Resin composition, and prepreg, metal-clad laminate, laminated sheet, and printed circuit board each using same

Abstract

The present invention relates to a resin composition, and a prepreg, a metal-clad laminate, a laminated sheet, and a printed circuit board each using same, wherein the resin composition comprises: (a) an epoxy resin containing a modified dicyclopentadiene (DCPD) epoxy resin; (b) an aliphatic benzoxazine-based resin; and (c) a curing agent.

Description

Resin composition, prepreg, metal foil laminate, laminated sheet and printed circuit board using the same

[0001] The present invention relates to a resin composition, and a prepreg, a metal-clad laminate, a laminated sheet, and a printed circuit board using the same, and more particularly, to a resin composition having a low modulus after curing, a high glass transition temperature, and a low occurrence of surface stickiness, and to a prepreg, a metal-clad laminate, a laminated sheet, and a printed circuit board using the same.

[0002] As 5G technology advances, there's a trend toward its application in the automotive sector. The level of reliability required in the automotive sector exceeds conventional standards, and with the integration of 5G, which relies heavily on data collection and processing, failures during processing are crucial. Consequently, the standards for solder reliability between semiconductor chips and the main board are rising. However, due to the material properties, there is a mismatch in the coefficient of thermal expansion (CTE) between the chip, solder, and main board. Furthermore, there is a growing demand for improved solder crack resistance under harsh external conditions, such as vibration.

[0003] The present invention aims to provide a resin composition having a low modulus after curing, a high glass transition temperature, and low surface stickiness, and a prepreg, a metal-clad laminate, a laminated sheet, and a printed circuit board using the same.

[0004] To achieve the above-mentioned purpose, the present invention provides a resin composition comprising (a) an epoxy resin containing a modified dicyclopentadiene (DCPD) epoxy resin; (b) an aliphatic benzoxazine-based resin; and (c) a curing agent.

[0005] As an example of the present invention, the modified dicyclopentadiene epoxy resin may be an isocyanate-modified dicyclopentadiene epoxy resin.

[0006] As an example of the present invention, the modified dicyclopentadiene epoxy resin may have a modification rate of 5 to 30%.

[0007] In one example of the present invention, the modified dicyclopentadiene epoxy resin may have an epoxy equivalent of 200 to 400 g / eq.

[0008] As an example of the present invention, the epoxy resin may additionally contain at least one non-dicyclopentadiene epoxy resin selected from the group consisting of bisphenol-type epoxy resin, novolac-type epoxy resin, biphenyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, arylalkylene-type epoxy resin, naphthalene-type epoxy resin, anthracene-type epoxy resin, phenoxy-type epoxy resin, norbornene-type epoxy resin, adamantane-type epoxy resin, and fluorene-type epoxy resin.

[0009] In one example of the present invention, the modified dicyclopentadiene epoxy resin and the non-dicyclopentadiene epoxy resin may be contained in a weight ratio of 40:60 to 85:15.

[0010] As an example of the present invention, the epoxy resin may additionally contain a dicyclopentadiene type epoxy resin.

[0011] In one example of the present invention, the curing agent may contain a phenol-based curing agent.

[0012] As an example of the present invention, the resin composition may additionally include at least one selected from the group consisting of an inorganic filler, a flame retardant, and a curing accelerator.

[0013] As an example of the present invention, the resin composition may include, based on the total amount of the resin composition, 10 to 30 wt% of a modified dicyclopentadiene epoxy resin; 5 to 25 wt% of an aliphatic benzoxazine resin; and 5 to 20 wt% of a curing agent.

[0014] As an example of the present invention, the resin composition may have a modulus of 8 GPa or less after curing and a glass transition temperature (Tg) of 140°C or more.

[0015] In addition, the present invention provides a prepreg comprising a fiber substrate; and the above-described resin composition impregnated into the fiber substrate.

[0016] In addition, the present invention provides a metal foil laminate comprising a metal foil substrate; and a resin layer formed on one or both sides of the metal foil substrate and cured with the above-described resin composition.

[0017] In addition, the present invention provides a laminated sheet comprising a polymer film substrate; and a resin layer formed on one or both sides of the polymer film substrate and in which the above-described resin composition is cured.

[0018] In addition, the present invention provides a printed circuit board including the above-described prepreg or the above-described metal foil laminate.

[0019] Since the resin composition of the present invention has a low modulus and a high glass transition temperature after curing, it can absorb and relieve solder stress caused by external stimuli such as heat or vibration when applied to a printed circuit board, thereby improving the reliability of the printed circuit board.

[0020] In addition, since the resin composition of the present invention has a low occurrence of stickiness after curing, workability can be improved when manufacturing a printed circuit board, and resin peeling can be reduced, so that the product quality of the printed circuit board can be improved.

[0021] The effects according to the present invention are not limited to those exemplified above, and more diverse effects are included in this specification.

[0022] Hereinafter, the present invention will be described in detail.

[0023] All terms (including technical and scientific terms) used in this specification may be used with meanings commonly understood by those of ordinary skill in the technical field to which the present invention pertains. Furthermore, terms defined in commonly used dictionaries should not be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0024] Additionally, throughout the specification, whenever a part is said to "include" a component, this does not exclude other components, but rather includes other components, unless otherwise specifically stated. Furthermore, "cured product" means anything formed by curing the composition.

[0025]

[0026] Resin composition

[0027] The resin composition according to the present invention can be applied to a printed circuit board, and comprises (a) an epoxy resin containing a modified dicyclopentadiene (DCPD) epoxy resin; (b) an aliphatic benzoxazine resin; and (c) a curing agent, and may additionally include at least one selected from the group consisting of an inorganic filler, a flame retardant, and a curing accelerator, if necessary.

[0028] Specifically, both modified DCPD epoxy resin and aliphatic benzoxazine resin can lower the modulus of products (e.g., prepregs). In particular, aliphatic benzoxazine resin has superior low modulus characteristics compared to modified DCPD. However, when aliphatic benzoxazine resin is used alone, a sticky phenomenon occurs after semi-curing, making it unusable as a product. In addition, when aliphatic benzoxazine resin is used alone, the glass transition temperature (Tg) of the aliphatic compound is low due to its chemical structure and low polarity, which may result in low adhesive strength with metals. On the other hand, when modified DCPD epoxy resin is used alone, the targeted low modulus characteristics cannot be realized. Accordingly, in the present invention, by mixing a modified dicyclopentadiene epoxy resin that is stable to sticky and can lower the modulus of the product compared to other novolac epoxy resins with an aliphatic benzoxazine resin, not only can the low modulus characteristics of the product be implemented, but also the occurrence of a sticky phenomenon after semi-curing can be prevented, and the adhesive strength with metal can be increased.

[0029] Hereinafter, each component constituting the resin composition according to the present invention will be examined as follows.

[0030] (a) epoxy resin

[0031] In the resin composition according to the present invention, the epoxy resin includes a modified dicyclopentadiene (DCPD) epoxy resin.

[0032] The above-described modified dicyclopentadiene (DCPD) epoxy resin is an epoxy resin having a dicyclopentadiene (DCPD) structure in the molecule, and in which some of the epoxy groups are modified with isocyanate groups. This isocyanate-modified dicyclopentadiene epoxy resin has a larger volume than a conventional epoxy resin due to the DCPD structure, and thus can implement low dielectric properties of the resin composition. In addition, since the mobility of the chain is improved as some of the epoxy groups of the modified DCPD epoxy resin are substituted with isocyanate groups, the glass transition temperature (Tg) of the cured resin can be improved while implementing a low modulus.

[0033] According to an example, the modified DCPD epoxy resin may be represented by the following chemical formula 1.

[0034]

[0035] In the above chemical formula 1,

[0036] X1 is an isocyanate group or an epoxy group, provided that at least one of one or more X1s is an isocyanate group,

[0037] n is an integer from 1 to 100, specifically an integer from 1 to 50, and more specifically an integer from 1 to 20.

[0038] The above modified DCPD epoxy resin may have a modification ratio in the range of 5 to 30%. Since this modified DCPD epoxy resin has a large volume, excellent chain fluidity, and a low crosslinking density, the cured resin product can exhibit low dielectric properties while simultaneously implementing excellent thermal and modulus properties.

[0039] In one example, the modified DCPD epoxy resin may have an isocyanate content of 5 to 30 mol% and an epoxy equivalent of 200 to 400 g / eq. In this case, the cured product of the resin composition may have a glass transition temperature of about 140° C. or higher and a modulus of about 8 GPa or lower.

[0040] In the resin composition according to the present invention, the content of the modified DCPD epoxy resin is not particularly limited and can be appropriately adjusted in consideration of the physical properties of the resin composition. For example, the modified DCPD epoxy resin may be about 10 to 45 parts by weight, specifically about 15 to 40 parts by weight, based on 100 parts by weight of the resin composition [however, components excluding inorganic fillers, flame retardants, curing accelerators, and additives (e.g., epoxy resin components, benzoxazine-based components, and curing agent components)].

[0041] In the resin composition according to the present invention, the epoxy resin may additionally include a general-purpose epoxy resin generally known in the art in addition to the above-described modified DCPD epoxy resin.

[0042] For example, the epoxy resin may additionally include an epoxy resin other than a dicyclopentadiene-type (DCPD-type) epoxy resin (hereinafter, referred to as a "non-DCPD epoxy resin"). By further including such a non-DCPD epoxy resin as an epoxy resin component, the resin composition of the present invention can prevent a decrease in adhesive strength.

[0043] Non-limiting examples of the above non-DCPD epoxy resins include bisphenol type epoxy resins (e.g., bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin, etc.), novolac type epoxy resins (e.g., phenol novolac type epoxy resin, cresol novolac epoxy resin, etc.), biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, etc., which may be used alone or in combination of two or more.

[0044] In one example, the non-DCPD epoxy resin may be a bisphenol type epoxy resin, specifically a bisphenol A type epoxy resin.

[0045] The usage ratio (mixing ratio) of the above-mentioned modified dicyclopentadiene epoxy resin and non-DCPD epoxy resin may be a weight ratio of 40:60 to 85:15, specifically a weight ratio of 40:60 to 70:30, and more specifically a weight ratio of 55:45 to 70:30.

[0046] In the resin composition of the present invention, the epoxy resin may further contain a dicyclopentadiene type epoxy resin.

[0047] Dicyclopentadiene-based (DCPD-type) epoxy resin is a multifunctional epoxy resin with a dicyclopentadiene (DCPD) structure in the molecule. Since it has a hydrophobic double-ring hydrocarbon group, it has little electronic polarization, and thus can lower the dielectric constant of the cured resin.

[0048] Examples of DCPD type epoxy resins usable in the present invention are not particularly limited as long as they are known in the art, and may include, for example, those represented by the following chemical formula 2.

[0049]

[0050] In the above formula, n is an integer from 1 to 10.

[0051] The content of the dicyclopentadiene-type epoxy resin is not particularly limited. However, it is appropriate that the total content of the modified DCPD epoxy resin and the DCPD epoxy resin be in the range of about 60 to 80 wt%, specifically about 65 to 75 wt%, based on the total amount of the entire epoxy resin. At this time, the usage ratio (mixing ratio) of the modified DCPD epoxy resin and the DCPD-type epoxy resin may be in the range of 55:45 to 90:10, specifically in the range of 55:45 to 87:13.

[0052] For example, when the epoxy resin contains a modified DCPD epoxy resin, a DCPD epoxy resin, and a bisphenol-type epoxy resin (e.g., a bisphenol A epoxy resin), the mixing ratio of a) the entirety of the modified dicyclopentadiene epoxy resin and the DCPD epoxy resin and b) the bisphenol-type epoxy resin may be a weight ratio of 60:40 to 80:20. At this time, the usage ratio (mixing ratio) of the modified dicyclopentadiene epoxy resin and the DCPD epoxy resin may be a weight ratio of 40:60 to 90:10, specifically, a weight ratio of 55:45 to 90:10.

[0053] (b) Aliphatic benzoxazine resin

[0054] The resin composition according to the present invention contains an aliphatic benzoxazine resin.

[0055] The above aliphatic benzoxazine resin is a resin having a benzoxazine structure in its molecular structure and an aliphatic group (e.g., an alkylene group) between the benzoxazine functional groups in the backbone. This aliphatic benzoxazine resin forms a resin layer together with an epoxy resin by ring-opening polymerization of the benzoxazine ring in the molecule, and since the aliphatic group exists in the backbone, it has excellent flexibility, and can lower the modulus of the resin layer (cured product of the resin composition). In addition, when the above aliphatic benzoxazine resin reacts with a modified DCPD epoxy resin, it can form a cured product having a high crosslinking density, excellent flame retardancy, and excellent toughness.

[0056] According to an example, the aliphatic benzoxazine resin may be a resin represented by the following chemical formula 3.

[0057]

[0058] In the above chemical formula 3,

[0059] m is an integer from 1 to 10,

[0060] R1 is C1~C 40 alkylene group, C2~C 40 Alkenylene group, C2~C 40 Selected from the group consisting of alkynylene groups,

[0061] R2 and R3 are the same or different, and each independently represents hydrogen, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group and C6~C 40 is selected from the group consisting of aryl groups,

[0062] The alkylene group, alkenylene group and alkynylene group of the above R1, and the alkyl group, alkenyl group, alkynyl group and aryl group of the above R2 and R3 may each be independently substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen and cyano groups.

[0063] In the resin composition according to the present invention, the content of the aliphatic benzoxazine resin may be about 10 to 45 parts by weight, specifically about 15 to 40 parts by weight, based on 100 parts by weight of the resin composition (excluding the inorganic filler, flame retardant, curing accelerator, and additives). If the content of the aliphatic benzoxazine resin is less than 10 parts by weight, low-modulus characteristics may not be achieved. On the other hand, if the content of the aliphatic benzoxazine resin exceeds 45 parts by weight, a sticky phenomenon may occur after semi-curing.

[0064] Meanwhile, the resin composition according to the present invention may further include a benzoxazine compound in addition to the aliphatic benzoxazine resin.

[0065] The benzoxazine compound usable in the present invention is not particularly limited as long as it is known in the art, and may be, for example, a benzoxazine compound represented by the following chemical formula 4.

[0066]

[0067] In the above formula,

[0068] R4 and R5 are the same or different and are each independently hydrogen, C1~C 40 Alkyl group and C6~C 40 is selected from the group consisting of aryl groups,

[0069] The alkyl group and aryl group of the above R4 and R5 may each be independently substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen, and cyano groups.

[0070] The content of the benzoxazine compound is not particularly limited. However, it is appropriate that the total content of the benzoxazine compound and the aliphatic benzoxazine resin is about 10 to 45 parts by weight, specifically about 15 to 40 parts by weight, based on 100 parts by weight of the mixture of the epoxy resin, the aliphatic benzoxazine resin, the benzoxazine compound, and the curing agent. At this time, the usage ratio (mixing ratio) of the aliphatic benzoxazine resin and the benzoxazine compound may be a weight ratio of 55:45 to 70:30, specifically a weight ratio of 55:45 to 65:35, and more specifically a weight ratio of 55:45 to 60:40.

[0071] (c) hardener

[0072] The resin composition according to the present invention includes a curing agent.

[0073] Curing agents usable in the present invention include curing agents commonly known in the art, such as acid anhydride curing agents, amine curing agents, and phenol curing agents.

[0074] Non-limiting examples of the above curing agent include acid anhydride curing agents such as tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, trialkyl tetrahydrophthalic anhydride, methyl cyclohexenedicarboxylic anhydride, phthalic anhydride, maleic anhydride, and pyromellitic anhydride; aromatic amine curing agents such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; aliphatic amine curing agents such as diethylenetriamine and triethylenetetramine; Examples thereof include, but are not limited to, phenol-based curing agents such as phenol aralkyl-type phenol resins, phenol novolac-type phenol resins, xyloc-type phenol resins, cresol novolac-type phenol resins, naphthol-type phenol resins, terpene-type phenol resins, multifunctional phenol resins, dicyclopentadiene-type phenol resins, naphthalene-type phenol resins, and novolac-type phenol resins synthesized from bisphenol A and resol; and latent curing agents such as dicyandiamide. These may be used alone or in a mixture of two or more.

[0075] In one example, the curing agent may be a phenolic curing agent, specifically a phenol novolac-type phenol resin. The phenolic curing agent can compensate for the lowered glass transition temperature (Tg) of the aliphatic benzoxazine-type resin due to the aliphatic backbone.

[0076] The content of such a hardener may be about 10 to 20 wt%, specifically about 13 to 18 wt%, based on 100 parts by weight of the resin composition (excluding the inorganic filler, flame retardant, hardening accelerator, and additives).

[0077] (d) Weapon filler

[0078] The resin composition according to the present invention may further include a conventional inorganic filler known in the art, if necessary.

[0079] Inorganic fillers can effectively improve the bending properties, low expansion, mechanical strength (toughness), and low stress of the final product by reducing the difference in coefficient of thermal expansion (CTE) between the resin layer and other layers while increasing mechanical properties.

[0080] Non-limiting examples of usable inorganic fillers include silicas such as natural silica, fused silica, amorphous silica, and crystalline silica; boehmite, alumina, talc, spherical glass, calcium carbonate, magnesium carbonate, magnesia, clay, calcium silicate, titanium oxide, antimony oxide, glass fiber, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, and mica. These inorganic fillers may be used alone or in combination of two or more. Among the inorganic fillers, silica exhibiting a low coefficient of thermal expansion is preferred.

[0081] The size of the inorganic filler is not particularly limited, but considering the dispersibility, the average particle diameter (D 50 ) may be about 0.5 to 5 μm.

[0082] Additionally, the inorganic filler may be surface-treated with a silane coupling agent. Such silane coupling agents may be conventional ingredients known in the art, and may contain vinyl and / or allyl groups. Surface-treated with such a silane coupling agent improves compatibility with the resin, thereby improving the dielectric properties, heat resistance, processability, and other properties of the resin composition.

[0083] In the present invention, the content of the inorganic filler is not particularly limited and can be appropriately adjusted in consideration of the aforementioned bending characteristics, mechanical properties, etc. However, if the content of the inorganic filler is excessive, it may be detrimental to the formability. For example, based on 100 parts by weight of the resin composition (excluding the inorganic filler, flame retardant, curing accelerator, and additives), the content may be about 50 to 200 parts by weight, specifically about 60 to 180 parts by weight.

[0084] (e) flame retardants

[0085] The resin composition according to the present invention may further include a flame retardant, if necessary.

[0086] The flame retardant may be any conventional flame retardant known in the art without limitation to enhance flame retardancy. Examples thereof include halogen flame retardants containing bromine or chlorine; phosphorus-based flame retardants such as phosphates, phosphonates, phosphinates, phosphine oxides, and phosphazenes; antimony-based flame retardants such as antimony trioxide; and inorganic flame retardants such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide. It is preferable to use a phosphorus-based flame retardant that does not lower heat resistance and dielectric properties, and specific examples thereof include triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, and phosphazenes.

[0087] In the present invention, the content of the flame retardant is not particularly limited and can be appropriately adjusted within a content range known in the art. Considering the physical properties of the resin composition according to the present invention, the content may be about 5 to 25 parts by weight based on 100 parts by weight of the resin composition (excluding the inorganic filler, flame retardant, curing accelerator, and additives), and specifically, about 7 to 20 parts by weight.

[0088] (f) curing accelerator

[0089] In the present invention, a conventional curing accelerator known in the art may be further included as needed.

[0090] The above curing accelerator can be appropriately selected and used depending on the type of epoxy resin and curing agent. Non-limiting examples of curing accelerators that can be used include amine-based, phenol-based, and imidazole-based curing accelerators, and specific examples include amine complexes of boron trifluoride, imidazole derivatives, organic acids such as phthalic anhydride and trimellitic anhydride, and the like. Preferred examples of catalysts that can be used include imidazole derivative curing accelerators, and specifically include 1-methylimidazole, 2-methylimidazole, 2-ethyl 4-methyl imidazole, 2-phenylimidazole, 2-phenyl 4-methyl imidazole, cyanoethylated derivatives thereof, carboxylic acid derivatives, and hydroxymethyl group derivatives. The above-mentioned catalysts may be used alone or in combination of two or more.

[0091] Also, organometallic salts or organometallic complexes including one or more metals selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese, and tin may be mentioned. Specific examples of usable organometallic salts or organometallic complexes include iron napthenates, copper naphthenate, zinc naphthenate, cobalt naphthenate, nickel naphthenate, manganese naphthenate, tin naphthenate, zinc octanoate, tin octanoate, iron octanoate, copper octanoate, zinc 2-ethylhexanate, lead acetylacetonate, cobalt acetylacetonate, or dibutyltin maleate, and they may be used alone or in combination of two or more.

[0092] In the present invention, the content of the curing accelerator is not particularly limited and can be appropriately adjusted within a content range known in the art. Considering the physical properties of the resin composition, the content of the curing accelerator may be about 0.1 to 10 parts by weight based on 100 parts by weight of the resin composition (excluding the inorganic filler, flame retardant, curing accelerator, and additives), specifically about 0.5 to 10 parts by weight, and more specifically about 0.5 to 7 parts by weight.

[0093] (g) additives

[0094] The resin composition according to the present invention may further include, as needed, other polymers such as thermosetting resins or thermoplastic resins and oligomers thereof not described above, solid rubber particles, or other additives such as ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents, etc., as long as the inherent properties of the resin composition are not impaired.

[0095] For example, there are organic fillers such as silicone powder, nylon powder, and fluorine powder; thickeners such as olben and benton; antifoaming agents or leveling agents of silicone, fluorine, and polymer types; adhesion-imparting agents such as imidazole, thiazole, triazole, silane coupling agents, epoxysilane, aminosilane, alkylsilane, and mercaptosilane; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, and carbon black; release agents such as higher fatty acids, higher fatty acid metal salts, and ester waxes; and stress-relieving agents such as modified silicone oil, silicone powder, and silicone resin. In addition, additives commonly used in thermosetting resin compositions used in the production of electronic devices (particularly, printed wiring boards) may be included.

[0096] The above resin composition may further contain a thermoplastic resin for the purpose of imparting appropriate flexibility to the resin composition after curing. Non-limiting examples of usable thermoplastic resins include phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone, polysulfone, etc. Any one of these thermoplastic resins may be used alone, or two or more may be used in combination.

[0097] The content of the above additive is not particularly limited, and may be, for example, about 0.01 to 10 parts by weight, specifically about 0.1 to 5 parts by weight, based on 100 parts by weight of the resin composition.

[0098] The resin composition of the present invention described above has a low modulus and a high glass transition temperature after curing, so that when applied to a printed circuit board, it can absorb and relieve solder stress caused by external stimuli such as heat or vibration, thereby improving the reliability of the printed circuit board. In addition, since the resin composition of the present invention has a low occurrence of a sticky phenomenon after curing, workability can be improved during the manufacture of a printed circuit board, and also, since resin peeling occurs less, the product quality of the printed circuit board can be improved.

[0099] According to an example, the resin composition of the present invention may have a modulus of about 8 GPa or less, specifically about 5 to 8 GPa, after curing, and a glass transition temperature (Tg) of 140°C or more, specifically about 140 to 170°C.

[0100]

[0101] Prepreg

[0102] One embodiment of the present invention is a prepreg comprising the aforementioned resin composition or a cured product thereof. This prepreg is distinguished from conventional prepregs in that it comprises the aforementioned resin composition, and can be used in the printed circuit board described below.

[0103] A specific example of the prepreg includes a fiber substrate; and the aforementioned resin composition impregnated into the fiber substrate. Here, the resin composition may be a resin varnish dissolved or dispersed in a solvent, or a cured product of the resin composition. Such cured products include uncured products, semi-cured products, and / or fully cured products.

[0104] The fiber substrate includes any conventional inorganic fiber substrate, organic fiber substrate, or a mixture thereof that is flexible and arbitrarily bendable. The fiber substrate may be arbitrarily selected based on the intended use or performance.

[0105] Non-limiting examples of usable fiber substrates include glass fibers (inorganic fibers) such as E-glass, D-glass, S-glass, NE-glass, T-glass, Q-glass, etc.; organic fibers such as glass paper, glass web, glass cloth, aramid fibers, aramid paper, polyimide, polyamide, polyester, aromatic polyester, fluororesin, etc.; carbon fibers, paper, inorganic fibers, or mixtures of one or more thereof. The form of the fiber substrate may include woven or nonwoven fabrics made of the above-mentioned fibers, etc.; roving, chopped strand mat, surfacing mat, woven fabrics, nonwoven fabrics, mats made of metal fibers, carbon fibers, mineral fibers, etc. These substrates may be used alone or in combination of two or more. When a reinforced fiber substrate is mixed, the stiffness and dimensional stability of the prepreg can be improved. The thickness of the fiber substrate is not particularly limited and may range from about 0.01 mm to 0.3 mm, for example.

[0106] The prepreg according to the present invention can be manufactured according to a method known in the art. For example, the prepreg refers to a sheet-shaped material in which a fiber substrate or a glass substrate is coated or impregnated with a resin composition or a resin composition varnish and then cured to B-stage (semi-cured state) by heating, thereby impregnating the fiber substrate with a resin. At this time, the temperature and time for heating the fiber substrate impregnated with the resin composition of the present invention are not particularly limited, and for example, the temperature may be about 150 to 210°C, and the time may be about 3 to 10 minutes.

[0107] In addition to the above-described method, the prepreg of the present invention can also be manufactured by a method such as a solvent method or a hot melt method.

[0108] The solvent method involves dissolving a prepreg-forming resin composition in an organic solvent, impregnating a fiber substrate with the resulting resin composition varnish, and then drying the resulting resin composition. When employing this solvent method, a resin varnish is typically used. Examples of methods for impregnating a fiber substrate with the resin composition include immersing the substrate in the resin varnish, applying the resin varnish to the substrate using various coaters, and spraying the resin varnish onto the substrate. Immersing the fiber substrate in the resin varnish is preferred because it improves the impregnation properties of the resin composition into the fiber substrate. Examples of organic solvents that can be used when preparing the above resin composition varnish include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and tetrahydrofuran. The above-mentioned organic solvents may be used alone or in combination of two or more.

[0109] Furthermore, the hot melt method may be a method in which, without dissolving the resin composition in an organic solvent, the resin composition is coated on a release paper with excellent peelability, and then laminated onto a sheet-like fiber substrate, or directly coated using a die coater. Furthermore, an adhesive film made of the resin composition may be placed on both sides of a sheet-like fiber substrate, and then continuously laminated using heating and pressure.

[0110] The prepreg of the present invention can exhibit excellent adhesiveness, heat resistance, and glass transition temperature, as well as improved low-dielectric properties and cost-saving effects, because it includes a cured resin of the above-described resin composition.

[0111]

[0112] <Metal foil laminate>

[0113] One embodiment of the present invention is a metal foil laminate comprising the above-described resin composition or a cured product thereof.

[0114] For example, the metal foil laminate comprises a metal foil substrate; and a resin layer formed on one or both sides of the metal foil substrate and cured with the above-described resin composition.

[0115] The metal foil may be any metal or alloy known in the art without limitation. If the metal foil is copper, a metal foil laminate formed by coating and drying the resin composition according to the present invention may be used as a copper clad laminate (CCL). Copper foil is preferred.

[0116] These copper foils include all copper foils manufactured by rolling and electrolytic processes. The copper foils may be treated with an anti-rust treatment to prevent surface oxidation and corrosion. Non-limiting examples of available copper foils include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, and ILSIN.

[0117] In the present invention, the metal foil may have a predetermined surface roughness (Rz) formed on the surface where the resin composition comes into contact with the cured resin layer. The range of this surface roughness (Rz) is not particularly limited, and may be, for example, about 0.5 to 5 μm, specifically about 0.5 to 3 μm.

[0118] In addition, the thickness of the metal foil is not particularly limited, and considering the thickness and mechanical properties of the laminated sheet, it may be about 35 ㎛ or less, specifically about 1 to 18 ㎛.

[0119]

[0120] <Laminated sheet>

[0121] Another embodiment of the present invention is a laminated sheet comprising the above-described resin composition or a cured product thereof.

[0122] For example, the laminated sheet comprises a polymer film substrate; and a resin layer formed on one or both sides of the polymer film substrate and in which the above-described resin composition is cured.

[0123] The polymer film substrate is not particularly limited as long as it is an insulating film known in the art. Non-limiting examples of usable polymer film substrates include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetylcellulose films, triacetylcellulose films, acetylcellulose butyrate films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, ethylene-vinyl acetate copolymer films, polystyrene films, polycarbonate films, polymethylpentene films, polysulfone films, polyetheretherketone films, polyethersulfone films, polyetherimide films, polyimide (PI) films, fluororesin films, polyamide films, acrylic resin films, norbornene-based resin films, and cycloolefin resin films. Specifically, it can be a polyimide (PI) film, an epoxy resin film, a PET (polyethylene terephthalate) film, a PEN (polyethylene naphthalate) film, etc. These polymer films can be either transparent or translucent, and can be colored or uncolored, and can be appropriately selected depending on the intended use. In addition, the polymer film substrate can be a substrate on which at least one surface has been subjected to silicone release treatment, antistatic treatment, or both silicone release treatment and antistatic treatment.

[0124] The thickness of the polymer film substrate is not particularly limited, and may be 1 to 100 μm, and specifically 10 to 80 μm, considering the thickness and mechanical properties of the laminated sheet.

[0125]

[0126] Printed circuit board

[0127] Another embodiment of the present invention is a printed circuit board including the prepreg or metal foil laminate described above.

[0128] For example, the printed circuit board includes a laminate formed by overlapping two or more of the aforementioned prepregs and then heating and pressing them under normal conditions. This laminate serves as an insulating layer, an adhesive layer, or a coverlay layer in the printed circuit board.

[0129] The printed circuit board according to the present invention can be manufactured according to a method known in the art. For example, the printed circuit board can be manufactured by laminating copper foil on one or both sides of the prepreg described above, heating and pressurizing to form a copper foil laminate, forming a through-hole in the copper foil laminate, performing through-hole plating, and then etching the copper foil to form a circuit.

[0130] The printed circuit board of the present invention, which is configured as described above, can have improved reliability because it is manufactured using a prepreg or a metal foil laminate comprising a resin composition comprising an epoxy resin containing a modified DCPD epoxy resin, an aliphatic benzoxazine resin, and a curing agent, and a cured resin. Accordingly, the printed circuit board of the present invention can be usefully used as a printed circuit board and / or a material thereof applied to various electrical and electronic devices such as mobile communication devices, base station devices thereof, network-related electronic devices such as servers and routers, and large-scale computers.

[0131]

[0132] Hereinafter, the present invention will be described in detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited to the following examples.

[0133] <Examples 1-4>

[0134] 1-1. Preparation of resin composition

[0135] A resin composition was prepared by mixing each component according to the compositions described in Tables 1 and 2 below. At this time, the unit of content (amount used) of each component in Table 2 below is parts by weight, and is based on 100 parts by weight of the resin composition (components excluding inorganic fillers, flame retardants, curing accelerators, and additives).

[0136] 1-2. Preparation of prepreg

[0137] After impregnating the above-manufactured resin composition into glass fiber, it was dried and heated at 170°C for 4 minutes to manufacture a prepreg in a semi-cured (B-stage) state.

[0138] 1-3. Manufacturing of copper-clad laminates

[0139] After laminating 1 ply of the prepreg manufactured in Example 1-2 on copper foil, pressing was performed at 200°C for 3 hours to manufacture a copper foil laminate having a thickness of 70 mm.

[0140] 1-4. Manufacturing of printed circuit boards

[0141] A photosensitive dry film was applied to the copper-clad laminate manufactured in the above Example 1-3 by applying heat and pressure, and then a master film showing the circuit was used to irradiate light and develop the film to manufacture a printed circuit board (PCB). The copper foil including the unnecessary plating film on the surface of the completed printed circuit board was removed (etched) with a highly corrosive agent to form a circuit.

[0142] Composition details Epoxy resin component A-1 Modified DCPDKDCP-300 (Kukdo Chemical) (isocyanate content: 10 mol%, epoxy equivalent: 300 g / eq) A-2 DCPDXD-1000 (Nippon Explosives) A-3 Bisphenol A type epoxy resin YD-127 (Kukdo Chemical) Benzoxazine component B-1 Aliphatic benzoxazine resin KZH-5084 (Kolon) B-2 Benzoxazine KSB-6090F (Kangnam Chemical) Curing agent C Phenol novolac type curing agent KPN-2125 (Kangnam Chemical) Inorganic filler D Silica SC-2050MNS (Admatech) Flame retardant E Phosphorus flame retardant PX-200 (Daihachi)

[0143] Example Comparative Example 12341234A-135203530-35--A-2-15-535-3520A-3151515151515151515B-135352020--3550B-2--15153535--C1515151515151515D404040404040404040E1010101010101010

[0144]

[0145] Comparative Examples 1 to 4

[0146] A resin composition, prepreg, copper-clad laminate, and printed circuit board were each manufactured in the same manner as in Example 1, except that the compositions were changed as described in Table 2 above.

[0147]

[0148] <Experimental Example 1> - Physical Property Evaluation

[0149] The physical properties of the printed circuit boards manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated by the following methods, and the results are shown in Table 3 below.

[0150] 1) Peel Strength (P / S)

[0151] According to the evaluation standard of IPC-TM-650 2.4.8, the copper layer of the printed circuit board was pulled up in a 90° direction and the point at which the copper layer was peeled off was measured for evaluation.

[0152] 2) Glass transition temperature (Tg)

[0153] Glass transition temperature (Tg) was measured by IPC-TM-650-2. 4. 24. 4 (DMA Method) using DMA (Dynamic Mechanical Analysis), TA's Q800.

[0154] 3) Modulus (GPa)

[0155] Modulus was measured using a Universal Testing Machine (UTM) (Instron 5967, Instron) according to IPC-TM-650-2. 4. 4 (Flexural Strength of Laminates Method).

[0156] 4) Sticky

[0157] After preparing four prepregs in the size of 5 cm x 5 cm, they were laminated and vacuum-packed in plastic. After that, a SUS plate (size: 10 cm x 10 cm, weapon: 300 g) was placed on the vacuum-packed laminate and left for 2 hours under a temperature of 35 ℃ and a humidity of 50% RH. After 2 hours, the vinyl packaging was removed from the vacuum-packed laminate and the adhesion (stickiness) between the laminated prepregs was checked. At this time, if the resin peeled off, it was judged to be sticky and marked as "NG", and if the resin did not peel off, it was judged not to be sticky and marked as "OK".

[0158] Example Comparative Example 12341234P / S(kgf / cm)0.850.900.901.001.101.050.950.75Tg(℃)140145155165185170160135Modulus(GPa)677.5816141110stickyOKOKOKOKOKOKOKNG

[0159] As a result of the experiment, Examples 1 to 4 including modified DCPD epoxy resin and aliphatic DCPD showed better effects in terms of glass transition temperature (Tg), adhesiveness, modulus properties, and stickiness compared to Comparative Examples 1 to 4 which did not simultaneously include the aforementioned components.

Claims

1. (a) Epoxy resin containing modified dicyclopentadiene (DCPD) epoxy resin; (b) aliphatic benzoxazine resin; and (c) hardener; A resin composition comprising:

2. In paragraph 1, A resin composition wherein the above modified dicyclopentadiene epoxy resin is an isocyanate modified dicyclopentadiene epoxy resin.

3. In paragraph 1, The above modified dicyclopentadiene epoxy resin is an epoxy resin represented by the following chemical formula 1, a resin composition: [Chemical Formula 1] (In the above chemical formula 1, X1 is an isocyanate group or an epoxy group, provided that at least one of one or more X1s is an isocyanate group, n is an integer from 1 to 100).

4. In paragraph 1, A resin composition wherein the above modified dicyclopentadiene epoxy resin has a modification rate in the range of 5 to 30%.

5. In paragraph 1, A resin composition wherein the modified dicyclopentadiene epoxy resin has an epoxy equivalent of 200 to 400 g / eq.

6. In paragraph 1, A resin composition wherein the epoxy resin further contains at least one non-dicyclopentadiene epoxy resin selected from the group consisting of bisphenol-type epoxy resin, novolac-type epoxy resin, biphenyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, arylalkylene-type epoxy resin, naphthalene-type epoxy resin, anthracene-type epoxy resin, phenoxy-type epoxy resin, norbornene-type epoxy resin, adamantane-type epoxy resin, and fluorene-type epoxy resin.

7. In paragraph 6, A resin composition wherein the modified dicyclopentadiene epoxy resin and the non-dicyclopentadiene epoxy resin are contained in a weight ratio of 40:60 to 85:

15.

8. In paragraph 6, A resin composition wherein the above epoxy resin additionally contains a dicyclopentadiene type epoxy resin.

9. In paragraph 1, The above aliphatic benzoxazine resin is a resin composition represented by the following chemical formula 3: [Chemical Formula 3] (In the above chemical formula 3, m is an integer from 1 to 10, R1 is C1~C 40 alkylene group, C2~C 40 Alkenylene group, C2~C 40 Selected from the group consisting of alkynylene groups, R2 and R3 are the same or different, and each independently represents hydrogen, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group and C6~C 40 is selected from the group consisting of aryl groups, The alkylene group, alkenylene group and alkynylene group of the above R1, and the alkyl group, alkenyl group, alkynyl group and aryl group of the above R2 and R3 are each independently substituted or unsubstituted with a substituent selected from the group consisting of deuterium, halogen and cyano group.

10. In paragraph 1, A resin composition wherein the above curing agent contains a phenol-based curing agent.

11. In paragraph 1, A resin composition further comprising at least one selected from the group consisting of an inorganic filler, a flame retardant, and a curing accelerator.

12. In paragraph 1, Based on the total amount of the resin composition, 10 to 30 wt% of modified dicyclopentadiene epoxy resin; 5 to 25 wt% of an aliphatic benzoxazine resin; and 5 to 20 wt% of hardener A resin composition comprising:

13. In paragraph 1, The above resin composition The modulus after curing is less than 8 GPa, A resin composition having a glass transition temperature (Tg) of 140 ℃ or higher.

14. Textile substrate; and A resin composition according to any one of claims 1 to 13 impregnated into the fiber substrate Prepreg containing .

15. Metal foil substrate; and A resin layer formed on one or both sides of the metal foil substrate and cured with the resin composition described in any one of claims 1 to 13. A metal foil laminate comprising:

16. Polymer film substrate; and A resin layer formed on one or both sides of the polymer film substrate and cured with the resin composition described in any one of claims 1 to 13. A laminated sheet comprising:

17. A printed circuit board comprising the prepreg of clause 14 or the metal foil laminate of clause 15.