TWI609779B - Copper foil containing adhesive layer,copper clad laminate and printed wiring board - Google Patents

Abstract

An object of the present invention is to provide a copper foil, a copper-clad laminate, and a printed wiring board having an adhesive layer which has sufficient tear strength and high desmear liquid resistance and which has less moisture absorption deterioration. In order to achieve the object, an adhesive copper foil having an adhesive layer on one side of a copper foil is used, and the adhesive layer is contained in an amount of 5 parts by mass or more and 65 parts by mass based on 100 parts by mass of the polyphenylene ether compound. The layer formed by the resin composition of the following styrene butadiene block copolymer. Further, the present invention provides a copper-clad laminate obtained by using the copper foil having the adhesive layer, and a printed wiring board obtained by using the copper-clad laminate.

Description

Copper foil with adhesive layer, copper laminated board and printed wiring board

The present invention relates to a copper foil provided with an adhesive layer for a printed wiring board, a copper laminated board using the copper foil provided with the adhesive layer, and a printed wiring board.

In the past, when a copper-clad laminate or a printed wiring board was produced, as disclosed in Patent Document 1 or Patent Document 2, a copper foil having an extremely thin adhesive layer (primer resin layer) was used (hereinafter referred to as "with an adhesive". Layer of copper foil"). The side surface of the copper foil-based adhesive layer having the adhesive layer is laminated on a resin substrate or a prepreg which is an interlayer insulating film, or a resin substrate such as a paper phenol resin substrate, and is heated and pressurized. Through the adhesive layer, good adhesion of the resin substrate to the copper foil can be ensured.

The adhesive disclosed in the patent document 1 (Japanese Patent Application Laid-Open No. Hei. No. 2005-53218) or the patent document 2 (Japanese Patent Application Laid-Open No. Hei No. 2009-148962) has a thickness of 0.5 μm to 10 μm. A resin layer in a thin semi-hardened state. The adhesive layer is a resin composition (hereinafter referred to as "PA-based resin composition") obtained by mixing an epoxy resin, an aromatic polyamine resin soluble in a solvent, a curing accelerator, or the like, or a mixture thereof. A resin composition (hereinafter referred to as "PES-based resin composition") formed of an epoxy resin, a polyether oxime resin, and a curing accelerator is formed.

When such a copper foil having an adhesive layer is used, the adhesion to the resin substrate can be ensured even with a low-roughness copper foil, so that the roughening treatment step which has to be performed in the past can be eliminated. According to this, the manufacturing efficiency can be improved, and the manufacturing cost can be reduced. Further, when the copper foil having the adhesive layer is used, when the conductor pattern is formed by etching, since it is not necessary to provide an overetching time for dissolving the roughened portion, it is possible to form a fine etching pitch with a good etching factor. The excellent effect of the micro circuit.

However, the copper foil provided with the adhesive layer exemplified above is required to improve chemical resistance to degreased liquid or the like or to improve moisture absorption deterioration resistance.

For example, when manufacturing a multilayer printed wiring board, a hole for connecting a through hole or a blind hole between layers may be opened by a drill or laser processing. At this time, in order to remove the resin (slag) remaining in the inside of the hole, a degumming liquid made of potassium permanganate or the like is used, and the desmear treatment for removing the dross is performed. In this case, since the adhesive layer formed using the PA-based resin composition is easily dissolved in the degreasing liquid during the desmear treatment, the adhesion between the resin substrate and the copper foil is in the through-hole or The surrounding area of the blind hole or the like is locally lowered.

On the other hand, the adhesive layer formed using the PES resin composition has high desmear resistance and does not dissolve even if subjected to desmear treatment. However, there is a problem that the tear strength after moisture absorption is remarkably deteriorated.

Accordingly, an object of the present invention is to provide a copper foil, a copper-clad laminate, and a printed wiring board having an adhesive layer which has sufficient tear strength and is excellent in degreasing resistance and excellent in moisture absorption deterioration resistance.

Therefore, as a result of active research by the inventors of the present invention, it has been found that the above problem can be attained by using a layer composed of the following resin composition as an adhesive layer.

The copper foil with an adhesive layer of the present invention is a copper foil having an adhesive layer provided with an adhesive layer on one surface of a copper foil, wherein the adhesive layer is 100 parts by mass for the polyphenylene ether compound. A layer composed of a resin composition of 5 parts by mass or more and 65 parts by mass or less of the styrene butadiene block copolymer.

In the copper foil provided with the adhesive layer of the present invention, the above-mentioned adhesive layer is preferably provided on the surface of the copper foil having a surface roughness (Rzjis) of 2 μm or less.

In the copper foil provided with the adhesive layer of the present invention, the thickness of the adhesive layer is preferably from 0.5 μm to 10 μm.

In the copper foil with an adhesive layer of the present invention, the adhesive layer preferably contains an amino functional decane coupling agent, an acrylic functional decane coupling agent, a methacrylic functional decane coupling agent, and a vinyl functional group. One or more surface-treated filler particles selected from the decane coupling agent.

The copper-clad laminate of the present invention is characterized in that the copper foil having the adhesive layer described above is used.

The printed wiring board of the present invention is characterized by being obtained by using the copper-clad laminate of the present invention. Moreover, it is also preferable to use a printed wiring board characterized by using the copper-clad laminate of the present invention to remove the copper foil layer on the surface of the copper-clad laminate by etching and semi-additive process. ) The circuit is formed by the winner.

According to the invention, a layer composed of a resin composition containing 5 parts by mass or more and 65 parts by mass or less of the styrene-butadiene block copolymer for 100 parts by mass of the polyphenylene ether compound is used as the adhesive layer. The adhesion when the copper foil having the adhesive layer is bonded to the resin substrate can be improved. At the same time, when the desmear treatment is included in the manufacturing step of the printed wiring board, the adhesive layer can be prevented from being dissolved in the desmear liquid, and a printed wiring board having less deterioration in tear strength after moisture absorption can be formed.

Hereinafter, embodiments of the copper foil, the copper-clad laminate, and the printed wiring board provided with the adhesive layer of the present invention will be described.

<copper foil with adhesive layer>

The copper foil provided with the adhesive layer of the present invention is used as a material for manufacturing a printed wiring board, and is a copper foil having an adhesive layer on one surface of a copper foil. In the present invention, the adhesive layer provided on one side of the copper foil is a styrene butadiene block containing 5 parts by mass or more and 65 parts by mass or less based on 100 parts by mass of the polyphenylene ether compound. A layer formed by the resin composition of the copolymer. Hereinafter, the constitution of each layer will be described in the order of (1) copper foil and (2) adhesive layer. Further, in the present invention, the adhesive layer may be a composition containing filler particles. The filler particles are described separately from the adhesive layer. Further, in the present embodiment, a case where the copper foil having the adhesive layer is bonded to the resin substrate will be mainly described. However, the embodiment of the copper foil having the adhesive layer of the present invention is not limited thereto, and a resin layer having a function as an insulating layer or the like on the adhesive layer of the copper foil having the adhesive layer is also included in the present invention. in. That is, the invention only It is sufficient to provide an adhesive having the characteristics described below on one side of the copper foil described below. The example of the adhesive layer is as long as it is a copper-clad laminate or a printed wiring board. The copper foil and the resin portion constituting the insulating layer or the like may have a function of bringing the two together or in close contact.

(1) Copper foil

In the present invention, any one of an electrolytic copper foil or a rolled copper foil may be used as the copper foil provided with the adhesive layer, and the type of the copper foil is not limited. Further, when an adhesive layer is provided on the electrodeposited copper foil, an adhesive layer can be provided on either the gloss surface (roller surface) or the deposition surface (rough surface). Further, the thickness of the copper foil is not particularly limited, but it is preferable to provide the adhesive layer on the copper foil in the range of 1.0 μm to 18 μm. As long as the characteristics required for the manufacture of the printed wiring board are used, an appropriate and suitable copper foil can be used.

In the present invention, for example, when a single layer (one surface side) of a copper foil of 5.0 μm or less is provided with an adhesive layer, a so-called carrier foil (support) may be provided on the other surface of the copper foil. By using a copper foil of 5.0 μm or less, a high-definition circuit having a narrower circuit pitch can be formed with a good etching factor.

In the present invention, it is preferred to provide an adhesive layer to a copper foil having a surface roughness (Rzjis) of 2 μm or less. Further, when the copper foil itself is subjected to etching processing to form a circuit, it is preferable to use a copper foil which is not subjected to roughening treatment. Moreover, the term "back surface" refers to a surface on which a copper foil is bonded to the side of the resin substrate, and refers to a surface on which an adhesive layer is provided. The copper foil provided with the adhesive layer of the present invention is a smooth copper foil on the surface having a surface roughness (Rzjis) of 2 μm or less, regardless of the type of the electrolytic copper foil and the rolled copper foil, and may be separated by a spacer. The adhesive layer between the copper foil and the resin substrate provides sufficient adhesion strength between the copper foil and the resin substrate. In other words, the copper foil provided with the adhesive layer of the present invention can obtain sufficient adhesion strength to the resin substrate even if it is a non-roughened copper foil, so that it is not necessary to form a conductor pattern by etching in the past. The roughening treatment partially dissolves, and the time required for etching can be reduced. Therefore, a circuit having a good etching factor can be formed. The surface roughness of the copper foil is more preferably 1.8 μm or less, and still more preferably 1.5 μm or less from the viewpoint of forming a higher fine circuit.

On the other hand, after attaching the copper foil provided with the adhesive layer of the present invention to a resin substrate to obtain a copper-clad laminate, the copper foil on the surface thereof is etched away to expose the adhesive layer. In the case where the seed layer (electroless copper layer, etc.) is completely provided, a plating resist is formed on a portion of the seed layer where no circuit is formed, and a half-addition process for forming a circuit by plating only in a portion where the circuit is formed (Semi Additive Process=SAP method) It is preferred to use a copper foil subjected to roughening treatment. The reason for this is that by using the copper foil subjected to the roughening treatment, the copying shape of the roughening treatment can be left on the hardened adhesive layer, and the specific surface area of the bonding surface can be increased to realize the circuit formed by the SAP method. The adhesion is improved. The surface roughness (Rzjis) of the copper foil subjected to the roughening treatment at this time is also preferably 2 μm or less. Next, the adhesive layer is placed on the surface subjected to the roughening treatment to form a copper foil having an adhesive layer of the present invention. When the surface roughness of the copper foil exceeds 2 μm, the roughening treatment with a large uneven shape tends to be high, and it is difficult to remove the seed layer by flash etching, and insulation between circuits is required. The tendency to lower is therefore less preferred. Further, the SAP method is described in detail later.

Further, in the present invention, the surface of the copper foil may be subjected to a rust-preventing treatment, and an adhesive layer may be provided on the surface of the rust-preventing treatment layer. The anti-rust treatment of the copper foil is exemplified by inorganic rust-preventing treatment using zinc, nickel, cobalt, etc., chromate treatment using chromate, organic rust-preventing treatment using benzotriazole or an imidazole organic agent. Further, in the present invention, the following is a case where the copper foil is referred to as a copper foil which has been subjected to rustproof treatment.

Further, in the present invention, a decane coupling agent may be applied to one side surface of the copper foil, and an adhesive layer may be provided on the surface of the decane coupling agent layer. By providing the adhesive layer on the surface of the copper foil via the decane coupling agent layer, the wettability of the surface of the copper foil and the adhesive layer is improved, and when the copper foil having the adhesive layer is attached to the resin substrate, Then, if the strength is better, the adhesion of the bonding can be made better. Further, by interposing the decane coupling agent layer, the copper foil can be more firmly adhered to the resin substrate than in the case where the decane coupling agent layer is not present. Further, in the present invention, in the following, when only copper foil is used, it may mean a copper foil which has been treated with a decane coupling agent.

As the decane coupling agent layer, specifically, an amine functional decane coupling agent layer, an acrylic functional decane coupling agent layer, a methacrylic functional decane coupling agent layer, a vinyl functional decane coupling agent layer, a thiol functional group may be employed. A layer formed of various decane coupling agents, such as a decane coupling agent layer.

When the decane coupling agent layer is formed, it is preferred to dissolve the decane coupling agent in water as a solvent at a temperature of from 0.5 g/l to 10 g/l, at a temperature of room temperature, by a dipping method, a leaching method, The surface of the copper foil is uniformly contacted with the decane coupling agent by a spray method or the like to uniformly adsorb the decane coupling agent on the surface of the copper foil. The decane coupling agent forms a film by condensation bonding with an OH group protruding from the surface of the copper foil. When the concentration of the decane coupling agent is less than 0.5 g/l, the adsorption speed of the decane coupling agent on the surface of the copper foil is slow, which is not suitable for the actuarial calculation based on the commercial basis. In addition, it is also less preferable because the decane coupling agent does not uniformly adsorb the surface of the copper foil. On the other hand, even when a solution having a concentration of the decane coupling agent exceeding 10 g/l is used, the adsorption rate or the uniform adsorption property cannot be correspondingly improved, which is not economically preferable.

The decane coupling agent used in the formation of the above decane coupling agent layer is specifically exemplified below. Vinyltrimethoxydecane, vinylphenyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, 4-shrinkage can be used. Glyceroxybutyltrimethoxydecane, γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-3-(4- (3-Aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolyl decane, triazine decane, γ-mercaptopropyltrimethoxydecane, 3-propene oxime A decane coupling agent such as propyltrimethoxydecane.

Further, when it is referred to as a copper foil hereinafter, a copper foil which forms a layer of a decane coupling agent on the surface of a copper foil is also referred to as a surface of a copper foil, and is also a surface of a layer of a decane coupling agent.

(2) Subsequent layer

Next, the adhesive layer will be described. In the present invention, the adhesive layer is a layer composed of a resin composition containing 5 parts by mass or more and 65 parts by mass or less of the styrene-butadiene block copolymer for 100 parts by mass of the polyphenylene ether compound. .

First, the polyphenylene ether compound will be described. The polyphenylene ether compound is highly resistant to degumming in terms of its structure and hardly dissolves in the desmear liquid. Therefore, by forming a binder layer with a polyphenylene ether compound as a main component, the amount of the resin dissolved in the degreasing liquid can be reduced. According to this, in the manufacturing steps of the printed wiring board and the like, even in the case where the desmear treatment step is present, the adhesive layer is not partially dissolved after the desmear treatment, and the resin base is applied before and after the desmear treatment. The adhesion between the material and the copper foil is not locally lowered, and the good adhesion between the copper foil and the resin substrate can be ensured after the desmear treatment. Further, by using a polyphenylene ether compound, an adhesive layer having good dielectric properties of low dielectric constant and low dielectric tangent can be obtained.

The polyphenylene ether compound used in the present invention is represented by the following formula. But, under In the above formula, R1, R2, R3 and R4 each represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

As the above polyphenylene ether compound, specifically, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-extension) can be used. Phenyl)ether, poly(2,6-dipropyl-1,4-phenylene)ether, and the like. Further, in the polyphenylene ether compound represented by the above formula, the terminal group is preferably a hydroxyl group. However, in the present invention, not only a polyphenylene ether compound having a terminal group of a hydroxyl group but also a compound having a styryl group or a glycidyl group can be preferably used, and the terminal group is modified by a conventional method. The styrene-modified polycondensation-based ether compound may be preferably a glycidyl-modified polyphenylene ether compound or the like. In addition, such commercial products can also be used.

The number average molecular weight of the polyphenylene ether compound is preferably from 500 to 4,000, more preferably from 1,000 to 3,000. When the number average molecular weight of the polyphenylene ether compound is less than 500, the flexibility of the obtained adhesive layer becomes low, which is not preferable. On the other hand, when the number average molecular weight of the polyphenylene ether compound exceeds 4,000, the solubility in a solvent such as methyl ethyl ketone or toluene becomes low, which is not preferable.

Next, the styrene butadiene block copolymer will be described. The styrene butadiene block copolymer is a component which polymerizes (crosslinks) a polyphenylene ether compound. By polymerizing the polyphenylene ether compound and the styrene butadiene block copolymer, the adhesive layer exhibits elasticity and flexibility by utilizing high flexibility derived from the butadiene structure portion. In particular, when a styrene-modified polyphenylene ether compound or a glycidyl-modified polyphenylene ether compound is used, this tendency becomes remarkable. As a result, the adhesion of the adhesive layer to the copper foil is improved, and the crack resistance can be improved. Further, when a printed wiring board is produced using the copper foil having the adhesive layer, the tear strength of the circuit can be made practically required. In addition, by using the styrene butadiene block copolymer, The hygroscopic deterioration resistance property can be improved, and the tear strength can be prevented from deteriorating over time in a humid environment. Furthermore, the styrene butadiene block copolymer has less influence on the low dielectric properties of the polyphenylene ether compound due to the less polar group, and thus can be maintained from the polyphenylene ether compound. Good electrical properties of low dielectric and low dielectric tangent.

Next, the compounding ratio of the polyphenylene ether compound to the styrene butadiene block copolymer will be described. In the present invention, the styrene butadiene block copolymer is preferably used in an amount of from 5 parts by mass to 65 parts by mass per 100 parts by mass of the polyphenylene ether compound. When the styrene-butadiene block copolymer is more than 65 parts by mass based on 100 parts by mass of the polyphenylene ether compound, the tear strength is lowered in a normal state, and the PCT (pressure cooker test) or the like is used in a high-temperature and high-humidity environment. When accelerating the test, it is difficult to maintain the required peeling strength of the PCT after the market is required. In addition, when the styrene-butadiene block copolymer is less than 5 parts by mass based on 100 parts by mass of the polyphenylene ether compound, it is difficult to obtain sufficient elasticity and flexibility, and it is not preferable. Here, the blending ratio of the styrene-butadiene block copolymer to 100 parts by mass of the polyphenylene ether compound is more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more. By disposing 10 parts by mass or more, preferably 20 parts by mass or more of the styrene butadiene block copolymer, 100 parts by mass of the polyphenylene ether compound, film formation becomes easy, and elasticity can be imparted to the adhesive layer. And flexibility.

In addition, from the viewpoint of high tear strength in the normal state and high moisture absorption deterioration resistance, it is more preferable to formulate styrene butyl 2 to 100 parts by mass to 55 parts by mass based on 100 parts by mass of the polyphenylene ether compound. The olefin block copolymer further preferably has a styrene butadiene block copolymer in an amount of from 35 parts by mass to 45 parts by mass based on 100 parts by mass of the polyphenylene ether compound. By blending the styrene butadiene block copolymer in an amount of from 30 parts by mass to 55 parts by mass based on 100 parts by mass of the polyphenylene ether compound, the tear strength in any of the normal state and after the PCT is changed. High, can reduce the degradation rate of tear strength before and after PCT. By blending the styrene butadiene block copolymer in an amount of from 35 parts by mass to 45 parts by mass relative to 100 parts by mass of the polyphenylene ether compound, the tear strength after PCT is made higher, and the PCT is made The deterioration rate of the tear strength before and after is further reduced.

Further, the resin composition may be composed of various additives such as an epoxy resin, a curing agent, a curing accelerator, a thermoplastic particle, a colorant, an antioxidant, a flame retardant, and a coupling agent, as needed. The various additives may be suitably present within the scope of the spirit of the invention. Add to.

Next, the thickness of the adhesive layer will be described. In the present invention, the thickness of the adhesive layer (thickness measured by thickness) is preferably in the range of 0.5 μm to 10 μm. When the thickness of the subsequent layer is less than 0.5 μm, the adhesive layer is too thin, and the adhesion between the copper foil and the adhesive layer cannot be improved. On the other hand, even if the thickness of the adhesive layer exceeds 10 μm, the adhesion between the copper foil and the adhesive layer cannot be increased correspondingly, and the waste of resources is not preferable.

(3) filler particles

Next, the filler particles will be described. In the present invention, as described above, the adhesive layer may be configured to include filler particles. By containing the filler particles in the adhesive layer, the tear strength and the moisture absorption deterioration resistance in the normal state can be improved as compared with the adhesive layer containing no filler particles. Further, when the filler particles are formed in the adhesive layer formed of the above resin composition, the adhesion of the adhesive layer to the copper foil is further improved by using the filler particles to which the specific surface treatment is applied. The copper foil and the resin substrate having the adhesive layer can be adhered more firmly. As a result, the tear strength can be further improved, and the occurrence of delamination can be suppressed.

The filler particles usable in the present invention may, for example, be molten cerium oxide, crystalline cerium oxide, aluminum oxide, aluminum hydroxide, calcium carbonate, barium sulfate, mica or talc. Any one of these may be used or a mixture of two or more types may be used.

The filler particles used in the present invention are preferably surface-treated with a decane coupling agent. As the decane coupling agent, an amine functional decane coupling agent, an acrylic functional decane coupling agent, a methacrylic functional decane coupling agent, an epoxy functional decane coupling agent, an olefin functional decane coupling agent, a thiol functional decane can be used. Various decane coupling agents such as a coupling agent and a vinyl functional decane coupling agent. Among the above, an amine functional decane coupling agent, an acrylic functional decane coupling agent, a methacrylic acid functional decane coupling agent, a vinyl functional decane coupling agent, and the like are more preferable.

By applying the above surface treatment to the filler particles, the wettability with the solvent can be improved, and the filler particles can be favorably dispersed in the resin solution. As a result, the filler particles can be uniformly dispersed in the layer to obtain an adhesive layer. In addition, by applying the surface treatment to the filler particles, the compatibility between the filler particles and the resin composition is good, and the adhesion between the filler particles and the resin composition can be improved.

Specific examples of the above decane coupling agent include the following. First, as the amino acid functional decane coupling agent, it is exemplified as N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)- 3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3- Dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, and the like.

As for the methacrylic acid functional decane coupling agent and the acrylic functional decane coupling agent, it is exemplified by 3-methacryloxypropylmethyldimethoxydecane and 3-methylpropenyloxypropyltrimethoxy. Decane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, and the like.

Further, examples of the ethylene functional decane coupling agent include vinyltrimethoxydecane, vinyltriethoxysilane, vinylphenyltriethoxysilane, and the like.

Further, methyltrimethoxydecane, dimethyldimethoxydecane, phenyltrimethoxydecane, methyltriethoxydecane, dimethyldiethoxydecane, phenyltriethyl may also be used. An alkoxy decane such as oxydecane.

The surface treatment method using these decane coupling agents is not particularly limited, and it can be carried out by an appropriate and appropriate method.

Further, when the filler particles are contained in the adhesive layer, the content thereof is preferably 40% by mass or less. When the content of the filler particles exceeds 40% by mass, the contact area between the resin composition constituting the adhesive layer and the copper foil is lowered, and the strength of the bonding is rapidly lowered.

Further, filler particles comprising the next layer, it is preferred to use a laser diffraction scattering measuring particle size distribution measuring method of volume cumulative particle diameter D ₅₀ is in a range of 0.01μm ~ 1.0μm of persons, make better use of Within the range of 0.01 μm to 0.5 μm. When the value of the volume cumulative particle diameter D ₅₀ of the filler particles is less than 0.01 μm, the filler particles are too fine particles, so that it is difficult to uniformly disperse in the resin solution prepared when the adhesive layer is formed, which is not preferable. On the other hand, when the value of the volume cumulative particle diameter D ₅₀ of the filler particles exceeds 1.0 μm, the adhesion between the copper foil and the resin layer may be lowered, which is not preferable. From this point of view, the volume cumulative particle diameter D ₅₀ of the filler particles is _more preferably 0.5 μm or less. By using the filler particles of such fine particles, the tear strength at the time of forming a circuit using the copper foil having the adhesive layer can be further improved.

<Method for Producing Copper Foil with Adhesive Layer>

Next, an example of a method of producing the copper foil having the adhesive layer described above will be described. The manufacturing step of the copper foil having the adhesive layer described above can be roughly divided into, for example, (1) a resin solution preparation step, (2) a resin solution coating step, and (3) a drying step. The following describes each step.

(1) Resin solution preparation step

The resin solution preparation step is to prepare a styrene-butadiene block copolymer in a range of 5 parts by mass to 65 parts by mass based on 100 parts by mass of the polyphenylene ether compound, and the solid content of the resin is 10% by mass to 40%. The step of mass% of the resin solution. When the resin solution is prepared, for example, a resin composition obtained by mixing a polyphenylene ether compound and a styrene butadiene block copolymer in a predetermined blending ratio may be dissolved in a solvent, or a polyphenylene ether may be obtained. The compound and the styrene butadiene block copolymer are respectively dissolved in a solvent, so that the polyphenylene ether compound and the styrene butadiene block copolymer are mixed in a specific blending ratio, and the resin solution is prepared. There are no special restrictions.

Since the polyphenylene ether compound used in this step can be the same as the above-mentioned polyphenylene ether compound, the description thereof is omitted here. Similarly, since the styrene butadiene block copolymer can be used in the same manner as the above styrene butadiene block copolymer, the description of the styrene butadiene block copolymer will be omitted. Further, the compounding ratio of the polyphenylene ether compound to the styrene butadiene block copolymer in the resin composition is also the block of the polyphenylene ether compound and the styrene butadiene block in the above adhesive layer. Since the blending ratio of the copolymer is the same, the description of the preferred range of the blending ratio of the polyphenylene ether compound to the styrene butadiene block copolymer is omitted.

As the solvent of the resin solution, a ketone solvent such as methyl ethyl ketone or an aromatic solvent such as toluene can be used. The resin composition is easily dissolved by using the solvent, and the viscosity of the resin solution is adjusted easily. In addition, when any of these solvents is heated and pressurized when the copper foil having the adhesive layer is bonded to the resin substrate, the solvent can be volatilized efficiently, and the purification process of the volatilized gas is also easy.

In addition, when the resin solid content concentration is 10% by mass to 40% by mass, the solution viscosity can be made appropriate, and when the resin solution is applied onto the surface of the copper foil, the coating of the desired film thickness can be accurately formed. membrane. When the solid content of the resin is less than 10% by mass, the viscosity of the solution is low, and the resin solution flows immediately after being applied to the surface of the copper foil, and it is difficult to form a coating having a uniform film thickness. membrane. On the other hand, when the resin solid content concentration exceeds 40% by mass, since the solution viscosity is too high, it is difficult to form a coating film of 10 μm or less.

Further, when the filler layer is contained in the adhesive layer, the filler particles which have been subjected to the specific surface treatment in this stage are appropriately mixed in the resin composition. Since the filler particles, the surface treatment, the blending amount, and the like are as described above, the description thereof is omitted here. In addition, when it is hereinafter referred to as a resin composition, the resin composition may contain a filler particle.

(2) Resin solution coating step

The resin solution coating step is a step of applying the resin solution to one side of the copper foil so that the thickness of the adhesive layer after drying is 0.5 μm to 10 μm. The coating method at the time of applying the resin solution is not particularly limited as long as it is appropriate and appropriate depending on the thickness of the formed adhesive layer. However, in consideration of forming an extremely thin adhesive layer of 0.1 μm to 10 μm, a method advantageous for film formation is preferably employed, and for example, a gravure coater is preferably used to apply a resin solution on the surface of the copper foil.

(3) Drying step

The drying method can be suitably carried out according to a conventionally known method, and is not particularly limited. By this step, the solvent is volatilized from the coating film, and the hardening reaction of the resin composition is terminated at the intermediate stage to become a semi-hardened state resin. By the above steps, the copper foil with the adhesive layer of the present invention can be produced.

<Copper laminated board>

Next, an embodiment of the copper-clad laminate of the present invention will be described. The copper-clad laminate of the present invention is characterized in that the copper foil having the adhesive layer of the present invention described above is used. Here, as is well-known, the copper-clad laminate is a prepreg sheet or a paper phenol resin substrate in which a copper foil is placed on a sheet obtained by impregnating an insulating resin with paper or glass cloth, and the number of sheets is overlapped. A plate obtained by laminating one or both sides of a resin substrate by heat and pressure, and used as a material for manufacturing a printed wiring board. In the present invention, as the copper foil placed on the resin substrate such as the prepreg, the above-described copper foil having the adhesive layer is used. Next, the copper foil having the adhesive layer is placed on the back surface of the resin substrate so that the side surface of the adhesive layer of the copper foil having the adhesive layer is on the adhesive surface side of the resin substrate, and is heated. Pressurize. Thereby, the resin of the resin base material and the adhesive layer are melted and hardened, and the resin of the resin base material and the adhesive layer are integrated, and the resin base material and the copper foil are firmly adhered.

<Printed wiring board>

Further, the printed wiring board of the present invention is characterized in that the copper-clad laminate having the adhesive layer of the present invention is preferably used. Further, the printed wiring board of the present invention may of course be a multilayer printed wiring board. For example, a build-up printed wiring board may be formed using the copper foil provided with the adhesive layer. Further, the printed wiring board may be manufactured by any method using a copper-clad laminate.

The copper-clad laminate of the present invention can also be preferably used in the case of producing a printed wiring board by the above-described semi-additive process (SAP method). In other words, by using the copper-clad laminate using the copper foil having the adhesive layer of the present invention, it is possible to prevent the adhesion between the finally formed circuit and the resin substrate from being lowered. As for the general SAP method, any one of SAP-1 or SAP-2 described below is employed.

SAP-1: "To completely remove the copper foil of the copper-clad laminate" → "Drilling by laser method" → "Slag removal treatment" → "Electroless copper plating, forming a seed on a resin substrate "The electroless copper layer of the crystal layer" → "The plating resist is formed in the portion where the electroless copper layer is not formed" → "The circuit is formed by plating on the portion where the photoresist is not plated by copper plating" → "Peeling plating" "Photoresist" → "Photolithography to remove the electroless copper layer in the part where the circuit is not formed" → "Complete the circuit"

In the above-mentioned process of SAP-1, in order to completely etch and remove the copper foil of the copper-clad laminate before the hole processing, by fully exposing it and etching it into the desmear solution, in general, The formed inner wall of the perforation is etched by the desmear treatment and the adhesiveness of the finally formed circuit and the resin substrate tends to decrease. However, in the process of the SAP-1, when the copper-clad laminate of the present invention is used, even if the copper foil of the copper-clad laminate is completely etched and removed before the hole processing, the desmear resistance is still present on the surface of the resin substrate. Since the adhesive layer is excellent, even if it is fully exposed to the desmearing solution, the adhesion between the finally formed circuit and the resin substrate can be suppressed.

SAP-2: "Drilling by laser method" → "Slag removal" → "To completely remove the copper foil of the copper-clad laminate" → "Pre-electrolytic copper plating, forming on the resin substrate "The electroless copper layer of the seed layer" → "The plating resist is formed on the portion of the circuit where the electroless copper layer is not formed" → "The circuit is formed by copper plating on the portion where the photoresist is not plated" → "Peeling Plated photoresist" → "Photolithography removes the electroless copper layer at the portion where the circuit is not formed" → "Complete circuit"

In the process of using the SAP-2, before the copper foil of the copper-clad laminate is completely etched and removed, since the hole is processed by the laser method and the desmear treatment is performed, the adhesive layer existing around the formed perforation may be The tendency to etch due to desmear treatment. However, in the process of the SAP-2, when the copper-clad laminate of the present invention is used, the adhesive layer existing around the perforated opening portion is excellent in the desmear resistance, so that the portion can be prevented from being treated by the desmear. Since the etching is caused, it is preferable to maintain good adhesion between the pad forming portion and the resin substrate.

The embodiments of the copper foil, the copper-clad laminate, and the printed wiring board having the adhesive layer of the present invention described above are merely the same as those of the present invention, and may be appropriately modified without departing from the spirit of the invention. Further, the present invention will be more specifically described by the following examples, but the present invention is of course not limited by the following examples. The following Comparative Examples 1 to 3 are the same as those of Examples 1 to 5. Further, Comparative Example 4 is compared with Example 6.

[Example 1] <Manufacture of Copper Foil with Adhesive Layer>

In Example 1, a copper foil provided with an adhesive layer was produced as follows. First, 200 g of polyphenylene ether resin (manufactured by SABIC Co., Ltd.; MX-90) and 400 g of toluene were fed into a one-liter four-necked flask equipped with a stirring device, a temperature regulator, and a reflux tube, and the mixture was stirred and dissolved at 60 °C. Next, 10 g of chloromethylstyrene was introduced into the flask, and the mixture was stirred and dissolved to adjust the liquid temperature to 80 °C. Next, 24 g of a 50% by mass aqueous solution of sodium hydroxide was added dropwise thereto with stirring, and stirring was continued at 80 ° C for 3 hours. Next, the content was neutralized with a 1 N aqueous hydrochloric acid solution, and then methanol was added to precipitate a compound, followed by filtration. After washing the filtrate twice with an aqueous methanol solution (methanol: distilled water = 4:1), the solvent and water were removed by drying to obtain a polyphenylene ether compound.

Next, the polyphenylene ether compound obtained above was dissolved in toluene to prepare a 50% by mass solution of the polyphenylene ether compound. Further, a styrene butadiene block copolymer (manufactured by JSR Co., Ltd.; TR2003) was dissolved in toluene to prepare a 30% by mass styrene butadiene block copolymer solution. The styrene butadiene block copolymer is mixed with 100 parts by mass of the polyphenylene ether compound in an amount of 10 parts by mass, and the resin solution (varnish) is prepared so that the resin solid content concentration becomes 25%. .

Next, the surface of the ultra-thin non-roughened copper foil (surface roughness (Rzjis) 0.7 μm) of the carrier having a thickness of 3 μm was applied with the prevention of nickel 21 mg/m ² , zinc 8 mg/m ² , and chromium 3 mg/m ² . After the rust treatment, the surface of the rust-preventing treatment layer is treated with an amine-based decane coupling agent to form a decane coupling agent layer. Next, the resin solution was applied to the surface of the decane coupling agent layer by gravure printing so that the thickness of the adhesive layer after drying became 2.5 μm. After the coating film was formed, the resin composition was semi-cured at 180 ° C for 2 minutes to produce a copper foil having an adhesive layer containing an adhesive layer.

<Manufacture of copper-clad laminates>

The side of the adhesive layer of the copper foil having the adhesive layer produced as described above was brought into contact with one side of a 100 μm thick FR-4 prepreg (manufactured by Mitsubishi Gas Chemical Co., Ltd.: GHPL-830NS) at 220 ° C. The copper-clad laminate was produced by hot press forming under the heating and pressing conditions of ×90 minutes and 40 kgf/cm ² .

<Production of sample for measurement of tear strength>

After the copper foil layer of the copper-clad laminate produced as described above was peeled off from the carrier, plating was performed by electrolytic copper plating on the surface to a thickness of 10 μm, and the dry film was bonded to form an etching photoresist layer. Next, the photoresist layer was exposed and exposed to a 0.4 mm wide tear strength measuring circuit pattern to form an etching pattern. Subsequently, circuit etching and etching peeling were performed using a copper etching solution to prepare a sample for measuring the peeling strength of a circuit thickness of 10 μm.

<Production of sample for evaluation of desmear resistance test>

Further, in the present Example, a sample for evaluation of the desmear liquid resistance was prepared as follows. First, two sheets were prepared so that the resin solution prepared above was applied to the surface of the heat-resistant film so as to have a thickness of 100 μm, and dried to form a resin layer. Then, the resin layers were bonded to each other by heat processing, and then the heat-resistant film was peeled off and cut into a square of 5 cm × 5 cm to prepare a sample for evaluation of the desmear liquid resistance.

[Embodiment 2]

A copper foil having an adhesive layer and a desmear liquid resistance evaluation were prepared in the same manner as in Example 1 except that 20 parts by mass of the styrene butadiene block copolymer was used per 100 parts by mass of the polyphenylene ether compound. sample. In addition, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil having the adhesive layer of Example 2 was used, and a sample for measuring the peel strength was prepared.

[Example 3]

A copper foil having an adhesive layer and a desmear liquid resistance evaluation were prepared in the same manner as in Example 1 except that 40 parts by mass of the styrene butadiene block copolymer was used in an amount of 100 parts by mass based on 100 parts by mass of the polyphenylene ether compound. sample. In addition, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil having the adhesive layer was used, and a sample for measuring the peel strength was prepared.

[Example 4]

A copper foil having an adhesive layer and a desmear liquid resistance evaluation were prepared in the same manner as in Example 1 except that 60 parts by mass of the styrene butadiene block copolymer was used in an amount of 100 parts by mass based on 100 parts by mass of the polyphenylene ether compound. sample. In addition, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil having the adhesive layer was used, and a sample for measuring the peel strength was prepared.

[Example 5]

In addition to 30% by mass of filler particles (volume cumulative particle diameter D ₅₀ : 0.3 μm, cerium oxide) obtained by treating a surface using vinyl trimethoxy decane as a vinyl decane coupling agent, the same as in Example 3 Similarly, a copper foil having an adhesive layer and a sample for evaluation of the desmear liquid resistance were prepared. In addition, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil having the adhesive layer was used, and a sample for measuring the peel strength was prepared.

Next, Comparative Example 1 to Comparative Example 3 will be described.

[Comparative Example 1]

A copper foil having an adhesive layer and a desmear liquid resistance evaluation were prepared in the same manner as in Example 1 except that 70 parts by mass of the styrene butadiene block copolymer was used in an amount of 100 parts by mass based on 100 parts by mass of the polyphenylene ether compound. sample. In addition, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil having the adhesive layer of Comparative Example 1 was used, and a sample for measuring the peel strength was prepared.

[Comparative Example 2]

In Comparative Example 2, the resin solution described in Comparative Sample 3 of Patent Document 2 was prepared, and a coating film was formed using the resin solution, and the subsequent drying temperature was changed to 150 ° C, and the same procedure as in Example 1 was carried out. A copper foil for the agent layer and a sample for evaluation of the desmear resistance. In addition, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil having the adhesive layer of Comparative Example 2 was used, and a sample for measuring the peel strength was prepared. The preparation method of the resin solution of Comparative Example 2 will be described below.

In Comparative Example 2, an aromatic polyamide resin polymer (Nippon Chemical Co., Ltd.) was used. 70 parts by mass of BPAM-155) and epoxy resin (manufactured by Nippon Kayaku Co., Ltd.; EPPN-502) 30 parts by mass as a PA-based resin composition. Then, 1 part by mass of imidazole-based 2P4MHZ (manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator was mixed with 100 parts by mass of the PA-based resin composition to prepare a resin composition. The resin composition was dissolved in dimethylacetamide to prepare a resin solution so that the resin solid content concentration became 15% by mass.

[Comparative Example 3]

In the comparative example 3, the primer resin solution was prepared using the second resin composition C described in Example 3 of Patent Document 1, and the coating film was formed using the primer resin solution, and the subsequent drying temperature was 150 ° C. In the same manner as in Example 1, a copper foil having an adhesive layer and a sample for evaluation of the desmear liquid resistance were prepared. In addition, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil having the adhesive layer of Comparative Example 3 was used, and a sample for measuring the peel strength was prepared. The preparation method of the resin solution of Comparative Example 3 will be described below.

In Comparative Example 3, 70 parts by mass of a polyether oxime resin (manufactured by Sumitomo Chemical Co., Ltd.; SUMIKA EXCEL PES-5003P) and 30 parts by mass of an epoxy resin (manufactured by Nippon Kayaku Co., Ltd.; EPPN-502) were used as the PES system. Resin composition. Then, 1 part by mass of imidazole-based 2P4MHZ (manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator was mixed with 100 parts by mass of the PES-based resin composition to prepare a resin composition. The resin composition was dissolved in dimethylacetamide to prepare a resin solution so that the resin solid content concentration became 15% by mass.

[Evaluation 1]

Using each of the samples of Examples 1 to 5 and Comparative Examples 1 to 3 produced as described above, (1) evaluation of desmear resistance, (2) evaluation of tear strength, and (3) welding characteristics were performed. Evaluation. The evaluation methods and evaluation results are described below separately.

Evaluation method (1) Evaluation of the resistance of desmear liquid

The evaluation of the desmear resistance was carried out as follows. Three samples of the desmear liquid resistance evaluation samples prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were used, and each of the desmear liquid resistance evaluation samples was immersed in a swelling liquid at 75 ° C (Solomon) After 20 minutes, a potassium permanganate solution at 80 ° C (made by Rohm and Haas Electronic Materials Co., Ltd.) Made) (base equivalent: 1.25 N) for 20 minutes. Subsequently, it was immersed in a liquid (manufactured by Rohm and Haas Electronic Materials Co., Ltd.) at 45 ° C for 5 minutes, and washed with water. The weight of each sample for desmear resistance evaluation before and after the series of desmearing treatments was measured, and the weight reduction rate (%) before and after the desmear treatment was determined, and the average value was obtained.

(2) Evaluation of tear strength

The evaluation of the tear strength was carried out as follows. Using the samples for tear strength measurement prepared in Examples 1 to 5 and Comparative Examples 1 to 3, the tear strength before PCT was measured, and the tear strength was taken as the normal state. Further, the tear strength after holding for 24 hours in a pressure cooker tank at 121 ° C, 2 atm, and 100% RH was measured, and this was taken as the peeling strength after PCT. The measurement of the tear strength was carried out in accordance with JIS C-6481.

(3) Evaluation of welding characteristics

The evaluation of the welding characteristics was carried out as follows. The copper foil having the adhesive layer produced in Examples 1 to 5 and Comparative Examples 1 to 3 was cut into a square of 5 cm × 5 cm so that the copper foil portion became 1/2 size (2.5 cm × 5 cm) was applied as an etchant as a sample for evaluation of welding characteristics. Each sample for evaluation of the welding property was held in a pressure cooker tank at 121 ° C, 2 atm, and 100% RH for 5 hours, and then immersed in a solder bath at 260 ° C for 1 minute, and the presence or absence of expansion was observed. Further, in the case where no expansion occurred, it was judged that the welding property after the PCT was a level of pass and was marked as "○". On the other hand, the sample in which expansion occurred was referred to as "x".

2. Evaluation results (1) Evaluation of the resistance of desmear liquid

Table 1 shows the average value of the weight reduction rate (%) before and after the desmear treatment. As shown in Table 1, Examples 1 to 4 and Comparative Example 1 comprising an adhesive layer formed of a polyphenylene ether compound and a styrene butadiene block copolymer were compared with Comparative Example 2. The weight reduction rate (%) after the treatment of the slag is low, and it can be confirmed that the use of the polyphenylene ether compound and the styrene butadiene block copolymer to form the adhesive layer can provide improved desmear resistance. A copper foil having an adhesive layer. On the other hand, it was confirmed that the weight reduction rate (%) after the desmear treatment of Comparative Example 3 was 1% or less.

(2) Evaluation of tear strength

Next, Table 2 shows the tear strength in the normal state measured using the samples for tear strength measurement produced in Examples 1 to 5 and Comparative Examples 1 to 3, and the peel strength after PCT, and PCT. The rate of deterioration afterwards.

As shown in Table 2, in Comparative Example 3 in which the desmear liquid resistance was high, it was confirmed that the deterioration rate after PCT was extremely high at 83%, and the tear strength after PCT was also 0.10 kgf/cm on average, and hygroscopic deterioration was remarkable. . On the other hand, in Comparative Example 2, the tear strength at the normal state was 0.63 kgf/cm on average, and the tear strength after PCT was 0.55 kgf/cm on average. Comparative Example 2 maintained the peeling strength required by the market after PCT, but the deterioration rate was 12.7%.

On the other hand, in Examples 1 to 5 and Comparative Example 1 in which the polyphenylene ether compound and the styrene-butadiene block copolymer were used to form the adhesive layer (12), it was confirmed that the deterioration rate was 20% or less. The moisture absorption deterioration resistance is improved. In addition, the styrene butadiene block copolymer is blended in an amount of from 5 parts by mass to 65 parts by mass based on 100 parts by mass of the polyphenylene ether compound, and it is considered to be 0.5 kgf/cm or more in the normal state, and is after PCT. A value of 0.45 kgf/cm or more. In particular, by blending the styrene butadiene block copolymer in an amount of from 35 parts by mass to 45 parts by mass based on 100 parts by mass of the polyphenylene ether compound, it is considered that the peeling strength after obtaining PCT is 0.54 kgf/cm. The above values. According to this, it is confirmed that the styrene butadiene block copolymer can be provided in a range of 5 parts by mass to 65 parts by mass based on 100 parts by mass of the polyphenylene ether compound, and it is confirmed that the peeling strength can be provided at the same time. A copper foil having an adhesive layer having high slag resistance and high moisture absorption deterioration resistance. Further, in Comparative Example 1, as described above, although improvement in moisture absorption deterioration resistance was observed, the tear strength at normal time and after PCT was slightly lower than in Examples 1 to 5.

(3) Evaluation of welding characteristics

As shown in Table 1, Example 1 to Example 5 and Comparative Example 1 each having an adhesive layer composed of a polyphenylene ether compound and a styrene butadiene block copolymer were compared with Comparative Example 3. Confirm that the welding characteristics are good.

3. Other

Example 3 and Example 5 differ only in the presence or absence of filler particles in the adhesive layer. As shown in Table 2, the tear strength in the normal state and after the PCT showed a high value in Example 5 containing the filler particles, and it was confirmed that the addition of the filler particles can effectively improve the tear strength.

[Embodiment 6]

In the sixth embodiment, the adhesion between the copper circuit and the resin substrate in the process of the above-mentioned SAP-1 was evaluated, and the evaluation was carried out by the following simple process. The following describes each process.

Copper-clad laminate: A copper foil having an adhesive layer was produced in the same manner as in Example 1 except that the same resin composition as in the above Example 3 was used. Further, the ultra-thin copper foil with a carrier used here is a copper foil layer of an extremely thin non-roughened copper foil (surface roughness (Rzjis) 0.7 μm) of a carrier of 3 μm thick used in Example 1. Fine copper particles were adhered to the surface and roughened, and the surface roughness (Rzjis) after the roughening treatment was 1.9 μm. Next, in the same manner as in Example 1, a copper-clad laminate was obtained.

Removal of the copper foil layer: using a commercially available sulfuric acid-hydrogen peroxide aqueous copper etching solution, The copper foil layer exposed on the surface of the copper-clad laminate is completely dissolved and formed on the surface of the resin substrate having the cured adhesive layer on the surface.

Desizing treatment: a resin substrate having a hardened adhesive layer on the surface is immersed in the degumming liquid used in the above "(1) Evaluation of degreasing resistance", and the same degumming is performed. deal with.

Electroless copper plating: Next, on the surface of the resin substrate having the hardened adhesive layer on the surface after the desmear treatment, an electroless copper plating layer is formed as a seed layer to form an electroless copper plating layer. Resin substrate. At this time, a process used in commercially available electroless copper-plated copper (using an electroless copper plating process manufactured by Shangcun Industrial Co., Ltd.) was used.

Baking: At the end of electroless copper plating, the resin substrate with the electroless copper plating layer is subjected to heat treatment at 150 ° C for 30 minutes in an atmospheric environment.

Circuit formation: a plating resist is formed at a portion where a circuit for forming an electroless copper plating layer of a resin substrate with an electroless copper plating layer is not formed. Next, copper plating is performed, and copper is deposited in a portion where the plating resist does not exist to form an electric circuit. Further, peeling of the plating resist is performed to form a circuit shape on the surface of the substrate.

Photolithography: Finally, a commercially available sulfuric acid-hydrogen peroxide aqueous copper etching solution is used to remove the electroless copper plating layer on the surface of the resin substrate with the electroless copper plating layer exposed between the circuits, and washed with water. After drying, a copper circuit having a circuit width of 0.4 mm and a circuit thickness of 18 μm was obtained, and a printed wiring board having an evaluation sample for obtaining soldering characteristics was obtained. Next, the sample for peeling strength measurement and the sample for evaluation of welding characteristics were obtained from the printed wiring board.

[Comparative Example 4]

In Comparative Example 4, a printed wiring board was produced by the SAP method in the same manner as in Example 6 except that the resin composition of the above Comparative Example 2 was used, and the sample for measuring the peel strength and the sample for evaluation of the welding property were obtained.

[Evaluation 2]

Using the samples of Example 6 and Comparative Example 4 produced as described above, (1) evaluation of tear strength and (2) evaluation of welding characteristics were performed. The evaluation methods and evaluation results are described below.

table 3.

Evaluation method

In the evaluation 2, "evaluation of tear strength" and "evaluation of welding characteristics" were the same as those of "evaluation 1" described above. Therefore, it is omitted because it is repeated.

2. Evaluation results (1) Evaluation of tear strength

Table 3 shows "Tear strength at normal time", "Tear strength after PCT", and "Degradation rate after PCT" measured using the samples for tear strength measurement produced in Example 6 and Comparative Example 4. As shown in Table 3, Example 6 using the same resin composition composed of a polyphenylene ether compound and a styrene butyl diblock copolymer as in Example 3 showed an average peeling strength of 0.52 in the normal state. Kgf/cm, the tear strength after PCT was 0.47 kgf/cm on average, and it was confirmed that the deterioration rate was 9.8%, and the moisture absorption deterioration resistance was obtained. On the other hand, Comparative Example 4 of the resin composition of Comparative Example 2 having the low desmear resistance described above showed an average tear strength of 0.28 kgf/cm in the normal state and an average peeling strength of 0.22 kgf after the PCT. /cm, the deterioration rate was 21.4%, and it was confirmed that the moisture absorption deterioration resistance was lowered. Therefore, the tear strength of Comparative Example 4 was lower than that of Example 6, and it was considered that the reason was that in the case of Comparative Example 4, the surface of the resin substrate was dissolved by the desmear treatment, and the roughening of the copper foil was replicated. The shape of the concavo-convex shape is reduced, and the specific surface area of the adjoining surface is reduced.

(2) Evaluation of welding characteristics

As shown in Table 3, Example 6 having an adhesive layer composed of a polyphenylene ether compound and a styrene butadiene block copolymer was confirmed to have good soldering properties as compared with Comparative Example 4.

Industrial availability

The copper foil with an adhesive layer of the present invention is a resin composition comprising a styrene butadiene block copolymer in an amount of from 10 parts by mass to 65 parts by mass based on 100 parts by mass of the polyphenylene ether compound. The formed layer is used as an adhesive layer, and can be bonded to the copper foil having the adhesive layer. When the resin substrate is used, the adhesion is good. Further, at the same time, even when the desmear treatment is included in the manufacturing step of the printed wiring board, the adhesive layer can be prevented from being dissolved in the desmear liquid. Further, it is possible to manufacture a printed wiring board having a sufficient tear strength in the normal state and having less deterioration in tear strength. Therefore, it is possible to provide a copper foil having an adhesive layer which can be preferably used as a material for producing a printed wiring board.

Claims (8)

A copper foil having an adhesive layer which is a copper foil having an adhesive layer on a single side of a copper foil and having an adhesive layer, wherein the adhesive layer is a polyphenylene ether derived from a main component a compound comprising 100 parts by mass or more and 65 parts by mass or less of a resin composition of a styrene butadiene block copolymer; wherein the polyphenylene ether compound has a hydroxyl group, a styryl group or a terminal thereof; The glycidyl group; and the above polyphenylene ether compound have a number average molecular weight of 500 to 4,000. The copper foil having an adhesive layer according to claim 1, wherein the adhesive layer is a styrene butadiene block copolymer containing 30 parts by mass or more and 55 parts by mass or less based on 100 parts by mass of the polyphenylene ether compound. A layer formed of a resin composition. A copper foil having an adhesive layer according to claim 1, wherein the adhesive layer is provided on a surface of a copper foil having a surface roughness (Rzjis) of 2 μm or less. The copper foil provided with an adhesive layer according to any one of claims 1 to 3, wherein the thickness of the adhesive layer is 0.5 μm to 10 μm. The copper foil with an adhesive layer according to claim 1, wherein the adhesive layer comprises an amine functional decane coupling agent, an acrylic functional decane coupling agent, a methacrylic acid functional decane coupling agent, and a vinyl functional group. One or more surface-treated filler particles selected from the decane coupling agent. A copper-clad laminate characterized by using a copper foil having an adhesive layer as claimed in claim 1. A printed wiring board characterized by using a copper clad laminate as claimed in claim 6. A printed wiring board characterized by using a copper-clad laminate according to claim 7, and removing a copper foil layer on the surface of the copper-clad laminate by etching, and forming a circuit by a semi-additive process .