TWI405519B - A conductive paste composition for hole filling, a printed circuit board using the same, and a method for manufacturing the same - Google Patents

Abstract

Disclosed is a conductive paste composition for via hole filling, which contains 30-70% by volume of a conductive particle having an average particle diameter of 0.5-20 µm and a specific surface area of 0.05-1.5 m<SUP>2</SUP>/g, and 70-30% by volume of a resin which contains not less than 10% by weight of an epoxy compound having one or more epoxy groups in a molecule, wherein the total amount of hydroxy groups, amino groups and carboxyl groups is not more than 5% by mole of the epoxy groups and the epoxy equivalent is 100-350 g/eq. This conductive paste composition for via hole filling contains chlorine in an amount of 20-2000 ppm.

Description

Conductive paste composition for through-hole filling, printed substrate using the same, and method of producing the same Technical field

The present invention relates to a conductor paste composition for via filling, a double-sided printed board and a multilayer printed board using the same, and a method of manufacturing the same.

Background technique

In recent years, with the increase in performance and miniaturization of electronic equipment, high-density and high-density of circuit boards are being sought. It is known that the interlayer connection method of the substrate which can be connected at the shortest distance is connected between the ICs or between the parts by the through holes, and the density is increased. The through-hole connection used in a general glass epoxy multilayer substrate is difficult to connect only between the required layers because of the connection through the through-hole plating, and the structure having the platform of the electrode on the uppermost layer of the substrate is The electrode land that does not constitute the surface package part on the uppermost layer of the substrate is not easy to increase the package density due to such limitations. Although it is possible to perform a method in which one of the substrate is half-opened to replace the through-hole to reduce the through-hole, and the through-hole is filled with the conductive paste and the uppermost layer of the substrate is plugged by a plating process to increase the package density, etc. The method of the problem, but the manufacturing process is complicated.

On the other hand, the inner via connection can be connected only between the required layers, and there is no through hole in the uppermost layer of the substrate, and the package is excellent. An example of applying the connection method to a resin substrate (for example, a glass epoxy substrate) includes embedding a low-viscosity solvent-type silver paste into a through-hole on a double-sided substrate by using a printing method, and drying and hardening it to obtain a conduction. Substrate. However, its Contact resistivity up to 10m Ω. About cm, and lack of reliability against thermal shock such as thermal cycling. Further, a method of using a small amount of a conductor particle, a solvent having a low boiling point, or a reactive diluent can be used as a method of lowering the viscosity of the conductor paste to improve the embedding property of the conductor paste to the through hole.

However, when the amount of addition of the conductor particles is reduced, the contact point between the fillers is reduced, the contact resistance of the via hole is increased, and reliability is not ensured in the test for generating thermal stress such as thermal cycle. Further, in the method of adding a solvent having a low boiling point or a reactive diluent, the amount of weight loss due to volatilization of the components during hardening is increased, and the substrate is swelled or lowered by the volatile component. The adhesion of the wiring copper foil. Therefore, by containing a high concentration of conductive particles and using linoleic acid dimer glycidyl epoxy resin as a main component, it is possible to realize a solvent-free and low-viscosity, high-conductivity, heat-resistant and impact-resistant conductive connection. Body paste.

Further, prior art document information related to the invention of the aforementioned application, for example, Patent Document 1 is known.

However, the conventional example has a linoleic acid dimer glycidyl ester epoxy resin as a main component, and has a low viscosity and a strong thermal shock due to a decrease in the crosslinking density of the resin, but a high humidity test due to a high water absorption rate. The reliability of the conductive connection is insufficient. In addition, since the linoleic acid dimer glycidyl ester epoxy resin is a lower adhesive strength in the epoxy resin, when a conductive paste containing the main component is used in the through hole, it is bonded to the wiring copper foil. Then the power is insufficient.

In general, in order to lower the water absorption rate of the epoxy resin and increase the bonding strength, the mixing can further increase the crosslinking density and the epoxy equivalent is low, and a method such as a bisphenol type epoxy resin is known. However, reducing the water absorption rate and improving the connection The low epoxy equivalent resins of the strength have a higher viscosity than the linoleic acid dimer glycidyl epoxy resin. Therefore, it becomes a conductor paste which cannot fill a through-hole.

Further, as long as the existence ratio of the conductive particles in the inner via hole is large, the conductor resistance can be reduced. Therefore, the conductive paste can be made to contain a large amount of conductive particles as much as possible to enhance conductivity. However, since the solid conductive particles and the liquid binder are mixed, the mixing ratio of the gelatinization is limited, and if the viscosity is too high, the filling property to the through holes is impaired. In particular, the smaller the diameter of the inner via hole, the more susceptible it is to the density of the conductive particles. Therefore, the continuity of the inner through hole is seriously affected.

On the other hand, in order to reduce the on-resistance in the via hole, the conductive paste may contain chlorine to reduce the surface of the conductive particles contained in the conductive paste, but if the chlorine content is too large, the printed substrate The insulation is reduced. In particular, if the chlorine content in the conductive paste is higher than the chlorine content in the prepreg, the chlorine in the conductive paste contained in the through holes will intrude into the prepreg, so that the insulating properties of the printed substrate are easier. reduce.

[Patent Document 1] JP-A-7-176466

Invention

The present invention provides a conductive paste composition which can be connected by a through hole in a small aperture to obtain electrical connection between the electrode layers, high thermal shock resistance, high moisture resistance, and high connection strength. Further, in the present invention, a multilayer printed board is produced from a double-sided printed board including the through holes in the paste.

Further, the conductor paste composition of the present invention is a conductive paste composition filled in a via hole, and comprises: (a) 30 to 70% by volume of conductive particles having an average particle diameter of 0.5 to 20 μm, and The specific surface area is 0.05 to 1.5 m ² /g; (b) 70 to 30% by volume of the resin is 10% by weight or more of the epoxy compound, and the epoxy compound has one or more rings in one molecule. The oxy group and the total amount of the hydroxyl group, the amine group and the carboxyl group are 5 mol% or less of the epoxy group, the epoxy equivalent is 100 to 350 g/eq, and the chlorine is 20 to 2000 ppm.

According to the double-sided printed board using the conductive paste for through-hole filling of the present invention, the method of forming the same, and the multilayer substrate using the same, it is possible to realize a small aperture in which high reliability can be easily achieved without using a through-hole plating technique. The double-sided printed substrate of the through hole can also be easily multi-layered.

Simple illustration

Fig. 1 is a cross-sectional view showing the structure of a double-sided printed board according to an embodiment of the present invention.

Fig. 2A is a plan view showing a method of forming a double-sided printed board of the same embodiment.

Fig. 2B is a plan view showing a method of forming a double-sided printed circuit board of the same embodiment.

Fig. 2C is a plan view showing a method of forming a double-sided printed board of the same embodiment.

Fig. 2D is a drawing showing a method of forming a double-sided printed board of the same embodiment.

Fig. 3A is a plan view showing a method of forming a multilayer printed substrate of the same embodiment.

3B is a method of forming a multilayer printed substrate of the same embodiment. Drawings.

Fig. 4A is a plan view showing another method of forming a multilayer printed board of the same embodiment.

Fig. 4B is a plan view showing another method of forming a multilayer printed board of the same embodiment.

Fig. 5 is a structural view showing conductive particles used in a printed circuit board of the same embodiment.

Best form for implementing the invention (Embodiment 1)

Hereinafter, a double-sided printed board using the via paste for conductive filling of the present invention, a method of forming the same, and a multilayer printed board using the same will be described in detail with reference to the drawings.

Fig. 1 is a structural sectional view showing an embodiment of a double-sided printed circuit board of the present invention. In the first embodiment, the double-sided printed circuit board 104 is composed of a laminated base material 101, a copper foil 102 (a copper foil of a wiring pattern), and a conductor through hole 103, and the conductor through hole 103 is hardened and filled with a conductor. The pore size of the paste is a small pore size of 150 μm or less. The focus of the present invention is that the conductor paste composition is low in viscosity and therefore easy to fill, and is filled with a high content of conductive particles. That is to say, the present invention is low resistivity, low coefficient of thermal expansion, and the resin in the electrical conductor paste composition has low water absorption, high adhesion strength, and low volatility without solvent, so that in all environmental tests, A through-hole substrate having a small aperture with high connection reliability is fabricated. In addition, the inner via connection is a method of connecting the double-sided and the layers of the multilayer printed substrate at any position.

The conductor particles in the conductor paste composition forming the via hole 103 need to have a high concentration in the conductor composition. The reason for this is that, as described above, the connection reliability is improved by increasing the contact probability between the conductor particles, and the connection reliability is increased when the substrate is skewed due to thermal or mechanical stress. In order to disperse the conductor particles at a high concentration, the average particle diameter of the conductor particles is in the range of 0.2 to 20 μm, and the smaller the specific surface area, the better, and the value is preferably 0.05 to 1.5 m ² /g. If the average particle diameter is less than 0.2 μm, the specific surface area will be greater than 1.5 m ² /g, but it will not be dispersed at a high concentration. If it is larger than 20 μm, the number of conductive particles filled in the conductive paste of one via hole will be Too little to reduce connection reliability. Further, due to the difficult surface area less than 0.05m ² / g manipulation average particle diameter of 20 μm or less, and the conductive particles could not be dispersed so that a high concentration of poorly if greater than 1.5m ² / g. Further, in order to improve the filling property of the conductor paste composition to the via hole, the viscosity and the TI value are preferably as low as possible, and the TI value is preferably 1.0 or less. In addition, the TI value is expressed in the paste having a viscosity dependence on the viscosity, and the relative ratio of each viscosity at different shear rates. In the present invention, the TI value is a ratio (A/B) of a viscosity (A) of 1 [1/sec] at a temperature of 25 ° C and a viscosity (B) of 2 [1/sec] at a temperature of 25 ° C. In addition, the viscosity measurement system was made by Toki Shoji Co., Ltd., E-type viscometer (DVU-E type), R = 14 mm at 25 ° C, 3 ° cone, 0.5 rpm (corresponding to shear rate 1 (1/s) ))).

In order to ensure insulation, the chlorine content in the present invention needs to be lower than the chlorine content in the prepreg, and is preferably from 20 to 2,000 ppm. If it is more than 2000 ppm, the insulation of the printed substrate is lowered. Further, if it is less than 20 ppm, the contact resistance value of the via hole becomes large, which is not preferable.

The situation when it is greater than 2000 ppm is explained in more detail. At this time, since the content of chlorine in the conductor paste filled in the through hole is higher than the content of chlorine in the prepreg, there is a concern that the prepreg is invaded and the chlorine concentration in the prepreg is increased. The insulation of the substrate is lowered and displacement is likely to occur. Further, when the semiconductor device is packaged on the platform directly above the via hole, chlorine in the via hole is easily moved to the semiconductor device, and the insulation property to the semiconductor device is lowered.

Further, as the type of the conductor particles, a noble metal such as gold, platinum, silver or palladium or a base metal such as copper, nickel, tin, lead or indium may be used, or two or more kinds thereof may be used in combination.

Fig. 5 is a structural view showing conductive particles used in a printed circuit board according to an embodiment of the present invention. In Fig. 5, the core 501 is spherical, and the conductive material 502 has a function as a conductive filler covering the surface of the core 501. In this way, it is also possible to use a conductive material to cover not only a single metal but also an alloy, a metal or an insulating core. Further, the shape of the conductor particles is not particularly limited as long as it has the above average particle diameter and specific surface area. In particular, copper powder is preferably used as the conductor particles in view of suppression of displacement, economic supply, and stability of price. However, since copper powder is generally easily oxidized, oxidation of copper powder hinders conductivity when used as a through-hole filling application. Therefore, the oxygen concentration of the copper powder is preferably 1.0% by weight or less.

Next, the resin in the conductor paste 203 in which the conductor via 103 is formed will be described. In order to form a conductor composition for an internal via hole having high connection reliability, a resin which is substantially solvent-free and has low viscosity, low water absorption, and high adhesion strength is required. In order to obtain a composition of the physical property resin, a resin containing 10% by weight or more of an epoxy compound containing one or more epoxy groups in one molecule, and a hydroxyl group, an amine group and a carboxyl group are epoxy groups are used. It is 5 mol% or less, and the epoxy equivalent is 100-350 g/eq. The reason why an epoxy compound is an essential component is to obtain a high adhesion strength. In the epoxy compound, the hydroxyl group, the amine group, and the carboxyl group are required to have a low concentration of 5 mol% or less of the epoxy group. Since these have a functional group having a high hydrogen bonding force, even if the resin has a low viscosity, The viscosity of the conductor paste is still high. On the contrary, as long as the functional group having such a high hydrogen bonding strength is a low concentration of 5 m or less of the epoxy group, a low-viscosity conductor paste can be obtained even if the resin has a high viscosity. In addition, the ratio of a hydroxyl group, an amine group, and a carboxyl group to an epoxy group can be confirmed by chemical quantitative analysis, and the absorbance in the vicinity of 3500 cm ^-1 (produced by a hydroxyl group, an amine group, and a carboxyl group), and 910 cm can be simply analyzed by infrared spectroscopic analysis. The ratio of the absorbance near ^-1 (produced by the epoxy group) was confirmed. In the epoxy compound, when the epoxy equivalent is 100 to 350 g/eq, when the crosslinking density is 350 g/eq or more, the water absorption rate is increased to become a low adhesion strength, and when it is less than 100 g/eq. If the crosslink density is too high, the hardening shrinkage will increase and the strength will be low. When 10% by weight or more of the epoxy compound is contained in the resin, an electrode paste composition having low water absorption and high adhesion strength can be obtained. The resin component other than the epoxy compound is not particularly limited as long as it is solvent-free. Further, an epoxy hardener for reacting and curing the epoxy compound may be mixed as needed. In addition, the viscosity of the conductive paste should be 2000Pa. Below s, the TI value is 1 or less. When the viscosity is 2000Pa. When s or more and the TI value is greater than 1, there is a problem that the through hole filling operation cannot be performed. Further, in the present invention, the resin is made solvent-free. When the solvent is contained, when the conductor composition is filled in the through hole and then heated and compressed, the volatile component is volatilized and discharged, and the composition is filled in the through hole. A void is generated in the middle, or peeling of the prepreg or the like occurs, resulting in unstable connection.

Examples of the epoxy compound to be used include a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, and an alicyclic epoxy resin. Among them, by using a bisphenol glycidyl ether type epoxy resin, for example, a bisphenol A type epoxy resin (chemical 1), a bisphenol F type epoxy resin (chemical 2), a bisphenol AD type (chemical 3), Hydrogenated bisphenol epoxy resin (chemical 4), alkylene oxide modified bisphenol epoxy resin (chemical 5), alkoxy modified bisphenol epoxy resin (chemical 6), etc., can be low in low viscosity Water absorption and high adhesion strength. These bisphenol glycidyl ether type epoxy resins may be used singly or in any combination.

However, n≧0.

However, n≧0.

However, n≧0.

However, n≧0.

However, R = CpH2p + 1 (p ≧ 1), and m + n ≧ 2.

However, R = CpH2p + 1 (p ≧ 1).

Further, the epoxy compound is a 90- to 20% by weight bisphenol glycidyl ether type epoxy resin (Group A), and 10 to 80% by weight of a long-chain aliphatic alcohol glycidyl ether type ring selected from C8 or higher. A resin composed of at least one epoxy resin (Group B) of an oxygen resin and a long-chain fatty acid glycidyl ester type epoxy resin having a C8 or higher. In particular, a low water absorption rate and a high adhesion strength can be obtained with a low viscosity, and the stress relaxation effect is strong, so that the connection reliability of the through holes can be improved.

Here, for the resin group contained in Group A, bisphenol A type epoxy resin can be used. (Chemical Formula 1), bisphenol F type epoxy resin (chemical 2), bisphenol AD type (chemical 3), hydrogenated bisphenol type epoxy resin (chemical 4), alkylene oxide modified bisphenol type epoxy resin ( 5), alkoxy modified bisphenol type epoxy resin (chemical 6) and the like. Further, examples of the resin contained in the group B include: linoleic acid dimer glycidyl type epoxy resin (chemical 7), isoprene hexanoic acid dimer glycidyl ester type epoxy resin (chemical 8) An alkane carboxylic acid glycidyl ester type epoxy resin (chemical formula 9), a lauryl glycidyl ether type epoxy resin (10). The resins of the Group A Group B may be used singly or in any combination.

However, R1, R2 and R3 are all alkyl groups, and the total number of carbon atoms thereof is 8.

Further, other suitable epoxy compounds are exemplified by epoxy oligomers having an average molecular weight of 600 to 10,000. The amount of the hydroxyl group, the amine group, and the carboxyl group of the epoxy oligomer is extremely small with respect to the amount of the epoxy group, and when it is used as the conductor paste, the shear rate dependence (TI value) of the viscosity increases as the molecular weight of the resin increases. It becomes smaller, so it has the effect of obtaining a low-viscosity conductor paste. In addition, the epoxy oligomer also has the effect of improving the peeling strength.

Further, the epoxy compound is composed of 90 to 19% by weight of a bisphenol glycidyl ether type epoxy resin (Group A), and 9 to 80% by weight of a C8 or higher long chain aliphatic alcohol glycidyl ether type epoxy resin. When a long-chain fatty acid glycidyl ester epoxy resin (group B) of C8 or higher and a resin composed of 1 to 30% by weight of an epoxy oligomer (group C) having an average molecular weight of 600 to 10,000 are used, The low viscosity gives low water absorption and high adhesion strength, and its effect on stress relaxation is strong, so the connection reliability of the through holes can be improved.

Here, examples of the resin contained in Group A can be used: bisphenol A type epoxy resin (chemical 1), bisphenol F type epoxy resin (chemical 2), bisphenol AD type (chemical 3), hydrogenated bisphenol Type epoxy resin (chemical 4), alkylene oxide modified bisphenol type epoxy resin (chemical 5), alkoxy modified bisphenol type epoxy resin (chemical 6), and the like. Further, examples of the resin contained in the group B include: linoleic acid dimer glycidyl type epoxy resin (chemical 7), isoprene hexanoic acid dimer glycidyl ester type epoxy resin (chemical 8) An alkane carboxylic acid glycidyl ester type epoxy resin (chemical formula 9), a lauryl glycidyl ether type epoxy resin (10). In addition, the resin case contained in the C group can be Use: epoxidized unsaturated fatty acid modifier (11), epoxidized polybutadiene (12), epoxidized polystyrene butadiene copolymer (Chemical 13). The resins of the Group A Group B Group C may be used singly or in any combination.

However, R1 and R4 are each an alkyl group having 1 to 18 carbon atoms, and R2 and R3 are each an alkylene group having a carbon number of 0 to 8, and n≧1.

However, R and R' are each an alkyl group having a carbon number of 0 to 8, and q ≧ 1, r ≧ 1, s ≧ 1, t ≧ 1.

However, R and R' are each an alkyl group having a carbon number of 0 to 8, and v ≧ 1, w ≧ 1, x ≧ 1, y ≧ 1, z ≧ 1.

Further, a resin other than the epoxy compound may be added to the conductor paste as needed. For the resin to be used, for example, an yttrium imide resin or a phenol resin for the purpose of improving heat resistance, and an ethylene polymer, an acrylic resin, a polyether, and a polyester such as polyolefin for the purpose of improving the peeling strength of the copper foil. Gather Indoleamine, polyurethane, and the like. These resins may be used singly or in any combination.

Further, an epoxy hardener may be mixed in the conductor paste as needed. As the epoxy hardener, a hardener which is generally used as a one-component composition can be used. For example, an amine-based curing agent such as dicyandiamide or carboxyhydrazine, an imidazole curing agent such as heptadecyl imidazole, or 3-(3,4-trichlorophenyl)-1,1-dimethylurea, or the like can be used. An acid-based curing agent such as a urea-based curing agent, methyl hexaphthalic anhydride or nematic tetrahydrophthalic anhydride; a phosphine-based curing agent such as triphenylphosphine; and a Lewis acid such as hexafluoroantimony salt. Among these, a latent curing agent is preferred from the viewpoint of stability of the composition and workability. Here, the latent curing agent system has a long-term characteristic that does not change and can be stored when the reaction is stopped at room temperature, and when heated above a predetermined temperature, the particles melt, decompose or dissolve, and appear to be sealed. The active group, together with the function of the start of the reaction and rapid hardening.

Further, the dispersant may be mixed in the conductor paste as needed. As the dispersing agent, a dispersing agent which is generally used can be used, and the first one of the representative ones, the ethylene oxide of a higher fatty acid, an esterified product of propylene oxide, an ester compound of sorbitan and a fatty acid, and sorbitan can be used. a nonionic dispersing agent such as an ethylene oxide of an alcohol, an ether compound of a propylene oxide, an ethylene oxide of an alkylbenzene, or a propylene oxide additive; and a second alkali metal salt of an alkylbenzenesulfonate, a higher alcohol An anionic dispersing agent such as an alkali metal salt of a sulfate, a phosphate compound, a higher fatty acid, an ethylene oxide of a higher fatty acid, or an alkali metal sulfate of a propylene oxide additive; and a cationic dispersant of a third-stage ammonium salt type . The dispersant referred to herein has an affinity for increasing the viscosity of the organic resin mixed with the binder on the surface of the metal particles, and promotes low viscosity and low viscosity of the paste. The effect of TI value.

The laminated base material 101 is not particularly limited as long as it is thinner than the prepreg after curing, and any laminated substrate which is known at present can be used. For example, a composite material of a glass woven fabric, a glass non-woven fabric, a guanamine woven fabric, a guanamine non-woven fabric, and a thermosetting resin such as an epoxy resin, or a glass woven fabric, a glass non-woven fabric, a amide woven fabric, or a enamel can be used. a composite material of any of the amine non-woven fabrics and a thermoplastic resin (for example, a wholly aromatic polyester resin, a polyether oxime, a polyether ketone, a polyether ether ketone, etc.) having a glass transition temperature of 180 ° C or higher, or a film material, Forming an insulating material.

2A to 2D are drawings showing a method of forming a double-sided substrate of the present invention. In FIG. 2A, the laminated substrate 201 is a prepreg, and the prepreg has a through hole having a hole diameter of 150 μm or less. Generally, a hole is often used, but a laser beam or the like may be used depending on the material. Other processing methods. Further, a conductive paste 203 is filled in the through hole. Fig. 2B shows a state in which the second foil is sandwiched by the copper foil 202. Fig. 2C shows a state after applying heat and pressure to Fig. 2B. Further, in the second embodiment, the state in which the metal filling amount is increased after the heating and pressing of the through-holes in the prepreg, the thickness of the prepreg is reduced, and the resin is cured, and the conductor paste 203 is in a compressed state. And the conductive paste is in a compressed state, and the conductor through hole 103 is formed. The conductor through hole 103 has a function of electrically connecting the upper and lower surfaces. The 2D drawing shows a state in which the surface copper foil 202 (etching or the like) is processed and a wiring pattern is formed. The processed copper foil 102 becomes a circuit conductor. The usable printed substrate may be followed by a step of applying a solder resist, a printed character or a mark, and a hole for inserting the component, which is omitted here because it is not the essence of the present invention.

Figs. 3A and 3B show the steps of repeatedly forming the above-described double-sided substrate to form a multilayer printed substrate. Fig. 3A shows a state in which the through-holes of the second layer printed substrate 104 are placed on both sides (upper and lower sides) of the core double-sided printed substrate 104, and the conductive paste is filled, and the copper foil 202 is provided. In this state, when the upper and lower surfaces are heated and pressurized, the multilayer printed board of Fig. 3B can be produced and connected as an inner via. Further, if the upper and lower copper foils 202 are processed into a patterned shape, a four-layer multilayer printed substrate can be completed. Thereafter, this step is repeated to make a multilayer printed circuit board having a larger number of layers.

In the method of forming a multilayer printed board according to FIGS. 3A and 3B, the double-sided board of the present invention is used for the double-sided printed board of the core layer, but it is not necessary, and a conventional through-hole double-sided board can be used. Therefore, it is not necessary to newly prepare a device which can be made into a double-sided substrate, and the cost can be reduced. At this time, it is preferable to provide a through hole (through hole) in advance. The through-via substrate herein refers to a resin substrate. Further, a ceramic substrate or the like may be used for the through-hole substrate in addition to the resin substrate.

4A and B are views showing other methods of forming a multilayer printed substrate. In Fig. 4A, the laminated substrate 201 before the heating and pressurization filled with the conductor paste 203 is sandwiched between the two double-sided printed boards 104. By heating and pressurizing in this state, a four-layer multilayer printed board of Fig. 4B can be obtained. In addition to the four layers, if a plurality of double-sided printed substrates are prepared and the laminated substrate before heating and pressing filled with the conductive particles is sandwiched between the double-sided substrates, more heat can be produced. Multilayer printed substrate of the layer.

Although the double-sided board of the present invention is used for the double-sided board in the method of forming the multilayer printed board of FIGS. 4A and 4B, it is not essential, and a conventional through-hole double-sided board can be used. Moreover, the through-hole substrate is in addition to the resin substrate A ceramic substrate or the like can also be used.

Next, the characteristics of the printed wiring board with respect to the chlorine content of the conductor paste composition of the present invention will be described using a graph.

The first watch shows the through-hole contact resistance value and the insulation resistance value with respect to the amount of hydrolyzable chlorine contained in the paste and the diameter of the through-hole.

As shown in the first table, as long as the amount of hydrolyzable chlorine of the conductor paste composition filled in the through hole of the printed wiring board of the present invention is 20 ppm or more, the contact resistance value is 10 m even if the through hole diameter is 150 μm or less. Below Ω/through hole, The result of good electrical conductivity is obtained.

Further, when the amount of hydrolyzable chlorine in the conductor paste composition is lower than the chlorine content in the prepreg, that is, 2000 ppm, good results can be obtained from the insulation resistance value.

Further, a composite material of a glass woven fabric, a glass nonwoven fabric, a guanamine woven fabric, or a guanamine non-woven fabric, and a thermosetting resin such as an epoxy resin, or a glass woven fabric, a glass nonwoven fabric, a amide woven fabric, or a enamel may be used. a composite material of any of the amine non-woven fabrics and a thermoplastic resin (for example, a wholly aromatic polyester resin, a polyether oxime, a polyether ketone, a polyether ether ketone, etc.) having a glass transition temperature of 180 ° C or higher, or a film material, Forming an insulating material.

As described above, according to the first embodiment, the conductor paste composition of the present invention contains at least (a) 30 to 70% by volume of the conductor particles having an average particle diameter of 0.5 to 20 μm and a specific surface area thereof. When the resin is 0.05 to 1.5 m ² /g, and (b) 70 to 30% by volume of the epoxy resin is contained in an amount of 10% by weight or more, the epoxy compound has one or more epoxy groups in one molecule. Further, the total amount of the hydroxyl group, the amine group and the carboxyl group is 5 mol% or less of the epoxy group, the epoxy equivalent is 100 to 350 g/eq, and the chlorine is 20 to 2000 ppm. Therefore, the conductive paste composition is filled in Through-holes with a hole diameter of 150 μm or less can realize double-sided or multi-layer printed boards with high reliability through-holes.

Further, in the first embodiment of the present invention, the diameter of the through hole is 150 μm or less, but it may be a hole larger than 150 μm.

Industrial use possibility

The conductor paste composition of the present invention can be used as a high-density wiring substrate, and has a high-frequency circuit for high-speed transmission, a semiconductor package, and the like. The high connection reliability required for wiring pattern use and portable electronic equipment applications requiring small size and light weight, and contributes to the formation of a low-cost printed wiring board.

101,201‧‧‧Layered substrate

102,202‧‧‧ copper foil

103‧‧‧Electrical through hole

104‧‧‧Double-sided printed circuit board

203‧‧‧Electrical paste

501‧‧‧nuclear

502‧‧‧Electrical materials

Fig. 1 is a cross-sectional view showing the structure of a double-sided printed board according to an embodiment of the present invention.

Fig. 2A is a plan view showing a method of forming a double-sided printed board of the same embodiment.

Fig. 2B is a plan view showing a method of forming a double-sided printed circuit board of the same embodiment.

Fig. 2C is a plan view showing a method of forming a double-sided printed board of the same embodiment.

Fig. 2D is a drawing showing a method of forming a double-sided printed board of the same embodiment.

Fig. 3A is a plan view showing a method of forming a multilayer printed substrate of the same embodiment.

Fig. 3B is a plan view showing a method of forming a multilayer printed substrate of the same embodiment.

Fig. 4A is a plan view showing another method of forming a multilayer printed board of the same embodiment.

Fig. 4B is a plan view showing another method of forming a multilayer printed board of the same embodiment.

Fig. 5 is a structural view showing conductive particles used in a printed circuit board of the same embodiment.

101‧‧‧Laminated substrate

102‧‧‧ copper foil

103‧‧‧Electrical through hole

104‧‧‧Double-sided printed circuit board

Claims (13)

The conductive paste composition for through-hole filling comprises: 30 to 70% by volume of conductive particles having an average particle diameter of 0.5 to 20 μm and a specific surface area of 0.05 to 1.5 m ² /g; and 70 to 30% by volume a resin containing 10% by weight or more of an epoxy compound, wherein the epoxy compound has one or more epoxy groups in one molecule, and the total amount of the hydroxyl group, the amine group, and the carboxyl group is 5 mol% or less of the epoxy group. And the epoxy equivalent is 100-350 g/eq; and the hydrolyzable chlorine content of the conductive paste composition for the through-hole filling is 20 to 2000 ppm. The conductive paste composition for via filling according to the first aspect of the invention, wherein the conductive particles are selected from the group consisting of at least one of the following (1) to (4): (1) selected from the group consisting of gold and platinum. At least one particle of silver, palladium, copper, nickel, tin, lead, indium; (2) an alloy selected from any combination of gold, platinum, silver, palladium, copper, nickel, tin, lead, indium, zinc, chromium (3) particles having conductive or non-conductive particles as a core and coated with at least one metal selected from the group consisting of gold, platinum, silver, palladium, copper, nickel, tin, lead, and indium; and (4) A particle coated with an electroconductive or non-conductive particle as a core and an alloy selected from any combination of gold, platinum, silver, palladium, copper, nickel, tin, lead, indium, zinc, and chromium. For example, the electrical conductor paste composition for through-hole filling according to item 1 of the patent application scope, The conductor particles include copper having a surface oxygen concentration of 1.0% by weight or less. The conductive paste composition for through-hole filling according to the first aspect of the invention, wherein the epoxy compound is selected from the group consisting of a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, and a glycidylamine type epoxy resin. And at least one epoxy resin of the alicyclic epoxy resin. The conductive paste composition for via filling according to the first aspect of the invention, wherein the epoxy compound is a bisphenol glycidyl ether type epoxy resin. The conductive paste composition for via filling according to the first aspect of the invention, wherein the epoxy compound contains an epoxy oligomer having a weight average molecular weight of 600 to 10,000. The conductive paste composition for through-hole filling according to the first aspect of the invention, wherein the epoxy compound is 90 to 20% by weight of a bisphenol glycidyl ether type epoxy resin, and 10 to 80% by weight of the epoxy resin is selected from the group consisting of A resin composed of a long-chain aliphatic alcohol glycidyl ether type epoxy resin having a C8 or higher and a long-chain fatty acid glycidyl ester type epoxy resin having a C8 or higher. The conductive paste composition for through-hole filling according to the first aspect of the invention, wherein the epoxy compound is 90 to 19% by weight of a bisphenol glycidyl ether type epoxy resin, and 9 to 80% by weight of the epoxy resin is selected from the group consisting of a long-chain aliphatic alcohol glycidyl ether type epoxy resin having a carbon number (C) of 8 or more and at least one resin having a carbon number (C) of 8 or more long-chain fatty acid glycidyl ester type epoxy resins, and 1 to 30% by weight A resin composed of an epoxy oligomer having a weight average molecular weight of 600 to 10,000. The conductive paste composition for through-hole filling according to the first aspect of the patent application, wherein the viscosity characteristic of the paste composition is at a temperature of 25 ° C, a viscosity of 1 [1/sec] (A) and 2 [1/ The ratio (A/B) of the viscosity (B) of sec] is 1 or less. A printed circuit board is filled in a through hole formed in an insulating substrate, filled with a conductive resin composition, and electrically connected to a lower electrode layer on a surface of the insulating substrate, wherein the conductive resin composition includes: 30 ~70% by volume of conductive particles having an average particle diameter of 0.5 to 20 μm and a specific surface area of 0.05 to 1.5 m ² /g; 70 to 30% by volume of a resin containing 10% by weight or more of an epoxy compound, the epoxy compound In order to have one or more epoxy groups in one molecule, and the total amount of the hydroxyl group, the amine group and the carboxyl group is 5 mol% or less of the epoxy group, and the epoxy equivalent is 100 to 350 g/eq; and 20~ 2000 ppm of hydrolyzable chlorine, and the aforementioned conductive resin composition was hardened in the aforementioned through holes. The printed circuit board of claim 10, wherein the through hole has a hole diameter of 150 μm or less. A manufacturing method of a printed circuit board comprising the steps of: forming a through hole in a prepreg for manufacturing a printed substrate; filling the through hole with a conductive paste composition, and the conductive paste composition comprises: 30 ~70% by volume of conductive particles having an average particle diameter of 0.5 to 20 μm and a specific surface area of 0.05 to 1.5 m ² /g; 70 to 30% by volume of a resin containing 10% by weight or more of an epoxy compound, the epoxy compound In order to have one or more epoxy groups in one molecule, and the total amount of the hydroxyl group, the amine group and the carboxyl group is 5 mol% or less of the epoxy group, and the epoxy equivalent is 100 to 350 g/eq; and 20~ 2000 ppm of hydrolyzable chlorine; heating and pressing the copper foil under the lower layer of the prepreg; and etching the copper foil to form an electric circuit. The method for producing a printed circuit board according to claim 12, further comprising the step of forming the aperture of the through hole to be 150 μm or less.