KR100644749B1 - Copper clad laminate and multi layer board - Google Patents

Abstract

A copper clad laminate used in a thin film type of printed circuit board is provided to have less bending or distortion of the laminate during reflow treatment and to be employed in fabricating microfine wiring by fabricating outermost insulation layer and internal insulation layer both of which comprise thermosetting resin compositions with different glass transition temperatures. The copper clad laminate comprises: an outermost insulation layer which includes thermosetting resin composition having glass transition temperature higher than upper most temperature at reflow treatment; and an internal insulation layer which includes alternative thermosetting resin composition having glass transition temperature lower than the upper most temperature at reflow treatment. The reflow treatment has elasticity higher than 2000 kgf/mm^2. The outermost insulation layer has the glass transition temperature 10deg.C higher than the upper most temperature of the reflow treatment. The internal insulation layer contains polyamide fibrous woven cloth as a reinforcing base.

Description

Copper Clad Laminates and Multilayer Printed Circuit Boards {COPPER CLAD LAMINATE AND MULTI LAYER BOARD}

The present invention relates to a copper clad laminate and a multilayer printed circuit board. In particular, it relates to a copper foil laminated board and a thin printed circuit board that can be used in a thin printed circuit board.

In recent years, electronic devices have become smaller, thinner, and lighter, and printed circuit boards used for them are also required to have a thinner thickness. In addition, the yield of the product was not good due to a large number of defects such as twisting and bending of the substrate due to problems in handling or processing during processing of the printed circuit board. In addition, environmentally demanding printed circuit boards using halogen-free and lead-free solders are required. In the case of using lead-free solders, the reflow temperature is higher than that of the conventional semiconductor chip, especially in the process of mounting semiconductor chips, especially flip chips. There was a drawback that the problem of bending or twisting frequently occurs. As a method for improving this problem, Japanese Patent Application Laid-Open No. 08-125310 or Japanese Patent Application Laid-Open No. 08-102580 discloses a method of using a ceramic substrate having a high elastic modulus close to the thermal expansion rate (2.5 ppm / ° C) of a semiconductor chip. It is. However, this method increases the manufacturing cost, increases the weight of the substrate, and makes it difficult to form high-density wiring, which is rarely used in fine printed circuit boards. As a further improvement, Japanese Laid-Open Patent Publication No. 2002-249606 discloses a multilayer printed circuit board using a wholly aromatic polyamide fiber woven fabric as an organic substrate. However, this method also does not devise a method of using the resin in the reflow treatment, the problem of bending and twisting the substrate still remains. In addition, there is a limit to the conventional subtractive (subtractive) process to form a fine wiring on the printed circuit board.

The present invention improves the above-described problems and provides a copper clad laminate and a printed circuit board having small warpage and torsion during reflow processing. It also provides a printed circuit board that can form a fine wiring.

According to an aspect of the present invention, the outermost insulating layer comprising a thermosetting resin composition having a glass transition temperature of at least the highest temperature at the time of the reflow treatment, and located inside the outermost insulating layer or less than the maximum temperature at the time of the reflow treatment The copper clad laminated board containing the inner insulation layer containing the thermosetting resin composition which has a glass transition temperature of can be proposed.

Herein, the elastic modulus of the outermost insulating layer and the inner insulating layer during reflow treatment is preferably 2000 kgf / mm 2 or more, and the outermost insulating layer has a glass transition temperature of 10 ° C. or more higher than the maximum temperature during the reflow treatment. It is preferable. In addition, it is preferable that the said inner insulation layer contains a wholly aromatic polyamide fiber woven fabric as a reinforcement base material.

In addition, the thickness of the total insulating layer including the outermost insulating layer and the inner insulating layer is preferably 0.05 to 0.5 mm. According to a preferred embodiment, the thermosetting resin composition is at least one resin selected from the group consisting of epoxy resins, cyanic acid ester resins, bis maleimide resins, polyimide resins, functional group-containing polyphenylene ether resins and flame retardant resins thereof It may include.

According to another aspect of the present invention, it is possible to provide a flip chip mounting printed circuit board using the copper-clad laminate.

According to another aspect of the present invention, the outermost insulating layer comprising a thermosetting resin composition having a glass transition temperature of at least the highest temperature at the time of reflow treatment, and is located inside the outermost insulating layer, the highest at the time of reflow treatment A printed circuit board may include an inner insulation layer including a thermosetting resin composition having a glass transition temperature of less than or equal to a temperature.

Herein, the elasticity modulus of the outermost insulating layer and the inner layer insulating layer during reflow treatment is preferably 2000 kgf / mm 2 or more, and the outermost insulating layer has a glass transition temperature of 10 ° C. or more higher than the maximum temperature during the reflow treatment. It is preferable. In addition, it is preferable that the said inner insulation layer contains a wholly aromatic polyamide fiber woven fabric as a reinforcement base material.

According to another aspect of the invention, the outermost insulating layer comprising a resin capable of forming a circuit in an additive manner with a thermosetting resin composition, and located inside the outermost insulating layer or more than the maximum temperature at the time of reflow treatment A printed circuit board may include a first internal insulating layer including a thermosetting resin composition having a glass transition temperature.

Herein, the outermost insulating layer and the first inner insulating layer preferably have elastic modulus of 2000 kgf / mm 2 or more during reflow treatment.

According to a preferred embodiment may further include a second inner insulating layer formed on the inside of the first inner insulating layer, and comprising a thermosetting resin composition having a glass transition temperature of less than the maximum temperature of the reflow treatment. Herein, the second internal insulating layer preferably has a modulus of elasticity of 2000 kgf / mm 2 or more during reflow treatment.

Here, the first inner insulating layer preferably has a glass transition temperature of 10 ° C. or higher than the highest temperature at the time of the reflow treatment, and the outermost insulating layer is preferably reinforced by a base material. According to this, the substrate-reinforced insulating layer may be used as a solder resist.

In addition, the thickness of the total insulating layer including the outermost insulating layer and the first inner insulating layer is preferably 0.05 to 0.5mm. According to a preferred embodiment, the thermosetting resin composition is at least one resin selected from the group consisting of epoxy resins, cyanic acid ester resins, bis maleimide resins, polyimide resins, functional group-containing polyphenylene ether resins and flame retardant resins thereof It may include.

Hereinafter, a copper foil laminate according to the present invention will be described in detail.

As a thermosetting resin composition which comprises the copper clad laminated board of this invention, a well-known thing can be used generally. For example, an epoxy resin, a cyanic acid ester resin, a bismaleimide resin, a polyimide resin, a functional group containing polyphenylene ether resin, etc. are mentioned, These well-known resin can be used individually or in mixture of 2 or more types. In order to prevent the movement between conductor circuits, it is preferable to use a cyanate ester resin composition. In addition, bromine is added to the above-mentioned resins, and flame retardant resins can also be used. When using with no solvent, it is preferable to add and use a liquid resin at well-known room temperature.

The maximum temperature during the reflow treatment is about 240 to 280 ° C., about 260 ° C., but is not limited thereto, and this is determined according to specific process conditions. Therefore, a resin having a glass transition temperature of at least the highest temperature at the time of reflow treatment among these thermosetting resin compositions may be selected according to the specific process conditions. Examples of such resins include, but are not necessarily limited to, bismalade triazine resins and mixed resins with other resins.

In addition, the resin whose glass transition temperature is below the maximum temperature in the reflow process is also in the specific process, so it can be selected according to the maximum temperature in the reflow process. Examples of such resins include, but are not necessarily limited to, most epoxy resins.

In general, the resin constituting the insulating layer of a copper clad laminate or a printed circuit board is rarely used as a single material, and is suitably used in consideration of desired physical properties and price, so it is limited if the resin satisfies the conditions of glass transition temperature. Various known additives can be mixed in a range that does not significantly affect the properties of these thermosetting resin compositions. For example, for the purpose or use of various additives such as thermosetting resins, thermoplastic resins, known inorganic, organic fillers, dyes, thickeners, lubricants, antifoaming agents, dispersing agents, leveling agents, brightening agents, and polymerization initiators other than the above-mentioned thermosetting resin compositions. Can be added accordingly. In addition, as the flame retardant, for example, a compound flame retarded with phosphorus, bromine, a halogen-free type, a non-flame retardant, and the like can be used. Moreover, this flame retardant can use all the functional groups which exist or do not exist in a molecule | numerator.

The thermosetting resin composition of the present invention may be cured by heating the resin itself, but may further include a suitable amount of a known curing agent and a thermosetting catalyst because the curing rate is slow and productivity is poor.

Moreover, a reinforcing base material can be used for this thermosetting resin composition. As this reinforcing base material, well-known organic and inorganic base materials are mentioned. The substrate is not particularly limited, but examples thereof include a woven fabric and a nonwoven fabric which are woven using polyoxazole fibers, wholly aromatic polyamide fibers, liquid crystal polyester fibers, and the like as organic substrates. Moreover, as an example of an inorganic base material, well-known glass fiber woven fabrics, nonwoven fabrics, such as E, S, T, NE, and D glass, and these mixed fabrics are mentioned. Of these, woven fabrics are preferred. It is preferable to use a type such that the fibers are opened to a woven fabric so that the distribution of the fibers is uniform, or to bend using a non-twisted yarn (manufactured by Asahi Shuebel Co., Ltd., Japan).

Moreover, it is preferable to use the woven fabric which used wholly aromatic polyamide fiber as a reinforcement base material of the insulating layer formed inside. This is because the thermal expansion of the entire substrate can be suppressed by using this. Moreover, when using this wholly aromatic polyamide fiber woven fabric, it is preferable to use a laser for punching processing, cutting | disconnection, etc. in a later step.

Moreover, a well-known thing can be used as a film-shaped base material, For example, heat resistant films, such as a polyimide film, a polyoxazole film, a wholly aromatic polyamide film, and a liquid crystalline polyester film, can be used. However, it is not suitable to use a release film such as PET film. These base materials can apply a well-known process to the surface of a crawfish, in order to improve adhesiveness with resin.

Using a prepreg reinforced with such a substrate, these are laminated to form a copper clad laminate. Although the conditions of lamination are not specifically limited, Generally lamination | stacking is carried out at the temperature of 100-300 degreeC and the pressure of 5-50 kgf / cm <2>, Preferably it is 30 minutes-3 hours under vacuum. Although the structure of lamination is not specifically limited, It is preferable that at least the outermost insulating layer contains the thermosetting resin composition whose glass transition temperature by dynamic mechanical analyzing (DMA) at the time of hardening is more than the maximum temperature at the time of reflow process. Do. At this time, it is preferable that this glass transition temperature is 10 degreeC or more higher than the maximum temperature at the time of reflow process, and it is so preferable that this temperature difference is large. However, since the manufacturing cost rises in an economic aspect, this is considered when selecting the thermosetting resin composition. Before and after the glass transition temperature, the resin composition changes from a glass state to a rubber state. When using a resin having a glass transition temperature higher than the reflow treatment temperature of 260 ° C., the glass state is maintained even when the chip is mounted. Or deformation will be reduced. Therefore, in order to obtain such a desired effect, it is preferable that the difference of 10 degreeC or more which is this temperature difference differs.

Moreover, it is preferable that the inner side insulating layer contains the thermosetting resin composition whose glass transition temperature by DMA is below the maximum temperature at the time of reflow process. The inner side means a side close to the center of the copper clad laminate in a meaning opposite to the outer side described above. It is more preferable here that an inner insulation layer is a center layer. Thus, when laminated with an insulating layer containing a thermosetting resin composition having a different glass transition temperature, the outer insulating layer has a low thermal expansion rate at a temperature during reflow treatment. Therefore, since the inner side softens at the temperature at the time of this reflow treatment, even if it becomes a rubber state and the thermal expansion rate becomes large, thermal expansion is suppressed by the outer insulating layer having a low thermal expansion rate, and the warping and the warping of the copper clad laminate itself become small. Moreover, at the time of cooling, the inside resin composition absorbs a stress, and the curvature after cooling also becomes small. Therefore, a copper foil laminated plate having a very small warpage or twist can be obtained, which has an advantage that the effect of mounting is extremely small. Of course, it can be used for wire bonding among components mounting methods, and in case of connecting through reflow furance by flip chip bonding, it is preferable to use the copper clad laminate or the printed circuit board of the present invention. Can be.

At this time, it is preferable to use the substrate-reinforced preflag for each insulation layer, but in the case of the outer insulation layer, you may use only a thermosetting resin composition. At this time, it is preferable to include another resin composition or a supplementary base material for substrate reinforcement. This can prevent the outermost insulating layer having a modulus of elasticity of 2000 kgf / cm 2 or more at the maximum temperature during reflow treatment, which can prevent bending or twisting of the entire substrate. Such elastic modulus further includes other resin compositions or supplementary materials. Because it can be guaranteed. The elastic modulus here can be measured by DMA.

The copper-clad laminate of the present invention can be processed by a known method to form a printed circuit board. Also, the multilayer printed circuit board may be formed using the same. Hereinafter, the printed circuit board of the present invention will be described in detail. However, the general contents of the thermosetting resin composition, the supplementary base material, the additives, and the laminating conditions constituting the printed circuit board of the present invention are not different from those of the above-described copper foil laminated plate, and thus the repeated description thereof will be omitted.

According to an aspect of the present invention, the outermost resin layer is formed of a thermosetting resin composition capable of forming wirings in an additive manner in order to form fine wirings, that is, ultrafine circuit widths and gaps between conductor circuits. Here, the additive method means a method of forming a wiring pattern by forming an electroless plating in a state where only a portion to form a pattern is formed and all other portions are coated with a plating resist. Here, in the case of a multilayer printed circuit board, an outermost layer forms an insulating layer with a thermosetting resin composition capable of forming a circuit in an additive manner in order to form fine wiring. Moreover, the insulating layer below contains the thermosetting resin composition whose glass transition temperature is more than the maximum temperature at the time of reflow process. It is preferable that this glass transition temperature is 10 degreeC or more than the maximum temperature at the time of reflow process. The insulating layer formed further inside of this contains a thermosetting resin composition whose glass transition temperature is below the maximum temperature at the time of reflow process. It is preferable that such an insulating layer is reinforced with a base material so that an elasticity modulus may be 2000 kgf / cm <2> or more at the maximum temperature at the time of a reflow process, selects the kind of thermosetting resin composition, or adds additives, such as an inorganic filler. In this case, it is more preferable that the outermost thermosetting resin composition for the additive can be reinforced with a base material to suppress warpage and warpage. In order to apply copper plating to the insulating layer containing the additive thermosetting resin composition before forming the circuit, the insulating layer is roughened, that is, roughness is formed on the surface of the insulating layer to roughen the surface to improve adhesion between Cu and the resin. The thickness of the thermosetting resin composition is formed so that the roughened end does not contact the reinforcing base material.

The copper foil multilayer laminate is laminated using a pre-strength reinforced substrate as in the above copper foil laminate. The configuration of the lamination is not limited to this, but for example, an inner substrate is made of a thermosetting resin composition having a glass transition temperature at curing lower than the maximum temperature at the time of reflow treatment, preferably black copper oxide treatment and CZ treatment of Mack's company. Etc. On both sides of this substrate, an insulating layer is formed of a thermosetting resin composition having a glass transition temperature upon curing higher than the highest temperature during reflow treatment, preferably 10 ° C or more. A copper foil layer or another insulating layer may be formed outside of this surface. However, the outermost insulating layer forms a thermosetting resin composition in an additive manner, and the glass transition temperature at the time of curing inside the outermost insulating layer is higher than the maximum temperature at the reflow treatment, preferably 10 ° C. or higher. The insulating layer is formed from the composition. It is preferable that all of these insulating layers use the substrate-reinforced preflag, but some layers may form the insulating layer which consists only of a resin composition. Here, it is more preferable that these insulating layers have an elastic modulus of 2000 kgf / cm 2 or more at the highest temperature during reflow treatment in order to prevent warpage or distortion of the substrate. Although lamination conditions are not specifically limited, Generally lamination | stacking is carried out at the temperature of 100-300 degreeC and the pressure of 5-50 kgf / cm <2>, Preferably it is 30 minutes-3 hours under vacuum. The copper foil multilayer laminate of the present invention can be processed by a known method to form a multilayer printed circuit board. In this case, when a wholly aromatic polyamide fiber woven fabric is used as the substrate, it is preferable to use a laser for processing such as drilling and cutting.

Thus, when the outermost circuit is formed by the additive method, a very fine circuit width and a space between circuits of line / space = 30/30 µm or less can be formed. Such fine wiring is difficult to obtain by the subtractive method.

Hereinafter, a copper foil laminate and a multilayer printed circuit board according to the present invention will be described in more detail with examples and comparative examples. "Part" shows a weight part unless there is particular notice.

Example 1-1 Formation of Copper Clad Laminated Plates and Printed Circuit Boards

450 parts of 2,2, -bis (4-cyanatephenyl) propane monomers were melted at 160 degreeC, and it reacted for 4.5 hours, stirring, and the mixture of a monomer and a prepolymer was obtained. This is dissolved in methyl ethyl ketone, and 300 parts of bisphenol A type epoxy resin (brand name: Epicoat 1001, Japan epoxy resin Co., Ltd. product), phenol novolak type epoxy resin (brand name: DEN-431, Dow Chemical < 100 parts and 150 parts of cresol novolak-type epoxy resins (brand name: ESCN-220F, Sumitomo Chemical Co., Ltd. make) were mix | blended. 1000 parts of calcined talc (trade name: BST200, manufactured by Nippon Talc Co., Ltd.) was added thereto, and zinc octylate was dissolved in 0.2 parts of methyl ethyl ketone and added as a curing catalyst, and the compound obtained by stirring well was varnish A. It was.

This varnish A was impregnated and dried in a 0.02 mm-thick glass woven fabric, and after attaching the resin amount so that the thickness after molding might be 30 m, prepreg B having a gelation time (at170 ° C) of 121 seconds was produced. The glass transition temperature by DMA after this preflag B hardened 250 degreeC * 2 hours was 236 degreeC. After using 1 piece of this preflag B and the bismaleimide-cyanate ester resin composition produced so that the thickness after hardening may be 40 micrometers (glass woven fabric thickness 0.03mm) on both sides, 250 degreeC after 2 hours of hardening Each of prepreg C (brand name: BN300GF, Mitsui Chemicals Co., Ltd.) whose glass transition temperature by DMA is 270 degreeC was arrange | positioned. The electrolytic copper foil with a thickness of 12 micrometers was provided on both outer sides of this preflag C, and it laminated | stacked for 2 hours under the vacuum of 250 degreeC and 5 mmHg or less, and produced the multilayer double-sided copper foil laminated board D of 110 micrometers of insulating layer thicknesses. A printed circuit board was fabricated by forming a permanent protective film on the surface and the back surface of the copper-clad laminate D using a UV-type thermosetting resist of a film type having a thickness of 30 µm, followed by nickel plating and gold plating. Table 1 shows the results of this evaluation.

Example 1-2 Formation of Copper Clad Laminated Plate and Printed Circuit Board

Using varnish A of Example 1-1, prepreg E was produced by impregnating and drying the 0.1mm-thick wholly aromatic polyamide fiber woven fabric to a thickness of 110 占 퐉 after lamination at 134 seconds for gelation time. Each prepreg C of Example 1-1 was arrange | positioned at both sides of this one prepreg. Electrolytic copper foil having a thickness of 12 µm was disposed on both outer sides of the preflag C, and laminated molding was performed in the same manner as in Example 1-1 to prepare a double-sided copper foil laminated sheet F having an insulating layer thickness of 190 µm, using Example 1-1. The printed circuit board is formed through the same conditions and steps as described above. However, for drilling and cutting, use UV-YAG laser. The evaluation results are shown in Table 1.

Example 1-3 Formation of Copper Clad Laminated Plate and Printed Circuit Board

Using the double-sided copper-clad laminate D of Example 1-1, a circuit was formed on both surfaces thereof by a regular method, and black copper oxide treatment was performed to prepare a substrate G. Using two board | substrates G, two preflags B of Example 1-1 were inserted in between, and each prepreg C used in Example 1-1 was arrange | positioned at the outermost side. The electrolytic copper foil of thickness 12micrometer was arrange | positioned at the outer side of this preflag, it laminated | stacked-molded similarly at 250 degreeC, and produced six copper foil multilayer laminated boards H with an insulation layer thickness of 0.36 mm. Using this copper foil multilayer laminate H, a printed circuit board was fabricated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 2-1 Formation of Printed Circuit Board

Using 1 piece of preflag B of Example 1-1, the electrolytic copper foil of 12 micrometers in thickness was put on both sides, and it laminated | stacked for 1.5 hours under the vacuum of 190 degreeC and 5 mmHg or less, and double-sided copper foil of 30 micrometers of insulation layers Laminate I was produced. After forming a circuit on both surfaces and performing a black copper oxide process, each prepreg C of Example 1-1 was arrange | positioned on this both surfaces. The electrolytic copper foil with a thickness of 12 micrometers was provided on both outer sides of this preflag C, and it laminated | stacked and molded for 2 hours under the vacuum of 250 degreeC and 5 mmHg or less, and produced the multilayer double-sided copper foil laminated board J with an insulation layer thickness of 110 micrometers. On the front and back surfaces, a permanent protective film was formed using a film-type UV selective thermosetting resist having a thickness of 30 µm, and nickel-plated and gold-plated were printed to prepare a printed wiring board. The evaluation results are shown in Table 1.

Example 2-2 Formation of Printed Circuit Board

The varnish A of Example 1-1 was used to impregnate and dry the 0.1mm-thick wholly aromatic polyamide fiber woven fabric, and to prepare the preflag K which produced 120 micrometers of thickness after lamination | stacking in 134 second of gelation time. Using this 1 piece of preflag K, the electrolytic copper foil of thickness 12micrometer was arrange | positioned on both sides, it laminated | stacked and molded like Example 2-1, and produced the double-sided copper foil laminated board L of 120 micrometers of insulating layer thicknesses. Forming a circuit on both surfaces of the double-side copper-clad laminate L, and subjected to CZ processing maekkeu's, and that on both outer sides, carried in a thickness of 125 μ is formed such that in Example 1-1 was placed in a pre-flag C every 1 each. The laminate molding was performed in the same manner to produce four layers of copper foil multilayer boards M. Using this copper foil multilayer board M, a multilayer printed circuit board was manufactured through the same steps as in Example 1-1. However, for drilling and cutting, UV-Vanadate laser was used. The thickness of only the said insulating layer was 370 micrometers. The evaluation results are shown in Table 1.

Example 3-1 Formation of Printed Circuit Board

Using one piece of prepreg B of Example 1-1, the electrolytic copper foil of 12 micrometers in thickness was put on both sides, and it laminated | stacked and molded under 190 degreeC and 5 mmHg or less for 1.5 hours, and double-sided copper foil of 35 micrometers of insulating layer thicknesses Laminated plate N was produced. The copper foil on the surface of this double-sided copper foil laminated plate N is removed by etching to thickness of 3 micrometers, the through-hole of 100 micrometers in diameter is formed with a carbon dioxide gas laser from the surface, and is desmear-processed. After the surface of the copper-clad laminate including the through hole was attached with 0.5 µm of electrolytic copper plating and 15 µm of electroplating, a circuit was formed on the front and back surfaces, and a black copper oxide treatment was applied to form the substrate O. Preflag P (trade name: BN-300, manufactured by Mitsui Chemical Co., Ltd.) having a glass transition temperature of 298 ° C. at 230 ° C. and 2 hours of curing after DMA, which was formed on both sides of the substrate O to have a thickness of 40 μm. 1 piece each. The electrolytic copper foil with a thickness of 12 micrometers was provided on both outer sides of this preflag P, and it laminated | stacked for 2 hours under the vacuum of 250 degreeC and 5 mmHg or less, and produced the four-layer double-sided copper foil laminated board Q of 115 micrometers of insulation layer thicknesses. The surface of this copper foil laminated board Q was etched and removed to 3 micrometers of copper foil thickness, and the inside of the hole was filled with copper plating through the blind via of diameter 60micrometer by UV-YAG laser on it. After a circuit was formed on both surfaces of this etched copper foil laminated plate Q, and black copper oxide process was carried out, the thermosetting resin composition P (brand name: ABF GX13, the product made by Ajinomoto Co., Ltd.) of semi-additives with a thickness of 60 micrometers was formed on each of these 1 each. Each batch was laminated and molded for 80 minutes under a vacuum of 170 ° C., 20 kgf / cm 2, and 5 mmHg or less. Both surfaces were filled with blind vias having a diameter of 60 µm by UV-YAG laser to fill the holes with copper plating. Then, the circuit of line / space = 25/25 micrometers was formed in both surfaces, and the 6-layer double-sided copper foil multilayer laminated board S was produced. After applying the CZ process of Mack company to the circuit of this double-sided copper foil multilayer laminated board S, each preflag P of 40 micrometers in thickness was arrange | positioned outside. A 50-micrometer-thick fluororesin film was placed on the outer side, and laminated molding was performed in the same manner, and used as a solder resist. After peeling off the fluororesin film, the substrate was irradiated with a UV-YAG laser to pierce the pad for flip tip contact and the pad for handball until the copper foil was reached. Thereafter, the metal surface was treated in a plasma apparatus, and then nickel-plated and gold-plated were attached to prepare a flip-tip mounted printed circuit board. The total insulation layer thickness was 315 μm including solder resist. The evaluation results are shown in Table 1.

Example 3-2 Formation of Printed Circuit Board

An electrolytic copper foil having a thickness of 12 µm was placed on each of both surfaces of the substrate O of Example 3-1 using one preflag K of Example 2-2, and laminated and molded in the same manner as in Example 3-1 to form an insulating layer. 275 micrometers double-sided copper clad laminated board T was produced. Circuits were formed on both surfaces of this double-sided copper-clad laminated board T, CZ treatment of Mack Corporation was applied, and each prepreg P of Example 3-1 in which the thickness after molding becomes 40 micrometers was arrange | positioned at each outside. These were laminated | molded similarly and the four-layer copper foil multilayer board U was produced. The copper foil of both surfaces of this copper foil multilayer board U was etched and removed to 3 micrometers in thickness, and the inside of the hole was filled with copper plating through the blind via of diameter of 60 micrometers by UV-YAG laser on it. After circuits were formed on both sides of the etched copper foil laminate U and subjected to CZ treatment, Mack's pre-preg W (trade name: ABF GX02S, manufactured by Ajinomoto Co., Ltd.) having a thickness of 40 µm was applied to each of the two surfaces. Each batch was laminated and molded for 80 minutes under a vacuum of 170 ° C., 20 kgf / cm 2, and 5 mmHg or less. Both surfaces were filled with blind vias having a diameter of 60 µm by UV-YAG laser to fill the holes with copper plating. Then, the circuit of line / space = 25/25 micrometers was formed in both surfaces, and the 6-layer double-sided copper foil multilayer laminated board X was produced. A sheet-like UV selective thermosetting solder resist having a thickness of 30 µm was placed on the double-sided copper foil multilayer laminate X surface, and after the laminate was bonded at 80 ° C., the development of noble metal plating in the conventional method was removed, followed by nickel plating and gold plating. The multilayer printed circuit board was fabricated. However, the hole was cut and UV-Vanadate laser was used. The thickness of only the said insulating layer was 370 micrometers. The evaluation results are shown in Table 1.

Example 3-3 Formation of Printed Circuit Board

Double-sided copper-clad laminate Y having a copper foil thickness of 3 μm with a carrier copper foil having a thickness of 35 μm attached to an insulating layer having a thickness of 40 μm (trade name: CCL-HL890, Tg by DMA after curing: manufactured by Mitsubishi Gas Chemical Co., Ltd.) After peeling off and removing the carrier copper foil of one side of this, the inside of this hole was filled with the blind via of 60 micrometers diameter by UV-YAG laser, and the inside of this hole was filled with copper plating. Thereafter, circuits were formed on both sides, and after CZ treatment, one sheet of each semi-additive preflag W having a thickness of 40 μm in Example 3-2 was placed on each of these surfaces, and laminated and molded in the same manner. The hole was filled with a blind via having a diameter of 50 μm by UV-YAG laser to fill the hole with copper plating. Thereafter, circuits of line / space = 25/25 mu m were formed on both surfaces. One piece of prepreg P having a thickness of 40 μm is disposed on the front and back surfaces of the solder resist, and a fluorine resin film having a thickness of 50 μm is placed on the outer side thereof, and the thickness is 1.5 at 230 ° C., 20 kgf / cm 2 and 5 mmHg or less. Time laminated molding. Afterwards, a printed circuit board was manufactured by performing nickel plating and gold plating by drilling a portion of the noble metal plating with a UV-YAG laser to copper foil. The thickness of only this insulating layer is 200 µm. The evaluation results are shown in Table 1.

Comparative Example 1-1

The varnish A of Example 1-1 was used to impregnate and dry a glass cloth substrate having a thickness of 100 µm to obtain a preflag B 'produced in a gelation time of 127 seconds so that the thickness after molding was 110 µm. One piece of this preflag B 'was placed and laminated molding was performed to produce a copper foil laminated plate C' having a thickness of 110 µm, and a printed circuit board was manufactured in the same manner as in Example 1-1. The evaluation results are shown in Table 1.

Comparative Example 1-2

The varnish A of Example 1-1 was used to impregnate and dry a 30-micrometer-thick glass woven fabric base material, to obtain a preflag D 'produced in a gelation time of 122 seconds so that the thickness after molding was 40 µm. Using one preflag B of Example 1-1, one prepreg D 'was arranged on both sides thereof, and a 12 μm electrolytic copper foil was placed on the outside thereof. The copper clad side plate E 'was produced. Using this, a printed circuit board was manufactured in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 1-3

Three preflags C of Example 1-1 were laminated and formed in the same manner to prepare a copper-clad laminate F 'having an insulating layer thickness of 120 μm, and a printed circuit board was manufactured using the same. The evaluation results are shown in Table 1.

[Comparative Example 1-4]

In Example 1-3, the six-layer copper multilayer board using the preflag B was produced for lamination, and the printed circuit board was similarly manufactured. The evaluation results are shown in Table 1.

Comparative Example 1-5

In Example 1-2, two preflags G 'of the wholly aromatic polyamide fiber woven fabric were laminated and molded in the same manner to prepare a double-sided copper-clad laminate having an insulating layer thickness of 220 µm, and the printed circuit board was used in the same manner. It was made. The evaluation results are shown in Table 1.

Comparative Example 2-1

In Example 2-1, varnish A was impregnated into a 30-micrometer-thick glass woven fabric base material, and it dried, and obtained prepreg H 'which produced the thickness after shaping to be 40 micrometers in 125 second of gelation time. After the circuits were formed on both surfaces of the double-sided dynamic layer plate I of Example 2-1 and subjected to black copper oxide treatment, one piece of prepreg H 'was placed on each of the two surfaces, and the temperature was 1.5 ° C at 190 ° C and 5 mmHg or less. It laminated by time and produced the multilayer double-sided copper foil laminated board I 'whose total thickness of an insulating layer is 110 micrometers. Using this, it was carried out similarly to Example 2-1, and set it as the multilayer printed wiring board. The evaluation results are shown in Table 1.

Comparative Example 2-2

In Example 2-1, after forming a circuit on both surfaces of copper foil laminated board J '(trade name: HL890, Mitsubishi Gas Chemical Co., Ltd.) whose insulating layer thickness of 12 micrometers of double-side copper foils is 30 micrometers, black copper oxide process is performed It carried out, it laminated | stacked similarly using each prepreg C used in Example 1-1 on both surfaces, and produced the multilayer double-sided copper foil laminated board K 'with an insulation layer thickness of 110 micrometers, and uses it similarly. It was set as the multilayer printed wiring board. The evaluation results are shown in Table 1.

Comparative Example 2-3

In Example 2-2, after forming a circuit on both surfaces of the double-sided dynamic laminated board L, and performing CZ process of Mack Corporation, 1 piece of preflag K is arrange | positioned on this both surfaces, and it is 190 degreeC and 5 mmHg or less vacuum It laminated | stacked-molded under 1.5 hours, and produced the multilayer double-sided copper foil laminated board L 'of 360 micrometers of insulating layer total thickness using the same thing as a wholly aromatic polyamide woven base material, and the thermosetting resin composition. Using this, it was set as the multilayer printed wiring board similarly. The evaluation results are shown in Table 1.

Comparative Example 3-1

About Example 3-3, the prepreg M 'produced by impregnating and drying a 30-micrometer-thick glass woven base material with varnish A, and having a thickness of 40 micrometers after shaping | molding with 125 second gelation time was obtained. The electrolytic copper liquid with a thickness of 12 micrometers was arrange | positioned on both surfaces using this preflag M 'piece, and the double-sided copper foil laminated board N' formed by laminating like Example 3-1 was obtained. After etching the copper foil of one side of this copper clad laminated board to 3 micrometers, a blind via hole was formed similarly, copper foil of the opposite side was also etched in substantially the same thickness, and the inside of the blind via was filled with copper plating. . After forming a circuit on both surfaces and performing black copper oxide processing, one prepreg M 'was arrange | positioned on each both surfaces, and it laminated | stacked-molded at 190 degreeC and 5 mmHg or less for 1.5 hours, and double-sided copper foil multilayer laminated board N' was formed. Produced. Using this, a general 40 µm UV selective thermosetting solder resist was applied to the surface, dried, and exposed and developed to form a permanent protective film on both sides. The total thickness of the insulating layer of this printed circuit board was 200 mu m. The evaluation results are shown in Table 1.

Comparative Example 3-2

In Example 3-1, except for the inner side plate, all of them were built up twice using a 60-μm semi-additive resin composition sheet to obtain a six-layer printed circuit board. A general UV selective thermosetting solder resist was applied to this surface to have a thickness of 40 µm, dried, and exposed and developed to form a permanent protective film on both surfaces. The total thickness of the insulating layer of this printed circuit board was 315 mu m. The evaluation results are shown in Table 1.

[How to measure]

(1) warping and twisting

36 printed wiring boards of a 30x30 mm size were affixed in the work size 250x250 mm, and the multilayer printed wiring board was produced by the structure of each Example and a comparative example. The warp and twist of the multilayer printed wiring board alone and the one mounted with a 13 x 13 mm flip chip in the center of the printed wiring board through the reflow furnace are measured, and the maximum value is shown. Here, the reflow furnace has a maximum temperature of 260 ° C.

(2) modulus of elasticity

In the structure of each Example and a comparative example, without using copper foil, it laminated | stacked similarly and produced the laminated board, measured by DMA method, and showed the elasticity modulus at 260 degreeC.

<Table 1> Twisting and Warping of Printed Circuit Board (㎛)

division Printed circuit board alone After flip chip mounting Elastic modulus (kgf / ㎠) 260 ℃ Example 1-1 <100 189 2213 Example 1-2 <100 161 2169 Example 1-3 <100 155 2067 Comparative Example 1-1 <100 721 1478 Comparative Example 1-2 <100 433 1601 Comparative Example 1-3 <100 319 2108 Comparative Example 1-4 <100 381 1555 Comparative Example 1-5 <100 368 1389 Example 2-1 <100 183 2221 Example 2-2 <100 118 2197 Comparative Example 2-1 <100 441 1608 Comparative Example 2-2 <100 339 2105 Comparative Example 2-3 <100 355 1477 Example 3-1 <50 78 2017 Example 3-2 <50 67 2223 Example 3-3 <50 100 2319 Comparative Example 3-1 <50 597 1320 Comparative Example 3-2 <50 713 1106

The present invention is not limited to the above embodiments, and many variations are possible by those skilled in the art within the spirit of the present invention.

As described above, the copper-clad laminate and the printed circuit board according to an aspect of the present invention include a thermosetting resin composition having a different glass transition temperature, and thus, when the semiconductor chip is connected through a reflow furnace in flip chip bonding, the bending and twisting of the substrate are very high. It can be mounted stably. In addition, of course, the bending and torsion are very small in other mounting by wire bonding. According to another aspect of the present invention, the outermost layer can form a circuit by the additive method, thereby forming a fine wiring having a fine circuit width and an interval between circuits with a line / space = 30/30 μm or less.

The high density multilayer printed circuit board formed in accordance with the present invention can be mainly used in a small, lightweight semiconductor plastic package, etc. by mounting and connecting a semiconductor chip, of course, can be used for the main board.

Claims (20)

The outermost insulating layer containing the thermosetting resin composition which has a glass transition temperature more than the maximum temperature at the time of reflow processing, and the thermosetting resin which is located inside the outermost insulating layer and has the glass transition temperature below the maximum temperature at the time of reflow processing. Copper clad laminated board comprising an inner insulating layer comprising a composition. The method according to claim 1, A copper clad laminate having an elastic modulus of at least 2000 kgf / mm 2 during reflow treatment of the outermost insulating layer and the inner insulating layer. The method according to claim 1, And said outermost insulating layer has a glass transition temperature that is at least 10 [deg.] C. higher than the highest temperature during said reflow process. The method according to claim 1, The inner insulation layer is a copper clad laminate comprising a wholly aromatic polyamide fiber woven fabric as a reinforcing substrate. delete The method according to any one of claims 1 to 4, The thermosetting resin composition is a copper-clad laminate comprising at least one resin selected from the group consisting of epoxy resins, cyanic acid ester resins, bis maleimide resins, polyimide resins, functional group-containing polyphenylene ether resins and flame retardant resins thereof. The method according to any one of claims 1 to 4, A printed circuit board for flip chip mounting using the copper clad laminate. The outermost insulating layer containing the thermosetting resin composition which has a glass transition temperature more than the maximum temperature at the time of reflow processing, and the thermosetting property which is located inside the outermost insulating layer and has the glass transition temperature below the maximum temperature at the time of said reflow processing. A printed circuit board comprising an inner insulating layer comprising a resin composition. The method according to claim 8, The elasticity modulus of the outermost insulating layer and the inner layer insulating layer in the reflow process is more than 2000kgf / mm2. The method according to claim 8, The outermost insulating layer is a printed circuit board having a glass transition temperature 10 ℃ or more higher than the maximum temperature during the reflow process. The method according to claim 8, The inner insulation layer is a printed circuit board comprising a wholly aromatic polyamide fiber woven fabric as a reinforcing substrate. A thermosetting resin composition having an outermost insulating layer containing a resin capable of forming a circuit in an additive manner with a thermosetting resin composition, and having a glass transition temperature of at least the highest temperature at the time of reflow treatment, which is located inside the outermost insulating layer. A printed circuit board comprising a first internal insulating layer comprising a. The method according to claim 12, The outermost insulating layer and the first inner insulating layer has a modulus of elasticity of at least 2000 kgf / mm 2 during reflow treatment. The method according to claim 12, And a second inner insulation layer formed inside the first inner insulation layer, the second inner insulation layer including a thermosetting resin composition having a glass transition temperature below a maximum temperature of the reflow process. The method according to claim 14, The second internal insulating layer has a modulus of elasticity of at least 2000 kgf / mm 2 during reflow. The method according to claim 12, And the first internal insulating layer has a glass transition temperature of 10 ° C. or higher than a maximum temperature during the reflow process. The method according to claim 12, The outermost insulating layer is a printed circuit board reinforced by a substrate. The method according to claim 17, Printed circuit board using the substrate reinforced insulating layer as a solder resist. delete The method according to any one of claims 8 to 18, The thermosetting resin composition is a printed circuit board comprising at least one resin selected from the group consisting of an epoxy resin, a cyanic acid ester resin, a bis maleimide resin, a polyimide resin, a functional group-containing polyphenylene ether resin, and flame retardant resins thereof. .