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

Abstract

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

Description

Technical Field

[0001] This invention relates to a resin composition, a prepreg using the same, a metal foil laminate, a laminate, and a printed circuit board. Specifically, it relates to a resin composition with low modulus after curing, high glass transition temperature, and low incidence of surface stickiness, as well as a prepreg using the same, a metal foil laminate, a laminate, and a printed circuit board. Background Technology

[0002] With the development of 5G technology, its application in the automotive sector is also trending. The automotive industry demands higher levels of reliability than usual, especially when combined with 5G, which is crucial for data collection and processing; there can be no room for error during the process. Therefore, the standards for solder reliability between semiconductor chips and the mainboard are rising. However, due to the characteristics of the materials, there is a mismatch in the coefficients of thermal expansion (CTE) between the chip, solder, and mainboard. Furthermore, there is a need to improve solder crack resistance in harsh external environments, specifically against vibration. Summary of the Invention

[0003] Technical issues

[0004] The present invention aims to provide a resin composition with low modulus after curing, high glass transition temperature and low surface stickiness, as well as prepregs, metal foil laminates, laminates and printed circuit boards using the same.

[0005] Methods for solving problems

[0006] To achieve the above objectives, the present invention provides a resin composition comprising: (a) an epoxy resin containing a modified dicyclopentadiene (DCPD) epoxy resin; (b) an aliphatic benzoxazine resin; and (c) a curing agent.

[0007] As an example of the present invention, the modified dicyclopentadiene epoxy resin may be an isocyanate-modified dicyclopentadiene epoxy resin.

[0008] As an example of the present invention, the modification rate of the modified dicyclopentadiene epoxy resin can be 5 to 30%.

[0009] As an example of the present invention, the modified dicyclopentadiene epoxy resin may have an epoxy equivalent of 200 to 400 g / eq.

[0010] As an example of the present invention, the epoxy resin may further contain one or more non-dicyclopentadiene epoxy resins selected from the group consisting of bisphenol type epoxy resins, phenolic varnish type epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, arylalkylene type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, phenoxy type epoxy resins, norbornene type epoxy resins, adamantane type epoxy resins, and fluorene type epoxy resins.

[0011] As an example of the present invention, the weight ratio of the modified dicyclopentadiene epoxy resin to the non-dicyclopentadiene epoxy resin may be 40:60 to 85:15.

[0012] As an example of the present invention, the epoxy resin may further contain a dicyclopentadiene-type epoxy resin.

[0013] As an example of the present invention, the curing agent may contain a phenolic curing agent.

[0014] As an example of the present invention, the resin composition may further comprise one or more selected from the group consisting of inorganic fillers, flame retardants and curing accelerators.

[0015] As an example of the present invention, based on the total amount of the resin composition, the resin composition may contain 10 to 30 by weight of modified dicyclopentadiene epoxy resin; 5 to 25 by weight of aliphatic benzoxazine resin; and 5 to 20 by weight of curing agent.

[0016] As an example of the present invention, the cured modulus of the resin composition can be below 8 GPa, and the glass transition temperature (Tg) can be above 140°C.

[0017] Furthermore, the present invention provides a prepreg comprising: a fiber substrate and the aforementioned resin composition impregnated in the fiber substrate.

[0018] Furthermore, 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 from the aforementioned resin composition.

[0019] In addition, the present invention provides a laminate comprising: a polymer film substrate, and a resin layer formed on one or both sides of the polymer film substrate and cured from the aforementioned resin composition.

[0020] Furthermore, the present invention provides a printed circuit board comprising the aforementioned prepreg or the aforementioned metal foil laminate.

[0021] Invention Effects

[0022] The resin composition of the present invention has a low modulus after curing and a high glass transition temperature. Therefore, when applied to printed circuit boards, it can absorb and eliminate solder stress caused by external stimuli such as heat or vibration, thereby improving the reliability of printed circuit boards.

[0023] Furthermore, the resin composition of the present invention has a low rate of stickiness after curing, which improves workability during the manufacture of printed circuit boards, and less resin shedding occurs, thereby improving the product quality of the printed circuit boards.

[0024] The effects of the present invention are not limited to the examples described above, and further effects are included in this specification. Detailed Implementation

[0025] The present invention will now be described in detail.

[0026] All terms used in this specification (including technical and scientific terms) are to be used in the sense that would be commonly understood by one of ordinary skill in the art to which this invention pertains. Furthermore, unless explicitly defined otherwise, terms as defined in commonly used dictionaries are not to be interpreted ideally or excessively.

[0027] Furthermore, throughout this specification, when a part is described as "containing" a certain component, unless specifically stated to the contrary, it means that other components may also be included, rather than excluding other components. Additionally, "cured product" refers to all substances formed by the curing of the composition.

[0028] <Resin Composition>

[0029] The resin composition of the present invention can be applied to a printed circuit board, comprising: (a) an epoxy resin containing a modified dicyclopentadiene (DCPD) epoxy resin; (b) an aliphatic benzoxazine resin; and (c) a curing agent, and may further comprise, as needed, one or more selected from the group consisting of inorganic fillers, flame retardants and curing accelerators.

[0030] Specifically, both modified DCPD epoxy resin and aliphatic benzoxazine resin can reduce the modulus of products (e.g., prepregs). In particular, aliphatic benzoxazine resin exhibits superior low-modulus characteristics compared to modified DCPD. It should be noted that when aliphatic benzoxazine resin is used alone, it becomes sticky after semi-curing, rendering it unusable in products. Furthermore, when used alone, the low glass transition temperature (Tg) and low polarity of aliphatic compounds may result in lower adhesion strength to metals. On the other hand, the target low-modulus characteristics cannot be achieved when using modified DCPD epoxy resin alone. Therefore, in this invention, by mixing a modified dicyclopentadiene epoxy resin that is stable against stickiness and can reduce the modulus of the product compared to other phenolic varnish epoxy resins with an aliphatic benzoxazine resin, not only can the low modulus characteristics of the product be achieved, but also the stickiness after semi-curing can be prevented, and the bonding strength with metal can be improved.

[0031] The components constituting the resin composition of the present invention will be described below.

[0032] (a) Epoxy resin

[0033] In the resin composition of the present invention, the epoxy resin comprises a modified dicyclopentadiene (DCPD) epoxy resin.

[0034] The modified dicyclopentadiene (DCPD) epoxy resin is an epoxy resin with an intramolecular dicyclopentadiene (DCPD) structure and a portion of the epoxy groups modified by isocyanate groups. This isocyanate-modified dicyclopentadiene epoxy resin has a larger volume than conventional epoxy resins due to the DCPD structure, thereby achieving low dielectric properties in the resin composition. Furthermore, because a portion of the epoxy groups in the modified DCPD epoxy resin is replaced by isocyanate groups, the chain mobility is improved, thus enabling the achievement of a lower modulus while simultaneously increasing the glass transition temperature (Tg) of the cured resin.

[0035] According to one example, the modified DCPD epoxy resin can be represented by the following chemical formula 1:

[0036] [Chemical Formula 1]

[0037] ,

[0038] In the above chemical formula 1,

[0039] X1 is an isocyanate group or an epoxy group, and at least one of one or more X1 groups is an isocyanate group.

[0040] n is an integer from 1 to 100, specifically from 1 to 50, and more specifically from 1 to 20.

[0041] The modification rate of the modified DCPD epoxy resin can be in the range of 5% to 30%. Because such a modified DCPD epoxy resin has a large volume while exhibiting excellent chain flowability and no reduction in crosslinking density, the cured resin can achieve excellent thermal and modulus properties while displaying low dielectric properties.

[0042] According to 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 resin composition may have a glass transition temperature of about 140°C or higher while having a modulus of about 8 GPa or lower.

[0043] In the resin composition of the present invention, the content of modified DCPD epoxy resin is not particularly limited and can be appropriately adjusted according to the physical properties of the resin composition. For example, based on 100 parts by weight of the resin composition [provided that the components other than inorganic fillers, flame retardants, curing accelerators and additives (e.g., epoxy resin components, benzoxazine components and curing agent components)], the content of the modified DCPD epoxy resin can be about 10 to 45 parts by weight, specifically about 15 to 40 parts by weight.

[0044] In the resin composition of the present invention, in addition to the aforementioned modified DCPD epoxy resin, the epoxy resin may further comprise conventional epoxy resins known in the art.

[0045] For example, the epoxy resin may further comprise other epoxy resins besides dicyclopentadiene type (DCPD type) epoxy resins (hereinafter referred to as "non-DCPD epoxy resins"). By further comprising such non-DCPD epoxy resins as epoxy resin components, the resin compositions of the present invention can prevent a reduction in adhesive strength.

[0046] As non-limiting examples of the aforementioned non-DCPD epoxy resins, there are 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.), phenolic varnish type epoxy resins (e.g., phenolic varnish type epoxy resin, cresolic varnish type epoxy resin, etc.), biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, arylalkylene type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, phenoxy type epoxy resins, norbornene type epoxy resins, adamantane type epoxy resins, fluorene type epoxy resins, etc., which can be used alone or in combination of two or more.

[0047] According to one example, the non-DCPD epoxy resin can be a bisphenol type epoxy resin, specifically a bisphenol A type epoxy resin.

[0048] The aforementioned ratio (mixing ratio) of modified dicyclopentadiene epoxy resin to non-DCPD epoxy resin can be 40:60 ~ 85:15 by weight, specifically 40:60 ~ 70:30 by weight, and more specifically 55:45 ~ 70:30 by weight.

[0049] In the resin composition of the present invention, the epoxy resin may further contain a dicyclopentadiene-type epoxy resin.

[0050] Dicyclopentadiene (DCPD type) epoxy resin is a multifunctional epoxy resin with a dicyclopentadiene (DCPD) structure in the molecule. Due to its hydrophobic bicyclic hydrocarbon group, it has less electronic polarization, which can reduce the dielectric constant of the cured resin.

[0051] There is no particular limitation on the DCPD type epoxy resin that can be used in this invention, as long as it is a resin known in the art, such as the resin represented by the following chemical formula 2:

[0052] [Chemical Formula 2]

[0053] ,

[0054] In the above formula, n is an integer from 1 to 10.

[0055] There is no particular limitation on the content of such dicyclopentadiene-type epoxy resin. However, based on the total amount of epoxy resin, a total content of modified DCPD epoxy resin and DCPD epoxy resin of approximately 60 to 80% by weight, specifically approximately 65 to 75% by weight, is suitable. In this case, the usage ratio (mixing ratio) of modified DCPD epoxy resin to DCPD-type epoxy resin can be 55:45 to 90:10 by weight, specifically 55:45 to 87:13 by weight.

[0056] According to one example, when the aforementioned epoxy resin contains modified DCPD epoxy resin, DCPD epoxy resin, and bisphenol type epoxy resin (e.g., bisphenol A type epoxy resin), the overall mixing ratio of a) the modified dicyclopentadiene epoxy resin and DCPD epoxy resin to b) the bisphenol type epoxy resin can be a weight ratio of 60:40 to 80:20. In this case, the usage ratio (mixing ratio) of the modified dicyclopentadiene epoxy resin to DCPD epoxy resin can be a weight ratio of 40:60 to 90:10, specifically a weight ratio of 55:45 to 90:10.

[0057] (b) Aliphatic benzoxazine resins

[0058] The resin composition of the present invention contains an aliphatic benzoxazine resin.

[0059] The aliphatic benzoxazine resin is a resin having a benzoxazine structure in its molecular structure and aliphatic groups (e.g., alkylene groups) between the benzoxazine functional groups within the backbone. In such an aliphatic benzoxazine resin, the intramolecular ring-opening polymerization of the benzoxazine ring forms a resin layer together with the epoxy resin. Due to the presence of aliphatic groups within the backbone, it exhibits excellent flexibility, thereby reducing the modulus of the resin layer (the cured resin composition). Furthermore, when the aliphatic benzoxazine resin reacts with modified DCPD epoxy resin, a cured product with high crosslinking density and excellent flame retardancy and toughness can be formed.

[0060] For example, the above-mentioned aliphatic benzoxazine resin can be a resin represented by the following chemical formula 3:

[0061] [Chemical Formula 3]

[0062] ,

[0063] In the above chemical formula 3,

[0064] m is an integer from 1 to 10.

[0065] R1 can be chosen freely from C1 to C. 40 Alkylene, C2~C 40alkenyl group, C2~C 40 In the group composed of alkynyl groups.

[0066] R2 and R3 may be the same or different from each other, and each is independently chosen from hydrogen, C1~C2. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group and C6~C 40 In the group composed of aryl groups

[0067] The alkylene, alkenylene, and alkyneylene groups of R1, and the alkyl, alkenylene, alkyne, and aryl groups of R2 and R3, may each be independently substituted by one or more substituents selected from the group consisting of deuterium, halogen, and cyano, or may be unsubstituted.

[0068] In the resin composition of the present invention, based on 100 parts by weight of the resin composition (provided that the components other than inorganic fillers, flame retardants, curing accelerators, and additives), the content of the aliphatic benzoxazine resin can be about 10 to 45 parts by weight, specifically about 15 to 40 parts by weight. When the content of the aliphatic benzoxazine resin is less than 10 parts by weight, the low modulus property may not be achieved. On the other hand, when the content of the aliphatic benzoxazine resin is greater than 45 parts by weight, a sticky phenomenon may occur after semi-curing.

[0069] On the other hand, in addition to the aliphatic benzoxazine resins, the resin compositions of the present invention may further contain benzoxazine compounds.

[0070] The benzoxazine compounds that can be used in this invention are not particularly limited, as long as they are known in the art, such as the benzoxazine compounds represented by the following chemical formula 4:

[0071] [Chemical Formula 4]

[0072] ,

[0073] In the above formula,

[0074] R4 and R5 may be the same or different from each other, and each is independently chosen from hydrogen, C1~C2. 40 Alkyl groups and C6~C 40 In the group composed of aryl groups

[0075] The alkyl and aryl groups of R4 and R5 can each be independently substituted by one or more substituents selected from the group consisting of deuterium, halogen, and cyano, or remain unsubstituted.

[0076] There is no particular limitation on the content of such benzoxazine compounds. However, based on 100 parts by weight of a mixture of epoxy resin, aliphatic benzoxazine resin, benzoxazine compound, and curing agent, it is appropriate that the total content of benzoxazine compound and aliphatic benzoxazine resin is about 10 to 45 parts by weight, specifically about 15 to 40 parts by weight. In this case, the usage ratio (mixing ratio) of aliphatic benzoxazine resin to benzoxazine compound can be 55:45 to 70:30 by weight, specifically 55:45 to 65:35 by weight, and more specifically 55:45 to 60:40 by weight.

[0077] (c) Curing agent

[0078] The resin composition of the present invention includes a curing agent.

[0079] As curing agents that can be used in this invention, there are curing agent components commonly known in the art, such as acid anhydride curing agents, amine curing agents, phenol curing agents, etc.

[0080] Non-limiting examples of the aforementioned curing agents include: anhydride-based curing agents such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, phthalic anhydride, maleic anhydride, and pyromellitic anhydride; aromatic amine-based curing agents such as m-phenylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone; aliphatic amine-based curing agents such as diethylenetriamine and triethylenetetraamine; and phenolic aromatics. Phenolic curing agents include, but are not limited to, basic phenolic resins, phenolic varnish-type phenolic resins, phenol-aryl (Xylok) type phenolic resins, cresol phenolic varnish-type phenolic resins, naphthol type phenolic resins, terpene type phenolic resins, multifunctional phenolic resins, dicyclopentadiene-based phenolic resins, naphthol type phenolic resins, and phenolic varnish-type phenolic resins synthesized from bisphenol A and methyl phenolic resins; latent curing agents such as dicyandiamide; and others. These can be used alone or in combination of two or more.

[0081] According to one example, the curing agent described above can be a phenolic curing agent, specifically a phenolic varnish-type phenolic resin. The phenolic curing agent can compensate for the reduced glass transition temperature (Tg) caused by the aliphatic backbone of the aliphatic benzoxazine resin.

[0082] Based on 100 parts by weight of the resin composition (provided that the components other than inorganic fillers, flame retardants, curing accelerators and additives are included), the content of such curing agent may be about 10 to 20% by weight, specifically about 13 to 18% by weight.

[0083] (d) Inorganic packing

[0084] The resin composition of the present invention may, as needed, further comprise conventional inorganic fillers known in the art.

[0085] Inorganic fillers improve mechanical properties while reducing the difference in coefficient of thermal expansion (CTE) between the resin layer and other layers, thereby effectively improving the warpage characteristics, reducing expansion, increasing mechanical strength (toughness), and reducing stress of the final product.

[0086] Non-limiting examples of usable inorganic fillers include: silica-based materials such as natural silica, fused silica, amorphous silica, and crystalline silica; boehmite, alumina, talc, spherical glass, calcium carbonate, magnesium carbonate, magnesium oxide, clay, calcium silicate, titanium dioxide, antimony oxide, glass fiber, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium dioxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, and mica. These inorganic fillers can be used alone or in combination of two or more. Among the aforementioned inorganic fillers, silica exhibiting a low coefficient of thermal expansion is preferred.

[0087] There are no particular restrictions on the size of inorganic fillers, but when considering dispersibility, the average particle size (D) is important. 50 The size can be approximately 0.5 to 5 μm.

[0088] Furthermore, the inorganic filler can be surface-treated with a silane coupling agent. Such a silane coupling agent can be a conventional component known in the art, or it can be a silane coupling agent containing vinyl and / or allyl groups, etc. When surface-treated with such a silane coupling agent, it exhibits excellent compatibility with the resin, thereby improving the dielectric properties, heat resistance, processability, etc., of the resin composition.

[0089] In this invention, the content of inorganic filler is not particularly limited and can be appropriately adjusted considering the aforementioned warpage characteristics, mechanical properties, etc. However, if the content of inorganic filler is too high, it may be detrimental to moldability. For example, based on 100 parts by weight of the resin composition (provided that the components other than inorganic filler, flame retardant, curing accelerator, and additives) can be about 50 to 200 parts by weight, specifically about 60 to 180 parts by weight.

[0090] (e) Flame retardants

[0091] The resin composition of the present invention may further include a flame retardant if necessary.

[0092] To improve flame retardancy, conventional flame retardants known in the art can be used without limitation. Examples include halogenated flame retardants containing bromine or chlorine; phosphorus-based flame retardants such as phosphate esters, phosphonates, hypophosphonates, phosphine oxide, and phosphazenes; antimony-based flame retardants such as antimony trioxide; and inorganic flame retardants such as metal hydroxides like aluminum hydroxide and magnesium hydroxide. Preferably, phosphorus-based flame retardants that do not reduce heat resistance and dielectric properties are used; specific examples include triphenyl phosphate, trimethylbenzene phosphate, trichloropropyl phosphate, and phosphazenes.

[0093] In this invention, the content of the flame retardant is not particularly limited and can be appropriately adjusted within a range known in the art. When considering the physical properties of the resin composition of this invention, based on 100 parts by weight of the resin composition (provided that the components other than inorganic fillers, flame retardants, curing accelerators and additives), the content of the flame retardant can be about 5 to 25 parts by weight, specifically about 7 to 20 parts by weight.

[0094] (f) Curing accelerator

[0095] In this invention, conventional curing accelerators known in the art may also be included as needed.

[0096] The curing accelerator can be appropriately selected based on the type of epoxy resin and curing agent. Non-limiting examples of usable curing accelerators include amine-based, phenol-based, and imidazole-based curing accelerators. Specific examples include amine complexes of boron trifluoride, imidazole derivatives, phthalic anhydride, and trimellitic anhydride, among other organic acids. A preferred example of a usable catalyst is an imidazole derivative curing accelerator, specifically 1-methylimidazolium, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, their cyanoethylated derivatives, carboxylic acid derivatives, and hydroxymethyl derivatives. The aforementioned catalysts can be used alone or in combination of two or more.

[0097] In addition, organometallic salts or organometallic complexes containing one or more metals selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese, and tin can be cited. Specific examples of usable organometallic salts or organometallic complexes include iron naphthenates, copper naphthenates, zinc naphthenates, cobalt naphthenates, nickel naphthenates, manganese naphthenates, tin naphthenates, zinc octanoate, tin octanoate, iron octanoate, copper octanoate, zinc 2-ethylhexanoate, lead acetylacetonate, cobalt acetylacetonate, or dibutyltin maleate, which can be used alone or in combination of two or more.

[0098] In this invention, the content of the curing accelerator is not particularly limited and can be appropriately adjusted within a range known in the art. Taking into account the physical properties of the resin composition, based on 100 parts by weight of the resin composition (provided that the components other than inorganic fillers, flame retardants, curing accelerators and additives), the content of the curing accelerator can be about 0.1 to 10 parts by weight, specifically about 0.5 to 10 parts by weight, and more specifically about 0.5 to 7 parts by weight.

[0099] (g) Additives

[0100] The resin composition of the present invention may, as needed, contain other polymers such as thermosetting resins or thermoplastic resins and their oligomers not described above, solid rubber particles or other additives such as ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents, etc., without impairing the inherent properties of the resin composition described above.

[0101] For example, the additives mentioned above include: organic fillers such as silicone powder, nylon powder, and fluorine powder; thickeners such as Orben and Bentone; silicone-based, fluorine-based, and polymeric defoamers or leveling agents; imidazole-based, thiazole-based, triazole-based, silane coupling agents, epoxy silanes, amino silanes, alkyl silanes, and mercapto silanes; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, and carbon black; release agents such as higher fatty acids, higher fatty acid metal salts, and ester waxes; and stress relievers such as modified silicone oils, silicone powders, and silicone resins. Furthermore, additives commonly used in thermosetting resin compositions for the production of electronic devices (especially printed wiring substrates) may also be included.

[0102] To impart suitable flexibility and other properties to the cured resin composition, a thermoplastic resin may be further incorporated into the resin composition. Non-limiting examples of usable thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimides, polyamide-imides, polyethersulfones, polysulfones, etc. These thermoplastic resins may be used alone or in combination of two or more.

[0103] The content of the above-mentioned additives is not particularly limited. For example, based on 100 parts by weight of the resin composition, it can be about 0.01 to 10 parts by weight, specifically about 0.1 to 5 parts by weight.

[0104] The resin composition of the present invention, due to its low modulus and high glass transition temperature after curing, can absorb and eliminate solder stress caused by external stimuli such as heat or vibration when applied to printed circuit boards, thereby improving the reliability of the printed circuit boards. Furthermore, the resin composition of the present invention has a low incidence of stickiness after curing, thus improving workability during the manufacture of printed circuit boards, and reducing resin shedding, thereby improving the product quality of the printed circuit boards.

[0105] According to one example, the cured modulus of the resin composition of the present invention can be about 8 GPa or less, specifically about 5 to 8 GPa, and the glass transition temperature (Tg) can be 140°C or more, specifically about 140 to 170°C.

[0106] <Prepreg>

[0107] One embodiment of the present invention relates to a prepreg comprising the aforementioned resin composition or a cured thereof. Such a prepreg differs from conventional prepregs in that it comprises the resin composition described above and can be used in the printed circuit board described later.

[0108] As a specific example of the aforementioned prepreg, it comprises: a fiber substrate and the aforementioned resin composition impregnated in 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.

[0109] Fiber substrates include conventional inorganic fiber substrates, organic fiber substrates, or mixtures thereof that are flexible and can be bent at will. Fiber substrates can be selected arbitrarily based on the intended use or performance requirements.

[0110] 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 cellophane, glass web, glass cloth, aramid fiber, aramid paper, polyimide, polyamide, polyester, aromatic polyester, fluoropolymer, etc.; carbon fiber, paper, inorganic fibers, or a mixture thereof. Examples of the aforementioned fiber substrate forms include woven or nonwoven fabrics composed of the aforementioned fibers; woven fabrics, nonwoven fabrics, and felts composed of roving, chopped strand mat, surfacing mat, metal fibers, carbon fibers, mineral fibers, etc. These substrates can be used alone or in combination. When reinforcing fiber substrates are used in combination, the rigidity and dimensional stability of the prepreg can be improved. The thickness of the fiber substrate is not particularly limited, and can be, for example, in the range of about 0.01 mm to 0.3 mm.

[0111] The prepreg of the present invention can be manufactured according to methods known in the art. As a specific example, the aforementioned prepreg refers to a sheet material impregnated with resin by coating or impregnating a sheet-like fiber substrate or glass substrate made of fibers with or without the resin composition or resin composition varnish, and then curing it to stage B (semi-cured state) by heating. In this case, the temperature and time for heating the fiber substrate impregnated with the resin composition of the present invention are not particularly limited; for example, the temperature can be about 150 to 210°C, and the time can be about 3 to 10 minutes.

[0112] In addition to the methods described above, the prepreg of the present invention can also be manufactured by solvent method, hot melt method, and other methods.

[0113] The solvent method involves impregnating a fiber substrate with a resin composition varnish formed by dissolving a prepreg forming resin composition in an organic solvent, followed by drying. When using such a solvent method, a resin varnish is typically used. Examples of methods for impregnating the fiber substrate with the aforementioned resin composition include impregnating the substrate with a resin varnish, applying the resin varnish to the substrate using various coating machines, and spraying the resin varnish onto the substrate. In these cases, impregnating the fiber substrate with a resin varnish improves the impregnation properties of the resin composition with the fiber substrate, and is therefore preferred. Examples of organic solvents that can be used in the manufacture of the above-mentioned resin composition varnish include: ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosol acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosol and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and tetrahydrofuran. The aforementioned organic solvents can be used alone or in combination of two or more.

[0114] Furthermore, the hot-melt method can be used without dissolving the resin composition in an organic solvent. Instead, the resin composition is coated onto a release paper with excellent peelability and then laminated onto a sheet fiber substrate, or it can be directly coated using a die-coating machine. Alternatively, an adhesive film made of the resin composition can be deposited on both sides of a sheet fiber substrate and then continuously laminated by heating and pressurizing.

[0115] The prepreg of the present invention, which contains a resin cured from the above-mentioned resin composition, exhibits excellent adhesion, heat resistance and glass transition temperature, while also displaying improved low dielectric properties and cost reduction effects.

[0116] <Metal Foil Laminate>

[0117] One embodiment of the present invention relates to a metal foil laminate comprising the above-described resin composition or its cured form.

[0118] As a specific example, the aforementioned metal foil laminate includes: a metal foil substrate and a resin layer formed on one or both sides of the metal foil substrate and cured from the aforementioned resin composition.

[0119] The metal foil can be any metal or alloy known in the art without limitation. When the metal foil is copper foil, a metal foil laminate formed by coating and drying the resin composition of the present invention can be used as a copper foil laminate (CCL). Copper foil is preferred.

[0120] Such copper foil includes all copper foils manufactured by rolling and electrolysis. To prevent surface oxidation and corrosion, the copper foil may be treated with an anti-rust agent. Non-limiting examples of usable copper foils include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, and ILSIN.

[0121] In this invention, the metal foil may have a predetermined surface roughness (Rz) formed on the surface that contacts the resin layer formed by curing the resin composition. The range of such surface roughness (Rz) is not particularly limited, but may be, for example, about 0.5 to 5 μm, specifically about 0.5 to 3 μm.

[0122] Furthermore, the thickness of the metal foil is not particularly limited. Considering the thickness and mechanical properties of the laminate, it can be less than about 35 μm, specifically about 1 to 18 μm.

[0123] <Laminated film>

[0124] Another embodiment of the present invention relates to a laminate comprising the above-described resin composition or a cured thereof.

[0125] As a specific example, the above-mentioned laminate includes: a polymer film substrate, and a resin layer formed on one or both sides of the polymer film substrate and cured from the above-mentioned resin composition.

[0126] The aforementioned polymeric membrane substrate is not particularly limited, as long as it is an insulating film known in the art. Non-limiting examples of usable polymeric membrane substrates include: polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; polyethylene films; polypropylene films; cellophane; diacetyl cellulose films; triacetyl cellulose films; acetyl cellulose 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; fluoropolymer films; polyamide films; acrylic resin films; norbornene resin films; and cyclic olefin resin films. Specifically, it can be polyimide (PI) films, epoxy resin films, PET (polyethylene terephthalate) films, PEN (polyethylene naphthalate) films, etc. These polymer films can be either transparent or translucent, and can be colored or uncolored, depending on the application. Furthermore, the polymer film substrate can be a substrate that has undergone silicone release treatment, antistatic treatment, or both on at least one side.

[0127] The thickness of the polymer film substrate is not particularly limited. Considering the thickness and mechanical properties of the laminate, it can be 1 to 100 μm, specifically 10 to 80 μm.

[0128] Printed Circuit Boards

[0129] Another embodiment of the present invention relates to a printed circuit board comprising the aforementioned prepreg or metal foil laminate.

[0130] As a specific example, the aforementioned printed circuit board comprises a laminate formed by overlapping two or more of the aforementioned prepregs and then heating and pressurizing them under conventional conditions. Such a laminate functions as an insulating layer, adhesive layer, or cover layer in the printed circuit board.

[0131] The printed circuit board of the present invention can be manufactured according to methods known in the art. As an embodiment, it can be manufactured by laminating copper foil on one or both sides of the prepreg and heating and pressing to form a copper foil laminate, forming through holes on the copper foil laminate and performing through hole plating, and then etching the copper foil to form a circuit.

[0132] The printed circuit board of the present invention, as described above, is manufactured using a prepreg metal foil laminate made by curing a resin composition comprising an epoxy resin containing a modified DCPD epoxy resin, an aliphatic benzoxazine resin, and a curing agent, thus improving reliability. Therefore, the printed circuit board of the present invention can be effectively used as a printed circuit board and / or material for various electrical and electronic devices such as mobile communication devices or their base station devices, servers, routers, and large computers.

[0133] The present invention will now be described in detail through embodiments. However, the following embodiments are merely illustrative of the invention, and the invention is not limited to these embodiments.

[0134] <Examples 1-4>

[0135] 1-1. Preparation of the resin composition

[0136] The resin composition is prepared by mixing the components according to the compositions described in Tables 1 and 2 below. In this case, the content (amount) of each component in Table 2 below is in parts by weight, based on 100 parts by weight of the resin composition (provided that the components other than inorganic fillers, flame retardants, curing accelerators and additives are included).

[0137] 1-2. Prepreg Manufacturing

[0138] After impregnating the above-prepared resin composition into glass fibers, it is dried and heated at 170°C for 4 minutes to produce a prepreg in a semi-cured (stage B) state.

[0139] 1-3. Manufacturing of Copper Foil Laminates

[0140] After laminating 1 ply of the prepreg manufactured in Examples 1-2 onto copper foil, it is pressed at 200°C for 3 hours, thereby producing a copper foil laminate with a thickness of 70 mm.

[0141] 1-4. Manufacturing of Printed Circuit Boards

[0142] After photosensitive dry film is laminated onto the copper foil laminates manufactured in Examples 1-3 above by heat and pressure, a printed circuit board (PCB) is obtained by irradiating a master film displaying the circuit with light and developing it. On the surface of the completed PCB, copper foil containing unnecessary coatings is removed (etched) with strong corrosive chemicals, thereby forming the circuit.

[0143] [Table 1]

[0144]

[0145] [Table 2]

[0146]

[0147] <Comparative Examples 1 ~ 4>

[0148] Except for the composition as shown in Table 2 above, the resin composition, prepreg, copper foil laminate and printed circuit board are manufactured by the same method as in Example 1 above.

[0149] <Experimental Example 1> - Physical Property Evaluation

[0150] The physical properties of the printed circuit boards manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated using the following methods, and the results are shown in Table 3 below.

[0151] 1) Copper foil adhesion (Peel Strength, P / S)

[0152] According to the evaluation criteria of IPC-TM-650 2.4.8, the copper foil layer of the printed circuit board is pulled upwards at a 90° angle and the time point of copper foil layer peeling is measured for evaluation.

[0153] 2) Glass transition temperature (Tg)

[0154] The glass transition temperature (Tg) was measured using DMA (Dynamic Mechanical Analysis) and TA's Q800 via IPC-TM-650-2.4.24.4 (DMA Method).

[0155] 3) Modulus (GPa)

[0156] The modulus was measured using a UTM (Universal Testing Machine) (Instron 5967 from Instron) via IPC-TM-650-2.4.4 (Flexural Strength of Laminates Method).

[0157] 4) Sticky

[0158] Prepare four 5cm × 5cm prepreg sheets, stack them, and vacuum-pack them in plastic. Then, place a 10cm × 10cm SUS board (300g) on ​​top of the vacuum-packed stack and leave it at 35°C and 50% RH for 2 hours. After 2 hours, remove the plastic packaging from the vacuum-packed stack and check for adhesion (stickiness) between the prepreg sheets. If resin detachment occurs, it is considered sticky and marked "NG"; if no resin detachment occurs, it is considered non-sticky and marked "OK".

[0159] [Table 3]

[0160]

[0161] Experiments showed that Examples 1 to 4, which contained modified DCPD epoxy resin and aliphatic DCPD, exhibited superior performance in terms of glass transition temperature (Tg), adhesion, modulus properties, and anti-sticking properties compared to Comparative Examples 1 to 4, which did not simultaneously contain the aforementioned constituent elements.

Claims

1. A resin composition comprising: (a) Epoxy resin containing modified dicyclopentadiene DCPD epoxy resin; (b) Aliphatic benzoxazine resins; and (c) Curing agent.

2. The resin composition according to claim 1, wherein the modified dicyclopentadiene epoxy resin is an isocyanate-modified dicyclopentadiene epoxy resin.

3. The resin composition according to claim 1, wherein the modified dicyclopentadiene epoxy resin is an epoxy resin represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, X1 is an isocyanate group or an epoxy group, and at least one of one or more X1 groups is an isocyanate group. n is an integer from 1 to 100.

4. The resin composition according to claim 1, wherein the modification rate of the modified dicyclopentadiene epoxy resin is in the range of 5% to 30%.

5. The resin composition according to claim 1, wherein the modified dicyclopentadiene epoxy resin has an epoxy equivalent of 200 to 400 g / eq.

6. The resin composition according to claim 1, wherein the epoxy resin further comprises one or more non-dicyclopentadiene epoxy resins selected from the group consisting of bisphenol type epoxy resins, phenolic varnish type epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, arylalkylene type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, phenoxy type epoxy resins, norbornene type epoxy resins, adamantane type epoxy resins, and fluorene type epoxy resins.

7. The resin composition according to claim 6, wherein the weight ratio of the modified dicyclopentadiene epoxy resin to the non-dicyclopentadiene epoxy resin is 40:60 to 85:

15.

8. The resin composition according to claim 6, wherein the epoxy resin further comprises a dicyclopentadiene-type epoxy resin.

9. The resin composition according to claim 1, wherein the aliphatic benzoxazine resin is a compound 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 can be chosen freely from C1 to C. 40 Alkylene, C2~C 40 alkenyl group, C2~C 40 In the group composed of alkynyl groups. R2 and R3 may be the same or different from each other, and each is independently chosen from hydrogen, C1~C2. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group and C6~C 40 In the group composed of aryl groups The alkylene, alkenylene, and alkyneylene groups of R1, and the alkyl, alkenylene, alkyne, and aryl groups of R2 and R3, are each independently substituted or unsubstituted by substituents selected from the group consisting of deuterium, halogen, and cyano.

10. The resin composition according to claim 1, wherein the curing agent contains a phenolic curing agent.

11. The resin composition according to claim 1, further comprising one or more selected from the group consisting of inorganic fillers, flame retardants and curing accelerators.

12. The resin composition according to claim 1, comprising, based on the total amount of the resin composition: 10 to 30% by weight of modified dicyclopentadiene epoxy resin Aliphatic benzoxazine resins 5 to 25% by weight; and Hardener 5 to 20% by weight.

13. The resin composition according to claim 1, wherein the cured modulus of the resin composition is less than 8 GPa and the glass transition temperature Tg is greater than 140°C.

14. A prepreg comprising: Fiber substrate, and The resin composition according to any one of claims 1 to 13 impregnated in the fiber substrate.

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

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

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

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