Thermosetting resin composition and its insulating adhesive film

Abstract

To provide a thermosetting resin composition and an insulating adhesive film thereof.MEANS: A thermosetting resin composition comprises 30-70 pts.wt. of an epoxy resin (A), 5 to 500 pts.wt. of a modified spherical silicon fine powder (B), and 30 to 70 pts.wt. of a curing agent (C), wherein the spherical silicon fine powder comprises an amino-modified spherical silicon fine powder, with D50 of the modified spherical silicon fine powder being 0.1 to 2.0 μm, and with a coefficient of variation in a particle size distribution≥35%. By using the epoxy-based modified spherical silicone fine powder, and controlling the range of D50 and the coefficient of variation in the particle size distribution, when the resin composition is used for an insulation adhesive film, a problem that a high filling insulation adhesive film has high melt viscosity can be solved, low melt viscosity can be acquired, and it is applicable to manufacturing of a high filling laminate adhesive film for FC-BGA which is advantageous for filling a thin circuit with an adhesive, is strong in resistance against consumption / corrosion, is low in surface roughness after Desmear treatment, is high in chemical copper adhesive force and has low dielectric loss.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention belongs to the field of insulating material technology, and relates to a thermosetting resin composition and its insulating adhesive film.

Background Art

[0002] With the development of printed circuit technology, the additive process is favored by carrier plate manufacturers because it can produce extremely low line widths / line spacings. Therefore, several requirements have been put forward for insulating materials. 1. After manufacturing a single-layer circuit, since it is necessary to laminate on the surface, the insulating adhesive film material needs to have excellent rheological properties for adhesive filling to the circuit. Therefore, the insulating adhesive film needs to have a low melting viscosity. 2. Since the circuit is thin, sufficient bonding force between the circuit and the adhesive film is required, and the adhesive film needs to have the basic characteristics of the additive manufacturing method to obtain a high copper wire bonding force. 3. Since it is necessary to manufacture a thin circuit, the roughness after roughening the adhesive film should not be too large, otherwise, the electroplated copper will penetrate too deep into the insulating adhesive film and the interlayer insulation will fail. By adding a filler to the adhesive film, a low coefficient of thermal expansion can be obtained. The filler manufacturer removes the moisture on the filler surface by physical high temperature during the preparation process. However, even after high-temperature heating at 300 °C, it is difficult to completely remove the trace amount of bound water remaining on the filler surface. The existence of this trace amount of bound water affects the dielectric performance of the low dielectric loss adhesive film.

[0003] Therefore, in this field, it is desired to find an insulating material that can solve the above problems.

Summary of the Invention

Problems to be Solved by the Invention

[0004] In view of the deficiencies of the prior art, the object of the present invention is to provide a thermosetting resin composition and its insulating adhesive film.

Means for Solving the Problems

[0005] To achieve this object, the present invention adopts the following technical solutions.

[0006] In one aspect, the present invention contains 30 to 70 parts by weight of an epoxy resin (A), 5 to 500 parts by weight of a modified spherical silicon fine powder (B), and 30 to 70 parts by weight of a curing agent (C), wherein the spherical silicon fine powder contains an amino-modified spherical silicon fine powder, the D50 particle size of the modified spherical silicon fine powder is 0.1 to 2.0 μm, and the coefficient of variation of the particle size distribution is ≧ 35%. provides a thermosetting resin composition.

[0007] In the present invention, by using a modified spherical silicon fine powder in an epoxy system and controlling the range of its D50 particle size and the coefficient of variation of the particle size distribution, when the resin composition is used as an insulating adhesive film, the problem that the melt viscosity of a high-filling system is high can be solved, a low melt viscosity can be obtained, which is advantageous for the adhesive filling of thin circuits, has strong wear and corrosion resistance, a low surface roughness after Desmear treatment, a high chemical copper bonding force, a low dielectric loss, and is applicable to the production of a laminated adhesive film for a high-filling FC-BGA.

[0008] In the thermosetting resin composition of the present invention, the dosage of the epoxy resin may be 30 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight.

[0009] In the thermosetting resin composition of the present invention, the dosage of the modified spherical silicon fine powder may be 5 parts by weight, 10 parts by weight, 50 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, 500 parts by weight.

[0010] In the thermosetting resin composition of the present invention, the dosage of the curing agent may be 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight.

[0011] In the present invention, the D50 particle size of the modified spherical silicon fine powder is 0.1 to 2.0 μm (for example, 0.1 μm, 0.5 μm, 1 μm, 1.3 μm, 1.5 μm, 1.8 μm, or 2.0 μm), the coefficient of variation of the particle size distribution is ≧ 35% (for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%, etc.), and the coefficient of variation of the particle size distribution can be adjusted within the range of the coefficient of variation of a predetermined particle size distribution and within the range of a predetermined D50 particle size by classifying the spherical silicon fine powder. If the coefficient of variation of the particle size distribution is within this range, the melting viscosity of the semi-cured insulating adhesive film to be produced is low, and the filling property and fluidity are good.

[0012] In the present invention, when the D50 particle size of the modified spherical silicon fine powder is smaller than 0.1 μm, the melting viscosity of the semi-cured insulating adhesive film to be produced increases significantly, and the fluidity deteriorates. When the D50 particle size of the modified spherical silicon fine powder is larger than 2.0 μm, the ability to be embedded in a fine circuit becomes weak. When the coefficient of variation of the particle size distribution is smaller than 35%, the melting viscosity of the semi-cured insulating adhesive film to be produced increases. The coefficient of variation is also called the "standard deviation rate" and is one of the statistical quantities for determining the degree of particle size variation of each particle in the standard substance. The coefficient of variation of the particle size distribution of the standard substance is used to represent the degree of particle size dispersion of the particles of the standard substance, and is often expressed by the standard deviation or the percentage of the ratio of the standard deviation to the average particle size of the standard substance. The latter is also called the degree of dispersion. The calculation formula is coefficient of variation = standard deviation / average particle size. The standard deviation needs to be further calculated based on the statistical data of the Malvern particle size distribution, and the average particle size can be substituted using D50. The particle size according to the present invention is measured by the laser diffraction method, and the measuring device is a Malvern laser particle size distribution measuring device with a model number of MS3000.

[0013] Preferably, the amino-modified spherical silicon fine powder includes spherical silicon fine powder modified with an aminosilane coupling agent, and the dosage of the aminosilane coupling agent is 0.1 to 2% of the weight of the spherical silicon fine powder, for example, 0.1%, 0.3%, 0.5%, 0.8%, 1.0%, 1.3%, 1.5%, 1.8%, or 2%.

[0014] Preferably, the amino-modified spherical silicon fine powder is obtained by pretreating the spherical silicon fine powder with a silazane compound and then modifying it with an aminosilane coupling agent. First, by pretreating the spherical silicon fine powder with a silazane compound, the OH groups (bound water) on the filler surface are thoroughly removed, the consistency of the surface treatment effect of the aminosilane coupling agent is improved, and the spherical silicon fine powder as an inorganic substance and the resin compound as an organic substance can be more uniformly and sufficiently fused. Furthermore, it is advantageous for reducing the dielectric loss of the insulating adhesive film.

[0015] Preferably, the silazane compound is any one or at least a combination of two selected from hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa(t-butyl)disilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilazane, trisilazane, cyclotrisilazane, or 1,1,3,3,5,5-hexamethylcyclotrisilazane.

[0016] Preferably, the carbon amount per unit surface area of the amino-modified spherical silicon fine powder is 0.20 mg / m 2 ~0.50 mg / m 2 , for example, 0.20 mg / m 2 , 0.30 mg / m 2 , 0.35 mg / m 2 , 0.4 mg / m 2 , 0.45 mg / m 2 , or 0.50 mg / m 2If the carbon content is too high, the lamination stability, reliability, and environmental resistance performance of the adhesive film will deteriorate. If the carbon content is too low, the bonding strength between the spherical silicon fine powder as an inorganic substance and the resin compound as an organic substance will decrease, and the resin will no longer be able to coat the filler.

[0017] In the present invention, the degree of surface treatment with the surface treatment agent can be evaluated by the carbon content per unit surface area. The carbon content per unit surface area of the amino-modified spherical silicon fine powder is measured by a method of washing the amino-modified spherical silicon fine powder after surface treatment with methyl ethyl ketone and then measuring. Specifically, 30 g of methyl ethyl ketone is added to 15 g of the amino-modified spherical silicon fine powder after surface treatment with the surface treatment agent, ultrasonically washed at 25°C for 5 minutes, the supernatant is removed, the solid content is dried, and then the carbon content per unit surface area of 0.3 g of the weighed amino-modified spherical silicon fine powder can be measured with a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by Horiba, Ltd. can be used.

[0018] Preferably, the aminosilane coupling agent is any one or at least a combination of two selected from N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, aminopropylmethoxysilane, or aminopropyltriethoxysilane.

[0019] Preferably, the epoxy resin is any one or at least a combination of two selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, dicyclopentadiene type novolac type epoxy resin, biphenyl type novolac type epoxy resin, aralkyl type novolac type epoxy resin, aralkyl biphenyl type novolac type epoxy resin, aralkyl naphthol type novolac type epoxy resin, or naphthalene type epoxy resin.

[0020] Preferably, the curing agent is any one or at least a combination of two selected from amine-based curing agents, cyanate resins, active esters, phenolic resins, or acid anhydride-based curing agents.

[0021] Preferably, the thermosetting resin composition further contains a carbodiimide resin.

[0022] Preferably, the carbodiimide resin is any one or a combination of two of the carbodiimide resins containing an aliphatic structure or an aromatic structure.

[0023] Preferably, taking the total weight of component (A), component (C), and component (D) as 100 parts by weight, the dosage of the carbodiimide resin is 1 to 10 parts, for example, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, or 10 parts.

[0024] Preferably, the thermosetting resin composition further contains another filler (E).

[0025] Preferably, the other filler contains an inorganic filler and / or an organic filler.

[0026] Preferably, the inorganic filler is any one or a combination of at least two selected from crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate, or mica.

[0027] Preferably, the organic filler is any one or a combination of at least two selected from polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenylene ether, or polyether sulfone powder.

[0028] Preferably, with the total weight of components (A), (C), and (D) being 100 parts by weight, the total addition amount of the modified spherical silicon micropowder (B) and other filler (E) is 5 to 500 parts, for example, 5 parts by weight, 10 parts by weight, 30 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, or 500 parts by weight.

[0029] In the present invention, on the premise of not affecting the comprehensive performance of the thermosetting resin composition, a thermoplastic resin may be further added. The thermoplastic resin is, for example, a polyimide resin, a phenoxy resin, a polyphenylene ether, an acrylate resin, a polyvinyl acetal resin, a polyamideimide resin, a polyether sulfone resin, a polysulfone resin, or a core-shell rubber.

[0030] Preferably, the thermosetting composition further contains a curing accelerator (F).

[0031] Preferably, the curing accelerator is any one or a combination of at least two selected from organometallic salt compounds, imidazole compounds and their derivatives, piperidine-based compounds, or tertiary amines.

[0032] Preferably, the curing accelerator is any one or at least a mixture of two or more selected from 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, tri-n-butylamine, triphenylphosphine, boron trifluoride complex, metal octylate, metal acetylacetonate, metal naphthenate, metal salicylate, or metal stearate, and the metal is any one or at least a combination of two or more selected from zinc, copper, iron, tin, cobalt, or aluminum.

[0033] Preferably, with the total weight of components (A), (C), and (D) being 100 parts by weight, the dosage of the curing accelerator (F) is 0.01 to 1 part, for example, 0.01 part by weight, 0.03 part by weight, 0.05 part by weight, 0.08 part by weight, 0.1 part by weight, 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, or 1 part by weight.

[0034] In another aspect, the present invention provides a resin adhesive solution containing the above thermosetting composition and a solvent.

[0035] Preferably, the solvent is any one or at least a combination of two or more selected from acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene, or xylene.

[0036] In another aspect, the present invention provides an insulating adhesive film containing the above thermosetting composition.

[0037] In the present invention, the method for preparing the insulating adhesive film includes the steps of mixing the thermosetting composition and a solvent to obtain a resin adhesive solution, applying the resin adhesive solution to a substrate, baking, removing the substrate, and obtaining the insulating adhesive film.

[0038] Preferably, the substrate is any one of a PET release film, a polyethylene film, a polypropylene film, or a polyvinyl chloride film.

[0039] Preferably, the thickness of the base material is 10 to 150 μm, for example, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, or 150 μm, and more preferably, it is 20 to 60 μm.

[0040] Preferably, the baking temperature is 80 to 120 °C, for example, 80 °C, 90 °C, 100 °C, 110 °C, or 120 °C.

[0041] Preferably, the baking time is 1 to 10 min, for example, 1 min, 3 min, 5 min, 8 min, or 10 min.

[0042] Preferably, the thickness of the insulating adhesive film is 10 to 100 μm, for example, 10 μm, 30 μm, 50 μm, 80 μm, or 100 μm.

[0043] Preferably, the melt viscosity of the insulating adhesive film is 500 to 2100 Pa·s, for example, 500 Pa·s, 600 Pa·s, 700 Pa·s, 800 Pa·s, 900 Pa·s, 1000 Pa·s, 1200 Pa·s, 1500 Pa·s, 1800 Pa·s, 2000 Pa·s, or 2100 Pa·s.

[0044] Preferably, the dielectric loss after curing of the insulating adhesive film is ≦0.0182, for example, 0.0112, 0.0129, 0.0131, 0.0133, 0.0134, 0.0136, 0.0166, 0.0176, or 0.0182.

[0045] Preferably, the surface roughness Ra value after Desmear treatment of the insulating adhesive film is ≦0.360 μm (for example, 0.36 μm, 0.35 μm, 0.32 μm, 0.31 μm, 0.29 μm, 0.28 μm, 0.27 μm, 0.25 μm, or 0.22 μm), and the chemical copper bonding strength is ≧5.7 N / cm (for example, 5.70 N / cm, 6.10 N / cm, 6.40 N / cm, 6.50 N / cm, 6.60 N / cm, 7.10 N / cm, 7.90 N / cm, or 8.10 N / cm).

[0046] The insulating adhesive film according to the present invention is used in the manufacturing scene in FC-BGA (Flip Chip Ball Grid Array, a package format of flip chip ball grid array) by manufacturing a circuit by a semi-additive method or an additive method. The insulating adhesive film simultaneously has a low surface roughness and a high chemical copper bonding strength after wear and corrosion, and solves the technical problem that it is difficult to balance the low surface roughness and the high copper foil peeling strength, which has been a long-term problem in this field.

Effect of the Invention

[0047] Compared with the prior art, the present invention has the following beneficial effects.

[0048] In the present invention, by using a modified spherical silicon fine powder based on epoxy and controlling the range of its D50 particle size and the coefficient of variation of the particle size distribution, when the resin composition is used for an insulating adhesive film, the problem that the melt viscosity of a high-filling system is high can be solved, and a low melt viscosity can be obtained, which is advantageous for the adhesive filling of thin circuits, has strong wear and corrosion resistance, a low surface roughness after Desmear treatment, a high chemical copper bonding strength, a low dielectric loss, and is applicable to the production of a laminated adhesive film for high-filling FC-BGA.

Embodiments for Carrying out the Invention

[0049] 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.

[0050] The information of the modified spherical silicon fine powder used in the examples and comparative examples is as follows.

[0051] Modified spherical silicon micropowder 1: Put 100 parts by weight of spherical silicon micropowder into a stirrer, stir the spherical silicon micropowder while spraying the gasified aminosilane coupling agent (0.2 parts by weight, 3-aminopropyltrimethoxysilane, KBM-903, Shin-Etsu Chemical), react for 10 min to obtain the amino-modified pretreated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 1 is 0.5 μm, and the coefficient of variation of the particle size distribution is 50%.

[0052] Modified spherical silicon micropowder 2: Put 100 parts by weight of spherical silicon micropowder into a stirrer, stir the spherical silicon micropowder while spraying the gasified aminosilane coupling agent (0.4 parts by weight, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical), react for 10 min to obtain the amino-modified pretreated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 2 is 0.5 μm, and the coefficient of variation of the particle size distribution is 50%.

[0053] Modified spherical silicon micropowder 3: Put 100 parts by weight of spherical silicon micropowder into a stirrer, stir the spherical silicon micropowder while spraying the gasified silazane compound (0.2 parts by weight, hexamethyldisilazane, SZ-31, Shin-Etsu Chemical), react for 10 min to obtain the silazane-pretreated spherical silicon micropowder, and then stir the spherical silicon micropowder while spraying the gasified aminosilane coupling agent (0.4 parts, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical), react for 10 min to obtain the amino-modified pretreated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 3 is 0.5 μm, and the coefficient of variation of the particle size distribution is 50%.

[0054] Modified spherical silicon micropowder 4: Put 100 parts by weight of spherical silicon micropowder into a stirrer, stir the spherical silicon micropowder while spraying the gasified aminosilane coupling agent (0.4 parts by weight, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical), react for 10 min to obtain the amino-modified pretreated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 4 is 0.7 μm, and the coefficient of variation of the particle size distribution is 50%.

[0055] Put 100 parts by weight of spherical silicon micropowder of modified spherical silicon micropowder 5 into a stirrer, stir the spherical silicon micropowder while spraying the gasified aminosilane coupling agent (0.4 parts by weight, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical), react for 10 min, and obtain aminated pre-treated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 5 is 1.0 μm, and the coefficient of variation of the particle size distribution is 50%.

[0056] Put 100 parts by weight of spherical silicon micropowder of modified spherical silicon micropowder 6 into a stirrer, stir the spherical silicon micropowder while spraying the gasified aminosilane coupling agent (0.4 parts by weight, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical), react for 10 min, and obtain aminated pre-treated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 6 is 0.5 μm, and the coefficient of variation of the particle size distribution is 40%.

[0057] Put 100 parts by weight of spherical silicon micropowder of modified spherical silicon micropowder 7 into a stirrer, stir the spherical silicon micropowder while spraying the gasified aminosilane coupling agent (0.4 parts by weight, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical), react for 10 min, and obtain aminated pre-treated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 7 is 0.5 μm, and the coefficient of variation of the particle size distribution is 60%.

[0058] Put 100 parts by weight of spherical silicon micropowder of modified spherical silicon micropowder 8 into a stirrer, stir the spherical silicon micropowder while spraying the gasified aminosilane coupling agent (0.4 parts by weight, ethyltrimethoxysilane, KBM-1003, Shin-Etsu Chemical), react for 10 min, and obtain aminated pre-treated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 8 is 0.5 μm, and the coefficient of variation of the particle size distribution is 40%.

[0059] Modified spherical silicon micropowder 9: 100 parts by weight of spherical silicon micropowder was put into a stirrer, and while spraying the gasified aminosilane coupling agent (0.4 parts by weight, 3-glycidoxypropyltrimethoxysilane, KBM-403, Shin-Etsu Chemical), the spherical silicon micropowder was stirred and reacted for 10 min to obtain the amino-modified pretreated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 9 is 0.5 μm, and the coefficient of variation of the particle size distribution is 40%.

[0060] Modified spherical silicon micropowder 10: 100 parts by weight of spherical silicon micropowder was put into a stirrer, and while spraying the gasified aminosilane coupling agent (0.4 parts by weight, 3-methacryloxypropyltrimethoxysilane, KBM-503, Shin-Etsu Chemical), the spherical silicon micropowder was stirred and reacted for 10 min to obtain the amino-modified pretreated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 10 is 0.5 μm, and the coefficient of variation of the particle size distribution is 40%.

[0061] Modified spherical silicon micropowder 11: 100 parts by weight of spherical silicon micropowder was put into a stirrer, and while spraying the gasified aminosilane coupling agent (0.4 parts by weight, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical), the spherical silicon micropowder was stirred and reacted for 10 min to obtain the amino-modified pretreated spherical silicon micropowder. The D50 of the modified spherical silicon micropowder 11 is 0.5 μm, and the coefficient of variation of the particle size distribution is 20%.

Example

[0062] 45 parts by weight of an epoxy resin (NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), 50 parts by weight of a phenol resin (MEH-7851H, manufactured by Meiwafosis Co., Ltd.), 100 parts by weight of modified spherical silicon micropowder 1, 5 parts by weight of a carbodiimide resin (HMV-10B, manufactured by Nisshinbo Industries, Inc.), 10 parts by weight of another filler (spherical silica, SC-2050MB, manufactured by Admatechs Co., Ltd.), and 0.1 part by weight of a curing accelerator (2E4MZ) were placed in a butanone solvent and stirred for 2 hours to form a resin adhesive solution with a solid content of 65%. The resin adhesive solution was applied to a PET release film and baked in an oven at 120°C for 5 minutes to obtain an insulating adhesive film.

[0063] The compositions of the thermosetting resin compositions of Examples 2 to 12 and Comparative Examples 1 to 4 are as shown in Tables 1 to 3, where the dosages of the components were calculated in parts by weight.

[0064] [Table 1]

[0065] [Table 2]

[0066] [Table 3]

[0067] Performance tests were conducted on the obtained insulating adhesive film, and the test methods were as follows.

[0068] <Minimum melt viscosity> Using 350 mg of a semi-cured insulating adhesive film as a sample, it was ground into powder and measured using a vibrating rheometer. The heating rate was 3°C / min, the test temperature was 40 to 180°C, the obtained test curve had the temperature on the horizontal axis and the melt viscosity on the vertical axis, and the numerical value was read at the minimum melt viscosity point, with the unit being Pa·s.

[0069] <Value of dielectric loss (D f)> A sample of a fully cured insulating adhesive film with a length of 80 mm, a width of 80 mm, and a thickness of 40 μm was taken. The sample was fixed to an Agilent impedance material analyzer using an Agilent 16453A type measuring jig, and a test scan was performed to measure the value of dielectric loss at 1 GHz.

[0070] <Arithmetic mean value of roughness profile (Ra)> The insulating adhesive film was pressure-bonded to the surface of the core board and cured in an oven at 180 °C for 30 min to obtain a pre-cured insulating adhesive film. For the insulating adhesive film, it was immersed in an aqueous solution of ethylene glycol ether and sodium hydroxide (MV Sweller, ATOTECH) at 70 °C for 10 min, washed with deionized water for 2 min, immersed in a potassium permanganate solution (MV P-Etch, ATOTECH) at 80 °C for 30 min, washed with deionized water for 2 min, and immersed in an acidic aqueous solution (MV Reduction Cleaner, ATOTECH) at 50 °C for 5 min for Desmear treatment to obtain a roughened insulating adhesive film. The surface Ra after roughening treatment was tested using a laser confocal microscope (OLYMPUS).

[0071] <Chemical copper bonding strength (PS)> For the above roughened insulating adhesive film, it was immersed in a chemical copper solution (MV TP1, ATOTECH) for 20 min, the thickness of the electroplated copper was set to 25 μm, and copper deposition, electroplating, and post-curing treatments were performed by curing in an oven at 200 °C for 60 min. The chemical copper bonding strength of the insulating adhesive film was tested using a copper foil peel strength measuring device.

[0072] As can be seen from Tables 1 to 3, the minimum melt viscosity of the insulating adhesive films of Examples 1 to 12 of the present application was 500 to 2100 Pa·s, the surface roughness Ra value after Desmear treatment was 0.22 to 0.36 μm, the chemical copper bonding strength was 5.7 to 8.1 N / cm, and the dielectric loss was 0.0112 to 0.0182. In Example 6, compared with the modified spherical silicon fine powder of Example 5, after pretreatment with a silazane compound, the OH groups (bound water) on the filler surface were thoroughly removed, the consistency of the surface treatment effect of the coupling agent was improved, and the insulating adhesive film obtained a lower dielectric loss.

[0073] In Comparative Examples 1 to 3, spherical silicon fine powder modified with vinyl, epoxy or methacryl silane coupling agent was used respectively. The effect of the minimum melt viscosity of the prepared insulating adhesive film was ordinary, and the surface roughness Ra value after Desmear treatment was significantly increased, but it did not contribute to the improvement of the chemical copper bonding strength. Furthermore, the electroplated copper penetrated too deep into the insulating adhesive film, and there was concern about the long-term reliability of the interlayer insulation. The coefficient of variation of the particle size distribution of the modified spherical silicon fine powder used in Comparative Example 4 was only 20%, and the minimum melt viscosity of the prepared insulating adhesive film was too high, which was disadvantageous for the adhesive filling of fine circuits.

[0074] The applicant declares that although the present invention has been described with respect to the thermosetting resin composition and its insulating adhesive film of the present invention by the above examples, the present invention is not limited to the above examples, that is, the applicant declares that the present invention does not mean that it must be implemented depending on the above examples. Those skilled in the art should understand that any improvement to the present invention, equivalent substitution of the raw materials used in 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 30 to 70 parts by weight of an epoxy resin (A), 5 to 500 parts of a modified spherical silicon fine powder (B), and 30 to 70 parts of a curing agent (C). The spherical silicon fine powder contains an amino-modified spherical silicon fine powder. The D50 particle size of the modified spherical silicon fine powder is 0.1 to 2.0 μm, and the coefficient of variation of the particle size distribution is ≧35%. The amino-modified spherical silicon fine powder contains a spherical silicon fine powder modified with an aminosilane coupling agent. The dosage of the aminosilane coupling agent is 0.1 to 2% of the weight of the spherical silicon fine powder. A thermosetting resin composition characterized by the above.

2. The amino-modified spherical silicon fine powder is obtained by pretreating the spherical silicon fine powder with a silazane compound and then modifying it with an aminosilane coupling agent. The silazane compound is selected from any one or at least two combinations of hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexakis(t-butyl)disilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilazane, trisilazane, cyclotrisilazane, or 1,1,3,3,5,5-hexamethylcyclotrisilazane. The thermosetting resin composition according to Claim 1, characterized by the above.

3. The amino-silane coupling agent is any one or at least a combination of two selected from N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, aminopropylmethoxysilane, or aminopropyltriethoxysilane. The thermosetting resin composition according to claim 1, characterized in that.

4. The epoxy resin is any one or at least a combination of two selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, dicyclopentadiene type novolac type epoxy resin, biphenyl type novolac type epoxy resin, aralkyl type novolac type epoxy resin, aralkyl biphenyl type novolac type epoxy resin, aralkyl naphthol type novolac type epoxy resin, or naphthalene type epoxy resin. The curing agent is any one or at least a combination of two selected from amine-based curing agents, cyanate resins, active esters, phenolic resins, or acid anhydride-based curing agents. The thermosetting resin composition according to claim 1, characterized in that.

5. The thermosetting resin composition further contains a carbodiimide resin (D). The carbodiimide resin is any one or a combination of two of carbodiimide resins containing an aliphatic structure or an aromatic structure. Taking the total weight of component (A), component (C), and component (D) as 100 parts by weight, the dosage of the carbodiimide resin is 1 to 10 parts. The thermosetting resin composition according to claim 1, characterized in that.

6. The thermosetting resin composition further contains another filler (E). The other filler contains an inorganic filler and / or an organic filler. The inorganic filler is any one or at least a combination of two or more selected from crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate, or mica, The organic filler is any one or at least a combination of two or more selected from polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenylene ether, or polyether sulfone powder, The thermosetting resin composition according to claim 5, characterized in that.

7. The thermosetting resin composition further contains another filler (E), With the total weight of component (A), component (C) and component (D) being 100 parts by weight, the total addition amount of the modified spherical silicon fine powder (B) and another filler (E) is 5 to 500 parts, The thermosetting resin composition according to claim 6, characterized in that.

8. The thermosetting resin composition further contains a curing accelerator (F), The curing accelerator is any one or at least a combination of two or more selected from organometallic salt compounds, imidazole compounds and their derivatives, piperidine-based compounds, or tertiary amines, The thermosetting resin composition according to claim 6, characterized in that.

9. The curing accelerator is any one or at least a mixture of two or more selected from 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, tri-n-butylamine, triphenylphosphine, boron trifluoride complex, metal octylate, metal acetylacetonate, metal naphthenate, metal salicylate, or metal stearate, and the metal is any one or at least a combination of two or more selected from zinc, copper, iron, tin, cobalt, or aluminum, The thermosetting resin composition according to claim 8, characterized in that.

10. The thermosetting resin composition further contains a curing accelerator (F), With the total weight of component (A), component (C) and component (D) being 100 parts by weight, the dosage of the curing accelerator (F) is 0.01 to 1 part, The thermosetting resin composition according to claim 8, characterized in that.

11. A resin adhesive liquid comprising the thermosetting resin composition according to claim 1 and a solvent, wherein the solvent is any one selected from acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene, or xylene, or a combination of at least two thereof, and the resin adhesive liquid is characterized by this.

12. An insulating adhesive film comprising the thermosetting resin composition according to claim 1, wherein the thickness of the insulating adhesive film is 10 to 100 μm, the melt viscosity of the insulating adhesive film is 500 to 2100 Pa·s, the dielectric loss after curing of the insulating adhesive film is ≦ 0.0182, the surface roughness Ra value after Desmear treatment of the insulating adhesive film is ≦ 0.360 μm, and the chemical copper bonding strength is ≧ 5.7 N / cm, and the insulating adhesive film is characterized by this.

Images