Resin composition and application thereof

Abstract

The invention provides a resin composition and application thereof, the resin composition comprises (A) epoxy resin, (B) an active polyester compound, (C) a carbodiimide compound and (D) thermoplastic resin, and the active polyester compound has a structure as shown in formula (1). 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 has a deficiency in toughness and dielectric loss tangent of a cured product due to the structure itself.

[0003] Therefore, in the field, it is desired to develop a composition having a good peel strength and a cured product having a low dielectric loss tangent and a low coefficient of thermal expansion. 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 (A) an epoxy resin, (B) an active polyester compound, (C) a carbodiimide compound, (D) a thermoplastic resin,

[0007] The active polyester compound has a structure as shown in formula (1):

[0008]

[0009] wherein m is an integer of 1 to 20 (for example, 1, 2, 5, 8, 10, 12, 15, 18, or 20), and n is an integer of 0 to 20 (for example, 1, 2, 5, 8, 10, 12, 15, 18, or 20);

[0010] X1is a substituted or unsubstituted C3-C30 (e.g., C3, C4, C5, C6, C8, C10, C12, C15, C18, C20, C25, or C30) divalent aliphatic cycloalkyl, a substituted or unsubstituted C6-C50 (e.g., C6, C7, C8, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, or C50) divalent polycycloalkyl, the substituents of which are selected from the group consisting of halogen, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight chain or branched alkyl;

[0011] X2is a substituted or unsubstituted divalent aromatic group selected from the group consisting of

[0012] in combination, the divalent aromatic group can further have substituents selected from the group consisting of halogen, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight chain or branched alkyl, C2-C5 (e.g., C2, C3, C4, or C5) straight chain or branched alkenyl, C2-C5 (e.g., C2, C3, C4, or C5) straight chain or branched alkynyl;

[0013] Y 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 substituents of Y are selected from the group consisting of halogen, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight chain or branched alkyl;

[0014] Ar is a substituted or unsubstituted C6-C30 (e.g., C6, C8, C10, C12, C15, C18, C20, C25, or C30) arylene group; the substituents of Ar are selected from the group consisting of halogen, C1-C5 (e.g., C1, C2, C3, C4, or C5) straight chain or branched alkyl, C2-C5 (e.g., C2, C3, C4, or C5) straight chain or branched alkenyl, C2-C5 (e.g., C2, C3, C4, or C5) straight chain or branched alkynyl,

[0015]

[0016] wherein R1and R2are independently 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.

[0017] In the present application, the resin composition contains the active polyester compound having the specific structure, which has excellent dielectric properties and toughness, while balancing the performance in terms of CTE (coefficient of thermal expansion), and the resin composition containing the active polyester compound has good peel strength, low dielectric loss factor, low coefficient of thermal expansion, and good toughness after curing, and can sufficiently meet the application requirements of high-performance circuit substrates or build-up adhesive films.

[0018] In the present application, the divalent monoaliphatic cycloalkyl group can be exemplified by: and the like.

[0019] The divalent polyaliphatic cycloalkyl group can be exemplified by:

[0020] and the like.

[0021] In the present application, the short straight line on one side or both sides of the group structure represents the access bond of the group, and does not represent a methyl group. In the following description referring to the same, the same meaning is intended.

[0022] In the present application, 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., -O-, -S-, a carbonyl group, a sulfone group, an alkylene group, a cycloalkylene group, or an arylenealkylene group, etc.). In the following description referring to the same, the same meaning is intended.

[0023] In the present application, the number of carbon atoms in the group is defined in a range, which means that the number of carbon atoms in the group can be selected as any integer within the defined range, for example, C3-C30 means that the number of carbon atoms can be 3, 6, 8, 10, 12, 15, 18, 20, 25, or 30, etc.; C6-C18 means that the number of carbon atoms can be 6, 8, 10, 12, 14, 15, 16, or 18, etc.; C1-C5 means that the number of carbon atoms can be 1, 2, 3, 4, or 5; C1-C30 means that the number of carbon atoms can be 1, 3, 6, 8, 10, 12, 15, 18, 20, 25, or 30, etc.; and the like.

[0024] In the present application, the method for preparing the active polyester compound includes reacting a diol compound having an alicyclic alkane structure as shown in Formula A1, a diacyl compound having a structure as shown in Formula A2, and a monophenol compound having a structure as shown in Formula A3 to obtain the active polyester compound.

[0025] HO-X1-OH

[0026] Formula A1;

[0027]

[0028] Ar-OH

[0029] Formula A3;

[0030] Y1 is selected from halogen or hydroxyl.

[0031] In the present application, the molar ratio of the diacyl compound to the diol compound having an alicyclic alkane structure is 1:(0.5-0.95), such as 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 diol compound having an alicyclic alkane structure is preferably 1:(0.55-0.8), such as 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.

[0032] In the present application, the molar ratio of the diacyl compound to the monophenol 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 monophenol 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.

[0033] In the present application, the diacyl compound is 1 mol, and the sum of the hydroxyl groups in the alicyclic structure-containing diol compound and the monophenol compound is 2 mol in theory. The diacyl compound is in excess relative to the alicyclic structure-containing diol compound, the reaction of the alicyclic structure-containing diol compound and the diacyl compound plays a role in chain extension, and the monophenol compound is a capping agent and plays a role in terminating chain extension. The inventors have found that, If O-R is an aryloxy structure, the formed aryl ester group can crosslink with the epoxy group, otherwise, if O-R is an alkoxy structure, the formed alcohol ester group cannot crosslink with the epoxy group. The introduction of linear or branched alcohol ester groups in the active polyester compound has a significant effect on reducing the dielectric properties and improving the toughness of the resin, but the introduction of flexible segments causes the CTE of the cured product to deteriorate significantly, and cannot form a reaction crosslinking point, further exacerbating this deterioration. The active polyester compound provided by the present application effectively reduces the dielectric loss factor of the resin by introducing a certain rigid alicyclic structure into the molecular structure, compared with the introduction of linear or branched alkyl groups in the structure, the active polyester compound of the present application can be toughened while avoiding the problem of CTE deterioration of the cured product.

[0034] The raw material for preparing the active polyester compound provided by the present application can also include a diphenol compound having a structure as shown in formula A4:

[0035] HO-X2-OH

[0036] Formula A4;

[0037] In this invention, the molar ratio of the diacyl compound to the dihydroxy compound (a diol compound containing an alicyclic alkyl structure + a diphenol 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. The molar ratios of the diacyl compound and the dihydroxy compound (diol compound containing an alicyclic alkyl structure + diphenol compound) are 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.

[0038] The introduction of bisphenol compounds can form arylate groups in the intermediate units of the resin structure, that is, introduce crosslinking points that can react with epoxy groups into the intermediate chain segments of the resin. This can further improve the problem of a large coefficient of thermal expansion (CTE) caused by the lack of crosslinking points with epoxy groups in the intermediate chain segments. This invention does not impose any particular limitation on the molar ratio of the diol compound to the bisphenol compound. However, considering the need for lower dielectric properties or toughening, the proportion of the bisphenol compound should not be too high. Preferably, the molar ratio of the bisphenol compound to the diol compound is 1:(1-20), for example, 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, 1:15, 1:18, 1:19, or 1:20, etc.

[0039] In this invention, by combining a diol compound having an alicycloalkane structure as shown in Formula A1, a diphenol compound having a structure as shown in Formula A4, a diacyl compound having a structure as shown in Formula A2, and a monophenol compound having a structure as shown in Formula A3, the prepared active polyester compound exhibits excellent dielectric properties and toughness, while balancing CTE performance. The resin composition containing the active polyester compound exhibits excellent dielectric properties and adhesion after curing, which can fully meet the application requirements of high-performance circuit boards or multilayer adhesive films.

[0040] Preferably, the temperature of the reaction 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, and specific point values between the above-mentioned point values, the present application does not exhaustively list the specific point values included in the range for the sake of brevity and simplicity.

[0041] Preferably, the reaction is carried out in the presence of a basic catalyst.

[0042] Preferably, the basic catalyst includes an inorganic basic compound and / or an organic base; the inorganic basic compound includes 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 includes 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 hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.

[0043] Preferably, the reaction is carried out in a protective atmosphere, which is preferably nitrogen or argon.

[0044] Preferably, the reaction is carried out in the presence of a solvent.

[0045] 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, and exemplarily includes, but is not limited to, any one or a combination of at least two of 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 the solvent can be appropriately adjusted depending on the different solubility of the raw materials and the product, so that each of the raw materials and the product can be dissolved in the solvent, preferably 3 to 15 times, 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, etc. of the sum of the mass of each of the raw materials.

[0046] Preferably, the reaction further includes post-treatment of the product after completion.

[0047] Preferably, the method of post-treatment includes filtration, water washing, concentration, extraction, recrystallization, or column chromatography, etc. to achieve separation and purification of the active polyester compound.

[0048] Preferably, the epoxy resin includes any one or a combination of two or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol-aldehyde epoxy resin, naphthalene-containing epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, isocyanate-modified epoxy resin, silicone-modified epoxy resin.

[0049] Preferably, the carbodiimide compound is selected from any one or a combination of two or more of carbodiimide compounds containing aliphatic structure or aromatic structure.

[0050] Preferably, the thermoplastic resin includes any one or a combination of two or more of phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide-imide resin, polyether-imide resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, acrylic resin.

[0051] Preferably, the resin composition includes the following weight parts of each component: (A) epoxy resin 10-30 parts by weight (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) active polyester compound 5-20 parts by weight (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) carbodiimide compound 1-15 parts by weight (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), (D) thermoplastic resin 1-20 parts by weight (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).

[0052] Preferably, the resin composition further includes (E) inorganic filler.

[0053] Preferably, the inorganic filler includes any one or a combination of two or more of silicon dioxide, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica.

[0054] Preferably, the content of the inorganic filler in the resin composition is 10 to 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.

[0055] Preferably, the average particle size of the inorganic filler is 0.01 to 3 micrometers, for example, 0.01 micrometer, 0.05 micrometer, 0.1 micrometer, 0.5 micrometer, 1 micrometer, 1.3 micrometer, 1.5 micrometer, 1.8 micrometer, 2 micrometer, 2.3 micrometer, 2.5 micrometer, 2.8 micrometer, or 3 micrometer.

[0056] Preferably, the resin composition further comprises a curing accelerator.

[0057] Preferably, the curing accelerator is any one or a combination of at least two of a pyridine-based, imidazole-based, or phosphonium salt accelerator, preferably 4-dimethylaminopyridine and / or 1-benzyl 2-phenylimidazole.

[0058] Preferably, the content of the curing accelerator in the resin composition is 0.01 to 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.

[0059] Preferably, the resin composition further comprises an organic filler.

[0060] Preferably, the organic filler comprises any one or a combination of at least two of polytetrafluoroethylene particles, polyurethane microparticles, rubber particles, polyamide microparticles, or silicone particles.

[0061] Preferably, the content of the organic filler in the resin composition is 5 to 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.

[0062] In the present application, the term "comprising" means that the resin composition can further comprise other components in addition to the components described, and these other components impart different properties to the resin composition. In addition, the term "comprising" in the present application can be replaced by the closed terms "consisting of" or "consisting of".

[0063] In another aspect, the present application provides a resin glue solution obtained by dissolving or dispersing the resin composition described above in a solvent.

[0064] As the solvent in the present application, there is no particular limitation, and as specific examples, there can be mentioned alcohols such as methanol, ethanol, butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, butyl carbitol, ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, mesitylene, esters such as ethoxyethyl acetate, ethyl acetate, nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone. The above-mentioned solvents can be used singly or in a mixture of two or more kinds, and aromatic hydrocarbon solvents such as toluene, xylene, mesitylene are preferably used in combination with ketone solvents such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone. The amount of the solvent used can be selected by the person skilled in the art according to his experience, so that the resulting resin solution has a viscosity suitable for use.

[0065] On the other hand, the present application provides a build-up adhesive film comprising a release film and a resin composition as described above attached to the release film by coating and drying.

[0066] In the present application, the copper foil peeling strength after copper plating of the build-up adhesive film is 5.9-7.1 N / cm, for example 6.1 N / cm, 6.2 N / cm, 6.5 N / cm, 6.8 N / cm or 7 N / cm.

[0067] Preferably, the surface roughness after debonding of the build-up adhesive film is 61-98 nm, for example 65 nm, 70 nm, 80 nm, 90 nm or 95 nm.

[0068] On the other hand, the present application provides a resin-coated copper foil comprising a copper foil and a resin layer attached to the copper foil by coating and drying, the resin layer being composed of a resin composition as described above.

[0069] Preferably, the thickness of the resin layer of the resin-coated copper foil is 5-300 μm, for example 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, preferably 10-200 μm; further preferably 20-100 μm.

[0070] Preferably, the thickness of the copper foil is 1-105 μm, for example 1 μm, 3 μm, 5 μm, 8 μm, 10 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or 105 μm, preferably 3-35 μm; further preferably 5-18 μm.

[0071] In another aspect, the present application provides a prepreg including a reinforcing material and the resin composition as described above attached to the reinforcing material.

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

[0073] In another aspect, the present application provides a circuit substrate including at least one of the build-up film as described above, or the resin-coated copper foil as described above, or the prepreg as described above.

[0074] Compared with the prior art, the present application has the following advantages:

[0075] The resin composition of the present application has good peel strength, low dielectric loss factor, low coefficient of thermal expansion and good toughness after curing, and can fully meet the application requirements of high-performance circuit substrates or build-up films. BRIEF DESCRIPTION OF DRAWINGS

[0076] Figure 1 An infrared spectrum of the active polyester compound provided for Preparation Example 1;

[0077] Figure 2 An ultra-high performance polymer chromatogram of the active polyester compound provided for Preparation Example 1;

[0078] Figure 3 An infrared spectrum of the active polyester compound provided for Preparation Example 2;

[0079] Figure 4 An ultra-high performance polymer chromatogram of the active polyester compound provided for Preparation Example 2. DETAILED DESCRIPTION

[0080] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application, and should not be regarded as specific limitations of the present application.

[0081] In the following detailed description of the present application, some materials involved are as follows:

[0082] (1) Epoxy resin

[0083] Biphenyl-type epoxy resin, NC3000H, Japan Chemicals;

[0084] Bisphenol A-type epoxy resin, NPES-901, South Asia Electronic Materials Co., Ltd.

[0085] (2) Active polyester compound

[0086] Dicyclopentadiene type active ester resin, HPC-8000-65T, DIC, Japan, active ester equivalent weight is about 223 g / eq., the structural formula is as follows:

[0087]

[0088] X represents naphthyl, j is 0 or 1, k is 0 or 1, and n is 0.25-1.25.

[0089] (3) Thermoplastic resin

[0090] Phenoxy resin, PKHH, Inchem Co., Ltd.;

[0091] Polyether sulfone resin, 3000RP, SOLVAY Co., Ltd.

[0092] (4) Carbodiimide compound

[0093] V-07, Nippon Shokubai Co., Ltd.;

[0094] V-03, Nippon Shokubai Co., Ltd.

[0095] (5) Inorganic filler

[0096] Silica, SO-C1, Japan admatechs;

[0097] Silica, SO-C2, Japan admatechs.

[0098] (6) Curing accelerator

[0099] DMAP, 4-dimethylaminopyridine, Guangrong Chemical.

[0100] Preparation Example 1

[0101] An active polyester compound K-1, the preparation method comprising the following steps:

[0102] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 1,4-cyclohexanediol 58.1 g (0.5 mol), isophthaloyl chloride 203 g (1.0 mol), 1-naphthol 144.2 g (1.0 mol) and dichloromethane 2100 g were put, and the system was subjected to nitrogen replacement under reduced pressure while being stirred to dissolve. The reaction system was controlled below 30°C, and then triethylamine 232.3 g (2.3 mol) was added dropwise for 3 h, and after the dropwise addition was completed, stirring was continued for 2 h. After the reaction was completed, deionized water was added and stirred for 15 min, and the water layer was removed by standing and separating, and the dichloromethane layer obtained was repeatedly washed with water until the pH of the water layer was 7. Finally, active polyester compound K-1 was obtained by drying under heating and reduced pressure.

[0103] The active polyester compound K-1 provided in this preparation example has an active ester group equivalent of 332 g / eq. as calculated and measured from the feeding ratio.

[0104] Preparation Example 2

[0105] An active polyester compound K-2, the preparation method of which includes the following steps:

[0106] In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 72.1 g of hydrogenated bisphenol A (0.3 mol), a diphcnol compound 132 g (0.4 mol, hydroxyl group equivalent 165 g / eq.) of a dicyclopentadiene and phenol polyaddition reaction, isophthaloyl chloride 203 g (1.0 mol), 1-naphthol 86.5 g (0.6 mol), and dichloromethane 1730 g were charged, and the system was replaced with nitrogen under reduced pressure while being dissolved with stirring. The reaction system was controlled to be below 35°C, and then triethylamine 222.2 g (2.2 mol) was added dropwise over 3 h, and stirring was continued for 2 h after the end of the dropwise addition. After the completion of the reaction, deionized water was added and stirred for 15 min, and the water layer was removed by standing and separating, and the dichloromethane layer obtained was subjected to water washing until the pH of the water layer became 7. Finally, active polyester compound K-2 was obtained by drying under heating and reduced pressure.

[0107] The active polyester compound K-2 provided in this preparation example has an active ester group equivalent of 300 g / eq. as calculated and measured from the feeding ratio.

[0108] Preparation Example 3

[0109] An active polyester compound K-3, the preparation method of which includes the following steps:

[0110] In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 72.1 g of hydrogenated bisphenol A (0.3 mol), a diphcnol compound 132 g (0.4 mol, hydroxyl group equivalent 165 g / eq.) of a dicyclopentadiene and phenol polyaddition reaction, isophthaloyl chloride 203 g (1.0 mol), 1-naphthol 86.5 g (0.6 mol), and dichloromethane 1730 g were charged, and the system was replaced with nitrogen under reduced pressure while being dissolved with stirring. The reaction system was controlled to be below 35°C, and then triethylamine 222.2 g (2.2 mol) was added dropwise over 3 h, and stirring was continued for 2 h after the end of the dropwise addition. After the completion of the reaction, deionized water was added and stirred for 15 min, and the water layer was removed by standing and separating, and the dichloromethane layer obtained was subjected to water washing until the pH of the water layer became 7. Finally, active polyester compound K-2 was obtained by drying under heating and reduced pressure.

[0111] The active polyester compound K-3 provided in this preparation example has an active ester group equivalent of 995 g / eq. as calculated and measured from the feeding ratio.

[0112] Preparation Example 4

[0113] An active polyester compound K-4, the preparation method comprising the steps of:

[0114] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 1,4-cyclohexanediol 11.6 g (0.1 mol), 154.2 g of diallyl bisphenol A (0.5 mol), isophthaloyl chloride 203 g (1.0 mol), 1-naphthol 115.4 g (0.8 mol) and toluene 3000 g were charged, and the system was replaced with nitrogen under reduced pressure while stirring to dissolve. The reaction system was controlled to be below 60°C, and 20% sodium hydroxide aqueous solution 460 g (2.3 mol) was added dropwise over 3 h, and stirring was continued for 1 h after the completion of the dropwise addition. After the completion of the reaction, the water layer was removed by standing and separating. Deionized water was added to the obtained toluene layer and stirred for 15 min, and the water layer was removed by standing and separating, and the toluene layer obtained was subjected to the water washing operation repeatedly until the pH of the water layer became 7. Finally, active polyester compound K-4 was obtained by drying under heating and reduced pressure.

[0115] The active polyester compound K-4 provided in this Preparation Example was calculated and measured to have an active ester group equivalent of 228 g / eq.

[0116] Preparation Example 5

[0117] An active polyester compound K-5, the preparation method comprising the steps of:

[0118] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 48.1 g of hydrogenated bisphenol A (0.2 mol), 2,5-dihydroxyphenyl diphenyl phosphine oxide 124.2 g (0.4 mol), adipoyl chloride 183 g (1.0 mol), 1-naphthol 115.4 g (0.8 mol) and dichloromethane 2850 g were charged, and the system was replaced with nitrogen under reduced pressure while stirring to dissolve. The reaction system was controlled to be below 35°C, and triethylamine 232.3 g (2.3 mol) was added dropwise over 3 h, and stirring was continued for 2 h after the completion of the dropwise addition. After the completion of the reaction, deionized water was added and stirred for 15 min, and the water layer was removed by standing and separating, and the dichloromethane layer obtained was subjected to the water washing operation repeatedly until the pH of the water layer became 7. Finally, active polyester compound K-5 was obtained by drying under heating and reduced pressure.

[0119] The active polyester compound K-5 provided in this Preparation Example was calculated and measured to have an active ester group equivalent of 249 g / eq.

[0120] Comparative Preparation Example 1

[0121] An active polyester compound L-1, its preparation method is referred to synthesis example 1 and example 1 in patent CN115210213A, the structure general formula is shown as formula A5, and the active ester group equivalent is 319 g / eq.

[0122]

[0123] Performance test of the active polyester compound:

[0124] (1) Structure characterization: the active polyester compounds provided by preparation examples 1-5 are characterized by infrared testing by using a Fourier infrared spectrometer (FT-IR).

[0125] For example, the infrared spectrum of the active polyester compound K-1 provided by preparation example 1 is shown in Figure 1 From Figure 1 it can be known that the active polyester compound K-1 has a strong characteristic absorption peak of alcohol ester group at a wave number of 1715 cm -1 , a characteristic absorption peak of phenolic ester group at 1735 cm -1 , and no strong absorption peak of alcohol hydroxyl group or phenolic hydroxyl group near 3400 cm -1 , which indicates that the alcohol hydroxyl group and the phenolic hydroxyl group have been esterified; the infrared spectrum of the active polyester compound K-2 provided by preparation example 2 is shown in Figure 3 From Figure 3 it can be known that the active polyester compound K-2 has strong characteristic absorption peaks of alcohol ester group and phenolic ester group at wave numbers of 1716 cm -1 and 1736.5 cm -1 respectively, and the absorption peaks of alcohol hydroxyl group or phenolic hydroxyl group near 3400 cm -1 disappear basically, which indicates that the alcohol hydroxyl group and the phenolic hydroxyl group have been esterified.

[0126] (2) Molecular weight test: the weight average molecular weight M w of the active polyester compounds provided by preparation examples 1-5 is determined by using an ultra-high performance polymer chromatography system (APC) of Waters company.

[0127] For example, the ultra-high performance polymer chromatogram (APC chart) of the active polyester compound K-1 provided by preparation example 1 is shown in Figure 2 From Figure 2 it can be known that the weight average molecular weight M w of the active polyester compound K-1 is 1881; the ultra-high performance polymer chromatogram (APC chart) of the active polyester compound K-2 provided by preparation example 2 is shown in Figure 4 From Figure 4 it can be known that the weight average molecular weight M w of the active polyester compound K-2 is 2307.

[0128] Example 1

[0129] A resin composition comprising the following components in parts by weight: 20 parts by weight of epoxy resin NC3000H, 15 parts by weight of active polyester 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-C1, and 0.5 parts by weight of curing accelerator DMAP.

[0130] A laminated adhesive film and a circuit substrate comprising the resin composition are prepared as follows:

[0131] (1) The components of the resin composition are mixed with butanone in the amounts specified in the foregoing formulation to produce a resin adhesive solution having a solid content of 65%; the resin adhesive solution is coated on a release film, and after drying, the coated film is baked in an oven at 100°C for 5 min to obtain a laminated adhesive film of a semi-cured resin layer having a thickness of 40 μm;

[0132] (2) The laminated adhesive film obtained in step (1) and the roughened inner layer PCB are pressed together using a vacuum laminating machine at 100°C for 1 min at a pressure of 0.5 MPa, and then baked at 100°C and 180°C for 30 min each, the release film is removed and the surface is treated to remove the adhesive, copper plating is performed, and a circuit substrate with circuit lines is formed.

[0133] Examples 2-5 and Comparative Examples 1-2

[0134] A resin composition, a laminated adhesive film and a circuit substrate comprising the resin composition, the components and contents of the resin composition are shown in Table 1, wherein the amount of each component is in parts by weight of solid content, and the laminated adhesive film and the circuit substrate are prepared in the same manner as in Example 1.

[0135] The laminated adhesive films and circuit substrates provided in Examples 1-5 and Comparative Examples 1-2 are tested for the following properties:

[0136] (1) Surface roughness Ra

[0137] The lamination adhesive film was pressed on the surface of the core board, and cured in an oven at 180°C for 30 min to obtain a pre-cured lamination adhesive film. The lamination adhesive film was subjected to the following Desmear treatment: soaking in ethylene glycol ether, aqueous sodium hydroxide solution (MV Sweller, ATOTECH) at 70°C for 10 min - water washing with deionized water for 2 min - soaking in potassium permanganate solution (MV P Etch, ATOTECH) at 80°C for 30 min - water washing with deionized water for 2 min - soaking in acidic aqueous solution (MV Reduction Cleaner, ATOTECH) at 50°C for 5 min to obtain a roughened lamination adhesive film, and the surface roughness Ra of the roughened lamination adhesive film was tested using a laser confocal instrument (OLYMPUS).

[0138] (2) Copper foil peel strength PS

[0139] The roughened lamination adhesive film was subjected to the following copper plating, electroplating and post-curing treatment: soaking in chemical copper solution (MV TP1, ATOTECH) for 20 min - electroplating copper to a thickness of 25 μm - curing in an oven at 190°C for 60 min, and the copper plating adhesion of the lamination adhesive film was tested using a copper foil peel strength tester according to the method of IPC-TM-650 2.4.9.

[0140] (3) Toughness (elongation)

[0141] After the lamination adhesive film was cured at 190°C for 60 min, the elongation was calculated by the length at break and the initial length of the sample using the dynamic mechanical analysis (DMA) method, 150°C constant temperature for 5 min, pre-load 0.01 N, 3 N / min to 17.5 N / min.

[0142] (4) Dielectric loss factor D f

[0143] The D of the lamination adhesive film at 10 GHz was determined according to the SPDR method specified in the standard IEC61189-2-721. f .

[0144] (5) Coefficient of thermal expansion CTE: The CTE of the lamination adhesive film was determined according to the TMA test method specified in IPC-TM-650 2.4.24.5.

[0145] Table 1

[0146]

[0147] As can be seen from Table 1, the lamination adhesive film and the circuit board prepared from the resin composition of Examples 1-5 of the present application have good peel strength, low dielectric loss factor, low coefficient of thermal expansion and good toughness.

[0148] The molecular structure of the active polyester compound L-1 used in Comparative Example 1 does not contain a rigid alicyclic alkane structure, resulting in a CTE and D f variation of the laminate adhesive film.

[0149] The molecular structure of the dicyclopentadiene type active ester resin used in Comparative Example 2 does not contain an alcohol ester group, resulting in a significant variation in the elongation of the laminate adhesive film.

[0150] The applicant states that the resin composition of the present application and the use thereof are illustrated by the above examples, but the present application is not limited to the above examples, i.e. it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A resin composition, characterized by comprising: The resin composition comprises (A) an epoxy resin, (B) an active polyester compound, (C) a carbodiimide compound, (D) a thermoplastic resin, The active polyester compound has a structure as shown in formula (1): wherein m is an integer of 1 to 20, and n is an integer of 0 to 20; X1 is a substituted or unsubstituted C3-C30 divalent mono-lipid cycloalkyl, a substituted or unsubstituted C6-C50 divalent multi-lipid cycloalkyl, and the substituent of the substitution is selected from halogen, C1-C5 straight chain or branched alkyl; X2is a substituted or unsubstituted divalent aromatic group selected from one or more combinations of two or more of the foregoing, the substituted divalent aromatic group having substituents selected from the group consisting of halogen, C1-C5straight or branched chain alkyl, C2-C5straight or branched chain alkenyl, C2-C5straight or branched chain alkynyl; Y is a substituted or unsubstituted C6-C18 divalent aromatic group, a substituted or unsubstituted C1-C20 divalent alkyl, a substituted or unsubstituted C3-C30 divalent cycloalkyl; the substituent of Y is selected from halogen, C1-C5 straight chain or branched alkyl; Ar is a substituted or unsubstituted C6-C30 arylene; the substituents of the substitution in Ar are selected from the group consisting of halogen, C1-C5 linear or branched alkyl, C2-C5 linear or branched alkenyl, C2-C5 linear or branched alkynyl, wherein R1and R2are independently selected from the group consisting of halogen, C1-C5 linear or branched alkyl, C2-C5 linear or branched alkenyl, C2-C5 linear or branched alkynyl.

2. The resin composition according to claim 1, characterized by said divalent mononaphthenic cycloalkyl is selected from Preferably, said divalent polyaliphatic cycloalkyl is selected from 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 amounts by weight: 10-30 parts by weight of the epoxy resin (A), 5-20 parts by weight of the active polyester compound (B), 1-15 parts by weight of the carbodiimide compound (C), and 1-20 parts by weight of the thermoplastic resin (D).

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 a pyridine-based, imidazole-based, or phosphonium salt accelerator, preferably 4-dimethylaminopyridine and / or 1-benzyl 2-phenylimidazole; Preferably, the content of the curing accelerator in the resin composition is 0.01-0.5 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 includes 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 peel strength of the copper foil after copper plating of the build-up adhesive film is 5.9 to 7.1 N / cm. Preferably, the surface roughness after debonding of the build-up adhesive film is 61 to 98 nm.

8. A resin-coated copper foil, characterized in that, The resin-coated copper foil includes 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 includes 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 includes 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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