WO2014104739A1 - Epoxy resin composition having excellent adhesive properties and resin composite copper foil using same - Google Patents

Epoxy resin composition having excellent adhesive properties and resin composite copper foil using same Download PDF

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Publication number
WO2014104739A1
WO2014104739A1 PCT/KR2013/012171 KR2013012171W WO2014104739A1 WO 2014104739 A1 WO2014104739 A1 WO 2014104739A1 KR 2013012171 W KR2013012171 W KR 2013012171W WO 2014104739 A1 WO2014104739 A1 WO 2014104739A1
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WIPO (PCT)
Prior art keywords
epoxy resin
epoxy
resin composition
copper foil
weight
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PCT/KR2013/012171
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French (fr)
Korean (ko)
Inventor
정수임
박광석
김형규
김인욱
Original Assignee
주식회사 두산
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Publication of WO2014104739A1 publication Critical patent/WO2014104739A1/en

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    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention uses a novel epoxy resin composition and the composition which can improve the adhesion between the copper foil and the insulating layer by mixing a high equivalent epoxy, a low equivalent epoxy and a curing agent having a low polydispersity index (PDI) with a narrow molecular weight distribution.
  • the present invention relates to a resin composite copper foil and a laminate for a printed circuit board, which exhibit good adhesion, heat resistance, and fine circuit implementation.
  • LTE CTE low thermal expansion coefficient
  • an inorganic resin having a low polarity is used to increase the content of the inorganic filler or to implement a low dielectric constant.
  • an alternative for improving the adhesive strength is required.
  • copper foil having a low roughness value is used for low dielectric properties and fine patterns, and thus, a problem of lowering adhesive strength has been raised.
  • the copper foil used for conventional printed wiring board manufacture formed the unevenness
  • a rust inhibitor, a polyimide (PI) resin, or the like has been used as a surface treatment agent.
  • PI polyimide
  • the method of applying the primer resin layer which is excellent in adhesive strength is urgently required.
  • the present invention has been made to solve the above-mentioned problems, a novel epoxy that can improve the adhesion between the insulating layer and the copper foil by mixing a high equivalent epoxy and a low equivalent epoxy having a narrow molecular weight distribution with a low polydispersity index (PDI) It aims at providing the primer resin composite copper foil which can apply
  • PDI polydispersity index
  • the present invention comprises: (a) a high equivalent first epoxy resin having an epoxy equivalent (EEW) in the range of 400 to 1000 g / eq; (b) low equivalent second epoxy resins having an epoxy equivalent weight (EEW) in the range of 100-300 g / eq; (c) dimer acid-modified epoxy resins; And (d) a curing agent, wherein at least one of the first epoxy resin and the second epoxy resin has a polydispersity index (PDI) of 2 or less.
  • PDI polydispersity index
  • the weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is in the range of 500 to 2,000.
  • the use ratio of the said 1st epoxy resin and the 2nd epoxy resin is 50-90: 10-10 weight ratio.
  • the dimer acid-modified epoxy resin has a modification rate of 5 to 30%, epoxy equivalent of 100 to 500g / eq is preferred.
  • curing agent is 1 or more types chosen from the group which consists of a cresol novolak, a bisphenol A novolak, a naphthalene type, an amine hardener, and an aminotriazine novolak.
  • the curing agent and the epoxy resin is preferably included in a weight ratio of 20 to 50: 50 to 80.
  • the epoxy resin composition may further comprise a curing accelerator, wherein the curing accelerator is preferably at least one selected from the group consisting of amine-based, phenol-based and imidazole-based curing accelerators.
  • the composition comprises 5 to 40 parts by weight of the dimer acid-modified epoxy resin (c) based on 100 parts by weight of the mixture of the epoxy resin and the curing agent, 0.005 to 0.05 parts by weight of the curing accelerator It is preferable to include.
  • this invention is copper foil; And a primer resin layer formed on one or both surfaces of the copper foil using the epoxy resin composition described above.
  • the present invention provides a laminate for a printed circuit board comprising a primer resin layer formed on the one surface or both surfaces of the substrate using the epoxy resin composition described above.
  • the epoxy resin composition which concerns on this invention is excellent in the adhesive force between an insulating layer and copper foil, the resin composite copper foil containing the primer resin layer formed using the said composition is excellent in heat resistance and workability, without reducing adhesive force.
  • the printed circuit board including the primer resin layer may simultaneously exhibit a low thermal expansion coefficient and a fine circuit pattern implementation effect.
  • an epoxy resin by using an epoxy resin, a dimer acid-modified epoxy resin, a curing agent and an inorganic filler to provide an adhesive composition that can further improve the adhesive force between the copper foil and the insulating layer, but the low molecular weight index (PDI) as a component It is characterized by mixing a high equivalent first epoxy resin, a low equivalent second epoxy resin, and a hardening
  • Polydispersity Index is a criterion indicating the extent of the molecular weight distribution of the polymer, and is defined as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
  • PDI polydispersity index
  • the resin having a narrow molecular weight distribution is significantly reduced in the content of relatively high high molecular weight material (eg High Mw species) and low molecular weight material (eg Oligomer), The distribution is generally uniform. Since the ND resin has a relatively high content of a high molecular weight material, as the viscosity is lowered, wetting property of the coating surface is excellent. This is good primer resin coating property along the roughness of copper foil, which contributes to the improvement of adhesion.
  • the degree of viscosity decrease of the resin is low, and the filling property is excellent.
  • low viscosity and gel time increase due to narrow dispersity contribute to stable press formability with primer adhesive copper foil (low adhesive strength) PPG (or product). This means improvement in adhesion.
  • the Tg, Td properties are improved by reducing the content of oligomers, which are low molecular weight materials, which contributes to improved heat resistance and reliability. Therefore, in the present invention, by applying the ND resin, it is possible to improve not only the adhesive strength but also the heat resistance and the glass transition temperature (Tg).
  • the resin composition of the present invention can exhibit excellent adhesiveness by applying to not only copper foil which has not been conventionally treated but also to substrates having low adhesive strength.
  • the epoxy resin composition according to the present invention comprises: (a) a high equivalent first epoxy resin having an epoxy equivalent weight (EEW) of 400 to 1000 g / eq; (b) a low equivalent second epoxy resin having an epoxy equivalent weight (EEW) of 100-300 g / eq; (c) dimer acid-modified epoxy resins; And (d) a curing agent, wherein at least one of the resins (a) and (b) may be configured using an ND resin having a polydispersity index (PDI) of 2 or less.
  • PDI polydispersity index
  • it may further include a curing accelerator.
  • this is not particularly limited.
  • the first component of the epoxy resin composition according to the invention is an epoxy resin.
  • the epoxy resin of the present invention is not particularly limited as long as it contains two or more epoxy groups in the molecule.
  • Non-limiting examples of the epoxy resins that can be used include bisphenol A, bisphenol F, cresol novolac, dicyclopentazene, trisphenylmethane, naphthalene, biphenyl type and hydrogenated epoxy resins thereof, alone or in combination. More than one species can be used by mixing. In particular, when using a hydrogenated epoxy resin, it is preferable to use bisphenol A or a biphenyl type epoxy resin.
  • two or more kinds of epoxy resins having different equivalents are mixed as epoxy resins, and at least one or more of epoxy resins having different equivalents has a polydispersity index (PDI) of ND having a narrow molecular weight distribution of 2.0 or less. (narrow dispersity) It is characterized by using a resin.
  • PDI polydispersity index
  • an epoxy equivalent weight (EEW) epoxy resin has a good melt property at low melt viscosity and adhesion, and a high equivalent epoxy resin (EEW) has plasticity in itself. It is possible to further improve molding characteristics such as bending property (bending workability) and punching property of the copper foil or laminate for printed circuit board. Therefore, when an epoxy resin having a degree of polymerization (n) or an equivalent difference is mixed as in the present invention, in addition to the effect due to the use of an ND resin having a narrow molecular weight distribution, high adhesiveness, excellent moisture resistance reliability, moldability, and the like can be exhibited. have.
  • first epoxy resin having an epoxy equivalent of about 400 to 1000 g / eq and a low equivalent second epoxy resin having an epoxy equivalent of about 100 to 300 g / eq as the epoxy resin.
  • first epoxy resin and the second epoxy resin may be used alone, or two or more kinds of resins having the aforementioned equivalent ranges may be used.
  • the weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is preferably in the range of 500 to 2,000.
  • the use ratio of the first epoxy resin and the second epoxy resin may be 50 to 90: 10 to 50 weight ratio, preferably 50 to 70: 30 to 50 range. have.
  • the first epoxy resin, the second epoxy resin, or both may have a polydispersity index (PDI) of 2 or less, preferably 1 to 1.7, and more preferably 1.1 to 1.5.
  • PDI polydispersity index
  • T g glass transition temperature of the epoxy resin
  • it may range from 80 to 250 ° C, or may be from 90 to 200 ° C.
  • the present invention may further include a conventional epoxy resin known in the art, and is not particularly limited thereto.
  • the content of the epoxy resin may be in the range of 40 to 80 parts by weight relative to 100 parts by weight of the total resin composition, preferably 50 to 70 parts by weight.
  • the content of the epoxy resin falls within the above-mentioned range, the curability, molding processability and adhesion of the resin composition are good.
  • the third component constituting the epoxy resin composition according to the present invention is a dimer acid-modified epoxy resin.
  • the dimer acid-modified epoxy resin forms an adhesive composition by a curing reaction, it is easy to form a cured product given flexibility by structural factors of the dimer acid-modified portion, and by imparting elastomeric properties to the adhesive layer (insulator)
  • the adhesiveness, heat resistance, and moisture resistance of the copper base which is a metal base, and an adhesive bond layer (insulator) can be improved.
  • Non-limiting examples of the dimer acid-modified epoxy resin that can be used are KSR-200 (Kukdo Chemical), SER-200 (Shin-A T & C), etc. These may be used alone or in combination of two or more.
  • examples of the dimer acid-modified epoxy resin include an epoxy resin represented by the following Chemical Formula 1, but are not limited thereto.
  • the dimer acid-modified epoxy resin has a modification rate of about 5 to 30%, cracking and peeling phenomena do not occur during punching processing, and thus heat resistance and moisture resistance may be further improved.
  • the epoxy equivalent and viscosity of the dimer acid-modified epoxy resin are not particularly limited, but when the epoxy equivalent is about 100 to 500 g / eq and the viscosity is about 5,000 to 30,000 cps, the bending property (bending) is not caused while agglomeration fracture occurs. Processability) and punching processability, such as moldability and heat resistance and moisture resistance can be further improved.
  • the content of the dimer acid-modified epoxy resin may be in the range of about 5 to 40 parts by weight, and preferably in the range of 5 to 30 parts by weight, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent. Can be.
  • the content of the dimer acid-modified epoxy resin falls within the above-mentioned range, molding processability, heat resistance, adhesiveness and the like of the resin composition are good.
  • the fourth component constituting the epoxy resin composition according to the present invention is a curing agent.
  • the curing agent may be appropriately selected and used depending on the type of the epoxy resin, and may be used without limitation as long as it is usually used as a curing agent of the epoxy resin.
  • the polydispersity index (PDI) of the curing agent may be 2 or less, preferably 1 to 1.7, more preferably 1.1 to 1.5 range.
  • Non-limiting examples of the curing agent that can be used include a phenol-based curing agent, an anhydride-based curing agent, a dicyanamide-based curing agent, among which a phenolic curing agent is preferable because it can further improve the heat resistance and adhesion.
  • Non-limiting examples of the phenol-based curing agent include phenol novolak, cresol novolak, bisphenol A novolak, naphthalene type, etc. These may be used alone or in combination of two or more.
  • Non-limiting examples of the acid anhydride curing agent include phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydro phthalic anhydride, and the like.
  • curing agent can be used individually by 1 type, or may use 2 or more types together.
  • the content of the curing agent may be appropriately adjusted according to the content of the epoxy resin.
  • the curing agent and the epoxy resin may be reduced from 20 to 50:50 to 50%. It is preferable to mix and use in 80 weight ratio.
  • it may further include a conventional curing accelerator known in the art.
  • the curing accelerator may be appropriately selected and used depending on the type of the epoxy resin and the curing agent.
  • curing accelerators that can be used include amine-based, phenol-based, and imidazole-based curing accelerators, and more specific examples thereof include amine complexes of boron trifluoride, imidazole derivatives, organic acids such as phthalic anhydride, and trimellitic anhydride. have.
  • the curing accelerators include imidazole derivative curing accelerators, specifically 1-methylimidazole, 2-methylimidazole, 2-ethyl 4-methyl imidazole, 2-phenylimidazole. , 2-phenyl4-methyl imidazole, cyanoethylation derivatives thereof, carboxylic acid derivatives, hydroxymethyl group derivatives, and the like, but are not limited thereto.
  • These hardening accelerators can be used individually by 1 type, or can also use 2 or more types together.
  • the content of the curing accelerator may range from about 0.005 to 0.05 parts by weight, preferably from 0.01 to 0.04, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent.
  • the epoxy resin composition of the present invention inorganic fillers, flame retardants, other thermosetting resins and thermoplastic resins not mentioned above, and oligomers thereof, which are generally known in the art as necessary, as long as they do not impair the intrinsic properties of the resin composition.
  • Various polymers such as, solid rubber particles or other additives such as ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents and the like may be further included.
  • Examples include flame retardants such as organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides; Organic fillers such as silicone powder, nylon powder, and fluororesin powder, and thickeners such as orbene and benton; Polymeric antifoaming agents or leveling agents such as silicone-based and fluorine-based resins; Adhesion imparting agents such as imidazole series, thiazole series, triazole series, and silane coupling agents; Phthalocyanine, carbon black, etc. can be mentioned a coloring agent.
  • flame retardants such as organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides
  • Organic fillers such as silicone powder, nylon powder, and fluororesin powder, and thickeners such as orbene and benton
  • Polymeric antifoaming agents or leveling agents such as silicone-based and fluorine-based resins
  • Adhesion imparting agents such as imidazole
  • thermoplastic resin can be mix
  • thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimides, polyamideimide, polyethersulfone, polysulfone and the like. Any one of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.
  • the resin composite copper foil 100 of the present invention is located on the copper foil 110 and one or both surfaces of the copper foil, and the primer resin layer 120 formed using the epoxy resin composition described above. ).
  • the copper foil 110 may use any conventional copper foil known in the art without limitation, and includes all copper foils produced by a rolling method and an electrolytic method, for example.
  • the copper foil may be subjected to rust prevention treatment in order to prevent the surface from being oxidized and corroded.
  • the copper foil may have a predetermined surface roughness Rz formed on one surface of the copper foil in contact with the first insulating resin layer, and the surface roughness Rz may be in a range of 0.6 ⁇ m to 3.0 ⁇ m.
  • the thickness of the copper foil is not particularly limited, but may be used less than 10 ⁇ m in consideration of the thickness and mechanical properties of the final product, preferably in the range of 1 to 5 ⁇ m.
  • Examples of copper foil that can be used include Mitsui 18MT-EX, F2-WS, F1-WS, FWL-WS, T4X, and the like.
  • the primer resin layer 120 is formed on the surface of the copper foil, the copper foil serving as the substrate, and the insulating resin layer or prepreg (PRG) formed on the resin layer.
  • the adhesive force with can be improved more.
  • the thickness of the primer resin layer 120 may be appropriately adjusted within a range capable of securing the adhesiveness between the copper foil and the insulating layer, for example, may be in the range of 1 to 10 ⁇ m, preferably 1 to 7 ⁇ m More preferably, it may be 1-5 micrometers.
  • Primer resin layer 120 includes a cured layer formed by curing the above-mentioned epoxy resin composition, wherein the epoxy resin composition does not necessarily need to be completely heat-cured, so that the effect of the present invention is exhibited It should just be hardened.
  • the resin composite copper foil 100 may further include a conventional insulating resin layer, a prepreg layer, or both of which are known in the art on the primer resin layer 120.
  • the resin composite copper foil 100 according to the present invention may be manufactured according to conventional methods known in the art.
  • the epoxy resin composition varnish may be applied to the surface of the copper foil and then heated, dried and cured, or the adhesive sheet or film obtained by heating and drying the resin varnish applied on the support may be coated on the surface of the copper foil. It can also be obtained by arranging in the adhesive.
  • the epoxy resin composition when applied on a substrate, conventional coating methods known in the art, such as dip coating, die coating, roll coating, comma coating, casting or their Various methods such as a mixing method can be used without limitation.
  • the drying method and drying conditions may be adjusted within the conventional range known in the art, for example, it may be carried out by drying for 1 to 30 minutes at a temperature of 50 to 170 °C.
  • organic solvents examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like.
  • Carboxols such as acetic acid ester, cellosolve, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use an organic solvent 1 type or in combination of 2 or more types.
  • the organic resin component and the inorganic solid component and organic solvent added as needed may be mixed using a pot mill, a ball mill, a homogenizer, a super mill, and the like.
  • the present invention provides a laminate for a printed circuit board comprising a primer resin layer formed by using the above-described epoxy resin composition on one side or both sides of the substrate.
  • the substrate may be used as a core substrate, and may be an inner layer wiring board.
  • the printed circuit board exhibits excellent performances such as excellent adhesiveness, heat resistance, and the like due to the novel epoxy resin composition, it can contribute to high functionalization and long life of various electronic devices.
  • a first epoxy resin, a second epoxy resin, a curing agent, a dimer acid-modified epoxy resin, a curing accelerator, and the like were mixed to prepare epoxy resin compositions, respectively.
  • the amount of each unit used is parts by weight, where "parts by weight” is based on 100 parts by weight of a mixture of a high equivalent epoxy resin, a low equivalent epoxy resin, and a curing agent.
  • the epoxy resin composition prepared above was coated with 1 to 5 ⁇ m on a general 1 / 2Oz copper foil and dried at 160 ° C. for 3 minutes. At this time, the coating method was performed using a casting or gravure coater.
  • a prepreg Doosan, DS-7402HFE (PPG) was applied to the copper foil coated with the primer resin layer to form a laminate, and the improvement effect of the adhesive strength was evaluated.
  • prepreg Doosan, DS-7402HFE (PPG) was applied to form the laminate of Comparative Example 6, and the improvement effect of the adhesive strength was evaluated.
  • Coating property 1-5 ⁇ m resin was coated on a Matt surface of a 12 ⁇ m (1 / 3Oz) copper foil which was not surface treated using a Gravure * pilot coater. (* Thin coatable micro coater) It was dried by B-stage for about 3 minutes at 180 degreeC temperature.
  • Epoxy Resin 2 PDI: 2.0 / EEW: 190g / eq
  • Hardener 1 phenol novolac hardener (KOLON KPH-F2003, PDI: 2.3)
  • the resin composite copper foil using the epoxy resin composition of the present invention showed excellent properties in terms of coating property, adhesiveness, heat resistance, and water absorption (see Table 1).

Abstract

The present invention provides an epoxy resin composition and a resin-coated copper foil comprising a resin layer formed by using the epoxy resin composition, the epoxy resin composition comprising: (a) a high equivalent weight first epoxy resin of which the epoxy equivalent weight (EEW) is within the range of 400 to 1000 g/eq; (b) a low equivalent weight second epoxy resin of which the epoxy equivalent weight (EEW) is within the range of 100 to 300 g/eq; (c) a dimer acid modified epoxy resin; and (d) a hardening agent, wherein the polydispersity index (PDI) of the first epoxy resin and/or the second epoxy resin is no more than 2. The present invention can provide a build-up printed circuit board which can achieve heat resistance, can have microcircuit patterns and can secure good adhesive properties by improving the adhesive force between a copper foil and an insulation layer due to using a mixture of the hardening agent, the low equivalent weight epoxy, and the high equivalent weight epoxy having narrow molecular weight distribution and a low polydispersity index (PDI).

Description

접착성이 우수한 에폭시 수지 조성물 및 이를 이용한 수지 복합 동박Epoxy resin composition excellent in adhesiveness and resin composite copper foil using same
본 발명은 다분산지수(PDI)가 낮아 좁은 분자량 분포를 갖는 고당량 에폭시, 저당량 에폭시 및 경화제를 혼용함으로써, 동박과 절연층 간의 접착력을 개선할 수 있는 신규 에폭시 수지 조성물 및 상기 조성물을 이용하여 양호한 접착성 확보, 내열성, 미세회로 구현을 발휘하는 수지 복합 동박 및 인쇄회로기판용 적층체에 관한 것이다. The present invention uses a novel epoxy resin composition and the composition which can improve the adhesion between the copper foil and the insulating layer by mixing a high equivalent epoxy, a low equivalent epoxy and a curing agent having a low polydispersity index (PDI) with a narrow molecular weight distribution. The present invention relates to a resin composite copper foil and a laminate for a printed circuit board, which exhibit good adhesion, heat resistance, and fine circuit implementation.
최근 전자재료의 저열팽창계수(Low CTE), 및 저유전 특성 등이 중요해짐에 따라 절연체의 동박 접착력 또한 이슈가 되고 있다. As the low thermal expansion coefficient (LTE CTE) and low dielectric properties of electronic materials become more important, copper foil adhesion of an insulator is also an issue.
낮은 열팽창계수 구현을 위해 무기 필러의 함량을 증가시키거나, 또는 저유전율 특성 구현을 위해 낮은 극성을 가지는 절연 수지를 사용하고 있는데, 이 경우 낮아지는 접착력을 개선하기 위한 대안이 요구되고 있다. 뿐만 아니라 저유전 특성 및 미세 패턴을 위해 낮은 조도값을 가지는 동박을 사용하고 있고, 이에 따라 접착력 저하 문제가 대두되고 있다.In order to realize a low coefficient of thermal expansion, an inorganic resin having a low polarity is used to increase the content of the inorganic filler or to implement a low dielectric constant. In this case, an alternative for improving the adhesive strength is required. In addition, copper foil having a low roughness value is used for low dielectric properties and fine patterns, and thus, a problem of lowering adhesive strength has been raised.
실제로, 종래의 프린트 배선판 제조에 사용되고 있는 동박은 동박면의 요철을 형성하고, 이러한 동박의 요철이 기재 수지 내에 박혀 동박과 수지층 간의 밀착성을 발휘하였다. 또한 밀착성 효과를 높이기 위해 표면처리제로 방청제, 폴리이미드(PI) 수지 등을 사용하여 왔다. 이러한 폴리이미드(PI) 수지의 경우 배선의 미세화나 내열성 측면에서는 유용하지만, 폴리이미드 필름과 동박과의 접착 강도 및 접속 신뢰성에 자주 문제가 되고 있다. In fact, the copper foil used for conventional printed wiring board manufacture formed the unevenness | corrugation of the copper foil surface, and the unevenness | corrugation of such copper foil was embedded in base resin, and showed the adhesiveness between copper foil and a resin layer. In addition, in order to enhance the adhesive effect, a rust inhibitor, a polyimide (PI) resin, or the like has been used as a surface treatment agent. Such a polyimide (PI) resin is useful in terms of miniaturization of wiring and in terms of heat resistance, but is often problematic in adhesive strength and connection reliability between the polyimide film and the copper foil.
또한 표면처리를 하지 않는 동박에 있어서는 접착 강도가 우수한 프라이머 수지층을 적용하는 방법이 절실히 요구되고 있는 실정이다. Moreover, in the copper foil which does not surface-treat, the method of applying the primer resin layer which is excellent in adhesive strength is urgently required.
본 발명은 전술한 문제점을 해결하기 위해서 안출된 것으로서, 다분산지수(PDI)가 낮아 좁은 분자량 분포를 갖는 고당량 에폭시와 저당량 에폭시를 혼용하여 절연층과 동박 간의 접착력을 개선할 수 있는 신규 에폭시 수지 조성물, 및 상기 조성물로 형성된 프라이머층을 얇게 도포하여 배선용 기판 및 패키지용 기판과의 양호한 접착성을 확보할 수 있는 프라이머 수지 복합 동박을 제공하는 것을 목적으로 한다.The present invention has been made to solve the above-mentioned problems, a novel epoxy that can improve the adhesion between the insulating layer and the copper foil by mixing a high equivalent epoxy and a low equivalent epoxy having a narrow molecular weight distribution with a low polydispersity index (PDI) It aims at providing the primer resin composite copper foil which can apply | coat thinly the resin composition and the primer layer formed from the said composition, and can ensure favorable adhesiveness with a wiring board and a package board.
본 발명은 (a) 에폭시 당량(EEW)이 400~1000 g/eq 범위인 고당량 제1에폭시 수지; (b) 에폭시 당량(EEW)이 100-300 g/eq 범위인 저당량 제2에폭시 수지; (c) 다이머산 변성 에폭시 수지; 및 (d) 경화제를 포함하며, 상기 제1에폭시 수지와 제2에폭시 수지 중 1종 이상은 다분산지수(PDI)가 2 이하인 것을 특징으로 하는 에폭시 수지 조성물을 제공한다.The present invention comprises: (a) a high equivalent first epoxy resin having an epoxy equivalent (EEW) in the range of 400 to 1000 g / eq; (b) low equivalent second epoxy resins having an epoxy equivalent weight (EEW) in the range of 100-300 g / eq; (c) dimer acid-modified epoxy resins; And (d) a curing agent, wherein at least one of the first epoxy resin and the second epoxy resin has a polydispersity index (PDI) of 2 or less.
본 발명의 바람직한 일례에 따르면, 상기 제1에폭시 수지의 중량 평균 분자량(Mw)이 1,000 내지 3,000 범위이며, 제2에폭시 수지의 중량 평균 분자량(Mw)이 500 내지 2,000 범위인 것이 바람직하다. According to a preferred example of the present invention, it is preferable that the weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is in the range of 500 to 2,000.
또한 상기 제1에폭시 수지와 제2에폭시 수지의 사용 비율은 50~90 : 10~50 중량 비율인 것이 바람직하다.Moreover, it is preferable that the use ratio of the said 1st epoxy resin and the 2nd epoxy resin is 50-90: 10-10 weight ratio.
본 발명의 다른 바람직한 일례에 따르면, 상기 상기 다이머산 변성 에폭시 수지는 변성율이 5 내지 30%이고, 에폭시 당량이 100 내지 500g/eq인 것이 바람직하다. According to another preferred embodiment of the present invention, the dimer acid-modified epoxy resin has a modification rate of 5 to 30%, epoxy equivalent of 100 to 500g / eq is preferred.
여기서, 상기 경화제는 크레졸노볼락, 비스페놀A 노볼락, 나프탈렌형, 아민 경화제 및 아미노트리아진 노볼락으로 구성된 군으로부터 선택되는 1종 이상인 것이 바람직하다.Here, it is preferable that the said hardening | curing agent is 1 or more types chosen from the group which consists of a cresol novolak, a bisphenol A novolak, a naphthalene type, an amine hardener, and an aminotriazine novolak.
또한 본 발명에서, 상기 경화제와 에폭시 수지는 20 ~ 50 : 50 ~ 80 중량 비율로 포함되는 것이 바람직하다.In addition, in the present invention, the curing agent and the epoxy resin is preferably included in a weight ratio of 20 to 50: 50 to 80.
본 발명에서, 상기 에폭시 수지 조성물은 경화촉진제를 더 포함할 수 있으며, 이때 경화촉진제는 아민계, 페놀계 및 이미다졸계 경화촉진제로 구성된 군으로부터 선택되는 1종 이상인 것이 바람직하다.In the present invention, the epoxy resin composition may further comprise a curing accelerator, wherein the curing accelerator is preferably at least one selected from the group consisting of amine-based, phenol-based and imidazole-based curing accelerators.
본 발명의 또 다른 바람직한 일례에 따르면, 상기 조성물은 에폭시 수지와 경화제의 혼합물 100 중량부를 기준으로 상기 다이머산 변성 에폭시 수지(c)를 5 내지 40 중량부로 포함하고, 경화 촉진제를 0.005 내지 0.05 중량부로 포함하는 것이 바람직하다.According to another preferred embodiment of the present invention, the composition comprises 5 to 40 parts by weight of the dimer acid-modified epoxy resin (c) based on 100 parts by weight of the mixture of the epoxy resin and the curing agent, 0.005 to 0.05 parts by weight of the curing accelerator It is preferable to include.
또한, 본 발명은 동박; 및 상기 동박의 일면 또는 양면 상에, 전술한 에폭시 수지 조성물을 이용하여 형성된 프라이머 수지층을 포함하는 수지 복합 동박을 제공한다.Moreover, this invention is copper foil; And a primer resin layer formed on one or both surfaces of the copper foil using the epoxy resin composition described above.
아울러, 본 발명은 기판의 일면 또는 양면상에, 전술한 에폭시 수지 조성물을 이용하여 형성된 프라이머 수지층을 포함하는 인쇄회로기판용 적층체를 제공한다. In addition, the present invention provides a laminate for a printed circuit board comprising a primer resin layer formed on the one surface or both surfaces of the substrate using the epoxy resin composition described above.
본 발명에 따른 에폭시 수지 조성물은 절연층 및 동박 간의 접착력이 우수하므로, 상기 조성물을 이용하여 형성된 프라이머 수지층을 포함하는 수지 복합 동박은 접착력을 저하시키지 않으면서 내열성, 가공성이 우수하다. Since the epoxy resin composition which concerns on this invention is excellent in the adhesive force between an insulating layer and copper foil, the resin composite copper foil containing the primer resin layer formed using the said composition is excellent in heat resistance and workability, without reducing adhesive force.
또한, 상기 프라이머 수지층을 포함하는 인쇄회로기판은 낮은 열팽창계수 및 미세회로 패턴 구현 효과를 동시에 발휘할 수 있다. In addition, the printed circuit board including the primer resin layer may simultaneously exhibit a low thermal expansion coefficient and a fine circuit pattern implementation effect.
도 1은 본 발명의 일 실시예에 따른 수지 복합 동박의 구성을 나타내는 단면도이다. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the structure of the resin composite copper foil which concerns on one Example of this invention.
<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>
100: 수지 복합 동박100: resin composite copper foil
110: 동박110: copper foil
120: 프라이머 수지층120: primer resin layer
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 에폭시 수지, 다이머산 변성 에폭시 수지, 경화제 및 무기물 필러를 사용하여 동박과 절연층 간의 접착력을 보다 향상시킬 수 있는 접착성 조성물을 제공하되, 상기 구성 성분으로 다분자지수(PDI)가 낮아 좁은 분자량 분포(narrow dispersity, ND)를 갖는 고당량 제1에폭시 수지, 저당량 제2에폭시 수지, 및 경화제를 혼용(混用)하는 것을 특징으로 한다.In the present invention, by using an epoxy resin, a dimer acid-modified epoxy resin, a curing agent and an inorganic filler to provide an adhesive composition that can further improve the adhesive force between the copper foil and the insulating layer, but the low molecular weight index (PDI) as a component It is characterized by mixing a high equivalent first epoxy resin, a low equivalent second epoxy resin, and a hardening | curing agent which have narrow molecular weight distribution (narrow dispersity, ND).
다분산지수(Polydispersity Index, PDI)는 고분자의 분자량 분포의 넓이를 나타내는 기준이 되며, 수평균 분자량(Mn)에 대한 무게평균 분자량(Mw)의 비로 정의된다. Polydispersity Index (PDI) is a criterion indicating the extent of the molecular weight distribution of the polymer, and is defined as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
일반적으로 고분자 화합물을 합성할 때 고분자 사슬이 만들어지는데, 고분자는 중합도에 따라 서로 다른 분자량을 갖게 된다. 이러한 분자 분포의 폭을 표시하는 척도가 다분산지수(PDI)로서, PDI가 클수록 분자량 분포가 넓으며, 1에 가까우면 가까울수록 좋은 물성을 가진 단일 분자량의 고분자에 해당된다.In general, when the polymer compound is synthesized, a polymer chain is made, and the polymer has different molecular weights depending on the degree of polymerization. A measure of the width of the molecular distribution is a polydispersity index (PDI). The larger the PDI, the wider the molecular weight distribution. The closer to 1, the closer the polymer is to a single molecular weight polymer having good physical properties.
본 발명에서 사용되는 좁은 분자량 분포(narrow dispersity)를 가진 수지(ND resin)는 상대적으로 높은 고분자량 물질(예, High Mw species)과 저분자량 물질(예, Oligomer)의 함량이 현저히 감소되고, 분자량 분포가 대체로 균일하다. 이러한 ND 수지는 상대적으로 고분자량 물질의 함량이 감소되었기 때문에, 점도가 낮아짐에 따라 코팅 표면에 대한 Wetting성이 우수해진다. 이는 동박의 조도를 따라 프라이머 수지 코팅성이 양호하며, 이는 접착력 향상에 기여한다. In the present invention, the resin having a narrow molecular weight distribution (narrow dispersity) (ND resin) is significantly reduced in the content of relatively high high molecular weight material (eg High Mw species) and low molecular weight material (eg Oligomer), The distribution is generally uniform. Since the ND resin has a relatively high content of a high molecular weight material, as the viscosity is lowered, wetting property of the coating surface is excellent. This is good primer resin coating property along the roughness of copper foil, which contributes to the improvement of adhesion.
또한 동일 온도 조건하에서 수지의 점성 저하 정도가 낮아 충진성이 우수하다. 그리고 Narrow dispersity로 인한 낮은 점도 및 Gel time 증가는 프라이머 접착 동박이 (접착력이 낮은) PPG (또는 제품)와의 안정적인 Press 성형성에 기여한다. 이는 곧 접착력 향상을 의미한다. In addition, under the same temperature conditions, the degree of viscosity decrease of the resin is low, and the filling property is excellent. And low viscosity and gel time increase due to narrow dispersity contribute to stable press formability with primer adhesive copper foil (low adhesive strength) PPG (or product). This means improvement in adhesion.
아울러, 저분자량 물질인 올리고머의 함량 감소로 Tg, Td 특성이 향상되며, 이는 내열 및 신뢰성 향상에 기여한다. 따라서 본 발명에서는 ND 수지를 적용함으로써, 접착 강도 증가는 물론 내열성 및 유리전이온도(Tg) 또한 개선시킬 수 있다. In addition, the Tg, Td properties are improved by reducing the content of oligomers, which are low molecular weight materials, which contributes to improved heat resistance and reliability. Therefore, in the present invention, by applying the ND resin, it is possible to improve not only the adhesive strength but also the heat resistance and the glass transition temperature (Tg).
나아가 본 발명의 수지 조성물은 종래 표면처리되지 않은 동박 뿐만 아니라 접착강도가 떨어지는 기판에도 적용하여 우수한 접착성을 발휘할 수 있다. Furthermore, the resin composition of the present invention can exhibit excellent adhesiveness by applying to not only copper foil which has not been conventionally treated but also to substrates having low adhesive strength.
<접착성이 우수한 에폭시 수지 조성물><Epoxy resin composition excellent in adhesiveness>
본 발명에 따른 에폭시 수지 조성물은 (a) 에폭시 당량(EEW)이 400~1000 g/eq인 고당량 제1에폭시 수지; (b) 에폭시 당량(EEW)이 100-300 g/eq인 저당량 제2에폭시 수지; (c) 다이머산 변성 에폭시 수지; 및 (d) 경화제를 포함하며, 상기 (a)와 (b) 수지 중 적어도 1종 이상은 다분산지수(PDI)가 2 이하인 ND 수지를 사용하여 구성될 수 있다. 여기에, 추가로 경화촉진제를 더 포함할 수 있다. 그러나 이에 특별히 한정되지 않는다.The epoxy resin composition according to the present invention comprises: (a) a high equivalent first epoxy resin having an epoxy equivalent weight (EEW) of 400 to 1000 g / eq; (b) a low equivalent second epoxy resin having an epoxy equivalent weight (EEW) of 100-300 g / eq; (c) dimer acid-modified epoxy resins; And (d) a curing agent, wherein at least one of the resins (a) and (b) may be configured using an ND resin having a polydispersity index (PDI) of 2 or less. Here, it may further include a curing accelerator. However, this is not particularly limited.
<에폭시 수지><Epoxy resin>
본 발명에 따른 에폭시 수지 조성물을 구성하는 첫번째 성분은 에폭시 수지이다. The first component of the epoxy resin composition according to the invention is an epoxy resin.
본 발명의 에폭시 수지는 분자 중에 2개 이상의 에폭시기를 포함하는 것이라면, 특별히 한정되지 않는다. The epoxy resin of the present invention is not particularly limited as long as it contains two or more epoxy groups in the molecule.
사용 가능한 에폭시 수지의 비제한적인 예로는 비스페놀A, 비스페놀F, 크레졸노볼락, 디시클로펜타젠, 트리스페닐메탄, 나프탈렌, 바이페닐형 및 이들의 수소 첨가 에폭시 수지 등이 있는데, 이들은 단독으로 또는 2종 이상이 혼합하여 사용할 수 있다. 특히, 수소 첨가 에폭시 수지를 사용할 경우에는 비스페놀A 또는 바이페닐형 에폭시 수지를 사용하는 것이 바람직하다.Non-limiting examples of the epoxy resins that can be used include bisphenol A, bisphenol F, cresol novolac, dicyclopentazene, trisphenylmethane, naphthalene, biphenyl type and hydrogenated epoxy resins thereof, alone or in combination. More than one species can be used by mixing. In particular, when using a hydrogenated epoxy resin, it is preferable to use bisphenol A or a biphenyl type epoxy resin.
한편, 본 발명에서는 에폭시 수지로서, 당량이 상이한 에폭시 수지를 2종 이상 혼용(混用)하며, 이중 당량이 상이한 에폭시 수지 중 적어도 1종 이상은 다분산지수(PDI)가 2.0 이하인 좁은 분자량 분포의 ND(narrow dispersity) 수지를 사용하는 것을 특징으로 한다. Meanwhile, in the present invention, two or more kinds of epoxy resins having different equivalents are mixed as epoxy resins, and at least one or more of epoxy resins having different equivalents has a polydispersity index (PDI) of ND having a narrow molecular weight distribution of 2.0 or less. (narrow dispersity) It is characterized by using a resin.
상기와 같이 당량이 상이한 에폭시 수지를 혼용하면, 저당량(epoxy equivalent weight, EEW) 에폭시 수지는 낮은 용융점도 및 접착에 있어서 양호한 습윤성을 가지며, 고당량 에폭시 수지(EEW)는 그 자체로 가소성을 가져 동박 또는 인쇄회로기판용 적층체의 벤딩성(굽힘 가공성) 및 펀칭성 등과 같은 성형 특성을 보다 더 향상시킬 수 있다. 따라서 본 발명에서와 같이 중합도 (n) 또는 당량차가 있는 에폭시 수지를 혼용하는 경우, 좁은 분자량 분포를 갖는 ND 수지의 사용으로 인한 효과와 더불어, 높은 접착성, 탁월한 내습 신뢰도, 성형성 등을 나타낼 수 있다. When epoxy resins having different equivalents are mixed as described above, an epoxy equivalent weight (EEW) epoxy resin has a good melt property at low melt viscosity and adhesion, and a high equivalent epoxy resin (EEW) has plasticity in itself. It is possible to further improve molding characteristics such as bending property (bending workability) and punching property of the copper foil or laminate for printed circuit board. Therefore, when an epoxy resin having a degree of polymerization (n) or an equivalent difference is mixed as in the present invention, in addition to the effect due to the use of an ND resin having a narrow molecular weight distribution, high adhesiveness, excellent moisture resistance reliability, moldability, and the like can be exhibited. have.
이에 따라, 본 발명에서는 에폭시 수지로서, 에폭시 당량이 약 400 ~ 1000g/eq인 고당량 제1에폭시 수지와 에폭시 당량이 약 100 ~ 300 g/eq인 저당량 제2에폭시 수지를 혼합하여 사용하는 것이 바람직하다. 이때, 제1에폭시 수지와 제2에폭시 수지는 각각 단독으로 사용되거나 또는 전술한 당량 범위를 갖는 2종 이상의 수지를 혼용될 수 있다. Accordingly, in the present invention, it is preferable to mix and use a high equivalent first epoxy resin having an epoxy equivalent of about 400 to 1000 g / eq and a low equivalent second epoxy resin having an epoxy equivalent of about 100 to 300 g / eq as the epoxy resin. desirable. In this case, the first epoxy resin and the second epoxy resin may be used alone, or two or more kinds of resins having the aforementioned equivalent ranges may be used.
상기 제1에폭시 수지의 중량 평균 분자량(Mw)이 1,000 내지 3,000 범위이며, 제2에폭시 수지의 중량 평균 분자량(Mw)이 500 내지 2,000 범위인 것이 바람직하다. The weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is preferably in the range of 500 to 2,000.
또한, 본 발명의 에폭시 수지에 있어서, 상기 제1에폭시 수지와 제2에폭시 수지의 사용 비율은 50~90 : 10~50 중량 비율일 수 있으며, 바람직하게는 50~70 : 30~50 범위일 수 있다.In addition, in the epoxy resin of the present invention, the use ratio of the first epoxy resin and the second epoxy resin may be 50 to 90: 10 to 50 weight ratio, preferably 50 to 70: 30 to 50 range. have.
상기 제1에폭시 수지, 제2에폭시 수지, 또는 이들 모두는 다분산지수(PDI)가 2 이하일 수 있으며, 바람직하게는 1 내지 1.7이며, 보다 바람직하게는 1.1 내지 1.5 범위이다. 또한 상기 에폭시 수지의 유리전이온도 (Tg)는 높을수록 바람직하다. 일례로 80 내지 250℃ 범위일 수 있으며, 또는 90 내지 200℃일 수 있다. The first epoxy resin, the second epoxy resin, or both may have a polydispersity index (PDI) of 2 or less, preferably 1 to 1.7, and more preferably 1.1 to 1.5. In addition, the higher the glass transition temperature (T g ) of the epoxy resin is, the more preferable. For example, it may range from 80 to 250 ° C, or may be from 90 to 200 ° C.
전술한 제1에폭시 수지와 제2에폭시 수지 이외에, 본 발명에서는 당 업계에 알려진 통상적인 에폭시 수지를 더 포함할 수 있으며, 이의 성분, 함량 등에 특별히 한정되지 않는다. In addition to the first epoxy resin and the second epoxy resin described above, the present invention may further include a conventional epoxy resin known in the art, and is not particularly limited thereto.
본 발명에 따른 에폭시 수지 조성물에서, 상기 에폭시 수지의 함량은 전체 수지 조성물 100 중량부 대비 40 내지 80 중량부 범위일 수 있으며, 바람직하게는 50 내지 70 중량부 범위일 수 있다. 에폭시 수지의 함량이 전술한 범위에 해당되는 경우, 수지 조성물의 경화성, 성형 가공성 및 접착력이 양호하다.In the epoxy resin composition according to the present invention, the content of the epoxy resin may be in the range of 40 to 80 parts by weight relative to 100 parts by weight of the total resin composition, preferably 50 to 70 parts by weight. When the content of the epoxy resin falls within the above-mentioned range, the curability, molding processability and adhesion of the resin composition are good.
<다이머산 변성 에폭시 수지><Dimer acid modified epoxy resin>
본 발명에 따른 에폭시 수지 조성물을 구성하는 세번째 성분은 다이머산 변성 에폭시 수지이다. The third component constituting the epoxy resin composition according to the present invention is a dimer acid-modified epoxy resin.
상기 다이머산 변성 에폭시 수지는 경화 반응에 의해 접착제 조성물을 형성할 때, 다이머산 변성 부분의 구조적 요인에 의해 가요성을 부여한 경화물을 형성하기 쉽고, 접착제층(절연체)에 엘라스토머적인 성질을 부여함으로써 금속 베이스인 동박과 접착제층(절연체)의 밀착성, 내열성 및 내습특성을 향상시킬 수 있다. When the dimer acid-modified epoxy resin forms an adhesive composition by a curing reaction, it is easy to form a cured product given flexibility by structural factors of the dimer acid-modified portion, and by imparting elastomeric properties to the adhesive layer (insulator) The adhesiveness, heat resistance, and moisture resistance of the copper base which is a metal base, and an adhesive bond layer (insulator) can be improved.
사용 가능한 다이머산 변성 에폭시 수지의 비제한적인 예로는 KSR-200(국도화학), SER-200(신아 T&C) 등이 있는데, 이들은 단독으로 사용하거나 또는 2종 이상이 혼합하여 사용될 수 있다. Non-limiting examples of the dimer acid-modified epoxy resin that can be used are KSR-200 (Kukdo Chemical), SER-200 (Shin-A T & C), etc. These may be used alone or in combination of two or more.
바람직하게는, 다이머산 변성 에폭시 수지의 예로는 하기 화학식 1로 표시되는 에폭시 수지가 있는데, 이에 제한되지 않는다.Preferably, examples of the dimer acid-modified epoxy resin include an epoxy resin represented by the following Chemical Formula 1, but are not limited thereto.
화학식 1
Figure PCTKR2013012171-appb-C000001
 Formula 1
Figure PCTKR2013012171-appb-C000001
이러한 다이머산 변성 에폭시 수지는 변성율이 약 5 내지 30%일 경우, 펀칭 가공시 크랙 및 박리 현상이 발생되지 않으면서, 내열성 및 내습성이 보다 더 향상될 수 있어 바람직하다. When the dimer acid-modified epoxy resin has a modification rate of about 5 to 30%, cracking and peeling phenomena do not occur during punching processing, and thus heat resistance and moisture resistance may be further improved.
또한, 다이머산 변성 에폭시 수지의 에폭시 당량 및 점도는 특별히 제한되지 않으나, 에폭시 당량이 약 100 내지 500g/eq이고, 점도가 약 5,000 내지 30,000cps일 경우, 응집 파괴가 일어나지 않으면서, 벤딩성(굽힘 가공성) 및 펀칭 가공성 등의 성형성과 내열성 및 내습성이 보다 더 향상될 수 있다.In addition, the epoxy equivalent and viscosity of the dimer acid-modified epoxy resin are not particularly limited, but when the epoxy equivalent is about 100 to 500 g / eq and the viscosity is about 5,000 to 30,000 cps, the bending property (bending) is not caused while agglomeration fracture occurs. Processability) and punching processability, such as moldability and heat resistance and moisture resistance can be further improved.
본 발명에 따른 에폭시 수지 조성물에서, 상기 다이머산 변성 에폭시 수지의 함량은 에폭시 수지 및 경화제의 혼합물 100 중량부 기준으로 약 5 내지 40 중량부 범위일 수 있으며, 바람직하게는 5 내지 30 중량부 범위일 수 있다. 다이머산 변성 에폭시 수지의 함량이 전술한 범위에 해당되는 경우, 수지 조성물의 성형 가공성, 내열성, 접착성 등이 양호하다. In the epoxy resin composition according to the present invention, the content of the dimer acid-modified epoxy resin may be in the range of about 5 to 40 parts by weight, and preferably in the range of 5 to 30 parts by weight, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent. Can be. When the content of the dimer acid-modified epoxy resin falls within the above-mentioned range, molding processability, heat resistance, adhesiveness and the like of the resin composition are good.
<경화제><Hardener>
본 발명에 따른 에폭시 수지 조성물을 구성하는 네번째 성분은 경화제이다. The fourth component constituting the epoxy resin composition according to the present invention is a curing agent.
상기 경화제는 에폭시 수지의 종류에 따라 적절하게 선택하여 사용할 수 있으며, 에폭시 수지의 경화제로서 통상 사용되는 것이라면 제한 없이 사용할 수 있다.The curing agent may be appropriately selected and used depending on the type of the epoxy resin, and may be used without limitation as long as it is usually used as a curing agent of the epoxy resin.
상기 경화제의 다분산지수(PDI)는 2 이하일 수 있으며, 바람직하게는 1 내지 1.7이며, 보다 바람직하게는 1.1 내지 1.5 범위이다. The polydispersity index (PDI) of the curing agent may be 2 or less, preferably 1 to 1.7, more preferably 1.1 to 1.5 range.
사용 가능한 경화제의 비제한적인 예로는 페놀계 경화제, 무수물계 경화제, 디시안아미드계 경화제가 있는데, 이 중에서 페놀계 경화제가 내열성 및 접착성을 더 향상시킬 수 있어 바람직하다.Non-limiting examples of the curing agent that can be used include a phenol-based curing agent, an anhydride-based curing agent, a dicyanamide-based curing agent, among which a phenolic curing agent is preferable because it can further improve the heat resistance and adhesion.
상기 페놀계 경화제의 비제한적인 예로는 페놀노볼락, 크레졸노볼락, 비스페놀A노볼락, 나프탈렌형 등이 있는데, 이들은 단독으로 또는 2종 이상이 혼합하여 사용될 수 있다.Non-limiting examples of the phenol-based curing agent include phenol novolak, cresol novolak, bisphenol A novolak, naphthalene type, etc. These may be used alone or in combination of two or more.
상기 산 무수물계 경화제의 비제한적인 예로는, 무수 프탈산, 피로멜리트산 무수물, 트리멜리트산 무수물, 헥사히드로무수 프탈산 등이 있다. 상기 경화제는 1종 단독으로 이용할 수 있으며, 또는 2종 이상을 병용할 수도 있다. Non-limiting examples of the acid anhydride curing agent include phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydro phthalic anhydride, and the like. The said hardening | curing agent can be used individually by 1 type, or may use 2 or more types together.
상기 경화제의 함량은 에폭시 수지의 함량에 따라 적절하게 조절될 수 있다. 다만, 내열성 및 접착 강도를 보다 더 향상시키면서, 절연층의 경질화로 인해 벤딩성(굽힘 가공성) 및 펀칭 가공성 등과 같은 성형 특성이 저하되는 것을 방지하기 위해, 경화제와 에폭시 수지를 20 ~ 50 : 50 ~ 80 중량 비율로 혼합하여 사용하는 것이 바람직하다.The content of the curing agent may be appropriately adjusted according to the content of the epoxy resin. However, in order to further improve the heat resistance and the adhesive strength, in order to prevent deterioration of molding characteristics such as bending property (bending workability) and punching workability due to the hardening of the insulating layer, the curing agent and the epoxy resin may be reduced from 20 to 50:50 to 50%. It is preferable to mix and use in 80 weight ratio.
<경화 촉진제><Hardening accelerator>
본 발명에서는, 필요에 따라 당 업계에 알려진 통상적인 경화촉진제를 더 포함할 수 있다.In the present invention, if necessary, it may further include a conventional curing accelerator known in the art.
이때 경화촉진제는 에폭시 수지 및 경화제의 종류에 따라 적절하게 선택하여 사용할 수 있다. 사용 가능한 경화촉진제의 예로는 아민계, 페놀계, 이미다졸계 경화촉진제 등이 있으며, 보다 구체예로는 삼불화붕소의 아민 착체, 이미다졸 유도체, 무수 프탈산 및 무수 트리멜리트산 등의 유기산 등이 있다. In this case, the curing accelerator may be appropriately selected and used depending on the type of the epoxy resin and the curing agent. Examples of curing accelerators that can be used include amine-based, phenol-based, and imidazole-based curing accelerators, and more specific examples thereof include amine complexes of boron trifluoride, imidazole derivatives, organic acids such as phthalic anhydride, and trimellitic anhydride. have.
상기 경화촉진제의 바람직한 비제한적인 예로는, 이미다졸 유도체 경화촉진제가 있고, 구체적으로 1-메틸이미다졸, 2-메틸이미다졸, 2-에틸 4-메틸 이미다졸, 2-페닐이미다졸, 2-페닐4-메틸 이미다졸, 이들의 시아노에틸레이션 유도체, 카르복실산 유도체, 히드록시메틸기 유도체 등이 있는데, 이에 한정되지 않는다. 이들 경화 촉진제는 1종 단독으로 이용할 수 있으며 또는 2종 이상을 병용할 수도 있다. Preferred non-limiting examples of the curing accelerators include imidazole derivative curing accelerators, specifically 1-methylimidazole, 2-methylimidazole, 2-ethyl 4-methyl imidazole, 2-phenylimidazole. , 2-phenyl4-methyl imidazole, cyanoethylation derivatives thereof, carboxylic acid derivatives, hydroxymethyl group derivatives, and the like, but are not limited thereto. These hardening accelerators can be used individually by 1 type, or can also use 2 or more types together.
상기 경화촉진제의 함량은 에폭시 수지 및 경화제의 혼합물 100 중량부를 기준으로 약 0.005 내지 0.05 중량부 범위일 수 있으며, 바람직하게는 0.01 내지 0.04 범위일 수 있다.The content of the curing accelerator may range from about 0.005 to 0.05 parts by weight, preferably from 0.01 to 0.04, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent.
한편, 본 발명의 에폭시 수지 조성물은, 상기 수지 조성물의 고유 특성을 해하지 않는 한, 필요에 따라 당 업계에 일반적으로 알려진 무기물 필러, 난연제, 상기에서 기재되지 않은 다른 열경화성 수지나 열가소성 수지 및 이들의 올리고머와 같은 다양한 고분자, 고체상 고무 입자 또는 자외선 흡수제, 항산화제, 중합개시제, 염료, 안료, 분산제, 증점제, 레벨링제 등과 같은 기타 첨가제 등을 추가로 포함할 수 있다. 일례로, 유기인계 난연제, 유기계 질소 함유 인 화합물, 질소 화합물, 실리콘계 난연제, 금속 수산화물 등의 난연제; 실리콘계 파우더, 나일론 파우더, 불소수지 파우더 등의 유기충전제, 오르벤, 벤톤 등의 증점제; 실리콘계, 불소수지계 등의 고분자계 소포제 또는 레벨링제; 이미다졸계, 티아졸계, 트리아졸계, 실란계 커플링제 등의 밀착성 부여제; 프탈로시아닌, 카본 블랙 등이 착색제 등을 들 수 있다. On the other hand, the epoxy resin composition of the present invention, inorganic fillers, flame retardants, other thermosetting resins and thermoplastic resins not mentioned above, and oligomers thereof, which are generally known in the art as necessary, as long as they do not impair the intrinsic properties of the resin composition. Various polymers such as, solid rubber particles or other additives such as ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents and the like may be further included. Examples include flame retardants such as organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides; Organic fillers such as silicone powder, nylon powder, and fluororesin powder, and thickeners such as orbene and benton; Polymeric antifoaming agents or leveling agents such as silicone-based and fluorine-based resins; Adhesion imparting agents such as imidazole series, thiazole series, triazole series, and silane coupling agents; Phthalocyanine, carbon black, etc. can be mentioned a coloring agent.
상기 에폭시 수지 조성물에는 경화 후의 수지 조성물에 적당한 가요성을 부여하는 것 등을 목적으로 하여, 열가소성 수지를 배합할 수 있다. 이러한 열가소성 수지의 예를 들면, 페녹시 수지, 폴리비닐아세탈 수지, 폴리이미드, 폴리아미드이미드, 폴리에테르설폰, 폴리설폰 등을 들 수 있다. 이들의 열가소성 수지는 어느 1종만을 단독으로 사용하여도 좋고, 2종 이상을 병용하여도 좋다. A thermoplastic resin can be mix | blended with the said epoxy resin composition for the purpose of providing suitable flexibility to the resin composition after hardening, etc. Examples of such thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimides, polyamideimide, polyethersulfone, polysulfone and the like. Any one of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.
<수지 복합 동박 및 이의 제조방법><Resin composite copper foil and manufacturing method thereof>
이하, 첨부된 도면을 참조하여 본 발명의 일 실시예에 따른 수지 복합 동박에 대하여 상세히 설명한다. Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the resin composite copper foil according to an embodiment of the present invention.
도 1을 참조하여 설명하면, 본 발명의 수지 복합 동박(100)은, 동박(110), 및 상기 동박의 일면 또는 양면상에 위치하며, 전술한 에폭시 수지 조성물을 이용하여 형성된 프라이머 수지층(120)을 포함한다.Referring to FIG. 1, the resin composite copper foil 100 of the present invention is located on the copper foil 110 and one or both surfaces of the copper foil, and the primer resin layer 120 formed using the epoxy resin composition described above. ).
본 발명에 따른 수지 복합 동박에 있어서, 동박(110)은 당 분야에 알려진 통상적인 동박을 제한없이 사용할 수 있으며, 일례로 압연법 및 전해법으로 제조되는 모든 동박을 포함한다. 여기서, 동박은 표면이 산화 부식되는 것을 방지하기 위해서, 녹방지 처리되어 있을 수 있다. In the resin composite copper foil according to the present invention, the copper foil 110 may use any conventional copper foil known in the art without limitation, and includes all copper foils produced by a rolling method and an electrolytic method, for example. Here, the copper foil may be subjected to rust prevention treatment in order to prevent the surface from being oxidized and corroded.
상기 동박은 제1절연 수지층과 접하는 일면 상에 소정의 표면 조도(Rz)가 형성되어 있을 수가 있으며, 이때 표면조도(Rz)는 0.6 ㎛ 내지 3.0 ㎛ 범위일 수 있다.The copper foil may have a predetermined surface roughness Rz formed on one surface of the copper foil in contact with the first insulating resin layer, and the surface roughness Rz may be in a range of 0.6 μm to 3.0 μm.
또한 상기 동박의 두께는 특별히 제한되지 않으나, 최종물의 두께와 기계적 특성을 고려하여 10 ㎛ 미만인 것을 사용할 수 있으며, 바람직하게는 1 내지 5 ㎛ 범위일 수 있다. In addition, the thickness of the copper foil is not particularly limited, but may be used less than 10 ㎛ in consideration of the thickness and mechanical properties of the final product, preferably in the range of 1 to 5 ㎛.
사용 가능한 동박의 예로는, Mitsui 18MT-EX, F2-WS, F1-WS, FWL-WS, T4X 등이 있다. Examples of copper foil that can be used include Mitsui 18MT-EX, F2-WS, F1-WS, FWL-WS, T4X, and the like.
본 발명에 따른 수지 복합 동박에 있어서, 상기 프라이머 수지층(120)은 동박의 표면상에 형성되며, 기재(substrate)인 동박, 및 상기 수지층 상에 형성되는 절연 수지층 또는 프리프레그(PRG)와의 접착력을 보다 향상시킬 수 있다.In the resin composite copper foil according to the present invention, the primer resin layer 120 is formed on the surface of the copper foil, the copper foil serving as the substrate, and the insulating resin layer or prepreg (PRG) formed on the resin layer. The adhesive force with can be improved more.
이러한 프라이머 수지층(120)의 두께는 동박과 절연층 간의 접착성을 확보할 수 있는 범위 내에서 적절히 조절할 수 있으며, 일례로 1 내지 10 ㎛ 범위일 수 있으며, 바람직하게는 1 내지 7 ㎛ 범위이며, 보다 바람직하게는 1 내지 5㎛ 일 수 있다. The thickness of the primer resin layer 120 may be appropriately adjusted within a range capable of securing the adhesiveness between the copper foil and the insulating layer, for example, may be in the range of 1 to 10 ㎛, preferably 1 to 7 ㎛ More preferably, it may be 1-5 micrometers.
본 발명에 따른 프라이머 수지층(120)은 전술한 에폭시 수지 조성물을 경화시켜 형성된 경화층을 포함하는데, 이때 상기 에폭시 수지 조성물은 반드시 완전히 열 경화되어 있을 필요는 없고, 본 발명의 효과가 발휘될 정도로 경화되어 있으면 좋다. Primer resin layer 120 according to the present invention includes a cured layer formed by curing the above-mentioned epoxy resin composition, wherein the epoxy resin composition does not necessarily need to be completely heat-cured, so that the effect of the present invention is exhibited It should just be hardened.
본 발명의 일례에 따르면, 상기 수지 복합 동박(100)은 상기 프라이머 수지층(120) 상에 당 업계에 알려진 통상적인 절연수지층, 프리프레그층 또는 이들 모두를 더 포함할 수 있다. According to an example of the present invention, the resin composite copper foil 100 may further include a conventional insulating resin layer, a prepreg layer, or both of which are known in the art on the primer resin layer 120.
본 발명에 따른 수지 복합 동박(100)은, 당 분야에 알려진 통상적인 방법에 따라 제조될 수 있다. 일례로, 동박의 표면 상에 상기 에폭시 수지 조성물 바니쉬를 도포한 후 가열, 건조 및 경화시켜 얻을 수 있으며, 또는 지지체 상에 도포된 수지 바니쉬를 가열 및 건조하여 얻어진 접착 시트나 필름을 동박의 표면 상에 배치한 후 접착하여 얻을 수도 있다.The resin composite copper foil 100 according to the present invention may be manufactured according to conventional methods known in the art. For example, the epoxy resin composition varnish may be applied to the surface of the copper foil and then heated, dried and cured, or the adhesive sheet or film obtained by heating and drying the resin varnish applied on the support may be coated on the surface of the copper foil. It can also be obtained by arranging in the adhesive.
이때 에폭시 수지 조성물을 기재 상에 도포하는 경우, 당 분야에 알려진 통상적인 도포방법, 예컨대 딥(Dip) 코팅, 다이(Die) 코팅, 롤(roll) 코팅, 콤마(comma) 코팅, 캐스팅 또는 이들의 혼합 방식 등 다양한 방식을 제한 없이 사용될 수 있다. 또한 건조 방법 및 건조 조건은 당 분야에 알려진 통상적인 범위 내에서 조절할 수 있으며, 일례로 50 내지 170℃의 온도에서 1 내지 30분간 건조하여 수행할 수 있다.In this case, when the epoxy resin composition is applied on a substrate, conventional coating methods known in the art, such as dip coating, die coating, roll coating, comma coating, casting or their Various methods such as a mixing method can be used without limitation. In addition, the drying method and drying conditions may be adjusted within the conventional range known in the art, for example, it may be carried out by drying for 1 to 30 minutes at a temperature of 50 to 170 ℃.
상기 에폭시 수지 조성물을 조제시 사용 가능한 유기 용제의 예를 들면, 아세톤, 메틸에틸케톤, 시클로헥사논 등의 케톤류, 아세트산에틸, 아세트산부틸, 셀로솔브아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 카비톨아세테이트 등의 아세트산 에스테르류, 셀로솔브, 부틸카비톨 등의 카비톨류, 톨루엔, 크실렌 등의 방향족 탄화수소류, 디메틸포름아미드, 디메틸아세트아미드, N-메틸피롤리돈 등을 들 수 있다. 유기 용제는 1종을 사용하거나 2종 이상을 조합하여 사용하여도 좋다. Examples of organic solvents that can be used when preparing the epoxy resin composition include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like. Carboxols such as acetic acid ester, cellosolve, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use an organic solvent 1 type or in combination of 2 or more types.
본 발명의 에폭시 접착제 조성물 중에서 유기 수지 성분과 필요에 따라 첨가되는 무기 고형 성분 및 유기 용제는 포트 밀, 볼 밀, 균질기, 수퍼 밀 등을 이용하여 혼합될 수 있다. In the epoxy adhesive composition of the present invention, the organic resin component and the inorganic solid component and organic solvent added as needed may be mixed using a pot mill, a ball mill, a homogenizer, a super mill, and the like.
한편, 본 발명은 기판의 일면 또는 양면 상에 전술한 에폭시 수지 조성물을 이용하여 형성된 프라이머 수지층을 포함하는 인쇄회로기판용 적층체를 제공한다. On the other hand, the present invention provides a laminate for a printed circuit board comprising a primer resin layer formed by using the above-described epoxy resin composition on one side or both sides of the substrate.
이때, 기판은 코어 기판으로 사용되는 것일 수 있으며, 내층 배선판 등일 수 있다. In this case, the substrate may be used as a core substrate, and may be an inner layer wiring board.
상기 인쇄 회로 기판은 신규 에폭시 수지 조성물에 기인하는 우수한 접착성, 내열성, 등 제반 성능이 지속적으로 발휘하므로, 각종 전자기기 등의 고기능화 및 장수화에 공헌할 수 있다. Since the printed circuit board exhibits excellent performances such as excellent adhesiveness, heat resistance, and the like due to the novel epoxy resin composition, it can contribute to high functionalization and long life of various electronic devices.
이하, 본 발명의 실시예 및 실험예를 들어 상세히 설명하기로 한다. 다만, 하기의 실시예는 본 발명의 바람직한 실시예에 해당될 뿐, 본 발명이 하기 실시예 및 실험예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples. However, the following examples correspond only to the preferred embodiments of the present invention, and the present invention is not limited to the following examples and experimental examples.
[실시예 1~6]EXAMPLES 1-6
1-1. 에폭시 수지 조성물의 제조1-1. Preparation of Epoxy Resin Composition
하기 표 1에 기재된 조성에 따라 제1에폭시 수지, 제2에폭시 수지, 경화제, 다이머산 변성 에폭시 수지, 경화촉진제 등을 혼합하여 에폭시 수지 조성물을 각각 제조하였다. 하기 표 1에서 각 조성물의 사용량 단위는 중량부이며, 여기서, "중량부"는 고당량 에폭시 수지, 저당량 에폭시 수지 및 경화제의 혼합물 100 중량부를 기준으로 한 것이다.According to the composition shown in Table 1 below, a first epoxy resin, a second epoxy resin, a curing agent, a dimer acid-modified epoxy resin, a curing accelerator, and the like were mixed to prepare epoxy resin compositions, respectively. In Table 1 below, the amount of each unit used is parts by weight, where "parts by weight" is based on 100 parts by weight of a mixture of a high equivalent epoxy resin, a low equivalent epoxy resin, and a curing agent.
1-2. 수지 복합 동박 및 인쇄회로기판용 적층체의 제조1-2. Fabrication of Resin Composite Copper Foil and Laminates for Printed Circuit Boards
상기에서 제조된 에폭시 수지 조성물을 일반 1/2Oz 동박에 1~5㎛으로 코팅하여 160℃에서 3분간 건조하여 적용하였다. 이때 코팅방법은 캐스팅 또는 그라비아 코터를 사용하여 진행하였다. The epoxy resin composition prepared above was coated with 1 to 5 μm on a general 1 / 2Oz copper foil and dried at 160 ° C. for 3 minutes. At this time, the coating method was performed using a casting or gravure coater.
이후 프라이머 수지층이 코팅된 동박에 프리프레그(Prepreg, 두산, DS-7402HFE (PPG)를 적용하여 적층체를 형성하였으며, 이를 통해 접착 강도의 개선 효과를 평가하였다Thereafter, a prepreg (Doosan, DS-7402HFE (PPG)) was applied to the copper foil coated with the primer resin layer to form a laminate, and the improvement effect of the adhesive strength was evaluated.
[비교예 1~3][Comparative Examples 1-3]
하기 표 2에 기재된 조성에 따른 것을 제외하고는, 상기 실시예와 동일한 방법으로 에폭시 수지 조성물, 수지 복합 동박 및 인쇄회로기판용 적층체를 각각 제조하였다. 하기 표 2에서 각 조성물의 사용량 단위는 중량부이다. Except that according to the composition shown in Table 2, the epoxy resin composition, a resin composite copper foil and a laminate for a printed circuit board were prepared in the same manner as in the above Examples. In Table 2 below, the amount of each unit used is in parts by weight.
[비교예 4][Comparative Example 4]
프라이머 수지층이 도포되지 않은 일반 동박 상에, 프리프레그(Prepreg, 두산, DS-7402HFE (PPG)를 적용하여 비교예 6의 적층체를 형성하였으며, 이를 통해 접착 강도의 개선 효과를 평가하였다On the general copper foil to which the primer resin layer was not applied, prepreg (Doosan, DS-7402HFE (PPG)) was applied to form the laminate of Comparative Example 6, and the improvement effect of the adhesive strength was evaluated.
[실험예 1] - 물성 평가Experimental Example 1-Property Evaluation
실시예 1 ~ 6 및 비교예 1 ~ 4에서 각각 제조된 인쇄회로기판용 적층체에 대하여 하기 실험을 하였고, 그 결과를 하기 표 1~2에 각각 나타내었다.The following experiments were carried out for the laminates for printed circuit boards manufactured in Examples 1 to 6 and Comparative Examples 1 to 4, respectively, and the results are shown in Tables 1 and 2, respectively.
1) 코팅성: Gravure* pilot 코팅기를 사용하여 표면처리되지 않은 12㎛ (1/3Oz) 동박의 Matt면에 1~5㎛ 수지를 코팅하였다. (*박막코팅 가능한 마이크로 코팅기) 180℃ 온도 하에서 약 3분 B-stage로 건조시켰다. 1) Coating property: 1-5 μm resin was coated on a Matt surface of a 12 μm (1 / 3Oz) copper foil which was not surface treated using a Gravure * pilot coater. (* Thin coatable micro coater) It was dried by B-stage for about 3 minutes at 180 degreeC temperature.
2) 접착성(Peel Strength, P/S): IPC-TM-650 2.4.8의 평가 규격에 의해 인쇄 회로 기판용 적층체에 회로 패턴을 형성한 후 형성된 회로 패턴을 90° 방향에서 끌어 올려 회로 패턴(구리층)이 박리되는 시점을 측정하여 평가하였다.2) Peel Strength (P / S): According to the evaluation standard of IPC-TM-650 2.4.8, a circuit pattern is formed on a laminate for a printed circuit board, and then the circuit pattern formed is pulled up in a 90 ° direction. The time of peeling of a pattern (copper layer) was measured and evaluated.
3) 내열성: IPC TM-650 2. 4. 13 평가 규격에 따라 Solder 288℃에서 인쇄회로 기판용 적층체를 Floating하여 프라이머 수지층과 동박 간의 분리 현상이 일어나는 시점까지의 시간을 측정하여 평가하였다.3) Heat resistance: According to the IPC TM-650 2. 4. 13 evaluation standard, it was evaluated by measuring the time until the separation phenomenon between the primer resin layer and the copper foil by floating the laminate for printed circuit board at Solder 288 ℃.
4) 흡수율: IPC-TM-650 2.6.2.1의 평가 규격에 따라 평가하였다. 4) Absorption rate: According to the evaluation standard of IPC-TM-650 2.6.2.1.
표 1
　 실시예1 실시예2 실시예3 실시예4 실시예5 실시예6
다이머산 변성 에폭시 5 15 25 5 5 5
에폭시1 　 　 　 　 35 　
*ND 에폭시 1 35 35 35 35 　 35
에폭시2 　 　 　 　 　 35
ND 에폭시 2 35 35 35 35 35 　
경화제1 　 　 　 30 　 　
ND 경화제 1 30 30 30 　 30 30
경화촉진제 0.006 0.006 0.006 0.006 0.006 0.006
코팅성 ◎ ◎ ◎ ◎ ◎ ◎
P/S (@1/3 Oz-kgf/cm) 1.4 1.35 1.2 1.2 1.3 1.27
내열성(S/D @288) > 10min > 10min > 10min > 10min > 10min > 10min
흡수율(D-2/100) 0.38 0.5 0.7 0.38 0.38 0.38
*ND: Narrow Dispersity
Table 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Dimer Acid Modified Epoxy 5 15 25 5 5 5
Epoxy 1 35
* ND epoxy 1 35 35 35 35 35
Epoxy 2 35
ND epoxy 2 35 35 35 35 35
Curing agent 1 30
ND Curing Agent 1 30 30 30 30 30
Curing accelerator 0.006 0.006 0.006 0.006 0.006 0.006
Coating ◎ ◎ ◎ ◎ ◎ ◎
P / S (@ 1/3 Oz-kgf / cm) 1.4 1.35 1.2 1.2 1.3 1.27
Heat resistance (S / D @ 288) > 10min > 10min > 10min > 10min > 10min > 10min
Absorption rate (D-2 / 100) 0.38 0.5 0.7 0.38 0.38 0.38
* ND: Narrow Dispersity
표 2
　 비교예1 비교예2 비교예3 비교예4
다이머산 변성 에폭시 5 15 25 일반 동박 적용
에폭시1 35 35 35
*ND 에폭시 1 　 　 　
에폭시2 35 35 35
ND 에폭시 2 　 　 　
경화제1 30 30 30
ND 경화제 1 　 　 　
경화촉진제 0.006 0.006 0.006
코팅성 ○ ○ ○ -
P/S (@1/3 Oz-kgf/cm) 0.9 0.8 0.8 0.65
내열성(S/D @288) > 10min 8 min 7 min 5 min
흡수율(D-2/100) 0.4 0.5 0.7 0.4
*ND: Narrow Dispersity
TABLE 2
Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Dimer Acid Modified Epoxy 5 15 25 Normal copper foil applied
Epoxy 1 35 35 35
* ND epoxy 1
Epoxy 2 35 35 35
ND epoxy 2
Curing agent 1 30 30 30
ND Curing Agent 1
Curing accelerator 0.006 0.006 0.006
Coating ○ ○ ○ -
P / S (@ 1/3 Oz-kgf / cm) 0.9 0.8 0.8 0.65
Heat resistance (S / D @ 288) > 10min 8 min 7 min 5 min
Absorption rate (D-2 / 100) 0.4 0.5 0.7 0.4
* ND: Narrow Dispersity
㈜ Corporation
1) ND에폭시 수지1: PDI: 1.57/ EEW: 600g/eq1) ND epoxy resin 1: PDI: 1.57 / EEW: 600g / eq
2) ND에폭시 수지 2: PDI: 1.26/ EEW: 190g/eq2) ND epoxy resin 2: PDI: 1.26 / EEW: 190g / eq
3) 다이머산 변성 에폭시 수지 : 국도 화학 KSR-2003) Dimer acid modified epoxy resin: Kukdo Chemical KSR-200
4) ND 경화제 1: PDI: 1.40/ EEW 106.84) ND Curing Agent 1: PDI: 1.40 / EEW 106.8
5) 경화촉진제: 2E4Mz (이미다졸 촉매)5) Curing accelerator: 2E4Mz (imidazole catalyst)
6) 에폭시 수지1: PDI: 3.45/ EEW: 600g/eq6) Epoxy Resin 1: PDI: 3.45 / EEW: 600g / eq
7) 에폭시 수지2: PDI: 2.0/ EEW: 190g/eq7) Epoxy Resin 2: PDI: 2.0 / EEW: 190g / eq
8) 경화제1: phenol novolac hardener (코오롱 KPH-F2003, PDI: 2.3)8) Hardener 1: phenol novolac hardener (KOLON KPH-F2003, PDI: 2.3)
실험 결과, 본 발명의 에폭시 수지 조성물을 이용한 수지 복합 동박은 코팅성, 접착성, 내열성, 흡수율 면에서 뛰어난 특성을 보였다(표 1 참조).As a result of the experiment, the resin composite copper foil using the epoxy resin composition of the present invention showed excellent properties in terms of coating property, adhesiveness, heat resistance, and water absorption (see Table 1).
따라서 향후 신뢰성이 높은 빌드업 인쇄회로기판을 제조할 수 있으며, 소형, 경량의 신규 반도체 패키지의 구성 재료로서 유용하게 사용될 것으로 판단된다.Therefore, it is possible to manufacture a reliable build-up printed circuit board in the future, and it is judged that it will be usefully used as a constituent material of a small and lightweight new semiconductor package.

Claims (11)

  1. (a) 에폭시 당량(EEW)이 400~1000 g/eq 범위인 고당량 제1에폭시 수지;(a) a high equivalent first epoxy resin having an epoxy equivalent (EEW) in the range of 400-1000 g / eq;
    (b) 에폭시 당량(EEW)이 100-300 g/eq 범위인 저당량 제2에폭시 수지; (b) low equivalent second epoxy resins having an epoxy equivalent weight (EEW) in the range of 100-300 g / eq;
    (c) 다이머산 변성 에폭시 수지; 및(c) dimer acid-modified epoxy resins; And
    (d) 경화제(d) curing agent
    를 포함하며, 상기 제1에폭시 수지와 제2에폭시 수지 중 1종 이상은 다분산지수(PDI)가 2 이하인 것을 특징으로 하는 에폭시 수지 조성물. Wherein the at least one of the first epoxy resin and the second epoxy resin has a polydispersity index (PDI) of 2 or less.
  2. 제1항에 있어서, 제1에폭시 수지의 중량 평균 분자량(Mw)이 1,000 내지 3,000 범위이며, 제2에폭시 수지의 중량 평균 분자량(Mw)이 500 내지 2,000 범위인 것을 특징으로 하는 에폭시 수지 조성물.The epoxy resin composition according to claim 1, wherein the weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is in the range of 500 to 2,000.
  3. 제1항에 있어서, 제1에폭시 수지와 제2에폭시 수지의 사용 비율은 50~90 : 10~50 중량 비율인 것을 특징으로 하는 에폭시 수지 조성물.The epoxy resin composition according to claim 1, wherein the use ratio of the first epoxy resin and the second epoxy resin is 50 to 90: 10 to 50 weight ratio.
  4. 제1항에 있어서, 상기 다이머산 변성 에폭시 수지는 변성율이 5 내지 30%이고, 에폭시 당량이 100 내지 500g/eq인 것을 특징으로 하는 에폭시 수지 조성물. The epoxy resin composition of claim 1, wherein the dimer acid-modified epoxy resin has a modification rate of 5 to 30% and an epoxy equivalent of 100 to 500 g / eq.
  5. 제1항에 있어서, 상기 경화제는 크레졸노볼락, 비스페놀A 노볼락, 나프탈렌형, 아민 경화제 및 아미노트리아진 노볼락으로 구성된 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 에폭시 수지 조성물. The epoxy resin composition according to claim 1, wherein the curing agent is at least one selected from the group consisting of cresol novolac, bisphenol A novolac, naphthalene type, amine curing agent and aminotriazine novolac.
  6. 제1항에 있어서, 상기 경화제는 다분산지수(PDI)가 2 이하인 것을 특징으로 하는 에폭시 수지 조성물. The epoxy resin composition of claim 1, wherein the curing agent has a polydispersity index (PDI) of 2 or less.
  7. 제1항에 있어서, 상기 경화제와 에폭시 수지는 20 ~ 50 : 50 ~ 80 중량 비율로 포함되는 것을 특징으로 하는 에폭시 수지 조성물.The epoxy resin composition of claim 1, wherein the curing agent and the epoxy resin are included in a weight ratio of 20 to 50:50 to 80.
  8. 제1항에 있어서, 상기 조성물은 에폭시 수지와 경화제의 혼합물 100 중량부를 기준으로 상기 다이머산 변성 에폭시 수지(c)를 5 내지 40 중량부로 포함하는 것을 특징으로 하는 에폭시 수지 조성물.The epoxy resin composition of claim 1, wherein the composition comprises 5 to 40 parts by weight of the dimer acid-modified epoxy resin (c) based on 100 parts by weight of the mixture of the epoxy resin and the curing agent.
  9. 제1항에 있어서, 상기 수지 조성물은 아민계, 페놀계 및 이미다졸계 화합물로 구성된 군으로부터 선택되는 1종 이상의 경화촉진제를 더 포함하며, The method of claim 1, wherein the resin composition further comprises one or more curing accelerators selected from the group consisting of amine-based, phenol-based and imidazole-based compounds,
    상기 경화촉진제는 에폭시 수지와 경화제의 혼합물 100 중량부 기준으로 0.005 내지 0.05 중량부로 포함되는 것을 특징으로 하는 에폭시 수지 조성물. The curing accelerator is 0.005 to 0.05 parts by weight based on 100 parts by weight of the mixture of the epoxy resin and the curing agent epoxy resin composition.
  10. 동박; 및Copper foil; And
    상기 동박의 일면 또는 양면 상에, 제1항 내지 제9항 중 어느 한 항에 기재된 에폭시 수지 조성물을 이용하여 형성된 프라이머 수지층을 포함하는 수지 복합 동박.The resin composite copper foil which contains the primer resin layer formed using the epoxy resin composition of any one of Claims 1-9 on one or both surfaces of the said copper foil.
  11. 기판의 일면 또는 양면상에, 제1항 내지 제9항 중 어느 한 항에 기재된 에폭시 수지 조성물을 이용하여 형성된 프라이머 수지층을 포함하는 인쇄회로기판용 적층체. A laminate for printed circuit boards, comprising a primer resin layer formed on one or both surfaces of a substrate using the epoxy resin composition according to any one of claims 1 to 9.
PCT/KR2013/012171 2012-12-26 2013-12-26 Epoxy resin composition having excellent adhesive properties and resin composite copper foil using same WO2014104739A1 (en)

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CN114516204A (en) * 2022-01-25 2022-05-20 铜川光速芯材科技有限公司 LED transparent circuit board and preparation method thereof

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CN114516204A (en) * 2022-01-25 2022-05-20 铜川光速芯材科技有限公司 LED transparent circuit board and preparation method thereof

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