A resin composition and use thereof

Abstract

This invention provides a resin composition and its application. The resin composition comprises, by weight, the following components: 100 parts epoxy resin, 30-120 parts bio-based resin, and 20-140 parts curing agent. The bio-based resin includes any one or a combination of at least two of bio-based furan resin, terpene resin, and terpene phenol resin. The curing agent includes a combination of benzoxazine resin and phenolic resin. Through the design and synergistic compounding of the components, this invention enables the resin composition and the metal foil laminate containing it to not only reduce carbon dioxide emissions but also exhibit excellent processability, reliable insulation, low water absorption, high heat and damp heat resistance, good mechanical properties and insulation reliability, and excellent overall performance, conforming to IPC standards. This fully meets the development needs of high-density integrated printed circuit boards for low carbon footprint, multifunctionality, high performance, and high reliability.

Description

Technical Field

[0001] This invention belongs to the field of copper clad laminate technology, specifically relating to a resin composition and its application. Background Technology

[0002] Copper-clad laminate (CCL) is a plate-shaped material used in the production of printed circuit boards. It plays a crucial role in supporting and assembling electronic components, forming conductive circuit patterns, and providing insulation between layers / circuits. It is an important basic material for electronics.

[0003] Copper-clad laminates (CCLs) are typically made by impregnating electronic fiberglass cloth or other reinforcing materials with resin, covering one or both sides with copper foil, and then hot-pressing them together. Traditional CCLs are composed of resins synthesized from petrochemical raw materials such as petroleum, coal, and natural gas, combined with copper foil and reinforcing fibers. However, the extraction and chemical conversion processes of these petrochemical raw materials release large amounts of greenhouse gases such as CO2, which are major contributors to global warming. Therefore, the CCL industry urgently needs to develop solutions that meet the low-carbon requirements of the electronics industry.

[0004] "Carbon reduction level" is one of the main means of measuring low-carbon initiatives, generally compared through carbon footprint. Carbon footprint refers to the emissions of various greenhouse gases (GHGs) throughout a product's entire life cycle, from raw materials to production, use, disposal, and reuse. According to the Kyoto Protocol, greenhouse gases mainly include six gases: carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and sulfur hexafluoride (SF6). In carbon footprint calculations, emissions are generally converted to carbon dioxide. In recent years, the degree of carbon reduction has also become an important consideration for copper-clad laminate products.

[0005] Bio-based materials, using renewable resources as their main raw materials, play a role in carbon reduction and carbon sequestration. They can reduce dependence on petrochemical resources and reduce emissions of greenhouse gases such as CO2, and are therefore considered one of the important means of developing a low-carbon economy. In recent years, the industry has attempted to use bio-based materials to partially or completely replace petroleum-based resins in the preparation of copper-clad laminates. For example, CN116041911A discloses a high heat-resistant and toughened epoxy resin for copper-clad laminates, comprising the following components: 200-240 parts modified epoxy resin, 50-90 parts lignin-modified epoxy resin, and 120 parts epoxy resin. The preparation method of the lignin-modified epoxy resin is as follows: take brominated lignin and water, stir evenly, add polyethylene glycol diglycidyl ether, stir at 75-85℃ until the water is completely evaporated, add bisphenol A diglycidyl ether, stir for 1-2 hours, cool, add polyetheramine, stir evenly, and vacuum to obtain lignin-modified epoxy resin. CN102702683A discloses an epoxy resin for prepregs, comprising an epoxy resin mixture (component A) and a rosin green curing agent mixture (component B). The epoxy resin mixture includes 50-70 parts epoxy resin, 5-30 parts toughening agent, and 0-10 parts flame retardant. The rosin green curing agent mixture includes 5-30 parts rosin and 1-10 parts accelerator. This epoxy resin can be used to prepreg plant fibers to prepare green and environmentally friendly prepregs.

[0006] Although there is considerable research and development on bio-based materials, technologies specifically designed for copper-clad laminate (CCL) applications remain limited. Furthermore, most bio-based materials can only be used as small-volume auxiliary components and cannot be extensively incorporated into resin compositions for thermosetting CCLs, failing to meet the requirements for low-carbon circuit boards. Moreover, thermosetting bio-based materials generally lack in mechanical properties, heat resistance, damp heat resistance, insulation reliability, and processability, making it difficult to meet the performance requirements of CCLs. Therefore, developing bio-based materials and CCLs incorporating them with excellent heat resistance, damp heat resistance, insulation reliability, mechanical properties, and processability is a key research focus in this field. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a resin composition and its application. Through the design and synergistic compounding of components, the resin composition and the metal foil laminate containing it not only reduce carbon dioxide emissions but also exhibit excellent processability, reliable insulation, low water absorption, high heat and damp heat resistance, good mechanical properties and insulation reliability, and excellent overall performance. It conforms to IPC standards and fully meets the development needs of high-density integrated printed circuit boards for low carbon footprint, multifunctionality, high performance, and high reliability.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a resin composition comprising, by weight, the following components:

[0010] 100 parts epoxy resin

[0011] 30-120 parts of bio-based resin

[0012] 20-140 parts of curing agent;

[0013] The bio-based resin includes any one or a combination of at least two of bio-based furan resin, terpene resin, and terpene phenol resin; the curing agent includes a combination of benzoxazine resin and phenolic resin.

[0014] The resin composition provided by this invention uses epoxy resin as the main resin and a blend of benzoxazine resin and phenolic resin as a curing agent. Simultaneously, specific types of bio-based resins can participate in the physical / chemical cross-linking network structure of the cured product, forming a multi-dimensional cross-linked network structure jointly constructed by epoxy resin, bio-based resin, benzoxazine resin, and phenolic resin. This allows the resin composition to reduce its carbon footprint while also possessing excellent heat resistance, damp heat resistance, insulation, toughness, strength, adhesion, mechanical strength, performance reliability, and processability. Furthermore, the resin composition exhibits excellent impregnation properties with various reinforcing materials such as wood pulp paper, cotton pulp paper, fiberglass paper, and glass cloth, fully leveraging the reinforcing effect of these materials on the resin composition matrix, and contributing to further optimization of the moisture resistance and damp heat resistance of metal-coated laminates.

[0015] This invention, based on the design and synergistic compounding of epoxy resin, bio-based resin, benzoxazine resin, and phenolic resin components, enables the resin composition to be used in prepregs, laminates, and metal foil-coated laminates. This allows the boards to possess excellent comprehensive properties such as processability, electrical insulation and mechanical properties, high heat resistance, low water absorption, high resistance to damp heat, and alkali resistance. This fully meets the needs of high-density integrated printed circuit boards to achieve low-carbon goals while ensuring that processing and board performance meet the requirements of the electronics industry.

[0016] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0017] In the resin composition of the present invention, the mass of the epoxy resin is 100 parts, and the mass of the bio-based resin is 30-120 parts, for example, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts or 110 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0018] Based on 100 parts by weight of the epoxy resin, the curing agent has a mass of 20-140 parts, for example, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts or 130 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0019] The terms "parts" and "parts by weight" used in this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0020] Preferably, the number-average molecular weight (M) of the epoxy resin is... n The range is 200-2000, for example, it can be 220, 250, 280, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1200, 1500 or 1800, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0021] Preferably, the epoxy equivalent of the epoxy resin is 150-570 g / eq, for example, it can be 160 g / eq, 180 g / eq, 195 g / eq, 200 g / eq, 220 g / eq, 250 g / eq, 280 g / eq, 300 g / eq, 320 g / eq, 350 g / eq, 380 g / eq, 400 g / eq, 420 g / eq, 450 g / eq, 480 g / eq, 500 g / eq, 520 g / eq, or 550 g / eq, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 180-480 g / eq is further preferred.

[0022] In this invention, the term "epoxy equivalent" refers to the weight of epoxy resin equivalent to one gram equivalent of epoxy groups; the epoxy value refers to the number of gram equivalents of epoxy groups contained in 100g of resin. The epoxy equivalent and epoxy value are related by the following formula: Epoxy value = 100 / Epoxy equivalent.

[0023] The present invention does not impose any special restrictions on the type of epoxy resin, as long as each molecule of the epoxy resin contains at least two epoxy groups.

[0024] Preferably, the epoxy resin has a functionality of 2-6, for example, 2, 3, 4, 5 or 6.

[0025] Preferably, the epoxy resin includes any one or a combination of at least two of the following: glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, epoxidized olefin, and hydantoin epoxy resin.

[0026] For example, the epoxy resin includes, but is not limited to, any one or a combination of at least two of the following: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic epoxy resin, biphenyl type epoxy resin, phenolic epoxy resin, o-cresol phenolic epoxy resin, XYLOK phenolic epoxy resin, dicyclopentadiene (DCPD) type epoxy resin, bisphenol A phenolic epoxy resin, organosilicon modified epoxy resin, phosphorus-containing epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, and o-cresol epoxy resin.

[0027] Preferably, the viscosity of the epoxy resin is 250-5500 mPa·s, for example, it can be 300 mPa·s, 400 mPa·s, 500 mPa·s, 800 mPa·s, 1000 mPa·s, 1200 mPa·s, 1500 mPa·s, 1800 mPa·s, 2000 mPa·s, 2200 mPa·s, 2500 mPa·s, 2800 mPa·s, 3000 mPa·s, etc. The specific point values ​​included in the ranges are 3200 mPa·s, 3500 mPa·s, 3800 mPa·s, 4000 mPa·s, 4200 mPa·s, 4500 mPa·s, 4800 mPa·s, 5000 mPa·s, 5200 mPa·s, or 5400 mPa·s, as well as specific point values ​​between the above-mentioned point values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the ranges.

[0028] In this invention, the viscosity of the epoxy resin was obtained by testing at 25°C.

[0029] Preferably, the bio-based furan resin includes any one or a combination of at least two of furfuryl alcohol phenol-formaldehyde resin, furfuryl alcohol resin, furfuryl alcohol urea-formaldehyde resin, furfural acetone resin, and furfuryl ketone-formaldehyde resin.

[0030] Preferably, the terpene-based resin includes terpene resin and / or terpene-styrene resin.

[0031] Preferably, the bio-based resin includes any one or a combination of at least two of furfuryl alcohol phenol-formaldehyde resin, furfuryl alcohol resin, furfuryl alcohol urea-formaldehyde resin, furfuryl alcohol furfural resin, furfural acetone resin, furfuryl ketone-formaldehyde resin, terpene resin, terpene-styrene resin, and terpene-phenol resin. More preferably, it includes any one or a combination of at least two of furfuryl ketone-formaldehyde resin, furfuryl alcohol furfural resin, furfuryl alcohol resin, furfuryl alcohol phenol-formaldehyde resin, and terpene-phenol resin.

[0032] Optionally, the furfuryl aldehyde resin includes furfuryl aldehyde resin.

[0033] Preferably, the benzoxazine resin comprises any one or a combination of at least two of the following: bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, dicyclopentadiene type benzoxazine resin, phenolphthalein type benzoxazine resin, fluorenyl benzoxazine resin, allyl benzoxazine resin, propargyl benzoxazine resin, cyano benzoxazine resin, and bismaleimide benzoxazine resin.

[0034] Preferably, based on 100 parts by weight of the epoxy resin, the mass of the benzoxazine resin is 10-60 parts, for example, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or 55 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0035] Preferably, the phenolic resin includes any one or a combination of at least two of the following: bisphenol A type phenolic resin, phenolic resin, o-cresol phenolic resin, triphenol phenolic resin, naphthalene type phenolic resin, biphenyl type phenolic resin, and dicyclopentadiene phenolic resin.

[0036] Preferably, based on 100 parts by weight of the epoxy resin, the phenolic resin is 15-70 parts by weight, for example, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 or 65 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0037] Preferably, the resin composition further includes any one or a combination of at least two of the following: accelerator, toughening agent, flame retardant, filler, and coupling agent.

[0038] As a preferred embodiment of the present invention, the resin composition includes an accelerator to control the curing reaction rate of the resin composition. The amount of accelerator added should not be too much, as too much will lead to an excessively fast reaction rate of the resin composition, excessive by-products, reduced performance of the cured product, and poor processability. If the amount of accelerator is too little, the reaction will be too slow, which is not conducive to the production of prepreg and affects production efficiency. Therefore, it is generally advisable to control the gelation time of the resin liquid in the resin composition to 100-200s by using an accelerator.

[0039] Preferably, the resin composition further comprises 0.02-3 parts by weight of an accelerator, wherein the accelerator may be 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, or 2.8 parts by weight, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0040] Preferably, the accelerator comprises any one or a combination of at least two of the following: tertiary amines, tertiary phosphines, organometallic complexes, quaternary ammonium salts, and imidazole compounds.

[0041] Preferably, the imidazole compound includes any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0042] Preferably, the resin composition further comprises 15-85 parts by weight of a toughening agent, wherein the toughening agent may be in the following weight ranges: 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 82 parts, or 84 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0043] Preferably, the toughening agent comprises any one or a combination of at least two of the following: epoxy soybean oil resin, cashew phenol modified resin, tung oil modified resin, castor oil modified resin, phenoxy resin, rubber resin, nitrile rubber, and core-shell rubber material.

[0044] Preferably, the resin composition further comprises 15-110 parts by weight of flame retardant, wherein the parts by weight of flame retardant may be 18, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 105 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0045] In this invention, the type of flame retardant is not particularly limited, and flame retardants (small molecules, resins, compounds, powders) with flame retardant effects can be used in the resin composition.

[0046] Preferably, the flame retardant includes any one or a combination of at least two of the following: halogenated flame retardants (e.g., bromine-containing flame retardants), phosphorus-containing flame retardants, and nitrogen-containing flame retardants.

[0047] Preferably, the flame retardant contains any one or a combination of at least two of the elements bromine, phosphorus, and nitrogen.

[0048] For example, the flame retardant contains bromine, and the mass percentage of bromine is 15%-60%, for example, it can be 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or 55%, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0049] For example, the flame retardant contains phosphorus, and the mass percentage of phosphorus is 2%-30%, for example, it can be 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0050] For example, the flame retardant contains nitrogen, and the mass percentage of nitrogen is 5%-50%, for example, it can be 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0051] Preferably, the decomposition temperature Td-5% (5% thermal decomposition temperature) of the flame retardant is ≥250℃, for example, it can be 255℃, 260℃, 265℃, 270℃, 275℃, 280℃, 290℃, 300℃, 310℃, 320℃, 350℃ or 380℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0052] Preferably, the flame retardant includes reactive flame retardants and / or additive flame retardants.

[0053] Preferably, the flame retardant includes, but is not limited to, any one or a combination of at least two of the following: tetrabromobisphenol A, tribromophenol, melamine cyanurate, zinc borate, modified zinc borate, polysiloxane, phosphazene, magnesium hydroxide, antimony trioxide, aluminum hydroxide, phosphorus-containing phenolic resin, phosphorus-containing maleimide phenolic resin, phenoxyphosphazene, DOPO-based phosphorus-containing epoxy resin, DOPO-based phosphorus-containing phenolic resin, phosphazene-based phenolic resin, modified benzoxazine resin, nitrogen-containing phenolic resin, epoxy-containing flame retardant resin, hydroxyl-containing flame retardant resin, and amino-containing flame retardant resin.

[0054] Preferably, the resin composition further comprises 20-300 parts of filler by weight, for example, the filler being 30, 50, 80, 100, 120, 150, 180, 200, 220, 250, or 280 parts by weight, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0055] Preferably, the filler comprises any one or a combination of at least two of the following: aluminum hydroxide, aluminum oxide, magnesium hydroxide, magnesium oxide, aluminum trioxide, silicon dioxide, calcium carbonate, aluminum nitride, boron nitride, silicon carbide, titanium dioxide, zinc borate, zinc molybdate, barium metaborate, zinc sulfide, aluminum silicate, zinc oxide, zirconium oxide, mica, boehmite, talc, calcium nitride, and kaolin.

[0056] This invention relates to the average particle size (D) of the filler. 50 There are no specific limitations; from the perspective of dispersibility, the average particle size (D) 50 The preferred particle size distribution (PPD) is 0.1-20 μm, for example, it can be 0.2 μm, 0.5 μm, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, or 18 μm, as well as specific values ​​between the above values. For space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range, but 0.15-10 μm is further preferred. Different types of fillers with different particle size distributions or different average particle sizes can be used alone or in combination as needed.

[0057] Preferably, the resin composition further comprises 0.1-5 parts by weight of a coupling agent, wherein the parts by weight of the coupling agent may be 0.2 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, or 4.5 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0058] Preferably, the coupling agent includes any one or a combination of at least two of silane coupling agents, organochromium coupling agents, and titanate coupling agents.

[0059] Preferably, the silane coupling agent includes, but is not limited to, any one or a combination of at least two of the following: vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-propylmethacrylatetrimethoxysilane, γ-aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, γ-glycidyl etherpropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, anilinemethyltriethoxysilane, γ-ethylenediaminopropyltriethoxysilane, hexamethylenediaminomethyltriethoxysilane, cyanopropyltrimethoxysilane, and p-cyanophenyltrimethoxysilane.

[0060] As a preferred embodiment of the present invention, the resin composition comprises the following components in parts by weight:

[0061]

[0062]

[0063] Preferably, the resin composition further includes other additives that those skilled in the art are motivated to add, such as antioxidants and / or viscosity modifiers.

[0064] A solvent may also be added to the above-mentioned resin composition, in which other components of the resin composition are dissolved or dispersed to form a resin adhesive. The amount of solvent added is selected by those skilled in the art based on experience and process requirements, so that the resin composition reaches a suitable viscosity for use, facilitating impregnation, coating, etc. Subsequently, during drying, semi-curing, or complete curing stages, the solvent in the resin composition will partially or completely evaporate.

[0065] On the other hand, the present invention provides a resin adhesive comprising a resin composition as described in the first aspect and a solvent, wherein the resin composition is dissolved or dispersed in the solvent.

[0066] Preferably, the solid content of the resin solution is 60%-80%, for example, it can be 62%, 65%, 68%, 70%, 72%, 75%, or 78%, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 68%-78% is further preferred. The resin solution with this solid content can improve the permeability to the reinforcing material, thereby obtaining a prepreg with a highly uniform resin layer thickness.

[0067] The solvent is not particularly limited. Generally, ketones such as acetone, butanone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, or butanol; alcohol ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, or butyl carbitol; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are acceptable. The solvent can be used alone or in mixtures of two or more. Preferably, any one or a combination of at least two of the following: methanol, ethanol, acetone, butanone, ethylene glycol monobutyl ether, methyl acetate, ethyl acetate, and cyclohexanone are preferred.

[0068] Preferably, the boiling point of the solvent is 50-180℃, for example, it can be 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, or 170℃, as well as specific values ​​between the above ranges. For space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range. The boiling point of the solvent matches the drying / semi-curing processing temperature of the prepreg, which can meet the solvent removal requirements of the semi-curing stage; at the same time, the solvent satisfies the requirements of the resin adhesive for the permeability of various reinforcing materials and compatibility with the resin composition.

[0069] By way of example, the resin composition provided by the present invention is prepared by the following method, the preparation method comprising: mixing and dispersing the components in the resin composition evenly to obtain the resin composition.

[0070] Preferably, the method for preparing the resin solution includes: mixing each component in the resin composition with a solvent and dispersing them evenly to obtain the resin solution.

[0071] In a second aspect, the present invention provides a prepreg, the prepreg comprising a reinforcing material and a resin composition as described in the first aspect attached to the reinforcing material.

[0072] Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

[0073] Preferably, the reinforcing material includes any one of glass fiber paper, glass fiber cloth, quartz glass fiber blended cloth, quartz cloth, and cellulose paper (e.g., wood pulp paper or cotton pulp paper), and more preferably glass fiber cloth.

[0074] For example, the method for preparing the prepreg is as follows: impregnate the reinforcing material with the resin solution of the resin composition, and then dry it to obtain the prepreg.

[0075] Preferably, the drying temperature is 50-180℃, for example, it can be 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃ or 170℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0076] Preferably, the drying time is 1-30 min, for example, it can be 2 min, 5 min, 8 min, 10 min, 15 min, 20 min or 25 min, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0077] Thirdly, the present invention provides a laminate comprising at least one prepreg as described in the second aspect.

[0078] Fourthly, the present invention provides a metal foil-coated laminate, the metal foil-coated laminate comprising a metal foil, and at least one of the prepreg as described in the second aspect and the laminate as described in the third aspect.

[0079] Preferably, the number of prepreg sheets in the metal foil laminate is 1-20, for example, 2, 3, 5, 6, 8, 10, 12, 15, 18 or 19, and specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0080] Preferably, the metal foil is copper foil, and thus, the metal foil laminate is a copper-clad laminate.

[0081] In a preferred embodiment, the metal foil laminate is a glass fiber cloth-based metal foil laminate.

[0082] In another preferred embodiment, the metal foil laminate is a composite base metal foil laminate, which includes a laminate and metal foils disposed on one or both sides of the laminate; the laminate includes a core material semi-cured sheet and fabric semi-cured sheets disposed on both sides of the core material semi-cured sheet, and at least one of the core material semi-cured sheet and the fabric semi-cured sheet is a semi-cured sheet provided by the present invention.

[0083] For example, the method for preparing the metal foil laminate includes: pressing a metal foil onto one or both sides of a prepreg, curing it, and obtaining the metal foil laminate; or, stacking at least two prepregs into a laminate, then pressing a metal foil onto one or both sides of the laminate, curing it, and obtaining the metal foil laminate.

[0084] Preferably, the curing is carried out in a press.

[0085] Preferably, the curing temperature is 120-280℃, for example 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃ or 270℃, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0086] Preferably, the curing pressure is 1-10 MPa, for example 1.5 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa or 9 MPa, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0087] Preferably, the curing time is 30-150 min, for example 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min or 145 min, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0088] Fifthly, the present invention provides a printed circuit board, the printed circuit board comprising at least one of the following: a prepreg as described in the second aspect, a laminate as described in the third aspect, and a metal foil-coated laminate as described in the fourth aspect.

[0089] Compared with the prior art, the present invention has the following beneficial effects:

[0090] (1) The resin composition provided by the present invention introduces bio-based resin with specific dosage and components, which effectively reduces the amount of petrochemical materials used and helps to reduce the life cycle carbon emissions of the metal foil laminate containing it, making it more green and environmentally friendly.

[0091] (2) Through the design and synergistic compounding of components, the present invention enables the formation of a rich multidimensional cross-linked network structure in the cured resin composition, which is jointly constructed by epoxy resin, bio-based resin, benzoxazine resin and phenolic resin, etc. This makes the resin composition and the prepreg, laminate and metal foil laminate containing it have excellent heat resistance and damp heat resistance, low water absorption, small thermal expansion, excellent processability, structural and dimensional stability, mechanical properties and alkali resistance, and outstanding comprehensive performance, which fully meets the requirements of printed circuit applications. Detailed Implementation

[0092] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0093] In the following specific embodiments of the present invention, the materials involved are as follows:

[0094] (1) Epoxy resin, the specific information is shown in the table below, the information shown in the table is from the purchasing manufacturer;

[0095]

[0096] (2) Specific information on other materials is shown below, all of which are commercially available chemicals:

[0097]

[0098]

[0099] Examples 1-7, Comparative Examples 1-8

[0100] A resin composition, the types and amounts of each component are shown in Tables 1 and 2, and the unit of amount of each component is "parts" (parts by mass).

[0101] A prepreg comprising the resin composition and a metal foil laminate (copper clad laminate) are prepared by the following method:

[0102] (1) The resin composition is mixed with solvent (acetone) according to the formula amount and stirred evenly with a high-speed disperser to prepare a resin solution with a solid content of 76%; the resin solution is impregnated with electronic grade glass fiber cloth, and then baked at 120°C for 5 minutes, and then baked in an oven at 170°C for 3 minutes to obtain a semi-cured sheet.

[0103] (2) Stack the three semi-cured sheets obtained in step (1), cover the two outer sides of the stack with copper foil, and hot press at 175°C and 4MPa for 60 minutes in a press to make a copper-clad laminate of 0.8mm.

[0104] The copper-clad laminate was subjected to performance testing, and the specific method is as follows:

[0105]

[0106]

[0107] Table 1

[0108]

[0109]

[0110] Table 2

[0111]

[0112]

[0113]

[0114] As shown in Table 1, this invention, through the design and synergistic compounding of its components, forms a rich cross-linked network structure in the cured product, jointly constructed by epoxy resin, bio-based resin, benzoxazine resin, and phenolic resin. Combined with toughening agents, flame retardants, fillers, and coupling agents, the resin composition and its contained prepregs, laminates, and metal foil-coated laminates exhibit excellent heat resistance, moisture resistance, flame retardancy, processability, structural stability, and mechanical properties. Specifically, in Examples 1-3, the 288℃ immersion soldering time is ≥238s, the PCT immersion soldering time is ≥254s, the PCT water absorption rate is ≤0.13%, and the warp bending strength is ≥661 N / mm. 2 Woven bending strength ≥503 N / mm 2 It can achieve V-0 flame retardancy and a volume resistivity ≥5.33×10⁻⁶. 9 With a strength of MΩ·cm, Z-PTE ≤ 3.89%, good alkali resistance, low water absorption, and good punching processability, this resin composition exhibits excellent overall performance, meeting the performance requirements of printed circuit boards for copper-clad laminates. Furthermore, it effectively reduces the use of petrochemical materials, contributing to lower carbon emissions throughout the copper-clad laminate's lifecycle and making it more environmentally friendly.

[0115] Comparing Examples 1-3 with Examples 4-5, it can be seen that, as a preferred technical solution of the present invention, benzoxazine resin and phenolic resin are compounded in a specific ratio to synergistically construct a chemical cross-linking network with bio-based resin and epoxy resin, which can further optimize the performance of the cured product and the board. In Examples 4-5, the amounts of benzoxazine resin and phenolic resin exceed the preferred range of the present invention, resulting in varying degrees of reduction in processability, CTE, mechanical strength, and other properties. Furthermore, the resin composition of the present invention contains a toughening agent, which helps to improve the mechanical and processability properties of the cured product and the board. Example 6 does not contain a toughening agent, resulting in a decrease in the flexural strength of the board and the appearance of halos during punching.

[0116] Comparative Examples 1-8 did not use a resin system composed of epoxy resin, bio-based resin, benzoxazine resin and phenolic resin, which resulted in the absence of a suitable chemical cross-linking network in the cured product. This led to a significant deterioration in the heat resistance, damp heat resistance, alkali resistance, processability, structural stability and mechanical properties of the boards, and their overall performance failed to meet the IPC standard.

[0117] The applicant declares that the above embodiments illustrate the resin composition and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components in parts by weight: 100 parts epoxy resin 30-120 parts of bio-based resin 20-140 parts of curing agent; The bio-based resin includes any one or a combination of at least two of bio-based furan resin, terpene resin, and terpene phenol resin. The curing agent comprises a combination of benzoxazine resin and phenolic resin.

2. The resin composition according to claim 1, characterized in that, The number average molecular weight of the epoxy resin is 200-2000; Preferably, the epoxy equivalent of the epoxy resin is 150-570 g / eq, more preferably 180-480 g / eq; Preferably, the epoxy resin has a functionality of 2-6.

3. The resin composition according to claim 1 or 2, characterized in that, The bio-based furan resin includes any one or a combination of at least two of furfuryl alcohol phenol-formaldehyde resin, furfuryl alcohol resin, furfuryl alcohol urea-formaldehyde resin, furfuryl alcohol furfural resin, furfural acetone resin, and furfuryl ketone-formaldehyde resin. Preferably, the terpene-based resin includes terpene resin and / or terpene-styrene resin.

4. The resin composition according to any one of claims 1-3, characterized in that, The benzoxazine resin includes any one or a combination of at least two of the following: bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, dicyclopentadiene type benzoxazine resin, phenolphthalein type benzoxazine resin, fluorenyl benzoxazine resin, allyl benzoxazine resin, propargyl benzoxazine resin, cyano benzoxazine resin, and bismaleimide benzoxazine resin. Preferably, the benzoxazine resin is 10-60 parts by weight, based on 100 parts by weight of the epoxy resin; Preferably, the phenolic resin includes any one or a combination of at least two of bisphenol A type phenolic resin, phenolic resin, o-cresol phenolic resin, triphenol phenolic resin, naphthalene type phenolic resin, biphenyl type phenolic resin, and dicyclopentadiene phenolic resin; Preferably, the phenolic resin comprises 15-70 parts by weight of 100 parts of epoxy resin.

5. The resin composition according to any one of claims 1-4, characterized in that, The resin composition further includes any one or a combination of at least two of the following: accelerator, toughening agent, flame retardant, filler, and coupling agent; Preferably, the resin composition further comprises 0.02-3 parts by weight of an accelerator; Preferably, the accelerator comprises any one or a combination of at least two of the following: tertiary amines, tertiary phosphines, organometallic complexes, quaternary ammonium salts, and imidazole compounds.

6. The resin composition according to any one of claims 1-5, characterized in that, The resin composition further includes 15-85 parts toughening agent by weight; Preferably, the toughening agent comprises any one or a combination of at least two of the following: epoxy soybean oil resin, cashew phenol modified resin, tung oil modified resin, castor oil modified resin, phenoxy resin, rubber resin, nitrile rubber, and core-shell rubber material. Preferably, the resin composition further comprises 15-110 parts by weight of flame retardant; Preferably, the flame retardant includes any one or a combination of at least two of halogen-containing flame retardants, phosphorus-containing flame retardants, and nitrogen-containing flame retardants; Preferably, the flame retardant includes reactive flame retardants and / or additive flame retardants; Preferably, the resin composition further comprises 20-300 parts by weight of filler; Preferably, the filler comprises any one or a combination of at least two of the following: aluminum hydroxide, aluminum oxide, magnesium hydroxide, magnesium oxide, aluminum trioxide, silicon dioxide, calcium carbonate, aluminum nitride, boron nitride, silicon carbide, titanium dioxide, zinc borate, zinc molybdate, barium metaborate, zinc sulfide, aluminum silicate, zinc oxide, zirconium oxide, mica, boehmite, talc, calcium nitride, and kaolin. Preferably, the resin composition further comprises 0.1-5 parts by weight of coupling agent; Preferably, the coupling agent includes any one or a combination of at least two of silane coupling agents, organochromium coupling agents, and titanate coupling agents.

7. A semi-cured sheet, characterized in that, The prepreg comprises a reinforcing material and a resin composition as described in any one of claims 1-6 attached to the reinforcing material; Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

8. A laminate, characterized in that, The laminate includes at least one prepreg as described in claim 7.

9. A metal foil-coated laminate, characterized in that, The metal foil-coated laminate includes a metal foil, and at least one of the prepreg as described in claim 7 and the laminate as described in claim 8.

10. A printed circuit board, characterized in that, The printed circuit board includes at least one of the prepreg as described in claim 7, the laminate as described in claim 8, and the metal foil-coated laminate as described in claim 9.

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