Source: http://www.google.com/patents/US5055321?dq=6,952,563
Timestamp: 2016-05-05 23:54:06
Document Index: 601991338

Matched Legal Cases: ['in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine']

Patent US5055321 - Adhesive for electroless plating, printed circuit boards and method of ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsAn adhesive for electroless plating is formed by dispersing particular heat-resistant granules easily soluble in an oxidizing agent into a particular heat-resistant resin sparingly soluble in the oxidizing agent through a curing treatment. A printed circuit board is manufactured by using such an adh...http://www.google.com/patents/US5055321?utm_source=gb-gplus-sharePatent US5055321 - Adhesive for electroless plating, printed circuit boards and method of producing the sameAdvanced Patent SearchPublication numberUS5055321 APublication typeGrantApplication numberUS 07/344,968Publication dateOct 8, 1991Filing dateApr 28, 1989Priority dateApr 28, 1988Fee statusPaidAlso published asDE3913966A1, DE3913966B4, US5589255Publication number07344968, 344968, US 5055321 A, US 5055321A, US-A-5055321, US5055321 A, US5055321AInventorsRyo Enomoto, Motoo AsaiOriginal AssigneeIbiden Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (7), Non-Patent Citations (2), Referenced by (133), Classifications (35), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetAdhesive for electroless plating, printed circuit boards and method of producing the same
US 5055321 AAbstract
1. A method of producing a printed circuit board, which comprises:(a) forming a cured adhesive layer on a substrate, with the forming including dispersing cured heat-resistant particles easily soluble in an oxidizing agent in a heat-resistant resin exhibiting a sparingly soluble property to said oxidizing agent, said cured heat-resistant particles being selected from the group consisting of a mixture of a heat-resistant resin particles having an average particle size of 2-10 μm and heat-resistant resin fine particles having an average particle size of not more than 2 μm, false particles obtained by adhering at least one of heat-resistant resin fine powder having an average particle size of not more than 2 μm and inorganic fine powder having an average particle size of not more than 2 μm to surfaces of heat-resistant particles having an average particle size of 2-10 μm, and agglomerated particles obtained by agglomerating heat-resistant resin fine powder having an average particle size of not more than 2 μm into an average particle size of 2-10 μm, and mixtures thereof; (b) dissolving and removing heat-resistant particles existent on the surface portion of said adhesive layer with the use of an oxidizing agent whereby the surface portion is roughened; and (c) forming a conductor layer through electroless plating. 2. The method according to claim 1, wherein said substrate is provided with a conductor layer.
3. The method according to claim 1, wherein said heat-resistant resin exhibiting a sparingly soluble property to said oxidizing agent is a photo-sensitive resin.
4. The method according to claim 1, wherein said heat-resistant resin exhibiting a sparingly soluble property to said oxidizing agent is at least one resin selected from the group consisting of epoxy resin, epoxy-modified polyimide resins, polyimide resins and phenolic resins.
5. The method according to claim 1, wherein said heat-resistant particles are compounded in an amount of 2-350 parts by weight per 100 parts by weight as a solid content of said heat-resistant resin having a sparingly soluble property to an oxidizing agent.
6. The method according to claim 5, wherein said heat-resistant particles are compounded in an amount of 5-200 parts by weight per 100 parts by weight as a solid content of said heat-resistant resin having a sparingly soluble property to an oxidizing agent.
7. The method according to claim 1, wherein said oxidizing agent is at least one substance selected from the group consisting of chromic acid, chromate, permanganate and ozone.
8. The method according to claim 1, wherein said electroless plated film is at least one film selected from electroless copper plated film, electroless nickel plated film and electroless gold plated film.
Lately, therefore, there is proposed an additive method wherein an adhesive layer is formed on the surface of the substrate. The surface of the adhesive layer is then roughened and subjected to electroless plating to form a conductor circuit as the method of forming the conductor circuit on the printed circuit board.
As the adhesive used in this additive method, there are known an adhesive containing diene series synthetic rubber, an adhesive disclosed in U.S. Pat. No. 4,216,246 and the like. However, the former adhesive containing the synthetic rubber has drawbacks that the adhesion strength becomes much lower at high temperatures, and the electroless plated film swells during soldering, and the like. Further, the thermal resistance is low and electric properties, such as surface resistance and the like, are insufficient, so that the use region is fairly restricted. On the other hand, in the adhesive as disclosed in U.S. Pat. No. 4,216,246, a thermosetting resin component constituting the spherical granule for the formation of an anchor in the adhesive is not etched, and such spherical granule for the formation of the anchor is simultaneously cured together with a heat-resistant resin as a matrix, so that it is difficult to control the shape and size of the granule. Further, the roughened surface of the adhesive layer formed on the substrate is of a relatively uneven roughness, so that it is also difficult to obtain a conductor circuit of fine pattern.
As a printed circuit board capable of overcoming the above difficulty, there has been developed printed circuit boards wherein conductor circuits and organic insulating films are alternately built up on each other. Such a printed circuit board is suitable for extra-high densification and high speed access, but it is difficult to form an electroless plated film onto the organic insulating film with a good reliablity. In this printed circuit board, therefore, the conductor circuit is formed by PVD process such as vapor deposition, sputtering and the like, or by using electroless plating together with the above PVD process. However, the method of forming a conductor circuit through the PVD process is poor in productivity and undesirably high in cost.
According to a second aspect of the invention, there is the provision of a printed circuit board obtained by forming electroless plated conductor circuit pattern onto an adhesive layer made from a heat-resistant resin, wherein the adhesive layer is an adhesive layer made from the adhesive for electroless plating as mentioned above. Further, recesses for the formation of an anchor on said electroless plated film, which are formed by dissolving out and removing portions of said heat-resistant particles through a treatment with an oxidizing agent, are formed on the surface of said adhesive layer forming the electroless plated film thereon.
FIGS. 1a-d, 2a-2d, 3a-3d, 4a-4f to 5a-5f are partly sectional views illustrating production steps for the formation of the printed circuit board provided with a multilayered conductor circuit pattern according to Examples 1 to 5 as mentioned later, respectively.
The reason why the heat-resistant particles used in the invention is limited to at least one selected from a mixture of heat-resistant resin particles having an average particle size of 2-10 μm and heat-resistant resin fine powder having an average particle size of not more than 2 μm, quasi-particles of heat-resistant resin fine powder having an average particle size of not more than 2 μm or inorganic fine powder having an average particle size of not more than 2 μm adhered to surfaces of heat-resistant resin particles having an average particle size of 2-10 μm, and agglomerate particles having an average particle size of 2-10 μm and made from heat-resistant resin fine powder having an average particle size of not more than 2 μm is due to the fact that anchors of very complicated shape can be formed by using these particles or the mixture as the heat-resistant particle. Particularly, the use of the above mixture as the heat-resistant particle is preferable.
The compounding amount of the heat-resistant particle to the heat-resistant resin forming the matrix is advantageous to by 2-350 parts be weight per 100 parts by weight of the heat-resistant resin forming the matrix. Particularly, the amount is preferable to be 5-200 parts by weight from a viewpoint that the adhesion strength between the adhesive layer and the electroless plated film is increased. When the amount of the heat-resistant particles is less than 2 parts by weight, the density of the anchor formed by dissolution and removal means is low and the sufficient adhesion property between the adhesive layer and the electroless plated film is not obtained, while when it is more than 350 parts by weight, the surface of the adhesive layer is substantially dissolved and removed, so that it is difficult to form clear anchors.
Furthermore, the multilayer printed circuit board can be manufactured by laminating the conductor circuits through the adhesive layer an an electrical insulation layer. In this case, the adhesive layer composed of the heat-resistant resin has a low dielectric constant, is easy to form into a thick film, and is suitable for the high speed formation.
According to the invention, the adhesive layer for electriess plating is first formed on the substrate.
According to the invention, the conductor circuit pattern can be formed by the conventionally known methods for the printed circuit board. For example, a method of subjecting the substrate to a electroless plating and then etching the circuit pattern, a method of directly forming the circuit pattern during the non-electrolytic plating and the like may be applied.
(2) Into a suspension of 200 g of epoxy resin particles (made by Toray, Toraypeal EP-B, average particle size: 3.9 micrometers) dispersed in 500 liters of acetone was added dropwise a suspension of 300 g of epoxy resin powder (made by Toray, Toraypeal EP-B, average particle size: 0.5 micrometers) dispersed in an acetone solution containing epoxy resin (made by Mitsui Toatsu Chemicals, trade name: TA-1800) in an amount of 30 g per 1 liter of acetone with stirring in a Henshell mixer (made by Mistui Miike Seisakusho, FM10B model), whereby the epoxy resin powder was adhered to the surfaces of the epoxy resin particles. After the removal of acetone, the mixture was heated at 150� C. to form quasiparticles. The quasi-particle had an average particle size of about 4.3 micrometers, wherein about 75% by weight of the false particles was existent within �2 micrometers of the above average particle size.
(3) Sixty parts by weight of 50% acrylated cresol novolak type epoxy resin (made by Yuka Shell, trade name: Epikote 180S), 40 parts by weight of bisphenol A type epoxy resin (made by Yuka Shell, trade name: Epikote 1001) 15 parts by weight of diallyl terephthalate, 4 parts by weight of 2-methyl-1-[4-(methylthio) phenyl]-2-morpholinopropane-1 (made by Ciba Geigy, trade name: Irugacure 907), 4 parts by weight of imidazole (made by Shikoku Kasei, trade name: 2P4MHZ) and 50 parts by weight of the false particle obtained in the above item (2) were mixed and adjusted to a viscosity of 250 cp while being added with butyl cellosolve in a homodisper stirrer, which was kneaded through triple roll mill to obtain a solution of a photo-sensitive resin composition.
TABLE 1______________________________________Copper sulfate     0.06     mol/literFormalin (37%)     0.30     mol/literSodium hydroxide   0.35     mol/literEDTA               0.35     mol/literAdditive           slightPlating temperature              70-72� C.PH=                12.4______________________________________
(1) An epoxy resin particles (made by Toray, Toraypeal EP-B, average particle size: 0.5 micrometers) were placed in a hot air dryer and agglomerated by heating at 180� C. for 3 hours. The thus agglomerated epoxy resin particles were dispersed into acetone, pulverized in a ball mill for 5 hours, sieved through an air siever to form agglomerate particles. The agglomerate particles had an average particle size of about 3.5 micrometers, wherein about 68% by weight of the particles was existent within a range of �2 micrometers of the above average particle size.
(1) To the adhesive obtained in the item (1) of Example 4 was added 5% by weight of PhSi (OEt)3, (made by Toshiba Silicon, trade name: TSL8178) as a coupling agent, which was added with butylcarbitol to adjust a viscosity to 120 cp.
(3) The prepreg obtained in the above item (2) was laminated onto a printed board obtained by photo-etching a surface copper foil of glass-epoxy laminated plate provided at both surfaces with copper and pressed at 170� C. under a pressure of 40 kgf/cm2.
As mentioned above, according to the invention, adhesives for electroless plating having very excellent thermal resistance, electrical insulating property, chemical stability and adhesion property to electroless plated film can be provided. Further, the printed circuit boards using this adhesive are very excellent in the adhesion property between the conductor circuit pattern composed of the electroless plated film and the insulating layer and have a complicated wiring pattern and are suitable for high densification and high speed fabrication. Therefore, the invention is very large in the industrial contribution.
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