Resin composition and application thereof

Abstract

The invention provides a resin composition and application thereof. The resin composition comprises the following components: (A) epoxy resin, (B) an active ester compound, (C) a carbodiimide compound and (D) thermoplastic resin, the active ester compound has a structure as shown in a formula I. The cured resin composition has the advantages of favorable peel strength, low dielectric loss factor, low thermal expansion coefficient and favorable toughness, and can fully meet the application requirements of high-performance circuit substrates or laminated adhesive films.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of laminated boards, and relates to a resin composition and application thereof. BACKGROUND

[0002] As a manufacturing technique of a printed wiring board, a manufacturing method using a build-up method in which an insulating layer and a conductor layer are alternately overlaid is known. In the manufacturing method using the build-up method, a resin composition is generally cured to form an insulating layer. For example, Japanese Patent Application Publication No. 2006-335834 discloses a technique in which a resin composition containing an epoxy resin, an active ester compound, and a carbodiimide compound is cured to form an insulating layer having a low dielectric loss tangent. The active ester compound disclosed in Japanese Patent Application Publication No. 2006-335834 is insufficient in toughness and dielectric loss tangent of a cured product due to the structure itself.

[0003] Therefore, it is desired in the art to develop a resin composition that allows a cured product to have good toughness, and also allows low dielectric loss tangent, low thermal expansion coefficient, and good peel strength. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application aims to provide a resin composition and application thereof.

[0005] To achieve the above object, the present application adopts the following technical solution:

[0006] In one aspect, the present application provides a resin composition, which comprises the following components:

[0007] (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, and (D) a thermoplastic resin.

[0008] The active ester compound has the following structure of Formula I:

[0009]

[0010] wherein m and n are independently an integer of 1 to 20 (e.g., 1, 2, 5, 8, 10, 12, 15, 18, or 20);

[0011] X is a substituted or unsubstituted C2-C50 (e.g., C2, C3, C4, C5, C6, C7, C8, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, or C50) divalent linear or branched alkyl group, or has the following structure of Formula A2-1, and the substituent of the substitution is selected from halogen, C1-C5 (e.g., C1, C2, C3, C4, or C5) linear or branched alkyl group;

[0012] — X — Y — X2—

[0013] Formula A2-1;

[0014] wherein X1, X2are independently selected from substituted or unsubstituted C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C10, C12, C15, C18, or C20) bivalent linear or branched alkane, Y is O, S, substituted or unsubstituted C3-C30 (e.g., C6, C8, C10, C12, C15, C18, C20, C25, or C30) bivalent cycloalkyl, substituted or unsubstituted C6-C30 (e.g., C6, C8, C10, C12, C15, C18, C20, C25, or C30) bivalent aryl, the substituents of the substitution being selected from halogen, C1-C5 (e.g., C1, C2, C3, C4, or C5) linear or branched alkyl;

[0015] The bivalent cycloalkyl can be exemplified by:

[0016] and the like.

[0017] The bivalent aryl can be exemplified by:

[0018] and the like.

[0019] Ar is a substituted or unsubstituted C6-C50 (e.g., C6, C7, C8, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, or C50) bivalent aromatic group;

[0020] Preferably, the bivalent aromatic group is selected from one or a combination of at least two of

[0021]

[0022]

[0023] The substituents of the substitution in Ar are selected from halogen, C1-C5 (e.g., C1, C2, C3, C4, or C5) linear or branched alkyl, C2-C5 (e.g., C2, C3, C4, or C5) linear or branched alkenyl, C2-C5 (e.g., C2, C3, C4, or C5) linear or branched alkynyl.

[0024] ​In the present invention, the "divalent aromatic group" means a group having 2 bonding sites containing an aryl group, including an arylene group, and a substituent formed by connecting at least 2 aryl groups through a linking group (e.g., -0-, -S-, carbonyl, sulfone group, alkylene group, cycloalkylene group, or arylenealkylene group, etc.). The same meaning is applied when the same description is referred to hereinafter.

[0025] In the present invention, a short straight line on one side or both sides of a group structure represents a bonding key of the group, not a methyl group. The same meaning is applied when the same description is referred to hereinafter.

[0026] The "C1-C5 linear or branched alkyl group" includes a C1, C2, C3, C4, or C5 linear or branched alkyl group, exemplarily including but not limited to a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a t-butyl group, a pentyl group, or an iso-pentyl group, etc. The same meaning is applied when the same description is referred to hereinafter.

[0027] Z is a substituted or unsubstituted C6-C18 (e.g., C6, C7, C8, C10, C12, C14, C15, C16, or C18) divalent aromatic group, a substituted or unsubstituted C1-C20 (e.g., C1, C2, C3, C4, C6, C8, C10, C12, C15, C18, or C20) divalent alkyl group, a substituted or unsubstituted C3-C30 (e.g., C3, C4, C6, C8, C10, C15, C20, C25, or C30) divalent cycloalkyl group, the substituent of Z being selected from a halogen, a C1-C5 (e.g., C1, C2, C3, C4, or C5) linear or branched alkyl group;

[0028] R is a substituted or unsubstituted C6-C30 (e.g., C6, C8, C10, C12, C15, C18, C20, C25, or C30) arylene group, a substituted or unsubstituted C3-C20 (e.g., C3, C4, C6, C8, C10, C12, C15, C18, or C20) cycloalkyl group, a substituted or unsubstituted C2-C10 (e.g., C2, C3, C4, C6, C8, C10, C12, C15, C18, or C20) linear or branched alkenyl group; the substituent of R being selected from a halogen, a C1-C5 (e.g., C1, C2, C3, C4, or C5) linear or branched alkyl group, a C2-C5 (e.g., C2, C3, C4, or C5) linear or branched alkenyl group, a C2-C5 (e.g., C2, C3, C4, or C5) linear or branched alkynyl group, a phenyl group, a naphthyl group, wherein R1and R2are independently selected from a halogen, a C1-C5 (e.g., C1, C2, C3, C4, or C5) linear or branched alkyl group.

[0029] The resin composition system of the present application is composed of the active ester compound, epoxy resin, carbodiimide compound and thermoplastic resin, so that the cured product of the resin composition has good toughness, low dielectric loss factor, low thermal expansion coefficient and good peel strength.

[0030] In the present application, the preparation method of the active ester compound comprises the following steps: a dihydric phenol compound having the structure shown in Formula A1, a dihydric alcohol compound having the structure shown in Formula A2, a diacyl compound having the structure shown in Formula A3 and a monofunctional compound having the structure shown in Formula A4 are reacted to obtain the active ester compound:

[0031] HO-Ar-OH

[0032] Formula A1;

[0033] HO-X-OH

[0034] Formula A2;

[0035]

[0036] R-OH

[0037] Formula A4.

[0038] In the present application, the molar ratio of the diacyl compound to the dihydroxy compound (dihydric phenol compound + dihydric alcohol compound) is 1:(0.5-0.95), for example, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.87, 1:0.89, 1:0.9, 1:0.92 or 1:0.95, etc.; the molar ratio of the diacyl compound to the dihydroxy compound (dihydric phenol compound + dihydric alcohol compound) is preferably 1:(0.55-0.8), for example, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78 or 1:0.8.

[0039] In the present application, the molar ratio of the diacyl compound to the monofunctional compound is 1:(0.1-1), for example 1:0.1, 1:0.12, 1:0.15, 1:0.18, 1:0.2, 1:0.22, 1:0.25, 1:0.28, 1:0.3, 1:0.32, 1:0.35, 1:0.38, 1:0.4, 1:0.42, 1:0.45, 1:0.48, 1:0.5, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.88, 1:0.9, 1:0.92, 1:0.95, 1:0.98 or 1:1, etc. The molar ratio of the diacyl compound to the monofunctional compound is preferably 1:(0.4-0.9), for example 1:0.4, 1:0.42, 1:0.45, 1:0.48, 1:0.5, 1:0.52, 1:0.55, 1:0.58, 1:0.6, 1:0.62, 1:0.65, 1:0.68, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.88 or 1:0.9.

[0040] In the present application, the diacyl compound is 1 mol, and the sum of the hydroxyl groups in the dihydric phenol compound, the dihydric alcohol compound and the monofunctional compound is 2 mol in theory. The diacyl compound is in excess relative to the dihydric phenol compound and the dihydric alcohol compound. The reaction of the dihydric phenol compound and the dihydric alcohol compound with the diacyl compound plays a role in chain extension, and the monofunctional compound is a capping agent, which plays a role in terminating chain extension. The inventors have found that In ester structures, if OR is an aryloxy structure, the formed aryl ester group can undergo a cross-linking reaction with the epoxy group; conversely, if OR is an alkoxy structure, the formed alkyl ester group cannot undergo a cross-linking reaction with the epoxy group. Introducing only straight-chain or branched alkyl ester groups into the structure of reactive ester compounds has a significant effect on reducing the dielectric properties and improving the toughness of the resin. However, the introduction of flexible segments leads to a significant deterioration in the CTE of the cured product. Furthermore, if reactive cross-linking points cannot be formed in the intermediate segments, this deterioration is further exacerbated. The active ester compound provided by this invention effectively reduces the dielectric properties of the active ester compound by introducing diol ester groups. At the same time, the introduction of diol ester groups introduces crosslinking points that can react with epoxy groups in the middle chain segment of the active ester compound, which helps to improve the problem of large coefficient of thermal expansion (CTE) caused by the lack of reaction crosslinking points with epoxy groups in the middle chain segment. Therefore, compared with introducing only straight-chain or branched alcohol ester groups into the structure, the active ester compound of this invention can avoid the problem of CTE degradation of the cured product while reducing dielectric properties and toughening.

[0041] This invention does not impose any particular limitation on the molar ratio of the diol compound to the diphenol compound. However, considering the need to obtain lower dielectric properties or toughening, the proportion of the diphenol compound should not be too high. Preferably, the molar ratio of the diphenol compound to the diol compound is 1:(1 to 20), such as 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:3, 1:4, 1:5, 1:8, 1:10, 1:12, or 1:15, 1:18, 1:19, or 1:20. More preferably, the molar ratio of the diphenol compound to the diol compound is 1:(1 to 10), such as 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:3, 1:4, 1:5, 1:8, or 1:10.

[0042] In this invention, by combining a diphenol compound having the structure shown in Formula A1, a diol compound having the structure shown in Formula A2, a diacyl compound having the structure shown in Formula A3, and a monofunctional compound having the structure shown in Formula A4, the prepared active ester compound exhibits excellent dielectric properties and toughness, while balancing CTE performance. The resin composition containing the active ester compound exhibits excellent dielectric properties and adhesion after curing, which can fully meet the application requirements of high-performance circuit boards or multilayer films.

[0043] In this invention, the number of carbon atoms in the group is defined within a range. This range means that the number of carbon atoms in the group can be any integer within the defined range. For example, C3 to C30 represents 3, 6, 8, 10, 12, 15, 18, 20, 25, or 30 carbon atoms; C6 to C18 represents 6, 8, 10, 12, 14, 15, 16, or 18 carbon atoms; C1 to C5 represents 1, 2, 3, 4, or 5 carbon atoms; C1 to C30 represents 1, 3, 6, 8, 10, 12, 15, 18, 20, 25, or 30 carbon atoms, and so on.

[0044] Preferably, the reaction temperature is -10 to 65°C, for example -10°C, -8°C, -5°C, -2°C, -0°C, 2°C, 5°C, 8°C, 10°C, 12°C, 15°C, 18°C, 20°C, 22°C, 25°C, 28°C, 30°C, 32°C, 35°C, 38°C, 40°C, 42°C, 45°C, 48°C, 50°C, 52°C, 55°C, 58°C, 60°C, 62°C, or 65°C, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0045] Preferably, the reaction is carried out in the presence of a basic catalyst.

[0046] Preferably, the alkaline catalyst comprises an inorganic alkaline compound and / or an organic base; the inorganic alkaline compound comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium bicarbonate, or potassium bicarbonate; the organic base comprises any one or a combination of at least two of triethylamine, pyridine, 4-dimethylaminopyridine, tributylamine, N,N-diisopropylethylamine, benzyltriethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, or tetradecyltrimethylammonium chloride.

[0047] Preferably, the reaction is carried out in a protective atmosphere, which is preferably nitrogen or argon.

[0048] Preferably, the reaction is carried out in the presence of a solvent.

[0049] Preferably, the reaction is carried out in the presence of a solvent, which is not particularly limited, as long as it does not hinder the reaction. Exemplary examples include, but are not limited to, any one or a combination of at least two of the following: tetrahydrofuran, dioxane, benzene, toluene, xylene, dichloromethane, dichloroethane, butanone, methyl isobutyl ketone, cyclohexanone, 1,4-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, or N-methylpyrrolidone. The amount of solvent can be appropriately adjusted according to the different solubilities of the raw materials and products, so that each raw material and product can dissolve in the solvent. Preferably, it is 3 to 15 times the sum of the masses of the raw materials, for example, 3.5 times, 4 times, 4.5 times, 5 times, 5.5 times, 6 times, 6.5 times, 7 times, 7.5 times, 8 times, 8.5 times, 9 times, 10 times, 11 times, 12 times, 13 times, or 14 times.

[0050] Preferably, the reaction further includes post-processing of the product after completion.

[0051] Preferably, the post-processing method includes filtration, washing, concentration, extraction, recrystallization, or column chromatography, etc., to achieve the separation and purification of the active ester compound.

[0052] Preferably, the epoxy resin includes 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, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenolic epoxy resin, naphthalene-containing epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, isocyanate-modified epoxy resin, and organosilicon-modified epoxy resin.

[0053] Preferably, the carbodiimide compound is selected from any one or a combination of two of carbodiimide compounds containing aliphatic or aromatic structures.

[0054] Preferably, the thermoplastic resin includes any one or a combination of at least two of the following: phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide-imide resin, polyether-imide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, and acrylic resin.

[0055] Preferably, the resin composition comprises the following components in parts by weight: (A) 10-30 parts by weight of epoxy resin (e.g., 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, or 30 parts by weight), (B) 5-20 parts by weight of reactive ester compound (e.g., 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, or 20 parts by weight), (C) 1-15 parts by weight of carbodiimide compound (e.g., 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, or 15 parts by weight), and (D) 1-20 parts by weight of thermoplastic resin (e.g., 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, or 20 parts by weight).

[0056] Preferably, the resin composition further includes (E) an inorganic filler.

[0057] Preferably, the inorganic filler includes any one or a combination of at least two of the following: silicon dioxide, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica.

[0058] Preferably, the content of inorganic filler in the resin composition is 10-80 parts by weight, for example 10 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, or 80 parts by weight.

[0059] Preferably, the average particle size of the inorganic filler is 0.01 micrometers to 3 micrometers, for example, 0.01 micrometers, 0.05 micrometers, 0.1 micrometers, 0.5 micrometers, 1 micrometer, 1.3 micrometers, 1.5 micrometers, 1.8 micrometers, 2 micrometers, 2.3 micrometers, 2.5 micrometers, 2.8 micrometers or 3 micrometers.

[0060] Preferably, the resin composition further includes a curing accelerator.

[0061] Preferably, the curing accelerator is any one or a combination of at least two of pyridine, imidazole or phosphate accelerators, preferably 4-dimethylaminopyridine and / or 1-benzyl-2-phenylimidazolium.

[0062] Preferably, the content of the curing accelerator in the resin composition is 0.01-0.5 parts by weight, for example 0.01 parts by weight, 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight or 0.5 parts by weight.

[0063] Preferably, the resin composition further includes organic fillers.

[0064] Preferably, the organic filler includes any one or a combination of at least two of the following: polytetrafluoroethylene particles, polyurethane microparticles, rubber particles, polyamide microparticles, and organosilicon particles.

[0065] Preferably, the content of organic filler in the resin composition is 5-20 parts by weight, for example 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight or 20 parts by weight.

[0066] In this invention, "comprising" means that, in addition to the stated components, it may include other components that impart different properties to the resin composition. Furthermore, the term "comprising" in this invention may also be replaced with the closed-ended "is" or "consisting of".

[0067] On the other hand, the present invention provides a resin adhesive obtained by dissolving or dispersing the resin composition described above in a solvent.

[0068] The solvent used in this invention is not particularly limited. Specific examples include alcohols such as methanol, ethanol, and butanol; ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl carbitol; ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; esters such as ethoxyethyl acetate and ethyl acetate; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. One of the above solvents can be used alone, or two or more can be mixed. Preferably, aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene are mixed with ketone fluxes such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. The amount of solvent used can be selected by those skilled in the art based on their experience, ensuring that the resulting resin solution reaches a suitable viscosity for use.

[0069] On the other hand, the present invention provides a laminated adhesive film, the laminated adhesive film comprising a release film and a resin composition as described above that is adhered to the release film after coating and drying.

[0070] In this invention, the copper foil peel strength after copper plating of the laminated adhesive film is 6.1-6.9 N / cm, for example 6.2 N / cm, 6.3 N / cm, 6.4 N / cm, 6.5 N / cm, 6.7 N / cm or 6.9 N / cm.

[0071] Preferably, the surface roughness of the laminated adhesive film after adhesive removal is 65-94nm, for example 65nm, 70nm, 75nm, 80nm, 85nm, 90nm or 94nm.

[0072] On the other hand, the present invention provides a resin-coated copper foil, the resin-coated copper foil comprising a copper foil and a resin layer attached to the copper foil after coating and drying, the resin layer being composed of the resin composition described above.

[0073] Preferably, the thickness of the resin layer of the resin-coated copper foil is 5-300 μm, such as 5 μm, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 130 μm, 150 μm, 180 μm, 200 μm, 230 μm, 250 μm, 280 μm or 300 μm, more preferably 10-200 μm; and more preferably 20-100 μm.

[0074] Preferably, the thickness of the copper foil is 1-105 μm, such as 1 μm, 3 μm, 5 μm, 8 μm, 1020 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or 105 μm, more preferably 3-35 μm; and even more preferably 5-18 μm.

[0075] On the other hand, the present invention provides a prepreg comprising a reinforcing material and a resin composition as described above attached to the reinforcing material.

[0076] Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

[0077] On the other hand, the present invention provides a circuit board comprising at least one of the following: a multilayer adhesive film as described above, a resin-coated copper foil as described above, or a prepreg as described above.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] The resin composition of the present invention, after curing, has good peel strength, low dielectric loss factor, low coefficient of thermal expansion and good toughness, which can fully meet the application requirements of high-performance circuit boards or multilayer films. Attached Figure Description

[0080] Figure 1 Infrared spectrum of the active ester compound provided in Example 1;

[0081] Figure 2 Ultra-high performance polymer chromatogram of the active ester compound provided in Example 1;

[0082] Figure 3 Infrared spectrum of the active ester compound provided in Example 2;

[0083] Figure 4Ultra-high performance polymer chromatogram of the active ester compound provided in Example 2. Detailed Implementation

[0084] 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.

[0085] Preparation Example 1

[0086] An active ester compound K-1 is prepared by the following steps:

[0087] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 38.5 g (0.35 mol) of resorcinol, 47 g (0.35 mol) of di(2-hydroxypropyl) ether, 203 g (1.0 mol) of isophthaloyl chloride, 86.5 g (0.6 mol) of 1-naphthol, and 1315 g of dichloromethane were added. The system was purged with nitrogen under reduced pressure while stirring to dissolve the compounds. The reaction system was kept below 35°C, and then 232.3 g (2.3 mol) of triethylamine was added dropwise over 3 hours. After the addition was completed, stirring was continued for 2 hours. After the reaction was complete, deionized water was added and stirred for 15 minutes. The aqueous layer was removed by separation and allowed to stand. The resulting dichloromethane layer was repeatedly washed with water until the pH of the aqueous layer reached 7. Finally, the active ester compound K-1 was obtained by heating and drying under reduced pressure.

[0088] Based on the feed ratio, the active ester compound K-1 provided in this preparation example has an active ester equivalent of 233 g / eq., calculated and determined.

[0089] Preparation Example 2

[0090] An active ester compound K-2 is prepared by the following steps:

[0091] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 70.1 g of bisphenol fluorene (0.2 mol), 40.3 g of di(2-hydroxypropyl) ether (0.3 mol), 203 g of isophthaloyl chloride (1.0 mol), 108.1 g of o-cresol (1.0 mol), and 2100 g of dichloromethane were added. The system was purged with nitrogen under reduced pressure while stirring to dissolve the compounds. The reaction system was kept below 35°C, and then 222.2 g of triethylamine (2.2 mol) was added dropwise over 3 hours. After the addition was completed, stirring was continued for 2 hours. After the reaction was complete, deionized water was added and stirred for 15 minutes. The aqueous layer was removed by separation after standing. The resulting dichloromethane layer was repeatedly washed with water until the pH of the aqueous layer reached 7. Finally, the active ester compound K-2 was obtained by heating and drying under reduced pressure.

[0092] Based on the feed ratio, the active ester compound K-2 provided in this preparation example has an active ester equivalent of 249 g / eq., calculated and determined.

[0093] Preparation Example 3

[0094] An active ester compound K-3 is prepared by the following steps:

[0095] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 48.5 g of 3,3',5,5'-tetramethylbiphenyl (0.2 mol), 87.7 g of 1,8-octanediol (0.6 mol), 203 g of isophthaloyl chloride (1.0 mol), and 4000 g of dichloromethane were added. The system was purged with nitrogen under reduced pressure while stirring to dissolve the compounds. The reaction system was kept below 35°C, and then 242.4 g of triethylamine (2.4 mol) was added dropwise over 4 hours. After the addition was complete, stirring was continued for 0.5 hours. Then, 75.7 g of 4-maleimide-based phenol (0.4 mol) was added, and the reaction was continued with stirring for 2 hours. After the reaction was complete, deionized water was added and stirred for 15 minutes. The aqueous layer was removed by separation after standing. The resulting dichloromethane layer was repeatedly washed with water until the pH of the aqueous layer reached 7. Finally, the active ester compound K-3 was obtained by heating and drying under reduced pressure.

[0096] Based on the feed ratio, the active ester compound K-3 provided in this preparation example has an active ester equivalent of 428 g / eq., calculated and determined.

[0097] Preparation Example 4

[0098] An active ester compound K-4 is prepared by the following steps:

[0099] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 46.3 g of diallyl bisphenol A (0.15 mol), 103.7 g of terephthalic acid (0.75 mol), 203 g of isophthaloyl chloride (1.0 mol), 10.0 g of cyclohexanol (0.2 mol), and 3000 g of toluene were added. The system was purged with nitrogen under reduced pressure while stirring to dissolve the compounds. The reaction system was kept below 60°C, and 460 g (2.3 mol) of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours, followed by stirring for 1 hour after the addition was complete. After the reaction was complete, the aqueous layer was removed by separation under static pressure. Deionized water was added to the obtained toluene layer and stirred for 15 minutes. The aqueous layer was then removed by separation under static pressure. The toluene layer was repeatedly washed with water until the pH of the aqueous layer reached 7. Finally, the active ester compound K-4 was obtained by heating and drying under reduced pressure.

[0100] Based on the feed ratio, the active ester compound K-4 provided in this preparation example has an active ester equivalent of 966 g / eq., calculated and determined.

[0101] Preparation Example 5

[0102] An active ester compound K-5 is prepared by the following steps:

[0103] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 124.2 g (0.4 mol) of 2,5-dihydroxyphenyl diphenylphosphine oxide, 28.8 g (0.2 mol) of 1,4-cyclohexanediethanol, 183 g (1.0 mol) of adipic acid chloride, 115.4 g (0.8 mol) of 1-naphthol, and 2850 g of dichloromethane were added. The system was purged with nitrogen under reduced pressure while stirring to dissolve the compounds. The reaction system was kept below 35°C, and then 232.3 g (2.3 mol) of triethylamine was added dropwise over 3 hours. After the addition was completed, stirring was continued for 2 hours. After the reaction was completed, deionized water was added and stirred for 15 minutes. The aqueous layer was removed by separation after standing. The resulting dichloromethane layer was repeatedly washed with water until the pH of the aqueous layer reached 7. Finally, the active ester compound K-5 was obtained by heating and drying under reduced pressure.

[0104] Based on the feed ratio, the active ester compound K-5 provided in this preparation example has an active ester equivalent of 236 g / eq., calculated and determined.

[0105] Comparative Preparation Example 1

[0106] An active ester compound L-1 is prepared by referring to Synthesis Example 1 and Example 1 in patent CN115210213A. Its general structural formula is shown in Formula A5, and the active ester equivalent is 319 g / eq.

[0107]

[0108] Performance testing of active ester compounds:

[0109] (1) Structural characterization: The active ester compounds provided in Preparation Examples 1 to 5 were characterized by infrared testing using Fourier transform infrared spectroscopy (FT-IR).

[0110] For example, the infrared spectrum of the active ester compound K-1 provided in Preparation Example 1 is as follows: Figure 1 As shown, from Figure 1 As can be seen from the data, the active ester compound K-1 exhibits a wavenumber of 1720 cm⁻¹. -1 and 1736cm -1 Strong characteristic absorption peaks for alcohol and phenol ester groups appear at 3400 cm⁻¹, respectively, while those at 3400 cm⁻¹ show strong characteristic absorption peaks for alcohol and phenol ester groups. -1 The absorption peaks of nearby alcoholic or phenolic hydroxyl groups have largely disappeared, indicating that the alcoholic and phenolic hydroxyl groups have undergone esterification; the infrared spectrum of the active ester compound K-2 provided in Preparation Example 2 is shown below. Figure 3 As shown, from Figure 3As can be seen from the data, the active ester compound K-2 exhibits a wavenumber of 1720 cm⁻¹. -1 and 1735cm -1 Strong characteristic absorption peaks for alcohol and phenol ester groups appear at 3400 cm⁻¹, respectively, while those at 3400 cm⁻¹ show strong characteristic absorption peaks for alcohol and phenol ester groups. -1 The absorption peaks of nearby alcoholic or phenolic hydroxyl groups have largely disappeared, indicating that the alcoholic and phenolic hydroxyl groups have undergone esterification.

[0111] (2) Molecular weight determination: The weight-average molecular weight M of the active ester compounds provided in Examples 1-5 was determined using a Waters ultra-high performance polymer chromatography (APC) system. w .

[0112] For example, the ultra-high performance polymerase chromatogram (APC chromatogram) of the active ester compound K-1 provided in Preparation Example 1 is as follows: Figure 2 As shown, from Figure 2 As can be seen from the above, the weight-average molecular weight M of the active ester compound K-1 is... w The value is 1795; the ultra-high performance polymer chromatogram (APC chromatogram) of the active ester compound K-2 provided in Preparation Example 2 is as follows: Figure 4 As shown, from Figure 4 As can be seen from the above, the weight-average molecular weight M of the active ester compound K-2 is... w The value is 2276.

[0113] In the following specific embodiments of the present invention, some of the materials involved are shown below:

[0114] (1) Epoxy resin

[0115] Biphenyl-type epoxy resin, NC3000H, Nippon Kayaku;

[0116] Bisphenol A type epoxy resin, NPES-901, Nan Ya Electronic Materials Co., Ltd.

[0117] (2) Active ester compounds

[0118] Dicyclopentadiene-type reactive ester resin, HPC-8000-65T, manufactured by DIC Japan, has an active ester equivalent of approximately 223 g / eq., and its structural formula is as follows:

[0119]

[0120] X represents naphthyl, j is 0 or 1, k is 0 or 1, and n is 0.25-1.25.

[0121] (3) Thermoplastic resin

[0122] Phenoxy resin, PKHH, Inchem Corporation;

[0123] Polyethersulfone resin, 3000RP, SOLVAY.

[0124] (4) Carbodiimide compounds

[0125] V-07, Nisshinbo;

[0126] V-03, Nisshinbo.

[0127] (5) Inorganic fillers

[0128] Silica, SO-Cl, Admatechs, Japan;

[0129] Silica, SO-C2, from Admatechs, Japan.

[0130] (6) Curing accelerator

[0131] DMAP, 4-Dimethylaminopyridine, Guangrong Chemical.

[0132] Example 1

[0133] A resin composition comprising, by weight, the following components: 20 parts by weight of epoxy resin NC3000H, 15 parts by weight of active ester compound K-1, 5 parts by weight of carbodiimide compound V-07, 5 parts by weight of thermoplastic resin phenoxy resin PKHH, 70 parts by weight of silica SO-Cl, and 0.5 parts by weight of curing accelerator DMAP.

[0134] A multilayer adhesive film comprising the resin composition and a circuit board are prepared by the following method:

[0135] (1) Mix each component of the resin composition with methyl ethyl ketone according to the above formula to prepare a resin solution with a solid content of 65%; coat the resin solution onto the release film, dry it, and bake it in an oven at 100°C for 5 minutes to obtain a laminated film of resin layer in a semi-cured state with a thickness of 40 μm.

[0136] (2) Press the laminated adhesive film obtained in step (1) and the roughened inner PCB board at 100°C for 1 minute using a vacuum laminator with a pressure of 0.5MPa. Then bake at 100°C and 180°C for 30 minutes each. Remove the release film and perform surface de-adhesion treatment, copper plating, to form a circuit board with lines.

[0137] Examples 2-5, Comparative Examples 1-2

[0138] A resin composition and a multilayer adhesive film and circuit board comprising the resin composition are disclosed. The components and contents of the resin composition are shown in Table 1, wherein the amount of each component is expressed in "parts by weight" of solid content. The preparation methods of the multilayer adhesive film and circuit board are the same as those in Example 1.

[0139] The following performance tests were performed on the multilayer adhesive films and circuit boards provided in Examples 1-5 and Comparative Examples 1-2:

[0140] (1) Surface roughness Ra

[0141] The laminated adhesive film was pressed onto the surface of the core board and cured in an oven at 180°C for 30 minutes to obtain a pre-cured laminated adhesive film. The laminated adhesive film was then subjected to the following desmear treatment: immersion in an aqueous solution of ethylene glycol ethers and sodium hydroxide (MV Sweller, ATOTECH) at 70°C for 10 minutes – rinsing with deionized water for 2 minutes – immersion in a potassium permanganate solution (MV P Etch, ATOTECH) at 80°C for 30 minutes – rinsing with deionized water for 2 minutes – immersion in an acidic aqueous solution (MV Reduction Cleaner, ATOTECH) at 50°C for 5 minutes to obtain a roughened laminated adhesive film. The surface roughness Ra of the roughened film was tested using a laser confocal microscopy instrument (OLYMPUS).

[0142] (2) Copper foil peel strength PS

[0143] The roughened laminated film was subjected to the following copper plating, electroplating, and post-curing treatment: soaking in chemical copper solution (MVTP1, ATOTECH) for 20 min, electroplating copper to a thickness of 25 μm, and curing in an oven at 190℃ for 60 min. The copper plating adhesion of the laminated film was tested using the IPC-TM-6502.4.9 method and a copper foil peel strength tester.

[0144] (3) Toughness (elongation)

[0145] After curing the laminated film at 190℃ for 60 min, dynamic thermomechanical analysis (DMA) was used. The film was kept at 150℃ for 5 min, with a pre-force of 0.01 N, which was increased from 3 N / min to 17.5 N / min. The elongation was calculated from the length at fracture and the initial length of the sample.

[0146] (4) Dielectric loss factor D f The D of the laminated film at 10 GHz was determined according to the SPDR method specified in standard IEC61189-2-721. f .

[0147] (5) Coefficient of thermal expansion (CTE): The CTE of the laminated film was determined according to the TMA test method specified in IPC-TM-650 2.4.24.5.

[0148] Table 1

[0149]

[0150]

[0151] As can be seen from Table 1, the laminated films and circuit boards prepared by the resin compositions of Examples 1-5 of the present invention have good peel strength, low dielectric loss factor, low coefficient of thermal expansion and good toughness.

[0152] Compared to Example 1, the active ester compound used in Comparative Example 1 did not contain phenolic ester groups in its intermediate chain segment, resulting in a poorer CTE of the laminated film.

[0153] Compared with Example 1, the dicyclopentadiene-type reactive ester resin used in Comparative Example 2 does not contain alcohol ester groups in its molecular structure, resulting in a significantly worse elongation of the laminated film.

[0154] 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 by comprising: The resin composition comprises the following components: (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin; The active ester compound has the following formula I: wherein m, n are independently an integer of 1 to 20; X is a substituted or unsubstituted C2-C50 bivalent linear or branched alkyl, or has the following formula A2-1 structure, the substituted substituent is selected from halogen, C1-C5 linear or branched alkyl; —X1—Y—X2— Formula A2-1; wherein X1, X2 are independently selected from substituted or unsubstituted C1-C20 bivalent linear or branched alkane, Y is O, S, substituted or unsubstituted C3-C30 bivalent cycloalkyl, substituted or unsubstituted C6-C30 bivalent aryl, the substituted substituent is selected from halogen, C1-C5 linear or branched alkyl; Ar is a substituted or unsubstituted C6-C50 bivalent aromatic group; The substituted substituent in Ar is selected from halogen, C1-C5 linear or branched alkyl, C2-C5 linear or branched alkenyl, C2-C5 linear or branched alkynyl; Z is a substituted or unsubstituted C6-C18 bivalent aromatic group, a substituted or unsubstituted C1-C20 bivalent alkyl, a substituted or unsubstituted C3-C30 bivalent cycloalkyl, the substituted substituent in Z is selected from halogen, C1-C5 linear or branched alkyl; R is a substituted or unsubstituted C6to C30arylene group, a substituted or unsubstituted C3to C20cycloalkyl group, a substituted or unsubstituted C2to C10straight chain or branched alkenyl group; the substituents of said substitution in R are selected from the group consisting of halogen, C1to C5straight chain or branched alkyl, C2to C5straight chain or branched alkenyl, C2to C5straight chain or branched alkynyl, phenyl, naphthyl, wherein R1and R2are independently selected from the group consisting of halogen, C1to C5straight chain or branched alkyl.

2. The resin composition according to claim 1, characterized by said divalent alicycloalkyl is selected from the group consisting of: et al. Preferably, said divalent aryl group is selected from: Preferably, the divalent aromatic group is selected from one or a combination of at least two of the following:

3. The resin composition according to claim 1 or 2, characterized by The epoxy resin comprises any one or a combination of at least two of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a dicyclopentadiene type epoxy resin, a biphenyl type epoxy resin, a phenolic epoxy resin, a naphthalene-containing epoxy resin, a phosphorus-containing epoxy resin, an alicyclic epoxy resin, an isocyanate-modified epoxy resin, and a silicone-modified epoxy resin; Preferably, the carbodiimide compound is selected from any one or a combination of at least two of a carbodiimide compound containing an aliphatic structure or an aromatic structure; Preferably, the thermoplastic resin comprises any one or a combination of at least two of a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyamide-imide resin, a polyether-imide resin, a polysulfone resin, a polyether sulfone resin, a polyphenylene ether resin, a polycarbonate resin, a polyether ether ketone resin, a polyester resin, and an acrylic resin.

4. The resin composition according to any one of claims 1 to 3, characterized by The resin composition comprises the following components in the following weight parts: (A) an epoxy resin 10-30 parts by weight, (B) an active ester compound 5-20 parts by weight, (C) a carbodiimide compound 1-15 parts by weight, and (D) a thermoplastic resin 1-20 parts by weight.

5. The resin composition according to any one of claims 1 to 4, characterized in that, The resin composition further comprises (E) an inorganic filler; Preferably, the inorganic filler comprises any one or a combination of at least two of silicon dioxide, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica; Preferably, the content of the inorganic filler in the resin composition is 10-80 parts by weight; Preferably, the average particle size of the inorganic filler is 0.01 microns to 3 microns; Preferably, the resin composition further comprises a curing accelerator; Preferably, the curing accelerator is any one or a combination of at least two of pyridine-based, imidazole-based or phosphonium salt-based accelerators, preferably 4-dimethylaminopyridine and / or 1-benzyl 2-phenylimidazole; Preferably, the content of the curing accelerator in the resin composition is 0.01 to 0.5 parts by weight; Preferably, the resin composition further comprises an organic filler; Preferably, the organic filler comprises any one or a combination of at least two of polytetrafluoroethylene particles, polyurethane microparticles, rubber particles, polyamide microparticles, and silicone particles; Preferably, the content of the organic filler in the resin composition is 5 to 20 parts by weight.

6. A resin glue solution, characterized by, It is obtained by dissolving or dispersing the resin composition according to any one of claims 1 to 5 in a solvent.

7. A build-up film, characterized by, The build-up adhesive film comprises a release film and a resin composition according to any one of claims 1 to 5 attached to the release film by coating and drying; Preferably, the copper foil peeling strength of the build-up adhesive film after copper plating is 6.1 to 6.9 N / cm; Preferably, the surface roughness of the build-up adhesive film after debonding is 65 to 94 nm.

8. A resin-coated copper foil, characterized in that, The resin-coated copper foil comprises a copper foil and a resin layer attached to the copper foil by coating and drying, the resin layer being composed of the resin composition according to any one of claims 1 to 5.

9. A prepreg, characterized by, The prepreg comprises a reinforcing material and the resin composition according to any one of claims 1 to 5 attached to the reinforcing material.

10. A circuit substrate, characterized by comprising: The circuit substrate comprises at least one of the build-up adhesive film according to claim 7, or the resin-coated copper foil according to claim 8, or the prepreg according to claim 9.

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