Low carbon resin composition, copper clad laminate, and printed circuit board

Abstract

A low-carbon resin composition is provided, comprising: (A) an epoxy resin, 100 parts by weight; and (C) a curing agent, 90-130 parts by weight. The epoxy resin (A) comprises: (A1) a bisphenol A type low-carbon epoxy resin, 25-80 parts by weight; (A2) a bisphenol F type epoxy resin, 5-60 parts by weight; and (A3) a multifunctional epoxy resin, 5-20 parts by weight, wherein the multifunctional epoxy resin has at least three epoxy groups per molecule.

Description

Technical Field

[0001] This invention relates to low-carbon resin compositions, copper foil substrates, and printed circuit boards, and particularly to low-carbon resin compositions, copper foil substrates, and printed circuit boards that can reduce carbon emissions. Prior Technology

[0002] As global warming continues to worsen, carbon reduction in electronic products has become an international industry trend. Major manufacturers have successively implemented carbon neutrality strategies and are beginning to move towards the goal of net-zero emissions.

[0003] The issue of carbon reduction in printed circuit board (PCB) substrate materials is also urgent. Current methods involve adjusting the type and amount of curing accelerator, reducing the baking temperature of the impregnation process, and reducing the temperature and time of the pressing and curing process to reduce process energy consumption and achieve the goal of carbon reduction. However, this results in insufficient stability of raw adhesives and prepreg materials during storage.

[0004] There is still a pressing need for new methods to reduce carbon emissions from substrate materials while maintaining substrate stability. Summary of the Invention

[0005] This project uses low-carbon epoxy resin to replace most of the traditional petrochemical-synthesized epoxy resin products, and combines it with multifunctional epoxy resin to improve the curing reaction rate. It also adds relevant toughening agents to reduce the problem of excessive rigidity of PCB materials, and introduces relevant low-dielectric filler powders to improve the dimensional stability and electrical properties of the resin composition.

[0006] In some embodiments, this invention provides a low-carbon resin composition comprising: (A) an epoxy resin, 100 parts by weight; and (C) a curing agent, 90-130 parts by weight. The epoxy resin (A) comprises (A1) a bisphenol A type low-carbon epoxy resin, 25-80 parts by weight; (A2) a bisphenol F type epoxy resin, 5-60 parts by weight; and (A3) a multifunctional epoxy resin, 5-20 parts by weight, wherein the multifunctional epoxy resin has at least three epoxy groups per molecule.

[0007] In other embodiments, this invention also provides a copper foil substrate made of glass fiber cloth impregnated with the low-carbon resin composition described above.

[0008] In some other embodiments, this invention provides a printed circuit board comprising the aforementioned copper foil substrate. Implementation

[0009] The following provides a detailed description of the low-carbon resin composition of this application. It should be understood that the following description provides many different embodiments or examples for implementing different variations of this application. The specific components and combinations described below are merely a simplified description of this application. Of course, these are for illustrative purposes only and not as limitations of this application. In this application, the term "about" means an amount that can be increased or decreased by a magnitude that is generally and reasonably understood by those skilled in the art.

[0010] This invention provides a low-carbon resin composition in which a low-carbon epoxy resin is incorporated into a raw adhesive formulation, thereby reducing carbon emissions at the substrate material raw material level. Simultaneously, by replacing traditional solid resin with a liquid resin, the amount of solvent used in the raw adhesive can be significantly reduced, achieving carbon reduction benefits at the manufacturing process level. In some embodiments, the low-carbon resin composition comprises: (A) an epoxy resin, optionally (B) a toughening agent, and (C) a curing agent. [(A) Epoxy Resin]

[0011] In some embodiments, the epoxy resin (A) of this invention comprises (A1) a bisphenol A type low-carbon epoxy resin; (A2) a bisphenol F type epoxy resin; and (A3) a multifunctional epoxy resin. By using epoxy resins (A1), (A2) and (A3) in combination, the low-carbon resin composition can maintain good workability while increasing the curing reaction rate. <(A1) Bisphenol A type low-carbon epoxy resin>

[0012] In some embodiments, (A1) bisphenol A type low carbon epoxy resin comprises a structure having the structure shown in formula (1) below, wherein n is 0 to 5, and R1 to R8 each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Equation (1)

[0013] In 100 parts by weight of epoxy resin (A), bisphenol A type low-carbon epoxy resin (A1) accounts for about 25 parts by weight to about 80 parts by weight, for example, about 30 parts by weight to about 75 parts by weight, about 30 parts by weight to about 70 parts by weight, about 30 parts by weight to about 65 parts by weight, about 30 parts by weight to about 60 parts by weight, about 40 parts by weight to about 70 parts by weight, etc. Bisphenol A type low-carbon epoxy resin (A1) can be used alone or in combination with two or more types.

[0014] In some embodiments, the (A1) bisphenol A type low-carbon epoxy resin is a product of the reaction between recycled bisphenol A (BPA) and bio-based epichlorohydrin (ECH). By using this (A1) bisphenol A type low-carbon epoxy resin, carbon emissions can be effectively reduced, and the carbon reduction benefits can be improved. In some embodiments, the recycled bisphenol A is obtained from recycled plastic materials, which include, for example, epoxy resin, polycarbonate, polyarylate, phenolic resin, unsaturated polyester resin, etc., or combinations thereof, as long as it is a recyclable bisphenol A, there is no particular limitation. The bio-based epichlorohydrin can be epichlorohydrin produced from glycerol, etc.

[0015] In some embodiments, recovered bisphenol A can be obtained by the following steps: Plastic recycled material is placed in a reaction vessel, and appropriate amounts of solvent (e.g., methanol, ethanol, ethylene glycol, tetrahydrofuran, etc.) and alkali (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, calcium oxide, etc.) are added sequentially, followed by stirring. The mixture is heated under reflux for approximately 0.5–1.5 hours and then neutralized to pH 6–7 with an acidic aqueous solution (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, etc.). Next, the remaining solid is removed by filtration, and the organic solvent is separated from the water. The organic solution is removed by vacuum concentration, and the resulting solid is purified with ethyl acetate and n-hexane. The solid is then filtered and dried to obtain recovered bisphenol A. In some embodiments, the yield of this method is approximately 85–95%, and the purity (HPLC) of the obtained recovered bisphenol A is approximately 99.5%–99.9%.

[0016] In some embodiments, (A1) bisphenol A type low-carbon epoxy resin can be obtained by the following steps: Weigh an appropriate amount of recovered bisphenol A obtained by the above method and place it in a reaction vessel. Add an appropriate amount of biomass epichlorohydrin (ECH), a catalyst (such as tetraethylammonium chloride, tetrabutylammonium bromide, hexadecyltrimethylammonium bromide, etc.) sequentially, and then stir continuously. Add an aqueous sodium hydroxide solution (e.g., 30%~55%) slowly to the reaction vessel over 0.5~1.5 hours. After reacting at room temperature and pressure for 20~30 hours, recover excess biomass epichlorohydrin by vacuum concentration. Extract the resulting liquid 2~5 times with ethyl acetate and water. After removing the aqueous layer, recover the ethyl acetate by vacuum concentration to obtain (A1) bisphenol A type low-carbon epoxy resin. In some embodiments, the yield of this method is about 85-95%, and the purity (HPLC) of the obtained (Al) bisphenol A type low carbon epoxy resin is about 95-98%, the epoxy equivalent is about 185-195 g / eq, and the viscosity is about 12000-13000 mPa·s. <(A2) Bisphenol F type epoxy resin>

[0017] In some embodiments, (A2) bisphenol F type epoxy resin comprises a structure having the structure shown in the following formula (2), wherein m is 0 to 5, and R1' to R8' each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Equation (2)

[0018] In 100 parts by weight of epoxy resin (A), bisphenol F type epoxy resin (A2) comprises approximately 5 parts by weight to approximately 60 parts by weight, for example, approximately 10 parts by weight to approximately 55 parts by weight, approximately 15 parts by weight to approximately 50 parts by weight, approximately 20 parts by weight to approximately 45 parts by weight, approximately 25 parts by weight to approximately 40 parts by weight, approximately 30 parts by weight to approximately 35 parts by weight, etc. Bisphenol F type epoxy resin (A2) can be used alone or in combination with two or more other types. This invention achieves heat resistance and good electrical properties by adjusting the content of bisphenol A type low-carbon epoxy resin (A1) and bisphenol F type epoxy resin (A2). <(A3) Multifunctional Epoxy Resins>

[0019] (A3) Multifunctional epoxy resins are epoxy resins having at least three epoxy groups per molecule, and are different from (A1) bisphenol A type low-carbon epoxy resins and (A2) bisphenol F type epoxy resins. Examples of (A3) multifunctional epoxy resins include phenolic varnish type epoxy resins, cresol phenolic varnish type epoxy resins, polyphenylmethane type epoxy resins, tetraglycidyl diamine type epoxy resins such as tetraglycidyl diamine diphenylmethane, triglycidyl aminophenol, tetra(glycidyloxyphenyl)ethane or tri(glycidyloxyphenyl)methane, etc., glycidyl phenyl ether type epoxy resins, and halogens, alkyl-substituted products, hydrides, etc., but are not limited thereto.

[0020] In 100 parts by weight of epoxy resin (A), the (A3) multifunctional epoxy resin may comprise approximately 5 to 20 parts by weight, for example, approximately 7 to 18 parts by weight, approximately 9 to 16 parts by weight, approximately 11 to 14 parts by weight, approximately 12 to 13 parts by weight, etc. The aforementioned (A3) multifunctional epoxy resin may be used alone or in combination with two or more types. By controlling the content of the (A3) multifunctional epoxy resin within the above range, the curing reaction rate can be appropriately increased. [。] [(B) Toughening agent]

[0021] The low-carbon resin composition of this application may further include (B) a toughening agent to increase the toughness of the material. The (B) toughening agent used in this application may be rubber, toughening resin, polymer, or a combination thereof.

[0022] In some embodiments, the toughening resin comprises, for example, polyimide, polycarbonate, polyphenylene ether, polyurethane, polyamide, epoxy acrylic polymer, bisphenol A phenolic epoxy resin, or combinations thereof.

[0023] In some embodiments, the rubber includes, for example, ethylene propylene rubber (e.g., binary ethylene propylene rubber, ternary ethylene propylene rubber, modified ethylene propylene rubber, and thermoplastic ethylene propylene rubber), cis-butadiene rubber (BR), polybutadiene derivatives, natural rubber (NR), isobutylene rubber (IBR), nitrile butadiene rubber (NBR), carboxyl-terminated liquid nitrile butadiene rubber (CTBN), hydroxyl-terminated nitrile butadiene rubber (HTBN), epoxy-based nitrile butadiene rubber, polysulfide rubber, silicone rubber, etc., or combinations thereof.

[0024] In some embodiments, the polymer includes, for example, acrylates (ACR), methyl acrylate-butadiene-styrene copolymer (MBS), ethylene-butyl acrylate-glycidyl methacrylate copolymer (PTW), ethylene-methyl acrylate-glycidyl methacrylate copolymer (E-MA-GMA), or combinations thereof.

[0025] In some embodiments, the toughening agent (B) is approximately 0 to approximately 30 parts by weight relative to 100 parts by weight of epoxy resin (A), for example, approximately 3 to approximately 30 parts by weight, approximately 5 to approximately 26 parts by weight, approximately 5 to approximately 24 parts by weight, approximately 5 to approximately 20 parts by weight, approximately 8 to approximately 30 parts by weight, approximately 8 to approximately 25 parts by weight, approximately 8 to approximately 20 parts by weight, approximately 10 to approximately 30 parts by weight, etc. In some embodiments, the low-carbon resin composition does not contain the toughening agent (B), and the toughening agent (B) is substantially 0 parts by weight relative to 100 parts by weight of epoxy resin (A). The toughening agent (B) described above can be used alone or in combination of two or more. By controlling the amount of toughening agent (B) added within the above range, the problem of excessive hardness in the formed cured product can be appropriately adjusted, giving it appropriate softness and elongation. [(C) Curing agent]

[0026] (C) The curing agent has functional groups (e.g., amine, amide, anhydride, etc.) that can react with the epoxy groups of (A) epoxy resin. In some embodiments, (C) the curing agent may include, for example, amine compounds, amide compounds, anhydride compounds, phenolic compounds, etc.

[0027] Examples of amine compounds include aliphatic amines such as diethylenetriamine (DETA) and triethylenetetramine (TETA); aromatic amines such as 4,4'-diaminodiphenyl ether (DDS), diaminodiphenylmethane (DDM), and 4,4'-diaminodicyclohexylmethane (PACM); etc.

[0028] Examples of acetamide compounds include dicyandiamide and its derivatives, polyacetamide resins, etc.

[0029] Examples of acid anhydride compounds include: phthalic anhydride, trimellitic anhydride, phenyl pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride (THPA), methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride (HHPA), methylhexahydrophthalic anhydride, etc.

[0030] Examples of phenolic compounds include: polyfunctional phenolic resins; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; phenolic resins such as phenol-formaldehyde resin, cresol-formaldehyde resin, bisphenol A-formaldehyde resin, poly-p-vinylphenol t-butylphenol novolak resin, phenol aralkyl resin, and naphthol-formaldehyde resin; dicyclopentadiene-based phenolic resins, xylok-type phenolic resins, and aralkylphenol resins.

[0031] (C) The curing agent, relative to 100 parts by weight of epoxy resin (A), is approximately 60 to 130 parts by weight, for example, approximately 60 to 120 parts by weight, approximately 60 to 110 parts by weight, approximately 60 to 100 parts by weight, approximately 70 to 120 parts by weight, approximately 70 to 110 parts by weight, approximately 70 to 100 parts by weight, approximately 80 to 120 parts by weight, etc. The aforementioned curing agent (C) can be used alone or in combination with two or more other ingredients. By ensuring the amount of curing agent (C) is within the above range, the composition can be fully cured and the desired chemical resistance, heat resistance, or mechanical properties can be obtained. [(D) Curing Accelerator]

[0032] In some embodiments, the low-carbon resin composition further comprises a (D) curing accelerator, and the peak temperature of the curing exothermic reaction can be adjusted by adjusting the type and amount of the (D) curing accelerator. Various compounds that promote the curing reaction of epoxy resins can be used as curing accelerators, such as: triarylphosphine (e.g., triphenylphosphine), trialkylphosphine (e.g., trialkylarylphosphine), alkyldiarylphosphine, phosphonate compounds (e.g., tetraphenylphosphonate tetraphenylborate), phosphonate salts (e.g., tetrabutylphosphonate decanoate), etc., phosphorus compounds; imidazole compounds (e.g., imidazole, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole), etc.; tertiary amine compounds; organic acid metal salts (e.g., zinc octoate, cobalt octoate), etc.; metal salt compounds (e.g., manganese, iron, cobalt, nickel, copper, zinc), etc.; amine salts, etc.

[0033] (D) Curing accelerator, compared to 100 parts by weight of (A) epoxy resin, is 0.01 to 0.3 parts by weight, for example, about 0.03 to about 0.25 parts by weight, about 0.05 to about 0.2 parts by weight, about 0.07 to about 0.3 parts by weight, about 0.09 to about 0.3 parts by weight, etc. The above-mentioned (D) curing accelerator can be used alone or in combination with two or more. By adding the curing accelerator (D) within the above range, the low-carbon resin composition can obtain better reactivity. [(E) Filler Powder]

[0034] In some embodiments, the low-carbon resin composition further includes (E) filler powder. (E) filler powder can be used to improve the dimensional stability and electrical properties of the resin composition. Examples of (E) filler powder include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, chromium oxide, vanadium oxide, molybdenum oxide, silicon nitride, boron nitride, aluminum nitride, tungsten nitride, titanium nitride, zinc nitride, silicon carbide, tungsten carbide, boron carbide, aluminum carbide, molybdenum carbide, titanium carbide, calcium carbonate, aluminum boride, titanium boride, magnesium boride, cobalt boride, polytetrafluoroethylene, etc.

[0035] The filler powder (E) is 50-150 parts by weight compared to 100 parts by weight of epoxy resin (A), for example, about 70-150 parts by weight, about 90-150 parts by weight, about 100-150 parts by weight, about 70-130 parts by weight, or about 90-130 parts by weight. The filler powder (E) can be used alone or in combination with two or more other fillers. By controlling the amount of filler powder (E) within the above range, the flame retardancy, formability, flexibility, and drilling processability of the resin composition can be appropriately improved. [(F) solvent]

[0036] In some embodiments, the low-carbon resin composition further includes solvent (F). Solvent (F) can act as a diluent to adjust the viscosity of the low-carbon resin composition and improve its workability. Solvent (F) is not particularly limited as long as it can dissolve the components used, and examples include acetone, methyl ethyl ketone, toluene, xylene, n-butanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Solvent (F) can be used alone or in combination of two or more. [Other Additives]

[0037] Without impairing the properties of the low-carbon resin composition, the low-carbon resin composition may optionally include additives such as silane coupling agents, colorants, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, or lubricants. These additives may be used alone or in combination of two or more. The amount of other additives may be adjusted appropriately according to requirements; for example, each other additive may be approximately 0.1 to 3.0 parts by weight relative to 100 parts by weight of epoxy resin (A). [Products made from low-carbon resin compositions]

[0038] The low-carbon resin composition of this invention can be used as an adhesive material, a resin-coated copper (RCC) material, etc. By subjecting the aforementioned low-carbon resin composition to appropriate processing, this invention can provide various resin composition products.

[0039] This invention provides a resin film comprising the low-carbon resin composition of this invention and a substrate, wherein the substrate includes a PET film (polyester film), a PI film (polyimide film), or a copper foil. For example, by coating the low-carbon resin composition of this invention onto a copper foil or a PI film coated with a PI film copper foil, and then heating it at a high temperature to form a semi-cured state, an adhesive-backed copper foil can be obtained.

[0040] This invention may also provide a copper foil substrate comprising two or more copper foils and at least one insulating layer. The insulating layer may be a film formed from a low-carbon resin composition, and may be formed, for example, by attaching the low-carbon resin composition to a reinforcing material such as fiberglass cloth by impregnation or other means, and then subjecting it to a high temperature of approximately 150-200°C for 3-10 minutes to semi-cur the low-carbon resin composition. The copper foil substrate may be formed, for example, by placing several layers of the aforementioned film between upper and lower copper foils, and pressing them together at a high temperature of approximately 200-250°C and a high pressure of 200-700 psi, followed by a high-temperature curing reaction for 3-5 hours.

[0041] This invention may also provide a printed circuit board comprising at least one of the aforementioned copper foil substrates, and the circuit board may be manufactured by a known process. [Specific Implementation Examples]

[0042] The following provides a more detailed explanation of this case using experimental and comparative examples. The following content is for illustrative purposes only and is not limited to the experimental examples described below.

[0043] [Synthesis of R-DGEBA, Example 1] First, recycled bisphenol A (r-BPA) was produced. A 500mL three-necked flask was used as the reaction vessel. 50g of recycled plastic material was weighed into the flask, and appropriate amounts of methanol, tetrahydrofuran, and sodium hydroxide were added sequentially. The mixture was stirred and heated under reflux for 1 hour, then neutralized with hydrochloric acid to pH 6-7. After filtering to remove the remaining solid, the organic solvent and water were separated. The organic solvent was removed by vacuum concentration. The obtained solid was purified with ethyl acetate and n-hexane. After filtration, the solid was dried to obtain r-BPA, with a yield of 90% and a purity (HPLC) of 99.88%. Next, the recovered bisphenol A was used to synthesize the low-carbon epoxy resin r-DGEBA (r-diglycidyl ether of bisphenol A). A 500 mL three-necked flask was used as the reaction vessel. 50 g of the obtained rBPA was weighed into the flask, and appropriate amounts of bio-epimeric chloropropane (ECH) and tetra-n-butylammonium bromide were added sequentially. After stirring, 45% sodium hydroxide aqueous solution was slowly added over 1 hour via a feed funnel. After reacting at room temperature and pressure for 24 hours, excess bio-epimeric chloropropane was recovered by vacuum concentration. The resulting liquid was extracted three times with ethyl acetate and water. After removing the aqueous layer, ethyl acetate was recovered by vacuum concentration to obtain r-DGEBA, with a yield of 91%; purity (HPLC) of 97.7%; epoxy equivalent of 187; and viscosity of 12537.

[0044] [Experimental Example 1] Weigh out 18.1g of the low-carbon epoxy resin (r-DGEBA) obtained in Manufacturing Example 1 and EPICLON 830-S (DGEBF: diglycidyl ether of bisphenol) manufactured by DIC Corporation of Japan. F) 16.0g, MF-4101 (4,4'-methylenebis(N,N-diglycidylaniline)) manufactured by Xinhe Xingye Co., Ltd. 6.0g. PF8110M60 (60% solid content) manufactured by Changchun Artificial Resin Co., Ltd. was added as (C) curing agent, with an addition amount of 44.1g. 2-Methylimidazole manufactured by Jingming Chemical Co., Ltd. was added as (D) curing accelerator, with an addition amount of 0.0664g. Silicon dioxide FS9 manufactured by Heqi Co., Ltd. was added as (E) filler powder, with an addition amount of 39.84g. The above materials were added in sequence to a plastic container containing an appropriate amount of solvent (butanone and cyclohexanone), and stirred until uniform for later use.

[0045] [Experimental Example 2] Weigh out 18.0g of the low-carbon epoxy resin (r-DGEBA) obtained in Example 1, 16.04g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 6.0g of MF-4101 manufactured by Shin Ho Hsing Yeh Co., Ltd. Use UG-4010 resin manufactured by Kemfar Corp. as (B) toughening agent; it is an acrylic-grafted GMA (glycidyl methacrylate) oligomer, added at a rate of 4.0g. Use PF8110M60 manufactured by Chang Chun Artificial Resin Co. as (C) curing agent, added at a rate of 48.5g. Use 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator, added at a rate of 0.0730g. Add silicon dioxide FS9 manufactured by Heqi Co. as (E) filler powder, added at a rate of 43.82g. Add the above materials in sequence to a plastic container containing an appropriate amount of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0046] [Experiment Example 3] Weigh out 18.06g of the low-carbon epoxy resin (r-DGEBA) obtained in Example 1, 16.03g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 6.07g of MF-4101 manufactured by Shin Ho Hsing Yeh Co., Ltd. Take 5.38g of BNE200A70 manufactured by Chang Chung Artificial Resin Co. as (B) toughening agent. Take 48.43g of PF8110M60 manufactured by Chang Chung Artificial Resin Co. as (C) curing agent. Take 0.0744g of 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator. Add 43.85g of silicon dioxide FS9 manufactured by Heqi Co. as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0047] [Comparative Example 1] Weigh out 18.0g of BONTEPONE 1010 epoxy resin (also referred to as "Zhenshi 1010" in this article) manufactured by Zhenshi Technology Materials Co., Ltd., 16.02g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 6.03g of MF-4101 manufactured by Xinhe Xingye Co., Ltd. Use 5.37g of BNE200A70 manufactured by Changchun Artificial Resin Co. as (B) toughening agent. Use 48.46g of PF8110M60 manufactured by Changchun Artificial Resin Co. as (C) curing agent. Use 0.0746g of 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator. Add 43.8g of FS9 silicon dioxide manufactured by Heqi Co. as (E) filler powder. Add the above materials in sequence to a plastic container containing an appropriate amount of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0048] [Experiment Example 4] Weigh out 18.0g of the low-carbon epoxy resin (r-DGEBA) obtained in Example 1, 16.04g of EPICLON EXA-830LVP (DGEBF: diglycidyl ether of bisphenol F) manufactured by DIC Corporation of Japan, and 6.02g of MF-4101 manufactured by Shin Ho Hsing Yeh Co., Ltd. Use PF8110M60 manufactured by Chang Chun Artificial Resin Co. as (C) curing agent, adding 44.03g. Use 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator, adding 0.0333g. Add 39.85g of silicon dioxide FS04-ARV from Sibelco as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0049] [Comparative Example 2] Weigh out 18.02g of BONTEPONE 1010 epoxy resin manufactured by Zhenshi Technology Materials Co., Ltd., 16.02g of EPICLON EXA-830LVP manufactured by DIC Corporation of Japan, and 6.01g of MF-4101 manufactured by Xinhe Xingye Co., Ltd. Use PF8110M60 manufactured by Changchun Artificial Resin Co. as (C) curing agent, adding 44.04g. Use 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator, adding 0.0332g. Add 39.86g of silicon dioxide FSO4-ARV from Sibelco as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0050] [Example 5] Weigh out 32.1g of the low-carbon epoxy resin (r-DGEBA) obtained in Example 1, 2.03g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 6.0g of MF-4101 manufactured by Shin Ho Hsing Yeh Co., Ltd. Take 4.01g of NISSO-PB JP-100 manufactured by Nippon Soda Co., Ltd. as (B) toughening agent. Take 47.04g of PF8110M60 manufactured by Chang Chun Artificial Resin Co. as (C) curing agent. Take 0.0362g of 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator. Add 43.32g of silicon dioxide FS9 from Heqi Co. as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0051] [Experiment Example 6] Weigh out 10.03g of the low-carbon epoxy resin (r-DGEBA) obtained in Example 1, 24.01g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 6.02g of MF-4101 manufactured by Shin Ho Hsing Yeh Co., Ltd. Take 4.03g of NISSO-PB JP-100 manufactured by Nippon Soda Co., Ltd. as (B) toughening agent. Take 47.05g of PF8110M60 manufactured by Chang Chun Artificial Resin Co. as (C) curing agent. Take 0.0368g of 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator. Add 43.37g of silicon dioxide FS9 manufactured by Heqi Co. as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0052] [Experiment Example 7] Weigh out 18.02g of the low-carbon epoxy resin (r-DGEBA) obtained in Example 1, 16.03g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 6.02g of MF-4101 manufactured by Shin Ho Hsing Yeh Co., Ltd. Take 4.0g of NISSO-PB JP-100 manufactured by Nippon Soda Co., Ltd. as (B) toughening agent. Take 47.05g of PF8110M60 manufactured by Chang Chun Artificial Resin Co. as (C) curing agent. Take 0.0362g of 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator. Add 43.32g of silicon dioxide FS9 manufactured by Heqi Co. as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0053] [Experiment Example 8] Weigh out 18.0g of the low-carbon epoxy resin (r-DGEBA) obtained in Example 1, 16.0g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 6.03g of MGC jER 630 epoxy resin from Mitsubishi Gas Chemical. Take 4.02g of NISSO-PB JP-100 manufactured by Nippon Soda Corporation as (B) toughening agent. Take 47.04g of PF8110M60 manufactured by Changchun Artificial Resin Corporation as (C) curing agent. Take 0.0361g of 2-methylimidazole manufactured by Jingming Chemical Corporation (brand: Thermo Scientific) as (D) curing accelerator. Add 43.34g of silicon dioxide FS9 manufactured by Heqi Corporation as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0054] [Experiment Example 9] Weigh out 31.66g of the aforementioned synthesized low-carbon epoxy resin (r-DGEBA), 23.03g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 3.22g of MF 4101 manufactured by Shin Ho Hsing Yeh Co., Ltd. Use 5.83g of NISSO-PB JP-100 manufactured by Nippon Soda Co., Ltd. as (B) toughening agent. Use 68.8g of PF8110M60 manufactured by Chang Chun Artificial Resin Co. as (C) curing agent. Use 0.0382g of 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator. Add 62.92g of silicon dioxide FS9 manufactured by Heqi Co. as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0055] [Comparative Example 3] Weigh out 32.78g of the aforementioned synthesized low-carbon epoxy resin (r-DGEBA) and 21.86g of EPICLON 830-S manufactured by DIC Corporation of Japan. Use PF8110M60 manufactured by Changchun Artificial Resin Corporation as (C) curing agent, adding 61.75g. Use 2-methylimidazole manufactured by Jingming Chemical Corporation (brand: Thermo Scientific) as (D) curing accelerator, adding 0.0458g. Add silica FS9 from Heqi Company as (E) filler powder, adding 64.2g. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0056] [Comparative Example 4] Weigh out 31.66g of BONTEPONE 1010 epoxy resin manufactured by Zhenshi Technology Materials Co., Ltd., 22.98g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 3.22g of MF 4101 manufactured by Xinhe Xingye Co., Ltd. Use 5.78g of NISSO-PB JP-100 manufactured by Nippon Soda Co., Ltd. as (B) toughening agent. Use 68.7g of PF8110M60 manufactured by Changchun Artificial Resin Co. as (C) curing agent. Use 0.0378g of 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator. Add 62.86g of silicon dioxide FS9 filler powder from Heqi Co. as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0057] [Comparative Example 5] Weigh out 31.66g of BONTEPONE 1010 epoxy resin manufactured by Zhenshi Technology Materials Co., Ltd., 23.0g of EPICLON 830-S manufactured by DIC Corporation of Japan, and 3.21g of MF 4101 manufactured by Xinhe Xingye Co., Ltd. Use 9.02g of NISSO-PB JP-100 manufactured by Nippon Soda Co., Ltd. as (B) toughening agent. Use 72.4g of PF8110M60 manufactured by Changchun Artificial Resin Co. as (C) curing agent. Use 0.0398g of 2-methylimidazole manufactured by Jingming Chemical Co. (brand: Thermo Scientific) as (D) curing accelerator. Add 66.17g of silicon dioxide FS9 filler powder from Heqi Co. as (E) filler powder. Add the above materials in sequence to a plastic container containing appropriate amounts of solvent (butanone and cyclohexanone), and stir until homogeneous.

[0058] [Sample Preparation - 1] Take an appropriate amount of the varnish obtained from Experimental Examples 1-8 and Comparative Examples 1-2 above, apply it to copper foil with a scraper, place it in an 80°C oven for 5 minutes, then place it in a 100°C oven for 10 minutes to bake it until semi-dry. Then place it in a high-temperature oven and slowly heat it to the maximum temperature of 230°C for a high-temperature curing reaction for 3.5 hours. Afterwards, cut it into appropriate shapes according to the sample requirements of the measuring equipment, etch the copper foil, and dry it at 110°C for 1 hour for later use.

[0059] [Sample Preparation - 2] Take an appropriate amount of the varnish obtained from Experimental Example 9 and Comparative Examples 3-5, impregnate it with glass fiber cloth for the Taiwan Glass #2116 epoxy resin system, and place it in a 165°C oven for 5 minutes to prepare a film. Cut the film to an appropriate size, place several layers of film between upper and lower copper foils, and then place it in a high-temperature press and slowly heat it to the maximum temperature of 230°C for a high-temperature curing reaction for 3.5 hours. Cut the film into appropriate shapes according to the sample requirements of the measuring equipment, etch the copper foil, and dry it at 110°C for 1 hour for later use. [Test Conditions] The test samples for each experimental example and comparative example were tested under the conditions shown below. The results for Experimental Examples 1-3 and Comparative Example 1 are shown in Table 1. The results for Experimental Example 4 and Comparative Example 2 are shown in Table 2. The results for Experimental Examples 5-8 are shown in Table 3. The results for Experimental Example 9 and Comparative Examples 3-5 are shown in Table 4.

[0060] [Electrical Analysis] Instrument: AET High-Frequency Microwave Dielectric Measurement System (Japan) Measurement conditions: Electrical analysis was performed at a measurement frequency of 2 GHz using the TM mode Cavity Resonator.

[0061] [Thermal Analysis] <tga> Instrument: TA Instruments Q500 thermogravimetric analyzer Measurement conditions: Under air, the temperature was increased from room temperature to 700°C at a heating rate of 20°C / min. <tma> Instrument: Waters Q400 thermomechanical analyzer Measurement conditions: Under nitrogen atmosphere, the temperature was increased from room temperature to 300°C at a rate of 10°C / min. The measurement was performed twice, and the result of the second measurement was taken. <dsc> Instrument: Perkin Elmer Differential Scanning Calorimeter DSC-7 Measurement conditions: In air, the temperature was increased from room temperature to 300°C at a rate of 10°C / min.

[0062] [Table 1] Electrical analysis Thermal analysis 2GHz -DK 2GHz -Df TGA-Td (°C) TMA-Tg (°C) Example 1 3.52 0.0245 379.5 101.7 Example 2 3.55 0.0237 376.1 93.2 Example 3 3.43 0.0243 382.7 100.2 Comparative Example 1 3.55 0.0238 367.4 87.4

[0063] As shown in Table 1, the thermal decomposition temperature (Td(5%)) of TGA in Experimental Examples 1-3 was approximately 380°C, which was significantly higher than that of Comparative Example 1. Among them, Experimental Example 3 differed from Comparative Example 1 in whether or not recycled DGEBA was used, and the 2GHz dielectric constant of Experimental Example 3 was better than that of Comparative Example 1, and its thermal decomposition temperature and glass transfer temperature were both higher than those of Comparative Example 1.

[0064] [Table 2] Electrical analysis Thermal analysis 2GHz -DK 2GHz -Df DSC-Peak (°C) TGA-Td (°C) Example 4 3.66 0.0268 214.87 402.4 Comparative Example 2 3.59 0.0262 218.37 400.0

[0065] As shown in Table 2, the DSC exothermic peak of Experimental Example 4 was approximately 215°C, lower than that of Comparative Example 2. This indicates that the resin system using r-DGEBA exhibited better reactivity than the resin system using DGEBA. Furthermore, compared to Examples 1-3, Example 4, using a lower viscosity bisphenol F epoxy resin, still achieved excellent dielectric constant and heat resistance. In other words, the viscosity of the low-carbon resin composition can be adjusted according to requirements, allowing for application in various scenarios.

[0066] [Table 3] Electrical analysis Thermal analysis 2GHz -DK 2GHz -Df TGA-Td (°C) Experimental Example 5 3.20 0.0251 407.72 Experimental Example 6 3.21 0.0254 403.74 Experimental Example 7 3.30 0.0258 408.92 Experimental Example 8 3.19 0.0260 404.72

[0067] As shown in Table 3, by using 100 parts by weight of epoxy resin as a base, and within the range of 25-80 parts by weight of (A1) bisphenol A type low-carbon epoxy resin, the low-carbon resin compositions all exhibit excellent heat resistance and dielectric constant. In Experiment 8, which used trifunctional jER 630 as the (A3) multifunctional epoxy resin, the heat resistance and dielectric constant were similar to those of Experiment 7, which used quadrufunctional MF 4101 as the (A3) multifunctional epoxy resin.

[0068] [Table 4] Electrical analysis Thermal analysis 2GHz -DK 2GHz- Df TGA-Td (°C) TMA-Tg (°C) Experimental Example 9 3.78 0.0175 425.2 145.0 Comparative Example 3 4.15 0.0181 416.3 105.6 Comparative Example 4 3.74 0.0172 411.9 129.9 Comparative Example 5 3.82 0.0174 412.7 150.4

[0069] As shown in Table 4, Example 9, compared to Comparative Example 3, contains (A3) multifunctional epoxy resin, exhibiting a higher glass transition temperature, a higher TGA pyrolysis temperature Td(5%), and greater thermal stability. Furthermore, compared to Comparative Examples 4 and 5, Example 9 uses r-DGEBA, achieving a superior pyrolysis temperature Td(5%) while maintaining dielectric properties. In other words, the low-carbon resin composition of this invention can be used to manufacture copper foil substrates with superior performance.

[0070] In summary, this project utilizes low-carbon epoxy resin [the product of the reaction between recycled bisphenol A and biomass epichlorohydrin] to reduce carbon emissions at the raw material stage, replacing traditional high-carbon petrochemical-synthesized epoxy resin products. This effectively reduces the high carbon emissions of PCB substrate materials and enhances the benefits of carbon reduction. Furthermore, it can be combined with multifunctional epoxy resins to increase the curing reaction rate, add relevant toughening agents to reduce the excessive rigidity of PCB materials, and add relevant low-dielectric filler powders to improve the dimensional stability and electrical properties of the resin composition.< / dsc> < / tma> < / tga>

Claims

1. A low-carbon resin composition comprising: (A) an epoxy resin, 100 parts by weight, comprising: (A1) a bisphenol A type low-carbon epoxy resin, 25-80 parts by weight; (A2) a bisphenol F type epoxy resin, 5-60 parts by weight; and (A3) a multifunctional epoxy resin, 5-20 parts by weight, wherein... The multifunctional epoxy resin has at least three epoxy groups in each molecule; and (C) a curing agent, 90-130 parts by weight, wherein the bisphenol A type low-carbon epoxy resin is a product of the reaction of recycled bisphenol A (BPA) and bio-epiochlorohydrin (ECH).

2. The low-carbon resin composition as described in claim 1, further comprising (B) a toughening agent, 3-30 parts by weight.

3. The low-carbon resin composition as claimed in claim 2, wherein the (B) toughening agent comprises a toughening resin, rubber, polymer, or a combination thereof.

4. The low-carbon resin composition as claimed in claim 3, wherein the toughening resin comprises an epoxy acrylic polymer and / or a bisphenol A phenolic epoxy resin, and the rubber comprises a polybutadiene derivative.

5. The low-carbon resin composition as claimed in claim 1 or 2, wherein the (C) curing agent comprises an amine compound, a amide compound, an anhydride compound, a phenolic compound, or a combination thereof.

6. The low-carbon resin composition as claimed in claim 1 or 2, wherein the (C) curing agent comprises a phenolic resin.

7. The low-carbon resin composition as described in claim 1 or 2 further comprises (D) a curing accelerator, 0.01-0.3 parts by weight.

8. The low-carbon resin composition as claimed in claim 7, wherein the (D) curing accelerator comprises a phosphorus compound, a tertiary amine compound, an imidazole compound, or a combination thereof.

9. The low-carbon resin composition as described in claim 1 or 2, further comprising (E) filler powder, 50-150 parts by weight.

10. The low-carbon resin composition as claimed in claim 9, wherein the (E) filler powder comprises silicon oxide, aluminum oxide, silicon nitride, titanium oxide, or a combination thereof.

11. A copper foil substrate made by impregnating glass fiber cloth with a low-carbon resin composition as described in any one of claims 1 to 10.

12. A printed circuit board comprising the copper foil substrate described in claim 11.