 보다 바람직하게， 상기 금속박막으로는 동박을 사용한다. 또한， 본 발명에 따르면 금속박막으로서 니켈, 니켈-인， 니켈-주석 합금, 니켈-철 합금, 납， 또는 납-주석 합금등을중간층으로하고, 이의 양면에 0.5내지 15쌔의 구리층과 5 10 내지 300 ，의 구리층을 설치한, 3층 구조의 복합박 또는 알루미늄과 동박을복합한 2층구조복합박을사용할수도있다. However, the thickness is preferably about 2 to 35 / pane. More preferably, a copper foil is used as the metal thin film . According to the present invention, an intermediate layer of nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead or lead-tin alloy is used as the metal thin film. A composite foil of a three-layer structure in which 10 to 300 copper layers are 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 경화된수지 코팅층을포함함으로써, 종래 대비 넓은 온도구간에서 최소복소 점도조건을만족할수 있고， 특히 흐름성 및 패턴 10 채움성이 우수한금속적층체를제공할수있다.  According to the above-described 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 temperature range, It is possible to provide a metal laminate having excellent properties.
이때， 상기 금속 적층체에서 수지 코팅층의 두께는 5 내지 90 判， 바람직하게는 5^ 내지 30 일 수 있다. 이러한 경화물은 금속박막상에 두께가 얇게 형성되어도， 금속박막에 대하여 우수한 열적， 기계적 물성을 나타내도록할수있다.  At this time, the thickness of the resin coating layer in the metal laminate may be 5 to 90, preferably 5 to 30. Such a cured product can exhibit excellent thermal and mechanical properties for a metal thin film even if it is formed thin on the metal foil.
15 또한， 본 발명의 금속 적층체는 경화후 수지의 유리전이온도 0^）는
Figure imgf000020_0001
15 Furthermore, in the metal laminate of the present invention, the glass transition temperature of the resin after curing is 0 &lt;
Figure imgf000020_0001
금속박막의 유전특성 （此/아）은 3.3八）.006로우수하다.  The dielectric properties of the metal thin films are 3.3.
또한, 본 발명은기존 단분자계열로 이루어진 수지 코팅 동박에 비해 20 동일 두께에서 비교 시 패턴 채움성이 더 우수하며, 경시 변화 테스트에서 상온안정성이 상대적으로더 우수하다.  In addition, the present invention is more excellent in pattern filling at a comparable thickness of 20 than the conventional monomolecular resin-coated copper foil, and is more stable at room temperature in the aging test.
상술한 바대로， 다른 구현예에 따르면, 상기 금속 적층체가 1매 이상 적층된금속박적층판이 제공될수있다.  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.
이러한 경우 금속판 적층판은 금속 박막을 더 포함할수 있다. 예를 25 들어 , 금속박막은금속적층체의 수지층이 맞다을수있다.  In this case, the metal plate laminate may further include a metal thin film. For example, the metal thin film 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 （ ）을 완전 에칭 또는 부분에칭을통한패턴화를시킨후, 그위에 금속판적층체의 수지 코팅층이 30 금속박막에 맞닿게하여， 제 2층을적층하는방법으로진행될수있다. 2019/117574 1»（：1^1{2018/015649 In addition, when providing the plate laminate, the metal thin film can be used in the production after the etching pattern and stacked. For example, when the second layer is laminated on the first layer, which is a metal thin film, the metal thin film (mainly the first layer) is patterned through complete etching or partial etching, and then the resin The coating layer is brought into contact with the metal thin film 30, and the second layer is laminated. 2019/117574 1 »(: 1 ^ {2018/015649
따라서, 이렇게 제조된 금속 적층체는 1매 이상 적층된 금속 적층판 형태로 제공될 수 있다. 바람직하게， 상기 금속 적층판은 금속 적층체에 형성된 수지층이 서로 마주하도록 적층된， 2매의 금속 적층체를 포함할 수 있다. 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, wherein the resin layers formed on the metal laminates are stacked so as to face each other.
더욱이， 본발명은상기 금속적층체를이용하여, 1매 이상으로적층한 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 회로가공은 일반적인 양면 또는다층 인쇄 회로 기판제조 공정에서 행해지는방법을적용할수있다.  Further, the present invention can be used for manufacturing a double-sided or multi-layer printed circuit board after stacking one or more sheets by using the metal laminate. In the present invention, the metal-clad laminate may be subjected to a circuit processing to produce a double-sided or multi-layer printed circuit board. The circuit processing may 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 모두적용가능한수지가코팅된 금속박막을제공할수있다.  As described above, according to the present invention, by using the above-mentioned thermosetting resin composition, it is possible to provide a metal foil film coated with a resin applicable to various printed circuit boards in various fields.
【발명의 효과】 【Effects of the Invention】
본 발명의 금속 박막 코팅용 열경화성 수지 조성물은 바인더를 구성하는 수지 종류와 이들의 혼합 비율을 최적화하고, 고무계 성분을 소량 사용함으로써, 수지의 경화 반응을 의도적으로 지연시킬 때 종래보다 적층 공정 온도구간내 흐름성이 높고패턴 채움성이 우수하게 하는효과를제공할 수 있다. 특히， 본발명에 따르면， 적층소재의 두께가얇아도 레오미터 최저 점도구간이 기존보다넓기 때문에， 패턴 채움성이 향상되어 기판의 박막화는 물론반도체소자의 신뢰성 및성능을향상시킬수있다. 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 use a small amount of the rubber component to intentionally retard the curing reaction of the resin, It is possible to provide an effect that flowability is high and pattern filling property is excellent . Particularly, according to the present invention, even if the thickness of the laminated material is thin, since the rheometer minimum viscosity range is wider than that of the prior art, 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.
또한， 본 발명은 경화 후 수지층의 열적 및 기계적 물성이 우수하고 유전 특성도우수한금속박막을 제공하는 효과가 있다. 즉 본 발명의 수지 조성물을이용하면, 유리 섬유를사용해서 프리프레그를제조해야하는방법을 사용하지 않아도, 간단한 방법으로 금속박에 직접 수지 조성물의 코팅을 진행하여 두께가얇은금속적층체를제공할수있다. 더욱이， 본발명은경화 후 수지의 유리전이온도가 상대적으로 높으며, 유전특성도 우수한 금속 적층체를 제공할 수 있다. 상기 금속 박막은 1매 이상으로 적층하여 전자 기기의 박막화에사용하는금속적층판을제공할수있다. \¥0 2019/117574 1»（江/10{2018/015649 In addition, the present invention has the effect of providing a metal thin film having excellent thermal and mechanical properties of the resin layer after curing and excellent dielectric properties. That is, when the 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 producing a prepreg using glass fiber, so that a thin metal laminate can be provided. Moreover, the present invention has a glass transition temperature of the resin is relatively high, after hardening, the dielectric properties can be provided an excellent metal laminate. The metal thin film may be laminated by one or more sheets to provide a metal laminate used for thinning an electronic device. \ ¥ 0 2019/117574 1 »(Jiang / 10 {2018/015649
【도면의 간단한설명】 BRIEF DESCRIPTION OF THE DRAWINGS
도 1은본발명의 실시예 1및 비교예 1, 2의 흐름성 및 패턴 채움성을 확인하기 위한레오미터 커브를나타낸것이다. 【발명을실시하기 위한구체적인내용】  Fig. 1 shows a rheometer curve for confirming flowability and pattern fillability of Example 1 of the present invention and Comparative Examples 1 and 2. Fig. 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. <실시예 1내지 6>  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. &Lt; Examples 1 to 6 >
수지 조성물이 코팅된동박적층체제조  A copper-clad laminate structure coated with a resin composition
(1) 열경화성 수지 조성물의 제조  (1) Production of thermosetting resin composition
다음 표 1과 같이， 에폭시 수지, 시아네이트 에스터 등 수지를 시클로핵사논 용매에 녹여 바니시를 제작하였다. 경화반응을 조절하기 위해, 상기 바니시에 벤즈옥사진 및 비스말레이미드수지를첨가하였다. 또한기계적 강도향상을위해， 상기 바니시에 실리카무기 충진제를첨가했다.  As shown in the following Table 1, varnishes were prepared by dissolving a resin such as an epoxy resin or a cyanate ester in a cyclohexanone solvent. To adjust the curing reaction, benzoxazine and bismaleimide resin were added to the varnish. Further, in order to improve the mechanical strength, a silica inorganic filler was added to the varnish.
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.
회전 증발 농축기 (rotary evaporator)를 사용해서 상기 코팅 용액의 점도조절및 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，, Mi tsui사제조)의 일면에 코팅 (코팅 두께: 16· )한 후， 230 °C 및 35 kg/cin의 조건으로 200 분간 경화시켰다. 이어서, 17 父 15cm 크기로 재단하여 수지 코팅된 동박 적층체 샘플을제작하였다.  The coating solution was coated (coating thickness: 16 占 퐉) on one side of a copper foil (thickness 2, manufactured by Mi Tsui) with a comma coater and then cured for 200 minutes at 230 占 폚 and 35 kg / cin. Subsequently, samples were made of resin-coated copper-clad laminate samples by cutting to size of 17 cm in height of 17 feet.
<비교예 1내지 3> &Lt; Comparative Examples 1 to 3 >
수지 조성물이 코팅된동박제조  Copper foil coated with resin composition
(1) 열경화성 수지 조성물의 제조 2019/117574 1»（：1^1{2018/015649 (1) Production of thermosetting resin composition 2019/117574 1 »(: 1 ^ {2018/015649
다음 표 2의 성분과 시클로핵사논 용매를 이용하여 바니시를 제조하였다. 이때， 아크릴계 고무 A 또는 아크릴계 고무 B를 사용하지 않는 경우를 비교예 1로 하였고， 그 함량 범위가 본원 범위를 벗어나는 경우를 비교예 2내지 4로하였다. Varnishes were prepared using the components of the following Table 2 and cyclohexanone solvents. In this case, the case where the acrylic rubber A or the acrylic rubber B was not used was designated as Comparative Example 1, and the case where the content of the acrylic rubber A or the acrylic rubber B deviated from the present invention was designated as 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.
회전 증발 농축기 (rotary evaporator)를 사용해서 상기 코팅 용액의 점도조절및 탈포를진행했다.  The viscosity of the coating solution was adjusted and defoamed using a rotary evaporator.
(2) 열경화성 수지 조성물이 코팅된금속박막제조  (2) Production of metal thin film coated with thermosetting resin composition
콤마코터로 상기 코팅 용액을 동박 (두께 2pm Mi t sui사 제조)에 코팅 (코팅 두께 : 16um )한 후， 230 °C 및 35 kg/cuf의 조건으로 200 분간 경화시켰다. 이어서, 17 x 15cm크기로 재단하여 수지 코팅 동박 샘플을 제작하였다. <비교예 4>  The coating solution was coated on a copper foil (thickness: 2 pm, manufactured by Mi-sui) with a comma coater (coating thickness: 16 μm) and cured for 200 minutes at 230 ° C and 35 kg / cuf. Subsequently, the sample was cut into a size of 17 x 15 cm to prepare a resin-coated copper foil sample. &Lt; Comparative Example 4 &
수지 조성물이 섬유 기재에 함침된 프리프레그와 일체화된 동박을 포함한적층판제조  Production of a laminated board including a copper foil in which a resin composition is integrated with a prepreg impregnated in a fiber substrate
(1) 열경화성 수지 조성물의 제조  (1) Production of thermosetting resin composition
하기 표 2와같은비율로수지를유기 용매에 녹여 바니쉬로 만든후， 24시간이상교반하였다.  The resin was dissolved in an organic solvent at a ratio shown in Table 2 below to make a varnish, which was then stirred for more than 24 hours.
(2)프리프레그및동박적층판의 제조  (2) Preparation of prepreg and copper-clad laminate
상기 교반한 바니쉬를 직조된 유리 섬유 ½1크33 크 八두께 1¾®， 쇼33 ( 크드사제조)에 함침시킨후， 1701：의 온도에서 2~5분간열풍건조하여 16^■의 프리프레그를제조하였다. Said a stirring varnish glass fabric ½1 greater than 33 greater八thickness 1¾ ®, shows 33 was impregnated in (greater deusa, Ltd.), 1701: 16 ^ and dried 2-5 minutes hot air at a temperature of prepreg manufacture him of ■ Respectively.
이후, 동박을 위 아래로 적층하여 동박적층판을 제작하였다. 즉， 상기에서 제조된 프리프레그 양면에 동박 (두께 2_, ¾1 3 사 제조)을 위치시켜 적층하고， 230
Figure imgf000023_0001
및 35 1¾/011의 조건으로 200분간 경화시켜 동박 적층판을제조하였다. 【표 1] 2019/117574 1»（：1/10公018/015649 Thereafter, the copper foil was stacked up and down to produce a copper clad laminate. That is, a copper foil (made of 2 -in- 3 -layer and 3 -in- 3 ) was placed on both surfaces of the prepared prepreg,
Figure imgf000023_0001
And 35 1 ¾ / 0 11 for 200 minutes to prepare a copper clad laminate. [Table 1] 2019/117574 1 »(: 1/10 公 018/015649
Figure imgf000024_0001
Figure imgf000024_0001
【표 2] 2019/117574 1»（그1^1{2018/015649 [Table 2] 2019/117574 1 »(1 ^ {2018/015649
Figure imgf000025_0001
Figure imgf000025_0001
주） 비교예 4는 유리섬유 기재의 중량을 제외한 레진들만의 중량부 구성비를 나타냄 Note) Comparative Example 4 shows the composition ratio of only the resin excluding the weight of the glass fiber substrate
에폭시 수지 : 나프탈렌계에폭시 수지 어므4710, 1）1（：사） Epoxy resin: naphthalene-based epoxy resin 4710, 1) 1 (g)
5 시아네이트 에스터 수지 비스페놀형 시아네이트 수지 犯쇼-30003, 5-cyanate ester resin Bisphenol-type cyanate resin culprit -30003,
［乂 크사） [Nucleus]
시아네이트에스터 수지 노볼락형 시아네이트수지 （肝 ， 크사） 비스말레이미드-트리아진수지: 8¾11-2300, 쇼사 2019/117574 1»(：1^1{2018/015649 Cyanate ester resin novolak cyanate resin (liver, xanthate) bismaleimide-triazine resin: 8,411-2300, Shosa 2019/117574 1 »(: 1 ^ {2018/015649
벤즈옥사진수지: 페놀프탈레인벤즈옥사진수지 (XU8282, Hunstman사) BT수지 : Nanozine 600, Nanokor사 Benzoxazine resin: phenolphthalein benzoxazine resin (XU8282, Hunstman) BT resin: Nanozine 600, Nanokor company
아크릴계 고무 SG-P3-PT197 (Mw 65X 104, Tg: 12 °C ) , Nagase Chemtex Coporat ion Acrylic rubber SG-P3-PT197 (Mw 65X 10 4, Tg: 12 ° C), Nagase Chemtex Coporat ion
아크릴계 고무 B: SG-P3-MW1 (Mw 30X 104, Tg： 12 °C ) , Nagase ChemtexAcrylic rubber B: SG-P3-MW1 (Mw 30 × 10 4 , Tg: 12 ° C), Nagase Chemtex
Coporat ion Coporate ion
실리콘계고무: AY42-119, Dow Corning  Silicone rubber: AY42-119, Dow Corning
부다디엔고무 A: B-1000, Nippon Soda  Buda diene rubber A: B-1000, Nippon Soda
부타디엔고무 B: RIC0N181, Cray Val ley  Butadiene rubber B: RIC0N181, Cray Valey
Fi l ler A： 메타아크릴실란처리된슬러리 타입의 필러， 평균입경 0.5um Fi l ler A: a slurry type filler with methacryl silane treatment, average particle diameter 0.5um
(SC2050MTM, Admatechs사) (SC2050MTM, Admatechs)
＜실험예＞ <Experimental Example>
실시예 및 비교예에서 제조한 동박 적층판에 대해 다음의 방법으로 물성을측정하였다:  Physical properties of the copper clad laminates prepared in Examples and Comparative Examples were measured by the following methods:
1. 점도및흐름성 분석 1. Viscosity and Flowability Analysis
온도에 따른수지 층의 점도및 흐름성을관찰하기 위해, 실시예 1및 비교예 1의 코팅액을 PET기재에 코팅한후， 라미네이터를통해 적층하여 적정 두께의 샘플을 만들어서 레오미터 점도를 측정했다 (온도에 따른 점도 측정 조건, 승온속도 5도/ min, 주파수: 10Hz) .  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-dependent viscosity measurement conditions, rate of temperature rise: 5 degrees / min, frequency: 10 Hz).
또한， 점도 및 흐름성은 패턴 적층 테스트에서 빈 공간 (Void) 생성 유무를 통해 확인하였다. 패턴 적층 테스트를 위해， 동박 두께 10um, 전체 면적의 약 60%가에칭되어 있는패턴을가진동박적층판 (CCL)을사용하여 그 위에 상기 실시예 또는 비교예를 통해 얻은 수지 동박 코팅 샘플 (또는 프리프레그)을 적층하였다. 보이드 (void)나 디라미네이션 (de laminat ion)이 발생하지 않은 경우 'OK' , 보이드 (void)나 디라미네이션 (delaminat ion)이 발생한 경우 로 평가하였다. 보이드 생성 유무 관찰 결과， 실시예 1은 빈공간생성이 발생하지 않았으나， 비교예 1및 2는보이드가발생되었다. 도 1은본발명의 실시예 1및 비교예 1， 2의 흐름성 및 패턴 채움성을 2019/117574 1»（：1^1{2018/015649 Viscosity and flowability were also confirmed by the presence or absence of void formation in the pattern stacking test. For the pattern stacking test, a copper-clad laminate (CCL) having a pattern in which a copper foil thickness of 10 mu m and a total area of about 60% of the total area was etched was used and the resin-coated copper clad samples (or prepreg ). 'OK' when no void or delamination occurred, and a case where void or delaminat ion 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 Examples 1 and 2. 1 shows the flowability and pattern filling properties of Example 1 of the present invention and Comparative Examples 1 and 2 2019/117574 1 »(: 1 ^ {2018/015649
확인하기 위한레오미터 커브를나타낸것이다. It shows the rheometer curve for confirmation.
도 1의 결과에서 보면， 패턴을채우는데 적합한복소점도를 3500 Pa . s 이하라고가정할 때, 본 발명의 실시예 1은 비교예 1 및 2에 비해， 레오미터 최저 점도 구간 (window)이 90 °C 내지 180°C로 매우 넓어져 흐름성 및 패턴 채움성이 더 유리함을확인할수있다. 1, the complex viscosity suitable for filling the pattern is 3500 Pa. s, the first embodiment of the present invention has a rheometer minimum viscosity window of 90 ° C to 180 ° C, which is much wider than those of Comparative Examples 1 and 2, You can see the advantage.
그러나, 상기 온도 구간에서 비교예 1의 복소점도는 너무 높아 흐름성이 매우불량하여， 패턴을채우기 어려웠다. 또한， 상기 온도구간에서 비교예 2는 복소점도가 3700 Pa. s으로 매우 높아 역시 패턴 불량 (Void)가 다수발생하였다.  However, in this temperature range, the complex viscosity of Comparative Example 1 was too high and the flowability was very poor, making it difficult to fill the pattern. In the temperature range of Comparative Example 2, the complex viscosity was 3700 Pa. s, and a large number of pattern defects (voids) were also generated.
2. 경시 변화 2. Over time variation
경시 변화를 위해, 3개월 간실시예 및 비교예의 수지 조성물에 대해 상온/냉장보관후패턴 테스트를통해 경시 변화를확인하였다. 경시 변화가 일어나 수지의 경화율이 증가되어 흐름성이 줄어들 경우, 보이드의 발생 가능성이 높아진다. 3개월 간상온/냉장보관후패턴 테스트 결과, 실시예의 경우， 보이드가 없는 것을 관찰하였고 이를 통해 경시 변화에 적은 것을 확인하였다.  For the aging change, the resin compositions of Examples and Comparative Examples for 3 months were subjected to pattern test after storage at room temperature / refrigeration to observe the change over time. If the curing rate of the resin increases with the passage of time, and the flowability is reduced, the possibility of occurrence of voids increases. As a result of the pattern test after 3 months of storage at room temperature / refrigeration, it was observed that there was no void in the examples.
3. 경화후수지 물성 3. Resin properties after curing
경화후수지의 물성을분석하기 위해， 상기 실시예의 수지 코팅 동박 In order to analyze the physical properties of the resin after curing, the resin-
2매를 이용해서 수지층이 마주하도록 적층하고， 진공 열프레스를 통해 230 °C 및 35 kg/cuf의 조건으로 200분간 경화를 진행하였다. 또한， 비교예 4는 상술한프리프레그를이용한동박적층판을이용하여 실험에사용하였다. Two sheets were stacked so that the resin layer was facing each other, and the curing was performed for 200 minutes under the conditions of 230 ° C and 35 kg / cuf through a vacuum heat press. In addition, Comparative Example 4 was used in the experiment using the above-mentioned prepreg-coated copper-clad laminate.
실험 진행시， 동박을 에칭하여 제거한후, 다음과같은 방법으로수지 층의 열적 (Tg) , 기계적 (Modulus) , 유전 특성 (Dk/Df) 등을 측정하여 그 결과를표 3및 4에 나타내었다. 열적， 기계적 특성은 DSC, TGA DMA, TMA등의 분석 장비를이용하여 측정하였다. 유전특성 측정은 SPDR방식으로 1GHz에서의 Dk,야를구하였다.  (Tg), mechanical modulus, dielectric property (Dk / Df) and the like of the resin layer were measured in the following manner, and the results are shown in Tables 3 and 4 . Thermal and mechanical properties were measured using DSC, TGA DMA, and TMA. The dielectric properties were measured by SPDR method at 1 GHz.
(1)유리전이온도 0½) 2019/117574 1»(：1^1{2018/015649 (1) Glass transition temperature 0 캜) 2019/117574 1 »(: 1 ^ {2018/015649
DMA를이용하여 유리전이온도를측정하였다. The glass transition temperature was measured using DMA.
(2)모듈러스 (Gpa) (2) Modulus (Gpa)
DMA를이용하여 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, S卵 R (spl i t post dielectr ic resonance) 방법으로 1GHz에서의 유전 상수 (Dk) 및 유전 손실 (Df )을측정하여 유전특성 (Dk/Dg)를계산하였다.  Dielectric properties (Dk / Dg) were measured by measuring the dielectric constant (Dk) and dielectric loss (Df) at 1 GHz using the Agi lent E5071B ENA instrument. Respectively.
(4)열팽창계수 (CTE) (4) Coefficient of thermal expansion (CTE)
상기 실시예 및 비교예에서 얻어진 동박 적층판의 동박층을 에칭하여 제거한후, TMA를이용하여 측정하였다. (50 °C 150 °C , 나방향) 【표 3] 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 TMA. (50 ° C at 150 ° C, direction B) [Table 3]
Figure imgf000028_0001
2019/117574 1»(：1/10公018/015649
Figure imgf000029_0002
Figure imgf000028_0001
2019/117574 1 »(: 1/10 公 018/015649
Figure imgf000029_0002
【표 4] [Table 4]
Figure imgf000029_0001
상기 실시예 및 비교예를 통해， 본원 실시예의 유리전이 온도 0¾）는 290도， 유전상수 ）는 3.3, 유전정접은（아） 0.006로측정되었다.
Figure imgf000029_0001
Through the above Examples and Comparative Examples, the glass transition temperature was found to be 290 deg., The dielectric constant was 3.3 and the dielectric loss tangent was 0.006.
또한， 본 발명의 실시예 1 내지 6은 비교예 1 내지 4에 비해， 최소 점도구간의 범위가 넓고, 흐름성이 우수한 것을 패턴 적층 테스트에서의 빈 공간 0 ）생성 유무를통해 확인하였다. In Examples 1 to 6 of the present invention, compared to Comparative Examples 1 to 4, the range of the minimum viscosity range was wide and the flowability was excellent was confirmed through the presence or absence of empty space 0 in the pattern lamination test.

Claims

2019/117574 1»（：1^1{2018/015649  2019/117574 1 »(: 1 ^ {2018/015649
【청구범위】 Claims:
【청구항 11 Claim 11
에폭시 수지， 시아네이트 에스터 수지， 비스말레이미드 수지 및 벤즈옥사진수지를포함한바인더 수지 ;  A binder resin including an epoxy resin, a cyanate ester resin, a bismaleimide resin, and a benzoxazine resin;
고무계성분; 및  Rubber system components; And
무기 충진제를포함하고,  An inorganic filler,
상기 고무계 성분은 스티렌 부타디엔계 고무 , 네오프렌계 고무， 니트릴계 고무， 부틸계 고무， 부타디엔계 고무， 에틸렌프로필렌계 고무, 실리콘계 고무, 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종이상을포함하며，  Wherein the rubber component comprises at least one member selected from the group consisting of a styrene butadiene rubber, a neoprene rubber, a nitrile rubber, a butyl rubber, a butadiene rubber, an ethylene propylene rubber, a silicone rubber, a urethane rubber,
상기 바인더 수지 100 중량부에 대해 상기 고무계 성분은 5 중량부 이상 20중량부이하로포함하고，  The rubber-based component is contained in an amount of 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the binder resin,
레오미터 최저 점도구간이 90내지 180°（：의 범위에서 3500?3.8 이하의 복소점도조건을만족하는， If the rheometer minimum viscosity range is between 90 and 180 ° (3500? 3 . 8 &lt; / RTI &gt;
금속박막코팅용열경화성 수지 조성물.  A thermosetting resin composition for metal thin film coating.
【청구항 2] [Claim 2]
제 1항에 있어서, 상기 고무계 성분은부타디인계 고무， 실리콘계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종 이상인 금속 박막 코팅용 열경화성 수지 조성물.  The 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]
제 1항에 있어서, 상기 고무계 성분은 상기 바인더 수지 100 중량부에 대해 5내지 15중량부를포함하는금속박막코팅용열경화성 수지 조성물.  The thermosetting resin composition according to claim 1, wherein the rubber component comprises 5 to 15 parts by weight based on 100 parts by weight of the binder resin.
【청구항 4] [4]
제 1항에 었어서, 상기 아크릴계 고무는 중량평분자량 30 X 104 내지 65>< 104이며 아크릴산 부틸 유래의 반복 단위와 아크릴로니트릴 유래의 반복 단위; 또는 부타디엔 유래의 반복 단위가 포함되는 아크릴산 에스테르 공중합체; 또는탄소수 2내지 10의 직쇄또는분지쇄의 알킬기 포함아크릴산 2019/117574 1»（：1^1{2018/015649 The acrylic rubber according to claim 1, wherein the acrylic rubber has a weight average molecular weight of 30 X 10 4 to 65 &lt; 10 4, and contains repeating units derived from butyl acrylate and repeating units derived from acrylonitrile; Or an acrylic acid ester copolymer containing a repeating unit derived from butadiene; Or a linear or branched alkyl group-containing acrylic acid having 2 to 10 carbon atoms 2019/117574 1 »(: 1 ^ {2018/015649
알킬 유래의 반복단위를포함하는혼합물인 금속 박막코팅용 열경화성 수지 조성물. Wherein the thermosetting resin composition is a mixture containing an alkyl-derived repeating unit.
【청구항 5】 [Claim 5]
제 1항에 있어서 , 상기 실리콘계 고무는에폭시기 또는폴리에테르변성 실리콘 반복단위: 또는 말단기가 아민기 또는 에폭시기로 치환된 실리콘 반복단위를 포함하고 중량평균분자량이 I X 103 내지 5 ñ< 104 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: in this comprises a silicone repeating units substituted with or terminal groups amine group or an epoxy group and a weight average molecular weight IX 10 3 to 5 ñ <10 4 air A thermosetting resin composition for metal thin film coating.
【청구항 6】 [Claim 6]
제 1항에 있어서， 상기 부타디엔계 고무는 말단기가 히드록시기로 치환된 부타디엔 반복단위; 또는 아크릴기를 포함하는 부타디엔 반복단위; 또는 에폭시기를 포함하는 부타디엔 반복단위를 포함하고 중량평균분자량이 1>< 103내지 5>< 104인 공중합체를포함하는 금속 박막코팅용 열경화성 수지 조성물. [3] The method of claim 1, wherein the butadiene 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 a butadiene repeating unit containing an epoxy group and having a weight average molecular weight of 1 >< 10 3 to 5 > 10 4 .
【청구항 7] [7]
제 1항에 있어서, 상기 바인더는  The method according to claim 1, wherein the binder
에폭시 수지 10 내지 60 중량%， 시아네이트 에스터 수지 20 내지 70 중량%， 비스말레이미드수지 5내지 60 중량%및 벤즈옥사진 수지 2내지 15 중량%를포함하는금속박막코팅용열경화성 수지 조성물.  Wherein the thermosetting resin composition comprises 10 to 60% by weight of an epoxy resin, 20 to 70% by weight of a cyanate ester resin, 5 to 60% by weight of a bismaleimide resin and 2 to 15% by weight of a benzoxazine resin.
【청구항 8】 8.
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, 마이카, 유리 단섬유， 글라스미세 파우더, 및중공글라스로이루어진군에서 선택된 1종이상의 화합물인， 금속박막코팅용열경화성 수지 조성물. 2019/117574 1»（：1^1{2018/015649 The inorganic filler is selected from the group consisting of silica, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined kaolin, Wherein the thermosetting resin composition is at least one kind of compound selected from the group consisting of glass short fibers, glass fine powder, and hollow glass. 2019/117574 1 »(: 1 ^ {2018/015649
【청구항 9] 9]
제 1항에 있어서,  The method according to claim 1,
상기 무기 충진제의 함량은바인더 수지 100중량부에 대하여 160내지 350중량부인금속박막코팅용열경화성 수지 조성물.  Wherein the content of the inorganic filler is 160 to 350 parts by weight based on 100 parts by weight of the binder resin.
【청구항 10】 Claim 10
제 1항에 있어서，  The method according to claim 1,
용제， 자외선흡수제， 산화방지제， 광중합개시제 , 형광증백제， 광증감제， 안료, 염료， 증점제， 활제, 소포제， 분산제， 레벨링제 및 광택제로이루어지는 군에서 선택된 1종 이상의 첨가제를더 포함하는, 금속박막코팅용열경화성 수지 조성물.  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 brightener, a photosensitizer, a pigment, a dye, a thickener, a lubricant, a defoamer, A thermosetting resin composition for thin film coating.
【청구항 11】 Claim 11
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
에폭시 수지, 시아네이트 에스터 수지, 비스말레이미드 수지 및 벤즈옥사진수자를포함한바인더 수지와스티렌부타디엔계 고무， 네오프렌계 고무， 니트릴계 고무, 부틸계 고무， 부타디엔계 고무， 에틸렌프로필렌계 고무, 실리콘계 고무， 우레탄계 고무 및 아크릴계 고무로 이루어진 군에서 선택된 1종이상의 고무계성분간의 경화물; 및  Butadiene rubber, neoprene rubber, nitrile rubber, butyl rubber, butadiene rubber, ethylene propylene rubber, silicone rubber, epoxy resin, cyanate ester resin, bismaleimide resin and benzoxazine resin, A cured product of one or more rubber-based components selected from the group consisting of urethane rubber and acrylic rubber; And
상기 경화물사이에 분산되어 있는충진제;  A filler dispersed among the cured products;
를포함하는금속적층체.  &Lt; / RTI &gt;
【청구항 12】 Claim 12
제 11항에 있어서,  12. The method of claim 11,
상기 수지 코팅층의 두께가 5 내자 90 이고， 유리전이온도 0 ）는 270내지 3101：인금속적층체.  Wherein the resin coating layer has a thickness of 5 angstroms and a glass transition temperature of 0 to 270 to 3101 mm.
【청구항 13】 2019/117574 1»（：1^1{2018/015649 Claim 13 2019/117574 1 »(: 1 ^ {2018/015649
제 1항의 열경화성 수지 조성물을금속 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 14】 14.
5 제 11항의 금속적층체가 1매 이상적층된금속박적층판.  5. The metal-clad laminate according to claim 11, wherein at least one metal laminate is laminated.
PCT/KR2018/015649 2017-12-11 2018-12-11 Thermosetting resin composition for metal thin film coating and metal laminate using same WO2019117574A1 (en)

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KR20100103942A (en) * 2009-03-16 2010-09-29 (주)켐텍 Epoxy resin composition and an adhesive film for a printed wiring boards prepared using the same
KR20130091099A (en) * 2012-02-07 2013-08-16 삼성전기주식회사 Manufacturing method for printed circuit board containing flame retardant insulating layer
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