JP2010021302A - Printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printed wiring board which has fine-wiring wirability and insulation reliability. <P>SOLUTION: The printed wiring board includes wiring and an insulating material and has substantially no electroless plating catalyst between wiring lines of the printed wiring board, and is characterized in that the ratio X/Y of a wiring thickness X to an insulating layer thickness Y is 0.01 to 0.5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a printed wiring board.

  2. Description of the Related Art In recent years, electronic devices have been rapidly improved in performance, function, and size, and accordingly, there is an increasing demand for downsizing and weight reduction of electronic components used in electronic devices. In response to the above requirements, semiconductor device packaging methods and wiring boards on which they are mounted are required to have higher density, higher functionality, and higher performance.

  As a method for obtaining a printed wiring board, a full additive printed wiring board can be exemplified.

  As a conventional method for producing a full additive printed wiring board, an adhesive layer containing an electroless plating catalyst is applied and formed on a glass epoxy substrate containing an electroless plating catalyst to obtain a laminate. Next, through holes are selectively formed in the laminate. Next, desmear removal is performed, after which an electroless copper plating catalyst is applied in the through hole, and a permanent resist layer is applied and formed by a screen printing method. Next, there is a method in which the permanent resist is patterned by a method such as exposure and development, and further electroless plating is performed to obtain a wiring at a desired location (see, for example, Patent Document 1). A method of forming a thick wiring layer only by electroless plating is called a full additive method, and is distinguished from a subtractive method and a semi-additive method.

However, in the above manufacturing method, because the electroless plating catalyst that retains the activity is contained in the entire surface of the insulating resin, the wiring is caused by abnormal deposition at the location where the electroless plating catalyst exists, particularly in the case of fine wiring. There is a problem in that they are electrically connected to each other and the insulation reliability is lowered.
Japanese Patent Laid-Open No. 11-40923

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a printed wiring board having high insulation reliability between layers as well as within the layers.

  As a result of intensive investigations in view of the above problems, the present inventors have determined that the ratio X / Y of the thickness between the wiring thickness X and the insulating layer thickness Y is substantially absent between the wirings and the wiring thickness X and the insulating layer thickness Y are specified. The inventors have found that the problem can be solved by making the range, and have completed the present invention.

  That is, the present invention is a printed wiring board containing wiring and an insulating material, and there is substantially no electroless plating catalyst between the wirings of the printed wiring board, and the wiring thickness X and insulating layer thickness Y The present invention relates to a printed wiring board having a thickness ratio X / Y in the range of 0.01 to 0.5. The printed wiring board is preferably manufactured by a manufacturing method including at least a step of forming a wiring by forming a groove in an insulating layer and depositing electroless plating inside the formed groove. Further, it is preferable that at least a part of the insulating layer contains at least one compound selected from the group consisting of a compound having sulfur, a compound having chromium, and a compound having an oxime structure.

  The printed wiring board according to the present invention is excellent not only in the fine wiring formability but also in the insulation reliability between layers.

  Embodiments of the present invention will be described below.

(Printed wiring board)
The printed wiring board of the present invention is a printed wiring board containing wiring and an insulating material. There is substantially no electroless plating catalyst between the wirings of the printed wiring board, and the wiring thickness X and the insulating layer thickness Y. The thickness ratio X / Y is in the range of 0.01 to 0.5. Since there is no electroless plating catalyst between the wires, the insulation reliability within the layer is high. In addition, by forming an insulating layer sufficiently thicker than the wiring thickness, there is an advantage that insulation reliability between layers is excellent.
Such a printed wiring board is preferably manufactured by a manufacturing method including at least a step of forming a wiring by forming a groove in the insulating layer and depositing electroless plating inside the formed groove. In this case, a full additive type electroless plating is used for the electroless plating.

  Moreover, it is preferable that the insulating layer has a characteristic that electroless plating is deposited at the locations where the grooves are formed, and electroless plating is not deposited at other locations.

  Here, the printed wiring board referred to in the present invention refers to a board in which a conductive wiring pattern is formed on an insulating layer, and is composed of at least wiring and an insulating layer.

  Further, in the present invention, the fact that the electroless plating catalyst is substantially absent means that the corresponding portion is subjected to XPS analysis and the calculated atomic concentration is 0.2% or less.

(Insulating layer)
The insulating layer constituting the printed wiring board of the present invention will be described.

  It is preferable that the insulating layer preferably applicable to the printed wiring board of the present invention has a characteristic that electroless plating is deposited at a location where a groove is formed and electroless plating is not deposited at other locations.

  One of the preferred embodiments of the insulating layer having the characteristic that the electroless plating is deposited at the location where the groove is formed as described above and the electroless plating is not deposited at the other location is an insulation where the electroless plating is not deposited. It is an insulating layer using an insulating material in which electroless plating is specifically deposited only at a portion where a groove is formed. In order to deposit electroless plating specifically only at the location where the groove is formed, for example, when applying a method of forming the groove by laser irradiation, the resin surface of the groove formed portion is chemically modified by laser irradiation. Alternatively, the electroless plating may be formed by utilizing either or both of the physical modification or both.

  Another preferred embodiment is an insulating material on which electroless plating is deposited, and an insulating layer on which electroless plating is not deposited only on the surface. In order to prevent electroless plating from depositing only on the surface, for example, when applying a technique of forming grooves by laser irradiation, the resin surface of the groove-formed portion is chemically modified by laser irradiation or physically Any one or both of the modifications may be used so that the electroless plating is not formed.

  Also, the insulating layer is composed of an insulating resin layer on which electroless plating is not deposited / an insulating resin layer on which electroless plating is deposited, and the insulating resin layer on which electroless plating is not deposited is removed to deposit electroless plating. If the groove is formed so that the layer to be exposed is exposed, the electroless plating can be deposited only at the portion where the groove is formed.

  Here, an insulating material on which electroless plating is not deposited will be described.

  In the present invention, electroless plating does not deposit means that when electroless plating is deposited to a thickness of a μm at a location where electroless plating is deposited, a thickness of a × (1/7) μm or less is deposited. Is defined. For example, when electroless plating is deposited to a thickness of 7 μm at a location where electroless plating is deposited, the electroless plating is deposited to a thickness of 1 μm or less on an insulating material on which electroless plating is not deposited. Here, the electroless plating layer deposited by a thickness of a × (1/7) μm or less can be removed by a known method such as soft etching with an acidic aqueous solution. Therefore, finally, the electroless plating is not substantially formed on the insulating material on which the electroless plating does not deposit, and the electrical insulation can be maintained. Of course, when the electroless plating is not substantially deposited on the insulating material on which the electroless plating is not deposited, it is not necessary to perform soft etching or the like.

  The insulating material that does not deposit electroless plating according to the present invention may be an insulating material that does not deposit electroless plating because no electroless plating catalyst is applied. Insulating material that does not deposit electroless plating may be used, and an electroless plating catalyst is provided, but since the catalytic activity is low, the electroless plating has a thickness of a μm on the resin layer on which electrolytic plating is deposited. Alternatively, an insulating material that deposits only by a thickness of a × (1/7) μm or less may be used.

  In order to prevent the electroless plating catalyst from being applied, the electroless plating catalyst and the insulating material surface on which the electroless plating is not deposited may be in a state where they do not interact with each other. For example, when the electroless plating catalyst has a feature of interacting with and adsorbing amino groups, it can inhibit the application of the electroless plating catalyst by preventing the amino groups from being introduced into the resin layer surface. it can.

  Further, if the catalyst concentration on the surface of the insulating material where electroless plating does not deposit is 0.2% or less as the atomic concentration calculated by XPS analysis, electroless plating tends not to deposit, which is preferable. When the catalyst concentration is higher than 0.2%, the electroless plating is likely to be deposited.

  Although the above electroless plating catalyst is provided, in order not to show catalytic activity, a compound showing a catalyst poison for the electroless plating catalyst may be exposed on the surface of the insulating material where the electroless plating does not deposit. . In order to expose the compound showing the catalyst poison, the compound showing the catalyst poison may be added to the insulating material on which the electroless plating is not deposited, or it may be formed on the surface layer by a method such as coating and drying on the surface. good. For example, when the electroless plating catalyst loses catalytic activity due to the interaction with the phosphorus compound, the phosphorus compound is added to the resin layer, or the phosphorus compound is applied to the surface of the resin layer and dried. The catalytic activity of the electroplating catalyst can be deactivated.

  In addition, for example, when using an electroless plating catalyst, particularly a palladium catalyst generally used as an electroless copper plating catalyst, palladium is poisoned by a compound having sulfur and a compound having chromium. The catalytic activity of the electroless plating catalyst can be deactivated by a method such as coating and drying.

  The authors also discovered that palladium is poisoned by compounds having an oxime structure. This is considered because the compound having an oxime structure and palladium form a complex. Examples of the compound having an oxime structure include 1,2-octanedione-, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), and the like. For the compound having an oxime structure, the catalytic activity of the electroless plating catalyst can be deactivated by the same method as described above.

  To the insulating material on which the electroless plating of the present invention is not deposited, a thermoplastic resin, a thermosetting resin, a filler, a flame retardant, etc. are appropriately added for the purpose of improving mechanical properties and imparting flame retardancy. Also good.

  Next, an insulating material on which electroless plating is deposited will be described.

  As the resin layer on which the electroless plating according to the present invention is deposited, any insulating material may be used as long as the electroless plating is deposited.

  As a method for depositing electroless plating on an insulating material on which electroless plating according to the present invention is deposited, a method in which electroless plating is directly deposited, an electroless plating catalyst such as a palladium catalyst is applied, and then palladium is used as a nucleus. The method of depositing the electrolytic copper plating, etc. can be mentioned, but from the viewpoint of depositing the electroless copper plating evenly and uniformly, after applying an electroless plating catalyst such as a palladium catalyst, the electroless plating catalyst is used as a core. A method of depositing electroless copper plating is preferred. Resin from which the electroless plating according to the present invention is deposited from the viewpoint of adopting a method of depositing electroless plating using the electroless plating catalyst as a core, and from the viewpoint of insulation and heat resistance of the obtained printed wiring board. The layer preferably contains an epoxy resin and / or a polyimide resin, and more preferably contains a polyimide resin. Moreover, it is especially preferable to contain a thermoplastic polyimide resin from the viewpoint of adhesiveness with electroless plating.

  To the insulating material on which the electroless plating of the present invention is deposited, a thermoplastic resin, a thermosetting resin, a filler, a flame retardant, etc. are appropriately added for the purpose of improving mechanical properties and imparting flame retardancy. Also good.

  In the printed wiring board of the present invention, the thickness ratio X / Y between the wiring thickness X and the insulating layer thickness Y is in the range of 0.01 to 0.5. The wiring thickness X in the present invention refers to the thickness of wiring formed by electroless plating. The insulating layer thickness Y is the thickness of the insulating layer itself in the case of a printed wiring board made of a single insulating layer, and is a printed wiring board made by laminating an insulating material on an inner wiring board. In this case, it refers to the thickness of the insulating layer after being laminated. When X / Y is larger than 0.5, there is a risk that sufficient insulation reliability between layers may not be obtained. When X / Y is smaller than 0.01, insulation reliability between layers is sufficiently obtained. Since the wiring thickness is thin, the wiring function may not be achieved.

(Electroless plating)
The electroless plating used in the present invention is not particularly limited. Direct plating using carbon, palladium catalyst, organic manganese conductive film, etc., electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating , Electroless tin plating and the like, and can be used in the present invention.

  Among these, electroless copper plating and electroless nickel plating are preferable from the viewpoint of electrical characteristics such as productivity and migration resistance, and among electroless plating, electroless copper plating is particularly preferable. Hereinafter, electroless copper plating will be described.

  As a method for depositing electroless copper plating on the insulating material constituting the printed wiring board of the present invention, a method for directly depositing electroless copper plating, an electroless copper plating catalyst such as a palladium catalyst is applied, and then electroless copper plating is applied. A method of depositing electroless copper plating with a plating catalyst as a core, etc. can be mentioned, but from the viewpoint of depositing electroless copper plating uniformly, after applying an electroless copper plating catalyst such as a palladium catalyst, A method of depositing electroless copper plating using palladium as a nucleus is preferred.

  Here, the electroless plating catalyst referred to in the present invention refers to a catalyst that selectively forms a metal to be deposited on an insulating layer. For example, in the case of electroless copper plating, a palladium catalyst or the like is used as described above. Not limited to copper ions, metallic copper, and the like.

  The thickness of the electroless plating is not particularly limited and may be deposited up to a desired conductor layer thickness. However, from the viewpoint of forming fine wiring, the electroless plating thickness is preferably in the range of 1 μm to 30 μm.

  Moreover, after forming electroless plating with a thickness of about 5 μm or less, it may be deposited up to a desired conductor layer thickness by electrolytic plating.

  Further, a desmear process may be introduced before the electroless copper plating for the purpose of removing smear generated at the location where the groove is formed. As the desmear, any method such as wet desmear or dry desmear may be used.

  In the case of wet desmear, it is possible to use a commercially available desmear chemical solution and process, but generally it consists of three steps of swelling, roughening, and neutralization. An alkaline aqueous solution of potassium acid or sodium permanganate is used.

In the case of dry desmear, the case of using plasma, the case of using corona, etc. can be exemplified. In either case, both normal pressure and reduced pressure can be performed.
(Printed wiring board manufacturing method)
An example of the manufacturing method of the printed wiring board of this invention is shown.
The printed wiring board of the present invention can be manufactured by forming grooves in an insulating material and depositing electroless plating only in the formed grooves.

  The insulating material to be used is as described above. However, when roughly classified, the electroless plating is deposited at the location where the groove is formed, and the insulating material having the characteristic that the electroless plating is not deposited at the other location, or This is an insulating material on which electrolytic plating is deposited, and is an insulating material on which electroless plating is not deposited only on the surface.

  As a method for forming the groove, a known method such as photo, laser, or mechanical cutting may be applied.

  Thereafter, desmear treatment is performed as necessary, and then electroless copper plating is performed to form a wiring only at the location where the groove is formed.

  As mentioned above, although the example of the manufacturing method of the printed wiring board of this invention was shown, of course, it is not limited to this.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to these. In addition, the fine wiring formability in an Example and a comparative example was evaluated as follows.

[Fine wiring formability]
About the printed wiring board obtained by the Example and the comparative example, the case where conduction | electrical_connection was not confirmed by the wiring formation location of wiring width / wiring space | interval = 10micrometer / 10micrometer was made into pass, and the case where conduction was confirmed was made disqualified.

(Synthesis Example 1; Synthesis of thermoplastic polyimide precursor)
To a glass flask having a volume of 2000 ml, 58.46 g of DMF and 29.23 g (0.1 mol) of 1,3-bis (3-aminophenoxy) benzene were added and dissolved under stirring in a nitrogen atmosphere. , 4,4′-biphenyl ether tetracarboxylic dianhydride 31.02 g (0.1 mol) was added and stirred at 20 ° C. for about 3 hours to obtain a polyamic acid solution 1.

(Synthesis Example 2: Synthesis of thermoplastic polyimide resin)
In a glass flask with a volume of 2000 ml, 37 g (0.045 mol) of amino acid-modified silicone oil (KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.), 21 g (0.105 mol) of 4,4′-diaminodiphenyl ether, and DMF And dissolved with stirring, 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added, and the mixture was stirred at 20 ° C. for about 1 hour. A polyamic acid solution having a solid content concentration of 30% was obtained. The polyamic acid solution was put on a fluorine-coated vat and heated under reduced pressure at 665 Pa at 200 ° C. for 120 minutes in a vacuum oven to obtain polyimide resin 2.

(Formulation Example 1; Preparation 1 of a resin solution in which electroless plating does not deposit)
100 parts by weight of polyamic acid 1 obtained in Synthesis Example 1 (in terms of solid content), 10 parts by weight of bisphenol A EO-modified di (meth) acrylate (manufactured by Daicel Cytec Co., Ltd., product name EB150), bisphenol A EO-modified di ( 1,4-octanedione-, 1- [4- (phenylthio)-, 2- (O--) which is a compound having an oxime structure, 40 parts by weight of (meth) acrylate (manufactured by Hitachi Chemical Co., Ltd., product name FA321M) Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (Ciba Specialty Chemicals Co., Ltd.) Irgacure OXE 01) 2 parts by weight, bisphenol A bis (diphenyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name CR-741) 15 The amount unit, were mixed, homogeneously dissolved by adding dioxolane so that the solid content weight% (Sc) = 40%, to obtain a resin solution (a) electroless plating is not deposited.

(Formulation Example 2: Preparation 2 of a resin solution in which electroless plating does not deposit)
100 parts by weight of polyimide resin 2 obtained in Synthesis Example 2, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1 which is a compound having an oxime structure -(0-acetyl oxime) (Irgacure OXE 01 manufactured by Ciba Specialty Chemicals Co., Ltd.) 10 parts by weight is mixed, and dioxolane is added and uniformly dissolved so that the solid content weight% (Sc) = 20%. A resin solution (b) in which electroless plating does not precipitate was obtained.

(Formulation example 3; Preparation 1 of resin layer solution in which electroless plating is deposited)
The polyimide resin 2 obtained in Synthesis Example 2 was diluted with dioxolane to obtain a resin solution (c) in which electroless plating with a solid content of% by weight (Sc) = 20% is deposited.

(Formulation Example 4: Preparation of adhesive solution)
Into a glass flask having a capacity of 2000 ml, 87.7 g (0.30 mol) of 1,3-bis (3-aminophenoxy) benzene and DMF were added and dissolved while stirring, and 4,4 ′-(4,4 78 g (0.15 mol) of '-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred at 20 ° C. for about 1 hour to obtain a DMF solution of polyamic acid having a solid content concentration of 30%. The polyamic acid solution was placed on a fluorine-coated vat and heated under reduced pressure at 180 ° C. for 120 minutes at 665 Pa in a vacuum oven to obtain an imide oligomer.
12 g of dioxolane and 23 g of the imide oligomer 4 were weighed and dissolved by heating at 60 ° C. After adding 5.2 g of toluene, the mixture was cooled while stirring, 15 g of epoxy resin (JER152, manufactured by Japan Epoxy Resin Co., Ltd.) was added, and the mixture was stirred and mixed to obtain a solution X.
18 g of dioxolane and 2 g of polyimide resin (ULTEM-1000-1000, manufactured by GE Plastics) were weighed and dissolved by heating at 60 ° C. with stirring. After cooling, 6 g of filler (SFP-130MC phenylaminosilane-treated product, manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.53 μm) was added, and 7.7 g of toluene was further added, followed by mill dispersion. Liquid.
5.52 g of the X solution and 8.77 g of the Y solution were weighed and mixed with stirring, followed by filtration using a 40 μm diameter filter to obtain an adhesive solution (d).

Example 1
On a support (trade name: Lumirror T-60, manufactured by Toray Industries, Inc .; 38 μm), a resin solution (a) in which electroless plating does not precipitate is applied so that the final thickness of the resin layer is 10 μm, 100 ° C. Was heated for 10 minutes to obtain an insulating material composed of resin layer (A) / support on which electroless plating did not deposit. Subsequently, the resin solution (c) in which electroless plating is deposited is applied so that the final thickness of the resin layer is 2 μm, and is dried by heating at 60 ° C. for 1 minute, and the resin layer (C) in which electroless plating is deposited / An insulating resin material comprising a resin layer (A) / support that does not deposit electroless plating was obtained. Subsequently, the adhesive solution (d) was applied onto the resin layer (C) on which the electroless plating was deposited so that the final thickness was 38 μm, and dried by heating at 50 ° C., 70 ° C., 90 ° C., and 100 ° C. for 34 seconds each Thus, an insulating material consisting of adhesive layer (D) / resin layer (C) on which electroless plating is deposited / resin layer (A) on which electroless plating is not deposited / support is obtained. Adhesive layer (D) of the insulating material and a glass epoxy board (product number: CS-3665D, manufactured by Risho Kogyo Co., Ltd .; copper thickness 18 μm) with double-sided copper foil are opposed to each other, the first stage, temperature 90 ° C. After vacuum lamination under the conditions of vacuum drawing 30 seconds, release to the atmosphere, pressurization time 30 seconds, and the second stage, temperature 110 ° C., pressure 1 MPa, pressurization time 60 seconds, the support is peeled off, A laminate comprising glass epoxy substrate / adhesive layer (D) / resin layer (C) on which electroless plating was deposited / resin layer (A) on which electroless plating was not deposited was obtained.

A mask pattern having wiring width / wiring interval = 10 μm / 10 μm was placed on the resin layer (A) on which the electroless plating of the laminate was not deposited, and light having a wavelength of 405 nm was exposed by 300 mJ / cm ² . Subsequently, using a spray developing machine (etching machine ES-655D manufactured by Sanhayato Co., Ltd.), a 1% by weight sodium carbonate aqueous solution (liquid temperature: 40 ° C.) was used to carry out a spray development process, which was partially not applied. The resin layer (C) on which electrolytic plating is deposited was exposed. Subsequently, it was dried by heating at 180 ° C. for 2 hours to be cured. Subsequently, a palladium catalyst was applied, and electroless copper plating (CUPOSIT thickening type manufactured by Rohm and Haas) was applied to form a wiring having a thickness of 10 μm to obtain a printed wiring board. The thickness ratio X / Y between the wiring thickness X and the insulating layer thickness Y was 0.2. The results of evaluating the fine wiring formability of this printed wiring board are shown in Table 1.

(Example 2)
On a support (trade name: Lumirror T-60, manufactured by Toray Industries, Inc .; 38 μm), a resin solution (b) in which electroless plating does not precipitate is applied so that the final thickness of the resin layer is 2 μm, 60 ° C. Was heated for 2 minutes to obtain an insulating material composed of a resin layer (B) / support on which electroless plating did not deposit. Subsequently, the resin solution (c) in which electroless plating is deposited is applied so that the final thickness of the resin layer is 10 μm, and is dried by heating at 60 ° C. for 5 minutes, and the resin layer (C) in which electroless plating is deposited / An insulating resin material comprising a resin layer (B) / support that does not deposit electroless plating was obtained. Subsequently, the adhesive solution (d) was applied onto the resin layer (C) on which the electroless plating was deposited so that the final thickness was 38 μm, and dried by heating at 50 ° C., 70 ° C., 90 ° C., and 100 ° C. for 34 seconds each Thus, an insulating material comprising an adhesive layer (D) / a resin layer (C) on which electroless plating was deposited / a resin layer (B) on which electroless plating was not deposited / a support was obtained. Adhesive layer (D) of the insulating material and a glass epoxy board (product number: CS-3665D, manufactured by Risho Kogyo Co., Ltd .; copper thickness 18 μm) with double-sided copper foil are opposed to each other, the first stage, temperature 90 ° C. After vacuum lamination under the conditions of vacuum drawing 30 seconds, release to the atmosphere, pressurization time 30 seconds, and the second stage, temperature 110 ° C., pressure 1 MPa, pressurization time 60 seconds, the support is peeled off, Laminated body composed of glass epoxy substrate / adhesive layer (D) / resin layer (C) on which electroless plating is deposited / resin layer (B) on which electroless plating is not deposited Got.

  From the resin layer (B) on which the electroless plating of the laminate was not deposited, it was processed with a UV laser so that the line / space was 10 μm / 10 μm and the thickness was 5 μm.

  The laminated body thus obtained is subjected to a desmear treatment by a reduced pressure plasma treatment, followed by a palladium catalyst and electroless copper plating (CUPOSIT thickening type manufactured by Rohm and Haas) A copper wiring having a / space of 10 μm / 10 μm and a thickness of 5 μm was formed to obtain a printed wiring board. The thickness ratio X / Y between the wiring thickness X and the insulating layer thickness Y was 0.1. The results of evaluating the fine wiring formability of this printed wiring board are shown in Table 1.

(Example 3)
Solder resist ink (trade name Photofiner PSR-4000 AUS703 / CA-40 AUS703; Taiyo Ink Mfg. Co., Ltd.) is finally formed on a support (trade name: Lumirror T-60, manufactured by Toray Industries, Inc .; 38 μm). The coating was applied to a thickness of 10 μm and dried at 80 ° C. for 20 minutes to obtain an insulating material composed of a solder resist layer / support. Subsequently, the protective film of the epoxy resin sheet (trade name: ABF-GX-13, manufactured by Ajinomoto Fine-Techno Co., Ltd.) is peeled off as the resin layer on which the electroless plating is deposited, and the insulation composed of the solder resist layer / support. Lamination is performed under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a speed of 1 m / min, so as to be in contact with the solder resist layer of the material, and an insulating material composed of an epoxy resin sheet / solder resist layer / support is obtained. It was. The total thickness of the epoxy resin sheet and the solder resist was 50 μm.

  The above epoxy resin sheet and a glass epoxy substrate (product number: CS-3665D, manufactured by Risho Kogyo Co., Ltd .; copper thickness: 18 μm) with double-sided copper foil are opposed to each other, the first stage, the temperature is 90 ° C., and the vacuum is drawn for 30 seconds. , Air lamination, pressurization time 30 seconds, and second stage, temperature 110 ° C., pressure 1 MPa, pressurization time 60 seconds, after vacuum lamination, peel off the support, glass epoxy substrate / epoxy A laminate comprising a resin sheet / solder resist layer was obtained.

A mask pattern having a wiring width / wiring interval = 10 μm / 10 μm was placed on the solder resist of the laminate, and light having a wavelength of 405 nm was exposed by 300 mJ / cm ² . Subsequently, using a spray developing machine (etching machine ES-655D manufactured by Sanhayato Co., Ltd.), a 1% by weight sodium carbonate aqueous solution (liquid temperature: 40 ° C.) was used to perform a spray development process, and partially epoxy. The resin sheet was exposed. Subsequently, it was dried by heating at 180 ° C. for 1 hour to be cured. Subsequently, a palladium catalyst was applied, and electroless copper plating (CUPOSIT thickening type manufactured by Rohm and Haas) was applied to form a wiring having a thickness of 10 μm to obtain a printed wiring board. The thickness ratio X / Y between the wiring thickness X and the insulating layer thickness Y was 0.2. The results of evaluating the fine wiring formability of this printed wiring board are shown in Table 1.

Example 4
On a support (trade name: Lumirror T-60, manufactured by Toray Industries, Inc .; 38 μm), a resin solution (b) in which electroless plating does not precipitate is applied so that the final thickness of the resin layer is 2 μm, 60 ° C. Was heated for 2 minutes to obtain an insulating material composed of a resin layer (B) / support on which electroless plating did not deposit. Subsequently, as a resin layer on which electroless plating is deposited, a protective film of an epoxy resin sheet (trade name: ABF-GX-13, manufactured by Ajinomoto Fine-Techno Co., Ltd.) is peeled off, and a resin layer on which electroless plating is not deposited ( B) / Laminated so as to be in contact with the resin layer (B) where the electroplating of the insulating material made of the support is not deposited, and laminated under the conditions of temperature 50 ° C., pressure 0.5 MPa, speed 1 m / min, and epoxy resin An insulating material composed of a base sheet / resin layer (B) on which electroless plating was not deposited / support was obtained. The total thickness of the resin layer (B) on which the epoxy resin sheet and the electroless plating were not deposited was 42 μm.

  The above epoxy resin sheet and a glass epoxy substrate (product number: CS-3665D, manufactured by Risho Kogyo Co., Ltd .; copper thickness: 18 μm) with double-sided copper foil are opposed to each other, the first stage, the temperature is 90 ° C., and the vacuum is drawn for 30 seconds. , Air lamination, pressurization time 30 seconds and second stage, temperature 110 ° C., pressure 1 MPa, pressurization time 60 seconds, vacuum lamination was performed, and then the support was peeled off and 180 ° C. for 1 hour. It was cured by heating and drying to obtain a laminate composed of a resin layer (B) in which glass epoxy substrate / epoxy resin sheet / electroless plating did not precipitate.

  From the resin layer (B) on which the electroless plating of the laminate was not deposited, it was processed with a UV laser so that the line / space was 10 μm / 10 μm and the thickness was 5 μm.

  The laminated body thus obtained is subjected to a desmear treatment by a reduced pressure plasma treatment, followed by a palladium catalyst and electroless copper plating (CUPOSIT thickening type manufactured by Rohm and Haas) A copper wiring having a / space of 10 μm / 10 μm and a thickness of 5 μm was formed to obtain a printed wiring board. The thickness ratio X / Y between the wiring thickness X and the insulating layer thickness Y was 0.12. The results of evaluating the fine wiring formability of this printed wiring board are shown in Table 1.

(Comparative Example 1)
A photosensitive permanent resist layer (G) (Hitachi Chemical Industries, Ltd.) on one side of a glass epoxy substrate (F) (trade name: ACL3-E-168, 1.44t, manufactured by Hitachi Chemical Co., Ltd.) containing an electroless copper plating catalyst. Product name: negative photosensitive film FOTECH SR-3000) was laminated at a temperature of 110 ° C. at a rate of 2 m / min to obtain a laminate. The photosensitive permanent resist layer had a thickness of 10 μm. A mask pattern having wiring width / wiring interval = 10 μm / 10 μm was placed on the photosensitive permanent resist layer of the laminate, and light with a wavelength of 365 nm was exposed by 300 mJ / cm ² . Subsequently, using a spray developing machine (etching machine ES-655D manufactured by Sunhayato Co., Ltd.), with a developer (diethylene glycol, monobutyl ether: 200 ml / L, water: 800 ml / L, borax: 8 / L), A spray development treatment was performed at a liquid temperature of 40 ° C. to partially expose a glass epoxy substrate containing an electroless copper plating catalyst. Subsequently, electroless copper plating (CUPOSIT thickening type manufactured by Rohm and Haas) was applied to form a wiring having a thickness of 10 μm, thereby obtaining a printed wiring board. Here, in this comparative example, when the glass epoxy substrate (F) containing the electroless copper plating catalyst is not regarded as an insulating material, the thickness ratio X / Y of the wiring thickness X and the insulating layer thickness Y is 1. 0. The results of evaluating the fine wiring formability of this printed wiring board are shown in Table 1.

  As shown in the comparative example, the electroless copper plating catalyst is present in unnecessary places (the entire surface of the glass epoxy substrate), so the electroless copper plating is applied to the interface between the permanent resist layer and the glass epoxy substrate during electroless copper plating. As a result, abnormal precipitation occurs, resulting in electrical conduction at the fine wiring locations. Also in the thickness direction, when the glass epoxy substrate (F) containing the electroless copper plating catalyst is not regarded as an insulating material, the insulating reliability is inferior because there is no insulating layer between the wirings.

  On the other hand, in the examples, since there is no electroless plating catalyst at the interface between the resin layer where the electroless plating does not deposit and the resin layer where the electroless plating precipitates, abnormal deposition of the electroless copper plating is not seen, Good insulation reliability was exhibited even at fine wiring locations.

Claims (3)

  A printed wiring board containing wiring and an insulating material, wherein there is substantially no electroless plating catalyst between the wirings of the printed wiring board, and the thickness ratio X / Y between the wiring thickness X and the insulating layer thickness Y Is in the range of 0.01 to 0.5.   The printed wiring board is manufactured by a manufacturing method including at least a step of forming a wiring by forming a groove in an insulating layer and depositing electroless plating inside the formed groove. The printed wiring board as described.   3. The at least one compound selected from the group consisting of a compound having sulfur, a compound having chromium, and a compound having an oxime structure is contained in at least a part of the insulating layer. Printed wiring board.