TW201422419A - Copper foil with carrier - Google Patents

Abstract

Provided is a copper foil with a carrier, in which an ultrathin copper layer is not released from the carrier before a process of lamination on an insulating substrate but the ultrathin copper layer can be released after the process of lamination on an insulating substrate. A copper foil with a carrier, which is provided with a copper foil carrier, an intermediate layer that is laminated on the copper foil carrier, and an ultrathin copper layer that is laminated on the intermediate layer. The intermediate layer is configured of an Ni layer that is in contact with the interface with the copper foil carrier and a Cr layer that is in contact with the interface with the ultrathin copper layer. The amount of adhered Ni in the intermediate layer is 1,000-40,000 mug/dm2 and the amount of adhered Cr in the intermediate layer is 10-100 mug/dm2, while Zn additionally adheres to the intermediate layer in an amount of 1-70 mug/dm2.

Description

Carrier copper foil

The present invention relates to a copper foil with a carrier. More specifically, the present invention relates to a copper foil with a carrier used as a material for a printed wiring board.

The printed wiring board is usually produced by forming a conductor pattern on the copper foil surface by etching after the insulating substrate and the copper foil are bonded to each other to form a copper clad laminate. With the increase in the demand for miniaturization and high performance of electronic devices in recent years, the high-density mounting of components and the high frequency of signals have been promoted, and the conductor pattern has been required to be miniaturized (narrow pitch). (fine pitch) or high frequency response.

Recently, a copper foil having a thickness of 9 μm or less and a thickness of 5 μm or less is required in order to narrow the pitch. However, such an extremely thin copper foil has low mechanical strength and is liable to be broken or wrinkled during the manufacture of a printed wiring board. A metal foil having a thickness is used as a carrier, and a copper foil with a carrier on which an extremely thin copper layer is electrodeposited via a peeling layer is formed. The carrier copper foil is usually used by bonding the surface of the ultra-thin copper layer to the insulating substrate and thermocompression bonding, and then peeling the carrier through the peeling layer.

Previously, as the release layer, it has been known to form Cr, Ni, Co, Fe, Mo, Ti, W, P or the like alloys or the like. Further, in order to stabilize the peeling property in a high-temperature use environment such as heating and pressurization, it is also described that it is effective to provide Ni, Fe or the alloy layer on the base of the peeling layer (JP-A-2010-006071) , Japan Special Open 2007-007937 Bulletin).

In these documents, it is extremely difficult to perform uniform plating on the plating on the peeling layer due to the peeling property, and therefore, the extremely thin copper foil formed based on the plating conditions may have a number of pin holes. More circumstances. Therefore, it is also described that: first, copper copper plating is performed on the peeling layer, and copper is further plated on the test plating layer, whereby uniform plating can be performed on the peeling layer, thereby significantly reducing extremely thin copper. The number of pinholes in the foil.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-006071

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-007937

In the copper foil with a carrier, it is necessary to prevent the ultra-thin copper layer from being peeled off from the carrier before the step of laminating the insulating substrate, and on the other hand, the ultra-thin copper layer must be peeled off from the carrier after the lamination step to the insulating substrate. Further, in the copper foil with a carrier, the presence of pinholes on the surface of the extremely thin copper layer side causes poor performance of the printed wiring board, which is not preferable.

Regarding these aspects, the prior art has not been sufficiently studied and there is still room for improvement. Therefore, an object of the present invention is to provide a carrier copper which can be peeled off from a carrier after the step of laminating to an insulating substrate, and the ultra-thin copper layer can be peeled off from the carrier after the lamination step to the insulating substrate. Foil. Further, another object of the present invention is to provide a copper foil with a carrier which suppresses the occurrence of pinholes on the side surface of an extremely thin copper layer.

In order to achieve the above object, the present inventors have conducted intensive studies and found that it is extremely effective to use a copper foil as a carrier, and to form a layer of a Ni layer and an extremely thin Cr layer between the ultra-thin copper layer and the carrier. The intermediate layer is formed, and a trace amount of Zn is further added to the intermediate layer.

The present invention has been completed based on the above findings. One aspect of the present invention is a copper foil with a carrier provided with a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an extremely thin copper layer laminated on the intermediate layer. The intermediate layer is composed of a Ni layer contacting the interface with the copper foil carrier and a Cr layer contacting the interface with the ultra-thin copper layer, and the adhesion amount of Ni in the intermediate layer is 1000 to 40000 μg/dm ² , in the middle layer the deposition amount of Cr is 10 ~ 100μg / dm ^2, the presence of Zn in the further intermediate layer 1 ~ 70μg / dm ² amount of adhesion.

In one embodiment, a copper foil with a carrier of the present invention, the amount of deposition of Ni is 2000 ~ 10000μg / dm ^2, the deposition amount of Cr 20 ~ 40μg / dm ^2.

In another embodiment of the copper foil with a carrier of the present invention, the mass ratio of Zn to Cr present in the intermediate layer is in the range of 0.01 to 5.

In still another embodiment of the copper foil with a carrier of the present invention, Cr is adhered by electrolytic chromate.

In still another embodiment of the copper foil with a carrier of the present invention, the carrier is formed of an electrolytic copper foil or a rolled copper foil.

In still another embodiment of the copper foil with a carrier of the present invention, the surface of the ultra-thin copper layer has a roughened layer.

In still another embodiment of the copper foil with a carrier of the present invention, the roughening treatment layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. A layer composed of an alloy containing any one or more elements selected from the group.

In still another embodiment of the copper foil with a carrier of the present invention, the surface of the roughened layer has a layer selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer, and a decane coupling treatment layer. One or more layers.

In still another embodiment of the copper foil with a carrier of the present invention, the surface of the ultra-thin copper layer is selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. One or more layers.

In still another embodiment of the copper foil with a carrier of the present invention, the ultra-thin copper layer is provided with a resin layer.

In still another embodiment of the copper foil with a carrier of the present invention, a resin layer is provided on the roughened layer.

In still another embodiment of the copper foil with a carrier of the present invention, the resin is provided on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. Floor.

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer is formed of a resin.

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer is formed of a resin in a semi-hardened state.

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer contains a dielectric.

Another aspect of the present invention is a printed wiring board manufactured using the copper foil with a carrier of the present invention.

Still another aspect of the present invention is a printed circuit board manufactured using the carrier-attached copper foil of the present invention.

Still another aspect of the present invention is a copper clad laminate which is produced using the copper foil with a carrier of the present invention.

Still another aspect of the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention, laminating the copper foil and the insulating substrate with the carrier, and laminating the copper with the carrier After the foil and the insulating substrate, the carrier with the carrier copper foil is peeled off, and a copper clad laminate is formed through the above steps, and then subjected to a semi-additive method, a subtractive method, a partial addition ( Partial-additive method or modified semi-additive method A method to form a circuit.

Still another aspect of the present invention is a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of the copper foil with a carrier of the present invention; and attaching the circuit to the above a side surface of the ultra-thin copper layer of the carrier copper foil is formed with a resin layer; an electric circuit is formed on the resin layer; after the circuit is formed on the resin layer, the carrier is peeled off; and after the carrier is peeled off, the ultra-thin is removed The copper layer is thereby exposed to the circuit buried in the resin layer on the side surface of the ultra-thin copper layer.

In one embodiment of the method for producing a printed wiring board according to the present invention, the step of forming a circuit on the resin layer is a step of laminating another carrier copper foil from the side of the ultra-thin copper layer on the resin layer, and The above circuit is formed using a copper foil with a carrier attached to the above resin layer.

In another embodiment of the method for producing a printed wiring board according to the present invention, the other carrier copper foil bonded to the resin layer is the copper foil with a carrier of the present invention.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Perform any of the methods.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the copper foil with a carrier on the surface forming circuit has a substrate or a resin layer on the surface of the carrier on which the carrier copper foil is attached.

The copper foil with carrier of the present invention can obtain the necessary adhesion between the carrier and the ultra-thin copper layer before the step of laminating the insulating substrate, and on the other hand, the ultra-thin copper layer can be easily obtained after the lamination step to the insulating substrate. Carrier peeling. Moreover, the copper foil with carrier of the present invention inhibits the production of pinholes It is a raw material, so it can stably supply a high-quality ultra-thin copper layer.

Fig. 1A to C are circuit plating using a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention. Resist removes the pattern diagram of the wiring board profile in the previous step.

D to F of Fig. 2 is a cross section of a wiring board in which a resin of a specific example of a method for producing a printed wiring board with a copper foil with a carrier of the present invention and a second layer of a carrier-attached copper foil are laminated to a laser opening. Pattern diagram.

G to I of FIG. 3 is a via-filling of a specific example of a method for producing a printed wiring board with a copper foil with a carrier of the present invention, and a cross section of the wiring board in the step of peeling off the carrier of the first layer is formed. Pattern diagram.

Fig. 4, J to K are flash etching to bump using a specific example of a method for manufacturing a printed wiring board with a copper foil with a carrier of the present invention. A schematic view of a cross section of a wiring board in the step of forming a copper pillar.

<1. Carrier>

A copper foil is used as a carrier which can be used in the present invention. Typically, the support is provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by electroplating copper from a copper or copper stainless steel drum, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As a material of the copper foil, in addition to high-purity copper such as tough-pitch copper or oxygen-free copper, for example, copper doped with Sn, copper doped with Ag, added with Cr, Zr or Mg, or the like may be used. A copper alloy or a copper alloy to which a Cason copper alloy such as Ni or Si is added. Further, when the term "copper foil" is used alone in the present specification, a copper alloy foil is also included.

Regarding the thickness of the carrier usable in the present invention, there is no particular limitation as long as it can The thickness may be appropriately adjusted to a suitable thickness under the action of the carrier, and may be, for example, 12 μm or more. However, if the production cost becomes too large, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically from 12 to 70 μm, more typically from 18 to 35 μm.

<2. Middle layer>

An intermediate layer composed of two layers of Ni and Cr is provided on one or both sides of the copper foil carrier. The layer is laminated such that the Ni layer is in contact with the interface with the copper foil carrier and the Cr layer is in contact with the interface with the ultra-thin copper layer. As described below, the adhesion between Ni and Cu is higher than the adhesion between Cr and Cu, so that when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and the Cr layer is peeled off. The Ni layer in the intermediate layer is expected to have a barrier effect of preventing the Cu component from diffusing from the carrier to the ultra-thin copper foil. In the case where the intermediate layer is provided only on one side, it is preferable to provide a rust-proof layer such as a Ni plating layer on the opposite side of the copper foil carrier. Further, in the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on a shiny surface from the viewpoint of reducing pinholes.

The Ni layer constituting the intermediate layer can be plated by electroplating, electroless plating, and immersion plating, for example. Such as wet plating, or dry plating such as sputtering, CVD, and PDV. Electroplating is preferred from the viewpoint of cost.

The Cr layer in the intermediate layer is thinly present at the interface of the extremely thin copper layer. It is extremely important that the extremely thin copper layer is not peeled off from the carrier before the lamination step to the insulating substrate, and on the other hand, the ultra-thin copper layer can be peeled off from the carrier after the lamination step to the insulating substrate. When the Ni layer is not provided and the Cr layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property is hardly improved, and when the Ni layer and the ultra-thin copper layer are directly laminated without the Cr layer, the peel strength is It is too strong or too weak corresponding to the amount of Ni in the Ni layer, so that appropriate peel strength cannot be obtained.

Further, when the Cr layer is present at the boundary between the carrier and the Ni layer, the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, peeling occurs between the carrier and the intermediate layer, which is not preferable. This situation is not only caused by the case where the Cr layer is placed at the interface with the carrier, but even if Cr is The layer is disposed at the interface with the ultra-thin copper layer, and may be generated if the amount of Cr is too large. The reason is considered to be that Cu and Ni are easily dissolved in a solid state. Therefore, when these contacts are in contact with each other, the adhesion force is increased and the adhesion is less likely to occur. On the other hand, Cr and Cu are not easily dissolved and are not easily diffused. Therefore, the interface between Cr and Cu has a weaker adhesion and is easily peeled off. Further, when the amount of Ni in the intermediate layer is insufficient, only a small amount of Cr exists between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and are not easily peeled off.

In order to make the Cr layer exist at the interface of the extremely thin copper layer, it can be realized as follows Now, after the Ni layer is formed, a trace amount of Cr is obtained by wet plating such as electrolytic chromate, electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. Attached and formed a very thin copper layer thereon. From the viewpoint of attaching a trace amount of Cr at a low cost, electrolytic chromate is preferred.

In the present invention, the amount of Ni contained in the intermediate layer is 20% by mass. The sample was dissolved in nitric acid and measured by ICP emission analysis. The amount of Cr deposited and the amount of Zn deposited in the intermediate layer were measured by dissolving the sample in hydrochloric acid having a concentration of 7 mass% and performing quantitative analysis by atomic absorption. Further, when a plating layer containing Ni, Cr, or Zn is provided on the surface of the ultra-thin copper layer, the carrier layer is subjected to the above measurement after the ultra-thin copper layer is peeled off, whereby the intermediate layer can be measured. The Ni adhesion amount, the Cr adhesion amount, and the Zn adhesion amount contained.

In the above aspect, in the present invention, the adhesion amount of Cr in the intermediate layer is set to 10 to 100 μg/dm ² , and the adhesion amount of Ni is set to 1000 to 40,000 μg/dm ² . Further, as the amount of Cr adhesion or the amount of Ni adhesion increases, the amount of pinholes tends to increase, but the number of pinholes is also suppressed as long as it is within this range. To all views are uniformly peeled off of the ultra-thin copper layer, and in terms of suppressing the pinhole, Cr deposition amount is preferably set to 10 ~ 50μg / dm ^2, more preferably set to 15 ~ 40μg / dm ² Further, it is preferably 10 to 20 μg/dm ² . Ni deposition amount is preferably set to 2000 ~ 10000μg / dm ^2, more preferably set to 2000 ~ 9000μg / dm ^2, and further preferably set to 2000 ~ 4000μg / dm ^2.

Further, it is more important in the present invention that the intermediate layer contains a trace amount of Zn. borrow Therefore, the occurrence of pinholes can be remarkably reduced, and the appropriate peel strength can be easily obtained, which greatly contributes to quality stability. It is not intended to limit the invention to the theory, but by the presence of a trace amount of Zn in the intermediate layer, an oxide film composed of Cr and Zn is formed, so that the conductivity of the intermediate layer is more uniform, and the conductivity is extremely high. The part or the part with extremely low conductivity disappears. The reason for this is considered to be that the electrodeposited particles of copper are uniformly adhered to the oxide film composed of Cr and Zn when the ultra-thin copper layer is formed, and the peel strength is an appropriate value (the peel strength is not extremely high, or Peel strength will not be extremely low).

Zn may be present in either or both of the Ni layer and the Cr layer in the intermediate layer. example For example, by adding a zinc component to the plating solution when the Ni layer is formed, a nickel-zinc alloy is deposited to obtain a Ni layer containing zinc. Further, a Cr layer containing zinc can be obtained by adding a zinc component to the chromate treatment liquid. However, in either case, since Zn diffuses in the intermediate layer, it is usually detected in both the Ni layer and the Cr layer. Further, in the case where an oxide film composed of Cr and Zn is easily formed, Zn is preferably present in the Cr layer.

However, if the amount of adhesion of Zn in the intermediate layer is too small, the effect is limited, so it should be 1 μg/dm ² or more, and preferably 5 μg/dm ² or more. On the other hand, if the amount of deposition of the intermediate layer is too large, the peel strength of Zn is too large, and therefore should be set to 70μg / dm ² or less, is preferably set to 30μg / dm ² or less, more preferably to 20μg / dm ² or less .

Further, the mass ratio of Zn to Cr (the amount of Zn adhesion/Cr adhesion) It is preferably in the range of 0.01 to 5.00, more preferably in the range of 0.1 to 1.0, and preferably 0.2 to 0.8. This is because the occurrence of pinholes is suppressed or the peeling characteristics of the ultra-thin copper foil are improved by setting the amount of Zn to Cr to the range.

<3. Very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, which is used for the usual electrolytic copper foil and can be used for high current. It is preferred to form a copper foil at a density. The thickness of the very thin copper layer is not It is particularly limited, but is usually thinner than the carrier, for example, 12 μm or less. Typically it is from 0.5 to 12 μm, more typically from 2 to 5 μm.

<4. Roughening layer and other layers>

On the surface of the ultra-thin copper layer, for example, in order to improve the adhesion to the insulating substrate, a roughening treatment layer may be provided by performing a roughening treatment. The roughening treatment can be carried out, for example, by forming roughened particles with copper or a copper alloy. The roughening treatment can also be fine. The roughening treatment layer may be composed of any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or may contain any one or more selected from the group. A layer composed of an alloy of elements. Further, after the roughened particles are formed of copper or a copper alloy, a roughening treatment may be performed in which secondary particles or tertiary particles are provided in a simple substance such as nickel, cobalt, copper or zinc or an alloy. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of a single substance or an alloy of nickel, cobalt, copper or zinc, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. Alternatively, the heat-resistant layer or the rust-preventing layer may be formed of a single substance or an alloy of nickel, cobalt, copper or zinc, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. In other words, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be formed in an extremely thin copper layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer are formed on the surface. Further, the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer may be formed as a plurality of layers of, for example, two or more layers and three or more layers.

Therefore, in one embodiment of the present invention, the ultra-thin copper layer may be provided with a roughened layer, or the heat-treated layer or the rust-preventing layer may be provided on the roughened layer, or the heat-resistant layer may be The rustproof layer is provided with a chromate treatment layer, and a decane coupling treatment layer may be provided on the chromate treatment layer.

As the heat-resistant layer and the rust-preventing layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat resistant layer and/or the rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. a layer of one or more elements of the group of bismuth, which may also be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, A metal layer or an alloy layer composed of one or more elements selected from the group consisting of platinum group elements, iron, and antimony. Moreover, the heat-resistant layer and/or the rust-preventing layer may further contain an oxide, a nitride, and a telluride, and the oxide, nitride, and telluride may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, and phosphorus. One or more elements of the group consisting of arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and antimony. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may also contain 50% by weight to 99% by weight of nickel and 50% by weight to 1% by weight of zinc for removing unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , preferably 20 to 100 mg/m ² . Further, the ratio of the adhesion amount of nickel to the nickel-zinc alloy layer or the nickel-zinc alloy layer to the adhesion amount of zinc (=the adhesion amount of nickel/the adhesion amount of zinc) is preferably 1.5 to 10. Further, the adhesion amount of the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer is preferably 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² . When the heat-resistant layer and/or the rust-preventive layer is a layer containing a nickel-zinc alloy, when the inner wall portion of the through hole or the via hole is in contact with the desmear liquid The interface between the copper foil and the resin substrate is not easily eroded by the degreasing liquid, thereby improving the adhesion between the copper foil and the resin substrate.

For example, the heat-resistant layer and/or the rust-preventing layer may be a nickel or nickel alloy layer having an adhesion amount of 1 mg / m ² to 100 mg / m ² (preferably 5 mg / m ² to 50 mg / m ² ), and attached thereto. The nickel alloy layer may also be composed of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt in an amount of 1 mg/m ² to 80 mg/m ² (preferably 5 mg/m ² to 40 mg/m ² ). Any one of the components. Further, in the heat-resistant layer and/or the rust-preventive layer, the total adhesion amount of nickel or a nickel alloy to tin is preferably 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, in the heat-resistant layer and/or the rust-preventive layer, [the amount of nickel deposited in the nickel or nickel alloy] / [the amount of tin adhesion] is preferably 0.25 to 10, more preferably 0.33 to 3. When the heat-resistant layer and/or the rust-preventing layer are used, the peeling strength of the circuit after the copper foil with a carrier is processed into a printed wiring board, the chemical-resistant deterioration rate of the peeling strength, etc. become favorable.

Further, a known decane coupling agent can be used for the decane coupling treatment. As the decane coupling agent, for example, an amine decane coupling agent, an epoxy decane coupling agent, or a decyl decane coupling agent can be used. Further, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-glycidoxypropyl trimethoxy decane, 4-epoxypropylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-3-( 4-(3-Aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, trioxane, γ-mercaptopropyltrimethoxydecane, etc. for decane coupling agents .

The above decane coupling treatment layer may also be an epoxy decane, an amine decane or a It is formed by a decane coupling agent such as a propylene oxy oxane or a decyl decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, it is preferred to use an amine decane coupling agent or an epoxy decane coupling agent.

The amine decane coupling agent mentioned herein may also be selected from the following compounds The group consisting of: N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyl Trimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, aminopropyltrimethoxydecane, N-A Aminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltriethoxy Decane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-(2-aminoethyl-3-aminopropyl)trimethyl Oxydecane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylaminopropyl)trimethoxynonane, amine Phenyltrimethoxydecane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxynonane, 3-aminopropyltris(methoxyethoxy) Ethyloxy)decane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane, 3-(2-N-benzyl Aminoethylaminopropyl)trimethoxyanthracene alkyl, Bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N,N-diethyl-3-aminopropyl)trimethoxynonane, (N,N-dimethyl 3-aminopropyl)trimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, 3-(N-styrylmethyl- 2-Aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N- 3-(4-(3-Aminopropyloxy)butoxy)propyl-3-aminopropyltrimethoxydecane.

The decane coupling treatment layer is preferably 0.05 mg/m ² to 200 mg/m ² , preferably 0.15 mg/m ² to 20 mg/m ² , preferably 0.3 mg/m ² to 2.0 mg/in terms of ruthenium atom. The range of m ² is set. In the case of the above range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

Further, the copper foil with a carrier may be on the ultra-thin copper layer or the roughening portion A resin layer is provided on the protective layer or the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, or the decane coupling treatment layer. The above resin layer may also be an insulating resin layer.

The above resin layer may be an adhesive or a semi-hardened state for subsequent use (B-stage) Insulating resin layer in the segment state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer can be stored in an overlapping manner even if the surface is touched by a finger, and the curing reaction can be performed by heat treatment.

Further, the resin layer may contain a thermosetting resin, and may also contain a thermoplastic Resin. The type thereof is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, a maleimide resin, and a polyethylene. Acetal resin, urethane resin, polyether oxime, polyether oxime resin, aromatic polyamide resin, polyamidoximine resin, rubber modified (modified) epoxy resin, phenoxy resin ( Phenoxy resin), carboxyl modified (modified) acrylonitrile-butadiene resin, polyphenylene ether, bis-xenylene diimide three resin, thermosetting polyphenylene ether resin, cyanate resin, polycarboxylic acid A resin such as an anhydride is preferred. Further, the above resin layer may also be a block copolymerized polyimine tree A resin layer of a lipid layer or a resin layer containing a block copolymerized polyimide resin and a polysynyleneimine compound. Further, the epoxy resin is one having two or more epoxy groups in the molecule, and is only applicable to electricity. Electronic materials users can use without any problems. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more epoxy propyl groups in the molecule. Further, a mixture selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac Epoxy resin, alicyclic epoxy resin, brominated epoxy resin, epoxy propyl amine epoxy resin, triglycidyl isocyanate, N, N-diepoxypropyl aniline, etc. A glycidyl ester compound such as a glycidylamine compound or a diglycidyl tetrahydrophthalate, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, a biphenyl novolac type epoxy resin, or a trihydroxybenzene One or two or more of the group consisting of a base methane type epoxy resin and a tetraphenylethane type epoxy resin, or a hydride or a halide of the above epoxy resin may be used.

The above polycarboxylic acid anhydride is preferably useful as a hardener for an epoxy resin. The ingredients. Further, the anhydride of the polyvalent carboxylic acid is preferably phthalic anhydride, maleic anhydride, 1,2,4-benzenetricarboxylic anhydride, pyromellitic dianhydride, tetrahydroxyphthalic anhydride, or hexahydroxyl Phthalic anhydride, methyl hexahydroxyphthalic anhydride, Nadic anhydride, methyl acid anhydride.

Further, the resin composition for forming the resin layer may contain an anhydride of a polyvalent carboxylic acid, a phenoxy resin, or an epoxy resin. The above acid anhydride preferably contains 0.01 mol to 0.5 mol with respect to 1 mol of the hydroxyl group contained in the phenoxy resin. The above phenoxy resin can be synthesized by a reaction of a bisphenol and a divalent epoxy resin. The content of the phenoxy resin may be 3 parts by weight to 30 parts by weight when the total amount of the resin composition is 100 parts by weight. The epoxy resin may be an epoxy resin obtained by epoxidizing a compound having two or more epoxy propyl groups in the molecule. Further, the resin composition can be obtained by reacting an anhydride of a polyvalent carboxylic acid with a phenoxy resin, ring-opening addition of a polyvalent carboxylic acid to a hydroxyl group of a phenoxy resin, and then adding an epoxy resin.

As the above bisphenol, bisphenol A, bisphenol F, bisphenol S, and tetrabromo-bis can be used. Phenol A, 4,4'-dihydroxybiphenyl, HCA (9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-Oxide) Bisphenol obtained in the form of an adduct with a terpene such as hydroquinone or naphthoquinone.

Further, the thermoplastic resin may be a thermoplastic resin having a functional group other than the alcohol-removing hydroxyl group polymerizable with the epoxy resin.

The composition of the resin layer is 50 to 90% by weight of epoxy resin, 5 to 20% by weight of polyvinyl acetal resin, and 0.1 to 20% by weight of urethane resin, based on the total amount of the resin component. 0.5 to 40% by weight may also be a rubber modified (modified) epoxy resin.

Further, the polyvinyl acetal resin may have a functional group other than an acid group or a hydroxyl group which is polymerizable with an epoxy resin or a maleimide compound. It may contain 40 to 80 parts by weight of the epoxy resin blend, 10 to 50 parts by weight of the maleimide compound, and have a hydroxyl group and 100 parts by weight based on 100 parts by weight of the total amount of the resin composition for the resin layer. 5 to 30 parts by weight of a polyvinyl acetal resin which is a functional group which can be polymerized with an epoxy resin or a maleimide compound other than a hydroxyl group. Further, the polyvinyl acetal resin may be one having a carboxyl group, an amine group or an unsaturated double bond introduced into the molecule.

Further, the resin layer may be an epoxy resin (containing a curing agent) in an amount of 20 to 80 parts by weight, 20 to 80 parts by weight of a solvent-soluble aromatic polyamide resin polymer, and if necessary, added in an appropriate amount. The resin composition composed of the hardening accelerator is formed. Further, the resin layer may be an epoxy resin (containing a curing agent) of 5 to 80 parts by weight, 20 to 95 parts by weight of a solvent-soluble aromatic polyamide resin polymer, and if necessary, added in an appropriate amount. The resin composition composed of the hardening accelerator is formed. The aromatic polyamide resin polymer used in the constitution of the resin composition for forming the above resin layer may be obtained by reacting an aromatic polyamide with a rubber resin. The above resin layer may also be a dielectric filler. The above resin layer may also be a material containing a skeleton.

Here, the aromatic polyamine resin polymer is obtained by reacting an aromatic polyamide resin with a rubber resin. Aromatic polyamine The resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. As the aromatic diamine at this time, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylphosphonium, m-diamine diamine, 3,3'-oxydiphenylamine, etc. are used. . Further, as the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.

Further, the above-mentioned rubber resin which reacts with the above aromatic polyamide resin The concept includes natural rubber and synthetic rubber. The latter synthetic rubbers include styrene-butadiene rubber, butadiene rubber, butyl rubber, and ethylene-propylene rubber. Further, in order to secure the heat resistance of the formed dielectric layer, it is also useful to use a heat-resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or an amine ester rubber. The rubber-based resin is preferably a compound having various functional groups at both ends in order to produce a copolymer by reacting with an aromatic polyamide resin. It is especially useful to use CTBN (carboxy terminal butadiene nitrile).

Aromatic polyamide resin and rubber constituting aromatic polyamide resin polymer The resin is preferably used in an amount of 25 wt% to 75 wt% of the aromatic polyamide resin and the remainder being a rubber resin. When the aromatic polyamide resin is less than 25% by weight, the ratio of the presence of the rubber component is too large to cause poor heat resistance. On the other hand, if it exceeds 75 wt%, the ratio of the presence of the aromatic polyamide resin is too large, and after hardening, The hardness is too high and becomes brittle. The aromatic polyamide resin polymer is used for the purpose of etching the copper foil processed into a copper clad laminate without being damaged by underetching due to the etching liquid.

The aromatic polyamide resin polymer is first required to have solubility in a solvent. quality. The aromatic polyamide resin polymer is used in a blending ratio of 20 parts by weight to 80 parts by weight. When the amount of the aromatic polyamide resin polymer is less than 20 parts by weight, it is excessively hardened and becomes brittle under ordinary pressurization conditions for producing a copper clad laminate, and it is easy to cause microcracking on the surface of the substrate. On the other hand, even if the aromatic polyamine resin polymer is added in an amount of more than 80 parts by weight, the strength of the aromatic polyamide resin polymer is not increased even if it is added in an amount of more than 80 parts by weight. . Therefore, it can be considered that 80 parts by weight is considered in consideration of economy. Limit.

The "hardening accelerator added in an appropriate amount as needed" is a tertiary amine, an imidazole, a urea-based hardening accelerator, and the like. In the invention of the present invention, the blending ratio of the hardening accelerator is not particularly limited. The reason for this is that the curing accelerator can be arbitrarily and selectively specified by the manufacturer in consideration of the production conditions and the like in the step of manufacturing the copper clad laminate.

The resin composition for forming the resin layer may be one in which three epoxy resins of a bisphenol A epoxy resin, a cresol novolak epoxy resin, and a brominated bisphenol A epoxy resin are dissolved in a solvent. A resin composition obtained by adding a curing agent such as a curing agent or finely pulverized ceria or antimony trioxide to the reaction catalyst. The hardener at this time is the same as described above. The resin composition also exhibits good adhesion between the copper foil and the base resin.

The resin composition for forming the above resin layer may also be a polyphenylene ether resin, 2,2-bis(4-cyanooxyphenyl)propane, a phosphorus-containing phenol compound, manganese naphthenate, 2,2- A polyphenylene ether-cyanate-based resin composition in which bis(4-epoxypropylphenyl)propane is dissolved in a solvent. The resin composition also exhibits good adhesion between the copper foil and the base resin.

The resin composition for forming the above resin layer may also be a decane modified polyamine amide which is obtained by dissolving a decane modified polyamidoximine resin or a cresol novolac type epoxy resin in a solvent. An imide resin composition. The resin composition also exhibits good adhesion between the copper foil and the base resin.

(In the case of a resin layer containing a dielectric (dielectric filler))

When any of the above resin layers or resin compositions contains a dielectric (dielectric filler), it can be used for forming a capacitor layer to increase the capacitance of the capacitor circuit. As the dielectric (dielectric filler), BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly known as PZT), and PbLaTiO _{3 are used} . A dielectric powder of a composite oxide having a perovskite structure such as PbLaZrO (commonly known as PLZT) or SrBi ₂ Ta ₂ O ₉ (commonly known as SBT).

The dielectric (dielectric filler) may also be in powder form. Dielectric (dielectric filler) In the case of a powder, the powder characteristics of the dielectric (dielectric filler) must first be in the range of 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. Regarding the particle diameter mentioned here, since the powder particles form a certain fixed secondary aggregation state, the measured values of the laser diffraction scattering particle size distribution measurement method or the BET method are estimated to be the same as the average particle diameter. The measurement accuracy is inferior and cannot be used, and refers to an average particle diameter obtained by directly observing a dielectric (dielectric filler) by a scanning electron microscope (SEM) and performing image analysis on the SEM image thereof. The particle size at this time is indicated as DIA in the specification of the present invention. Further, in the present specification, image analysis of a powder of a dielectric (dielectric filler) observed by a scanning electron microscope (SEM) is performed using IP-1000 PC manufactured by Asahi Engineering Co., Ltd. The circular particle analysis was performed with a roundness threshold of 10 and an overlap degree of 20, and the average particle diameter DIA was obtained.

Further required to be a dielectric powder: by laser diffraction scattering particles The volume cumulative particle diameter D50 obtained by the degree distribution measurement method is 0.2 μm to 2.0 μm, and the value of the agglomeration degree represented by the volume cumulative particle diameter D50 and the average particle diameter DIA obtained by image analysis and expressed by D50/DIA is obtained. Below 4.5, it has an approximately spherical shape and has a perovskite structure.

Volume accumulation by laser diffraction scattering particle size distribution measurement The particle diameter D50 is the particle diameter at 50% of the weight obtained by the laser diffraction scattering particle size distribution measurement method, and the smaller the value of the volume cumulative particle diameter D50 is in the dielectric body (dielectric filler) In the particle size distribution of the powder, the proportion of the fine particles is larger. In the present invention, the value is required to be 0.2 μm to 2.0 μm. In other words, when the value of the volume cumulative particle diameter D50 is less than 0.2 μm, regardless of the dielectric (dielectric filler) powder used in the production method, the agglomeration progresses remarkably, and the following cannot be satisfied. Describe the degree of agglutination. On the other hand, when the value of the volume cumulative particle diameter D50 exceeds 2.0 μm, the dielectric body (dielectric filler) for forming the built-in capacitor layer of the printed wiring board cannot be used as the object of the present invention. That is, the dielectric layer of the double-sided copper-clad laminate for forming the built-in capacitor layer has a thickness of usually 10 μm to 25 μm. Here, in order to uniformly disperse the dielectric filler, 2.0 μm becomes an upper limit.

The volume cumulative particle diameter D50 in the present invention is determined by dielectric (dielectric filling) The powder was mixed and dispersed in methyl ethyl ketone, and the solution was placed in a circulator of a laser diffraction scattering type particle size distribution analyzer Micro Trac HRA 9320-X100 (manufactured by Nikkiso Co., Ltd.).

Here, the concept of the so-called agglutination degree is used for the following reasons. also That is, it is considered that the value of the volume cumulative particle diameter D50 obtained by the laser diffraction scattering type particle size distribution measurement is not the one obtained by directly observing the diameter of one of the particles. The reason for this is that most of the powder constituting the dielectric powder is not a so-called monodisperse powder in which the respective particles are completely separated, but is a state in which a plurality of powder particles are aggregated and aggregated. The reason for this is that the laser diffraction scattering type particle size distribution measurement system can capture the aggregated powder particles as one particle (aggregated particles) to calculate the volume cumulative particle diameter.

In contrast, the dielectric observed by using a scanning electron microscope The observation of the body powder is performed by image processing, and the average particle diameter DIA is obtained by directly observing the image from the SEM. Therefore, the primary particles can be reliably captured, and from the reverse side, the aggregation of the particles is not reflected at all. The existence of the state.

Considering the above situation, the inventors of the present invention use a laser diffraction scattering type particle size distribution The volume cumulative particle diameter D50 of the measurement method and the average particle diameter DIA obtained by image analysis were used to obtain a value calculated by D50/DIA as the degree of aggregation. That is to say, it is assumed that in the same batch of copper powder, the values of D50 and DIA can be measured with the same accuracy. If the above theory is considered, it can be considered that the value of D50 reflecting the agglutination state is reflected in the measured value. Become a value greater than the DIA value.

At this time, if the agglomerated state of the powder of the dielectric (dielectric filler) is completed If it does not exist, the value of D50 will be infinitely close to the value of DIA, and the value of D50/DIA as the degree of agglutination will be close to 1. In the stage where the degree of agglomeration is 1, it can be said that the monodisperse powder is completely free from the agglomerated state of the powder. However, in reality, there is also a case where the degree of agglutination shows a value that does not reach one. Theoretically, in the case of a real ball, it will not become a value of less than 1, but in reality, The powder is not a true ball, so it will give a value of less than 1 agglutination.

In the present invention, the degree of agglomeration of the dielectric (dielectric filler) powder is preferably 4.5 or less. When the degree of agglomeration exceeds 4.5, the aggregation level of the particles of the dielectric filler becomes too high, and it is difficult to uniformly mix with the above resin composition.

As a method of manufacturing a dielectric (dielectric filler) powder, even if alkoxylation is employed Any one of the production methods such as the physical method, the hydrothermal synthesis method, and the oxalate method inevitably forms a certain agglomerated state, and therefore, a dielectric filler powder which does not satisfy the above-described degree of aggregation occurs. In particular, in the case of a wet method, that is, a hydrothermal synthesis method, there is a tendency that formation of agglomerated state is likely to occur. Here, the powder in the agglomerated state can be subjected to a granulation treatment of separating the particles into one particle, whereby the agglomerated state of the dielectric filler powder becomes the range of the degree of aggregation.

As long as it is only for the purpose of granulating, as a feasible means of granulation, Various means such as a high-energy ball mill, a high-speed conductor collision type air flow type pulverizer, an impact pulverizer, a cage mill, a medium agitation type mill, and a high-hydraulic type pulverizing apparatus can be used. However, in order to ensure the miscibility and dispersibility of the dielectric (dielectric filler) powder and the resin composition, the viscosity of the resin solution containing a dielectric (dielectric filler) described below is considered to be reduced. In order to reduce the viscosity of the resin solution containing a dielectric (dielectric filler), it is required that the specific surface area of the particles of the dielectric (dielectric filler) be small and smooth. Therefore, even if granulation can be carried out, it cannot be a granulation method which causes damage to the surface of the granules at the time of granulation and increases the specific surface area thereof.

Based on this insight, the inventors of the present invention have devoted themselves to research and found that two methods It is vaild. The common method of the two methods is to suppress the contact between the powder of the powder of the dielectric (dielectric filler) and the inner wall portion of the device, the stirring blade, the pulverizing medium, and the like to minimize the agglomeration. The powder particles collide with each other, whereby the method of granulation can be sufficiently performed. That is to say, contact with the inner wall portion of the apparatus, the stirring blade, the pulverizing medium, and the like may cause damage to the surface of the powder, increase the surface roughness, and deteriorate the true sphericity, so this is prevented. Thus, the following method can be employed: the particles in the agglutinated state are threshed by causing sufficient particles to collide with each other, At the same time, the surface of the powder can be smoothed by the collision of the particles with each other.

One of them uses a jet mill to couple the dielectric in a cohesive state (dielectric) The filler) powder is subjected to granulation treatment. Here, the "jet mill" uses a high-speed air stream of air, and a dielectric (dielectric filler) powder is placed in the air stream, and the particles collide with each other in the high-speed air stream to perform a granulation operation.

In addition, powder dispersion of a dielectric (dielectric filler) to be in an agglomerated state The slurry obtained by not damaging the stoichiometric solvent is subjected to a granulation treatment using a fluid mill using centrifugal force. By using the "fluid mill using centrifugal force" as described herein, the slurry is flowed at a high speed by drawing a circular orbit. At this time, the agglomerated particles collide with each other in the solvent by the centrifugal force generated. Perform the granulation operation. The slurry which has been subjected to the granulation operation in this manner is washed, filtered, and dried to obtain a dielectric (dielectric filler) powder which is subjected to the granulation operation. According to the above method, the adjustment of the degree of aggregation and the smoothing of the surface of the powder of the dielectric filler powder can be achieved.

The resin composition described above is mixed with a dielectric (dielectric filler) to form a resin containing a dielectric (dielectric filler) for forming a built-in capacitor layer of a printed wiring board. Further, as the resin used for the resin composition to be mixed with the dielectric (dielectric filler), a resin which can be used for the above resin layer can be mentioned. The blending ratio of the resin composition to the dielectric (dielectric filler) at this time is preferably such that the content of the dielectric (dielectric filler) is 75 wt% to 85 wt% and the remainder is a resin composition. .

When the content of the dielectric (dielectric filler) is less than 75% by weight, the relative dielectric constant 20 required by the market cannot be satisfied. If the content of the dielectric (dielectric filler) exceeds 85 wt% %, the content of the resin composition is less than 15% by weight, and the adhesion between the resin containing the dielectric (dielectric filler) and the copper foil bonded to the resin is impaired, and it is difficult to manufacture and satisfy the production as a printed wiring board. A copper clad laminate with the required characteristics.

Furthermore, the resin layer containing the above dielectric (dielectric filler) may also use a dielectric containing body. It is formed by a resin composition of a (dielectric filler), an epoxy resin, an active ester resin, a polyvinyl acetal resin, and a hardening accelerator.

Further, the resin layer containing the dielectric (dielectric filler) may be used when the weight of the resin composition containing the epoxy resin, the active ester resin, the polyvinyl acetal resin, and the curing accelerator is 100 parts by weight. It is formed by containing a resin composition of 25 parts by weight to 60 parts by weight of an epoxy resin and a dielectric (dielectric filler).

Further, the resin layer containing the dielectric (dielectric filler) may be used when the weight of the resin composition containing the epoxy resin, the active ester resin, the polyvinyl acetal resin, and the curing accelerator is 100 parts by weight. It is formed by containing a resin composition of 28 parts by weight to 60 parts by weight of the active ester resin and a dielectric (dielectric filler).

Further, the resin layer containing the dielectric (dielectric filler) may be used when the weight of the resin composition containing the epoxy resin, the active ester resin, the polyvinyl acetal resin, and the curing accelerator is 100 parts by weight. It is formed by containing a resin composition of a total of 78 parts by weight to 95 parts by weight of an epoxy resin and an active ester resin, and a dielectric (dielectric filler).

Further, the resin layer containing the dielectric (dielectric filler) may be used when the weight of the resin composition containing the epoxy resin, the active ester resin, the polyvinyl acetal resin, and the curing accelerator is 100 parts by weight. It is formed by containing a resin composition of 1 part by weight to 20 parts by weight of a polyvinyl acetal resin and a dielectric (dielectric filler).

Further, the resin layer containing the dielectric (dielectric filler) may be used when the weight of the resin composition containing the epoxy resin, the active ester resin, the polyvinyl acetal resin, and the curing accelerator is 100 parts by weight. It is formed by containing a resin composition of 0.01 to 2 parts by weight of a hardening accelerator and a dielectric (dielectric filler).

In addition, the resin layer containing the dielectric material (dielectric filler) may be used as an epoxy resin or an active ester resin constituting the resin composition when the weight of the resin composition constituting the resin layer is 100 parts by weight. The total amount of each component of the polyvinyl acetal resin and the hardening accelerator is 70 parts by weight. The above resin composition is formed with a dielectric (dielectric filler).

Further, it is preferable that the resin layer containing the dielectric body contains a dielectric body in a range of 65 wt% to 85 wt% when the weight of the resin containing the dielectric (dielectric filler) is 100 wt% (dielectric Body filler).

Further, as the epoxy resin, the active ester resin, the polyvinyl acetal resin, and the curing accelerator, a known epoxy resin, an active ester resin, a polyvinyl acetal resin, a curing accelerator, or a ring described in the present specification can be used. An oxygen resin, an active ester resin, a polyvinyl acetal resin, and a hardening accelerator.

Further, the resin layer containing the dielectric body (dielectric filler) preferably has a resin flow rate of less than 1% when measured in accordance with MIL-P-13949G in the MIL standard.

Further, as the curing accelerator or the epoxy resin, a curing accelerator or an epoxy resin described in the public or the present specification can be used. Further, as the curing accelerator, a known imidazole compound or an imidazole compound described in the specification can be used.

Moreover, as the dielectric (dielectric filler), at this stage, if considering For the production precision of the powder, it is preferred to use barium titanate in the composite oxide having a perovskite structure. As the dielectric (dielectric filler) at this time, either calcined barium titanate or unsintered barium titanate can be used. In the case where a higher dielectric constant is desired, it is preferred to use the calcined barium titanate as long as it is selected according to the design quality of the printed wiring board product.

Further, the dielectric filler of barium titanate is preferably a crystal structure having a cubic crystal By. Cubic and tetragonal crystals exist in the crystal structure of barium titanate, but have a cubic crystal structure as compared with the case of using a dielectric (dielectric filler) of barium titanate having only a tetragonal structure. The value of the dielectric constant of the dielectric layer finally obtained by the dielectric material (dielectric filler) of barium titanate is more stabilized. Therefore, it can be said that it is necessary to use a barium titanate powder having at least a crystal structure of both a cubic crystal and a tetragonal crystal.

According to the above embodiment, a copper foil with a carrier can be provided which improves the adhesion between the inner circuit surface of the inner core material and the resin layer containing the dielectric, and has a low dielectric loss. A dielectric layer-containing resin layer for forming a capacitor circuit layer is formed.

Further, the resin layer may be from the side of the copper foil (ie, a very thin copper layer with a carrier copper foil) The resin layer of the hardened resin layer (the "hardened resin layer" means the hardened resin layer) and the semi-hardened resin layer are formed in this order. The hardened resin layer may be composed of a polyimine resin having a thermal expansion coefficient of 0 ppm/° C. to 25 ppm/° C., a polyamidimide resin, or a resin component of any of these composite resins.

Moreover, the thermal expansion coefficient after hardening may be set to 0 on the hardened resin layer. Semi-hardened resin layer of ppm/°C~50ppm/°C. Moreover, the thermal expansion coefficient of the entire resin layer after the hardened resin layer and the semi-hardened resin layer are cured may be 40 ppm/° C. or less. The glass transition temperature of the above-mentioned cured resin layer may be 300 ° C or more. Further, the semi-cured resin layer may be formed using a maleimide-based resin, and the maleimide-based resin may have two or more maleimide groups in the molecule. The aromatic maleimide resin, and the maleimide-based resin may be an aromatic maleicene having two or more maleimide groups in the molecule. A polymeric adduct obtained by polymerizing an amine resin with an aromatic polyamine. Moreover, when the semi-hardened resin layer is 100 parts by weight, the semi-hardened resin layer may contain 20 parts by weight to 70 parts by weight of a maleimide-based resin. The resin composition for forming the above-mentioned semi-hardened resin layer is preferably an essential component of a maleimide-based resin, an epoxy resin, or a linear polymer having a crosslinkable functional group. Further, as the maleimide-based resin, a polymerized adduct obtained by polymerizing an aromatic maleimide resin and an aromatic polyamine can also be used. Further, a cyanoester resin or an epoxy resin reactive with a maleimide-based resin may be added to the semi-cured resin layer as needed. As the epoxy resin, a known epoxy resin or an epoxy resin described in the present specification can be used.

Further, the above linear polymer having a crosslinkable functional group preferably has a hydroxyl group A functional group such as a carboxyl group or a carboxyl group which contributes to the hardening reaction of the epoxy resin. Moreover, the linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of from 50 ° C to 200 ° C. Agent. When a linear polymer having a functional group mentioned herein is specifically exemplified, there are a polyvinyl acetal resin, a phenoxy resin, a polyether oxime resin, a polyamidoximine resin, and the like. The linear polymer having a crosslinkable functional group is preferably used in an amount of from 3 parts by weight to 30 parts by weight based on 100 parts by weight of the resin composition. When the epoxy resin is less than 3 parts by weight, the flow of the resin becomes large. As a result, the occurrence of the resin powder was observed in the end portion of the copper clad laminate which was produced, and the moisture absorption resistance of the resin layer in the semi-hardened state could not be improved. On the other hand, even if it exceeds 30 parts by weight, the resin flow may be small, and defects such as voids may easily occur in the insulating layer of the copper clad laminate produced.

As the maleimide-based resin mentioned here, 4,4'- can be used: Diphenylmethane bis-m-butylene iminoimide, polyphenylmethane maleimide, inter-phenyl bis-bis-succinimide, bisphenol A diphenyl ether, bis-butenylene Amine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis-n-butylene diimide, 4-methyl-1,3-phenylene double Maleimide, 4,4'-diphenyl ether, maleimide, 4,4'-diphenyl bis-bis-butenylene, 1,3-double (3- Maleimide phenoxy)benzene, 1,3-bis(4-methyleneimide phenoxy)benzene, and the like. When the content of the maleimide-based resin is less than 20 parts by weight, the effect of lowering the thermal expansion coefficient of the semi-hardened resin layer after curing may not be obtained. On the other hand, when the content of the maleimide-based resin is more than 70 parts by weight, if the semi-hardened resin layer is cured, it becomes a brittle resin layer, and the resin layer is likely to be cracked. There is a case where the reliability of the insulating layer as a printed wiring board is lowered.

Forming a fragrance having two or more maleimide groups in the molecule In the case of a polymerized adduct obtained by polymerizing a maleicinimide resin and an aromatic polyamine, it is preferred to use, for example, m-phenylenediamine, p-phenylenediamine, 4, 4 as an aromatic polyamine. '-Diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4'-diaminodiphenylmethane, 2,2-bis(4- Aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3-methyldiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4 , 4'-diaminobenzophenone, 4,4'-diaminodiphenyl hydrazine, Bis(4-aminophenyl)aniline, m-diamine, p-nonanediamine, 1,3-bis[4-aminophenoxy]benzene, 3-methyl-4,4'-diamino Diphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-ethyl 4-aminophenyl)propane, 2,2-bis(2,3-dichloro-4-aminophenyl)propane, bis(2,3-dimethyl-4-aminophenyl)benzene Ethane, ethylenediamine, hexamethylenediamine or the like is added to the resin composition to form a resin layer.

Moreover, in the case of an epoxy resin hardener, dicyandiamide, microphone An amine such as an azole or an aromatic amine; a phenol such as bisphenol A or brominated bisphenol A; a novolac such as a phenol novolac resin or a cresol novolak resin; an acid anhydride such as phthalic anhydride or the like. In this case, the amount of the epoxy resin hardener added to the epoxy resin is naturally derived from the respective equivalents, and thus the amount of addition is not particularly limited.

Moreover, it is provided with a resin layer suitable for the manufacture of a three-dimensionally formed printed wiring board. In the case of a carrier copper foil, the hardened resin layer is preferably a cured polymer layer having flexibility. In order to be able to withstand the solder mounting step, the above polymer layer is preferably composed of a resin having a glass transition temperature of 150 ° C or higher. The above polymer layer is preferably composed of a polyamide resin, a polyether oxime resin, an aramid resin, a phenoxy resin, a polyimine resin, a polyvinyl acetal resin, or a polyamidoxime. Any one or two or more kinds of mixed resins of an amine resin. Further, the thickness of the polymer layer is preferably from 3 μm to 10 μm. In addition, the polymer layer preferably contains one or more of an epoxy resin, a maleimide resin, a phenol resin, and an amine ester resin. Further, the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Further, the epoxy resin composition preferably contains the following components A to E. Each component.

Component A: an epoxy equivalent of 200 or less, and a bisphenol A ring selected from liquid at room temperature An epoxy resin composed of one or more of an oxygen resin, a bisphenol F-type epoxy resin, and a bisphenol AD-type epoxy resin.

Component B: High heat resistant epoxy resin.

Component C: a phosphorus-containing flame retardant resin, that is, any one of a phosphorus-containing epoxy resin and a phosphazene-based resin, or a resin obtained by mixing the same.

Component D: A rubber-modified (modified) polyamidoquinone imine resin which is soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C and modified (modified) with a liquid rubber component.

Component E: Resin hardener.

The component A has an epoxy equivalent of 200 or less and is selected from liquids selected from room temperature. An epoxy resin composed of one or more of a group of a phenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin. Here, the reason why the bisphenol epoxy resin is selected is that it has good compatibility with the following component D (rubber-modified (modified) polyamidoximine resin), and it is easy to be a resin film in a semi-hardened state. Give moderate flexibility. Further, when the epoxy equivalent exceeds 200, the resin becomes semi-solid at room temperature, and the flexibility in the semi-hardened state is reduced, which is not preferable. In addition, as long as it is a bisphenol type epoxy resin, you may use it either individually or in combination of 2 or more types. In addition, when two or more types are used in combination, the mixing ratio is not particularly limited.

The epoxy resin is preferably composed of an epoxy resin constituting a semi-hardened resin layer. When the amount is 100 parts by weight, it is used in a blending ratio of 3 parts by weight to 30 parts by weight. When the amount of the epoxy resin is less than 3 parts by weight, the thermosetting property is not sufficiently exhibited, and the function as a binder to the inner flexible printed wiring board is not sufficiently achieved, and the resin copper foil is not sufficiently realized. The adhesion to the copper foil. On the other hand, when it exceeds 30 parts by weight, the viscosity at the time of preparing a resin varnish becomes high due to the balance with other resin components, and it is difficult to form a resin film on the surface of the copper foil with a uniform thickness when producing a resin-attached copper foil. . Further, considering the addition amount of the following component D (rubber-modified (modified) polyamidoximine resin), the resin layer after curing cannot be obtained as a charge. The resilience.

The component B is a "high heat-resistant epoxy resin" in which the glass transition point Tg is high. The "high heat resistant epoxy resin" mentioned herein is preferably a polyfunctional ring such as a novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin. Oxygen resin. Further, the component B is preferably used in an amount of from 3 parts by weight to 30 parts by weight, based on 100 parts by weight of the epoxy resin composition constituting the semi-cured resin layer. When the amount of the component B is less than 3 parts by weight, the high Tg of the resin composition tends to be insufficient, which is not preferable. On the other hand, when the component B is more than 30 parts by weight, the resin after curing becomes brittle and impairs flexibility, so that it is not preferable as a flexible printed wiring board. More preferably, the component B is used in the range of 10 parts by weight to 20 parts by weight, whereby the high Tg of the resin composition and the good flexibility of the resin after curing can be stably achieved.

The component C is a halogen-free flame-retardant resin, and is a phosphorus-containing flame-retardant resin which is a resin containing one of a phosphorus-containing epoxy resin and a phosphazene-based resin or a mixture thereof. First, the phosphorus-containing epoxy resin is a general term for epoxy resins containing phosphorus in an epoxy skeleton. In addition, when the weight of the epoxy resin composition is 100% by weight, the phosphorus atom content of the epoxy resin composition constituting the semi-cured resin layer, that is, the phosphorus atom derived from the C component can be set to 0.5 weight. Any of the phosphorus-containing epoxy resins in the range of % to 3.0% by weight can be used. However, among the phosphorus-containing epoxy resins, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 is used when two or more epoxy groups are contained in the molecule. - The phosphorus-containing epoxy resin of the oxide derivative is excellent in the stability of the resin quality in a semi-hardened state, and is preferable because the flame retardancy effect is high. The structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown below for reference.

[Chemical 1]

Further, as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- A specific example of the phosphorus-containing epoxy resin of the oxide derivative is a compound having a structural formula represented by Chemical Formula 2. When the compound having the structural formula shown by the chemical formula 2 is used, the stability of the resin quality in the semi-hardened state is further excellent, and the flame retardancy effect is improved, which is preferable.

Further, the phosphorus-containing epoxy resin as the component C is preferably a compound having the structural formula shown by the following formula 3. In the same manner as the phosphorus-containing epoxy resin represented by Chemical Formula 2, the stability of the resin in the semi-hardened state is excellent, and it is preferable to impart high flame retardancy.

[Chemical 3]

Further, the phosphorus-containing epoxy resin as the component C is preferably a compound having the structural formula shown by the following formula 4. Similar to the phosphorus-containing epoxy resin represented by Chemicals 2 and 3, the resin quality in the semi-hardened state is excellent in stability and imparts high flame retardancy. Therefore, it is better.

The epoxy resin obtained in the form of a derivative derived from the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide may be exemplified by the following: naphthoquinone or p-phenylene Phenol and After reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to give a compound represented by the following 5 (HCA-NQ) or 6 (HCA-HQ), the ring is made The oxygen resin reacts with a portion of its OH group to form a phosphorus-containing flame retardant resin.

Here, when the phosphorus-containing epoxy resin is used as the phosphorus-containing flame-retardant resin, one type of phosphorus-containing epoxy resin may be used alone, or two or more types of phosphorus-containing epoxy resin may be used in combination. However, it is preferable to consider the total amount of the phosphorus-containing flame retardant resin as the component C, so that the weight of the epoxy resin composition constituting the semi-hardened resin layer is 100% by weight, and it is derived from C. The amount of addition is defined in such a manner that the phosphorus atom of the component is in the range of 0.5% by weight to 3.0% by weight. The phosphorus-containing epoxy resin differs in the amount of phosphorus atoms contained in the epoxy skeleton depending on the type thereof. Therefore, the content of the phosphorus atom can be designed as described above in preference to the addition amount of the component C.

Next, a case where a phosphazene-based resin is used as the phosphorus-containing flame retardant resin will be described. The phosphazene-based resin is a resin containing a phosphazene having a double bond as a constituent element of phosphorus and nitrogen. The phosphazene-based resin can greatly improve the flame retardancy performance by the synergistic effect of nitrogen and phosphorus in the molecule. Further, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, it is stably present in the resin, and an effect of preventing migration can be obtained.

In the case of using a phosphazene-based resin as the phosphorus-containing flame-retardant resin, one type of phosphazene-based resin may be used alone, or two or more kinds of phosphazene-based resins may be used in combination. However, it is preferable to consider the total amount of the phosphorus-containing flame-retardant resin as the component C, and to obtain the component derived from the component C when the weight of the phosphazene-based resin composition constituting the semi-hardened resin layer is 100% by weight. The amount of addition is defined in such a manner that the phosphorus atom is in the range of 0.5% by weight to 3.0% by weight. In this case, the same applies to the case where a phosphorus-containing epoxy resin and a phosphazene-based resin are used in combination as the component C.

In addition, any of the phosphorus-containing epoxy resin and the phosphazene-based resin may be used as the C-containing phosphorus-containing flame retardant resin, or may be mixed. When the phosphorus-containing epoxy resin is used alone as the phosphorus-containing flame retardant resin, the phosphorus-containing epoxy resin is preferably used when the epoxy resin composition constituting the semi-cured resin layer is 100 parts by weight. It is used in the range of 5 parts by weight to 50 parts by weight. When the C component composed of the phosphorus-containing epoxy resin is less than 5 parts by weight, considering the blending ratio of the other resin components, the phosphorus atom derived from the C component is insufficient, and it is difficult to obtain flame retardancy. On the other hand, even if the C component composed of the phosphorus-containing epoxy resin exceeds 50 parts by weight, the flame retardancy improving effect is saturated, and the resin layer after curing becomes brittle and is not preferable.

In the case where the phosphazene-based resin is used alone as the phosphorus-containing flame-retardant resin, the phosphazene-based resin is preferably used in an amount of 100 parts by weight based on the epoxy resin composition constituting the semi-cured resin layer. It is used in the range of 2 parts by weight to 18 parts by weight. Made of phosphazene-based resin When the C component is less than 2 parts by weight, considering the blending ratio of other resin components, the phosphorus atom derived from the C component is insufficient, and it is difficult to obtain flame retardancy. On the other hand, when the C component composed of the phosphazene-based resin is more than 18 parts by weight, the glass transition point Tg of the resin composition, solder heat resistance, and peel strength tend to be insufficient, which is not preferable.

The "high Tg" and "flexibility" of the above-mentioned hardened resin are usually Anti-proportional characteristics. In this case, the phosphorus-containing flame-retardant resin has an improvement in flexibility of the resin which contributes to hardening, and contributes to high Tg. Therefore, instead of using a phosphorus-containing flame retardant epoxy resin, it is better to blend well with the "phosphorus-containing flame retardant epoxy resin which contributes to high Tg" and "phosphorus which contributes to the improvement of flexibility". The use of a flame retardant epoxy resin can be used to form a resin composition suitable for use in a flexible printed wiring board.

The D component is soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C and is in the form of a liquid. A rubber modified (modified) polyamidoquinone imine resin modified (modified). The rubber modified (modified) polyamidoximine resin is obtained by reacting a polyamide amine imide resin with a rubber resin. The use of the polyamidoximine resin and the rubber resin as mentioned herein is carried out for the purpose of improving the flexibility of the polyamidoximine resin itself. In other words, the polyamidoximine resin is reacted with a rubber resin, and one of the acid components (such as cyclohexanedicarboxylic acid) of the polyamidoximine resin is partially substituted with a rubber component. The rubber component contains natural rubber and synthetic rubber, and the latter synthetic rubbers include styrene-butadiene rubber, butadiene rubber, butyl rubber, and ethylene-propylene rubber. Further, from the viewpoint of ensuring heat resistance, it is also useful to use a heat-resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or an amine ester rubber. In order to produce a copolymer by reacting with a polyamidoximine resin, it is preferable that these rubber-based resins have various functional groups at both ends. It is especially useful to use CTBN (carboxy terminal butadiene nitrile) having a carboxyl group. Further, the rubber component may be copolymerized in only one type or may be copolymerized in two or more types. Further, in the case of using a rubber component, it is preferred that the rubber component has a number average molecular weight of 1,000 or more from the viewpoint of stabilization of flexibility. By.

When used to polymerize a rubber modified (modified) polyamidoximine resin, The solvent in which the polyamidoximine resin and the rubber resin are dissolved is preferably one or more kinds of dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrole. Pyridone, dimethyl hydrazine, nitromethane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone and the like. Further, in order to cause a polymerization reaction to occur, a polymerization temperature in the range of 80 ° C to 200 ° C is preferably employed. When a solvent having a boiling point of more than 200 ° C is used in the polymerization, it is preferred to replace the solvent with a solvent having a boiling point in the range of 50 ° C to 200 ° C depending on the application.

Here, the solvent having the above boiling point in the range of 50 ° C to 200 ° C can be listed. A single solvent selected from the group consisting of methyl ethyl ketone, dimethyl acetamide, and dimethylformamide, or a mixed solvent of two or more kinds. When the boiling point is less than 50 ° C, the gas dispersion due to heating is remarkable, and in the case where a semi-hardened resin is produced from the state of the resin varnish, it is difficult to obtain a good semi-hardened state. On the other hand, when the boiling point exceeds 200 ° C, when a semi-hardened resin is produced from the state of the resin varnish, foaming easily occurs, so that it is difficult to obtain a good semi-cured resin film.

Rubber modified (modified) polyamidoximine used in epoxy resin composition In the resin, when the weight of the rubber modified (modified) polyamidoximine resin is 100% by weight, the copolymerization amount of the rubber component is preferably 0.8% by weight or more. When the copolymerization amount is less than 0.8% by weight, even if a rubber modified (modified) polyamidoximine resin is prepared, the resin formed by using the epoxy resin composition mentioned in the invention is lacking. The flexibility at the time of layer hardening and the adhesion to the copper foil are also lowered, which is not preferable. Further, more preferably, the amount of copolymerization of the rubber component is 3% by weight or more, and more preferably 5% by weight or more. According to experience, there is no particular problem even if the amount of the rubber component added is increased by more than 40% by weight. However, the effect of improving the flexibility of the hardened resin layer is saturated, resulting in waste of resources and thus being poor.

The above-mentioned rubber modified (modified) polyamidoximine resin is required Soluble in the nature of the solvent. The reason for this is that it is difficult to prepare a resin varnish if it is insoluble in a solvent. The rubber modified (modified) polyamidoximine resin is preferably used in a blending ratio of 10 parts by weight to 40 parts by weight when the weight of the resin composition is 100 parts by weight. When the rubber modified (modified) polyamidoximine resin is less than 10 parts by weight, the flexibility and embrittlement of the resin layer after hardening cannot be improved, and the resin layer is likely to be slightly cracked. On the other hand, even if more than 40 parts by weight of the rubber-modified (modified) polyamidoximine resin is added, there is no particular hindrance, but the flexibility of the resin layer after curing is not further improved, and the hardening is not achieved. High Tg of the resin. Therefore, if economic efficiency is considered, it can be said that 40 parts by weight is the upper limit.

The resin hardener of the E component will be described. The resin curing agent mentioned above is preferably one or more selected from the group consisting of a biphenyl type phenol resin and a phenol aralkyl type phenol resin. The amount of the resin hardener added is naturally derived from the reaction equivalent of the resin to be hardened, and does not require a particular amount. However, in the case of the epoxy resin composition of the present invention, it is preferred to use the E component in the range of 20 parts by weight to 35 parts by weight when the epoxy resin composition is 100 parts by weight. When the amount of the component E is less than 20 parts by weight, in consideration of the above resin composition, a sufficiently hardened state cannot be obtained, and flexibility cannot be obtained as a resin after curing. On the other hand, when the E component exceeds 35 parts by weight, the moisture absorption resistance of the resin layer after curing tends to be deteriorated, which is not preferable.

A solvent is added to the resin composition shown above and used as a resin varnish to form a thermosetting resin layer as an adhesive layer of a printed wiring board. The resin varnish is characterized in that a solvent is added to the resin composition to prepare a resin solid content of 30% by weight to 70% by weight, and a resin overflow can be formed according to MIL-P-13949G in the MIL standard. A semi-hardened resin film having a flow rate of 5% to 35%. As the solvent mentioned herein, it is preferred to use a group having a boiling point of from 50 ° C to 200 ° C and selected from the group consisting of methyl ethyl ketone, dimethyl acetamide, dimethylformamide, and the like. A single solvent or a mixture of two or more kinds. This is to obtain a good semi-hardened resin film as described above. Moreover, the amount of the resin solid component shown here When the surface is applied to the surface of the copper foil, the film thickness can be controlled to the range of the best accuracy. When the resin solid content is less than 30% by weight, the viscosity is too low, and it flows immediately after application to the surface of the copper foil, and it is difficult to ensure uniformity of film thickness. On the other hand, when the resin solid content exceeds 70% by weight, the viscosity becomes high, and it is difficult to form a film on the surface of the copper foil. In addition, when the resin overflow rate is less than 5%, air is trapped in the uneven portion of the inner layer circuit on the surface of the inner layer core material, and the like. On the other hand, when the resin overflow rate exceeds 35%, the resin overflow rate becomes excessively large, and the thickness of the insulating layer formed using the resin layer of the carrier-attached copper foil having the resin layer becomes uneven.

When the hardened resin layer and the semi-hardened resin layer are provided on the carrier-attached copper foil, a copper foil with a carrier having a resin layer suitable for the production of a three-dimensionally formed printed wiring board can be provided.

Further, it is preferable that the resin layer has a peelable protective film on one surface of the semi-hardened insulating layer. As the protective film, a known insulating film or resin film can be used. For example, a polyethylene terephthalate film, a polyethylene naphthalate film, a metal foil, or the like can be used for the above protective film.

Further, the resin layer may contain a curing agent and/or a curing accelerator.

The resin layer may be a resin layer formed of a resin composition having a resin overflow rate of 5% in accordance with MIL-P-13949G in the MIL standard.

The resin layer may also be used in an amount of from 5 parts by weight to 50 parts by weight of the epoxy resin (containing a curing agent), 50 parts by weight to 95 parts by weight of the solvent-soluble polyether oxime, and, if necessary, an appropriate amount of hardening promotion. The resin composition composed of the agent is composed of a resin composition.

In addition, the resin layer may contain the component A to the component D shown below in the range of the following content (in the case where the epoxy resin curing agent is excluded and the resin composition is 100 parts by weight) The composition of the resin composition.

Component A: 10 parts by weight to 20 parts by weight of a polyamidoximine resin having a tensile strength of 200 MPa or more at 25 ° C

Component B: 20 weight of polyamidoximine resin having a tensile strength of 100 MPa or less at 25 ° C Measured to 40 parts by weight

Composition C: Epoxy

Ingredient D: Epoxy resin hardener

The above resin layer may also be a semi-hardened resin layer.

The component A is a polyamidoximine resin having a tensile strength of 200 MPa or more at 25 °C. The "polyamido quinone imine resin having a tensile strength of 200 MPa or more" as referred to herein, for example, by using 1,2,4-benzenetricarboxylic anhydride, benzophenone tetracarboxylic anhydride, and phenylene A resin obtained by heating a bitylylene diisocyanate in a solvent such as N-methyl-2-pyrrolidone or /N,N-dimethylacetamide. Here, although the upper limit is not described, the upper limit of the tensile strength of the polyamidoximine resin is about 500 MPa in consideration of the tensile strength of the polyamidoximine resin. Further, the tensile strength of the polyamidoximine resin of the component A and the component B in the present invention is a film-like No. 2 test piece (full length 115 mm) prescribed in JIS K7113 from a polyamidoximine resin solution. The distance between the chucks was 80 ± 5 mm, the length of the parallel portion was 33 ± 2 mm, the width of the parallel portion was 6 ± 0.4 mm, and the film thickness was 1 to 3 mm), and the value was measured by a tensile tester.

The component B is a polyamidoximine resin having a tensile strength of 100 MPa or less at 25 °C. The "polyamidoximine resin having a tensile strength of 100 MPa or less" as referred to herein, for example, by using 1,2,4-benzenetricarboxylic anhydride, diphenylmethane diisocyanate, and carboxyl terminal acrylonitrile-butyl The diene rubber is obtained by heating in a solvent such as N-methyl-2-pyrrolidone or / and N,N-dimethylacetamide.

When the resin composition is 100 parts by weight, the content of the component C (epoxy resin) may be 40 parts by weight to 70 parts by weight. Further, as the epoxy resin, the above epoxy resin can be used. The content of the component D (epoxy resin hardener) is preferably an imidazole compound in which the resin composition contains a hardenable epoxy resin. The semi-hardened resin layer is preferably a resin layer in a semi-hardened state in which the volatile component formed by the above resin composition is less than 1% by weight. To meet the above content In this case, even if the carrier-attached copper foil having the resin layer is stored or conveyed in a roll shape, the organic solvent is not transferred from the resin layer of the carrier-attached copper foil having the resin layer to the copper foil with the carrier, and heat resistance can be obtained. A carrier-attached copper foil of a resin layer excellent in properties and adhesion to a copper foil with a carrier.

Here, as the imidazole compound, a known one can be used, and for example, 2-nine group can be cited. Imidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole or the like can be used singly or in combination.

Furthermore, the amount of hardener to be added is based on the amount of epoxy resin, It is inevitable to determine the hardening speed and so on. When the amount of the imidazole compound to be used as the curing agent is specifically described, when the resin composition is 100 parts by weight (in this case, the resin composition of all the components A to D is 100 parts by weight). In the case of the weight component, it is blended in the range of 0.01 part by weight to 2 parts by weight in the resin composition. Further, the blending amount of the imidazole compound is more preferably 0.02 part by weight to 1.5 parts by weight, still more preferably 0.03 part by weight to 1.0 part by weight. When the blending amount of the imidazole compound is less than 0.01 part by weight, if the content of the epoxy resin is considered, the curing may be insufficient, and the resin layers of the copper foil with a carrier layer having the resin layer may be bonded to each other. Then the intensity is reduced. On the other hand, when the blending amount of the imidazole compound exceeds 2 parts by weight, there is a case where the curing reaction of the epoxy resin becomes fast, the resin layer after hardening becomes brittle, the strength of the cured resin film, and the adhesion of the resin The adhesion of the resin layers of the copper foil to each other is lowered.

Further, as the epoxy resin of the component C and the epoxy resin curing agent of the component D, an epoxy resin of the known component C, an epoxy resin curing agent of the component D, or an epoxy of the component C described in the present specification can be used. Resin, epoxy resin hardener of component D.

The resin layer is a resin composition having moisture absorption resistance in a semi-hardened state In the resin composition, a resin group containing a phosphorus atom in a range of 0.5% by weight to 3.0% by weight when the weight of the resin composition is 100% by weight may be used. Formed by the object.

Component A: an epoxy equivalent of 200 or less, and one selected from the group consisting of a liquid bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin at 25 ° C or 2 or more types.

Component B: a linear polymer having a crosslinkable functional group.

Component C: Crosslinker.

Component D: Imidazole-based epoxy resin hardener.

Component E: Phosphorus-containing epoxy resin.

The linear polymer having a functional group as the component B is preferably a polymer component which is soluble in an organic solvent having a boiling point of from 50 ° C to 200 ° C . Specifically, it is a polyvinyl acetal resin, a phenoxy resin, a polyether oxime resin, a polyamidoximine resin, etc. The linear polymer having a crosslinkable functional group is preferably used in an amount of from 3 parts by weight to 30 parts by weight based on 100 parts by weight of the resin composition. When the epoxy resin is less than 3 parts by weight, the flow of the resin becomes large. As a result, it is possible to observe the occurrence of the resin powder in the end portion of the copper clad laminate which is manufactured, and it is also impossible to improve the moisture absorption resistance of the resin layer in the semi-hardened state. On the other hand, even if it exceeds 30 parts by weight, the resin flow may be small, and defects such as voids may easily occur in the insulating layer of the copper clad laminate produced.

Further, if the boiling point mentioned here is 50 ° C to 200 ° C, the temperature is specifically exemplified. The organic solvent is selected from the group consisting of methanol, ethanol, methyl ethyl ketone, toluene, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, and ethyl sulco. One of the solvent alone or a mixture of two or more solvents. When the boiling point is less than 50 ° C, there is a case where the gas dispersion due to heating is remarkable, and in the case where a semi-hardened resin is formed from the state of the resin varnish, it is difficult to obtain a good semi-hardened state. On the other hand, when the boiling point exceeds 200 ° C, the solvent tends to remain in the semi-hardened state. Further, there is a possibility that the volatilization speed which is usually required is not satisfied and the industrial productivity is not satisfied.

The component C is a crosslinking agent for causing a crosslinking reaction between the component B and the epoxy resin. Preferred An amine ester resin is used for the crosslinking agent. This crosslinking agent is added according to the mixing amount of the component B, and it is considered that the necessity of the blending ratio is not strictly described. However, when the resin composition is 100 parts by weight, it is preferably used in a blending ratio of 10 parts by weight or less. The reason for this is that when the component C, which is an amine ester-based resin, is present in excess of 10 parts by weight, the moisture absorption resistance of the resin layer in the semi-hardened state is deteriorated, and the resin layer after curing becomes brittle.

The D component is an imidazole epoxy resin hardener. The resin composition of the invention of the present invention Among them, from the viewpoint of improving the moisture absorption resistance of the resin layer in a semi-hardened state, it is preferred to selectively use an imidazole-based epoxy resin hardener. Among them, an imidazole-based epoxy resin curing agent having a structural formula represented by the following formula 7 is preferably used. By using the imidazole-based epoxy resin curing agent of the structural formula shown in Chemical Formula 7, the moisture absorption resistance of the resin layer in a semi-hardened state can be remarkably improved, and the long-term storage stability is excellent. Further, the amount of the epoxy resin hardener added to the epoxy resin is preferably an optimum amount obtained experimentally, and is not calculated based on the reaction equivalent. The imidazole-based epoxy resin hardener acts as a catalyst for hardening of the epoxy resin because it is used as a reaction initiator for causing self-polymerization of the epoxy resin in the initial stage of the hardening reaction. Help.

[Chemistry 7]

The phosphorus-containing epoxy resin as the above-mentioned E component is preferably derived from intramolecular An epoxy resin obtained in the form of a derivative of two or more epoxy groups of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

The structural formula of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is as follows.

The epoxy resin obtained in the form of the derivative derived from the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is used to make naphthoquinone or hydroquinone with 9,10 -dihydro-9 -Oxo-10-phosphaphenanthrene-10-oxide reacts to form a compound represented by the following 9 (HCA-NQ) or 10 (HCA-HQ), and then reacts the epoxy resin with a portion thereof The formation of phosphorus-containing epoxy resin.

The above-mentioned E component obtained by using the above compound as a raw material, that is, a phosphorus-containing epoxy resin It is preferred to use one or two kinds of compounds having a structural formula represented by any one of the following formulas 11 to 13 which are shown below. The reason for this is that the stability of the resin quality in the semi-hardened state is excellent, and the flame retardancy effect is high.

[化12]

The resin composition is preferably such that when the weight of the resin composition is 100 parts by weight, the component A is 3 parts by weight to 20 parts by weight, and the component B is 3 parts by weight to 30 parts by weight, and the resin is used. When the weight of the composition is 100% by weight, the weight fraction of the E component is defined so that the phosphorus atom is in the range of 0.5% by weight to 3.0% by weight.

The resin layer may be formed using a resin composition containing each component of the following components A to F.

Component A: an epoxy equivalent of 200 or less, and one selected from the group consisting of a liquid bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin at 25 ° C or 2 or more types.

Component B: a linear polymer having a crosslinkable functional group.

Component C: a crosslinking agent (may be omitted when the component A functions as a crosslinking agent of the component B).

Component D: 4,4'-diaminodiphenyl hydrazine or 2,2-bis(4-(4-aminophenoxy)phenyl)propane.

Component E: Flame retardant epoxy resin.

F component: a multifunctional epoxy resin.

Component G: Hardening accelerator.

The linear polymer having a crosslinkable functional group as the above component B is preferably a polyvinyl acetal resin or a polyamidoximine resin.

The crosslinking agent as the component C is preferably an amine ester-based resin.

The flame retardant epoxy resin as the component E is preferably a compound having the structure shown in Formula 14 obtained by mixing a derivative of tetrabromobisphenol A having two or more epoxy groups in the molecule. The brominated epoxy resin or one or two kinds of brominated epoxy resins having the structural formula shown by the following formula 15.

[Chemistry 14]

[化15]

The flame retardant epoxy resin as the component E is preferably used in the presence of two or more epoxy groups in the molecule, that is, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. A phosphorus-containing epoxy resin of a derivative.

The flame retardant epoxy resin as the above-mentioned component E is preferably one or two types of phosphorus-containing epoxy resins having a structural formula represented by any one of the following formulas 16 to 18.

[Chemistry 16]

[化17]

[化18]

As the polyfunctional epoxy resin of the above F component, an o-cresol novolac type epoxy resin is preferably used.

When the weight of the resin composition for forming the resin layer is 100 parts by weight, the component A is 3 parts by weight to 20 parts by weight, the component B is 3 parts by weight to 30 parts by weight, and the component C is 3 parts. Parts by weight to 10 parts by weight (0 parts by weight to 10 parts by weight when the component A functions as a crosslinking agent of the component B), the component D is 5 parts by weight to 20 parts by weight, and the F component is 3 parts by weight. 20 parts by weight, and 12% by weight when the weight of the resin composition is 100% by weight The weight fraction of the E component is defined in such a manner that the bromine atom derived from the component E is contained in the range of ~18% by weight.

When the weight of the resin composition for forming the resin layer is 100 parts by weight, the component A is 3 parts by weight to 20 parts by weight, the component B is 3 parts by weight to 30 parts by weight, and the component C is 3 parts. Parts by weight to 10 parts by weight (0 parts by weight to 10 parts by weight when the component A functions as a crosslinking agent of the component B), the component D is 5 parts by weight to 20 parts by weight, and the F component is 3 parts by weight. When the weight of the resin composition is 100% by weight, the weight fraction of the E component is defined so as to contain the phosphorus atom derived from the component E in the range of 0.5% by weight to 3.0% by weight.

The resin composition for forming the above resin layer preferably contains a curing accelerator as the G component.

The resin layer preferably has a resin varnish for forming a resin layer in the order of the following steps a and b, and the resin varnish is applied onto the surface of the copper foil with a carrier and dried to form a 5 μm to 100 μm. A semi-hardened resin film of average thickness.

Step a: In the above-mentioned A component, B component, and C component (may be omitted when the A component functions as a crosslinking agent of the B component), the D component, the E component, the F component, and the G component, When the weight of the resin composition in which the component -F component is an essential component is 100% by weight, the bromine atom derived from the component E is contained in the range of 12% by weight to 18% by weight or is contained in the range of 0.5% by weight to 3.0% by weight. The phosphorus atom is mixed in this manner to form a resin composition.

Step b: The resin composition is dissolved in an organic solvent to prepare a resin varnish having a resin solid content of 25% by weight to 50% by weight.

The resin layer is preferably formed using a resin composition containing each component of the following components A to E.

Component A: one of a group of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD type epoxy resins selected from liquid crystals at room temperature and having an epoxy equivalent of 200 or less. Or two or more types of epoxy resins.

Component B: High heat resistant epoxy resin.

Component C: a flame retardant epoxy resin containing phosphorus.

Component D: A rubber-modified (modified) polyamidoquinone imine resin which is soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C and modified (modified) with a liquid rubber component.

Component E: A resin curing agent comprising one or more of a biphenyl type phenol resin and a phenol aralkyl type phenol resin.

The resin layer is preferably formed by using a resin composition other than the components of the components A to E described above and further containing a phosphorus-containing flame retardant which is not reactive with an epoxy resin as the component F.

The component A has an epoxy equivalent of 200 or less and is selected from liquids selected from room temperature. An epoxy resin composed of one or more of a group of a phenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin. Here, the reason why the bisphenol epoxy resin is selected is that it has good compatibility with the following component D (rubber-modified (modified) polyamidoximine resin), and it is easy to be a resin film in a semi-hardened state. Give moderate flexibility. Further, when the epoxy equivalent exceeds 200, the resin becomes semi-solid at room temperature, and the flexibility in the semi-hardened state is reduced, which is not preferable. In addition, as long as it is a bisphenol type epoxy resin, you may use it either individually or in combination of 2 or more types. In addition, when two or more types are used in combination, the mixing ratio is not particularly limited.

The epoxy resin is preferably used when the resin composition is 100 parts by weight. The blending ratio of parts by weight to 20 parts by weight is used. When the amount of the epoxy resin is less than 3 parts by weight, the thermosetting property is not sufficiently exhibited, and it is difficult to sufficiently realize the function as a binder to the inner layer flexible printed wiring board, and it is difficult to sufficiently realize the copper foil as a resin. The adhesion to the copper foil. On the other hand, when it exceeds 20 parts by weight, the viscosity of the resin varnish becomes high due to the balance with other resin components, and it is difficult to form a resin film on the surface of the copper foil with a uniform thickness when manufacturing the resin-coated copper foil. . Further, considering the addition amount of the following component D (rubber-modified (modified) polyamidoximine resin), sufficient toughness cannot be obtained as the resin layer after curing.

The B component is a so-called "high heat resistant epoxy resin" having a high glass transition point. The "high heat resistant epoxy resin" mentioned herein is preferably a polyfunctional ring such as a novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin. Oxygen resin. Further, the component B is preferably used in an amount of from 3 parts by weight to 30 parts by weight, based on 100 parts by weight of the resin composition. When the amount of the component B is less than 3 parts by weight, the high Tg of the resin composition is not at all realized. On the other hand, when the component B is more than 30 parts by weight, the resin after curing becomes brittle, and the flexibility is completely impaired, so that it is not preferable as a flexible printed wiring board. More preferably, the component B is used in the range of 10 parts by weight to 20 parts by weight, whereby the high Tg of the resin composition and the good flexibility of the resin after curing can be stably achieved.

As a C component, it is a halogen-free flame retardant epoxy resin and is used. Phosphorus-containing flame retardant epoxy resin. The phosphorus-containing flame retardant epoxy resin is a general term for epoxy resins containing phosphorus in an epoxy skeleton. In addition, when the weight of the resin composition is 100% by weight, the phosphorus atom content of the resin composition of the present application, that is, the phosphorus atom derived from the C component may be in the range of 0.5% by weight to 30% by weight. Any of the phosphorus-containing flame retardant epoxy resins can be used. However, a phosphorus-containing flame retardant epoxy resin which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative having two or more epoxy groups in its molecule is used. It is preferable because the stability of the resin quality in the semi-hardened state is excellent and the flame retardancy effect is high. The structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in Figure 19 for reference.

[Chemistry 19]

Further, if a phosphorus-containing flame retardant epoxy resin of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is specifically exemplified, it is preferred to use 20 A compound of the formula shown. The resin in the semi-hardened state is excellent in stability of the quality and has a high flame retardancy effect.

Further, the phosphorus-containing flame retardant epoxy resin as the component C is preferably a compound having the structural formula shown by the following formula 21. In the same manner as the phosphorus-containing flame retardant epoxy resin shown in Chemical Formula 20, the stability of the resin quality in the semi-hardened state is excellent, and at the same time, it is preferable to impart high flame retardancy.

Further, the phosphorus-containing flame retardant epoxy resin as the component C is preferably further provided The compound of the structural formula shown by the formula 22 shown below. In the same manner as the phosphorus-containing flame retardant epoxy resin shown in Chemical Formulas 20 and 21, the resin quality in the semi-hardened state is excellent in stability, and it is preferable to impart high flame retardancy.

[化22]

The epoxy resin obtained in the form of a derivative derived from the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide may be exemplified by the following: naphthoquinone or p-phenylene Phenol and After reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to form a compound represented by the following 23 (HCA-NQ) or 24 (HCA-HQ), the ring is made The oxygen resin reacts with a portion of its OH group to form a phosphorus-containing flame retardant epoxy resin.

Here, in the case of using a phosphorus-containing flame retardant epoxy resin, one type of phosphorus-containing flame retardant epoxy resin as a component C may be used alone, or two or more types of phosphorus-containing flame retardant rings may be used in combination. Oxygen resin. However, it is preferable to consider the total amount of the phosphorus-containing flame retardant epoxy resin as the component C, and to make the phosphorus atom derived from the C component when the weight of the resin composition is 100% by weight. It is added so as to be in the range of 0.5% by weight to 3.0% by weight. The phosphorus-containing flame retardant epoxy resin differs in the amount of phosphorus atoms contained in the epoxy skeleton depending on the type thereof. Therefore, the content of the phosphorus atom can be specified as described above instead of the amount of the C component added. However, the component C is usually used in the range of 5 parts by weight to 50 parts by weight when the resin composition is 100 parts by weight. When the amount of the component C is less than 5 parts by weight, considering the blending ratio of the other resin component, it is difficult to set the phosphorus atom derived from the component C to 0.5% by weight or more, and flame retardancy cannot be obtained. On the other hand, even if the C component exceeds 50 parts by weight, the flame retardancy improving effect is saturated, and the cured resin layer becomes brittle and is not preferable.

The "high Tg" and "flexibility" of the above-mentioned hardened resin are generally inversely proportional. In this case, the phosphorus-containing flame retardant epoxy resin has an improvement in flexibility of the resin which contributes to hardening, and contributes to high Tg. Therefore, instead of using a phosphorus-containing flame retardant epoxy resin, it is better to blend well with the "phosphorus-containing flame retardant epoxy resin which contributes to high Tg" and "phosphorus which contributes to the improvement of flexibility". The use of a flame retardant epoxy resin can be used to form a resin composition suitable for use in a flexible printed wiring board.

The component D is a rubber-modified (modified) polyamidoximine resin which is soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C and modified (modified) with a liquid rubber component. The rubber modified (modified) polyamidoximine resin is obtained by reacting a polyamide amine imide resin with a rubber resin. The case where the rubber modified (modified) polyamidoximine resin is reacted with a rubber resin as mentioned herein is carried out for the purpose of improving the flexibility of the polyamide amine imide resin itself. In other words, the polyamidoximine resin is reacted with a rubber resin, and one of the acid components (such as cyclohexanedicarboxylic acid) of the polyamidoximine resin is partially substituted with a rubber component. The rubber component is described in terms of a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, and ethylene-propylene rubber. Further, from the viewpoint of ensuring heat resistance, it is also useful to use a heat-resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or an amine ester rubber. These rubber resins are preferably produced at both ends in order to react with a polyamide amidoxime resin to produce a copolymer. Prepare a variety of functional bases. It is especially useful to use CTBN (carboxy terminal butadiene nitrile) having a carboxyl group. Further, the rubber component may be copolymerized in only one type or may be copolymerized in two or more types. Further, in the case of using a rubber component, it is preferred that the rubber component has a number average molecular weight of 1,000 or more from the viewpoint of stabilization of flexibility.

When used to polymerize a rubber modified (modified) polyamidoximine resin, The solvent in which the polyamidoximine resin and the rubber resin are dissolved is preferably one or more kinds of dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrole. Pyridone, dimethyl hydrazine, nitromethane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone and the like. Further, in order to cause a polymerization reaction to occur, a polymerization temperature in the range of 80 ° C to 200 ° C is preferably employed. When a solvent having a boiling point of more than 200 ° C is used in the polymerization, it is preferred to replace the solvent with a solvent having a boiling point in the range of 50 ° C to 200 ° C depending on the application.

Here, as the solvent having a boiling point in the range of 50 ° C to 200 ° C, it can be listed. A single solvent selected from the group consisting of methyl ethyl ketone, dimethyl acetamide, and dimethylformamide, or a mixed solvent of two or more kinds. When the boiling point is less than 50 ° C, the dispersion of the solvent due to heating is remarkable, and in the case where a semi-hardened resin is formed from the state of the resin varnish, it is difficult to obtain a good semi-hardened state. On the other hand, when the boiling point exceeds 200 ° C, when a semi-hardened resin is formed from the state of the resin varnish, foaming easily occurs, so that it is difficult to obtain a good semi-cured resin film.

Rubber modified (modified) polyamidoxime used in the resin composition of the present invention In the amine resin, when the weight of the rubber-modified (modified) polyamidoximine resin is 100% by weight, the copolymerization amount of the rubber component is preferably 0.8% by weight or more. When the amount of the copolymerization is less than 0.8% by weight, even if a rubber-modified (modified) polyamidoximine resin is formed, there is a lack of hardening of the resin layer formed using the resin composition mentioned in the present invention. The flexibility and the adhesion to the copper foil are also lowered, which is not preferable. Further, more preferably, the amount of the copolymerization of the rubber component is more preferably 3% by weight or more, still more preferably 5% by weight or more. According to experience, even more than 40% by weight There is no particular problem in increasing the amount of rubber component added. However, the effect of improving the flexibility of the hardened resin layer is saturated, resulting in waste of resources and thus being poor.

The rubber modified (modified) polyamidoximine resin described above is required to have a solvent-soluble property. The reason for this is that it is difficult to prepare a resin varnish if it is insoluble in a solvent. The rubber modified (modified) polyamidoximine resin is preferably used in a blending ratio of 10 parts by weight to 40 parts by weight when the weight of the resin composition is 100 parts by weight. When the rubber modified (modified) polyamidoximine resin is less than 10 parts by weight, it is difficult to increase the flexibility and embrittlement of the resin layer after hardening, and it is easy to cause microcracking of the resin layer. On the other hand, even if more than 40 parts by weight of the rubber-modified (modified) polyamidoximine resin is added, there is no particular hindrance, but the flexibility of the resin layer after curing is not further improved, and the hardening is not achieved. High Tg of the resin. Therefore, it is considered that 40 parts by weight is an upper limit in consideration of economy.

The resin hardener of the E component will be described. The resin hardener mentioned here is one or two or more types of a biphenyl type phenol resin and a phenol aralkyl type phenol resin. In general, the amount of the resin hardener added is naturally derived from the reaction equivalent of the resin to be hardened, and no particular amount is required. However, in the case of the resin composition of the present invention, the component E is preferably used in an amount of from 20 parts by weight to 35 parts by weight based on 100 parts by weight of the resin composition. When the amount of the component E is less than 20 parts by weight, in consideration of the above resin composition, a sufficiently hardened state cannot be obtained, and flexibility cannot be obtained as a resin after curing. On the other hand, when the E component exceeds 35 parts by weight, the moisture absorption resistance of the resin layer after curing tends to be deteriorated, which is not preferable.

The phosphorus-containing flame retardant of the F component will be described. The phosphorus-containing flame retardant is an optional component added, and does not need to contribute to the hardening reaction of the resin, and is only used to greatly improve the flame retardancy. As such a phosphorus-containing flame retardant, a halogen-free flame retardant using a phosphazene compound is preferred. Therefore, the F component is used in the range of 0 part by weight to 7 parts by weight. Here, the reason for describing "0 parts by weight" is to clearly indicate that there is no need to use the F component, and the F component is an optional component. On the other hand, even if the F component exceeds 7 parts by weight, no significant improvement in flame retardancy is expected.

Preferably, when the weight of the above resin composition is 100 parts by weight, the component A is preferably 3 parts by weight to 20 parts by weight, component B is 3 parts by weight to 30 parts by weight, component C is 5 parts by weight to 50 parts by weight, component D is 10 parts by weight to 40 parts by weight, and component E is 20 parts by weight to 35 parts by weight. The component of the component is 0 parts by weight to 7 parts by weight, and when the weight of the resin composition is 100% by weight, the phosphorus derived from the component C is contained in the resin composition in an amount of 0.5% by weight to 3.0% by weight. atom.

Preferably, the component D is a single solvent selected from the group consisting of methyl ethyl ketone, dimethyl acetamide, and dimethylformamide, which is soluble in a boiling point of 50 ° C to 200 ° C or A rubber modified (modified) polyamidoquinone imine resin obtained by modifying (modifying) a liquid rubber component with the properties of two or more kinds of mixed solvents.

The rubber-modified (modified) polyamidoximine resin as the component D is preferably obtained by reacting polyamidoximine with a rubber resin.

The resin layer is preferably formed by using a resin composition (resin varnish) in which a solvent is added to the resin composition to prepare a resin solid content of 30% by weight to 70% by weight, and can be formed according to MIL standards. The semi-hardened resin layer in which the resin overflow flow rate in the measurement of MIL-P-13949G is in the range of 1% to 30%.

Preferably, the resin layer is prepared by preparing a resin varnish for forming a resin layer in the following steps a and b, and applying the resin varnish to the surface of the copper foil and drying it to form a film of 10 μm to 50 μm. A semi-hardened resin layer of thickness.

Step a: 3 parts by weight to 20 parts by weight of component A, 3 parts by weight to 30 parts by weight of component B, 5 parts by weight to 50 parts by weight of component C, and 10 parts by weight to 40 parts by weight of component D, and component E The components are mixed in an amount of from 20 parts by weight to 35 parts by weight, and the component F is from 0 parts by weight to 7 parts by weight to obtain a resin composition containing a phosphorus atom derived from the component C in a range of from 0.5% by weight to 3.0% by weight.

Step b: The resin composition is dissolved in an organic solvent to obtain a resin varnish having a resin solid content of 30% by weight to 70% by weight.

The resin layer is a resin composition for forming an adhesive layer for multilayering an inner flexible printed wiring board, and is preferably a resin composition containing the following components of the A component to the E component. Formed.

Component A: A high-temperature heat-resistant epoxy resin having a softening point of 50 ° C or higher (excluding a biphenyl type epoxy resin).

Component B: an epoxy resin curing agent comprising one or more of a biphenyl type phenol resin and a phenol aralkyl type phenol resin.

Component C: A rubber-modified polyamidoximine resin which is soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C.

Component D: Organic phosphorus-containing flame retardant.

Component E: Biphenyl type epoxy resin.

The resin composition for forming the resin layer preferably contains a phosphorus-containing flame retardant epoxy resin as the F component in addition to the components of the components A to E described above.

The resin composition for forming the above resin layer preferably further contains a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol having an epoxy equivalent of 200 or less and a liquid selected from room temperature. An epoxy resin composed of one or two or more types of AD type epoxy resins is used as the G component.

The resin composition for forming the resin layer preferably further contains a low elastic material composed of a thermoplastic resin and/or a synthetic rubber as the H component.

The high heat resistant epoxy resin having a solid shape of the above component A having a softening point of 50 ° C or higher is preferably one of a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type epoxy resin. 2 or more types.

It is preferable to form the resin layer by using a resin composition containing the above-mentioned high-temperature epoxy resin as the component A, which is a liquid phenolic aldehyde at room temperature. One or two or more of a varnish type epoxy resin, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type epoxy resin.

When the weight of the resin composition for forming the resin layer is 100 parts by weight, the component A is 3 parts by weight to 30 parts by weight, the B component is 13 parts by weight to 35 parts by weight, and the C component is 10 parts. The component D is from 3 parts by weight to 16 parts by weight, and the component E is from 5 parts by weight to 35 parts by weight.

It is preferred to form the above resin layer by using a resin varnish which is a resin varnish system. A solvent is added to the resin composition to prepare a resin solid content of 30% by weight to 70% by weight, which is characterized by MIL-P-13949G in the MIL standard when the semi-hardened resin layer is formed. The resin overflow rate when measured at a resin thickness of 55 μm is in the range of 0% to 10%.

The above resin layer is preferably prepared in the order of the following steps a and b. The resin varnish of the resin layer is applied onto the surface of the copper foil with a carrier and dried to form a semi-hardened resin layer having a thickness of 10 μm to 80 μm.

Step a: when the weight of the resin composition is 100 parts by weight, the component A is 3 parts by weight to 30 parts by weight, the B component is 13 parts by weight to 35 parts by weight, and the C component is 10 parts by weight to 50 parts by weight. The resin composition of each component is contained in the range of 3 parts by weight to 16 parts by weight of the D component and 5 parts by weight to 35 parts by weight of the E component.

Step b: The resin composition is dissolved in an organic solvent to obtain a resin varnish having a resin solid content of 30% by weight to 70% by weight.

A component is a high heat resistant epoxy tree with a softening point of 50 ° C or higher. fat. The A component is an epoxy resin having a high glass transition temperature Tg. The reason why a high heat-resistant epoxy resin having a solid shape of a softening point of 50 ° C or more in an epoxy resin is used is that a glass transition temperature Tg is high, and a high heat resistance can be obtained by adding a small amount.

The high heat resistance ring of the solid shape having a softening point of 50 ° C or more is mentioned here. The oxy-resin is preferably one or more selected from the group consisting of a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type epoxy resin.

Further, in the component A, the solid shape having a softening point of 50 ° C or more is used. In addition to the high heat-resistant epoxy resin, it may be made of any one or two of a novolac type epoxy resin, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type epoxy resin. A high heat resistant epoxy resin composed of the above. In this case, any one or two of a novolac type epoxy resin, a cresol novolak type epoxy resin, a phenol novolac type epoxy resin, and a naphthalene type epoxy resin which are liquid at room temperature are further prepared. When the high heat resistant epoxy resin composed of the above is used as the component A, the glass transition temperature Tg can be further improved and the effect of improving the B-stage cracking can be improved.

Further, the component A is preferably used when the resin composition is 100 parts by weight. It is used in the range of 3 parts by weight to 30 parts by weight. When the amount of the component A is less than 3 parts by weight, it is difficult to achieve high Tg of the resin composition. On the other hand, when the A component exceeds 30 parts by weight, the resin layer after curing becomes brittle, and the flexibility is completely impaired, so that it is not preferable as a flexible printed wiring board. The component A is more preferably used in the range of 10 parts by weight to 25 parts by weight, whereby the high Tg of the resin composition and the good flexibility of the resin layer after curing can be stably achieved.

The B component is one or two of a biphenyl type phenol resin and a phenol aralkyl type phenol resin. An epoxy resin curing agent composed of the above. The amount of the epoxy resin hardener added is naturally derived from the reaction equivalent of the resin to be hardened, and does not require a particular amount. However, in the case of the resin composition of the present invention, the component B is preferably used in the range of 13 parts by weight to 35 parts by weight, based on 100 parts by weight of the resin composition. When the amount of the component B is less than 13 parts by weight, considering the resin composition of the invention of the present invention, a sufficiently hardened state cannot be obtained, and the flexibility of the resin layer after curing cannot be obtained. On the other hand, when the B component exceeds 35 parts by weight, the moisture absorption resistance of the resin layer after curing tends to be deteriorated, which is not preferable.

A specific example of the biphenyl type phenol resin is shown in Chemical Formula 25.

Further, a specific example of the phenol aralkyl type phenol resin is shown in Chemical Formula 26.

The C component is a rubber which is soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C. Modified polyamidoximine resin. By blending the C component, the flexibility property is improved and the effect of suppressing the flow of the resin can be obtained. The rubber-modified polyamidoximine resin is obtained by reacting a polyamidoximine resin with a rubber resin, and is used for the purpose of improving the flexibility of the polyamide amine imide resin itself. In other words, the polyamidoximine resin is reacted with a rubber resin, and one of the acid components (such as cyclohexanedicarboxylic acid) of the polyamidoximine resin is partially substituted with a rubber component. The rubber component is described in terms of the concept of containing natural rubber and synthetic rubber. As the latter, the synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, and acrylonitrile butadiene rubber. Wait. Further, from the viewpoint of ensuring heat resistance, it is also useful to use a heat-resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or an amine ester rubber. In order to produce a copolymer by reacting with a polyamidoximine resin, these rubber-based resins are preferably provided with various functional groups at both ends. It is especially useful to use CTBN (carboxy terminal butadiene nitrile rubber) having a carboxyl group. Furthermore, the above rubber component may be copolymerized by only one type. It is also possible to copolymerize two or more kinds. Further, in the case of using a rubber component, from the viewpoint of stabilizing the flexibility, it is preferred to use a rubber having a number average molecular weight of 1,000 or more.

When used to polymerize a rubber modified polyamidoximine resin, it is used as a polyamide The solvent in which the imide resin and the rubber resin are dissolved is preferably one or more kinds of dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and the like. Methyl hydrazine, nitromethane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, and the like. Further, in order to cause a polymerization reaction to occur, a polymerization temperature in the range of 80 ° C to 200 ° C is preferably employed. When a solvent having a boiling point of more than 200 ° C is used in the polymerization, it is preferred to replace the solvent with a solvent having a boiling point in the range of 50 ° C to 200 ° C depending on the application.

Here, as the solvent whose boiling point is in the range of 50 ° C to 200 ° C, for example, A single solvent selected from the group consisting of methyl ethyl ketone, dimethyl acetamide, and dimethylformamide, or a mixed solvent of two or more kinds. When the boiling point is less than 50 ° C, the dispersion of the solvent due to heating is remarkable, and in the case where a semi-hardened resin is formed from the state of the resin varnish, it is difficult to obtain a good semi-hardened state. On the other hand, when the boiling point exceeds 200 ° C, when a semi-hardened resin is formed from the state of the resin varnish, the solvent is difficult to dry, so that it is difficult to obtain a good semi-cured resin layer.

In the rubber-modified polyamidoximine resin used in the resin composition of the present invention, it is preferred to copolymerize the rubber component when the weight of the rubber-modified polyamidoximine resin is 100% by weight. The amount is 0.8% by weight or more. When the amount of the copolymerization is less than 0.8% by weight, even if a rubber-modified polyamidoximine resin is formed, there is a lack of flexibility in hardening the resin layer formed by the resin composition mentioned in the present invention. Sex, and the adhesion to the copper foil is also reduced, which is not good. Further, more preferably, the amount of the copolymerization of the rubber component is more preferably 3% by weight or more, still more preferably 5% by weight or more. According to experience, there is no particular problem even if the amount of copolymerization exceeds 40% by weight. However, the effect of improving the flexibility of the hardened resin layer is saturated, resulting in waste of resources and thus being poor.

The above-mentioned rubber modified polyamidoximine resin is required to be soluble and soluble. The nature of the agent. The reason for this is that it is difficult to prepare a resin varnish if it is insoluble in a solvent. Further, the rubber-modified polyamidoximine resin is used in a blending ratio of 10 parts by weight to 50 parts by weight when the weight of the resin composition is 100 parts by weight. When the rubber-modified polyamidoximine resin is less than 10 parts by weight, it is difficult to exhibit the effect of suppressing the resin flow. Moreover, the resin layer after hardening becomes brittle, and it is difficult to improve flexibility. As a result, effects such as microcracking of the resin layer are likely to occur. On the other hand, when a rubber-modified polyamidoximine resin is added in an amount of more than 50 parts by weight, the embedding property to the inner layer circuit is lowered, and as a result, voids are likely to occur, which is not preferable.

The D component is an organic phosphorus-containing flame retardant for improving flame retardancy. Organic phosphorus Examples of the flame retardant include a phosphorus-containing flame retardant composed of a phosphate ester and/or a phosphazene compound. The component D is preferably used in an amount of from 3 parts by weight to 16 parts by weight per 100 parts by weight of the resin composition. When the content of the component D is less than 3 parts by weight, the effect of flame retardancy cannot be obtained. On the other hand, even if the content of the component D exceeds 16 parts by weight, the improvement in flame retardancy is not expected. Further, a more preferable content of the component D is from 5 parts by weight to 14 parts by weight.

Furthermore, the resin composition of the present invention is such that the weight of the resin composition is set When 100% by weight is added, the total content of phosphorus is added in the range of 0.5% by weight to 5% by weight, and it is preferable to ensure flame retardancy.

The E component is a biphenyl type epoxy resin. Biphenyl type epoxy resin contributes to the so-called glass The glass transition temperature Tg is improved and the bendability is improved. Examples of the biphenyl type epoxy resin include a biphenyl aralkyl type epoxy resin. The component E is preferably used in an amount of from 5 parts by weight to 35 parts by weight, based on 100 parts by weight of the resin composition. When the content of the component E is less than 5 parts by weight, the effect of improving the glass transition temperature Tg and the bendability cannot be obtained. On the other hand, even if the content of the component E exceeds 35 parts by weight, high Tg is not expected, and improvement in bendability is not expected. Further, a more preferable content of the component E is from 7 parts by weight to 25 parts by weight.

In addition to the above components A to E, it is contained as a component of the F component. The resin composition of the phosphorus flame retardant epoxy resin can further improve the flame retardancy. The phosphorus-containing flame retardant epoxy resin is a general term for epoxy resins containing phosphorus in an epoxy skeleton, and is a so-called halogen-free flame retardant epoxy resin. In addition, when the weight of the resin composition is 100% by weight, the phosphorus atom content of the resin composition of the present application, that is, the phosphorus atom derived from the F component may be in the range of 0.1% by weight to 5% by weight. Any of the phosphorus-containing flame retardant epoxy resins can be used. However, the use of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative for a phosphorus-containing flame retardant epoxy resin having two or more epoxy groups in the molecule is used. It is preferable because the stability of the resin quality in the semi-hardened state is excellent and the flame retardancy effect is high. The structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in Figure 27 for reference.

That is, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative The phosphorus-containing flame-retardant epoxy resin having two or more epoxy groups in the molecule is preferably such that naphthoquinone or hydroquinone is substituted with 9,10-dihydro-9-oxa-10-phosphonium. After the phenanthrene-10-oxide is reacted and formed into the compound represented by the following 28 or 29, the epoxy resin is reacted with a part of the OH group to prepare a phosphorus-containing flame retardant epoxy resin.

[化28]

Moreover, if specifically exemplified, it is 9,10-dihydro-9-oxa-10-phosphaphenanthrene When the 10-oxide derivative is a phosphorus-containing flame retardant epoxy resin having two or more epoxy groups in the molecule, it is preferred to use a compound having a structural formula represented by Chemical Formula 30, Chemical Formula 31 or Chemical Formula 32.

[化30]

[化31]

[化32]

The resin composition in the case where a phosphorus-containing flame retardant epoxy resin is used herein may be One type of phosphorus-containing flame retardant epoxy resin as the F component may be used alone, and two or more types of phosphorus-containing flame retardant epoxy resins may be used in combination. However, it is preferable to consider the total amount of the phosphorus-containing flame retardant epoxy resin as the F component, so that the phosphorus component derived from the F component is obtained when the weight of the resin composition is 100% by weight. The amount is added so as to be in the range of 0.1% by weight to 5% by weight. The phosphorus-containing flame retardant epoxy resin differs in the amount of phosphorus atoms contained in the epoxy skeleton depending on the type thereof. Therefore, the content of the phosphorus atom can be specified as described above instead of the addition amount of the F component. However, the F component is usually used in the range of 5 parts by weight to 50 parts by weight when the resin composition is 100 parts by weight. When the blending ratio of the other resin component is considered in the case where the F component is less than 5 parts by weight, it is difficult to obtain the phosphorus atom derived from the F component to be 0.1% by weight or more, and the effect of improving the flame retardancy cannot be obtained. On the other hand, even if the F component exceeds 50 parts by weight, the flame retardancy improving effect is saturated, and the resin layer after curing becomes brittle and is not preferable.

The "high Tg" and "flexibility" of the above-mentioned hardened resin are usually Anti-proportional characteristics. In this case, the phosphorus-containing flame retardant epoxy resin has an improvement in flexibility of the resin layer which contributes to hardening, and contributes to high Tg. Therefore, instead of using a phosphorus-containing flame retardant epoxy resin, it is better to blend well with the "phosphorus-containing flame retardant epoxy resin which contributes to high Tg" and "phosphorus which contributes to the improvement of flexibility". A flame retardant epoxy resin is used, whereby a resin composition suitable for use in a flexible printed wiring board can be obtained.

The resin composition of the invention of the present invention can also be made to further contain an epoxy equivalent of 200 In the following, an epoxy resin composed of one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin which are liquid at room temperature As a G component. Here, the reason why the bisphenol epoxy resin is selected to be used is that it has good compatibility with the component C (rubber-modified polyamidoximine resin), and it is easy to impart appropriate flexibility to the semi-hardened resin layer. Further, when the epoxy equivalent exceeds 200, the resin becomes semi-solid at room temperature, and the flexibility in the semi-hardened state is reduced, which is not preferable. Further, the bisphenol-based epoxy resin may be used singly or in combination of two or more kinds. Further, when two or more kinds are used in combination, the mixing ratio thereof is not particularly limited.

The epoxy resin of the G component is set to 100 parts by weight of the resin composition When it is used in a blending ratio of 2 parts by weight to 15 parts by weight, this fully exerts thermosetting property in half In the hardened state, the occurrence of a warp phenomenon called curl can be reduced, and further, the flexibility of the resin layer in a semi-hardened state can be further improved. When the epoxy resin exceeds 15 parts by weight, the flame retardancy is lowered or the resin layer after hardening tends to be hard in balance with other resin components. Further, when the amount of addition of the component C (rubber-modified polyamidoximine resin) is considered, it is difficult to obtain sufficient toughness as the resin layer after curing.

The resin composition of the invention of the present invention can also be made into a thermoplastic resin and / or a low-elastic substance composed of synthetic rubber as the H component. By forming the resin composition containing the H component, cracking in the semi-hardened state of the resin composition can be prevented, and flexibility after curing can be improved. Examples of the low elastic material of the H component include acrylonitrile butadiene rubber, acrylic rubber (acrylate copolymer), polybutadiene rubber, isoprene, hydrogenated polybutadiene, and polyvinyl butadiene. Aldehyde, polyether oxime, phenoxy group, polymer epoxy, aromatic polyamine. One type may be used alone or two or more types may be used in combination. It is especially preferred to use acrylonitrile butadiene rubber. In the case of the acrylonitrile butadiene rubber, if it is a carboxyl group-modified material, a crosslinked structure is formed with the epoxy resin, and the flexibility of the resin layer after curing can be improved. As the carboxyl group-modified material, a carboxyl terminal nitrile butadiene rubber (CTBN), a carboxyl terminal butadiene rubber (CTB), or a carboxyl-modified nitrile butadiene rubber (C-NBR) is preferably used.

The H component is preferably 25 weights when the resin composition is 100 parts by weight. The blending ratio below the amount is used. When the amount of the H component exceeds 25 parts by weight, the glass transition temperature Tg is lowered, the solder heat resistance is lowered, the peel strength is lowered, and the thermal expansion coefficient is increased, which is not preferable.

The resin composition of the invention of the present invention is obtained by combining the above components A to E. The flame retardancy can be improved, the glass transition temperature Tg can be increased, and thermal deterioration of the folding endurance can be prevented. Further, sufficient flexibility can be obtained without adding an inorganic filler such as the resin composition of the prior adhesive. Further, it is possible to prevent cracking in a semi-hardened state or powder falling during press working.

The resin varnish of the invention of the present invention: the resin varnish of the invention of the present invention is the above resin group The solvent is added to the product to prepare a resin solid content of 30% by weight to 70% by weight. Further, the semi-cured resin layer formed by the resin varnish is characterized in that the resin overflow amount at the time of measuring the resin thickness of 55 μm is 0% to 10% in accordance with MIL-P-13949G in the MIL standard. range. As the solvent mentioned herein, it is preferred to use a solvent selected from the group consisting of methyl ethyl ketone, dimethyl acetamide, dimethylformamide, etc. as a solvent having a boiling point in the range of 50 ° C to 200 ° C. One type of the solvent alone or a mixture of two or more types. This is to obtain a good semi-hardened resin layer as described above. Further, the range of the amount of the resin solid content shown here is such that when applied to the surface of the copper foil, the film thickness can be controlled to the range of the best accuracy. When the resin solid content is less than 30% by weight, the viscosity is too low, and it flows immediately after application to the surface of the copper foil, and it is difficult to ensure uniformity of film thickness. On the other hand, when the resin solid content exceeds 70% by weight, the viscosity is high, and it is difficult to form a film on the surface of the copper foil.

When the resin varnish is used to form a semi-hardened resin layer, the measured resin overflow amount is preferably in the range of 0% to 10%. If the resin overflow rate is high, the thickness of the insulating layer formed using the resin layer of the resin copper foil becomes uneven. However, the resin varnish of the present invention can control the resin overflow rate to a lower value of 10% or less. Further, the resin varnish of the present invention can achieve a level in which resin flow hardly occurs, so the lower limit of the resin overflow flow rate is set to 0%. Further, the resin overcoat of the resin varnish of the present invention has a better range of resin overflow of 0% to 5%.

In the present specification, the resin overflow is based on MIL-P-13949G in the MIL standard, and four 10 cm square samples are sampled from a resin-coated copper foil having a resin thickness of 55 μm, and the four samples are overlapped. The state (layered body) was bonded under the conditions of a pressurization temperature of 171 ° C, a pressurization pressure of 14 kgf / cm ² , and a pressurization time of 10 minutes, and the resin outflow weight at this time was measured, and based on the result, it was calculated based on the number 1. value.

[Number 1]

Further, the resin layer may contain 2 parts by weight to 50 parts by weight of the soluble solution. And a polymer component having one or two or more kinds of a hydroxyl group, a carboxyl group, and an amine group as a functional group in the molecule, and an epoxy resin having a boiling point of 200 ° C or higher and an amine having a boiling point of 200 ° C or more in an amount of 50 parts by weight or more An epoxy resin blend composed of an epoxy resin hardener. The resin layer may be a fluororesin base material or a fluororesin film followed by a resin. In addition, the polymer component may be one or more selected from the group consisting of a polyvinyl acetal resin, a phenoxy resin, an aromatic polyamine resin, a polyether oxime resin, and a polyamidoximine resin. Mixed by. The epoxy resin having a boiling point of 200 ° C or higher may be a group selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, rubber modified bisphenol A type epoxy resin, and biphenyl type epoxy resin. One type or two or more types are mixed.

The amine-based epoxy resin curing agent may be one selected from the group consisting of aromatic polyamines, polyamines, and amine adducts obtained by polymerizing or condensing these epoxy resins or polycarboxylic acids. 2 or more types.

Furthermore, the fluororesin base material or the fluororesin film may be selected from the use From PTFE (polytetrafluoroethylene (4 fluorinated)), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer (4.6 fluorinated)), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (2-fluorinated)), PCTFE (polychlorotrifluoroethylene (3 fluorinated)), polyarsenic, aromatic polysulfide and aromatic A substrate or a film such as a fluorine-based resin composed of at least one of a polyether and a "fluororesin". It may contain a skeleton material such as glass cloth or may not contain a skeleton material such as glass cloth. Further, the thickness of the fluororesin base material is not particularly limited.

Further, as the above-mentioned curing agent, it is possible to use only two for the purpose of hardening it. Amines such as cyanide diamine, imidazoles, and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolacs such as phenol novolac resin and cresol novolak resin, and anhydrides such as phthalic anhydride Place There is a hardener. These hardeners are especially effective for epoxy resins. However, from the viewpoint of remarkably improving the adhesion between the fluororesin base material and the metal foil, it is particularly preferable to use an amine-based epoxy resin curing agent having a boiling point of 200 ° C or higher. When the press molding temperature is in the vicinity of 180 ° C and the boiling point of the curing agent is present in the vicinity of the press molding temperature, the epoxy resin hardener is boiled by press molding, so that bubbles are easily generated in the cured insulating resin layer. Further, when an amine-based epoxy resin curing agent is used to form an adhesive layer between the fluororesin base material and the metal foil, the most stable adhesiveness can be obtained. In other words, the "amine-based epoxy resin curing agent having a boiling point of 200 ° C or higher" is obtained by using an aromatic polyamine or a polyamine, and polymerizing or condensing the epoxy resin or the polyvalent carboxylic acid. One or more of the group of amine adducts. Moreover, if more specifically, it is preferred to use 4,4'-diamine-based benzoquinone, 3,3'-diamine-based phenylhydrazine, 4,4-diaminodiphenyl. Any of methane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and bis[4-(4-aminophenoxy)phenyl]anthracene. Further, since the amount of the amine-based epoxy resin curing agent added to the epoxy resin is naturally derived from the respective equivalents, it is considered that the necessity of blending the ratio is not strictly described. Therefore, in the invention of the present invention, the amount of addition of the curing agent is not particularly limited.

Further, it is also preferred to use a curing accelerator which is added in an appropriate amount as needed. As mentioned here The hardening accelerator is a tertiary amine, an imidazole, a urea-based hardening accelerator, and the like. In the invention of the present invention, the blending ratio of the hardening accelerator is not particularly limited. The reason for this is that the curing accelerator is a heating condition at the time of press working, and the like, and the manufacturer can arbitrarily specify the amount of addition.

Further, the resin layer preferably contains a rubber resin. The rubbery resin mentioned here is described by the concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, and the like. . Further, in the case where heat resistance is required, it is also useful to use a heat resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or an amine ester rubber. In order to form a copolymer by reacting with the above polymer component, it is preferred that these rubber resins have various functional groups at both ends.

Further, it is also preferred to add a crosslinking agent of the above polymer as needed to make use. For example, when a polyvinyl acetal resin is used as the above polymer, an amine ester resin is used as a crosslinking material or the like.

The constituent component of the resin composition of the above resin layer may also be used in the resin group When the content is 100 parts by weight, the epoxy resin is 50 parts by weight to 80 parts by weight, the curing agent is 1 part by weight to 15 parts by weight, the hardening accelerator is 0.01 parts by weight to 1.0 part by weight, and the polymer component is 2 parts by weight. The composition is in the range of from 1 part by weight to 5 parts by weight, and the rubber resin is from 1 part by weight to 10 parts by weight. When it is contained in this composition range, the good adhesion between the fluororesin base material and the metal foil is maintained, and the unevenness of the adhesion of the product is reduced.

The above resin layer may also be used in an amount of 5 to 50 parts by weight of epoxy resin (including hardening) Or a resin mixture composed of 50 to 95 parts by weight of a polyether oxime resin (having a hydroxyl group or an amine group at the terminal and soluble in a solvent), and an appropriate amount of a hardening accelerator added as needed The mixture is semi-hardened.

The resin layer has a first thermosetting resin layer and a bit in order from the copper foil side. In the second thermosetting resin layer on the surface of the first thermosetting resin layer, the first thermosetting resin layer is a resin component of a drug which is not dissolved in the desmear treatment in the wiring board manufacturing process. In the form of a mold, the second thermosetting resin layer can be formed by using a resin which is dissolved in a desmear treatment process in a wiring board manufacturing process and can be washed and removed. The first thermosetting resin layer may be formed by using any one or two or more kinds of resin components in which a polyimine resin, a polyether oxime, or a polyphenylene ether is mixed. The second thermosetting resin layer may be formed by using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is when the roughened surface roughness of the copper foil with a carrier is Rz (μm) and the thickness of the second thermosetting resin layer is t2 (μm). , t1 is preferably a thickness satisfying the condition of Rz < t1 < t2.

The resin layer may be a prepreg obtained by impregnating a resin with a skeleton material. The resin impregnated with the skeleton material is preferably a thermosetting resin. The above prepreg can also be known Prepreg or prepreg used to make printed wiring boards. The prepreg may be a prepreg manufactured by a manufacturing method having the following steps. A liquid resin film forming step of forming a liquid resin layer in the form of a film having a predetermined thickness on a flat working surface using a liquid thermosetting resin. 2. A pre-drying step of forming a dry resin layer by drying the liquid resin layer on the working plane in this state. 3. A pre-step of a skeleton material by pre-heating and crimping the surface of the dried resin layer on the working plane to form a dry resin layer with a skeleton material. 4. A resin impregnation step of heating a thermosetting resin component in a state in which a resin is reflowable in a state in which a dry resin layer of a skeleton material is placed on a working plane, thereby impregnating the matrix material. 5. The cooling step, when the resin impregnation is completed, immediately performs a temperature lowering operation without completely curing the thermosetting resin, and maintains a semi-hardened state of the thermosetting resin impregnated with the skeleton material to be in a prepreg state.

The above skeleton material may also contain polyarmine fiber or glass fiber or full aromatic Family polyester fiber. The above-mentioned skeleton material is preferably a non-woven fabric or a woven fabric of polyarmine fiber or glass fiber or wholly aromatic polyester fiber. Further, the wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C or higher. The wholly aromatic polyester fiber having a melting point of 300 ° C or higher is a fiber produced by using a resin called a so-called liquid crystal polymer, and the liquid crystal polymer is 2-hydroxy-6-naphthoic acid and p-hydroxyl group. The polymer of benzoic acid is the main component. Since the wholly aromatic polyester fiber has a low dielectric constant and a low dielectric loss tangent, it has excellent performance as a constituent material of the electrical insulating layer, and can be used in the same manner as glass fibers and polyaramide fibers.

Further, it is preferred that the fibers constituting the nonwoven fabric and the woven fabric are treated with a decane coupling agent to improve the wettability of the resin on the surface thereof. In this case, the decane coupling agent may be a decane coupling agent such as an amine group or an epoxy group depending on the purpose of use.

Further, the prepreg may be formed by impregnating a thermosetting resin with a non-woven fabric using polyaramide fibers or glass fibers having a nominal thickness of 70 μm or less, or a glass cloth having a nominal thickness of 30 μm or less. Prepreg made of skeleton material.

Dissolving the resins in, for example, methyl ethyl ketone (MEK), cyclopentanone, and dimethyl Carbamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, B A solvent solution is prepared by using a solvent such as ketiselus, N-methyl-2-pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide, for example by roll coating. Applying the method to the ultra-thin copper layer or the heat-resistant layer, the rust-preventing layer, the chromate-treated layer or the decane coupling agent layer, and then drying and removing the solvent as needed to become B Stage status. For drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the above resin layer may be dissolved in a solvent to obtain a resin liquid having a resin solid content of 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone for dissolution at this stage.

A copper foil with a carrier (the carrier-attached copper foil with a resin) having the above resin layer It is used in such a manner that after the resin layer is superposed on the substrate, the entire resin layer is thermocompression-bonded to thermally harden the resin layer, and then the carrier is peeled off to expose the ultra-thin copper layer (of course, the pole is exposed) A surface of the intermediate layer side of the thin copper layer is formed to form a predetermined wiring pattern.

If the copper foil with the carrier attached to the resin is used, the multilayer printed wiring base can be reduced The number of sheets of prepreg material used in the manufacture of the board. Further, the thickness of the resin layer can be set to ensure the thickness of the interlayer insulation, or the copper clad laminate can be produced even if the prepreg material is not used at all. Further, at this time, the surface of the substrate may be undercoated with an insulating resin to further improve the smoothness of the surface.

Furthermore, when the prepreg material is not used, the prepreg material is saved. Since the material cost and the lamination step are also simple, it is economically advantageous, and the thickness of the multilayer printed wiring board which is manufactured correspondingly according to the thickness of the prepreg material is thin, so that the thickness of one layer can be made 100 μm or less. The advantages of a very thin multilayer printed wiring board.

The thickness of the resin layer is preferably from 0.1 to 120 μm.

If the thickness of the resin layer is thinner than 0.1 μm, the adhesion force is lowered, when it is not When the resin material-attached copper foil with a resin is laminated on the base material provided with the inner layer material, it is difficult to ensure interlayer insulation between the circuit and the inner layer material. Further, it is preferable that the total resin layer thickness of the cured resin layer and the semi-hardened resin layer is 0.1 μm to 120 μm, and practically preferably 35 μm to 120 μm. Further, in this case, the thickness is preferably 5 to 20 μm for the cured resin layer and 15 to 115 μm for the semi-hardened resin layer. The reason is that when the total resin layer thickness exceeds 120 μm, it is difficult to manufacture a multilayer printed wiring board having a small thickness. If the thickness is less than 35 μm, it is easy to form a multilayer printed wiring board having a small thickness, but the circuit between the inner layers is The resin layer as the insulating layer is too thin, and there is a tendency that the insulation between the circuits of the inner layer tends to be unstable. Further, when the thickness of the cured resin layer is less than 5 μm, it is necessary to consider the surface roughness of the roughened surface of the copper foil. On the other hand, if the thickness of the cured resin layer exceeds 20 μm, the effect of using the cured resin layer is not particularly improved, and the total thickness of the insulating layer becomes thick. Further, the thickness of the cured resin layer may be 3 μm to 30 μm. Further, the semi-hardened resin layer may have a thickness of 7 μm to 55 μm. Further, the total thickness of the cured resin layer and the semi-cured resin layer may be 10 μm to 60 μm.

Moreover, the copper foil with a carrier layer having a resin layer is used for manufacturing extremely thin multilayer printing In the case of the wiring board, the thickness of the resin layer is preferably from 0.1 μm to 5 μm, more preferably from 0.5 μm to 5 μm, even more preferably from 1 μm to 5 μm, and the thickness of the multilayer printed wiring board is reduced. Further, when the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil with a carrier, it is preferable to provide a heat-resistant layer on the ultra-thin copper layer and/or After the rustproof layer and/or the chromate treatment layer and/or the decane coupling treatment layer, a resin layer is formed on the heat-resistant layer or the rust-preventive layer or the chromate-treated layer or the decane coupling treatment layer.

Further, when the resin layer contains a dielectric material, the thickness of the resin layer is preferably from 0.1 to 50 μm, preferably from 0.5 μm to 25 μm, more preferably from 1.0 μm to 15 μm. Further, the thickness of the above resin layer means an average value of the thickness measured by a cross-sectional observation at any 10 points.

On the other hand, if the thickness of the resin layer is thicker than 120 μm, it is difficult to use 1 The secondary coating step forms a resin layer of a target thickness and costs an extra material cost and the number of steps, which is economically disadvantageous. Further, since the formed resin layer is inferior in flexibility, it is likely to be cracked during operation, and excessive resin is generated during thermal compression bonding with the inner layer. It becomes difficult to carry out the smooth accumulation.

Further, as another form of the product with the resin-attached carrier copper foil, Coating on the ultra-thin copper layer or the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, or the decane coupling treatment layer with a resin layer, and forming a semi-hardened state, followed by peeling off the carrier, thereby The form of a resin-attached copper foil in which no carrier is present is produced.

<5. With carrier copper foil>

In this manner, a carrier-attached copper foil having a copper foil carrier, an intermediate layer in which a Ni layer and a Cr layer are sequentially laminated on a copper foil carrier and containing a trace amount of Zn, and an extremely thin copper layer laminated on the intermediate layer is produced. . The method of using the carrier copper foil itself is well known. For example, the surface of the ultra-thin copper layer can be bonded to the paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth - Paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, etc., and the carrier is peeled off after thermocompression bonding. A very thin copper layer is then etched into the target conductor pattern with the insulating substrate to finally produce a printed wiring board. Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. In the case of the copper foil with a carrier of the present invention, the peeling portion is mainly an interface between the Cr layer and the extremely thin copper layer.

Hereinafter, an example of a manufacturing procedure of a printed wiring board using the copper foil with a carrier of the present invention will be described.

An embodiment of the method for producing a printed wiring board according to the present invention includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention, and laminating the copper foil and the insulating substrate with the carrier, and the copper foil with the carrier After the insulating substrate is laminated with the ultra-thin copper layer side facing the insulating substrate, the carrier of the carrier-attached copper foil is peeled off, and the copper-clad product is formed through the above steps. The laminate, after which the circuit is formed by any of a semi-additive method, a modified semi-additive method, a partial addition method, and a subtractive method. The insulating substrate may also be provided with an inner layer circuit.

In the present invention, the so-called semi-additive method refers to the following method: on an insulating substrate or Thin copper electroless plating is performed on the copper foil seed layer, and after patterning, a conductor pattern is formed using electroplating and etching.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention having a semi-additive method, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and laminating the copper foil and the insulating substrate with the carrier After laminating the carrier-attached copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an etching solution such as acid; Providing a through hole or/and a blind via to expose the resin by removing the ultra-thin copper layer by etching; performing desmear treatment on the region including the through hole or/and the blind hole; And providing an electroless plating layer in the region including the through hole or/and the blind hole; providing a plating resist on the electroless plating layer; exposing the plating resist, and then removing the plating resistance in the region where the circuit is formed a plating layer disposed in the circuit-formed region after removing the plating resist; removing the plating resist; and removing by flash etching or the like Electroless plating layer region other than the region of the road.

In another embodiment of the method for manufacturing a printed wiring board of the present invention having a semi-additive method, the method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; Laminating the carrier-attached copper foil and the insulating substrate; after laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil; and peeling off the carrier by etching or plasma etching using an etching solution such as acid The exposed ultra-thin copper layer is completely removed; an electroless plating layer is disposed on the surface of the resin exposed by removing the ultra-thin copper layer by etching; a plating resist is disposed on the electroless plating layer; and the plating resist is applied Performing exposure, thereafter removing the plating resist in the region where the circuit is formed; providing a plating layer in the circuit-formed region after removing the plating resist; removing the plating resist; and removing by rapid etching or the like An electroless plating layer and an extremely thin copper layer located in a region other than the region in which the circuit is formed.

In the present invention, the modified semi-additive method refers to a method of laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by plating a resist, and thickening the copper of the circuit forming portion by electroplating. Thereafter, the resist is removed, and the metal foil other than the above-described circuit forming portion is removed by (rapid) etching, thereby forming a circuit on the insulating layer.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the improved semi-additive method, the method comprises the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil with the carrier An insulating substrate; after laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier with the carrier copper foil; and providing a through hole or/and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier; The area of the through hole or/and the blind hole is subjected to desmear treatment; the electroless plating layer is disposed on the area including the through hole or/and the blind hole; and the plating resist is disposed on the surface of the extremely thin copper layer exposed by peeling off the carrier; After the plating resist is disposed, the circuit is formed by electroplating; the plating resist is removed; and the ultra-thin copper layer exposed by removing the plating resist is removed by rapid etching.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the improved semi-additive method, the method comprises the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the carrier and insulating the carrier a substrate; after laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil; and providing a plating resist on the extremely thin copper layer exposed by peeling off the carrier; and exposing the plating resist Thereafter, removing the plating resist in the region where the circuit is formed; providing a plating layer in the circuit-formed region after removing the plating resist; removing the plating resist; and removing the above-mentioned formation by rapid etching or the like An electroless plating layer and an extremely thin copper layer in areas outside the circuit area.

In the present invention, the partial addition method refers to a method in which a catalyst core is provided on a substrate on which a conductor layer is provided, and a via hole or a via hole is formed as needed, and etching is performed. After the conductor circuit is formed, if necessary, a solder resist or a plating resist is provided, and the via hole, the via hole, and the like are thickened on the conductor circuit by electroless plating treatment, thereby manufacturing a printed wiring board.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using a partial addition method, the method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil and the insulating substrate with the carrier After laminating the carrier-attached copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; and the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier are provided with through holes or/and blind holes; Desmear treatment is performed on the region including the through hole or/and the blind hole; the catalyst core is provided to the region including the through hole or/and the blind hole; and the etching resistance is set on the surface of the extremely thin copper layer exposed by peeling off the carrier Exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an acid or the like to form a circuit; removing the etching resist; Providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an acid or the like; and the solder resist is not provided or An electroless plating layer is provided in the region where the plating resist is applied.

In the present invention, the subtractive method refers to a method of selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like to form a conductor pattern.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing a copper foil with an insulating substrate and an insulating substrate of the present invention; and laminating the copper foil and the insulating substrate with the carrier; After laminating the carrier-attached copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; the ultra-thin copper layer exposed to the carrier is peeled off and the insulating substrate is provided with a through hole or/and a blind hole; And the area of the blind hole is subjected to desmear treatment; an electroless plating layer is disposed on the area including the through hole or/and the blind hole; a plating layer is disposed on the surface of the electroless plating layer; and the plating layer or/and the above is extremely thin An etching resist is disposed on the surface of the copper layer; the etching resist is exposed to form a circuit pattern; and the ultra-thin copper layer and the electroless plating layer and the plating layer are removed by etching or plasma etching using an etching solution such as acid To form a circuit; The above etching resist is removed.

In another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil and the insulating substrate with the carrier; After laminating the carrier-attached copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; the ultra-thin copper layer exposed to the carrier is peeled off and the insulating substrate is provided with a through hole or/and a blind hole; and the through hole or the pair is included And a region of the blind hole is subjected to desmear treatment; an electroless plating layer is disposed on the region including the through hole or/and the blind hole; a mask is formed on the surface of the electroless plating layer; and the mask is not formed a plating layer is disposed on the surface of the electroplated layer; an etching resist is disposed on the surface of the plating layer or/and the ultra-thin copper layer; and the etching resist is exposed to form a circuit pattern; etching or electrolysis by etching the solution using an acid or the like A method such as slurry removes the above-mentioned ultra-thin copper layer and the above electroless plating layer to form a circuit; and removes the above-mentioned etching resist.

The step of providing a through hole or/and a blind hole, and the subsequent desmear step may also be omitted.

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings. Here, the copper foil with a carrier having an extremely thin copper layer on which a roughened layer is formed is exemplified, but is not limited thereto, even if an ultrathin copper layer having a roughened layer is not used. The carrier copper foil can also be similarly produced in the following method for producing a printed wiring board.

First, as shown in Fig. 1-A, a carrier-attached copper foil (first layer) having an extremely thin copper layer having a roughened layer formed on its surface is prepared.

Then, as shown in FIG. 1-B, a resist is coated on the roughened layer of the ultra-thin copper layer for exposure. Development, etching the resist into a prescribed shape.

Then, as shown in FIG. 1-C, circuit plating of a predetermined shape is formed by removing the resist after plating for forming a circuit.

Then, as shown in FIG. 2-D, a resin layer is laminated on the ultra-thin copper layer by a method of covering the circuit plating (in the form of a buried circuit plating), and then another carrier copper foil is attached ( Layer 2) is followed by a very thin copper layer.

Then, as shown in Fig. 2-E, the carrier was peeled off from the second layer of the carrier-attached copper foil.

Then, as shown in FIG. 2-F, a laser opening is performed at a predetermined position of the resin layer to expose the circuit plating to form a blind hole.

Then, as shown in FIG. 3-G, copper is buried in the blind hole to form a hole.

Then, as shown in FIG. 3-H, circuit plating is formed on the filling holes in the manner of FIG. 1-B and FIG. 1-C described above.

Then, as shown in Fig. 3-I, the carrier was peeled off from the first layer of the carrier-attached copper foil.

Then, as shown in FIG. 4-J, the extremely thin copper layer on both surfaces is removed by rapid etching to expose the surface of the circuit plating in the resin layer.

Then, as shown in FIG. 4-K, a bump is formed on the circuit plating in the resin layer, and a copper pillar is formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced in this manner.

The above-mentioned other carrier copper foil (the second layer) can use the copper carrier of the present invention. For the foil, it is also possible to use the previously attached copper foil, and it is also possible to use a conventional copper foil. Alternatively, a layer 1 or a plurality of layers may be formed on the second layer circuit shown in FIG. 3-H, or may be formed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Any of the methods performs such circuit formation.

Moreover, in the manufacture of the printed wiring board, it is also possible to strengthen the copper foil with the carrier. A support for the carrier is attached to the surface of the carrier. Thereby, the handleability can be further improved. Make Examples of the support include an insulating substrate such as a prepreg or a resin. The resin may be the above resin layer.

The copper foil with a carrier of the present invention is preferably controlled so that the color difference of the surface of the ultra-thin copper layer satisfies any one of the following (1) to (4). In the present invention, the "chromatic aberration of the surface of the ultra-thin copper layer" means the chromatic aberration of the surface of the ultra-thin copper layer or the chromatic aberration of the surface of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention preferably has the chromatic aberration of the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-proof layer or the chromate-treated layer or the decane coupling layer, which satisfies the following (1)~( 4) Any of the above methods are controlled.

(1) The color difference ΔL based on JIS Z8730 of the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-preventive layer or the chromate-treated layer or the decane coupling treatment layer is -40 or less.

(2) The color difference ΔE*ab based on JIS Z8730 of the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-proof layer or the chromate-treated layer or the decane coupling treatment layer is 45 or more.

(3) The color difference Δa based on JIS Z8730 of the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-preventive layer or the chromate-treated layer or the decane coupling treatment layer is 20 or less.

(4) The color difference Δb based on JIS Z8730 of the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-preventive layer or the chromate-treated layer or the decane coupling treatment layer is 20 or less.

Here, the color difference ΔL, Δa, and Δb are measured by a color difference meter, and black/white/red/green/yellow/blue is added, and the color is expressed by the L*a*b color system based on JIS Z8730. The comprehensive index is expressed by △L: white black, △a: red green, △b: yellow blue. Further, ΔE*ab is expressed by the following formula using these chromatic aberrations.

The chromatic aberration can be adjusted by increasing the current density at the time of formation of the extremely thin copper layer, lowering the concentration of copper in the plating solution, and increasing the line flow rate of the plating solution.

Further, the chromatic aberration may be adjusted by subjecting the surface of the ultra-thin copper layer to a roughening treatment and providing a roughened layer. In the case where the roughening treatment layer is provided, the current density (for example, 40 to 60 A) can be increased by using an electrolyte containing one or more elements selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum. /dm ² ), adjust the processing time (for example, 0.1 to 1.3 seconds). In the case where the roughened layer is not provided on the surface of the ultra-thin copper layer, the plating bath having a concentration of Ni of twice or more of other elements can be used to lower the current density (0.1~). 1.3A/dm ² ) Set a longer processing time (20 seconds to 40 seconds) to treat the surface of the ultra-thin copper layer or the heat-resistant layer or the rust-proof layer or the chromate treatment layer or the decane coupling treatment layer. This is achieved, for example, by plating a Ni-W alloy, plating a Ni-Co-P alloy, or plating a Ni-Zn alloy.

If the surface of the ultra-thin copper layer is based on JIS Z8730, the color difference ΔL is -40 or less. For example, when an electric circuit is formed on the surface of the ultra-thin copper layer with the carrier copper foil, the contrast between the ultra-thin copper layer and the circuit is sharp, and as a result, the visibility of the circuit is good and the alignment of the circuit can be performed with high precision. The color difference ΔL based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably -45 or less, more preferably -50 or less.

If the surface of the ultra-thin copper layer is based on JIS Z8730, the color difference ΔE*ab is 45 or more. For example, when an electric circuit is formed on the surface of the ultra-thin copper layer with the carrier copper foil, the contrast between the ultra-thin copper layer and the circuit is sharp, and as a result, the visibility of the circuit is good and the alignment of the circuit can be performed with high precision. The color difference ΔE*ab based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

If the color difference Δa based on JIS Z8730 on the surface of the ultra-thin copper layer is 20 or less, then For example, when an electric circuit is formed on the surface of an ultra-thin copper layer with a carrier copper foil, the contrast between the ultra-thin copper layer and the circuit is sharp, and as a result, the visibility is further improved and the positional alignment of the circuit can be performed with high precision. The color difference Δa based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less.

If the color difference Δb based on JIS Z8730 on the surface of the ultra-thin copper layer is 20 or less, then For example, when an electric circuit is formed on the surface of an ultra-thin copper layer with a carrier copper foil, the contrast between the ultra-thin copper layer and the circuit is sharp, and as a result, the visibility is further improved and the positional alignment of the circuit can be performed with high precision. The color difference Δb based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less.

Control the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-proof layer as described above When the color difference of the surface of the chromate treatment layer or the decane coupling layer is used, the contrast with the circuit plating is sharp, and the visibility is good. Therefore, in the manufacturing steps shown in, for example, FIG. 1-C of the printed wiring board as described above, circuit plating can be formed accurately and at a predetermined position. Moreover, according to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, the circuit plating is affected by, for example, the rapid etching to remove the ultra-thin copper layer as shown in FIG. 4-J. The resin layer is protected and its shape is maintained, whereby a fine circuit is easily formed. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the wiring of the circuit is satisfactorily suppressed. Therefore, it is easy to form a fine circuit. Further, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 4-J and FIG. 4-K, the exposed surface of the circuit plating becomes a concave shape from the resin layer, so that it is easy to form on the circuit plating. The bumps, in turn, facilitate the formation of copper posts on the bumps, thereby improving manufacturing efficiency.

Further, as the resin, a known resin or prepreg can be used. For example, a prepreg which is a glass cloth impregnated with a BT (bis-synyleneimine III) resin or a BT resin, or an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. can be used. Or ABF. Further, the embedded resin may contain a thermosetting resin or a thermoplastic resin. Further, the embedded resin may contain a thermoplastic resin. The type of the embedded resin is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, a polyvinyl acetal resin, and an amine ester. Resin, block copolymerized polyimide resin, block copolymerized polyimide resin, polyether oxime, polyether oxime resin, aromatic polyamide resin, polyamide amide resin, rubber modification (modified) Epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, bis-xenylene diimide, three resins, heat a resin such as a curable polyphenylene ether resin, a cyanate resin, or a polycarboxylic acid anhydride, or a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate epoxy resin, or a glass cloth. Paper composite substrate epoxy resin, glass cloth. A glass non-woven composite substrate epoxy resin, a glass cloth substrate epoxy resin, a polyester film, a polyimide film, a liquid crystal polymer film, a fluororesin film, or the like is preferable.

[Examples]

Hereinafter, the present invention will be further described in detail by way of examples of the invention, but the invention is not limited by the examples.

1. Manufacture of carrier copper foil

<No.1>

As a copper foil carrier, a strip of electrolytic copper foil (JTC manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 35 μm was prepared. The shiny surface of the copper foil was plated by a roll-to-roll type continuous plating line under the following conditions, thereby forming a Ni layer having an adhesion amount of 1000 μm/dm ² .

. Ni layer (base plating)

Nickel sulfate: 270~280g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Trisodium citrate: 15~25g/L

Gloss agent: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 55~75ppm

pH: 4~6

Bath temperature: 55~65°C

Current density: 7~11A/dm ²

After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg/dm ² was adhered to the Ni layer by performing electrolytic chromate treatment under the following conditions on a roll-to-roll continuous plating line.

. Electrolytic chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0g/L

pH: 7~10

Liquid temperature: 40~60°C

Current density: 0.1~2.6A/dm ²

Coulomb amount: 0.5~30As/dm ²

Then, on the continuous plating line of the roll-to-roll type, an ultra-thin copper layer having a thickness of 2 to 10 μm was formed on the Cr layer by electroplating under the following conditions to produce a copper foil with a carrier.

. Very thin copper layer

Copper concentration: 30~120g/L

H ₂ SO ₄ concentration: 20~120g/L

Electrolyte temperature: 20~80°C

Current density: 10~100A/dm ²

<No.2~37>

With respect to No. 1, the Ni adhesion amount and the Cr adhesion amount were variously changed as described in Table 1 by adjusting the linear velocity. Further, in the formation of the Ni layer or the chromate treatment, zinc in the form of zinc sulfate (ZnSO ₄ ) is added to the Ni plating solution or the chromate treatment liquid, and the zinc concentration is adjusted in the range of 0.05 to 5 g/L. Thereby, the amount of Zn adhered to the intermediate layer was changed as described in Table 1. However, in Comparative Examples 15 and 16, the zinc concentrations were set to 10 g/L and 15 g/L, respectively. In the table, "Ni" is referred to as "Ni" in the case of substrate plating, and "Ni-Zn" is referred to as nickel-zinc alloy plating. In addition, in the table, "Cr" is referred to as a pure chromate treatment at the chromate treatment, and "Zn-Cr" is referred to as a zinc chromate treatment. The carrier copper foil of No. 2 to 37 was produced in this manner. The example in which the Ni adhesion amount or the Cr adhesion amount is 0 means that the Ni plating or the electrolytic chromate treatment is not performed. Further, by increasing the zinc concentration in the nickel-zinc alloy plating solution or the chromate treatment liquid, the adhesion amount of Zn can be increased. Further, by increasing the chromium concentration in the chromate treatment liquid, the adhesion amount of Cr can be increased.

2. Evaluation of the characteristics of copper foil with carrier

The characteristics of the copper foil with a carrier obtained in the above manner were evaluated in the following manner. The results are shown in Table 1.

<pinhole>

The number of pinholes was visually measured by using a backlight for photos of people's livelihood as a light source. The evaluation was carried out by the following criteria.

×: pinholes exceeding 10,000/dm ²

△: The pinhole is 5,000 / dm ² or more and 10,000 / dm ² or less

○: Pinholes are 100/dm ² or more ~ less than 5,000 / dm ²

◎: pinholes are 20 / dm ² or more ~ less than 100 / dm ²

◎◎: The pinhole is less than 20/dm ²

<Peel strength (after BT pressurization)>

The extremely thin copper layer side of the copper foil with a carrier was attached to the BT substrate and pressed at a temperature of 195 ° C for 2 hours, and then the carrier side of the copper foil with a carrier was pressed according to JIS C6471 at a peeling speed of 50 mm/min and a peeling angle of 90°. Peeling, thereby measuring the peel strength. The results are shown in Table 1.

N0.1 is an example in which the intermediate layer does not contain Zn. Due to the adhesion of Ni and Cr Suitably, the frequency and peel strength of the pinholes can be obtained to a practical extent. However, in the No. 2 in which the adhesion amount of Ni and Cr is the same as that of No. 1 and Zn is added in an appropriate amount in the intermediate layer, the number of pinholes is further reduced, and the peel strength is increased to a more appropriate value. The appropriate range of peel strength is from 0.5 to 120 g/cm, more suitably from 0.5 to 30 g/cm, and more suitably from 1 to 30 g/cm, and more suitably from 5 to 25 g/cm.

In other invention examples, the same reference value as the adhesion amount of Ni and Cr may be used. For comparison, it is known that the frequency of pinholes and the peel strength can be improved. On the other hand, No.15 And the 16 series is too high in peeling strength due to the excessive amount of Zn adhesion. No. 29 to 33 were not formed because the Ni layer or the Cr layer was not formed. In No. 36 to 37, since the adhesion amount of Ni is too large, the adhesion is insufficient, and peeling occurs during the transition of the continuous plating line.

Claims (26)

A carrier-attached copper foil comprising a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an extremely thin copper layer laminated on the intermediate layer, the intermediate layer being contacted by a Ni layer contacting the interface with the copper foil carrier Contacting a Cr layer at the interface with the ultra-thin copper layer, the adhesion amount of Ni in the intermediate layer is 1000 to 40000 μg/dm ² , and the adhesion amount of Cr in the intermediate layer is 10 to 100 μg/dm ² , further in the intermediate layer Zn is present in an amount of 1 to 70 μg/dm ² . The scope of the appended patent carrier copper foil, Paragraph 1, wherein the Ni deposition amount is 2000 ~ 10000μg / dm ^2, the deposition amount of Cr 20 ~ 40μg / dm ^2. The carrier copper foil according to claim 1 or 2, wherein the mass ratio of Zn to Cr present in the intermediate layer is in the range of 0.01 to 5. The carrier copper foil according to claim 1 or 2, wherein the Cr is adhered by electrolytic chromate. The carrier-attached copper foil according to claim 3, wherein the Cr is adhered by electrolytic chromate. The carrier copper foil according to claim 1, wherein the carrier is formed of an electrolytic copper foil or a rolled copper foil. The carrier-attached copper foil according to claim 1, which has a roughened layer on the surface of the ultra-thin copper layer. The copper foil with carrier of claim 7, wherein the roughening layer is composed of any element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. Or a layer composed of an alloy containing any one or more elements selected from the group. The carrier-attached copper foil according to claim 7, which has a surface selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer and a decane coupling treatment layer on the surface of the roughened layer. Above layer. The copper foil with carrier of the first aspect of the patent application, which has a surface of the ultra-thin copper layer One or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer are selected. The carrier copper foil according to claim 1, wherein the ultra-thin copper layer is provided with a resin layer. The carrier-attached copper foil according to claim 7, which is provided with a resin layer on the roughened layer. The copper foil with a carrier of the ninth aspect of the invention is provided with a resin layer on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer. The carrier-attached copper foil according to claim 10, wherein the resin layer is provided on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer. The carrier-attached copper foil according to any one of claims 11 to 14, wherein the resin layer is formed by using a resin. The carrier-attached copper foil according to any one of claims 11 to 14, wherein the resin layer is formed of a resin in a semi-hardened state. The carrier-attached copper foil according to any one of claims 11 to 14, wherein the resin layer contains a dielectric. A printed wiring board manufactured by using the carrier-attached copper foil according to any one of claims 1 to 17. A printed circuit board manufactured by using the carrier-attached copper foil according to any one of claims 1 to 17. A copper-clad laminate produced by using the carrier-attached copper foil according to any one of claims 1 to 17. A method of manufacturing a printed wiring board, comprising the steps of: preparing a carrier copper foil and an insulating base according to any one of claims 1 to 15 And laminating the carrier copper foil and the insulating substrate, after laminating the carrier copper foil and the insulating substrate, peeling off the carrier of the carrier copper foil, forming a copper clad laminate through the above steps, and then, by semi-addition A circuit is formed by any one of a semi-additive method, a subtractive method, a partial-additive method, or a modified semi-additive method. A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of a copper foil with a carrier of any one of claims 1 to 17; a side surface of the ultra-thin copper layer of the carrier copper foil is formed with a resin layer; an electric circuit is formed on the resin layer; after the circuit is formed on the resin layer, the carrier is peeled off; and after the carrier is peeled off, the pole is removed The thin copper layer is thereby exposed to the circuit buried in the resin layer on the side surface of the ultra-thin copper layer. The method for manufacturing a printed wiring board according to claim 22, wherein the step of forming a circuit on the resin layer is as follows: bonding another copper foil with a carrier on the resin layer from the side of the ultra-thin copper layer, The circuit is formed using a copper foil with a carrier attached to the resin layer. The method of manufacturing a printed wiring board according to claim 23, wherein the other carrier copper foil bonded to the resin layer is the carrier-attached copper foil according to any one of claims 1 to 17. The method of manufacturing a printed wiring board according to any one of claims 22 to 24, wherein the step of forming a circuit on the resin layer is by a semi-additive method, a subtractive method, a partial addition method or an improvement The method of any one of the semi-additive methods is carried out. The method of manufacturing a printed wiring board according to any one of claims 22 to 24, wherein the copper foil with a carrier on which the circuit is formed has a substrate or a resin layer on the surface of the carrier of the copper foil with the carrier.