JP5023732B2 - Laminated board - Google Patents

Description

  The present invention relates to a laminated board used for manufacturing a wiring board.

  As electronic devices become smaller, lighter, and more multifunctional, the form of LSIs and chip parts is rapidly changing to higher pins and smaller sizes. In connection with this, the necessity for further miniaturization of the wiring is increasing more about the printed wiring board which mounts an electronic component. The printed wiring board has responded to the miniaturization of wiring by reducing the thickness of the copper foil and increasing the etching accuracy, but the extension line of this technology has a limit due to the cost reduction. ing.

  In order to reduce the thickness of the copper foil, a total of three layers of metal foil with a thin film layer between the first layer copper foil and the second layer copper foil is used. The device which reduces copper foil thickness is performed (for example, refer patent document 1). However, newly incorporating a process for forming a thin film layer leads to complication of the process, and mixing of dust becomes a problem.

  On the other hand, copper foil reinforced with a plastic film or aluminum foil has been found in the market so that copper foil with an overall thickness of 5 μm or less called ultrathin copper foil can be easily handled. However, ultra-thin copper discards reinforced plastic film and aluminum foil, which is wasteful of resources and expensive, and technically thin, the pinhole inside the copper foil does not disappear completely. There are many issues such as.

  From such a background, a semi-additive method for forming a wiring without a copper foil has attracted attention. In this method, an insulating substrate that does not use copper foil is brought into contact with a chemical roughening treatment solution called desmear treatment to produce a concavo-convex shape on the insulating substrate, and then electroless plating that is a power supply layer for electrolytic plating After a layer is formed and a plating resist is further formed, only a portion necessary for electrolytic plating is pattern-plated. Therefore, since the thickness of copper can be adjusted arbitrarily, it is advantageous for miniaturization. Also, in order to ensure the adhesion between the electroless copper and the insulating substrate, an insulating resin layer dedicated to the electroless plating base is usually formed on the substrate, but do not provide an insulating resin layer for thinning. An electroless plating layer has been formed directly on a substrate. In this case, since the adhesiveness to the electroless plating layer is not taken into consideration for the base material, it is molded by pressurizing and heating so that the roughened surface of the copper foil becomes the side surface of the prepreg impregnated with the resin, Next, the copper foil is brought into contact with an etching solution such as ammonium persulfate, and the copper is chemically dissolved and removed to produce a copper foil roughened replica surface on the substrate surface on which the prepreg has been cured. Adhesiveness with the electroless plating is ensured by the anchoring effect due to the unevenness of the replica surface.

In such a background, the unevenness of the copper foil roughened surface tends to be smaller, and it is difficult to ensure adhesion with electroless plating by the anchoring effect due to the unevenness of the replica surface. The reason why the unevenness of the copper foil roughened surface is reduced is that when the wiring width and the wiring interval are narrowed, the flow of the etching solution becomes worse, and it becomes difficult to dissolve and remove the copper remaining in the concave portion. The unevenness of the replica surface is further reduced because the resin is dissolved in the desmear treatment process in addition to the unevenness of the copper foil roughened surface being reduced.
JP 2004-165547 A

  Therefore, it is desirable if a copper foil having a rough surface with small irregularities is used, and a base material that can ensure high adhesiveness with electroless copper after the desmear process has appeared.

  The present invention uses copper foil with small roughness on the roughened surface, and secures high adhesion to wiring copper used in the production of printed wiring boards produced by electroless copper plating in a state after passing through the desmear process. It aims at providing the laminated board which can be performed.

  The inventors of the present invention have intensively studied to solve the above-mentioned problems, and in order to ensure high adhesive strength with the wiring copper, the unevenness of the replica surface produced on the surface of the laminated board by removing the copper foil is not necessary. It is necessary that there is no change or little change before and after the desmear treatment. For this purpose, it has been found that it is important for the resin used for the laminate to exhibit poor solubility in the desmear treatment liquid, and the present invention has been completed based on these findings.

Thus, according to the present invention, the following inventions 1 to 7 are provided.
1. A glass cloth is impregnated with resin, and a laminated body is formed by stacking the glass cloth impregnated with resin to the required thickness, and copper foil having a surface roughness that becomes a circuit is formed on one or both surfaces of the laminated body. Are laminated with the surface having the surface roughness facing the surface of the laminate, pressed and heated together to form a laminate, and the copper foil of the laminate is chemically removed, and desmear is added to the laminate. Epoxy resin which is a laminated board used for manufacturing a wiring board by performing treatment and electroless copper plating, and the resin impregnating the glass cloth does not contain at least one of the second and third carbon atoms in the main skeleton , A resin composition containing any of polyphenylene ether and bismaleimide as an essential component, and further containing an epoxy resin, a curing agent for epoxy resin and an inorganic filler, and the surface roughness of the laminate after desmear treatment is an arithmetic average roughness Ra) at 0.1 to 1.5 [mu] m, laminates ten-point average roughness (Rz) is 1 to 6 m.
2. The copper foil has a surface roughness of 0.2 to 1.5 μm for arithmetic average roughness (Ra) display and 1.5 to 6 μm for ten-point average roughness (Rz) display. 2. The laminate as described in 1 above.
3. The laminated board of Claim 1 or 2 in which the said desmear process includes the contact process of swelling aqueous solution, and the contact process of permanganic-acid type strong alkali aqueous solution.
4). The electroless plating is in a range of 0.2 to 2 μm as a thickness of the electroless plating, and thereafter thickened to a predetermined wiring conductor thickness by electrolytic plating. Laminated board.
5. The laminate according to any one of 1 to 4, wherein the epoxy resin curing agent is blended in an amount of 0.5 to 1.5 equivalents relative to 1.0 equivalent of an epoxy group.
6). The laminated board as described in any one of 1 to 5 above, wherein the inorganic filler is blended in a range of 20 to 80% by mass in the whole solid sentence.
7). 2. The laminate according to 1, wherein the inorganic filler has an average primary particle size of 0.02 to 5 μm.

  The unevenness of the roughened surface due to desmear treatment is small, high unevenness difference is maintained, and when making a printed wiring board by performing electroless copper plating, a high anchoring effect is demonstrated and it is high with wiring copper A laminate having adhesiveness can be provided.

  The laminated board of the present invention has a small change in roughness of the roughened surface due to desmearing treatment, and the laminated board surface roughness after desmearing treatment is 0.1 to 1.5 μm in terms of arithmetic average roughness (Ra). The average roughness (Rz) is adjusted to 1 to 6 μm.

  The “ten-point average roughness (Rz)” referred to in the present invention is an average value of measured values obtained by dividing the scanning distance by ten.

  The reason why the roughness before and after the desmear process is important is that the adhesive strength between the copper circuit and the laminated board is ensured by the anchoring effect. This anchoring effect is sensitive to roughness, and the adhesive strength tends to decrease as the roughness decreases. That is, in order to ensure high adhesive strength, it is desirable that the surface roughness produced on the surface of the laminated board by removing the copper foil does not change or the change is as small as possible after the desmear treatment. For this purpose, it is preferable that the resin used for the laminate exhibits poor solubility in the desmear treatment liquid.

  In the present invention, the copper foil is removed, and the surface roughness of the laminated board after the desmear treatment is 0.1 to 1.5 μm in arithmetic average roughness (Ra) and 10-point average roughness (Rz). It adjusts so that it may become 1-6 micrometers. When the arithmetic average roughness is less than 0.1 μm in Ra and less than 1 μm in Rz, the anchoring effect is insufficient and the adhesive strength of the copper circuit to the laminate surface is not sufficient. Moreover, since the roughness is large when the arithmetic average roughness exceeds 1.5 μm in Ra and exceeds 6 μm in Rz, the wiring forming resist and the electroless copper are likely to remain between the irregularities, so that the wiring formability is improved. descend.

  In order to obtain the laminate surface roughness after the desmear treatment described above, the arithmetic average roughness (Ra) display is 0.2 to 1.5 μm, and the ten-point average roughness (Rz) display is 1.5 to 1.5. It is preferred to use any 6 μm copper foil. This is because it is necessary to reduce the roughness of the roughened surface in order to achieve finer wiring. For this purpose, the roughened surface roughness of the copper foil used is important. Since the roughened surface roughness of copper foil is often displayed as a ten-point average roughness (Rz) in a normal catalog, it may be adjusted with a ten-point average roughness. For example, a 10-point average roughness (Rz) with a copper foil roughened surface roughness of 4.0 μm has an arithmetic average roughness (Ra) of 0.7 μm. If this copper foil is used, the present invention The surface roughness of the laminate can be obtained.

  A commercial item can be used for the copper foil used by this invention. Examples of commercially available copper foil that can be used in the present invention include F1-WS foil (trade name: F1-WS foil, manufactured by Furukawa Circuit Foil Co., Ltd.), F2-WS foil (trade name: F2-WS foil). (10-point average roughness Rz: 2.1 μm), company name F3-WS foil (10-point average roughness Rz: 2.4 μm), company name GTS-MP foil (10-point average roughness Rz: 5. 5 μm), trade name YGP-9 foil (arithmetic mean roughness Ra: 0.84 μm) manufactured by Nippon Electrolytic Co., Ltd., trade name YGP-12 foil (arithmetic mean roughness Ra: 0.96 μm), trade name YGP- 18 foil (arithmetic average roughness Ra: 1.33 μm), trade name JTC-9 foil (ten-point average roughness Rz: 3.5 μm) manufactured by Nikko Materials Co., Ltd., trade name JTC-12 foil (ten points) Average roughness Rz: 4.0 μm), company name JTC-18 foil (ten-point average roughness Rz: 6) 0μm), and the like can be given.

  In order to produce the laminate of the present invention, a glass cloth is used as a substrate because it is excellent in chemical resistance, electrical insulation, heat resistance and dimensional stability. A glass cloth is impregnated with resin, and the glass cloth impregnated with resin is stacked by a desired thickness to form a laminate. The resin used is preferably a resin composition that is hardly soluble in a swelling aqueous solution or a permanganic acid strong alkaline aqueous solution used in the desmear treatment step.

  On one or both surfaces of the laminate, a copper foil having a surface roughness that becomes a circuit is laminated with the surface having the surface roughness facing the surface of the laminate, and the laminate is pressed and heated together. Is molded. Next, the copper foil of the laminate is chemically removed, and desmear treatment and electroless copper plating are applied to the laminate to produce a laminate.

  As a resin impregnated in the glass cloth, an epoxy resin, polyphenylene ether, or bismaleimide that does not contain at least one of the second and third carbon atoms in the main skeleton is included as an essential component, and further an epoxy resin and a curing agent for the resin And a resin composition containing an inorganic filler.

  The epoxy resin is not particularly limited as long as it is an epoxy resin having 2.0 or more epoxy groups, and includes biphenyl type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and the like. It can be used. These epoxy resins can be used in a liquid state, a solid state or a state containing a solvent.

  When a solvent is used, methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used. These solvents can be used alone or in combination.

  The blending amount of these epoxy resins is preferably in the range of 10 to 50% by mass, more preferably 15 to 40% by mass in the total solid component including the inorganic filler excluding the solvent. If the ratio of the epoxy resin is less than 10% by mass, the coating film becomes brittle, and the handling property in the state of the prepreg in which the glass cloth is impregnated with the resin is deteriorated. Moreover, when the ratio of an epoxy resin exceeds 50 mass%, a thermal expansion coefficient (thickness direction of a laminated board) will become large, and the connection resistance in a cooling-heat cycle test will deteriorate.

  A curing agent that cures the epoxy resin is also required. The curing agent is not particularly limited as long as it reacts with an epoxy group by heating, and a general one can be used. For example, various phenol resins, acid anhydrides, amines, hydragits, etc. can be used, but dicyandiamide is preferred from the viewpoint of adhesion to outer layer copper, and dicyandiamide and novolak phenol are used in combination considering heat resistance and insulation. More preferably.

  These epoxy resin curing agents are preferably used in an amount of 0.5 to 1.5 equivalents relative to 1.0 equivalent of epoxy groups. When the curing agent for epoxy resin is less than 0.5 equivalent with respect to the epoxy group, the solder heat resistance after the boiling treatment is reduced, and when it exceeds 1.5 equivalent, the solubility in the desmear treatment liquid is insufficient due to insufficient curing. As a result, the replica shape cannot be maintained, and Tg and insulation are lowered.

  In the present invention, as a component that plays an important role in suppressing the amount of change in replica shape before and after desmear treatment, an epoxy resin, polyphenylene ether, or bismaleimide that does not contain at least one of the second and third carbon atoms in the main skeleton is used. It is preferable to include any one or a mixture thereof as a component in the resin composition. Polyphenylene ether is also called modified PPE, and a copolymer of poly (2,6-dimethyl-1,4-phenylene) ether can be used, and both ends are hydroxyl, epoxy, cyanate, styrene, etc. Resin modified with can also be used.

  As the bismaleimide, 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′- Either diphenylmethane bismaleimide or 4-methyl-1,3-phenylenebismaleimide can be used.

Examples of the epoxy resin that does not include at least one of the second and third carbon atoms in the main skeleton include those that do not include a —CH group or a —CH ₂ group in the main chain, and include a biphenol type epoxy resin and a naphthalene type epoxy resin. , Dicyclopentadiene type epoxy resin, tetraphenylethane type epoxy resin, triphenylmethane type epoxy resin, xanthene type epoxy resin and the like.

  The amount of the epoxy resin, polyphenylene ether, and bismaleimide that does not contain at least one of the second and third carbon atoms in the main skeleton is the total solid component including the inorganic filler component excluding the solvent. The range of 0.3-10 mass% is preferable.

  When the compounding amount of the epoxy resin, polyphenylene ether or bismaleimide not containing at least one of the second and third carbon atoms in the main skeleton is less than 0.3% by mass, the effect of suppressing the amount of change in the replica shape is small. The adhesive strength between the copper circuit and the laminated board is 0.5 kN / m or less, causing problems such as peeling of the circuit. On the other hand, when the blending amount exceeds 10% by mass, the adverse effect on each characteristic becomes remarkable. For example, when the blending amount of polyphenylene ether exceeds 10% by mass, the solder heat resistance is lowered, and the blending amount of the epoxy resin containing no bismaleimide and at least one of the second and third carbon atoms in the main skeleton is 10%. When it exceeds%, the solder heat resistance after boiling water treatment decreases.

  In the present invention, it is preferable to use a material having an average primary particle diameter of 0.05 to 5 μm as the inorganic filler. When the average primary particle diameter is less than 0.05 μm, the filler tends to aggregate at the stage where it comes into contact with the solvent, which tends to cause a decrease in insulating properties. On the other hand, when the average primary particle diameter exceeds 5 μm, the insulating characteristics are likely to be similarly lowered.

  Specific examples of the inorganic filler are silica, aluminum hydroxide, talc, clay, titanium oxide, barium titanate, calcium carbonate, zirconium silicate, etc., but it has a low thermal expansion coefficient and high solder heat resistance when used as a laminate. From the viewpoint, it is most preferable to use silica. These inorganic fillers can be used either as solid (powder) or dispersed in a solvent. Moreover, you may process an inorganic filler with a coupling agent etc. as needed. As the silica, either crushed silica or synthetic spherical silica can be used, but synthetic spherical silica is preferred from the viewpoint of uniformity of flow rate distribution.

  The blending amount of the inorganic filler is preferably in the range of 20 to 80% by mass, more preferably 30 to 70% by mass in the total solid content. When the proportion of the inorganic filler is less than 20% by mass, the coefficient of thermal expansion increases and the connection resistance is deteriorated as described above. On the other hand, since the inorganic filler has a property of being easily dissolved in the desmear treatment liquid, it becomes difficult to maintain the replica shape before and after the desmear treatment when the blending amount exceeds 80% by mass.

  The resin impregnated in the glass cloth described above includes, as other components, a silane coupling agent that improves the wettability between the glass cloth and the resin, and suppresses oxidation due to heating of the copper foil contacting the resin side. Antioxidants, curing accelerators, flame retardants and the like may be added in amounts that do not impair the effects of the present invention.

  The resin composition impregnated into the glass cloth is dissolved in a solvent and impregnated into the glass cloth. Examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, xylene, toluene, acetone, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide and the like. Can be used. These solvents may be used alone or in a mixed system.

  The ratio of the solvent to the resin may be a ratio used in the past, and the amount used is adjusted according to the amount of adhesion impregnated into the glass cloth. The resin composition in the present invention is impregnated into a glass cloth and then dried to obtain a prepreg in a B-stage.

  A method for producing this prepreg may use a known technique and is not particularly limited. The drying conditions are adjusted by gel time to such an extent that the solvent is volatilized and the glass cloth is melted when heated and pressed to laminate with a copper foil.

  Next, a necessary number of prepregs are stacked so as to have a desired thickness of the laminated plate, and copper foil is placed on one side or both sides of the laminated plate and heated and pressed to be laminated. Lamination conditions can be carried out under the same conditions as for ordinary epoxy resin laminates. For example, the temperature is raised from 35 ° C. over 50 minutes at a rate of temperature rise of 3 ° C./min to 185 ° C., and the pressure is 2 Holding at 0.0 to 3.0 MPa for 60 to 90 minutes, and then cooling to room temperature in 30 minutes to produce a laminate.

  Without impregnating the glass cloth with the resin impregnated in the glass cloth, it is applied to the copper foil and dried to form a B-stage, and this copper foil with resin is epoxy resin-based, cyanate ester resin, benzoate. A laminate can also be produced by impregnating any oxazole resin-based resin and pressurizing and heating together with the B-staged prepreg. The application of the resin to the copper foil can be performed by roll coating, gravure coating or the like of an existing method. The drying conditions may be any conditions that allow the solvent to volatilize, and drying is performed, for example, at 70 to 120 ° C. for 2 to 15 minutes.

  The resin thickness or the coater gap is adjusted so that the thickness of the resin is in the range of 10 to 100 μm after drying. The prepreg to be pressed and heated together with the copper foil with resin can be any of epoxy resin, cyanate ester resin, and benzoxazole resin, and the resin is not limited.

  An electrical connection hole is formed in the manufactured laminate using a known technique such as a drill or a laser. This electrical connection hole may be formed after the copper is removed by etching. The copper foil is then etched away. This etching is to dissolve metals chemically. In the case of copper, copper is dissolved and removed using known techniques such as ferric chloride / hydrochloric acid aqueous solution, ammonium persulfate aqueous solution, sulfuric acid / hydrogen peroxide aqueous solution. To do. And it transfers to a desmear process and an electroless-plating process.

  The desmear treatment preferably includes a contact step of the swelling aqueous solution and a contact step of the permanganic acid strong alkaline aqueous solution. The contact step of the swelling aqueous solution is a step of treating the laminated board from which copper has been removed with a mixed aqueous solution of alcohol and alkali. This mixed aqueous solution of alcohol and alkali is an aqueous solution in which diethylene glycol monobutyl ether and sodium hydroxide are mixed. The ratio of the mixed aqueous solution is, for example, 100 to 400 ml / l for diethylene glycol monobutyl ether and 1 to 10 g / l for sodium hydroxide, and is also available as a commercial product. For example, Securigant P (trade name, manufactured by Atotech Japan Co., Ltd.), Circposite MLB Conditioner 211 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.), and the like are also referred to as sweller liquids.

  As a method of contacting the laminate with the swelling aqueous solution, a spray method, a dip method, a jet method, or the like can be used. In the case of the dip method, the condition is immersed in the swelling aqueous solution at 60 to 90 ° C. for 2 to 20 minutes. .

  Then, it passes to the contact process of a permanganate type strong alkali aqueous solution through a water washing process. This permanganate-based strong alkaline aqueous solution is obtained by, for example, dissolving an oxidizing agent such as sodium permanganate or potassium permanganate and sodium hydroxide as an alkali source in water. The ratio is 30 to 80 g / l for sodium permanganate or potassium permanganate and 20 to 60 g / l for sodium hydroxide.

  An aqueous solution in which such an oxidizing agent and an alkali source are dissolved in water is also available as a commercial product. For example, Concentrate Compact CP (manufactured by Atotech Japan Co., Ltd., trade name), Circoposit MLB promoter 213 ( Rohm & Haas Japan Co., Ltd., trade name), etc., also called a manganese etching solution.

  For example, a spray method, a dip method, a jet method, or the like can be used as a method for contacting the laminate with the permanganic acid strong alkaline aqueous solution. For example, in the case of the dip method, the laminate is immersed in a permanganic acid strong alkaline aqueous solution at 60 to 90 ° C. for 4 to 30 minutes.

  Thereafter, in order to neutralize manganese, for example, a hydroxylamine sulfate aqueous solution or a sulfuric acid / hydrogen peroxide aqueous solution is used for 3 to 10 minutes at 40 to 45 ° C. Such a neutralizing agent is also available as a commercial product. Reduction Solution Securigant P-500 (Atotech Japan Co., Ltd., trade name), MLB New Trizer 216 (Rohm & Haas Japan Co., Ltd., trade name) ) And the like.

  Next, the process proceeds to a pretreatment process of electroless plating, and these processes can adopt known methods. For example, the laminate is treated for 5 minutes at 60 ° C. in a 100 ml / l aqueous solution of a conditioner solution (trade name CLC-501) sold by Hitachi Chemical Co., Ltd., washed with water, and pre-dip solution (trade name PD -201) Treated in an aqueous solution at room temperature (25 ° C.) for 3 minutes, treated in an aqueous solution containing a metal palladium solution (trade name HS-202B) at room temperature (25 ° C.) for 10 minutes, washed with water, Trade name ADP-501) Treat in aqueous solution at room temperature (25 ° C.) for 5 minutes.

  Through these pretreatment steps, an electroless plating layer is formed on the laminate. The electroless plating layer can be produced by bringing a substrate that has been pretreated with the electroless plating into contact with an electroless plating solution. As this contact method, there are a horizontal conveyance type, a dip type, and the like, and any of them may be used.

  Moreover, it is preferable to make the thickness of electroless plating into the range of 0.2-2 micrometers. If the thickness of the electroless plating is less than 0.2 μm, the solder heat resistance is lowered. On the other hand, if the thickness exceeds 2 μm, the precipitation tends to occur between the electroless plated copper and the laminate, which is not preferable. The type of the electroless plating solution is not particularly limited, and a commercially available Rochelle salt-based or EDTA-based electroless copper plating solution can be used. As the electroless copper plating solution for the base, for example, Cust-201, Cust-1160, Cust-4600 (trade name, manufactured by Hitachi Chemical Co., Ltd.), Sulcup PEA (trade name, manufactured by Uemura Industrial Co., Ltd.), OPC Copper H (Trade name) manufactured by Okuno Pharmaceutical Co., Ltd. can be used.

Then, the substrate is washed with water, dried, and plated up to the required thickness using electrolytically plated copper. In the case of the semi-additive method, the plating resist is stripped, and in the case of the subtractive method such as the tenting method, the copper is used. Is dissolved and removed (etched) with a liquid such as ammonium persulfate to produce a wiring conductor to obtain a wiring board.
EXAMPLES Hereinafter, although this invention is demonstrated in detail according to an Example, this invention is not limited to these Examples.

Example 1
(1) Preparation of glass cloth impregnating resin A glass cloth impregnating resin having the following composition was prepared.
・ Novolac phenol type epoxy resin, N-770 (Dainippon Ink Co., Ltd., trade name) 30g
・ Novolac phenol resin, HP-850 (trade name, manufactured by Hitachi Chemical Co., Ltd.)
16g
・ Dicyandiamide (trade name, manufactured by Nippon Carbide Corporation) 0.04g
Silica, SO-G1, average particle size 0.2 to 0.4 m (trade name, manufactured by Admatechs Co., Ltd.) 48 g
・ Antioxidant, Yoshinox BB (trade name, manufactured by API Corporation) 0.6 g
・ Polyphenylene ether, PPO SA120 (trade name, manufactured by GE Plastics, Inc.) 6g
・ Solvent, methyl ethyl ketone (reagent) 80g

(2) Production of copper-clad laminate The resin produced in (1) was impregnated into a 0.2 mm thick glass cloth (basis weight 210 g / m 2) and heated at 160 ° C. for 3 minutes to be semi-cured (B stage state) ) Prepreg was obtained. Four prepregs are stacked, and 18 μm product name F2-WS copper foil (Rz: 2.0 μm, Ra: 0.3 μm) is stacked on both sides of the prepreg. Both surfaces are pressed at 175 ° C. for 90 minutes at 2.5 MPa. A copper clad laminate was prepared.

(3) Preparation of laminated board with plated copper The copper-clad laminate produced in (2) was immersed in an aqueous solution of ammonium persulfate 150 g / l at 40 ° C. for 20 minutes to remove the copper foil by etching. Next, a part of the laminated board from which the copper foil was removed was extracted, and this sample was measured with a measurement depth of 149 μm, a magnification of 2000 times, and a resolution of 0.05 μm using an ultra-deep shape measurement microscope VK-8500 manufactured by Keyence Corporation. Under the conditions, the arithmetic average roughness (Ra) and ten-point average roughness (Rz) in the measurement length of 149 μm were determined.

  Next, the laminate from which the sample was not removed was immersed in a circulated MLB conditioner 211 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.) of a swelling aqueous solution at 80 ° C. for 5 minutes by the dipping method. Further, after 3 minutes of treatment at room temperature in running water, Circoposit MLB promoter 213 (trade name, manufactured by Rohm & Haas Japan Co., Ltd.) is used as a strongly alkaline aqueous solution of permanganate, and similarly at 80 ° C. for 10 minutes by the dip method. Immersion treatment.

  Subsequently, immersion treatment was performed at 40 ° C. for 5 minutes by a dip method using MLB Neutralizer 216 (Rohm & Haas Japan Co., Ltd., trade name) as a neutralizing solution. After treatment with running water at room temperature for 3 minutes, conditioner solution CLC-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.) was used for 5 minutes at 60 ° C., washed with running water, and pre-dip solution PD-201 (product). Name, manufactured by Hitachi Chemical Co., Ltd.) in an aqueous solution at room temperature for 3 minutes, treated in an aqueous solution containing a metal palladium solution HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 10 minutes at room temperature, and washed with water. Then, it was treated at room temperature for 5 minutes in an aqueous solution of activation treatment liquid ADP-501 (trade name, manufactured by Hitachi Chemical Co., Ltd.). Then, by using Cust-201 as an electroless copper plating solution, a base copper having a thickness of 0.5 μm is formed on both sides of the laminate by dipping at room temperature for 15 minutes, and further on the electrolytic copper. Then, the copper was plated up to a thickness of 20 μm.

Then, a photosensitive dry film H-9638 (trade name, manufactured by Hitachi Chemical Co., Ltd.) is laminated and exposed through a photomask in which a line / space 30/30 μm is formed (50 mj / cm ² ), Development with 1% by weight of sodium carbonate was carried out, and the portion where the resist was not attached was removed with ammonium persulfate, and the wiring pattern formability was examined. In this wiring pattern formability, the wiring width and the space width are within ± 10% of the design value (30/30 μm), and the insulation resistance in the formed wiring pattern is 10 ¹⁰ Ω or more. did.

On the other hand, the wiring width and the space width varied by plus or minus 10% or more with respect to the design value (30/30 μm), and the insulation resistance in the formed wiring pattern was 10 ¹⁰ Ω or less. Moreover, the adhesive strength with a copper circuit was measured by a solder heat resistance test at 288 ° C., and the surface of the portion where the copper was removed by etching was measured with an ultra-deep shape measurement microscope VK-8500 manufactured by Keyence Corporation. The arithmetic average roughness (Ra) and ten-point average roughness (Rz) in the measurement length of 149 μm were determined under the conditions of a thickness of 149 μm, a magnification of 2000 times, and a resolution of 0.05 μm.

The adhesive strength and the 288 ° C. solder heat resistance test were measured by the following methods:
-Adhesive strength between the copper circuit and the laminated board The sample copper prepared in (2) above is processed into a copper width 10 mm, length 100 mm line by etching, this one end is peeled off and grasped with a grasping tool, and JIS-C- In accordance with 6421, the load when peeled off in the vertical direction at about 50 mm at room temperature was measured.
-288 degreeC solder heat resistance The sample produced by said (2) was cut | disconnected to 25 square mm, it floated in the solder bath adjusted to 288 degreeC +/- 2 degreeC, and the time until blistering was investigated.

Example 2
In the resin composition of Example 1 (1), polyphenylene ether is bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane BMI-5100 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) ) Without changing the blending amount. Others were performed in the same manner as in Example 1.

Example 3
In the resin composition of Example 1 (1), naphthalene type epoxy resin HP-4032 (trade name, manufactured by Dainippon Ink Co., Ltd.) is used as an epoxy resin that does not contain at least one of the second and third carbon atoms in the main skeleton. It was replaced without changing the blending amount. Others were performed in the same manner as in Example 1.

Example 4
In Example 1, the copper foil was changed from F2-WS to JTC 12 μm (Rz: 4 μm, Ra: 0.7 μm, trade name, manufactured by Nikko Materials Co., Ltd.). Others were performed in the same manner as in Example 1.

Example 5
In Example 1, electroless plating was replaced from Cust-201 to Cust-1160, and electroless plating was performed at 35 ° C. for 15 minutes to obtain an electroless plated copper thickness of 0.8 μm. Others were performed in the same manner as in Example 1.

Example 6
Without impregnating the glass cloth with the resin prepared in Example 1 (1), the surface of the copper foil was coated with a roll coater at a gap between rolls of 180 μm using a roll coater. And it dried at 110 degreeC for 10 minute (s) so that the resin film thickness after drying might be set to 50 micrometers. This resin-coated copper foil was pressure-heated together with LX-67 prepreg (trade name, manufactured by Hitachi Chemical Co., Ltd.) in four layers. The pressing was performed under the conditions of 210 ° C., 90 minutes, and 2.5 MPa. Others were performed in the same manner as in Example 1.

Example 7
In the resin composition of Example 1 (1), the amount of silica and SO-G1 was 24 g, and 30 g of aluminum hydroxide H-42M (trade name, manufactured by Showa Denko KK) was newly added. Others were performed in the same manner as in Example 1.

Example 8
In the resin composition of Example 1 (1), 3 g of bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane BMI-5100 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) Added. Others were performed in the same manner as in Example 1.

Comparative Example 1
In the resin composition of Example 1 (1), only polyphenylene ether was removed. Others were performed in the same manner as in Example 1.

Comparative Example 2
In Example 1, the copper foil was changed from F2-WS to YGP-18 [mu] m (Rz: 7.5 [mu] m, Ra: 1.33 [mu] m, trade name, manufactured by Nihon Electrolytic Co., Ltd.). Others were performed in the same manner as in Example 1.

Comparative Example 3
In the resin composition of Example 1 (1), the following composition was used in which the amount of the thermosetting agent used was 0.39 equivalent to the epoxy group. Others were performed in the same manner as in Example 1.
-Novolac phenol type epoxy resin, N-770 (Dainippon Ink Co., Ltd., epoxy equivalent 189): 46 g
-Novolac phenol resin, HP-850 (trade name, manufactured by Hitachi Chemical Co., Ltd., hydroxyl equivalent 102): 9.6 g
Dicyandiamide (Nippon Carbide Corporation, amine equivalent: 21): 0.02 g
Silica, SO-G1, average particle size 0.2 to 0.4 m (trade name, manufactured by Admatex Co., Ltd.): 48 g
・ Antioxidant, Yoshinox BB (trade name, manufactured by API Corporation): 1.6 g
・ Polyphenylene ether, PPO SA120 (trade name, manufactured by GE Plastics, Inc.): 6g
・ Solvent, methyl ethyl ketone (reagent): 80 g

  In these Examples and Comparative Examples, arithmetic average roughness (Ra) and ten-point average roughness (Rz) after desmear treatment were measured. Moreover, the adhesive strength with a copper circuit, a 288 degreeC solder heat resistance test, and the wiring formation property of a line / space 30/30 micrometer were evaluated.

  The results are shown in Tables 1 and 2. The units of arithmetic average roughness (Ra) and ten-point average roughness (Rz) in Tables 1 and 2 are “μm”.

  In Tables 1 and 2, the comb pattern is shown in FIG.

As is clear from Tables 1 and 2, in Comparative Example 1, the 10-point average roughness Rz after the desmear treatment was outside the range of the present invention, and in this case, the adhesive strength value was small.
In Comparative Example 2, the arithmetic average roughness Ra and the ten-point average roughness Rz for the laminate after desmear treatment were outside the scope of the present invention, and in this case, the line / space was short-circuited.
In Comparative Example 3, the arithmetic average roughness and the ten-point average roughness Rz after desmear treatment were outside the scope of the present invention, and in this case, the adhesive strength value was small.

  On the other hand, in Examples 1-8, all of adhesive strength, 288 degreeC solder heat resistance, and the line / space were favorable.

  The present invention can be suitably used as a laminate used for manufacturing a printed wiring board on which electronic components are mounted.

The comb pattern is shown.

Claims (7)

The resin composition was impregnated into glass cloth, the resin composition overlaid by the thickness of the necessary impregnated glass cloth molding the laminate on one or both surfaces of the laminate, the surface roughness of the circuit the copper foil with is, pressing a surface having a surface roughness with overlaid toward the surface of the laminate, heating and molding the laminate, for the laminate, chemical the copper foil after removal, de smear process, a laminate used to manufacture the wiring board is subjected to electroless copper plating,
The resin composition comprises an epoxy resin not containing at least one of the second and third carbon atoms in the main skeleton, at least one of polyphenylene ether and bismaleimide, and an epoxy resin (provided that the second and third carbon atoms are not included). Including an epoxy resin that does not contain at least one of the third carbon atoms in the main skeleton), a curing agent for epoxy resin, and an inorganic filler,
The content of at least one of epoxy resin, polyphenylene ether and bismaleimide not containing at least one of the second and third carbon atoms in the main skeleton is 0.3 to 0.3 in the solid component of the resin composition. (6 × 100 / 100.64)% by weight,
The laminated board surface roughness of the laminated board after the said desmear process is 0.1-1.5 micrometers in arithmetic mean roughness (Ra), and 10-point average roughness (Rz) is 1-6 micrometers.   The copper foil has a surface roughness of 0.2 to 1.5 μm for arithmetic average roughness (Ra) display and 1.5 to 6 μm for ten-point average roughness (Rz) display. The laminate according to claim 1.   The laminated board of Claim 1 or 2 in which the said desmear process includes the contact process of swelling aqueous solution, and the contact process of permanganic-acid type strong alkali aqueous solution.   The electroless plating is in a range of 0.2 to 2 μm as a thickness of the electroless plating, and is then thickened to a predetermined wiring conductor thickness by electrolytic plating. The laminated board of description.   The laminated board as described in any one of Claims 1-4 with which the said hardening | curing agent for epoxy resins is mix | blended 0.5-1.5 equivalent with respect to 1.0 equivalent of epoxy groups.   The laminated board as described in any one of Claims 1-5 with which the said inorganic filler is mix | blended in the range of 20-80 mass% in a total solid sentence.   The laminate according to claim 1, wherein the inorganic filler has an average primary particle diameter of 0.05 to 5 μm.

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