Insulating resin with improved ductility and build-up film using same

Abstract

The present invention relates to: an insulating resin that, as a circuit material, has a low coefficient of thermal expansion and a low dielectric loss for implementing a microcircuit, while also having excellent adhesion to copper plating and excellent ductility; and an insulating film or an insulating layer using same. The insulating resin is suitable for application as a build-up film for a printed circuit board.

Description

Insulating resin with improved flexibility and build-up film using the same

[0001] The present invention relates to an insulating resin with improved elongation characteristics while maintaining a low coefficient of thermal expansion and low dielectric loss for the implementation of microcircuits, and a build-up film or insulating layer using the same, and is suitable for application as a build-up film of a printed circuit board.

[0002]

[0003] With the increasing functionality of electronic devices and the high integration of semiconductor devices, there is a demand for high-density printed circuit boards, and multilayer printed circuit boards are currently the mainstream. The build-up method is known as a manufacturing method for multilayer printed circuit boards.

[0004] The build-up method is a multilayer method in which a copper laminate plate to be plated through holes is etched to form a circuit, masked by an insulating film, printed conductive paste ink on top to form a circuit, and then a copper plating film is formed on the conductive paste ink and through holes by repeating the process.

[0005] Currently, build-up printed circuit boards are manufactured using the subtractive process, the MSAP (modified semi-additive process), or the SAP (semi-additive process). Among these, the SAP process is used to manufacture the outer layer of the build-up. The SAP process is a process that creates a conductor circuit pattern by performing electroplating and bushing processes after plating.

[0006] The high integration and miniaturization of semiconductors used in electronic devices, communication devices, and personal computers are accelerating, and consequently, the various characteristics required for laminates used in semiconductor packages for printed circuit boards (e.g., metal foil-clad laminates) are becoming increasingly stringent. To explain more specifically, insulating resins (or insulating adhesive resins) for build-up films are generally manufactured by mixing curing agents, fillers, etc., based on epoxy resins. However, as the coefficient of thermal expansion increases, the curl or warpage defects of the printed circuit board occur frequently, leading to a decrease in the accuracy of circuit implementation. Furthermore, as dielectric loss increases, microcircuit design becomes difficult; therefore, low dielectric constant, low dielectric loss, low thermal expansion, and heat resistance are required.

[0007] To address this, the filler content in the insulating resin for build-up films is maximized to impart low coefficient of thermal expansion characteristics; however, a high filler content significantly degrades the elongation properties of the build-up film, which leads to increased brittleness, reduced processability, and problems such as increased defect rates including cracks.

[0008]

[0009] The present invention aims to provide an insulating resin of an optimal composition capable of improving handling performance and long-term product stability by maintaining a low coefficient of thermal expansion while enhancing ductility of the build-up film (thin film layer), which is an insulating layer material, in a method for manufacturing a multilayer printed circuit board of a build-up type in which a conductive circuit layer and an insulating layer are alternately laminated, and a build-up film (insulating layer) using the same.

[0010]

[0011] The insulating resin with improved flexibility according to the present invention for solving the above problem comprises an epoxy mixed resin, a modified epoxy resin, a binder resin, a curing agent, a curing accelerator, and a filler.

[0012] As a preferred embodiment of the present invention, the epoxy mixed resin may include two or more types selected from biphenyl-based epoxy resin, bisphenol-based A epoxy resin, and naphthalene-based epoxy resin.

[0013] As a preferred embodiment of the present invention, the epoxy mixed resin may contain a naphthalene-based epoxy resin and a biphenyl-based epoxy resin in a weight ratio of 1:0.3 to 0.8, or may contain a naphthalene-based epoxy resin, a biphenyl-based epoxy resin and a bisphenol A epoxy resin in a weight ratio of 1:0.3 to 0.8:0.5 to 1.2.

[0014] As a preferred embodiment of the present invention, the modified epoxy resin may include one or more selected from CTBN (carboxyl-terminated butadiene acrylonitrile) modified epoxy resin and NBR (nitrile-butadiene rubber) modified epoxy resin.

[0015] As a preferred embodiment of the present invention, the modified epoxy resin may be a modified epoxy resin having a modification rate of 13.0 to 22.0% by CTBN or NBR.

[0016] As a preferred embodiment of the present invention, the binder resin may include one or more selected from phenoxy resin, PVB (poly vinyl butyral) resin, and NBR (nitrile-butadiene rubber) resin.

[0017] As a preferred embodiment of the present invention, the curing agent may include one or more selected from a phenolic curing agent, a naphthalene-type curing agent, a dicyclopentadiene (DCPD) novolak-type curing agent, and a cresol novolak-type curing agent.

[0018] As a preferred embodiment of the present invention, the curing accelerator may include one or more selected from imidazole-based curing accelerators, trialyl isocyanurate-based curing accelerators, and dicumyl peroxide-based curing accelerators.

[0019] As a preferred embodiment of the present invention, the imidazole-based curing accelerator may include one or more selected from 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.

[0020] As a preferred embodiment of the present invention, the triallyl isocyanurate-based curing accelerator may include one or more selected from triallyl cyanurate, trialyl cyclohexane, and vinylbenzyl oxide.

[0021] As a preferred embodiment of the present invention, the dicumyl peroxide-based curing accelerator may include one or more selected from acetyl peroxide, benzol peroxide, and polyethylene.

[0022] As a preferred embodiment of the present invention, the filler may include one or more selected from silica (SiO2) and silica (SiO2) surface-modified with a silane compound.

[0023] As a preferred embodiment of the present invention, the filler has an average particle size (D 50 ) can be 0.20 ~ 3.5㎛.

[0024] As a preferred embodiment of the present invention, the silane compound may include a compound represented by the following chemical formula 1.

[0025] [Chemical Formula 1]

[0026] R 3 NHR 2 Si(OR 1 )3

[0027] In Chemical Formula 1, R 1is hydrogen or a C1–C5 straight-chain alkyl group, a C3–C5 branched alkyl group, or a C1–C5 straight-chain alkoxy group, and R 2 is an alkylene group having 1 to 5 carbon atoms, and R 3 is a hydrogen atom, a C1-C3 straight-chain alkyl group, a C3-C5 branched-chain alkyl group, a C3-C5 branched-chain alkyl group, or a phenyl group having or without substituents.

[0028] As a preferred embodiment of the present invention, the insulating resin with improved flexibility of the present invention may comprise, based on solid content, 8.0 to 20.0 wt% of an epoxy mixed resin, 1.0 to 4.0 wt% of a modified epoxy resin, 3.0 to 10.0 wt% of a binder resin, 5.0 to 15.0 wt% of a curing agent, 0.01 to 1.00 wt% of a curing accelerator, and the remaining amount of a filler among 100 wt%.

[0029] Another object of the present invention relates to a build-up film (or insulating film) comprising the insulating resin.

[0030] As a preferred embodiment of the present invention, the build-up film of the present invention may satisfy the following equation 1 for the coefficient of thermal expansion (CTE) at 30 to 150°C after curing.

[0031] [Equation 1]

[0032] 20.00 ppm / ℃ ≤ CTE α1 ≤ 25.00 ppm / ℃

[0033] In Equation 1, the CTE α1 value is the coefficient of thermal expansion in the X and / or Y directions.

[0034] As a preferred embodiment of the present invention, the build-up film of the present invention can satisfy an elongation of 5% or more when measured according to the JIS K7113 method.

[0035] As a preferred embodiment of the present invention, the build-up film of the present invention, after curing, has a dielectric constant (D) at 10 GHz when measured according to the SPDR (split post dielectric resonators) method. k ) is 3.50 or less, and dielectric loss (D f ) can satisfy 0.0010 ~ 0.0150.

[0036] As a preferred embodiment of the present invention, the build-up film of the present invention can satisfy an adhesion strength of 0.40 kgf / cm or more when measuring the adhesion strength to copper plating after curing.

[0037]

[0038] 9. Another objective of the present invention is to provide a printed circuit board comprising an insulating layer or a build-up film (or insulating film) formed by the cured product of the insulating resin described above.

[0039] In addition, the present invention may also provide a method of using the insulating resin described above when manufacturing a multilayer printed circuit board by applying a semi-additive patterning (SAP) process.

[0040]

[0041] The insulating resin of the present invention and the build-up film (insulating film) manufactured therefrom maintain a low dielectric constant, low dielectric loss, and a low coefficient of thermal expansion, while exhibiting excellent adhesion to insulators as well as conductors such as copper plating, and possessing improved elongation characteristics. The build-up film of the present invention is easy to handle during use, and can even be described as increasing reliability due to improved productivity of FC-BGA (flip chip-ball grey array) products and impact resistance during product use.

[0042]

[0043] FIG. 1 is a schematic cross-sectional view of a multilayer printed circuit board having an insulating film or a build-up film of the present invention laminated thereon.

[0044]

[0045] In this specification, expressions such as “have,” “may have,” “include,” or “may include” indicate the presence of such features (e.g., numerical values, functions, actions, or components, etc.) and do not exclude the presence of additional features.

[0046] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification shall be understood as being modified by the term "about" in all cases, unless otherwise stated.

[0047] The present invention will be described in more detail below.

[0048] Insulating resins used in the manufacture of build-up films generally comprise epoxy resin and binder resin, and an appropriate chain structure must be formed through the reaction between them. However, while physical mixing of these compositions is possible, chemical crosslinking is virtually impossible. To solve this problem, the present invention introduces a modified epoxy resin modified with a binder component having a specific structure within the epoxy resin to induce physical and chemical chain structures, thereby enabling the manufacture of an insulating resin that secures enhanced ductility while maintaining a low coefficient of thermal expansion, and a build-up film (insulating film, insulating layer) produced therefrom.

[0049] The insulating resin of the present invention comprises an epoxy mixed resin, a modified epoxy resin, a binder resin, a curing agent, a curing accelerator, and a filler.

[0050] The epoxy mixed resin in the insulating resin composition of the present invention may include two or more types selected from biphenyl-based epoxy resin, bisphenol-based A epoxy resin, and naphthalene-based epoxy resin.

[0051] As a preferred example, when the insulating resin comprises two types of epoxy resins, it may include a naphthalene-based epoxy resin and a biphenyl-based epoxy resin in a weight ratio of 1:0.3 to 0.8, preferably 1:0.40 to 0.70, and more preferably 1:0.40 to 0.60. At this time, if the amount of biphenyl-based epoxy resin used in the mixture is less than 0.3 weight ratio, there may be a problem with the coefficient of thermal expansion properties deteriorating, and if it is used in excess of 0.70 weight ratio, there may be a problem with increased brittleness.

[0052] In addition, when the insulating resin comprises three types of epoxy resins, it may include a naphthalene-based epoxy resin, a biphenyl-based resin, and a bisphenol-based A epoxy resin in a weight ratio of 1:0.3 to 0.8:0.5 to 1.2, preferably in a weight ratio of 1:0.42 to 0.78:0.55 to 1.1, and more preferably in a weight ratio of 1:0.44 to 0.75:0.55 to 1.1. At this time, if the amount of bisphenol-based A epoxy resin used in the mixture is less than 0.5 weight ratio, there may be no effect of improving brittleness, and if used in excess of 1.2 weight ratio, there may be a problem of reduced coefficient of thermal expansion and dielectric loss characteristics.

[0053] In addition, the above naphthalene epoxy resin may be 1,6-bis(2,3-epoxypropoxy) naphthalene (1,6-Bis(2,3-epoxypropoxy) naphthalene, CAS No. 27610-48-6).

[0054] In addition, the above-mentioned biphenyl-based epoxy resin may have one or more biphenyl-based moiety groups within the epoxy resin.

[0055] In addition, the above-mentioned biphenyl-based epoxy resin may be a solid or liquid epoxy resin at 25°C, preferably a liquid epoxy resin at 25°C. Furthermore, using the above-mentioned biphenyl-based epoxy resin having an epoxy equivalent of 250 g / eq to 300 g / eq may facilitate the realization of the effects of the present invention.

[0056] In addition, the bisphenol-A epoxy resin may include a conventional bisphenol-A epoxy resin known to those skilled in the art, and specifically, the bisphenol-A epoxy resin may have one or more bisphenol-A moiety groups within the epoxy resin. The bisphenol-A epoxy resin may be a solid or liquid epoxy resin at 25°C, preferably an epoxy resin that is liquid at 25°C. Furthermore, using a bisphenol-A epoxy resin having an epoxy equivalent of 150 g / eq to 190 g / eq may facilitate the realization of the effects of the present invention.

[0057] In addition, the content of the epoxy mixed resin in the total weight of the insulating resin of the present invention may be 8.0 to 20.0 weight% based on solid content, preferably 10.0 to 18.0 weight%, and more preferably 10.0 to 17.0 weight%. At this time, if the content of the epoxy mixed resin is less than 8.0 weight%, there may be a problem of significantly insufficient adhesion and insulation, and if it exceeds 15 weight%, a problem of deterioration in dielectric properties may occur.

[0058]

[0059] Next, among the insulating resin compositions of the present invention, the modified epoxy resin plays a role in improving elongation characteristics, and the modified component induces bonding with the binder resin to raise the overall energy level of the build-up film (insulating layer) and prevents phase separation between other compositions, thereby improving physical mixing properties.

[0060] The above modified epoxy resin comprises one or more selected from CTBN (carboxyl-terminated butadiene acrylonitrile) modified epoxy resin and NBR (nitrile-butadiene rubber) modified epoxy resin, preferably a modified epoxy resin in which the modification rate of the epoxy resin by CTBN or NBR is 13.0 to 22.0%, more preferably

[0061] It is preferable to use a modified epoxy resin with a modification rate of 15.0 to 20.0% by CTBN or NBR. However, if the modification rate is less than 13.0%, the effect of improving ductility due to the use of the modified epoxy resin may be insufficient, and even if the modification rate exceeds 22.0%, there may be a problem where the coefficient of thermal expansion increases without any additional effect of improving ductility.

[0062] In addition, the epoxy resin to be modified from CTBN or NBR may include one or more selected from trimethylolpropane triglycidyl ether, DGEBA (Diglycidyl Ether of Bisphenol A), and DGEBF (Diglycidyl Ether of Bisphenol F), and preferably may include one or more selected from trimethylolpropane triglycidyl ether and DGEBA.

[0063] In addition, the content of the modified epoxy resin in the total weight of the insulating resin of the present invention may be 1.0 to 4.0 weight% based on solid content, preferably 1.0 to 3.6 weight%, and more preferably 1.0 to 3.4 weight%. At this time, if the content of the modified epoxy resin is less than 1.0 weight%, the amount used is too small, so the effect of improving ductility due to its use may be insufficient, and if it exceeds 4 weight%, problems such as a decrease in dielectric properties and difficulty in maintaining a low coefficient of thermal expansion may occur.

[0064]

[0065] Next, among the insulating resin compositions of the present invention, the binder resin is a component that forms the framework of a cured body (build-up film, insulating layer) in which the insulating resin is cured, and may include one or more selected from phenoxy resin, PVB (poly vinyl butyral) resin, and NBR (nitrile-butadiene rubber) resin, and may include two or more selected from phenoxy resin, PVB resin, and NBR resin, and more preferably, may be used by mixing three types of the resins.

[0066] When using a mixture of these three types, it is appropriate to mix them in the range of 50 to 150 parts by weight of PVB resin and 50 to 150 parts by weight of NBR resin per 100 parts by weight of phenoxy resin.

[0067] In addition, the content of the binder resin in the total weight of the insulating resin of the present invention may be 3.0 to 10.0 weight% based on solid content, preferably 3.5 to 8.5 weight%, and more preferably 4.0 to 8.0 weight%. At this time, if the content of the binder resin is less than 3.0 weight%, the coating properties, shape retention of the cured body, mechanical properties, etc. may be poor, and if it exceeds 10.0 weight%, problems may arise in expressing the main characteristics of the build-up film, such as the coefficient of thermal expansion, dielectric loss, and mechanical properties.

[0068]

[0069] Next, the curing agent in the insulating resin composition plays a role in providing adhesion and strength to the build-up film by forming cross-links with the epoxy resin.

[0070] The above curing agent may include one or more selected from a phenolic curing agent, a naphthalene-type curing agent, a dicyclopentadiene (DCPD) novolak-type curing agent, and a cresol novolak-type curing agent; preferably, it may include one or more selected from a phenolic curing agent and a DCPD novolak-type curing agent; more preferably, it is preferable to use a mixture of a phenolic curing agent and a DCPD novolak-type curing agent in a weight ratio of 1:0.05 to 0.20.

[0071] In addition, the content of the curing agent in the insulating resin of the present invention is 5.0 to 15.0 weight% based on solid content, preferably 7.0 to 14.0 weight%, and more preferably 8.0 to 14.0 weight%. At this time, if the content of the curing agent in the insulating resin is less than 5.0 weight%, there may be difficult problems such as insufficient adhesion of the cured insulating resin and poor mechanical properties, and if it exceeds 15 weight%, there may be problems such as reduced compatibility and workability due to gelation of the resin, so it is appropriate to use it within the above range.

[0072]

[0073] Next, the curing accelerator in the insulating resin composition may include one or more selected from imidazole-based curing accelerators, trialyl isocyanurate-based curing accelerators, and dicumyl peroxide-based curing accelerators.

[0074] In addition, the above imidazole-based curing accelerator may include one or more selected from 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.

[0075] In addition, the triallyl isocyanurate-based curing accelerator may include one or more selected from triallyl cyanurate, trialyl cyclohexane, and vinylbenzyl oxide.

[0076] In addition, the above dicumyl peroxide-based curing accelerator may include one or more selected from acetyl peroxide, benzol peroxide, and polyethylene.

[0077] In addition, the content of the curing accelerator in the insulating resin of the present invention is 0.01 to 1.00 wt% based on solid content, preferably 0.02 to 0.50 wt%, and more preferably 0.02 to 0.30 wt%. If the content of the curing accelerator is less than 0.01 wt%, the amount used is too small, so the curing accelerating effect due to its use may be insufficient, and if it is used in excess of 1.00 wt%, there may be a problem of changes in the physical properties of the cured insulating resin over time, so it is appropriate to use it within the above range.

[0078]

[0079] Next, the filler in the insulating resin composition may be an inorganic filler such as general silica used in the industry, and in addition, to increase the effects such as the dispersibility of the filler in the insulating resin, the formation of surface roughness after desmearing, and the improvement of copper plating adhesion, the present invention may use silica (SiO2) surface-modified with a silane compound represented by the following chemical formula 1 as a filler.

[0080] [Chemical Formula 1]

[0081] R 3 NHR 2 Si(OR 1 )3

[0082] In Chemical Formula 1, R 1 is hydrogen or a C1–C5 straight-chain alkyl group, a C3–C5 branched alkyl group, or a C1–C5 straight-chain alkoxy group, and R 2 is an alkylene group having 1 to 5 carbon atoms, and R 3 is a hydrogen atom, a C1-C3 straight-chain alkyl group, a C3-C5 branched-chain alkyl group, a C3-C5 branched-chain alkyl group, or a phenyl group having or without substituents.

[0083] And, the above filler has an average particle size (D 50 A particle size having a value of 0.20 to 3.50 μm, preferably 0.50 to 3.50 μm, may be used, and within the above range, the coefficient of thermal expansion of the insulating film can be lowered and the effect of improving dielectric properties can be provided. The above average particle size (D 50 ) was measured using the laser diffraction method.

[0084] In addition, the silica of the surface-modified silica is a non-core-shell type silica, which can be solid silica or hollow silica, and can be spherical, amorphous, etc., but preferably spherical silica can be used.

[0085] And, the content of the filler in the insulating resin of the present invention is the remainder excluding the epoxy mixed resin, modified epoxy resin, binder resin, curing agent, and curing accelerator from the total weight percent of the insulating resin.

[0086]

[0087] In addition, the insulating resin of the present invention described above may further include a silane coupling agent to increase the peel strength of the insulating film when a film, insulating layer (coating layer), etc. are manufactured using the insulating resin. At this time, the silane coupling agent may include conventional silane coupling agents known to those skilled in the art, such as amino-based, epoxy-based, (meth)acrylic-based, and mercapto-based alkoxysilanes, and preferably, urido(C1-C5 alkyl)tri(C1-C5 alkoxy)silanes such as gamma-uridopropyltrimethoxysilane may be used. Furthermore, when using a silane coupling agent, using its content in an amount of approximately 0.01 to 1.00 weight% of the total weight% of the insulating resin based on solid content prevents the problem of uneven surface thickness of the insulating film, and the adhesive composition for the insulating film may not experience changes in the basic physical properties of the adhesive or chemical contamination during chemical copper plating.

[0088] In addition to this, the insulating resin of the present invention may further include additives such as BT (bismaleimide traizine) resin, surfactants, and dispersants.

[0089] Among the additives, the BT resin used to improve the heat resistance of the insulating film may be an inert cyanate-based ester. The BT resin may be a commercially available product or manufactured by a method known to those skilled in the art. When using the BT resin, its content is approximately 1.0 to 10.0 weight percent of the total weight percent of the insulating resin based on solid content, and using it within this range allows for appropriate improvement in the heat resistance of the insulating film while preventing brittleness of the insulating film.

[0090] Among the additives, the surfactant mentioned above increases the film-forming ability when forming an insulating resin into a film or a coating layer, and can be selected from common types known to those skilled in the art, for example, sodium dodecyl benzene sulfonate (SDBS), polyoxyethylene nonylphenol ether, Fluonic F127, etc., can be used. In addition, when using a surfactant, its content is about 0.01 to 1.00 weight% of the total weight% of the insulating resin based on solid content, and using it within this range is appropriate in terms of the film-forming ability of the insulating film.

[0091] Among the additives, the above-mentioned dispersant can be included in the adhesive composition for insulating films to prevent the aggregation of silica and to ensure good dispersion of silica, thereby allowing the coefficient of thermal expansion of the insulating film to be maintained stably. In addition, when using the dispersant, its content is approximately 0.1 to 2.0 weight percent of the total weight percent of the insulating resin based on solid content, and using it within this range prevents the problem of clumping of the filler and prevents the problem of changes in the basic physical properties of the insulating resin.

[0092]

[0093] A build-up film, an insulating film, or an insulating layer can be formed by applying the previously described insulating resin to one side of a carrier film and then performing drying.

[0094] Also, the thickness of the build-up film, insulating film, or insulating layer is not specifically limited, but considering the application to the printed circuit board, it can be 25㎛ to 50㎛.

[0095]

[0096] After curing, the coefficient of thermal expansion (CTE) of the build-up film, insulating film, or insulating layer of the present invention at 30 to 150°C can satisfy the following Equation 1.

[0097] [Equation 1]

[0098] 20.00 ppm / ℃ ≤ CTE α1 ≤ 25.00 ppm / ℃, preferably 21.00 ppm / ℃ ≤ CTE α1 ≤ 25.00 ppm / ℃

[0099] In Equation 1, the CTE α1 value is the coefficient of thermal expansion in the X and / or Y axis directions.

[0100] In addition, the above build-up film, insulating film, or insulating layer can satisfy an elongation of 5% or more, preferably 5.0 to 8.0%, when measured according to JIS K7113.

[0101] The build-up film, insulating film, or insulating layer of the present invention, after curing, has a dielectric constant (D) at 10 GHz when measured according to the SPDR (split post dielectric resonators) method. k ) is 5.50 or less, and dielectric loss (D f ) can satisfy 0.0010 ~ 0.0150, and preferably the permittivity (D) at 10 GHz) k ) is 3.40 or less, and dielectric loss (D f ) can satisfy 0.0010 ~ 0.0130.

[0102] The build-up film, insulating film, or insulating layer of the present invention can satisfy an adhesion force of 0.40 kgf / cm or more, preferably 0.40 to 0.80 kgf / cm, and more preferably 0.40 to 0.65 kgf / cm when measuring the adhesion force for copper plating, and such high adhesion force provides stable adhesion stability to the substrate and circuit.

[0103]

[0104] The present invention provides a printed circuit board comprising a build-up film, an insulating film, or an insulating layer formed by the cured product of the insulating resin described above.

[0105] In addition, a method can be provided for using the aforementioned insulating resin when manufacturing a multilayer printed circuit board by applying the Semi-Additive Patterning (SAP) method.

[0106] The above insulating film or the above build-up film can be used in the manufacture of a multilayer printed circuit board.

[0107] FIG. 1 illustrates a printed circuit board having insulating films (110a, 110b) laminated according to an embodiment of the present invention. As shown in FIG. 1, the insulating film (110a) is in contact with the laminated insulating film (110b), the substrate (200), the first circuit (210), and the second circuit (220).

[0108] A multilayer printed circuit board can be manufactured by conventional methods known to those skilled in the art. In one embodiment, an insulating film is formed by applying an adhesive composition for an insulating film to one side of a carrier film to a predetermined thickness and then drying it at a temperature of 80°C to 110°C for 1 minute to 10 minutes, and a cover film is attached to one side of the insulating film to manufacture a build-up film (or insulating film sheet) in which the cover film, insulating film, and carrier film are laminated.

[0109] An insulating film is obtained by peeling off a cover film from a build-up film, and the insulating film is vacuum-bonded to a substrate or the like using a vacuum laminator, and then pre-baked. Pre-baking can be performed at a temperature within a predetermined range (e.g., 100°C to 170°C) and for a time within a predetermined range (e.g., 60 minutes to 120 minutes). Then, a plating process is performed on the surface of the pre-baked insulating film to completely cure the insulating film in the pre-baked state. Complete curing of the insulating film can be performed at 150°C to 200°C for 60 minutes to 120 minutes, but is not limited thereto. Additionally, a desmear process may be performed before the plating process.

[0110] The method for manufacturing a printed circuit board according to the present invention includes the step of using an insulating film formed of the insulating resin of the present invention. The method for manufacturing a printed circuit board according to the present invention may involve using an insulating film formed of the adhesive composition for insulating films according to the present invention when manufacturing a conventional circuit board. Hereinafter, each step of the method for manufacturing a printed circuit board according to the present invention will be described in detail, but the present invention is not limited thereto.

[0111] A method for manufacturing a printed circuit board comprises the steps of: (A) applying a thermosetting insulating resin of the present invention to a support to form an insulating film coating, (B) bonding the support and the insulating film coating to a circuit board such that the insulating film coating is bonded to the circuit board, (C) curing the insulating film coating to form an insulating film, (D) perforating the insulating film to form via holes, (E) performing a desmear treatment, and (F) forming a conductor layer on the surface of the insulating layer.

[0112] (A) Process

[0113] (A) The process involves applying a thermosetting insulating resin to a support to a predetermined thickness to form a coating film for an insulating film.

[0114] Examples of supports include films made of plastic materials, metal foils (copper foil or aluminum foil), release paper, etc. The support may further have a release layer laminated on the surface bonded to the insulating resin.

[0115] The thermosetting insulating resin uses the insulating resin of the present invention described above, and can become a coating film for an insulating film by applying it to a support to a predetermined thickness and then drying it with a solvent.

[0116] (B) Process

[0117] (B) The process is to bond the support and the insulating film coating to the circuit board so that the insulating film coating is bonded to the circuit board.

[0118] The insulating film may be pretreated before being bonded to the circuit board. Pretreatment methods may include etching treatment such as CZ pretreatment.

[0119] Bonding can generally be performed using a vacuum laminate by appropriately adjusting the compression pressure, compression temperature, compression time, etc.

[0120] (C) Process

[0121] (C) The process is to form an insulating film by curing a coating film for an insulating film. Specifically, an insulating layer is formed by heat curing a coating film for an insulating film. The heat curing conditions are not particularly limited, and conditions commonly used when forming an insulating layer of a circuit board may be used. The heat curing conditions may be performed at 150°C to 200°C for 60 minutes to 120 minutes, but are not limited thereto.

[0122] Before heat-curing the insulating film, it may be pre-cured at a temperature lower than the heat-curing temperature. For example, before heat-curing the insulating film, it may be pre-cured at 30°C to 40°C and for 10 to 30 minutes.

[0123] (D) Process

[0124] (D) Process is to form via holes by drilling an insulating film. Via holes are formed for electrical connection between layers and, considering the characteristics of the insulating layer, can be formed by a drilling method using a laser, plasma, etc. Examples of laser light sources include carbon dioxide lasers, YAG lasers, and excimer lasers.

[0125] (E) Process

[0126] (E) The process is to perform desmear treatment. Resin residue is attached inside the via hole formed in process (D), and since this resin residue causes poor electrical connection between layers, it must be removed.

[0127] Desmearing treatment can be carried out by conventional methods and can be performed as dry desmearing, wet desmearing, or a combination thereof. Dry desmearing treatment may be desmearing treatment using plasma. Wet desmearing treatment may include desmearing treatment using an oxidizing agent solution.

[0128] (F) Process

[0129] (F) The process includes forming a conductor layer on the surface of an insulating layer.

[0130] A conductor layer can be formed by a semi-additive process (SAP), etc. A plating seed layer can be formed on the surface of an insulating layer by chemical plating, a mask pattern is formed to expose a portion of the plating seed layer corresponding to a desired wiring pattern, a metal layer is formed by electroplating on the exposed plating seed layer, the mask pattern is removed, and the unnecessary plating seed layer is removed by etching to form a conductor layer having a desired wiring pattern.

[0131]

[0132] The present invention will be explained in more detail below through examples, but the following examples are not intended to limit the scope of the invention and should be interpreted as being for the purpose of aiding understanding of the invention.

[0133] [Example]

[0134] The specific specifications of the components used in the examples and comparative examples below are as follows.

[0135] (A) Epoxy-based mixed resin

[0136] (A1) Bisphenol A-based epoxy resin (Product name: YD-128, Kukdo Chemical, Epoxy equivalent weight 150g / eq ~ 190g / eq)

[0137] (A2) Biphenyl-based epoxy resin (Product name: NC-3000, Nippon Kagaku, epoxy equivalent 250~300 g / eq)

[0138] (A3) Naphthalene-based epoxy resin (Product name: SE-80, Shin-A T&C, CAS No. 27610-48-6)

[0139] (B) Modified epoxy resin

[0140] (B1) CTBN-modified epoxy resin

[0141] It is an epoxy resin that is modified with CTBN at 15%, 20%, or 30% by adding trimethylolpropane triglycidyl ether (Cas No. 30499-70-8), which is an epoxy resin.

[0142] (B2) NBR modified epoxy resin

[0143] It is an epoxy resin that is 20% modified from DGEBA (Diglycidyl Ether of Bisphenol A), an epoxy resin, into NBR.

[0144] (B3) Acrylic Modified Epoxy Resin (Product Name: PARACRON EG26R, Manufacturer: Negami; Japan)

[0145] (B4) Rubber-modified epoxy resin (Product name: UME-305, Manufacturer: Kukdo Chemical), where the rubber is urethane rubber.

[0146] (C) Binder resin

[0147] (C1) Phenoxy Resin (Product Name: HE-1900, Manufacturer: HE Chem)

[0148] (C2) PVB (poly vinyl butyral) resin (Product name: BM-SZ, Manufacturer: Sekisui)

[0149] (C3) NBR Resin (Product Name: CBE-101, Manufacturer: Chembase)

[0150] (D) Curing agent

[0151] (D-1) Phenolic Curing Agent (Product Name: SCP-110, Manufacturer: Shin-A T&C)

[0152] (D-2) Dicyclopentadiene novolak curing agent (Product name: KDN-7280, Manufacturer: Kukdo Chemical)

[0153] (E) Curing accelerator

[0154] (E1) The imidazole-based curing accelerator 1 used was 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole, trade name: 2E4MZ, manufacturer: Shikoku Kasei Kogyo).

[0155] (E2) The imidazole-based curing accelerator 2 used was 1-benzyl-2-phenylimidazole (1-benzyl-2-phenylimidazole, trade name: 1B2PZ, manufacturer: Shikoku Kasei Kogyo).

[0156]

[0157] Example 1: Preparation of insulating resin

[0158] An epoxy mixed resin, which is a mixture of naphthalene-based epoxy resin and biphenyl-based epoxy resin, and CTBN-modified epoxy resin (modification rate 15%) were mixed, stirred, and heated to dissolve the mixture to prepare a mixed solution.

[0159] Then, a binder resin, a curing agent, a curing accelerator, and a filler were mixed into the above mixture and uniformly dispersed using a mixer to produce an insulating resin, and the composition content is shown in Table 1 below. At this time, the content is expressed based on solid content.

[0160] Phenoxy resin, PVB (poly vinyl butyral) resin, and NBR resin were used as the binder resins mentioned above.

[0161] In addition, phenolic resin and DCPD novolak resin were used as curing agents.

[0162] In addition, an imidazole-based curing accelerator 2 was used as a curing accelerator.

[0163] In addition, silica (average particle size D) as a filler 50 =0.5㎛) was used.

[0164]

[0165] Examples 2–11 and Comparative Examples 1–11

[0166] Insulating resins were prepared using the same composition as in Example 1 above, but with different compositional contents as shown in Tables 1 and 1 below, and Examples 1 to 11 and Comparative Examples 1 to 11 were carried out respectively.

[0167]

[0168] Experimental Example 1: Measurement of Physical Properties

[0169] Insulating films were manufactured using insulating resins prepared in the examples and comparative examples, and the properties of Tables 1 to 3 below were evaluated.

[0170] When measuring physical properties, the curing was heat curing, and the insulating film was heat cured at 190°C for 60 minutes.

[0171] (1) Coefficient of thermal expansion (unit: ppm / ℃): After curing the insulating film, the coefficient of thermal expansion was measured by using a TMA device to increase the temperature from 25℃ to 260℃ at a rate of 10℃, and the coefficient of thermal expansion in the X and Y axis directions was evaluated and the coefficient of thermal expansion values ​​in the range of 30 to 150℃ were shown.

[0172] (2) Genetic trait rate (D k ): After curing the insulating film, the dielectric constant at a frequency of 10 GHz (D) measured by a dielectric constant measuring device k ) and dielectric loss (D f ) was measured.

[0173] (3) Adhesion (kgf / cm): After curing the insulating film and electroplating copper to a thickness of 20 μm on the cured insulating film, the adhesion between the cured insulating film and the copper plating film was measured using an adhesion measuring device at a peeling temperature of 25°, a peeling angle of 90°, and a peeling speed of 50 mm / min.

[0174] (4) Elongation (%) : Measured using a UTM machine according to the JIS K7113 measurement method, and evaluated as acceptable if the elongation was 5% or more.

[0175] Classification Example 1 2 3 4 5 6 7 8 9 Epoxy Mixed Resin Bisphenol A Epoxy --- 44-44-Naphthalene Epoxy 10 10 9 7 4 10 7 4 10 Biphenyl Epoxy 5 5 4 5 2 5 5 Modified Epoxy Resin CTBN Modification (Modification Rate 15%) 1.5 -- 1 3 ---- CTBN Modification (Modification Rate 20%) ----- 1.5 1 3 - CTBN Modification (Modification Rate 30%) --------- NBR Modification (Modification Rate 20%) - 1 3 ----- 1.5 Acrylic Modification (Modification Rate 20%) --------- Rubber Modification (Modification Rate 20%) --------- Binder Resin Phenoxy Resin 1.5 2 2 2 5 1 1 5 2 5 1 1 5 PVB Resin 2 2 2 2 2 2 2 NBR Resin 1 1 1 5 2 1 1 5 2 1 1 5 1 Curing Agent Phenolic-based Curing Agent 998 1099 1099 DCPD Novolak Curing Agent 221 312 312 Curing Accelerator Imidazole-based Curing Accelerator 1 -0.05 -0.05 0.025 -0.05 0.025 -Imidazole-based Curing Accelerator 20.025 -0.025 --0.025 --0.025 Filler SiO2 Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Total (Weight%) 100 100 100 100 100 100 100 100 100 Physical Property Evaluation Coefficient of Thermal Expansion CTE α1 (ppm / ℃) 22 22 24 24 21 23 24 22 24 Dielectric Constant (D k )3.273.253.353.223.313.273.123.363.27Genetic Loss(D f )0.01140.01160.01090.01260.01030.01140.01280.01030.0114 Adhesion (kgf / cm) 0.48 10.41 20.47 90.42 10.59 00.48 10.42 10.58 80.48 1 Elongation (%) / Pass / Fail 5.5 / Pass 5.2 / Pass 5.8 / Pass 5.1 / Pass 5.1 / Pass 5.7 / Pass 5.4 / Pass 5.5 / Pass 5.8 / Pass

[0176] Classification Preliminary Comparative Example 10 1 1 1 2 3 4 5 6 7 Epoxy Mixed Resin Bisphenol A Epoxy 4 4 4 8 4 4 Naphthalene Epoxy 7 4 1 1 9.5 7 9 9.5 7 4 Biphenyl Epoxy 5 2 5 4.5 5 6 4.5 5 2 Modified Epoxy Resin CTBN Modification (Modification Rate 15%) 5 3 CTBN Modification (Modification Rate 20%) --------- CTBN Modification (Modification Rate 30%) ----- 1 3 NBR Modification (Modification Rate 20%) 1 3 0.5 5 5 Acrylic Modification (Modification Rate 20%) --------- Rubber Modification (Modification Rate 20%) --------- Binder Resin Phenoxy Resin 2 5 1 2 1 5 2 2 5 1 5 2 5 1 PVB Resin 2 2 1 1 5 2 5 1 2 2 NBR Resin 1.52 1.112 1.52 Curing Agent Phenolic Curing Agent 109 98.59 108.5 109 DCPD Novolak Curing Agent 3 12 123 131 Curing Accelerator Imidazole Curing Accelerator 10.05 0.025 0.05 -0.05 -0.05 0.05 0.025 Imidazole Curing Accelerator 2 0.025 -0.025 Filler SiO2 Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder Remainder 55% Remainder Remainder Remainder Remainder Remainder Total (Weight%) 100 100 100 100 100 100 100 100 100 Physical Property Evaluation Coefficient of Thermal Expansion CTE α1(ppm / ℃)242322342230322628 Permittivity (D k )3.193.253.253.323.273.183.273.193.26Dielectric loss(D f )0.0129 0.0103 0.0116 0.0111 0.0114 0.0141 0.0114 0.0152 0.0143 Adhesion (kgf / cm) 0.42 10.56 70.35 60.37 60.29 80.54 20.34 50.48 70.539 Elongation (%) / Pass / Fail 5.5 / Pass 5.7 / Pass 2.2 / Fail 7.6 / Pass 2.5 / Fail 6.1 / Pass 6.9 / Pass 5.6 / Pass 3.2 / Fail

[0177] Classification Comparison Example 89 10 11 Epoxy Mixed Resin Bisphenol A Epoxy 4 4 4 4 Naphthalene Epoxy 7 4 7 4 Biphenyl Epoxy 5 2 5 2 Modified Epoxy Resin CTBN Modification (Modification Rate 15%) ---- CTBN Modification (Modification Rate 20%) ---- CTBN Modification (Modification Rate 30%) ---- NBR Modification (Modification Rate 20%) ---- Acrylic Modification (Modification Rate 20%) 13 -- Rubber Modification (Modification Rate 20%) -- 13 Binder Resin Phenoxy Resin 2.5 1 2.5 1 PVB Resin 2 2 2 2 NBR Resin 1.5 2 1.5 2 Curing Agent Phenol-based Curing Agent 10 9 10 9 DCPD Novolak Curing Agent 3 1 3 1 Curing Accelerator Imidazole-based Curing Accelerator 10.0 5 0.0 2 5 0.0 5 0.0 2 5 Imidazole-based Curing Accelerator 2----Filler SiO2 Remainder Remaining Amount Remainder Remaining Amount Remainder Remaining Amount Remainder Remaining Amount Total (Weight%) 100 100 100 100 Physical Property Evaluation Coefficient of Thermal Expansion CTE α1 (ppm / ℃) 273 128 30 Dielectric Constant (D k )3.343.153.233.28Dielectric loss(D f )0.013 10.012 20.015 60.0176 Adhesion (kgf / cm) 0.36 60.54 20.37 20.469 Elongation (%) / Pass / Fail 3.2 / Fail 3.7 / Fail 6.2 / Pass 6.8 / Pass

[0178]

[0179] Looking at the physical property measurement results in Tables 1 to 3 above, the insulating resins of Examples 1 to 11 have a low dielectric constant of 3.50 or less (D k ) and low dielectric loss of 0.0150 or less (D f It was confirmed that it has an appropriate coefficient of thermal expansion (20.00 ~ 25.00 ppm / ℃), a high elongation of 5% or more, and high adhesion.

[0180] In contrast, Comparative Example 1 and Comparative Example 7, which did not use modified epoxy resin, had a problem with excessively low elongation, and Comparative Example 7 also had a problem with a coefficient of thermal expansion exceeding 25 ppm / ℃.

[0181] In addition, in Comparative Example 2, which used more than 4 weight percent of modified epoxy resin, there was a problem with the coefficient of thermal expansion being too high.

[0182] In addition, in the case of Comparative Example 3, which used NBR modified epoxy resin instead of CTBN modified epoxy resin, there was a problem with poor elongation.

[0183] In addition, in the case of Comparative Example 4, in which more than 20% by weight of epoxy mixed resin was used, the filler content was inevitably reduced relatively, and as a result, there was a problem of increased coefficient of thermal expansion.

[0184] In addition, Comparative Examples 5 and 6, which used CTBN-modified epoxy resins with a modification rate of 30% exceeding 22%, had a problem in that the coefficient of thermal expansion exceeded 25.00 ppm / ℃, which was too high.

[0185] In addition, Comparative Examples 8 and 9, which used acrylic modified epoxy resin instead of CTBN modified epoxy resin, had a problem of low elongation and a very high coefficient of thermal expansion, and Comparative Examples 10 and 11, which used rubber modified epoxy resin, had a problem of a high coefficient of thermal expansion and a dielectric loss exceeding 0.0150.

[0186] It can be confirmed that the insulating resin of the present invention and the insulating film made therefrom have a low dielectric constant, low dielectric loss, and a low coefficient of thermal expansion, while also having excellent adhesion to insulators as well as conductors such as copper plating, and that the elongation rate is improved by more than 5%.

[0187] In addition, the insulating film made of the insulating resin of the present invention has a low surface roughness and a uniform surface, so when applied as a build-up film, particularly in the SAP (semi additive process) method, it can maintain a uniform surface roughness even after plasma treatment and / or desmear process for manufacturing a multilayer printed circuit board.

Claims

1. It comprises an epoxy mixed resin, a modified epoxy resin, a binder resin, a curing agent, a curing accelerator, and a filler, and The above epoxy mixed resin comprises two or more types selected from biphenyl-based epoxy resin, bisphenol-based A epoxy resin, and naphthalene-based epoxy resin, and An insulating resin with improved flexibility, characterized by comprising one or more types selected from CTBN (carboxyl-terminated butadiene acrylonitrile) modified epoxy resin and NBR (nitrile-butadiene rubber) modified epoxy resin.

2. In claim 1, the epoxy mixed resin comprises a naphthalene-based epoxy resin and a biphenyl-based epoxy resin in a weight ratio of 1:0.3 to 0.8, or An insulating resin with improved flexibility characterized by containing a naphthalene-based epoxy resin, a biphenyl-based epoxy resin, and a bisphenol-based A epoxy resin in a weight ratio of 1:0.3 to 0.8:0.5 to 1.

2.

3. An insulating resin with improved flexibility according to claim 1, characterized in that the modified epoxy resin is a modified epoxy resin having a modification rate of 13.0 to 22.0% by CTBN or NBR.

4. An insulating resin with improved flexibility according to claim 1, characterized in that the binder resin comprises one or more types selected from phenoxy resin, PVB (poly vinyl butyral) resin, and NBR (nitrile-butadiene rubber) resin.

5. In claim 1, the curing agent comprises one or more selected from phenolic curing agents, naphthalene-type curing agents, dicyclopentadiene (DCPD) novolak-type curing agents, and cresol novolak-type curing agents, and The above curing accelerator comprises one or more selected from imidazole-based curing accelerators, trialyl isocyanurate-based curing accelerators, and dicumyl peroxide-based curing accelerators. The above imidazole-based curing accelerator comprises one or more selected from 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole, and The above triallyl isocyanurate-based curing accelerator comprises one or more selected from triallyl cyanurate, trialyl cyclohexane, and vinylbenzyl oxide, and An insulating resin with improved flexibility, characterized by comprising one or more types selected from acetyl peroxide, benzol peroxide, and polyethylene as the above-mentioned dicumyl peroxide-based curing accelerator.

6. In claim 1, the filler comprises one or more selected from silica (SiO2) and silica (SiO2) surface-modified with a silane compound, and An insulating resin with improved ductility, characterized in that the above silane compound comprises a compound represented by the following chemical formula 1. [Chemical Formula 1] R 3 NHR 2 Si(OR 1 )3 In Chemical Formula 1, R 1 is hydrogen or a C1–C5 straight-chain alkyl group, a C3–C5 branched alkyl group, or a C1–C5 straight-chain alkoxy group, and R 2 is an alkylene group having 1 to 5 carbon atoms, and R 3 is a hydrogen atom, a C1-C3 straight-chain alkyl group, a C3-C5 branched-chain alkyl group, a C3-C5 branched-chain alkyl group, or a phenyl group having or without substituents.

7. In paragraph 1, the filler has an average particle size (D 50 An insulating resin with improved ductility characterized by having a thickness of 0.20 to 3.5㎛.

8. An insulating resin with improved ductility according to claim 1, characterized by comprising, based on solid content, 8.0 to 20.0 wt% of an epoxy mixed resin, 1.0 to 4.0 wt% of a modified epoxy resin, 3.0 to 10.0 wt% of a binder resin, 5.0 to 15.0 wt% of a curing agent, 0.01 to 1.00 wt% of a curing accelerator, and the remaining amount of a filler among 100 wt%.

9. A build-up film characterized by comprising the insulating resin of any one of claims 1 to 8.

10. The build-up film according to claim 9, characterized in that, after curing, the coefficient of thermal expansion (CTE) at 30 to 150°C satisfies the following Equation 1; [Equation 1] 20.00 ppm / ℃ ≤ CTE α1 ≤ 25.00 ppm / ℃ In Equation 1, the CTE α1 value is the coefficient of thermal expansion in the X and Y directions.

11. A build-up film according to claim 9, characterized by satisfying an elongation of 5% or more when measured according to the JIS K7113 method.

12. In claim 9, the dielectric constant (D) at 10 GHz when measured according to the SPDR (split post dielectric resonators) method after curing of the build-up film k ) is 3.50 or less, and dielectric loss (D f A build-up film characterized by ) being 0.0010 to 0.0150.

13. The build-up film according to claim 9, characterized in that the adhesion force is 0.40 kgf / cm or more when measuring the adhesion force to copper plating after curing.

14. A printed circuit board comprising an insulating layer formed by a cured product of the insulating resin selected from any one of claims 1 to 8.

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