Resin composition and use thereof

Abstract

This material is capable of realizing processing capabilities for finer circuits and is applicable to multi-layer laminate printed wiring boards, particularly to multi-layer laminate printed wiring boards with finer circuits. [Means] A resin composition and its use, said resin composition contains, by weight, 40-70% crosslinkable curable resin and 30-60% filler, said filler being silica prepared by organosilicon hydrolysis, said silica having an average particle size D50 of 0.1-3 μm, and said silica particle size D100:D10 ratio ≦2.5. Adhesive films and resin-coated copper foils prepared by said composition can have higher elongation and high peel strength, low CTE, and low D f It has low hardness, good drillability and higher electrical strength.

Description

[Technical Field]

[0001] The present invention belongs to the technical field of laminates and relates to a resin composition and its use. [Background technology]

[0002] With the future design trend of electronic information products mainly toward lighter, thinner, shorter, smaller, and more multifunctional, printed wiring boards, as the main support for electronic components, will also be technologically improved accordingly to provide high-density wiring, thin shape, fine pore size, multi-dimensional three-dimensional, etc. Since the substrate material greatly determines the performance of printed wiring boards, the development of next-generation substrate materials is urgently needed.

[0003] Reinforced adhesive films or resin-coated copper foils are being developed and applied as next-generation substrate materials because they can achieve thinner designs, higher-density wiring, finer pore sizes, and multidimensional three-dimensional molding. Because they lack reinforcing materials, inorganic fillers are typically added to improve the thermal expansion coefficient, chemical resistance, mechanical strength, and processing performance of adhesive film materials. Silicon powder is a relatively ideal inorganic filler, but because typical silicon powders have a wide particle size distribution and high hardness, adding large amounts can result in problems such as low elongation, poor fluidity, and difficulty in processing.

[0004] CN112526823A discloses a photosensitive resin composition containing (A) a photosensitive resin, (B) silica, (C) a photopolymerization initiator, (D) a reactive diluent, and (E) an epoxy compound, wherein the cumulative volume percentage of the silica (B) is 50% by volume, and the particle size D50 is 0.50 μm or more and 2.00 μm or less. D1.0 is 0.20 μm or more and 0.54 μm or less, and D99 is 5.00 μm or more and 8.40 μm or less. The conversion D99 / D50 of this invention is greater than 2.5, and the D100 is not limited, and the filler particles are large.

[0005] CN103467927A disclosed a thermosetting resin composition containing 20-70 wt% of a thermosetting resin, 1-30 wt% of a curing agent, 0-10 wt% of an accelerator, and 1-50 wt% of micron-order silica aggregates synthesized by a chemical method and having an average particle size of 1-10 μm, which can be made into a prepreg by an impregnation method or into a coated object by a coating method.

[0006] None of the above conventional techniques can effectively solve the problem of improving the elongation rate and peel strength of the adhesive film. Therefore, in the present invention, there is a need to develop a resin composition that enables the adhesive film and resin-coated copper foil to have a better elongation rate and high peel strength, and has a low CTE and a low Df. Summary of the Invention [Problem to be solved by the invention]

[0007] In response to the shortcomings of the prior art, the object of the present invention is to provide a resin composition and its use.The adhesive film and resin-coated copper foil prepared by the resin composition of the present invention can have high elongation and peel strength, low CTE, low Df, good drilling processability, controllable flowability, and good adhesive filling ability, and can be used for multilayer laminate printed wiring boards, especially for the production of multilayer laminate printed wiring boards with fine circuits. [Means for solving the problem]

[0008] To achieve this goal, the present invention adopts the following technical solutions.

[0009] In one aspect, the present invention provides a resin composition comprising, by weight, 40 to 70% crosslinkable curable resin and 30 to 60% filler, wherein the filler is silica prepared by organosilicon hydrolysis, the average particle size D50 of the silica is 0.1 to 3 μm, and the ratio of particle sizes D100:D10 of the silica is ≦2.5.

[0010] In the present invention, silica obtained by hydrolysis of organosilicon is used as a filler in the resin composition, and its content is controlled to 30-60% (accounting for 30-60% of the entire resin composition), the average particle size D50 is 0.1-3 μm, and the particle size ratio D100:D10 of the silica is ≦2.5, which allows the composition to have better elongation, high tensile strength and peel strength, low CTE, low Df, good drillability, and higher electrical strength.

[0011] In the resin composition of the present invention, the crosslinkable curable resin of 40 to 70% means that the crosslinkable curable resin accounts for 40 to 70% of the entire resin composition, and may be 41%, 43%, 45%, 48%, 50%, 53%, 55%, 58%, 60%, 63%, 65%, 68%, or 69%, or a specific value between the above-mentioned values. For reasons of space and clarity, the present invention does not comprehensively exemplify specific values ​​included in the above range.

[0012] In the resin composition of the present invention, the content of the silica may be 31%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 53%, 55%, 57%, or 59%, and specific point values ​​between the above point values, and for the sake of space and clarity, the present invention does not comprehensively exemplify specific point values ​​included in the above ranges.

[0013] In the present invention, if the silica content is less than 30%, the elongation rate of the prepared adhesive film is not significantly improved, and if the silica content is more than 60%, the peel strength decreases.

[0014] In the present invention, the silica has an average particle size D50 of 0.1 to 3 μm (e.g., 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 1.3 μm, 1.5 μm, 1.8 μm, 2 μm, 2.3 μm, 2.5 μm, 2.8 μm, or 3 μm), and a D100:D10 ratio of ≦2.5 (e.g., 2.4, 2.3, 2.2, 2.0, 1.8, 1.7, 1.5, 1.3, 1.0, etc.). The silica of the present invention has a sharper particle size and higher purity, and the adhesive film and resin-coated copper foil prepared therefrom can have better elongation and high peel strength, low CTE, low Df, good drilling processability, higher electrical strength, and the ability to process thinner circuits.

[0015] Preferably, the average particle size D50 of the silica is 0.3 to 1.0 μm.

[0016] Preferably, the purity of the silica is greater than 99.9% (e.g., 99.91%, 99.93%, 99.95%, 99.97%, 99.99%, etc.). In the present invention, when the purity of the silica is greater than 99.9%, the adhesive film and resin-coated copper foil prepared can have better elongation and electrical strength properties.

[0017] The particle sizes (e.g., D50, D10, D100, etc.) of the present invention are all measured by a laser diffraction method using a Malvern laser particle size analyzer, model number MS3000. The purity of the silica of the present invention is measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES).

[0018] Preferably, the silica is obtained by obtaining an initial product through an organosilicon hydrolysis reaction and calcining the initial product.

[0019] Preferably, the firing temperature is 800°C to 1300°C, for example, 850°C, 900°C, 905°C, 910°C, 920°C, 930°C, 950°C, 980°C, 990°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, or 1250°C.

[0020] Preferably, the organosilicon is an alkoxysilane.

[0021] Preferably, the alkoxysilane includes tetraethoxysilane, tetramethoxysilane, tetraphenoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and more preferably tetraethoxysilane.

[0022] Preferably, the crosslinkable curable resin is a thermosetting resin, a photocurable resin, or a thermo-photocurable resin.

[0023] Preferably, the crosslinkable curable resin comprises one or a combination of at least two of epoxy resin, phenol resin, phenoxy resin, cyanate resin, active ester, polyphenylene oxide resin, maleimide resin, hydrocarbon resin, acrylate resin, polyimide resin, silicone resin, polybenzoxazole resin, polyester resin, or polystyrene, and a combination of epoxy resin and phenol resin is preferred, as this allows for better elongation and peel strength to be obtained.

[0024] Preferably, the epoxy resin comprises one or a combination of at least two of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phosphorus-containing epoxy resin, an MDI-modified epoxy resin, a novolac type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene-containing epoxy resin, or an alicyclic epoxy resin.

[0025] Preferably, the phenolic resin comprises one or a combination of at least two of bisphenol A type phenolic resin, phenol novolac resin, biphenyl type phenolic resin, dicyclopentadiene type phenolic resin, or naphthalene-containing phenolic resin.

[0026] In another aspect, the present invention provides a resin adhesive liquid obtained by dissolving or dispersing the above resin composition in a solvent.

[0027] The solvent used in the present invention is not particularly limited, and 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. The above solvents may be used alone or in combination of two or more. Preferably, aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene are mixed with ketone solvents such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. The amount of solvent used can be determined by those skilled in the art based on their own experience, as long as the resulting resin adhesive liquid achieves a viscosity suitable for use.

[0028] In another aspect, the present invention provides an adhesive film produced by applying the resin composition according to any one of the above aspects to a release material, followed by drying and / or baking.

[0029] Preferably, the thickness of the adhesive film is 5 to 300 μm, for example, 8 μm, 10 μm, 15 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, 250 μm, 280 μm, or 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm.

[0030] In another aspect, the present invention provides a resin-coated copper foil comprising a copper foil and the above-described resin composition applied, dried, and then adhered to the copper foil.

[0031] Preferably, the resin-coated copper foil further includes a protective film covering the resin composition.

[0032] Preferably, the thickness of the resin layer of the resin-coated copper foil (meaning a resin layer formed on a copper foil from the resin composition) is 5 to 300 μm, for example, 8 μm, 10 μm, 15 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, 250 μm, 280 μm, or 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm.

[0033] Preferably, the thickness of the resin-coated copper foil is 1 to 105 μm, for example, 3 μm, 5 μm, 8 μm, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 104 μm, etc., preferably 3 to 35 μm, and more preferably 5 to 18 μm.

[0034] In another aspect, the present invention provides a semi-cured adhesive sheet produced by impregnating a glass cloth with the above resin composition and then drying the same.

[0035] In the present invention, the glass cloth may be selected from 7628, 2116, 1131, 1080, 106, 1027, 1037, and 1078 glass cloths.

[0036] In another aspect, the present invention provides a copper-clad laminate using one or at least two of the above adhesive film, the above resin-coated copper foil, and the above semi-cured adhesive sheet.

[0037] In another aspect, the present invention provides a multilayer board using one or at least two of the above adhesive film, the above resin-coated copper foil, the above semi-cured adhesive sheet, and the above copper-clad laminate. [Effects of the Invention]

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] In the resin composition of the present invention, the chemically produced silica has good particle size uniformity, and when added in an amount of 30 to 60%, the adhesive film produced can achieve a better elongation rate (reaching 9 to 13%) and peel strength (high, 7.5 to 9.0 N / cm) compared to adhesive films produced with conventional silica. At the same time, the CTE and Df are also lower. The silica has a small average particle size and good uniformity, which can avoid the impact of large particles on the reliability of fine circuits, making it more suitable for multilayer laminated printed wiring boards with fine circuits. DETAILED DESCRIPTION OF THE INVENTION

[0040] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the above examples are only for understanding the present invention and should not be considered as specific limitations of the present invention.

[0041] The raw materials used in the following examples and comparative examples are as follows. Epoxy resin: NC-3000H (Nippon Kayaku). Phenolic resin: SN-485 (Nippon Steel Corporation, Japan). Active ester: HP-8000-65T (Japan DIC). Cyanate: XU-371 (HUNTSMAN). Hydrocarbon: B3000 (Nippon Soda). Polyphenylene oxide: MX9000 (SABIC). Maleimide resin: BMI3000. Crosslinking coagent divinylbenzene: DVB (Nippon Steel). Silica 1:D50 is 3.0 μm, D100:D10 is 2.3, purity is 98%, prepared by organosilicon hydrolysis method, originates from Jiangsu Huimai. Silica 2 prepared by organosilicon hydrolysis method: D50 is 0.1 μm, D100:D10 is 2.3, purity is 99.90%, and it is from Jiangsu Huimai. Silica 3 prepared by organosilicon hydrolysis method: D50 is 0.5 μm, D100:D10 is 2.0, purity is 99.90%, and it is from Jiangsu Huimai. Silica 4 prepared by organosilicon hydrolysis method: D50 is 3.5 μm, D100:D10 is 3.0, purity is 99.90%, and it is from Jiangsu Huimai. Silica 5 prepared by organosilicon hydrolysis method: D50 is 0.05 μm, D100:D10 is 2.3, purity is 99.00%, and it is from Jiangsu Huimai. [Example]

[0042] First, 40 parts of epoxy resin (NC-3000H) and 30 parts of phenol resin (SN-485) were dissolved in an appropriate amount of solvent, and the mixture was stirred for 2 hours or more.

[0043] Further, 30 parts of silica 3 obtained by organosilicon hydrolysis (D50: 0.5 μm, D100:D10: 2.0, purity: 99.90%) was added, and the mixture was stirred for 4 hours or more to achieve a homogeneous mixture and form a solution with a solid content of 65%.

[0044] The solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain a semi-cured resin layer adhesive film. The semi-cured adhesive film (40µm thick) was pressed against a browned PCB board to cure, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. [Example]

[0045] An adhesive film was prepared in the same manner as in Example 1, except that the oxygen content of the chemically synthesized silica used in Example 1 was changed.

[0046] First, 23 parts of epoxy resin (NC-3000H) and 17 parts of phenol resin (SN-485) were dissolved in an appropriate amount of solvent, and the mixture was stirred for 2 hours or more.

[0047] Further, 60 parts of silica 3 obtained by organosilicon hydrolysis (D50: 0.5 μm, D100:D10: 2.0, purity: 99.90%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture, thereby forming a solution with a solid content of 65%.

[0048] The solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain a semi-cured resin layer adhesive film. The semi-cured adhesive film (40µm thick) was pressed against a browned PCB board to cure, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. [Example]

[0049] First, 30 parts of epoxy resin (NC-3000H) and 25 parts of phenolic resin (SN-485) were dissolved in an appropriate amount of solvent, and the mixture was stirred for 2 hours or more.

[0050] Further, 45 parts of silica 2 obtained by organosilicon hydrolysis (D50: 0.1 μm, D100:D10: 2.3, purity: 99.90%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture and form a solution with a solid content of 65%.

[0051] The solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain a semi-cured resin layer adhesive film. The semi-cured adhesive film (40µm thick) was pressed against a browned PCB board to cure, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. [Example]

[0052] First, 30 parts of epoxy resin (NC-3000H), 15 parts of cyanate (XU-371), and 10 parts of active ester resin (HP-8000-65T) were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0053] Further, 45 parts of silica 3 obtained by organosilicon hydrolysis (D50: 0.5 μm, D100:D10: 2.0, purity: 99.90%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture and form a solution with a solid content of 65%.

[0054] The solution was applied to a release film, dried, and then baked in an oven at 120°C for 5 minutes to obtain a semi-cured resin layer adhesive film. The semi-cured adhesive film (40µm thick) was pressed against a browned PCB board to cure, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. [Example]

[0055] First, 35 parts of cyanate (XU-371) and 20 parts of maleimide resin (BMI3000) were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0056] Further, 45 parts of silica 3 synthesized by a chemical method (D50: 0.5 μm, D100:D10: 2.0, purity: 99.90%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture, thereby forming a solution with a solid content of 65%.

[0057] The solution was applied to a release film, dried, and then baked in an oven at 120°C for 5 minutes to obtain a semi-cured resin layer adhesive film. The semi-cured adhesive film (40µm thick) was pressed against a browned PCB board to cure, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. [Example]

[0058] First, 30 parts of polyphenylene oxide (MX9000), 20 parts of hydrocarbon resin (XU-371), and 5 parts of crosslinking coagent (DVB) were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0059] Further, 45% of chemically synthesized silica 3 (D50: 0.5 μm, D100:D10: 2.0, purity: 99.90%) was added, and the mixture was stirred for 4 hours or more to achieve a homogeneous mixture, forming a solution with a solid content of 65%.

[0060] The solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain a semi-cured resin layer adhesive film. The semi-cured adhesive film (40µm thick) was pressed against a browned PCB board to cure, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. [Example]

[0061] First, 30 parts of epoxy resin (NC-3000H) and 25 parts of phenolic resin (SN-485) were dissolved in an appropriate amount of solvent, and the mixture was stirred for 2 hours or more.

[0062] Further, 45 parts of silica 1 obtained by organosilicon hydrolysis (D50: 3.0 μm, D100:D10: 2.3, purity: 98.00%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture, thereby forming a solution with a solid content of 65%.

[0063] The above solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) was pressed against the browned PCB board and cured, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. Comparative Example 1

[0064] An adhesive film was produced in the same manner as in Example 1, except that the chemically synthesized silica in Example 1 was replaced with ordinary silicon fine powder.

[0065] First, the epoxy resin and phenolic resin were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0066] Further, 30% of silicon fine powder was added, and the mixture was stirred for 4 hours or more to mix thoroughly and uniformly, forming a solution with a solid content of 65%.

[0067] The above solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) was pressed against the browned PCB board and cured, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. Comparative Example 2

[0068] An adhesive film was produced in the same manner as in Example 1, except that the chemically synthesized silica in Example 2 was replaced with ordinary silicon fine powder.

[0069] First, the epoxy resin and phenolic resin were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0070] Further, 60% of silicon fine powder was added, and the mixture was stirred for 4 hours or more to mix thoroughly and uniformly, forming a solution with a solid content of 65%.

[0071] The above solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) was pressed against the browned PCB board and cured, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. Comparative Example 3

[0072] The proportion of chemically produced silica in Example 1 was adjusted.

[0073] First, the epoxy resin and phenolic resin were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0074] Further, 20% of chemically synthesized silica was added, and the mixture was stirred for 4 hours or more to be thoroughly and uniformly mixed, forming a solution with a solid content of 65%.

[0075] The above solution was applied to a release film, dried, and then baked in a 120°C oven for 3 to 5 minutes to obtain a semi-cured resin layer adhesive film. The semi-cured adhesive film (40 μm thick) was pressed against the browned PCB board and cured, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. Comparative Example 4

[0076] The proportion of chemically produced silica in Example 1 was adjusted.

[0077] First, the epoxy resin and phenolic resin were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0078] Further, 70% of the chemically synthesized silica was added, and the mixture was stirred for 4 hours or more to be thoroughly and uniformly mixed, forming a solution with a solid content of 65%.

[0079] The above solution was applied to a release film, dried, and then baked in a 120°C oven for 3 to 5 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) was pressed against a browned PCB board and cured, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. Comparative Example 5

[0080] First, 30 parts of epoxy resin (NC-3000H) and 25 parts of phenolic resin (SN-485) were dissolved in an appropriate amount of solvent, and the mixture was stirred for 2 hours or more.

[0081] Further, 45 parts of silica 5 obtained by organosilicon hydrolysis (D50: 0.05 μm, D100:D10: 2.3, purity: 99.00%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture and form a solution with a solid content of 65%.

[0082] The above solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) was pressed against a browned PCB board and cured, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. Comparative Example 6

[0083] First, 30 parts of epoxy resin (NC-3000H) and 25 parts of phenolic resin (SN-485) were dissolved in an appropriate amount of solvent, and the mixture was stirred for 2 hours or more.

[0084] Further, 45 parts of silica 4 obtained by organosilicon hydrolysis (D50: 3.5 μm, D100:D10: 3.0, purity: 99.90%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture and form a solution with a solid content of 65%.

[0085] The above solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) was pressed against the browned PCB board and cured, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. Comparative Example 7

[0086] First, 30 parts of epoxy resin (NC-3000H), 15 parts of cyanate (XU-371), and 10 parts of active ester resin (HP-8000-65T) were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0087] Further, 45 parts of silica 4 obtained by organosilicon hydrolysis (D50: 3.5 μm, D100:D10: 3.0, purity: 99.90%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture and form a solution with a solid content of 65%.

[0088] The above solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) was pressed against the browned PCB board and cured, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit. Comparative Example 8

[0089] First, 30 parts of polyphenylene oxide (MX9000), 20 parts of hydrocarbon resin (XU-371), and 5 parts of crosslinking coagent (DVB) were dissolved in an appropriate amount of solvent and stirred for 2 hours or more.

[0090] Further, 45 parts of silica 5 obtained by organosilicon hydrolysis (D50: 0.05 μm, D100:D10: 2.3, purity: 99.00%) was added, and the mixture was stirred for 4 hours or more to achieve a uniform mixture and form a solution with a solid content of 65%.

[0091] The solution was applied to a release film, dried, and then baked in an oven at 120°C for 3 minutes to obtain a semi-cured resin layer adhesive film. The semi-cured adhesive film (40µm thick) was pressed against a browned PCB board to cure, and the release film was removed, followed by surface treatment and copper electroplating to form a laminated printed wiring board with a circuit.

[0092] The laminated printed wiring boards of the above-mentioned Examples and Comparative Examples were subjected to performance tests, and the test items and methods were as follows.

[0093] (1) Elongation rate: (30℃): By DMA method, the specimen was kept at 30℃ for 5 minutes, and the prestress was increased from 3N / min to 17.5N / min with 0.01N prestress.

[0094] (2) Peel strength: The test was conducted according to the method of IPC-TM-650 2.4.9.

[0095] (3) Drilling processability: After laser drilling, the workpiece was sliced ​​and the hole squareness was observed. A squareness of 90 to 95 degrees was excellent, 96 to 100 degrees was good, 101 to 110 degrees was acceptable, and >110 degrees was unacceptable.

[0096] (4) Adhesive filling effect: After pressing the circuit board with the adhesive film, it was sliced ​​and the adhesive filling status between the wiring was observed. If there were no bubbles in the resin layer between the wiring, it was rated as "excellent." If there were bubbles in the resin layer between the wiring and the diameter of the bubbles was smaller than 1 μm, it was rated as "good." If there were bubbles in the resin layer between the wiring and the diameter of the bubbles was larger than 1 μm, it was rated as "unacceptable."

[0097] (5) Narrow circuit capability: The smallest line / space that can be fabricated was measured.

[0098] Performance test comparisons are shown in Tables 1 and 2 below.

[0099] [Table 1]

[0100] [Table 2]

[0101] As can be seen from Tables 1 and 2, Examples 1 to 7 had high elongation rates (9-13%) and peel strengths (8.2-9.0 N / cm), good drilling processability, good adhesive filling capacity, and good reliability for thin circuits. In Examples 1 to 3, the elongation rates of the epoxy and phenolic systems using chemically produced spherical silicone within the particle size range of the present invention were superior to those of other resin systems. In Example 7, due to the low purity of the filler, the elongation rate, peel strength, and processability were all slightly inferior to those using a higher purity filler. In Comparative Examples 1 and 2, adhesive films prepared using conventional silica had low elongation rates, low peel strengths, and poor drilling processability. In Comparative Examples 3 and 4, the proportion of chemically produced silica did not meet the limited range of the present invention, resulting in low elongation rates and low peel strengths. The average particle size of the chemically produced silica used in Comparative Example 5 was too small, resulting in a low elongation rate and low peel strength. The D100:D10 of Comparative Example 6 was greater than 2.5, resulting in a similarly low elongation rate, low peel strength, and poor ability to form thin circuits.

[0102] The present invention has been described with reference to the above examples of the resin composition of the present invention and its use, but the applicant declares that the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be carried out depending on the above examples. Those skilled in the art should understand that any improvements to the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific forms, etc., are all within the protection scope and disclosure of the present invention.

Claims

1. The composition comprises, by weight, 40-70% crosslinkable curable resin and 30-60% filler, wherein the filler is organosilicon hydrolysis silica, the average particle size D50 of the silica is 0.1-3 μm, the ratio of particle size D100:D10 of the silica is ≦2.5, and the purity of the silica is greater than 99.9%; Resin composition.

2. The crosslinkable curable resin is a thermosetting resin, a photocurable resin, or a thermo-photocurable resin. The resin composition according to claim 1 .

3. The crosslinkable curable resin includes any one or a combination of at least two of an epoxy resin, a phenolic resin, a phenoxy resin, a cyanate resin, an active ester, a polyphenylene oxide resin, a maleimide resin, a hydrocarbon resin, an acrylate resin, a polyimide resin, a silicone resin, a polybenzoxazole resin, a polyester resin, or a polystyrene; The resin composition according to claim 2 .

4. The epoxy resin includes one or a combination of at least two of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, MDI-modified epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene-containing epoxy resin, or alicyclic epoxy resin. The resin composition according to claim 3 .

5. The phenolic resin includes one or a combination of at least two of a bisphenol A type phenolic resin, a phenol novolac resin, a biphenyl type phenolic resin, a dicyclopentadiene type phenolic resin, or a naphthalene-containing phenolic resin. The resin composition according to claim 3 .

6. 1. A method for producing an adhesive film, comprising: The resin composition according to any one of claims 1 to 5 is applied to a release agent, and then dried and / or baked, The thickness of the adhesive film is 5 to 300 μm.

1. A method for producing an adhesive film comprising the steps of:

7. A method for producing a resin-coated copper foil, A copper foil and the resin composition according to any one of claims 1 to 5, which is applied, dried, and then adhered to the copper foil, The thickness of the resin layer of the resin-coated copper foil is 5 to 300 μm, The thickness of the resin-coated copper foil is 1 to 105 μm. A method for producing a resin-coated copper foil, comprising:

8. The resin composition according to any one of claims 1 to 5 is impregnated into a glass cloth and then dried. A method for producing a semi-cured adhesive sheet, comprising:

9. The present invention uses one or at least two of an adhesive film, a resin-coated copper foil, and a semi-cured adhesive sheet, and the adhesive film is produced by applying the resin composition according to any one of claims 1 to 5 to a release material, followed by drying and / or baking. The resin-coated copper foil includes copper foil and the resin composition according to any one of claims 1 to 5, which is applied, dried, and then attached to the copper foil. The semi-cured adhesive sheet is produced by infiltrating a glass cloth with the resin composition according to any one of claims 1 to 5, followed by drying. A method for producing a copper clad laminate.

10. The present invention relates to a method for manufacturing a laminated laminate using one or at least two of an adhesive film, a resin-coated copper foil, a semi-cured adhesive sheet, and a copper-clad laminate, and the adhesive film is produced by applying the resin composition according to any one of claims 1 to 5 to a release material, followed by drying and / or baking. The resin-coated copper foil comprises copper foil and the resin composition according to any one of claims 1 to 5, which is applied, dried, and then attached to the copper foil. The semi-cured adhesive sheet is produced by impregnating a glass cloth with the resin composition according to any one of claims 1 to 5, followed by drying. The copper-clad laminate uses one or at least two of the adhesive film, the resin-coated copper foil, and the semi-cured adhesive sheet. A method for manufacturing a multilayer board, comprising:

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