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WO2019117574A1 - Composition de résine thermodurcissable pour revêtement en couches minces métalliques et stratifié métallique utilisant celle-ci - Google Patents

Composition de résine thermodurcissable pour revêtement en couches minces métalliques et stratifié métallique utilisant celle-ci 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
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2018/015649
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English (en)
Korean (ko)
Inventor
윤민혁
김영찬
민현성
심창보
심희용
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
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/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2019566968A priority Critical patent/JP6938833B2/ja
Priority to US16/606,652 priority patent/US11274218B2/en
Priority to CN201880026892.9A priority patent/CN110573581B/zh
Publication of WO2019117574A1 publication Critical patent/WO2019117574A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : une composition de résine thermodurcissable pour un revêtement en couches minces métalliques présentant une fluidité élevée et une propriété de remplissage de motifs ; et un stratifié métallique utilisant celle-ci.
PCT/KR2018/015649 2017-12-11 2018-12-11 Composition de résine thermodurcissable pour revêtement en couches minces métalliques et stratifié métallique utilisant celle-ci Ceased WO2019117574A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2019566968A JP6938833B2 (ja) 2017-12-11 2018-12-11 金属薄膜コーティング用熱硬化性樹脂組成物およびこれを用いた金属積層体
US16/606,652 US11274218B2 (en) 2017-12-11 2018-12-11 Thermosetting resin composition for coating metal thin film and metal laminate using the same
CN201880026892.9A CN110573581B (zh) 2017-12-11 2018-12-11 用于涂覆金属薄膜的热固性树脂组合物和使用其的金属层合体

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KR10-2017-0169493 2017-12-11
KR20170169493 2017-12-11
KR10-2018-0157084 2018-12-07
KR1020180157084A KR102196881B1 (ko) 2017-12-11 2018-12-07 금속 박막 코팅용 열경화성 수지 조성물 및 이를 이용한 금속 적층체

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040015268A (ko) * 2001-06-28 2004-02-18 제너럴 일렉트릭 캄파니 성형가능한 폴리(아릴렌 에테르)열경화성 조성물, 방법 및제품
KR20100103942A (ko) * 2009-03-16 2010-09-29 (주)켐텍 에폭시 수지 조성물 및 이를 이용하여 제조된 프린트 배선판용 접착 필름
KR20130091099A (ko) * 2012-02-07 2013-08-16 삼성전기주식회사 난연성 절연층을 포함하는 인쇄회로기판의 제조방법
KR20160007599A (ko) * 2013-05-30 2016-01-20 셍기 테크놀로지 코. 엘티디. 시아네이트 수지 조성물 및 그 용도
KR20170084991A (ko) * 2016-01-13 2017-07-21 주식회사 엘지화학 반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040015268A (ko) * 2001-06-28 2004-02-18 제너럴 일렉트릭 캄파니 성형가능한 폴리(아릴렌 에테르)열경화성 조성물, 방법 및제품
KR20100103942A (ko) * 2009-03-16 2010-09-29 (주)켐텍 에폭시 수지 조성물 및 이를 이용하여 제조된 프린트 배선판용 접착 필름
KR20130091099A (ko) * 2012-02-07 2013-08-16 삼성전기주식회사 난연성 절연층을 포함하는 인쇄회로기판의 제조방법
KR20160007599A (ko) * 2013-05-30 2016-01-20 셍기 테크놀로지 코. 엘티디. 시아네이트 수지 조성물 및 그 용도
KR20170084991A (ko) * 2016-01-13 2017-07-21 주식회사 엘지화학 반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그

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