A black halogen-free resin composition, prepreg, metal-clad laminate, and printed circuit board

Abstract

The present application provides a kind of black halogen-free resin composition, prepreg, metal foil laminated board and printed circuit board, the black halogen-free resin composition includes the following weight parts of components: (A) epoxy resin: 100 parts, (B) black silicon dioxide: 10-30 parts, (C) low dielectric curing agent: 30-100 parts, the pH of the black silicon dioxide is 6-8, sodium ion content≤300ppm.In the present application, by controlling the Na ion content and pH of black silicon dioxide, reduce the influence of acidic substances and ionic conductor on dielectric loss in black silicon dioxide, and the influence of basic substances on the moisture resistance of plate, and reduce the interface polarization effect of matrix material, reduce the moisture absorption rate of plate, so that the cured product has excellent CAF performance, low dielectric loss under the condition of guaranteeing light shielding effect and fluidity, and maintains excellent insulation performance, heat resistance and low thermal expansion coefficient.

Description

Technical Field

[0001] This invention belongs to the field of laminate technology and relates to a black halogen-free resin composition, prepreg, metal foil-coated laminate, and printed circuit board. Background Technology

[0002] Black circuit boards not only possess aesthetic appeal but also exhibit excellent thermal stability and light shielding properties, leading to their widespread use in high-end mobile phones, tablets, game consoles, and other electronic devices. With the advancement of electronic technology, the signal transmission requirements of black circuit boards in terminals are constantly increasing. As electronic products continue to evolve, circuit boards are also continuously being miniaturized, made more dense, and more reliable. This makes the application of circuit boards in electronic devices more extensive and efficient, and the application scope of black circuit boards is constantly expanding.

[0003] Currently, commonly used black colorants for copper-clad laminates include aniline black, carbon black, titanium black, and black silica. Carbon black and titanium black, due to their conductivity, result in poor insulation in copper-clad laminates. Aniline black has excellent insulation properties, but its addition reduces the heat resistance of the laminate and, containing chromium, causes environmental pollution. CN118125458B provides a black silica synthesized by calcining silane, fundamentally solving the environmental pollution and safety hazards to operators caused by the easy floating of traditional carbon black powder during processing. Although the conductivity and dispersion problems of black colorants have been solved, with the increasing demands for signal transmission in modern society, the requirements for the electrical performance of laminates are also constantly increasing. Therefore, it is necessary to find materials that can provide better performance. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide a black halogen-free resin composition, a prepreg, a metal foil laminate, and a printed circuit board.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] On one hand, the present invention provides a black halogen-free resin composition, the black halogen-free resin composition comprising the following components in parts by weight:

[0007] (A) Epoxy resin: 100 parts

[0008] (B) Black silica: 10-30 parts

[0009] (C) Low dielectric curing agent: 30-100 parts

[0010] The black silica has a pH of 6-8 (e.g., 6, 6.2, 6.5, 6.8, 7.0, 7.3, 7.5, 7.7, 7.9 or 8) and a sodium ion content ≤300ppm (e.g., 0ppm, 50ppm, 120ppm, 160ppm, 180ppm, 230ppm, 260ppm, 290ppm or 300ppm).

[0011] In this invention, by controlling the pH and Na ion content of black silica, the influence of acidic substances and ionic conductors on dielectric loss in black silica, as well as the influence of alkaline substances on the moisture and heat resistance of the board, are reduced. This reduces the impact of ion polarization and ion migration on the CAF resistance and dielectric properties of copper clad laminate, and also reduces the interfacial polarization effect of the matrix material, thereby lowering the moisture absorption rate of the board. As a result, the cured product has excellent CAF resistance and low dielectric loss, while maintaining excellent insulation properties, heat resistance, and a low coefficient of thermal expansion. At the same time, black silica also has excellent flowability, dispersibility, and light shielding effect.

[0012] Preferably, the black silica is treated with a silane-based surface treatment agent.

[0013] Preferably, the silane-based surface treatment agent is selected from isocyanate-based surface treatment agents.

[0014] Preferably, the black silica has a particle size distribution D50 of 1-5 μm (e.g., 1 μm, 1.8 μm, 2.1 μm, 2.5 μm, 3.2 μm, 3.8 μm, 4.4 μm or 5 μm) and a D100 of 7-12 μm (e.g., 7 μm, 7.8 μm, 8.6 μm, 9.2 μm, 10.1 μm, 11.2 μm or 12 μm).

[0015] In this invention, the content of the black silica relative to 100 parts by weight of epoxy resin is 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, 29 parts by weight, or 30 parts by weight.

[0016] In this invention, the epoxy resin is selected from any one or a combination of at least two of the following: difunctional epoxy resin or polyfunctional epoxy resin.

[0017] Preferably, the epoxy resin is selected from any one or a combination of at least two of the following: dicyclopentadiene type epoxy resin, dimethylphenol type phenolic epoxy resin, tetramethylbiphenyl epoxy resin, biphenyl epoxy resin, phenolic epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, C1-C6 alkyl-containing epoxy resin, MDI modified epoxy resin, naphthalene-containing epoxy resin, or epoxidized polybutadiene.

[0018] Preferably, the epoxy equivalent of the epoxy resin is 100-600 g / eq, for example 100 g / eq, 150 g / eq, 200 g / eq, 250 g / eq, 300 g / eq, 350 g / eq, 400 g / eq, 450 g / eq, 500 g / eq, 550 g / eq or 600 g / eq.

[0019] The low dielectric curing agent of the present invention is selected from one or a combination of at least two of amine curing agents, cyanate ester curing agents, reactive ester curing agents, acid anhydride curing agents or maleimide curing agents.

[0020] In this invention, the content of the low-dielectric curing agent relative to 100 parts by weight of epoxy resin is 20 parts by weight, 24 parts by weight, 30 parts by weight, 36 parts by weight, 40 parts by weight, 43 parts by weight, 49 parts by weight, 51 parts by weight, 58 parts by weight, 66 parts by weight, 71 parts by weight, 75 parts by weight, 83 parts by weight, 86 parts by weight, 90 parts by weight, 94 parts by weight, or 100 parts by weight. Using a low-dielectric curing agent can further optimize the dielectric properties of the board and improve signal integrity; however, excessive use of non-polar molecules can lead to apparent defects such as resin deficiency, affecting the wettability and reliability of the board.

[0021] Preferably, the anhydride curing agent is selected from any one or a combination of at least two of the following formulas I or II:

[0022]

[0023] Where n:x = 1:1 to 8:1 (e.g., 1:1, 2:1, 3:1, 5:1, 7:1 or 8:1).

[0024] Formula II is a copolymer resin having structural units derived from aromatic vinyl compounds and structural units derived from maleic anhydride.

[0025] Preferably, the active ester curing agent is selected from any one or a combination of at least two active esters having the structure of Formula III or Formula IV:

[0026]

[0027] In III, X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n indicates that the repeating unit is 0.25 to 1.25 (e.g., 0.25, 0.35, 0.40, 0.50, 0.55, 0.70, 0.80, 0.95, 1.15, or 1.25).

[0028]

[0029] In IV, m, n, and q are independently integers from 1 to 6 (e.g., 1, 2, 3, 4, 5, or 6), X is phenyl or naphthyl, and Y is a group consisting of the following:

[0030]

[0031] Where K is 0 or 1.

[0032] Preferably, the low dielectric curing agent includes an active ester curing agent, and the content of the active ester curing agent is 1-30 parts by weight, for example, 1 part by weight, 4 parts by weight, 10 parts by weight, 12 parts by weight, 18 parts by weight, 23 parts by weight, 26 parts by weight or 30 parts by weight.

[0033] In this invention, the black halogen-free epoxy resin composition also includes other inorganic fillers.

[0034] In this invention, the other inorganic fillers are selected from any one or a combination of at least two of the following: aluminum hydroxide, silicon dioxide, talc, boehmite, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, montmorillonite, clay, or mica.

[0035] Preferably, the median particle size D50 of the inorganic filler is 1.1-2.8 μm (e.g., 1.1 μm, 1.3 μm, 1.6 μm, 1.9 μm, 2.0 μm, 2.5 μm or 2.8 μm), and the maximum particle size D100 is 4.0-12.0 μm (e.g., 4.0 μm, 4.8 μm, 5.9 μm, 6.3 μm, 7.6 μm, 8.8 μm, 9.5 μm, 10.1 μm, 11.2 μm and 12.0 μm).

[0036] Preferably, the inorganic filler may be in the form of flakes, rods, spheres, hollow spheres, granules, fibers, or plates.

[0037] In this invention, the content of the other inorganic fillers is 30-200 parts by weight relative to 100 parts by weight of epoxy resin, for example 30 parts by weight, 60 parts by weight, 100 parts by weight, 130 parts by weight, 180 parts by weight or 200 parts by weight.

[0038] Preferably, the black halogen-free epoxy resin composition further includes a phosphorus-containing flame retardant.

[0039] In this invention, the phosphorus-containing flame retardant is selected from reactive phosphorus-containing flame retardants and / or additive phosphorus-containing flame retardants.

[0040] Preferably, the reactive phosphorus-containing flame retardant is a compound containing phosphorus elements and reactive groups.

[0041] Preferably, the reactive groups include amino and / or phenolic hydroxyl groups, etc.

[0042] Preferably, the reactive phosphorus-containing flame retardant includes phosphorus-containing phenolic resin.

[0043] Preferably, the additive phosphorus-containing flame retardant includes any one or a combination of at least two of the following: tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, phosphazene compounds, or phosphate esters.

[0044] In this invention, the amount of the additive phosphorus-containing flame retardant added relative to 100 parts by weight of epoxy resin is 10-30 parts by weight, for example, 10 parts by weight, 12 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, 21 parts by weight, 24 parts by weight, 27 parts by weight, or 30 parts by weight. Phosphorus-containing flame retardants can provide good dielectric properties and flame retardancy, but excessive addition can lead to an increase in the coefficient of thermal expansion.

[0045] In this invention, the black halogen-free resin composition further includes a curing accelerator.

[0046] Preferably, the curing accelerator is selected from any one or a combination of at least two of imidazole accelerators, pyridine curing agents, Lewis acid curing agents, amine curing agents, phenolic curing agents, cyanate ester compounds, or reactive ester compounds.

[0047] On the other hand, the present invention provides a resin adhesive obtained by dissolving or dispersing the black halogen-free resin composition as described above in a solvent.

[0048] On the other hand, the present invention provides a prepreg comprising the black halogen-free resin composition as described above.

[0049] Preferably, the prepreg comprises a base material and a black halogen-free resin composition as described above, adhered to the base material.

[0050] Preferably, the prepreg comprises a base material and a black halogen-free resin composition as described above, which is attached to the base material after impregnation and drying.

[0051] On the other hand, the present invention provides a metal foil laminate, the metal foil laminate comprising at least one prepreg as described above and a metal foil covering one or both sides of the laminated prepreg.

[0052] On the other hand, the present invention provides a printed circuit board comprising at least one of the prepreg as described above or the metal foil laminate as described above.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] In this invention, by controlling the Na ion content of black silicon dioxide and by controlling the pH, the CAF resistance of the board is improved and the dielectric properties are further optimized while ensuring the light shielding effect and flowability. This meets the requirements of reliability and high-speed signal transmission in PCB applications and broadens the application fields of black copper clad laminates. Detailed Implementation

[0055] 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.

[0056] The materials and grade information involved in the following embodiments and comparative examples are as follows:

[0057] A1: CNE type epoxy resin (o-cresol epoxy resin): NPCN-704, epoxy equivalent: 200-220g / eq, Nan Ya Resin;

[0058] A2: NC3000H, biphenyl type epoxy resin, epoxy equivalent: 290-300g / eq, Nippon Kayaku;

[0059] A3: Bisphenol A epoxy resin, KE-8128, equivalent weight: 185-190g / eq, KOLON, South Korea;

[0060] B1: Black silica, SE0067, pH 5.3, Na ion content 534ppm, D50: 2.5-3.0μm, no surface treatment, Suzhou Jinyi;

[0061] B2: Black silica, pH 6.5, Na ion content 89ppm, D50: 2.2-2.8μm, treated with isocyanate-based silane coupling agent, self-made;

[0062] B3: Black silica, SE009Z, pH 6.4, Na ion content 289ppm, D50: 3.8-4.4μm, no surface treatment, Suzhou Jinyi;

[0063] B4: Black silica, pH 6.4, Na ion content 278ppm, D50: 3.8-4.4μm, treated with epoxy surface treatment agent, self-made;

[0064] B5: Black silica, DQM5010, pH 7.6, Na ion content 226ppm, D50: 1.0-1.8μm, no surface treatment, Suzhou Jinyi;

[0065] B6: Black silica, pH 8.5, Na ion content 198ppm, D50: 1.8-2.5μm, no surface treatment, homemade;

[0066] C1: Styrene-maleic anhydride copolymer: SMA-EF30, CrayValley, USA;

[0067] C2: Active ester curing agent: DFE-617L, Sichuan Dongcai;

[0068] C3: Bisphenol A type benzoxazine, LZ8290, HUNSTMAN;

[0069] D1: Phosphorus-containing phenolic resin: XZ92741, Dow, USA;

[0070] D2: Phosphate ester flame retardant: PX200, Daihachi, Japan;

[0071] E: Silica powder: DS2032A, D100 is 11μm, Jiangsu Lianrui;

[0072] F: Curing accelerator: 2-ethyl-4-methylimidazole, Shikoku Kasei.

[0073] Preparation example:

[0074] (1) Synthesis of B2 isocyanate-modified black silica

[0075] 5 kg of black silica NQL7030 was put into a high-speed mixer and heated to 110°C. The hydrolyzed mixture (30 g KBM-803, 30 g ethanol, and 60 g pure water hydrolyzed for 30 min) was added and stirred for 20 min to obtain epoxy-treated black silica B2.

[0076] (2) Synthesis of B4 epoxy-modified black silica

[0077] 5 kg of black silica SE009Z was added to a high-speed mixer. The equipment was heated to 110°C. A hydrolyzed mixture (30 g KBM-403, 30 g ethanol, and 60 g pure water hydrolyzed for 30 min) was added and stirred for 20 min to obtain epoxy-treated black silica B4.

[0078] (3) Synthesis of B6 black silica

[0079] 1000g of deionized water was placed in a reactor equipped with a stirrer at room temperature. Stirring was started, and 180g of methyltrimethoxysilane and a small amount of acetic acid were added by weight to adjust the pH to approximately 5. After the methyltrimethoxysilane dissolved, 80g of 5% ammonia solution was added and stirred for 10 seconds, then stirring was stopped. After standing for 1 hour, the mixture was filtered and dried to obtain spherical polysiloxane powder. The spherical polysiloxane powder was placed in a muffle furnace, and nitrogen gas was introduced at a flow rate of 300mL / min. Under a nitrogen atmosphere, the furnace temperature was increased to 850℃ at a rate of 5℃ / min and held for 10 hours to heat-treat the particles, causing the organic groups in the particles to thermally decompose into carbon elements, yielding black silica B6 with a pH of 8.5, a Na ion content of 198ppm, and a D50 of 1.8-2.5μm.

[0080] The resin compositions provided in the examples and comparative examples were used to prepare laminates for printed circuit boards according to the following method, and the performance of the prepared laminates was tested. The components of the resin composition and methyl ethyl ketone were placed in a container, stirred evenly to prepare an adhesive, and the adhesive was adjusted to a solid content of 60% using a solvent. The adhesive was impregnated with 2116 electronic-grade fiberglass cloth and baked in an oven to form a prepreg.

[0081] A laminate is made by bonding six prepreg sheets together through heating and pressurization, covering the top and bottom with metal foil, placing a smooth steel plate and a plastic pad outside the top and bottom metal foils, and pressing it in a laminator.

[0082] The lamination operation conditions are as follows: when the temperature is 80-140℃, the heating rate is controlled at 1.5-2.5℃ / min; when the outer layer material temperature is 80-100℃, full pressure is applied at around 350psi; during curing, the material temperature is controlled above 200℃ and kept at that temperature for more than 100min.

[0083] The formulation composition and physical property data of each embodiment are shown in Table 1, and the formulation composition and physical property data of the comparative examples are shown in Table 2.

[0084] Table 1

[0085]

[0086]

[0087] Table 2

[0088]

[0089]

[0090] The performance test items and specific test methods are as follows:

[0091] (1) Glass transition temperature: Differential scanning calorimetry (DSC) was used to determine the temperature according to the DSC method specified in 2.4.25 of IPC-TM-650.

[0092] (2) Dielectric constant (10 GHz): The dielectric constant was determined according to the method specified in section 2.5.5.9 of IPC-TM-650 using the SPDR method.

[0093] (3) CTE-Z: The determination shall be performed using a thermomechanical analyzer in accordance with the method specified in IPC-TM-650 2.4.24.

[0094] (4) Surface resistivity: Tested according to IPC-TM650 2.5.17.1;

[0095] (5) Volume resistivity: Tested according to IPC-TM650 2.5.17.1;

[0096] (6) CAF resistance: tested according to IPC-TM650 2.6.25;

[0097] (7) Light transmittance: Tested using a light transmittance meter.

[0098] (8) Water absorption rate: After etching the copper foil on the surface of the copper-clad laminate, the substrate is dried and weighed. Then the substrate is placed in a pressure cooker and treated for two hours at 120°C and 150KPa. After taking it out and wiping it dry with a dry cloth, the weight of the sample after water absorption is weighed. The PCT water absorption rate is (weight after cooking - weight before cooking) / weight before cooking.

[0099] (9) T288: The determination shall be performed using a thermomechanical analyzer in accordance with the method specified in IPC-TM-650 2.4.24.1.

[0100] (10) Flammability: Determined according to the vertical burning method of UL-94 standard.

[0101] (11) PCT limit: After being treated at 85°C and 85%RH for 6 hours, the heat resistance limit at 288°C was tested.

[0102] (12) PP resin deficiency: Observe the appearance of PP under strong light. ◎ indicates severe resin deficiency; ○ indicates slight resin deficiency; × indicates no resin deficiency.

[0103] (13) Board grooves: Visually inspect the surface of the board edge. ◎ indicates severe grooves; ○ indicates slight grooves; × indicates no grooves.

[0104] From the perspective of board performance, compared with Example 1, Comparative Example 1 did not add black silica, resulting in excessively high light transmittance. Compared with Example 1, Comparative Example 2 had a lower CAF resistance due to the low pH and high Na ion content of the black silica. Compared with Example 1, Comparative Example 3 had a higher pH of black silica, resulting in poorer resistance to damp heat and significant deterioration in CAF resistance. Compared with Example 1, Comparative Example 4 had a lower amount of low-dielectric curing agent, resulting in significant deterioration in dielectric properties. Compared with Example 1, Comparative Example 5 had a higher amount of curing agent, resulting in poor compatibility. Compared with Example 1, Comparative Example 6 had a higher light transmittance due to the lower amount of black silica added. Compared with Example 3, Comparative Example 7 had a lower resistivity and decreased CAF resistance due to the excessive amount of black silica.

[0105] The applicant declares that the present invention is illustrated through the above embodiments to describe the black halogen-free resin composition, the prepreg containing it, the laminate, and the printed circuit board of the present invention. However, 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 products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A black halogen-free resin composition, characterized in that, The black halogen-free resin composition comprises the following components in parts by weight: (A) Epoxy resin: 100 parts (B) Black silica: 10-30 parts (C) Low dielectric curing agent: 30-100 parts The black silica has a pH of 6-8 and a sodium ion content of ≤300ppm.

2. The black halogen-free resin composition according to claim 1, characterized in that, The black silica is treated with a silane-based surface treatment agent.

3. The black halogen-free resin composition according to claim 2, characterized in that, The silane surface treatment agent is selected from isocyanate-based silane surface treatment agents.

4. The black halogen-free resin composition according to claim 1, characterized in that, The black silica has a particle size distribution of D50 of 1-5 μm and D100 of 7-12 μm.

5. The black halogen-free resin composition according to claim 1, characterized in that, The epoxy resin is selected from any one or a combination of at least two of the following: difunctional epoxy resins or polyfunctional epoxy resins.

6. The black halogen-free resin composition according to claim 1, characterized in that, The epoxy resin is selected from any one or a combination of at least two of the following: dicyclopentadiene type epoxy resin, dimethylphenol type phenolic epoxy resin, tetramethylbiphenyl epoxy resin, biphenyl epoxy resin, phenolic epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, epoxy resin containing C1-C6 alkyl groups, MDI modified epoxy resin, epoxy resin containing naphthalene rings, or epoxidized polybutadiene.

7. The black halogen-free resin composition according to claim 1, characterized in that, The epoxy equivalent of the epoxy resin is 100~600g / eq.

8. The black halogen-free resin composition according to claim 1, characterized in that, The low dielectric curing agent is selected from one or a combination of at least two of the following: amine curing agents, cyanate ester curing agents, reactive ester curing agents, acid anhydride curing agents, or maleimide curing agents.

9. The black halogen-free resin composition according to claim 8, characterized in that, The anhydride curing agent is selected from any one or a combination of at least two of the following formulas I or II: I II Where n:x = 1:1 ~ 8:

1.

10. The black halogen-free resin composition according to claim 8, characterized in that, The active ester curing agent is selected from any one or a combination of at least two of the active esters having the structure of Formula III or Formula IV: III In III, X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n indicates that the repeating unit is 0.25 to 1.

25. IV In IV, m, n, and q are independent integers from 1 to 6, X is phenyl or naphthyl, and Y is a group such as: Where K is 0 or 1.

11. The black halogen-free resin composition according to claim 1, characterized in that, The low dielectric curing agent includes an active ester curing agent, and the content of the active ester curing agent is 1-30 parts by weight.

12. The black halogen-free resin composition according to claim 1, characterized in that, The black halogen-free resin composition also includes other inorganic fillers.

13. The black halogen-free resin composition according to claim 12, characterized in that, The other inorganic fillers are selected from any one or a combination of at least two of the following: aluminum hydroxide, silicon dioxide, talc, boehmite, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, montmorillonite, clay, or mica.

14. The black halogen-free resin composition according to claim 12, characterized in that, The median particle size D50 of the other inorganic fillers is 1.1-2.8 μm, and the maximum particle size D100 is 4.0-12.0 μm.

15. The black halogen-free resin composition according to claim 12, characterized in that, The other inorganic fillers are in the form of flakes, rods, granules or fibers.

16. The black halogen-free resin composition according to claim 12, characterized in that, The other inorganic fillers are spherical or plate-shaped.

17. The black halogen-free resin composition according to claim 12, characterized in that, The other inorganic fillers are in the form of hollow spheres.

18. The black halogen-free resin composition according to claim 12, characterized in that, The content of the other inorganic fillers is 30-200 parts by weight relative to 100 parts by weight of epoxy resin.

19. The black halogen-free resin composition according to claim 1, characterized in that, The black halogen-free resin composition also includes a phosphorus-containing flame retardant.

20. The black halogen-free resin composition according to claim 19, characterized in that, The phosphorus-containing flame retardant is selected from reactive phosphorus-containing flame retardants and / or additive phosphorus-containing flame retardants.

21. The black halogen-free resin composition according to claim 20, characterized in that, The reactive phosphorus-containing flame retardant is a compound containing phosphorus elements and reactive groups.

22. The black halogen-free resin composition according to claim 21, characterized in that, The reactive groups include amino and / or phenolic hydroxyl groups.

23. The black halogen-free resin composition according to claim 20, characterized in that, The reactive phosphorus-containing flame retardant includes phosphorus-containing phenolic resins.

24. The black halogen-free resin composition according to claim 20, characterized in that, The additive phosphorus-containing flame retardant includes any one or a combination of at least two of the following: tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, phosphazene compounds, or phosphate esters.

25. The black halogen-free resin composition according to claim 20, characterized in that, The amount of the additive phosphorus-containing flame retardant added is 10-30 parts by weight relative to 100 parts by weight of epoxy resin.

26. The black halogen-free resin composition according to claim 1, characterized in that, The black halogen-free resin composition also includes a curing accelerator.

27. The black halogen-free resin composition according to claim 26, characterized in that, The curing accelerator is selected from any one or a combination of at least two of imidazole accelerators, pyridine accelerators, Lewis acid accelerators, or cyanate ester compounds.

28. A resin adhesive, characterized in that, The resin solution is obtained by dissolving or dispersing the black halogen-free resin composition as described in any one of claims 1-27 in a solvent.

29. A prepreg, characterized in that, The prepreg comprises the black halogen-free resin composition as described in any one of claims 1-27.

30. A metal foil-coated laminate, characterized in that, The metal foil laminate includes at least one prepreg as described in claim 29 and a metal foil covering one or both sides of the laminated prepreg.

31. A printed circuit board, characterized in that, The printed circuit board includes at least one of the prepreg as described in claim 29 or the metal foil laminate as described in claim 30.

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