Resin Composition and Its Use

Abstract

The present invention provides a resin composition and use thereof. [Means] The resin composition contains, by weight, 15-39% crosslinkable curable resin and 61-85% filler, the filler being silica prepared by organosilicon hydrolysis, the average particle size D50 of the silica being 0.1-3 μm, the ratio of D100:D10 being 2.5 or less, and the purity of the silica being greater than 99.9%. The adhesive film and resin-coated copper foil prepared by the resin composition of the present invention can have high tensile strength and peel strength, good drilling processability, controllable fluidity, good adhesive filling ability, higher electrical strength, and can realize the processability of finer circuits, and are materials applicable to multilayer laminate printed wiring boards, particularly multilayer laminate printed wiring boards with finer circuits.

Description

Technical Field

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

Background Art

[0002] With the mass production of electronic information products, and the design trend towards thinner, lighter, shorter, and more multifunctional, printed wiring boards, which are the main supports for electronic components, are also technically improved to provide high-density wiring, thinness, fine hole diameters, and high heat dissipation. Since the substrate material greatly affects the performance of the printed wiring board, the development of the next-generation substrate material is urgently needed.

[0003] An adhesive film without a reinforcing material or copper foil with resin can achieve thinner thickness, higher density wiring, and finer hole diameters, so it is developed and applied as the next-generation substrate material. Since there is no reinforcing material, generally, an inorganic filler is added to improve the thermal expansion coefficient, chemical resistance, mechanical strength, and processing performance of the adhesive film. Silicon fine powder is a relatively ideal inorganic filler, but the particle size distribution of general silicon fine powder is wide and the hardness is high. Therefore, when the addition amount is large, there are problems such as unclear improvement in tensile strength, poor fluidity, and difficulty in processing.

[0004] CN112526823A discloses a photosensitive resin composition containing (A) a photosensitive resin, (B) silica, (C) a photoinitiator, (D) a reactive diluent, and (E) an epoxy compound. The cumulative volume percentage of the (B) silica 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 converted D99 / D50 of the invention is greater than 2.5, and D100 is not limited, and the filler particles are large.

[0005] CN103467927A discloses a thermosetting resin composition which contains 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 aggregates of silica synthesized by a chemical method with an average particle size of 1 - 10 μm, and can be prepared into a prepreg by an impregnation method or into a coated article by a coating method.

[0006] In the above prior arts, none of them limit D100, and there are defects in large particle size silica, so it is impossible to obtain high tensile strength and peel strength, and it cannot meet the application of thin circuits. Therefore, in the present invention, it is desired to develop a resin composition in which an adhesive film and a copper foil with resin can have high tensile strength and peel strength, good drillability, controllable fluidity, good adhesive filling ability, and higher electrical strength.

Summary of the Invention

Problems to be Solved by the Invention

[0007] In view of the deficiencies of the prior art, the object of the present invention is to provide a resin composition and its use. With the resin composition of the present invention, the prepared adhesive film and copper foil with resin can have high tensile strength and peel strength, good drillability, controllable fluidity, good adhesive filling ability, higher electrical strength, and can realize the processing ability of thinner circuits, and is a material applicable to printed wiring boards of multilayer laminates, especially a material applicable to printed wiring boards of multilayer laminates with thin circuits.

Means for Solving the Problems

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

[0009] In one aspect, the present invention provides a resin composition comprising 15 to 39% by weight of a crosslinkable curable resin and 61 to 85% of a filler, wherein the filler is silica prepared by an organosilicon hydrolysis method, the average particle size D50 of the silica is 0.1 to 3 μm, the ratio of D100:D10 ≦ 2.5, and the purity of the silica is greater than 99.9%.

[0010] In the present invention, silica obtained by an organosilicon hydrolysis method is used as a filler in a resin composition. Since the average particle size D50 thereof is 0.1 to 3 μm, the ratio of D100:D10 ≦ 2.5, and the content is greater than 99.9%, the composition has high tensile strength and peel strength, good drillability, and can have higher electrical strength.

[0011] In the resin composition of the present invention, the content of the crosslinkable curable resin being 15 to 39% means that it occupies 15 to 39% of the entire resin composition. For example, it may be 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 34%, 36%, 38% or 39%, and specific values between the above point values may also be possible. For the convenience of the paper and simplicity, specific point values included in the above range are not comprehensively exemplified in the present invention.

[0012] In the resin composition of the present invention, the content of the filler being 61 to 85% means that it occupies 61 to 85% of the entire resin composition. For example, it may be 61%, 63%, 65%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82% or 85%, and specific values between the above point values may also be possible. For the convenience of the paper and simplicity, specific point values included in the above range are not comprehensively exemplified in the present invention.

[0013] In the present invention, when the content of the filler is less than 61%, the improvement in tensile strength is not obvious. When the content of the filler is greater than 85%, the material is brittle and the peel strength decreases.

[0014] In the present invention, the silica has an average particle size D50 of 0.1 to 3 μm (for example, 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), the ratio of D100:D10 is less than 2.5 (for example, it may be 2.4, 2.3, 2.2, 2.0, 1.8, 1.7, 1.5, 1.3, 1.0, etc.), and the purity of the silica is greater than 99.9% (for example, 99.91%, 99.93%, 99.95%, 99.97%, 99.99%, etc.). The silica of the present invention has a sharper particle size and higher purity, and the prepared adhesive film and copper foil with resin can have high tensile strength and peel strength, good drillability, controllable fluidity, good adhesive filling ability, higher electrical strength, and the processing ability for finer circuits can be realized.

[0015] The particle sizes (for example, D50, D10, D100, etc.) according to the present invention are all measured by the laser diffraction method, and the measuring instrument is a Malvern laser particle size distribution measuring device with a model number of MS3000. The purity of the silica according to the present invention is measured by an inductively coupled plasma atomic emission spectrometer ICP - AES.

[0016] Preferably, the crosslinkable curable resin is a thermosetting resin or a photocurable resin.

[0017] Preferably, the crosslinkable curable resin is any one or at least a combination of two or more selected from epoxy resins, phenolic resins, cyanates, active esters, polyphenylene oxide resins, maleimide resins, silicone resins, polybenzoxazole resins, polyimide resins, hydrocarbon resins, or acrylate resins, and a combination of an epoxy resin and a phenolic resin is preferred. A combination of an epoxy resin and a phenolic resin is preferred, and more excellent tensile strength and peel strength can be obtained.

[0018] Preferably, the epoxy resin contains 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.

[0019] Preferably, the phenolic resin contains 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.

[0020] Preferably, the silica is obtained by obtaining an initial product through an organosilicon hydrolysis reaction and firing the initial product. Preferably, the firing temperature is 800 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, 1200 °C, 1250 °C.

[0021] Preferably, the organosilicon is alkoxysilane.

[0022] Preferably, the alkoxysilane includes tetraethoxysilane, tetramethoxysilane, tetraphenoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and more preferably is tetraethoxysilane.

[0023] Preferably, the average particle size D50 of the silica is 0.3 to 1 μm.

[0024] In another aspect, the present invention provides a resin adhesive liquid obtained by dissolving or dispersing the above resin composition in a solvent.

[0025] The solvent in the present invention is not particularly limited. Specific examples include alcohols such as methanol, ethanol, and butanol; ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol - methyl ether, carbitol, and butyl carbitol; ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; esters such as ethoxyethyl acetate and ethyl acetate; and nitrogen - containing solvents such as N,N - dimethylformamide, N,N - dimethylacetamide, and N - methyl - 2 - pyrrolidone. 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 and used. The amount of the solvent used can be selected by those skilled in the art according to their experience, as long as the resulting resin adhesive solution reaches a viscosity suitable for use.

[0026] In another aspect, the present invention provides an adhesive film which is prepared by applying the resin composition according to any one of the above items to a release material and then drying and / or baking.

[0027] Preferably, the adhesive film may further include a protective film covering the other side of the resin composition.

[0028] Preferably, the thickness of the adhesive film is 5 - 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, 300 μm. It is preferably 10 - 200 μm, and more preferably 10 - 100 μm.

[0029] In another aspect, the present invention provides a copper foil with resin, which includes a copper foil and the above resin composition applied and dried and adhered to the copper foil.

[0030] Preferably, the copper foil with resin further includes a protective film covering the resin composition.

[0031] Preferably, the thickness of the resin layer of the copper foil with resin (meaning the resin layer formed by the resin composition on the copper foil) 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, 300 μm, and preferably 10 to 200 μm, and more preferably 10 to 100 μm.

[0032] Preferably, the thickness of the copper foil of the copper foil with resin 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., and preferably 3 to 35 μm, and more preferably 3 to 12 μm.

[0033] In another aspect, the present invention provides a semi-cured adhesive sheet produced by immersing the above resin composition in a glass cloth and then drying it.

[0034] In the present invention, the glass cloth can be selected from 7628, 2116, 1131, 1080, 106, 1027, 1037, 1078 glass cloths.

[0035] In another aspect, the present invention provides a copper-clad laminate using one or at least two of the above adhesive film, the copper foil with resin, and the semi-cured adhesive sheet.

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

Advantages of the Invention

[0037] Compared with the prior art, the present invention has the following beneficial effects.

[0038] The silica of the present invention has good particle size uniformity, a sharper particle size distribution, and when 61-85% is added, the prepared adhesive film can obtain better tensile modulus and peel strength compared to the adhesive film made of general silica. The silica of the present invention has a small average particle size, good uniformity, can avoid the influence of large particles on the breakdown voltage of a thin insulating layer and the reliability of thin circuits, and is more suitable for thin circuit laminates. The silica of the present invention has high purity and better electrical properties (Df).

[0039] The adhesive film prepared from the resin composition of the present invention can reach a tensile strength of 50-100 Mpa, a peel strength of 7.0-9.0 N / cm, an electrical strength of 83-90 kV / mm, can have a low DK of 2.95-3.32 and a low DF of 0.004-0.014, and has good drill processability and good adhesive filling ability, with good comprehensive performance.

Embodiments for Carrying Out the Invention

[0040] Hereinafter, the technical solution of the present invention will be further described by specific embodiments. Those skilled in the art should understand that the above embodiments are only for understanding the present invention and should not be regarded 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 & Sumitomo Metal). Active ester: HP-8000-65T (DIC). Cyanate: XU-371 (Huntsman). Hydrocarbon resin: B3000 (Nippon Soda). Polyphenylene oxide: MX9000 (SABIC). The silica obtained by the organosilicon hydrolysis method 1: D50 is 3.0 μm, D100: D10 is 2.5, the purity is 99.98%, and it is derived from Jiangsu Huimai The silica obtained by the organosilicon hydrolysis method 2: D50 is 0.1 μm, D100: D10 is 2.5, the purity is 99.90%, and it is derived from Jiangsu Huimai The silica obtained by the organosilicon hydrolysis method 3: D50 is 0.5 μm, D100: D10 is 2.0, the purity is 99.90%, and it is derived from Jiangsu Huimai The silica obtained by the organosilicon hydrolysis method 4: D50 is 3.5 μm, D100: D10 is 5.0, the purity is 99.90%, and it is derived from Jiangsu Huimai The silica obtained by the organosilicon hydrolysis method 5: D50 is 2.0 μm, D100: D10 is 5.0, the purity is 99.00%, and it is derived from Jiangsu Huimai

Example

[0042] First, 28 parts of epoxy resin (NC-3000H) and 21 parts of phenolic resin (SN-485) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0043] Furthermore, 61% of silica 3 obtained by the organosilicon hydrolysis method (D50 is 0.5 μm, D100: D10 is 2.0, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix thoroughly and form a solution with a solid content of 70%.

[0044] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 5 minutes to obtain an adhesive film with a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits.

Example

[0045] An adhesive film was produced in the same manner as in Example 1, except that the oxygen ratio of the silica synthesized by the chemical method used in Example 1 was changed.

[0046] First, 28 parts of an epoxy resin (NC-3000H) and 21 parts of a phenolic resin (SN-485) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0047] Furthermore, 3 of silica obtained by the organosilicon hydrolysis method of 73% (D50 is 0.5 μm, D100:D10 is 2.0, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix uniformly sufficiently to form a solution with a solid content of 70%.

[0048] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was performed to form a laminated printed wiring board with circuits.

Example

[0049] An adhesive film was produced in the same manner as in Example 1, except that the ratio of the silica synthesized by the chemical method used in Example 1 was changed.

[0050] First, 28 parts of an epoxy resin (NC-3000H) and 21 parts of a phenolic resin (SN-485) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0051] Furthermore, 3 of silica obtained by the organosilicon hydrolysis method of 85% (D50 is 0.5 μm, D100:D10 is 2.0, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix uniformly sufficiently to form a solution with a solid content of 70%.

[0052] The above solution was applied to a release film, dried, and then placed in an oven at 100°C and baked for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, copper electroplating was carried out, and a laminated printed wiring board with circuits was formed.

Example

[0053] A copper foil with resin was manufactured using the resin composition of Example 1.

[0054] First, 28 parts of an epoxy resin (NC-3000H) and 21 parts of a phenol resin (SN-485) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0055] Furthermore, silica 3 obtained by the 61% organosilicon hydrolysis method (D50 is 0.5 μm, D100:D10 is 2.0, and purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0056] The above solution was applied to a copper foil, dried, and then placed in an oven at 100°C and baked for 5 minutes to obtain a copper foil with a semi-cured resin layer. After the copper foil with resin (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured, etching and electroplating were performed to obtain a laminated printed wiring board with circuits.

Example

[0057] An adhesive film was manufactured in the same manner as in Example 1, except that the silica synthesized by the chemical method used in Example 1 was changed.

[0058] First, 28 parts of an epoxy resin (NC-3000H) and 21 parts of a phenol resin (SN-485) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0059] Furthermore, 61% of silica 1 obtained by the organosilicon hydrolysis method (D50 is 3.0 μm, D100:D10 is 2.5, and the purity is 99.98%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0060] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 minutes to obtain an adhesive film with a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits.

Example

[0061] An adhesive film was produced in the same manner as in Example 1, except that the silica synthesized by the chemical method used in Example 1 was changed.

[0062] First, 28 parts of epoxy resin (NC-3000H) and 21 parts of phenolic resin (SN-485) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0063] Furthermore, 61% of silica 2 obtained by the organosilicon hydrolysis method (D50 is 0.1 μm, D100:D10 is 2.5, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0064] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 minutes to obtain an adhesive film with a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits.

Example

[0065] An adhesive film was produced in the same manner as in Example 1, except that the type of resin used in Example 1 was changed.

[0066] First, 20 parts of epoxy resin (NC-3000H), 10 parts of cyanate (XU-371), and 10 parts of active ester (HP-8000-65T) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0067] Furthermore, 61% silica 3 obtained by the organosilicon hydrolysis method (D50 is 0.5 μm, D100:D10 is 2.0, and purity is 99.90%) was added and stirring was continued for 4 hours or more to mix thoroughly and form a solution with a solid content of 70%.

[0068] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 minutes to obtain an adhesive film with a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits.

Example

[0069] An adhesive film was produced in the same manner as in Example 1, except that the type of resin used in Example 1 was changed.

[0070] First, 20 parts of hydrocarbon resin (XU-371), 20 parts of polyphenylene oxide resin (MX9000), and 5 parts of crosslinking aid (DVB) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0071] Furthermore, 61% silica 3 obtained by the organosilicon hydrolysis method (D50 is 0.5 μm, D100:D10 is 2.0, and purity is 99.90%) was added and stirring was continued for 4 hours or more to mix thoroughly and form a solution with a solid content of 70%.

[0072] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, copper electroplating was carried out, and a laminated printed wiring board with circuits was formed.

Example

[0073] An adhesive sheet was manufactured using the resin composition of Example 7.

[0074] First, 20 parts of an epoxy resin (NC-3000H), 10 parts of a cyanate (XU-371), and 10 parts of an active ester (HP-8000-65T) were dissolved using an appropriate amount of a solvent and stirred for 2 hours or more.

[0075] Furthermore, 3 of silica obtained by the 61% organosilicon hydrolysis method (D50 is 0.5 μm, D100:D10 is 2.0, and purity is 99.90%) was added and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0076] Using the above solution, an adhesive was applied to a glass cloth. After drying, it was placed in an oven at 100 °C and baked for 5 minutes to obtain a semi-cured adhesive sheet. A plurality of adhesive sheets were laminated, copper foils were attached on the top and bottom, and pressure-bonded and cured to obtain a copper-clad laminate. Comparative Example 1

[0077] An adhesive film was manufactured in the same manner as in Example 1, except that the silica synthesized by the chemical method used in Example 1 was changed.

[0078] First, an epoxy resin (NC-3000H) and 21 parts of a phenol resin (SN-485) were dissolved using an appropriate amount of a solvent and stirred for 2 hours or more.

[0079] Furthermore, 61% of silica 4 obtained by the organosilicon hydrolysis method (D50 is 3.5 μm, D100:D10 is 5.0, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0080] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 - 5 minutes to obtain an adhesive film with a resin layer in a semi-cured state. The semi-cured adhesive film (40 μm thick) and the browned PCB board were pressure-bonded and cured. After peeling off the release film, surface treatment was carried out, and copper electroplating was performed to form a laminated printed wiring board with circuits. Comparative Example 2

[0081] An adhesive film was manufactured in the same manner as in Example 1, except that the silica synthesized by the chemical method used in Example 1 was changed.

[0082] First, an appropriate amount of solvent was used to dissolve epoxy resin (NC-3000H) and 21 parts of phenolic resin (SN-485), and stirring was carried out for 2 hours or more.

[0083] Furthermore, 61% of silica 5 obtained by the organosilicon hydrolysis method (D50 is 2.0 μm, D100:D10 is 5.0, and the purity is 99.00%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0084] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 - 5 minutes to obtain an adhesive film with a resin layer in a semi-cured state. The semi-cured adhesive film (40 μm thick) and the browned PCB board were pressure-bonded and cured. After peeling off the release film, surface treatment was carried out, and copper electroplating was performed to form a laminated printed wiring board with circuits. Comparative Example 3

[0085] The oxygen in the silica synthesized by the chemical method in Example 1 was changed to silicon fine powder, and an adhesive film was manufactured in the same manner as in Example 1.

[0086] First, an appropriate amount of solvent was used to dissolve epoxy resin (NC-3000H) and 21 parts of phenolic resin (SN-485), and they were stirred for 2 hours or more.

[0087] Furthermore, 61% of silicon fine powder (SC2500-SQ) was added, and stirring was continued for 4 hours or more to mix them thoroughly and uniformly to form a solution with a solid content of 70%.

[0088] The above solution was applied to a release film, dried, then placed in an oven at 100°C and baked for 3 - 5 minutes to obtain an adhesive film with a resin layer in a semi-cured state. The semi-cured adhesive film (thickness 40 μm) and the browned PCB board were pressed and cured. After peeling off the release film, surface treatment was carried out, and copper electroplating was performed to form a laminated printed wiring board with circuits. Comparative Example 4

[0089] An adhesive film was manufactured in the same manner as in Example 1, except that the proportion of silica synthesized by the chemical method used in Example 1 was changed.

[0090] First, an appropriate amount of solvent was used to dissolve 28 parts of epoxy resin (NC-3000H) and 21 parts of phenolic resin (SN-485), and they were stirred for 2 hours or more.

[0091] Furthermore, 55% of silica 3 obtained by the organosilicon hydrolysis method (D50 is 0.5 μm, D100:D10 is 2.0, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix them thoroughly and uniformly to form a solution with a solid content of 70%.

[0092] The above solution was applied to a release film, dried, then placed in an oven at 100°C and baked for 3 minutes to obtain an adhesive film with a resin layer in a semi-cured state. The semi-cured adhesive film (thickness 40 μm) and the browned PCB board were pressed and cured. After peeling off the release film, surface treatment was carried out, and copper electroplating was performed to form a laminated printed wiring board with circuits. Comparative Example 5

[0093] An adhesive film was produced in the same manner as in Example 1, except that the ratio of the silica synthesized by the chemical method used in Example 1 was changed.

[0094] First, 28 parts of an epoxy resin (NC-3000H) and 21 parts of a phenolic resin (SN-485) were dissolved using an appropriate amount of a solvent and stirred for 2 hours or more.

[0095] Furthermore, 3 of silica obtained by the 90% organosilicon hydrolysis method (D50 is 0.5 μm, D100:D10 is 2.0, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0096] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 minutes to obtain an adhesive film with a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits. Comparative Example 6

[0097] An adhesive film was produced in the same manner as in Example 7, except that the silica synthesized by the chemical method used in Example 7 was changed.

[0098] First, 20 parts of an epoxy resin (NC-3000H), 10 parts of a cyanate (XU-371), and 10 parts of an active ester (HP-8000-65T) were dissolved using an appropriate amount of a solvent and stirred for 2 hours or more.

[0099] Furthermore, 4 of silica obtained by the 61% organosilicon hydrolysis method (D50 is 3.5 μm, D100:D10 is 5.0, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0100] The above solution was applied to a release film, dried, and then placed in an oven at 100°C and baked for 3 to 5 minutes to obtain an adhesive film with a resin layer in a semi-cured state. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits. Comparative Example 7

[0101] An adhesive film was produced in the same manner as in Example 7, except that the silica synthesized by the chemical method used in Example 7 was changed.

[0102] First, 20 parts of an epoxy resin (NC-3000H), 10 parts of a cyanate (XU-371), and 10 parts of an active ester (HP-8000-65T) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0103] Furthermore, 5 parts of silica obtained by the 61% organosilicon hydrolysis method (D50 is 2.0 μm, D100:D10 is 5.0, and the purity is 99.00%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0104] The above solution was applied to a release film, dried, and then placed in an oven at 100°C and baked for 3 to 5 minutes to obtain an adhesive film with a resin layer in a semi-cured state. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits. Comparative Example 8

[0105] The oxygen in the silica synthesized by the chemical method in Example 7 was changed to silicon fine powder, and an adhesive film was produced in the same manner as in Example 7.

[0106] First, 20 parts of an epoxy resin (NC-3000H), 10 parts of a cyanate (XU-371), and 10 parts of an active ester (HP-8000-65T) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0107] Furthermore, 61% of silicon fine powder (SC2500-SQ) was added and stirring was continued for more than 4 hours to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0108] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 - 5 minutes to obtain an adhesive film with a resin layer in a semi-cured state. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, copper electroplating was carried out, and a laminated printed wiring board with circuits was formed. Comparative Example 9

[0109] An adhesive film was produced in the same manner as in Example 7, except that the proportion of silica synthesized by the chemical method used in Example 7 was changed.

[0110] First, 20 parts of epoxy resin (NC-3000H), 10 parts of cyanate (XU-371), and 10 parts of active ester (HP-8000-65T) were dissolved using an appropriate amount of solvent and stirred for more than 2 hours.

[0111] Furthermore, 55% of silica 3 obtained by the organosilicon hydrolysis method (D50 is 0.5 μm, D100:D10 is 2.0, and purity is 99.90%) was added and stirring was continued for more than 4 hours to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0112] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 minutes to obtain an adhesive film with a resin layer in a semi-cured state. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, copper electroplating was carried out, and a laminated printed wiring board with circuits was formed. Comparative Example 10

[0113] An adhesive film was produced in the same manner as in Example 8, except that the silica synthesized by the chemical method used in Example 8 was changed.

[0114] First, 20 parts of hydrocarbon resin (XU-371), 20 parts of polyphenylene oxide resin (MX9000), and 5 parts of crosslinking aid (DVB) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0115] Furthermore, silica 4 (D50 is 3.5 μm, D100:D10 is 5.0, and purity is 99.90%) obtained by the 61% organosilicon hydrolysis method was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0116] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 - 5 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits. Comparative Example 11

[0117] An adhesive film was produced in the same manner as in Example 8, except that the silica synthesized by the chemical method used in Example 8 was changed.

[0118] First, 20 parts of hydrocarbon resin (XU-371), 20 parts of polyphenylene oxide resin (MX9000), and 5 parts of crosslinking aid (DVB) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0119] Furthermore, silica 5 (D50 is 2.0 μm, D100:D10 is 5.0, and purity is 99.00%) obtained by the 61% organosilicon hydrolysis method was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0120] The above solution was applied to a release film, dried, and then placed in an oven at 100°C and baked for 3 to 5 minutes to obtain an adhesive film with a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) and the browned PCB board were pressed and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits. Comparative Example 12

[0121] The oxygen of the silica synthesized by the chemical method in Example 8 was changed to silicon fine powder, and an adhesive film was manufactured in the same manner as in Example 8.

[0122] First, 20 parts of a hydrocarbon resin (XU-371), 20 parts of a polyphenylene oxide resin (MX9000), and 5 parts of a crosslinking aid (DVB) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0123] Furthermore, 61% of silicon fine powder (SC2500-SQ) was added, and stirring was continued for 4 hours or more to mix thoroughly and form a solution with a solid content of 70%.

[0124] The above solution was applied to a release film, dried, and then placed in an oven at 100°C and baked for 3 to 5 minutes to obtain an adhesive film with a semi-cured resin layer. The semi-cured adhesive film (40 μm thick) and the browned PCB board were pressed and cured. After peeling off the release film, surface treatment was performed, and copper electroplating was carried out to form a laminated printed wiring board with circuits. Comparative Example 13

[0125] An adhesive film was manufactured in the same manner as in Example 8, except that the ratio of the silica synthesized by the chemical method used in Example 8 was changed.

[0126] First, 20 parts of a hydrocarbon resin (XU-371), 20 parts of a polyphenylene oxide resin (MX9000), and 5 parts of a crosslinking aid (DVB) were dissolved using an appropriate amount of solvent and stirred for 2 hours or more.

[0127] Furthermore, 55% of silica 3 obtained by the organosilicon hydrolysis method (D50 is 0.5 μm, D100:D10 is 2.0, and the purity is 99.90%) was added, and stirring was continued for 4 hours or more to mix thoroughly and uniformly to form a solution with a solid content of 70%.

[0128] The above solution was applied to a release film, dried, then placed in an oven at 100 °C and baked for 3 minutes to obtain an adhesive film of a semi-cured resin layer. The semi-cured adhesive film (thickness 40 μm) and the PCB board after browning were pressure-bonded and cured. After peeling off the release film, surface treatment was performed, copper electroplating was carried out, and a laminated printed wiring board with circuits was formed.

[0129] Performance tests were conducted on the laminated printed wiring boards or copper-clad laminates of the above examples and comparative examples. The test items and methods are as follows.

[0130] (1) Tensile strength (30 °C): By the DMA method, it was kept at a constant temperature of 30 °C for 5 min, the prestress was 0.01 N, and it increased from 3 N / min to 17.5 N / min.

[0131] (2) Peel strength: The test was carried out by the IPC-TM-650 2.4.9 method.

[0132] (3) Drill processability: After laser drilling, it was sliced and the hole right angle was observed. When the right angle was 90 - 95 degrees, it was excellent; when it was 96 - 100 degrees, it was good; when it was 101 - 110 degrees, it was acceptable; when it was >110 degrees, it was unacceptable.

[0133] (4) Adhesive filling effect: After pressing the wiring board with the adhesive film, it was sliced and the adhesive filling situation between the wirings was observed. When there were no bubbles in the resin layer between the wirings, it was "excellent"; when there were bubbles in the resin layer between the wirings and the diameter of the bubbles was less than 1 μm, it was "good"; when there were bubbles in the resin layer between the wirings and the diameter of the bubbles was greater than 1 μm, it was "unacceptable".

[0134] (5) Electrical strength: The test was carried out by the IPC-TM-650 2.5.6.2A method.

[0135] (6) Ability of a thin circuit that can be realized: The smallest line / space that can be fabricated was measured.

[0136] (7) DK / DF: Tests were conducted using the SPDR (Splite Post Dielectric Resonator) method. The test conditions were in state A, and the frequency was 10 GHz.

[0137] The comparison of the performance tests is as shown in Tables 1 to 4 below.

[0138]

Table 1

[0139]

Table 2

[0140]

Table 3

[0141]

Table 4

[0142] As can be seen from Tables 1 to 4, the examples have high tensile strength (50 - 100 Mpa) and peel strength (7.0 - 9.0 N / cm), good drillability, good adhesive filling ability, higher electrical strength (83 - 90 kV / mm), and lower DK / DF. The DK can be reduced to 2.95 - 3.32, and the DF can be reduced to 0.004 - 0.014. It can realize the processing ability of thinner circuits and obtain better electrical characteristics.

[0143] Compared with Example 1, in Comparative Example 1 and Comparative Example 2, silica obtained by the organosilicon hydrolysis method with a particle size outside the scope of the invention was used, and the tensile strength, peel strength, and electrical strength of the produced adhesive film were all low. At the same time, the drill processability and adhesive filling ability deteriorated. In Comparative Example 3, silicon fine powder was used, and the decrease in the tensile strength and electrical strength of the produced adhesive film was obvious. At the same time, DK / DF also increased, and the wiring processability deteriorated. In Comparative Example 4, the proportion of silica was reduced to 55%, and the decrease in the tensile strength of the produced adhesive film was obvious. In Comparative Example 5, the proportion of silica was increased to 90%, and both the tensile strength and electrical strength of the produced adhesive film were low. The decrease in peel strength was obvious, and the adhesive filling ability deteriorated.

[0144] Compared with Example 7, in Comparative Example 6 and Comparative Example 7, silica obtained by the organosilicon hydrolysis method with a particle size outside the scope of the invention was used, and the tensile strength, peel strength, and electrical strength of the produced adhesive film were all low. At the same time, the drill processability and adhesive filling ability deteriorated. In Comparative Example 8, silicon fine powder was used, and the decrease in the tensile strength and electrical strength of the produced adhesive film was obvious. At the same time, DK / DF also increased, and the wiring processability deteriorated. In Comparative Example 9, the proportion of silica was reduced to 55%, and the decrease in the tensile strength of the produced adhesive film was obvious.

[0145] Compared with Example 8, in Comparative Example 10 and Comparative Example 11, silica obtained by the organosilicon hydrolysis method with a particle size outside the scope of the invention was used, and the tensile strength, peel strength, and electrical strength of the produced adhesive film were all low. At the same time, the drill processability and adhesive filling ability deteriorated. In Comparative Example 12, silicon fine powder was used, and the decrease in the tensile strength and electrical strength of the produced adhesive film was obvious. At the same time, DK / DF also increased, and the wiring processability deteriorated. In Comparative Example 13, the proportion of silica was reduced to 55%, and the decrease in the tensile strength of the produced adhesive film was obvious.

[0146] Although the resin composition of the present invention and its use have been described by the above embodiments, the applicant declares that the present invention is not limited to the above embodiments, that is, the present invention does not mean that it must be implemented depending on the above embodiments. Those skilled in the art should understand that any improvement to the present invention, equivalent substitution for the raw materials of the products of the present invention, addition of auxiliary components, selection of specific forms, etc. are all included within the protection scope and disclosure scope of the present invention.

Claims

1. It contains 15 to 39% of a crosslinkable curable resin and 61 to 85% of a filler by weight. The filler is silica prepared by an organosilicon hydrolysis method. The average particle size D50 of the silica is 0.1 to 3 μm, the ratio of D100:D10 ≦ 2.5, and the purity of the silica is greater than 99.9%. The silica is obtained by obtaining an initial product through an organosilicon hydrolysis reaction and firing the initial product. The firing temperature is 800 to 1300 °C. The organosilicon includes tetraethoxysilane, tetramethoxysilane, tetraphenoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, methyltriethoxysilane, dimethyldiethoxysilane. A resin composition characterized by the above.

2. The crosslinkable curable resin is a thermosetting resin or a photocurable resin. The crosslinkable curable resin is any one or at least a combination of two or more selected from epoxy resins, phenolic resins, cyanates, active esters, polyphenylene oxide resins, maleimide resins, silicone resins, polybenzoxazole resins, polyimide resins, hydrocarbon resins, or acrylate resins. The resin composition according to Claim 1, characterized by the above.

3. The crosslinkable curable resin is a combination of an epoxy resin and a phenolic resin. The epoxy resin includes any one or at least a combination of two or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, MDI-modified epoxy resin, novolak type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene-containing epoxy resin, or alicyclic epoxy resin. The phenolic resin includes any one or at least a combination of two or more of bisphenol A type phenolic resin, phenol novolak resin, biphenyl type phenolic resin, dicyclopentadiene type phenolic resin, or naphthalene-containing phenolic resin. The resin composition according to Claim 1, characterized by the above.

4. The organosilicon is tetraethoxysilane. The resin composition according to Claim 1, characterized by the above.

5. The average particle size D50 of the silica is 0.3 to 1 μm. The resin composition according to any one of Claims 1 to 4, characterized by the above.

6. An adhesive film, The adhesive film is produced by applying the resin composition according to any one of claims 1 to 4 to a release material and then drying and / or baking. The thickness of the adhesive film is 5 to 300 μm. An adhesive film characterized by this.

7. A copper foil with resin, The copper foil with resin includes a copper foil and the resin composition according to any one of claims 1 to 4 applied and dried and then adhered to the copper foil. The thickness of the resin layer of the copper foil with resin is 5 to 300 μm. The thickness of the copper foil of the copper foil with resin is 1 to 105 μm. A copper foil with resin characterized by this.

8. Produced by immersing the resin composition according to any one of claims 1 to 4 in a glass cloth and then drying. A semi-cured adhesive sheet characterized by this.

9. Using one or at least two of an adhesive film, a copper foil with resin, and a semi-cured adhesive sheet. The adhesive film is produced by applying the resin composition according to any one of claims 1 to 4 to a release material and then drying and / or baking. The copper foil with resin includes a copper foil and the resin composition according to any one of claims 1 to 4 applied and dried and then adhered to the copper foil. And the semi-cured adhesive sheet is produced by immersing the resin composition according to any one of claims 1 to 4 in a glass cloth and then drying. A copper-clad laminate characterized by this.

10. Using one or at least two of an adhesive film, a copper foil with resin, a semi-cured adhesive sheet, and a copper-clad laminate. The adhesive film is produced by applying the resin composition according to any one of claims 1 to 4 to a release material and then drying and / or baking. The copper foil with resin includes a copper foil and the resin composition according to any one of claims 1 to 4 applied and dried and then adhered to the copper foil. The semi-cured adhesive sheet is produced by immersing the resin composition according to any one of claims 1 to 4 in a glass cloth and then drying. And the copper-clad laminate uses one or at least two of the adhesive film, the copper foil with resin, and the semi-cured adhesive sheet. A multilayer board characterized by this.

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