Thermosetting insulating resin and insulating film using same

Abstract

The present invention relates to a thermosetting insulating resin, which is a circuit material, exhibiting excellent adhesion to copper plating while having a low coefficient of thermal expansion and low dielectric loss for implementing microcircuits, and to an insulating film or insulating layer using same. The present invention is suitable for application as a build-up film of a printed circuit board and, particularly, is suitable for application in the manufacture of a printed wiring board using a semi-additive patterning (SAP) method.

Description

Thermosetting insulating resin and insulating film using the same

[0001] The present invention relates to a thermosetting insulating resin having a low coefficient of thermal expansion and low dielectric loss for implementing microcircuits as a circuit material, and excellent adhesion to copper plating, and to an insulating film or insulating layer using the same, and is suitable for application as a build-up film for printed circuit boards, and is particularly suitable for application in the manufacture of printed wiring boards using a SAP (semi-additive pattering) method.

[0002] With the advancement of electronic devices and the increasing integration of semiconductor devices, printed circuit boards are also demanding higher density. Multilayer printed circuit boards are currently the mainstream. The build-up method is a well-known method for manufacturing multilayer printed circuit boards.

[0003] The build-up method is a method of forming a multilayer by repeating the process of forming a circuit by etching a copper laminate plate to be plated through holes, masking it with an insulating film, printing conductive paste ink on it to form a circuit, and then forming a copper plating film on the conductive paste ink and through holes.

[0004] Currently, build-up printed circuit boards are manufactured using the subtractive process, the modified semi-additive process (MSAP), or the semi-additive process (SAP). Among these, the SAP process is used to manufacture the build-up outer layer. The SAP process involves plating followed by electroplating and a bushing process to create a conductive circuit pattern.

[0005] The integration and miniaturization of semiconductors used in electronic devices, communication devices, and personal computers are accelerating, and along with this, the various properties required for laminates for semiconductor packages used in printed wiring boards (e.g., metal foil-clad laminates, etc.) are becoming more and more stringent. To explain more specifically, insulating resins (or insulating adhesive resins) for build-up films are generally manufactured by mixing hardeners and fillers with epoxy resins as the base. The higher the coefficient of thermal expansion, the more likely it is that the printed circuit board will warp (curl or wapage) and the lower the matching of the circuit implementation. In addition, the higher the dielectric loss, the more difficult it is to design fine circuits. Therefore, low permittivity, low dielectric loss, low thermal expansion, and heat resistance are required.

[0006] To this end, there are cases where the content of filler in the insulating resin for the build-up film is increased to improve the coefficient of thermal expansion and / or dielectric properties, but the brittle properties increase, resulting in a decrease in processability, and the epoxy resin content is relatively reduced, resulting in a problem of decreased adhesion to copper plating.

[0007] The present invention aims to provide an insulating resin having an optimal composition that satisfies low dielectric properties and a low coefficient of thermal expansion for implementing microcircuits in printed circuit boards, while also having excellent adhesion to conductors or insulators such as copper plating, and an insulating film, a build-up film, and a printed circuit board using the same.

[0008] The insulating resin of the present invention for solving the above problem is a thermosetting resin, and includes an epoxy mixed resin, a binder resin, a curing agent, a curing accelerator, and a filler.

[0009] As a preferred embodiment of the present invention, the insulating resin of the present invention may include, based on solid content, 3 to 15 wt% of epoxy mixed resin, 19 to 39 wt% of binder resin, 5 to 10 wt% of hardener, 0.7 to 4.0 wt% of hardening accelerator, and the remaining balance of filler among 100 wt%.

[0010] As a preferred embodiment of the present invention, the epoxy mixed resin may include a biphenyl-based epoxy resin, a bisphenol A-based epoxy resin, and an ester-modified epoxy resin.

[0011] As a preferred embodiment of the present invention, the epoxy mixed resin may include a biphenyl-based epoxy resin, a bisphenol A epoxy resin, and an ester-modified epoxy resin in a weight ratio of 1:0.2 to 2.5:0.4 to 3.0.

[0012] As a preferred embodiment of the present invention, the binder resin in the insulating resin composition may include phenoxy resin, PVB (poly vinyl butyral) resin, radical curing modified PPO (radical curing modified poly propylene oxide) resin, PPO (poly propylene oxide) resin, BMI (bismaleimide) resin, and vinyl terminated hydrocarbon resin.

[0013] As a preferred embodiment of the present invention, the binder resin may include 5.0 to 20.0 parts by weight of phenoxy resin, 5.0 to 20.0 parts by weight of PVB resin, 5.0 to 15.0 parts by weight of PPO resin, 0.50 to 3.50 parts by weight of BMI resin, and 5.0 to 16.0 parts by weight of vinyl-terminated hydrocarbon resin, based on 100 parts by weight of the radical curing modified PPO resin.

[0014] As a preferred embodiment of the present invention, the curing agent in the insulating resin composition may be an ester-modified compound including at least one selected from a phenol novolac curing agent, a naphthalene-type curing agent, and a cresol novolac-type curing agent.

[0015] As a preferred embodiment of the present invention, the curing accelerator in the insulating resin composition may include at least one selected from an imidazole-based curing accelerator, a triallyl isocyanurate-based curing accelerator, and a dicumyl peroxide-based curing accelerator.

[0016] As a preferred embodiment of the present invention, the imidazole-based curing accelerator may include at least one selected from 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, and 2-phenyl-4-methyl imidazole.

[0017] As a preferred embodiment of the present invention, the triallyl isocyanurate-based curing accelerator may include at least one selected from triallyl cyanurate, trivinyl cyclohexane, and vinylbenzyl oxide.

[0018] As a preferred embodiment of the present invention, the dicumyl peroxide-based curing accelerator may include at least one selected from acetyl peroxide, benzyl peroxide, and polyethylene.

[0019] As a preferred embodiment of the present invention, the curing accelerator may include an imidazole-based curing accelerator, a triallyl isocyanurate-based curing accelerator, and a dicumyl peroxide-based curing accelerator in a weight ratio of 1:0.05 to 0.35:0.20 to 0.50.

[0020] As a preferred embodiment of the present invention, the filler in the insulating resin composition includes silica (SiO2) surface-modified with a silane compound.

[0021] As a preferred embodiment of the present invention, the silane compound may include a compound represented by the following chemical formula 1.

[0022] [Chemical Formula 1]

[0023] R 1 3SiNR 2 R 3

[0024] In chemical formula 1, R 1 is hydrogen or a straight-chain alkyl group of C1~C5, a branched alkyl group of C3~C5, or a straight-chain alkoxy group of C1~C5, and R 2 is an alkylene group having 1 to 5 carbon atoms, and R 3 is a hydrogen atom, a straight-chain alkyl group having C1 to C3, a branched alkyl group having C3 to C5, a branched alkyl group having C3 to C5, or a phenyl group having or without a substituent.

[0025] As a preferred embodiment of the present invention, the filler has an average particle size (D 50 ) can be used with a size of 0.20 to 3.5㎛.

[0026] As a preferred embodiment of the present invention, the insulating resin of the present invention may further include a silane coupling agent including at least one selected from vinyl, phenylamino, and epoxy.

[0027] As a preferred embodiment of the present invention, the silane coupling agent may include ureido(C1-C5 alkyl)tri(C1-C5 alkoxy)silane.

[0028] Another object of the present invention relates to an insulating film, which means a state before semi-curing (pre-baking) of the insulating resin described above or a state before thermal curing of the insulating resin.

[0029] As a preferred embodiment of the present invention, the insulating film of the present invention, after curing, has a coefficient of thermal expansion (CTE) at 30 to 150°C that satisfies Equation 1 below, and a coefficient of thermal expansion (CTE) at 150 to 240°C that satisfies Equation 2 below.

[0030] [Equation 1]

[0031] 20.00 ppm / ℃ ≤ CTE α1 ≤ 25.00 ppm / ℃

[0032] [Equation 2]

[0033] 70.00 ppm / ℃ ≤ CTE α1 ≤ 85.00 ppm / ℃

[0034] In Equations 1 and 2, the CTE α1 values ​​are the coefficients of thermal expansion in the X and / or Y directions.

[0035] As a preferred embodiment of the present invention, the insulating film of the present invention has a dielectric constant (D) at 5.1 GHz when measured by the SPDR (split post dielectric resonators) method after curing. k ) is 3.50 or less, and the dielectric loss (D f ) can satisfy 0.0010 ~ 0.0060.

[0036] As a preferred embodiment of the present invention, the insulating film of the present invention can satisfy an adhesion of 0.70 kgf / cm or more when measuring adhesion to copper plating after curing.

[0037] Another object of the present invention is to provide a printed circuit board including an insulating layer or insulating film (or build-up film) formed by a cured product of the insulating resin described above.

[0038] In addition, another object of the present invention is to provide a method of using the insulating resin described above when manufacturing a multilayer printed circuit board by applying a semi-additive patterning (SAP) method.

[0039] The thermosetting insulating resin of the present invention and the insulating film manufactured from the same have a low dielectric constant, low dielectric loss, and low coefficient of thermal expansion, and have excellent adhesion not only to conductors such as copper plating but also to insulators. In addition, the insulating film manufactured from the insulating resin of the present invention has a low surface roughness and a uniform surface, and thus, when applied to a SAP (semi-additive process) method as a build-up film, it can maintain a uniform surface roughness even after a plasma treatment and / or a desmear process for manufacturing a multilayer printed circuit board.

[0040] Figure 1 is a schematic cross-sectional view of a multilayer printed circuit board on which an insulating film or build-up film of the present invention is laminated.

[0041] Figure 2 is an SEM measurement image of a Line / Space 10 / 10um circuit implementation based on the semi-adaptive chatter (SAP) process.

[0042] In this specification, expressions such as “has”, “may have”, “includes”, or “may include” indicate the presence of a feature (e.g., a component such as a number, function, operation, or part), and do not exclude the presence of additional features.

[0043] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification are to be understood as being modified in all cases by the term “about” unless otherwise stated.

[0044] In this specification, “comprising A and B in a weight ratio of 1:1 to 2” means comprising in a weight ratio range of A:B=1:1 to A:B=1:2.

[0045] Hereinafter, the present invention will be described in more detail.

[0046] The thermosetting insulating resin of the present invention comprises an epoxy mixed resin, a binder resin, a curing agent, a curing accelerator, and a filler.

[0047] Among the insulating resin compositions of the present invention, the epoxy mixed resin may include a biphenyl-based epoxy resin, a bisphenol-A epoxy resin, and an ester-modified epoxy resin, and preferably, the biphenyl-based epoxy resin, the bisphenol-A epoxy resin, and the ester-modified epoxy resin may be included in a weight ratio of 1:0.2 to 2.5:0.4 to 3.0, and more preferably, the biphenyl-based epoxy resin may be included in a weight ratio of 1:0.8 to 1.3:0.4 to 2.5. At this time, if the weight ratio of the bisphenol-A epoxy resin is less than 0.2, there may be a problem of lowering the coatability of the insulating resin, and if it exceeds 2.5, there may be a problem of increasing the dielectric constant and / or the thermal expansion coefficient of the insulating film. In addition, if the weight ratio of the ester-modified epoxy resin is less than 0.4, there may be problems such as uneven roughness formation on the surface of the insulating film and poor dispersion of the filler, and if the weight ratio exceeds 3.0, there may be problems such as poor adhesion of the insulating film and peeling of the desmear neutralizing adhesive, so it is appropriate to use it within the above weight ratio range.

[0048] In addition, the biphenyl-based epoxy resin may have at least one biphenyl-based moiety in the epoxy resin.

[0049] In addition, the biphenyl-based epoxy resin may be a solid or liquid epoxy resin at 25°C, preferably an epoxy resin that is liquid at 25°C. In addition, the biphenyl-based epoxy resin may be used with an epoxy equivalent of 250 g / eq to 300 g / eq to facilitate the implementation of the effects of the present invention.

[0050] In addition, the bisphenol A epoxy resin may include a typical bisphenol A epoxy resin known to those skilled in the art, and specifically, the bisphenol A epoxy resin may have at least one bisphenol A moiety in 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. In addition, it may be easy to implement the effects of the present invention when the bisphenol A epoxy resin has an epoxy equivalent of 150 g / eq to 190 g / eq.

[0051] In addition, the ester-modified epoxy resin has excellent heat resistance and is used for the purpose of low dielectric loss, low water absorption, and increased heat resistance. The ester, which is a modifying component, is an ester compound having a benzene ring structure, and can improve electrical, physical, mechanical, and / or thermal properties, including excellent heat stability, low dielectric constant, and dissipation factor.

[0052] A preferred embodiment of the ester-modified epoxy resin may include an epoxy resin composed of a compound represented by the following chemical formula 2, and an example of a commercially available product is SEC-4325 (manufacturer: Shin-A T&C).

[0053] [Chemical Formula 2]

[0054]

[0055] In the above chemical formula 2, R 1 silver and A is ,, or and B is or , R is a hydrogen atom, a straight-chain alkyl group of C1~C3, m is an integer from 0 to 4, n is an integer from 0 to 2, and * indicates a bonding site.

[0056] And, the content of the epoxy mixed resin in the insulating resin of the present invention is 3 to 15 wt%, preferably 3.5 to 12.0 wt%, and more preferably 4.0 to 10.0 wt% of the total weight of the insulating resin based on the solid content. At this time, if the content of the epoxy mixed resin in the insulating resin is less than 3 wt%, there may be a problem of significantly insufficient adhesiveness, and if it exceeds 15 wt%, there may be a problem of deterioration of solvent compatibility and dielectric properties, so it is appropriate to use it within the above range.

[0057] Next, the binder resin in the insulating resin composition serves to provide coating properties while minimizing the dielectric loss of the insulating film, and may include phenoxy resin, PVB (poly vinyl butyral) resin, radical curing modified PPO (radical curing modified poly propylene oxide) resin, PPO (poly propylene oxide) resin, BMI (bismaleimide) resin, and vinyl terminated hydrocarbon resin. Preferably, with respect to 100 parts by weight of the radical curing modified PPO resin, 5.0 to 20.0 parts by weight of phenoxy resin, 5.0 to 20.0 parts by weight of PVB resin, 5.0 to 15.0 parts by weight of PPO resin, 0.50 to 3.50 parts by weight of BMI resin, and 5.0 to 16.0 parts by weight of vinyl terminated hydrocarbon resin may be included, and more preferably, the radical curing modified PPO resin. For 100 parts by weight, it may contain 5.5 to 16.0 parts by weight of phenoxy resin, 6.0 to 20.0 parts by weight of PVB resin, 5.0 to 14.5 parts by weight of PPO resin, 0.80 to 2.50 parts by weight of BMI resin, and 5.5 to 15.0 parts by weight of vinyl-terminated hydrocarbon resin. At this time, if the amount of the phenoxy resin used is less than 5.0 parts by weight, the effect of forming surface roughness during desmear may be insufficient, and if it exceeds 20 parts by weight, there may be a problem of reduced copper plating adhesion. In addition, if the amount of the PVB resin used in the binder resin composition is less than 5.0 parts by weight, the effect of protecting the adhesive during desmear may be insufficient, and if it exceeds 20 parts by weight, there may be a problem of increased thermal expansion coefficient. In addition, if the amount of PPO resin used in the binder resin composition is less than 5.0 parts by weight, the effect on low dielectric loss value may be minimal, and if it exceeds 15 parts by weight, there may be a problem of reduced plating adhesion.In addition, if the amount of the BMI resin used in the binder resin composition is less than 0.50 parts by weight, the film implementation effect may be insufficient, and if it exceeds 3.50 parts by weight, there may be a problem of reduced plating adhesion. In addition, if the amount of the vinyl-terminated hydrocarbon resin used in the binder resin composition is less than 5.0 parts by weight, the effect of low dielectric loss value may be insufficient, and if it exceeds 16.0 parts by weight, there may be a problem of adhesive breakage.

[0058] And, among the binder resins, the radical curing modified PPO resin is a resin in which PPO (poly propylene oxide) resin is modified with a polyphenylene ether-based compound, and preferably includes a polyphenylene ether-based compound represented by the following chemical formula 3 at the terminal of the PPO resin, and a commercially available example thereof includes a product name MPE-8300 (manufacturer: ShinATNC).

[0059] [Chemical Formula 3]

[0060]

[0061] In chemical formula 3, R is a hydrogen atom or a methyl group, a is 1 or 2, b is 1 to 10, and preferably b is 1 to 3. In addition, * indicates a bonding site.

[0062] In addition, among the binder resins, the vinyl-terminated hydrocarbon resin represented by the following chemical formula 4 may be used, and examples of commercially available ones include those under the trade name KDPE-1100-65T (manufacturer: Kukdo Chemical).

[0063] [Chemical Formula 4]

[0064]

[0065] In chemical formula 4, R1 is -CH2CH2, -CH2CH2CH2, -C(=O)CH3, -C(=O)CH2CH3, or -C(=O)C(CH2)CH3, and R 2is a hydrogen atom or a methyl group, and A is or , a is 1 or 2, and b is 1 to 20. * indicates a binding site.

[0066] And, based on the solid content in the insulating resin of the present invention, the content of the binder resin is 19 to 39 wt%, preferably 21.0 to 32.0 wt%, and more preferably 21.0 to 28.0 wt% of the total weight of the insulating resin. At this time, if the content of the binder resin in the insulating resin is less than 19 wt%, there may be a problem that the cured insulating resin product has difficulty in exhibiting low dielectric properties, and if it exceeds 39 wt%, there may be a problem that compatibility is lowered and film implementation is difficult, so it is appropriate to use it within the above range.

[0067] Next, the curing agent in the insulating resin composition forms a cross-linking bond with an epoxy resin to provide adhesion and strength to the insulating film, and an ester-modified compound including at least one selected from a polyfunctional amine compound, a carboxylic acid series, and a polyfunctional epoxy resin can be used as the curing agent, and preferably, at least one selected from a phenol novolac curing agent, a naphthalene-type curing agent, and a cresol novolac-type curing agent can be included, and more preferably, at least one selected from a phenol novolac epoxy resin, a naphthalene epoxy resin, and a cresol novolac epoxy resin can be included, and even more preferably, an epoxy compound represented by the following chemical formula 4 can be included. In addition, a preferable commercially available example of the curing agent includes SHC-5600 (manufacturer: Shin-A T&C), etc.

[0068] [Chemical Formula 5]

[0069]

[0070] In chemical formula 5, R is a hydrogen atom, -OH, t-butyl group, and A is or , , , , or and A is and R 1 and R 2 Each independently represents a hydrogen atom or a straight-chain alkyl group of C1 to C3, and R 3 is -OH, -OCH3, or -OCH2CH3. * indicates a bonding site.

[0071] And, based on the solid content in the insulating resin of the present invention, the content of the hardener is 5 to 10 wt%, preferably 6.0 to 9.0 wt%, and more preferably 6.2 to 8.5 wt%. At this time, if the content of the hardener in the insulating resin is less than 5 wt%, there may be a problem that the cured insulating resin has insufficient adhesiveness and poor mechanical properties, and if it exceeds 10 wt%, there may be a problem that compatibility and workability are reduced due to gelation of the resin, so it is appropriate to use it within the above range.

[0072] Next, the curing accelerator in the insulating resin composition may include at least one selected from an imidazole-based curing accelerator, a triallyl isocyanurate-based curing accelerator, and a dicumyl peroxide-based curing accelerator. Preferably, a mixture of these three is advantageous in controlling the curing speed.

[0073] As a curing accelerator, when the three types of curing accelerators are mixed and used, it is appropriate to mix and use the imidazole-based curing accelerator, the triallyl isocyanurate-based curing accelerator, and the dicumyl peroxide-based curing accelerator in a weight ratio of 1:0.05 to 0.35:0.20 to 0.50, and preferably in a weight ratio of 1:0.10 to 0.25:0.20 to 0.35.

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

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

[0076] In addition, the dicumyl peroxide-based curing accelerator may include at least one selected from acetyl peroxide, benzyl peroxide, and polyethylene.

[0077] And, based on the solid content in the insulating resin of the present invention, the content of the curing accelerator is 0.7 to 4.0 wt%, preferably 1.5 to 4.0 wt%, and more preferably 2.0 to 3.8 wt%. If the content of the curing accelerator is less than 0.7 wt%, the amount used may be too small, and the curing acceleration effect due to its use may be insufficient. If it is used in excess of 4.0 wt%, there may be a problem in that the physical properties of the cured insulating resin change over time. Therefore, it is appropriate to use it within the above range.

[0078] Next, the filler in the insulating resin composition may be an inorganic filler such as silica commonly used in the art, but in order to enhance the effects of dispersibility of the filler in the insulating resin, formation of surface roughness after desmear, and improvement of copper plating adhesion, the present invention uses silica (SiO2) surface-modified with a silane compound represented by the following chemical formula 1 as the filler.

[0079] [Chemical Formula 1]

[0080] R 1 3SiNR 2 R 3

[0081] In chemical formula 1, R 1is a hydrogen atom, a straight-chain alkyl group of C1~C5 or a branched alkyl group of C3~C5, and R 2 and R 3 Each is independently a hydrogen atom, a C1~C3 straight-chain alkyl group, a C3~C5 branched alkyl group, or a phenyl group with or without a substituent.

[0082] And, the filler has an average particle size (D 50 ) can be used, preferably 0.50 to 3.5㎛, and within the above range, the thermal expansion coefficient of the insulating film can be lowered and the dielectric properties can be improved. The average particle size (D 50 ) was measured using the laser diffraction method.

[0083] And, 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 spherical silica is preferably used.

[0084] And, the content of the filler in the insulating resin of the present invention is the remaining amount excluding the epoxy mixed resin, binder resin, hardener, and hardening accelerator from the total weight % of the insulating resin.

[0085] In addition, the insulating resin of the present invention described above may further include a silane coupling agent in order to increase the peel strength of the insulating film when a film or the like is manufactured with the insulating resin. At this time, the silane coupling agent may include a common silane coupling agent known to those skilled in the art, including an alkoxysilane such as an amino group, an epoxy group, a (meth)acrylic group, a mercapto group, etc., and preferably, a ureido(C1~C5 alkyl)tri(C1~C5 alkoxy)silane including gamma-ureidopropyltrimethoxysilane may be used. In addition, when the silane coupling agent is used, the content thereof is preferably about 0.01 to 1.00 wt% based on the solid content of the total weight of the insulating resin, so that there is no problem of uneven surface thickness of the insulating film, and the adhesive composition for the insulating film may not have problems of changes in the basic physical properties of the adhesive and chemical contamination during chemical plating.

[0086] In addition, the insulating resin of the present invention may further include additives such as BT (bismaleimide traizine) resin, surfactant, and dispersant.

[0087] Among the additives, the BT resin is used to improve the heat resistance of the insulating film, and an inactive cyanate-based ester may be used. The BT resin may be a commercially available product or may be manufactured by a method known to those skilled in the art. In addition, when the BT resin is used, its content is approximately 5.0 to 15.0 wt% of the total weight of the insulating resin based on the solid content, and when used within this range, the effect of improving the heat resistance of the insulating film can be appropriately observed, while preventing the brittle phenomenon of the insulating film from occurring.

[0088] Among the additives, the surfactant increases the film formability when the insulating resin is formed into a film or a coating layer, and a common type known to those skilled in the art can be selected and used. For example, sodium dodecyl benzene sulfonate (SDBS), polyoxyethylene notyl phenyl ether, pluronic F127, etc. can be used. In addition, when the surfactant is used, its content is approximately 0.1 to 1.0 wt% of the total weight% of the insulating resin based on the solid content, and use within this range is appropriate in terms of the film formability of the insulating film.

[0089] Among the additives, the dispersant can be contained in the adhesive composition for insulating films to prevent silica agglomeration and ensure good dispersion of silica, thereby stably maintaining the thermal expansion coefficient of the insulating film. In addition, when using the dispersant, its content is approximately 1.0 to 3.0 wt% of the total weight% of the insulating resin based on the solid content, and when used within this range, there is no problem of agglomeration of the filler and no problem of change in the basic physical properties of the insulating resin.

[0090] An insulating film can be formed by applying the insulating resin described above to one side of a carrier film and then drying it. In the present invention, the insulating film refers to a state before the insulating resin is semi-cured (pre-baked), or a state before the insulating resin is thermally cured.

[0091] In addition, the build-up film includes an insulating film formed from the insulating resin. In addition to the insulating film, the build-up film of the present invention may further include a carrier film covering one side of the insulating film and a cover film covering the other side of the insulating film.

[0092] And, the thickness of the insulating film is not particularly limited, but considering the application to printed circuit boards, it can be 25㎛ to 50㎛.

[0093] After curing, the insulating film of the present invention can have a coefficient of thermal expansion (CTE) at 30 to 150°C that satisfies Equation 1 below, and a coefficient of thermal expansion (CTE) at 150 to 240°C that satisfies Equation 2 below.

[0094] [Equation 1]

[0095] 20.00 ppm / ℃ ≤ CTE α1 ≤ 25.00 ppm / ℃, preferably 21.00 ppm / ℃ ≤ CTE α1 ≤ 25.00 ppm / ℃

[0096] [Equation 2]

[0097] 70.00 ppm / ℃ ≤ CTE α1 ≤ 85.00 ppm / ℃, preferably 75.00 ppm / ℃ ≤ CTE α1 ≤ 82.00 ppm / ℃

[0098] In Equations 1 and 2, the CTE α1 value is the coefficient of thermal expansion in the X and / or Y direction.

[0099] The insulating film of the present invention has a dielectric constant (D) at 5.1 GHz when measured by the SPDR (split post dielectric resonators) method after curing. k ) is 5.50 or less, and the dielectric loss (D f ) can satisfy 0.0010 to 0.0060, and preferably the dielectric constant (D) at 5.1 GHz k ) is 3.35 or less, and the dielectric loss (D f ) can satisfy 0.0010 ~ 0.0050.

[0100] The insulating film of the present invention, after curing, can satisfy an adhesion of 0.70 kgf / cm or more, preferably 0.70 to 1.80 kgf / cm, and more preferably 1.8 to 2.0 kgf / cm, when measuring adhesion to copper plating, and such high adhesion provides stable adhesion stability to the substrate and the circuit.

[0101] The present invention provides a printed circuit board including an insulating layer or insulating film (or build-up film) formed by a cured product of the insulating resin described above, and in particular, provides a method of using the insulating resin described above when manufacturing a multilayer printed circuit board by applying a semi-additive patterning (SAP) method.

[0102] The above insulating film or the above build-up film can be used in the manufacture of a multilayer printed circuit board.

[0103] Fig. 1 illustrates a printed circuit board on which insulating films (110a, 110b) are laminated according to an embodiment of the present invention. As illustrated in Fig. 1, the insulating film (110a) is in contact with all of the laminated insulating films (110b), the substrate (200), the first circuit (210), and the second circuit (220).

[0104] A multilayer printed circuit board can be manufactured by a conventional method known to those skilled in the art. In one specific example, an adhesive composition for an insulating film is applied to one side of a carrier film to a predetermined thickness, and then dried at a temperature of 80°C to 110°C for 1 to 10 minutes to form an insulating film, 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 a cover film - an insulating film - a carrier film are laminated.

[0105] A cover film is peeled off from a build-up film to obtain an insulating film, and the insulating film is vacuum-sealed to a substrate, etc. using a vacuum laminator, etc., and then semi-cured (pre-baked). The semi-curing can be performed at a predetermined temperature range (e.g., 30 to 40°C) and for a predetermined time range (e.g., 10 to 30 minutes). Then, the surface of the semi-cured insulating film is plated through a plating process, and the semi-cured insulating film is completely cured. The complete curing of the insulating film can be performed at 150 to 200°C for 60 to 120 minutes, but is not limited thereto. A desmear process may also be performed before the plating process.

[0106] The method for manufacturing a printed circuit board of the present invention comprises a step of using an insulating film formed from the insulating resin of the present invention. The method for manufacturing a printed circuit board of the present invention may be a method for manufacturing a conventional circuit wiring board by using an insulating film formed from the adhesive composition for an insulating film of the present invention. Each step of the method for manufacturing a printed circuit board of the present invention will be described in detail below, but the present invention is not limited thereto.

[0107] A method for manufacturing a printed circuit board includes the steps of (A) applying a thermosetting insulating resin of the present invention to a support to a predetermined thickness to form a coating for an insulating film, (B) bonding the support and the coating for an insulating film to a circuit board so that the coating for an insulating film is bonded to the circuit board, (C) curing the coating for an insulating film to form an insulating film, (D) forming a via hole by perforating the insulating film, (E) performing a desmear treatment, and (F) forming a conductor layer on the surface of the insulating layer.

[0108] (A) Process

[0109] (A) The process is to form a coating for an insulating film by applying a thermosetting insulating resin to a support at a predetermined thickness.

[0110] The support may be a film made of a plastic material, a metal foil (copper foil or aluminum foil), a release paper, etc. The support may further have a release layer laminated on the surface that is in contact with the insulating resin.

[0111] The thermosetting insulating resin uses the insulating resin of the present invention described above, and can be applied to a support body at a predetermined thickness and then become a coating for an insulating film through solvent drying, etc.

[0112] (B) Process

[0113] (B) The process is to bond the coating for the support and insulating film to the circuit board so that the coating for the insulating film is bonded to the circuit board.

[0114] The coating for the insulating film may be pretreated before bonding to the circuit board. Pretreatment methods include etching, such as CZ pretreatment.

[0115] Bonding can generally be performed using a vacuum lamination machine by appropriately controlling the pressing pressure, pressing temperature, pressing time, etc.

[0116] (C) Process

[0117] (C) Process is to form an insulating film by curing a coating for an insulating film. Specifically, the coating for an insulating film is heat-cured to form an insulating layer. The heat-curing conditions are not particularly limited, and conditions commonly used when forming an insulating layer for a circuit wiring board may be used. The heat-curing conditions may be performed at 150°C to 200°C for 60 to 120 minutes, but are not limited thereto.

[0118] Before heat-curing the coating for insulating films, it may be pre-cured at a temperature lower than the heat-curing temperature. For example, before heat-curing the coating for insulating films, it may be pre-cured at 30 to 40°C for 10 to 30 minutes.

[0119] (D) Process

[0120] (D) Process is to form via holes by perforating an insulating film. The via holes are formed for electrical connection between layers, and can be formed by a drill, laser, plasma, or other method, taking into account the characteristics of the insulating layer. Examples of laser light sources include carbon dioxide lasers, YAG lasers, and excimer lasers.

[0121] (E) Process

[0122] (E) Process is to perform desmear treatment. Resin residue is attached to the inside of the via hole formed in (D) process, and this resin residue must be removed because it causes poor electrical connection between layers.

[0123] Desmear treatment can be performed by conventional methods, and can be performed by dry desmear treatment, wet desmear treatment, or a combination thereof. Dry desmear treatment can be desmear treatment using plasma. Wet desmear treatment can include desmear treatment using an oxidizing solution.

[0124] (F) Process

[0125] (F) The process includes a process of forming a conductive layer on the surface of the insulating layer.

[0126] The conductor layer can be formed by SAP (semi-additive process), etc. A plating seed layer can be formed on the surface of the insulating layer by chemical plating, a mask pattern is formed that exposes a portion of the plating seed layer corresponding to a desired wiring pattern, a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed, and unnecessary plating seed layers are removed by etching, thereby forming a conductor layer having a desired wiring pattern.

[0127]

[0128] Hereinafter, the present invention will be described in more detail through examples, but the following examples do not limit the scope of the present invention, and should be interpreted as helping to understand the present invention.

[0129] [Example]

[0130] The specific specifications of the components used in the examples and comparative examples below are as follows.

[0131] (A) Epoxy resin

[0132] (A1) Bisphenol A epoxy resin (trade name: YD-128, Kukdo Chemical)

[0133] (A2) Biphenyl epoxy resin (trade name: NC-3000, Nippon Gunpowder)

[0134] (A3) Ester-modified epoxy resin (trade name: SEC-4325, manufacturer: ShinATNC)

[0135] (B) Binder resin

[0136] (B1) Phenoxy resin (trade name: HE-1900, manufacturer: H-Chem)

[0137] (B2) PVB (poly vinyl butyral) resin (trade name: BM-SZ, manufacturer: Sekisui)

[0138] (B3) Radical curing modified PPO resin (Product name: MPE-8300, manufacturer: ShinATNC)

[0139] (B4) PPO resin (trade name: SA-90, manufacturer: Sabic)

[0140] (B5) BMI (bismaleimide) resin (trade name: SMI-30MT70, manufacturer: Nippon Gunyaku)

[0141] (B6) Vinyl-terminated hydrocarbon resin (trade name: KDPE-1100-65T, manufacturer: Kukdo Chemical)

[0142] (C) Hardener: Ester-modified compound (trade name: SHC-5600, manufacturer: ShinATNC)

[0143] (D) Curing accelerator

[0144] (D1) Imidazole-based curing accelerator (C11Z, Shikoku Chemical Co.)

[0145] (D2) Triallyl isocyanurate curing accelerator (trade name: TAIC, manufacturer: Evonik)

[0146] (D3) Dicumyl peroxide curing accelerator (trade name: DCP, manufacturer: Dongseong Chemical)

[0147] (E) Silane coupling agent: A-1524 (gamma-ureidopropyltrimethoxysilane, GE-Silicon)

[0148]

[0149] Example 1: Preparation of thermosetting insulating resin

[0150] To 100 parts by weight of a mixture of bisphenol A epoxy resin, biphenyl epoxy resin, and ester-modified epoxy resin SEC-4325, 50 parts by weight of naphtha (solvent) was added, stirred, heated, and dissolved to prepare an epoxy mixed resin.

[0151] Separately, as binder resins, phenoxy resin, PVB (poly vinyl butyral) resin, radical curing modified PPO resin, PPO resin, BMI (bismaleimide) resin, and SMI-30MT70, a vinyl-terminated hydrocarbon resin, were prepared.

[0152] Additionally, as a curing agent, SHC-5600 curing agent, which is an ester-modified compound, was prepared.

[0153] In addition, an imidazole-based curing accelerator, a triallyl isocyanurate-based curing accelerator, and a dicumyl peroxide-based curing accelerator were prepared as curing accelerators.

[0154] In addition, silica (average particle diameter (D)) surface-modified with a silane compound represented by the following chemical formula 1-1 50 ) = 0.5㎛, product name Q019, manufacturer: Genet) was prepared as a filler.

[0155] [Chemical Formula 1-1]

[0156] R 3 NHR 2 Si(OR 1 )3

[0157] In chemical formula 1-1, R 1 is -CH3, and R 2 is -C3H6-, and R 3 is a phenyl group.

[0158] After mixing the binder resin, the hardener, the hardening accelerator, and the filler into the epoxy mixed resin, the mixture was uniformly dispersed using a mixer to produce a thermosetting insulating resin, and the composition content is shown in Table 1 below. In this case, the content is expressed on a solid basis.

[0159]

[0160] Examples 2 to 9 and Comparative Examples 1 to 12

[0161] A thermosetting insulating resin was manufactured using the same composition as in Example 1, but the thermosetting insulating resin was manufactured by changing the composition content as shown in Tables 1 to 3 below, and Examples 2 to 9 and Comparative Examples 1 to 12 were performed, respectively.

[0162]

[0163] Experimental Example 1: Physical Property Measurement

[0164] An insulating film was manufactured using the insulating resin manufactured in the examples and comparative examples, and the physical properties shown in Tables 1 to 3 below were evaluated.

[0165] When measuring the physical properties, curing was thermal curing, and the insulating film was thermally cured at 190°C for 90 minutes.

[0166] (1) Thermal expansion coefficient (unit: ppm / ℃): After curing of the insulating film, the thermal expansion coefficient was measured while increasing the temperature from 25℃ to 260℃ at a heating rate of 10℃ / min using a TMA device, and the thermal expansion coefficient in the X and Y-axis directions was evaluated, and the thermal expansion coefficient value in the range of 30 to 150℃ was shown.

[0167] (2) Dielectric constant (D) k ): After curing of the insulating film, the dielectric constant (D) was measured using a dielectric constant measuring device at a frequency of 5.1 GHz. k ) and genetic loss ((D f ) was measured.

[0168] (3) Adhesion (kgf / cm): After curing the insulating film and electroplating copper with a thickness of 25㎛ on the cured insulating film, the adhesion between the cured product of the insulating film and the copper plating film was measured using an adhesion measuring device at a peeling temperature of 25°C, a peeling angle of 180°, and a peeling speed of 100 mm / min.

[0169] (4) Compatibility and film properties: If there is no brittle phenomenon in the insulating film, it is evaluated as ‘○’, and if there is even a little brittle phenomenon, it is evaluated as ‘×’.

[0170] (5) Surface roughness (㎛): After curing of the insulating film, the surface roughness Ra was measured using a thin film thickness measuring device.

[0171] Classification (weight%)Example 123456789Epoxy mixed resinBisphenol A epoxy2122224.522Biphenyl epoxy21222224.22Ester modified epoxy121111114.2Binder resinPhenoxy resin12111.51111PVB resin315343333Radical curing modifiedPPO resin1615161615.5161616PPO resin21221.52222BMI resin0.20.20.20.450.30.20.20.20.2Vinyl terminated hydrocarbon resin12111.52.8111Current ester modified Compound 757777777 Curing accelerator Imidazole 20.5 2222222 Triallyl iso-cyanoate 0.3 0.2 0.5 0.3 0.5 0.3 0.5 0.3 0.3 0.3 Dicumyl peroxide 0.5 0.1 0.5 0.5 0.3 0.5 0.5 0.5 0.5 0.5 Filler Surface modified SiO 2 Remaining ... 150℃)22.121.324.122.525.022.524.821.722.2 Dielectric constant (D) k )3.13.23.33.23.33.33.23.23.3 Genetic loss (D f )0.00380.0040.0040.00390.00320.0040.00390.00420.0035Adhesion (kgf / cm)≥0.4≥0.4≥0.4≤0.4≤0.4≤0.4≤0.4≥0.4≤0.4Compatibility, film property○○○○○○○○○Surface roughness (Ra, ㎛)0.3250.3340.2640.2980.3510.2640.3270.4050.382

[0172] Classification (weight%) Comparative example 1234567 Epoxy mixed resin Bisphenol A epoxy 2222111 Biphenyl epoxy 2222111 Ester modified epoxy 1111222 Binder resin Phenoxy resin 1110.5 311 PVB resin 33331-6 Radical curing modified PPO resin 16161615.5 151615 PPO resin 2222121 BMI resin -0.20.20.20.20.20.2 Vinyl terminated hydrocarbon resin 1111212 Curing agent Ester modified compound 7777555 Curing accelerator Imidazole system 22220.50.50.5 Triallyl iso-cyanoate system 0.50.30.50.50.20.2 Dicumyl Peroxide system 0.5 0.5 0.3 0.3 0.1 0.1 Filler Surface modified SiO 2 Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Silane Coupling agent Alkoxy silane--0.1 0.1---Total (weight %) 100 100 100 100 100 100 100 Property evaluation Coefficient of thermal expansion (ppm / ℃, 30 ~ 150℃) 23.2 21.4 22.3 25.2 28.7 19.2 3 1.1 Dielectric constant (D k )3.23.23.23.23.13.23.2 Genetic loss (D f )0.00420.00570.00550.00450.00430.00420.0052Adhesion (kgf / cm)×≤0.4×≤0.4≤0.4××Compatibility, film property○○○○○○○Surface roughness (Ra, ㎛)0.3130.3250.3240.3850.4050.3010.295

[0173] Classification (weight%) Comparative example 89 10 11 12 Epoxy mixed resin Bisphenol A epoxy 11 1 11 Biphenyl epoxy 11 1 11 Ester modified epoxy 22 2 22 Binder resin Phenoxy resin 11 2 11 PVB resin 23 1 33 Radical curing modified PPO resin 15 16 15 16 16 PPO resin 1-4 2 2 BMI resin 0.6 0.2 0.2 0.2 0.2 Vinyl terminated hydrocarbon resin 2 1 2 0.5 3.5 Curing agent Ester modified compound 5 5 5 5 Curing accelerator Imidazole 10.5 0.5 10.5 Triallyl iso-cyanoate 0.3 0.2 0.2 0.3 0.2 Dicumyl peroxide 0.1 0.1 0.1 0.1 1 Filler Surface modified SiO 2 Remainder Remainder Residual amountResidual amountResidual amountResidual amountSilane coupling agentAlkoxy silane-----Total (weight%)100100100100100100Physical property evaluationCoefficient of thermal expansion(ppm / ℃,30 ~ 150℃)21.522.420.223.422.2Dielectric constant(D k )3.03.33.23.23.1 Genetic loss (D f )0.0040.00650.00390.00520.0055Adhesion (kgf / cm)×≥0.4≥0.4≥0.4≥0.4Compatibility, film property○○×○○Surface roughness (Ra, ㎛)0.3320.3250.2950.3170.272

[0174] It can be confirmed that the thermosetting insulating resin of the present invention and the insulating film manufactured from the same have a low dielectric constant, low dielectric loss, and low thermal expansion coefficient, and have excellent adhesion not only to conductors such as copper plating but also to insulators. In addition, the insulating film manufactured from the insulating resin of the present invention has a low surface roughness and a uniform surface, and thus, when applied as a build-up film, especially to the SAP (semi additive process) method, a uniform surface roughness can be maintained even after a plasma treatment and / or a desmear process for manufacturing a multilayer printed circuit board.

Claims

Contains epoxy mixed resin, binder resin, hardener, hardening accelerator and filler. A thermosetting insulating resin characterized in that the above epoxy mixed resin includes a biphenyl-based epoxy resin, a bisphenol A epoxy resin, and an ester-modified epoxy resin. A thermosetting insulating resin characterized in that it comprises 3 to 15 wt% of epoxy mixed resin, 19 to 39 wt% of binder resin, 5 to 10 wt% of curing agent, 0.7 to 4.0 wt% of curing accelerator, and the remaining balance of filler among 100 wt% in the first clause. A thermosetting insulating resin according to claim 1, characterized in that the epoxy mixed resin comprises a biphenyl-based epoxy resin, a bisphenol A epoxy resin, and an ester-modified epoxy resin in a weight ratio of 1:0.2 to 2.5:0.4 to 3.

0. A thermosetting insulating resin according to claim 1, wherein the binder resin comprises a phenoxy resin, a PVB (poly vinyl butyral) resin, a radical curing modified PPO (radical curing modified poly propylene oxide) resin, a PPO (poly propylene oxide) resin, a BMI (bismaleimide) resin, and a vinyl terminated hydrocarbon resin. A thermosetting insulating resin, characterized in that in claim 4, the binder resin comprises 5.0 to 20.0 parts by weight of phenoxy resin, 5.0 to 20.0 parts by weight of PVB resin, 5.0 to 15.0 parts by weight of PPO resin, 0.50 to 3.50 parts by weight of BMI resin, and 5.0 to 16.0 parts by weight of vinyl-terminated hydrocarbon resin, based on 100 parts by weight of the radical curing modified PPO resin. In the first paragraph, the curing agent comprises an ester-modified compound including at least one selected from a phenol novolac curing agent, a naphthalene-type curing agent, and a cresol novolac-type curing agent. The above curing accelerator includes at least one selected from an imidazole-based curing accelerator, a triallyl isocyanurate-based curing accelerator, and a dicumyl peroxide-based curing accelerator. The above imidazole-based curing accelerator includes at least one selected from 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, and 2-phenyl-4-methyl imidazole, The above triallyl isocyanurate curing accelerator comprises at least one selected from triallyl cyanurate, trivinyl cyclohexane and vinylbenzyl oxide. A thermosetting insulating resin characterized in that the above dicumyl peroxide-based curing accelerator comprises at least one selected from acetyl peroxide, benzyl peroxide, and polyethylene. A thermosetting insulating resin characterized in that, in claim 6, it comprises an imidazole-based curing accelerator, a triallyl isocyanurate-based curing accelerator, and a dicumyl peroxide-based curing accelerator in a weight ratio of 1:0.05 to 0.35:0.20 to 0.

50. In the first paragraph, the filler comprises silica (SiO2) surface-modified with a silane compound, A thermosetting insulating resin 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 straight-chain alkyl group of C1~C5, a branched alkyl group of C3~C5, or a straight-chain alkoxy group of C1~C5, and R 2 is an alkylene group having 1 to 5 carbon atoms, and R 3 is a hydrogen atom, a straight-chain alkyl group having C1 to C3, a branched alkyl group having C3 to C5, a branched alkyl group having C3 to C5, or a phenyl group having or without a substituent. In the second paragraph, the filler has an average particle size (D 50 ) is characterized by a thermosetting insulating resin having a thickness of 0.20 to 3.5㎛. A thermosetting insulating resin characterized in that, in claim 1, it further comprises a silane coupling agent including ureido(C1~C5 alkyl)tri(C1~C5 alkoxy)silane. An insulating film characterized by comprising the insulating resin of any one of claims 1 to 10. In the 11th paragraph, the insulating film is characterized in that, after curing, the coefficient of thermal expansion (CTE) at 30 to 150°C satisfies the following equation 1, and the coefficient of thermal expansion (CTE) at 150 to 240°C satisfies the following equation 2; [Equation 1] 20.00 ppm / ℃ ≤ CTE α1 ≤ 25.00 ppm / ℃ [Equation 2] 70.00 ppm / ℃ ≤ CTE α1 ≤ 85.00 ppm / ℃ In equations 1 and 2, the CTE α1 values ​​are the coefficients of thermal expansion in the X and Y directions. In the 11th paragraph, the insulating film has a dielectric constant (D) at 5.1 GHz when measured by the SPDR (split post dielectric resonators) method after curing. k ) is 3.50 or less, and the dielectric loss (D f ) is 0.0010 to 0.0060. In claim 11, the insulating film is characterized in that, when the adhesive strength to copper plating is measured after curing, the adhesive strength is 0.70 kgf / cm or more. A printed circuit board comprising an insulating layer formed by a cured product of the insulating resin of any one of claims 1 to 10. A semi-additive patterning (SAP) method characterized by using the insulating resin of any one of claims 1 to 10.

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