Source: http://www.google.com/patents/US5741575?dq=%22edwin+asa+markham%22
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Matched Legal Cases: ['in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine']

Patent US5741575 - Adhesive for printed circuit board - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsThere are disclosed an adhesive obtained by dispersing a cured amino resin fine powder soluble in acid or oxidizing agent into an uncured heat-resistant resin matrix hardly soluble in acid or oxidizing agent when being subjected to a curing treatment as well as a printed circuit board using this adhesive...http://www.google.com/patents/US5741575?utm_source=gb-gplus-sharePatent US5741575 - Adhesive for printed circuit boardAdvanced Patent SearchPublication numberUS5741575 APublication typeGrantApplication numberUS 08/755,804Publication dateApr 21, 1998Filing dateDec 17, 1996Priority dateJul 23, 1991Fee statusPaidAlso published asDE4224070A1, US5344893, US5447996, US5688583, US5795618Publication number08755804, 755804, US 5741575 A, US 5741575A, US-A-5741575, US5741575 A, US5741575AInventorsMotoo Asai, Chie OnishiOriginal AssigneeIbiden Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (20), Non-Patent Citations (16), Referenced by (21), Classifications (47), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetAdhesive for printed circuit boardUS 5741575 AAbstract There are disclosed an adhesive obtained by dispersing a cured amino resin fine powder soluble in acid or oxidizing agent into an uncured heat-resistant resin matrix hardly soluble in acid or oxidizing agent when being subjected to a curing treatment as well as a printed circuit board using this adhesive and a method of producing the same. The adhesive has excellent properties such as resistance to chemicals, heat resistance, electric properties, hardness and adhesion property owing to the use of the amino resin fine powder. Therefore, the printed circuit board using such an adhesive is not influenced by service circumstance and is high in the connection reliability without forming short circuit between patterns. Furthermore, in the method of producing the printed circuit board, the adhesive is provided in form of a sheet or a prepreg, whereby the printed circuit board can be produced easily and cheaply.
What is claimed is: 1. A printed circuit board comprising of a roughened adhesive layer formed on at least one surface of a substrate and a conductor circuit formed on the roughened adhesive layer, in which said adhesive layer is composed of an adhesive comprising an uncured heat-resistant resin matrix being insoluble in an acid or an oxidizing agent when being subjected to a curing treatment, and a cured fine powder of amino resin soluble in an acid or an oxidizing agent and dispersed thereinto.
SUMMARY OF THE INVENTION It is an object of the invention to provide an adhesive having excellent resistance to chemicals, heat resistance, electrical properties, hardness and adhesion property.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The adhesive for printed circuit board according to the invention will be described in detail below.
A phenomenon that the value of surface resistivity lowers due to the aforementioned migration reaction is observed in the known adhesives. For this end, the inventors have examined a change of resistivity on various resins while conducting a long-period aging test under conditions that a temperature was 40� C. humidity was 90% and a voltage was 24 V.
EXAMPLE 1 (1) 1275 parts by weight of melamine resin was mixed with 1366 parts by weight of 37% formalin and 730 parts by weight of water, which was adjusted to pH=9.0 with 10% sodium carbonate, held at 90� C. for 60 minutes and then added with 109 parts by weight of methanol.
(4) The mixed resin powder was placed in a mold heated at 150� C. and held under a pressure of 250 kg/cm2 for 60 minutes to obtain a shaped body. Moreover, the mold was opened during the molding toescape gas.
(7) A glass epoxy substrate 1 was roughened by polishing to form a roughened surface of JIS B0601 Rmax=2-3, and then the adhesive solution of the above item (6) was applied onto the substrate by means of a roll coater. In this case, a coating roll for resist of middle and high viscosity (made by Dainihon Screen Co., Ltd.) was used as the coating roll, in which a gap between coating roll and doctor bar was 0.4 mm and a gap between coating roll and back-up roll was 1.4 mm and a travelling speed was 400 mm/s. Thereafter, it was left to stand at a horizontal state for 20 minutes and dried at 70� C. to obtain an adhesive layer 2 having a thickness of about 50 μm (see FIGS. 1b, 1c).
(8) The substrate 1 provided with the adhesive layer 2 was immersed in an oxidizing agent consisting of an aqueous solution of 500 g/l chromic acid (CrO3) at 70� C. for 15 minutes to roughen the surface of the adhesive layer 2, further immersed in a neutral solution (made by Shipley) and washed with water. A paradium catalyst (made by Shipley) was applied to the roughened adhesive layer 2 on the substrate 1 to activate the surface of the adhesive layer 2 (see FIG. 1d).
(9) Then, the substrate 1 was heat-treated at 120� C. in an atmosphere of nitrogen gas (10 ppm oxygen) for 30 minutes for the fixation of the catalyst. Thereafter, a photosensitive dry film was laminated thereon, exposed to a light and developed with a modified chlorocene to form a plating resist 3 (thickness 40 μm) (see FIG. 1e).
TABLE 1______________________________________copper sulfate   0.06        mol/lformalin (37%)   0.30        mol/lsodium hydroxide 0.35        mol/lEDTA             0.35        mol/ladditive         fewplating temperature            70-72� C.pH               12.4______________________________________
EXAMPLE 2 (1) A suspension obtained by dispersing 200 g of melamine resin particles (average particle size 3.9 μm) prepared in the same manner as in the items (1)-(5) of Example 1 into 5 l of acetone was added dropwise with a suspension obtained by dispersing 300 g of melamine resin fine powder (average particle size 0.5 μm) prepared in the same manner as in the items (1)-(5) of Example 1 into 10 l of acetone with stirring in a Henshel mixer (made by Mitsui Miike Kakoki Co., Ltd.), whereby the melamine resin fine powder was adhered to the surfaces of the melamine resin particles. After the removal of acetone, they were heated at 150� C. to prepare false particles. The false particles had an average particle size of about 4.3 μm. Moreover, about 75% by weight of the false particles were existent around the above average particle size with a range of �2 μm.
EXAMPLE 3 (1) The melamine fine powder (average particle size 3.9 μm) obtained in the same manner as in the items (1)-(5) of Example 1 was placed in a hot dryer and agglomerated by heating at 180� C. for 3 hours. The thus agglomerated melamine resin fine powder was dispersed into acetone, pulverized in a ball mill for 5 hours and seived in an air siever to prepare agglomerate particles. The agglomerate particles had an average particle size of about 3.5 μm, about 68% by weight of which was existent around the above average particle size within a range of �2 μm.
(3) After both surfaces of a glass epoxy substrate 1 were roughened by polishing to have a surface roughness of JIS B0601 Rmax=2-3 μm, the adhesive solution prepare in the above item (2) was applied to the substrate 1 by means of a roll coater, which was left to stand at a horizontal state for 20 minutes and dried at 70� C. to form an adhesive layer 2 having a thickness of about 45 μm (see FIGS. 3b, 3c).
(4) Then, the substrate 1 provided with the adhesive layer 2 was pierced by a drill and lightly buffed to expose the filler surface and thereater the substrate was immersed in an aqueous solution of 6N sulfuric acid at 70� C. for 15 minutes to roughen the surface of the adhesive layer 2, immersed in a neutral solution (made by Shipley) and washed with water. A paradium catalyst (made by Shipley) was applied onto the roughened adhesive layer on the substrate 1 to activate the surface of the adhesive layer (see FIGS. 3d, 3e).
(5) The substrate 1 treated in the above item (4) was heat-treated at 120� C. in an atmosphere of nitrogen gas (10 ppm oxygen) for 30 minutes for the fixation of the catalyst. Thereafter, a photosensitive dry film was laminated, exposed to a light and developed with a modified chlorocene to form a plating resist 3 (thickness 40 μm) (see FIG. 3f).
EXAMPLE 4 (1) A photosensitive dry film (made by DuPont) was laminated onto a glass epoxy copper laminated plate (made by Toshiba Chemical Products Co., Ltd.) and exposed to ultraviolet ray through a mask film having a desired conductor circuit pattern. Then, it was developed with 1,1,1-trichloroethane and non-conductor portion of copper was removed with an etching solution of copper chloride and thereafter the dry film was peeled off with ethylene chloride. Thus, there was obtained the substrate having a first conductor layer 4 comprised of plural conductor patterns (see FIG. 4a).
EXAMPLE 5 (1) 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) were dissolved in butylcellosolve acetate to obtain a resin matrix composition. Then, 100 parts by weight of this composition was mixed with 15 parts by weight of the resin particles having a particle size of 0.5 μm and 30 parts by weight of the resin particles having a particle size of 5.5 μm as prepared in the items (1)-(5) of Example 1, which was kneaded through three rolls and added with butylcellosolve acetate to prepare an adhesive solution having a solid content of 75%. This solution had viscosities of 5.2 Pa.s at 6 rpm and 2.6 Pa.s at 60 rpm as measured by means of a digital viscometer made by Tokyo Keiki Co., Ltd. at 20� C. for 60 seconds according to JIS K7117 and an SVI value (thixotropy) of 2.0.
(2) After the resin surface and conductor circuit surface of the substrate 1 having the first circuit layer 4 produced in the same manner as in the item (1) of Example 4 were roughened by polishing to have a surface roughness of JIS B0601 Rmax=2-3 μm, the adhesive solution prepared in the above item (1) was applied to the substrate 1 by means of a roll coater. In this application, a coating roll for resist in high-middle viscosity (made by Dainihon Screen Co., Ltd.) was used as the coating roll, in which a gap between coating roll and doctor bar was 0.4 mm, and a gap between coating roll and back-up roll was 1.4 mm and a travelling speed was 400 mm/s. Thereafter, it was left to stand at a horizontal state for 20 minutes and dried at 70� C. to form an adhesive layer 2 having a thickness of about 50 μm (see FIGS. 5b, 5c).
(4) The substrate 1 was heat-treated at 120� C. in an atmosphere of nitrogen gas (10 ppm oxygen) for 30 minutes for the fixation of the catalyst, and thereafter a photsensitive dry film was laminated and exposed to a light and developed with a modified chlorocene to form a plating resist (thickness 40 μm) (see FIG. 5e).
EXAMPLE 6 This example was Fundamentally the same as in Example 4 except that the adhesive solution was obtained by mixing 60 parts by weight of 60% acrylated product of cresol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.), 15 parts by weight of diallyl terephthalate, 4 parts by weight of 2-methyl-1- 4-(methylthio)phenyl!-2-morrpholinopropanone-1 (made by Ciba Geigey), 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) and 50 parts by weight of hollow melamine resin particles (made by Honen Co., Ltd.: particle size 2 μm), stirring them in a homodisper agitator while adding butylcellosolve and kneading through three rolls to have a solid content of 70%. The solution had viscosities of 5.0 Pa.s at 6 rpm and 2.5 Pa.s at 60 rpm and an SVI value of 2.0.
EXAMPLE 7 This example was fundamentally the same as in Example 4 except that the adhesive solution was obtained by mixing 100 parts by weight of 50% acrylated product of orthocresol-novolac type epoxy resin (made by Nihon Kayaku Co., Ltd.), 15 parts by weight of diallyl terephthalate, 4 parts by weight of 2-methyl-1- 4-(methylthio)phenyl!-2-morrpholinopropanone-1 (made by Ciba Geigey), 4 parts by weight of an imidazole curing agent (made by Shikoku KaSei Co., Ltd.), a photoinitiator (made by Ciba Geigey) and 50 parts by weight of hollow melamine resin particles (made by Honen Co., Ltd.: particle size 2 μm), stirring them in a homodisper agitator while adding butylcellosolve and kneading through three rolls to have a solid content of 70%. The solution had viscosities of 5.1 Pa.s at 6 rpm and 2.6 Pa.s at 60 rpm and an SVI value of 2.0.
EXAMPLE 8 This example was fundamentally the same as in Example 4 except that the adhesive solution was obtained by mixing 50 parts by weight of false particles prepared in the same manner as in the item (1) of Example 2, 100 parts by weight of 60% acrylated product of orthocresol-novolac type epoxy resin (made by Nihon Kayaku Co., Ltd.), 15 parts by weight of diallyl terephthalate, 4 parts by weight of 2-methyl-1- 4-(methylthio)phenyl!-2-morrpholinopropanone-1 (made by Ciba Geigey), 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) and a photoinitiator (made by Ciba Geigey), stirring them in a homodisper agitator while adding butylcellosolve and kneading through three rolls to have a solid content of 70%. The solution had viscosities of 5.1 Pa.s at 6 rpm and 2.6 Pa.s at 60 rpm and an SVI value of 2.0.
EXAMPLE 9 This example was iundamentally the same as in Example 4 except that the adhesive solution was obtained by dissolving 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of difunctional acrylic resin (made by Yuka Shell Co., Ltd.) and 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of the melamine resin particles having a particle size of 0.5 μm and 30 parts by weight of the melamine resin particles having a particle size of 5.5 μm through three rolls and adding butylcetlosolve so as to have a solid content of 75%.
EXAMPLE 10 This example was fundamentally the same as in Example 4 except that the adhesive solution was obtained by dissolving 60 parts by weight of 60% acrylated product of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of difunctional acrylic resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of the melamine resin particles having a particle size of 0.5 μm and 30 parts by weight of the melamine resin particles having a particle size of 5.5 μm through three rolls and adding butylcellosolve so as to have a solid content of 75%.
EXAMPLE 11 This example was fundamentally the same as in Example 4 except that the adhesive solution was obtained by dissolving 60 parts by weight of acrylic resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight or an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of the melamine resin particles having a particle size of 0.5 μm and 30 parts by weight of the melamine resin particles having a particle size of 5.5 μm through three rolls and adding butylcellosolve so as to have a solid content of 75%.
EXAMPLE 12 This example was fundamentally the same as in Example 4 except that the adhesive solution was obtained by dissolving 60 parts by weight of acrylic resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of difunctional acrylic resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of the melamide resin particles having a particle size of 0.5 μm and 30 parts by weight of the melamine resin particles having a particle size of 5.5 μm through three rolls and adding butylcellosolve so as to have a solid content of 75%.
EXAMPLE 13 This example was fundamentally the same as in Example 4 except that the adhesive solution was obtained by dissolving 100 parts by weight of acrylic resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of the melamine resin particles having a particle size of 0.5 μm and 30 parts by weight of the melamine resin particles having a particle size of 5.5 μm through three rolls and adding butylcellosolve so as to have a solid content of 75%.
EXAMPLE 14 (1) Urea and formalin were mixed at a mol ratio of 1:2 and heat-treated at 80� C. to obtain a polymer containing 45-50 wt % of monomethylol urea and dimethylol urea.
EXAMPLE 15 (1) A mixture of 500 parts by weight of melamine resin, 750 parts by weight of acetoguanamie resin, 1200 parts by weight of 37% formalin and 800 parts by weight of water was used as a starting material and cured and pulverized in the same manner as in the items (1)-(5) of Example 1 to obtain fine powder of melamine-acetoguanamine cocondensed resin.
EXAMPLE 16 (1) A resin matrix composition was obtained by dissolving 60 parts by weight of phenol-novolac type epoxy resin (made by Nihon Kayaku Co., Ltd.: molecular weight=3600, mp=90� C.), 40 parts by weight of bisphenol-A type epoxy resin (made by. Yuka Shell Co., Ltd.: molecular weight=900, mp=64� C.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Shell Co., Ltd.) in butylcellosolve acetate. Then, 100 parts by weight as a solid content of the composition was mixed with 15 parts by weight of the melamine resin fine powder having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm obtained in the same manner as in the items (1)-(5) of Example 1 in a ball mill and added with butylcellosolve acetate to prepare an adhesive solution having a solid content of 60%. This solution had a viscosity of 0.2 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
(3) After a glass epoxy substrate 1 was roughened at both surfaces by polishing to have a surface roughness of JIS B0601 Rmax=2-3 μm, the sheet-shaped adhesive of the item (2) was laminated onto the roughened surface of the substrate and heated at 80� C. under a pressure of 3 kg/cm2 to form an adhesive layer 2 having a thickness of about 50 μm (see FIGS. 6b, 6c).
EXAMPLE 17 (1) An adhesive solution having a solid content of 55% was prepared by dissolving 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Sheller Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve, mixing 100 parts by weight as a solid content of the resulting composition with 75 parts by weight of melamine resin fine powder (made by Honen Co., Ltd.) having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm pulverized in a ball mill, kneading through three rolls and adding butylcellosolve thereto. This solution had viscosities of 2.6 Pa.s at 6 rpm and 1.0 Pa.s at 60 rpm and an SVI value (thixotropy) of 2.6.
EXAMPLE 18 (7) An adhesive solution having a solid content of 50% was prepared butyl carbitol to a mixture of 50 parts by weight of false particles prepared in the same manner as in the item (1) of Example 2, 30 parts by weight of cresol-novolac type epoxy resin (made by Nihon Kayaku Co., Ltd.: molecular weight=2500, mp=60� C.), 40 parts by weight of phenol-novolac type epoxy resin (made by Yuma Shell Co., Ltd.: molecular weight=700, mp=40� C.), 30 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.: molecular weight=500, mp=25� C.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) and adjusting in a homodisper dispersing machine. The viscosity of this solution was 0.1 Pa.s at 60 rpm.
(2) The adhesive solution was applied to a Tedolar film 12 (made by DuPont) by means of a doctor blade, dried in a continuous furnace 15 at 100� C. for 5 minutes to provide B-stage (semi-cured state) and a cover film 11 of polyethylene (for protecting the adhesive surface) was laminated thereon to form a sheet-shaped adhesive (see FIG. 8a).
EXAMPLE 19 (1) An adhesive solution having a solid content of 65% was prepared by dissolving 50 parts by weight of false particles prepared in the same manner as in the item (1) of Example 3, 60 parts by weight of special functional epoxy resin (made by Nihon Kayaku Co., Ltd.: molecular weight=3200, mp=60� C.), 20 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.: molecular weight=500, mp=25� C.) and 7 parts by weight of a quazola curing agent (made by Shikoku Kasei Co., Ltd.) in butyl carbitol. The viscosity of this solution was 0.3 Pa.s at 60 rpm.
(2) The adhesive solution was applied to a commercially available preprag 13 by means of a doctor blade 16 and dried at 100� C. for 5 minutes to provide B-stage (semi-cured state) and a cover film 11 of polyethylene (for protecting the adhesive surface) and further PET (polyethylene terephthalate) film 14 for protecting the adhesive layer 2 were laminated thereon to prepare a sheet-shaped adhesive (see FIG. 9a).
EXAMPLE 20 This example was fundamentally the same as in Example 15 except that the adhesive solution was obtained by dissolving 50 parts by weight of special trifunctional epoxy resin (molecular weight=3000, mp=80� C.), 50 parts by weight of novolac type polyfunctional epoxy resin (molecular weight=500, mp=35� C.) and 7 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm obtained by the same method as in the items (1)-(5) of Example 1 in a ball mill and further adding butylcellosolve to provide a solid content of 455. This solution had a viscosity of 0.7 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
EXAMPLE 21 (1) 60 parts by weight of 50% acrylated product of cresol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 20 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.), 15 parts by weight of diallyl terephthalate, 4 parts by weight of 2-methyl-1- 4-(methylthio)phenyl!-2-morpholinopropanone-1 (made by Ciba Geigey), 4 parts by weight of an imidazole curing agent and 50 parts by weight of hollow melamine resin fine powder (made by Honen Co., Ltd.: particle size 2 μm) were mixed and added with a leveling agent, which was stirred in a homodisper agitator while adding butylcellosolve and then kneaded in a ball mill to prepare a photosensitive adhesive solution having a solid content of 50%. The viscosity of this solution was 0.5 Pa.s at 60 rpm.
(5) The substrate 1 treated in the item (4) was immersed in an aqueous solution of 500 g/l chromic acid (CrO3) as an oxidizing agent at 70� C. for 15 minutes to roughen the surface of the adhesive layer 2, which was immersed in a neutral solution (made by Shiplay) and washed with water. A paradium catalyst (made by Shiplay) was applied to the roughened adhesive layer 2 on the substrate 1 to activate the surface of the adhesive layer 2 (see FIG. 10d).
(6) The substrate 1 was heat-treated at 120� C. in an atmosphere of nitrogen gas (10 ppm oxygen) for 30 minutes for the fixation of the catalyst. Thereafter, a photosensitive dry film was laminated, exposed to a light and developed with a modified chlorocene to form a plating resist 3 (thickness 40 μm) (see FIG. 10e).
EXAMPLE 22 (1) An adhesive solution having a solid content of 55% was prepared by dissolving 60 parts by weight of 60% acrylated product of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type. epoxy resin (made by Yuka Shell Co., Ltd.), 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.), 15 parts by weight of diallyl terephthalate and 4 parts by weight of 2-methyl-1- 4-(methylthio)phenyl!-2-morpholinopropanone-1 (made by Ciba Geigey) in butylcellosolve, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder (made by Honen Co., Ltd.) having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm pulverized in a ball mill, kneading through three rolls and adding butylcellosolve. This solution had viscosities of 2.6 Pa.s at 6 rpm and 1.0 Pa.s at 60 rpm and an SVI value (thixotropy) or 2.6.
(2) The adhesive solution was applied to a polyethylene film 12 provided with a silicon coating by means of a roll coater and dried by heating at 120� C. for 30 minutes to form a sheets shaped adhesive (see FIGS. 11a, 11b).
EXAMPLE 23 (1) An adhesive solution having a solid content of 50% was prepared by dissolving 50 parts by weight of 75% acrylated product of cresol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 50 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 4 parts by weight of an imidazole curing agent (made by Shikofu Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder (made by Honen Co., Ltd.) having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm pulverized in a ball mill and further adding butylcellosolve acetate. The viscosity of the solution was 0.3 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
EXAMPLE 24 This example was fundamentally the same as in Example 21 except that the adhesive solution having a solid content of 45% was obtained by dissolving 60 parts by weight of 50% acrylated product of cresol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.), 4 parts by weight of 2-methyl-1- 4-(methylthio)phenyl!-2-morpholinopropane-1 (made by Ciba Geigey) and 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder made by Honen Co., Ltd.) having a particle size of 0.5 μm and 30 parts by the weight of the melamine resin line powder having a particle size of 5.5 μm pulverized in a ball mill and further adding butylcellosolve acetate. The viscosity of the solution was 0.1 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
EXAMPLE 25 This example was fundamentally the same as in Example 27 except that the adhesive solution having a solid content of 50% was obtained by dissolving 60 parts by weight of 50% acrylated product of orthocresol-novolac type epoxy resin (made by Nihon Kayaku Co., Ltd.), 40 parts by weight of bisphenol-F type epoxy resin (made by Yuka Shell Co., Ltd.), 15 parts by weight of diallyl terephthalate, 4 parts by weight of 2-methyl-1- 4-(methylthio)phenyl!-2-morpholinopropanone-1 (made by Ciba Geigey), 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.), a photoinitiator (made by Ciba Geigey) and 50 parts by weight of hollow melamine resin fine powder (made by Honen Co., Ltd.: particle size 2 μm) in butylcellosolve acetate, stirring in a homodisper agitator and kneading in a ball mill. The viscosity of the solution was 0.2 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
EXAMPLE 26 This example was fundamentally the same as in Example 21 except that the adhesive solution having a solid content of 60% was obtained by dissolving 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.) , 40 parts by weight of difunctional acrylic resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm, kneading through three rolls and further adding butylcellosolve acetate.
EXAMPLE 27 This example was fundamentally the same as in Example 21 except that the adhesive solution having a solid content of 65% was obtained by dissolving 60 parts by weight of 60% acrylated product of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of difunctional acrylic resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd,) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with parts by weight of melamine resin fine powder having a particle size of 0.5 μm and 30 parts weight of the melamine resin fine powder having a particle size of 5.5 μm, kneading through three rolls and further adding butylcellosolve acetate.
EXAMPLE 28 This example was fundamentally the same as in Example 21 except that the adhesive solution having a solid content of 65% was obtained by dissolving 60 parts by weight of acrylic resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm, kneading through three rolls and further adding butylcellosolve acetate.
EXAMPLE 29 This example was fundamentally the same as in Example 21 except that the adhesive solution having a solid content of 55% was obtained by dissolving 60 parts by weight of acrylic resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of difunctional acrylic resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm, kneading through three rolls and further adding butylcellosolve acetate.
EXAMPLE 30 This example was fundamentally the same as in Example 21 except that the adhesive solution having a solid content of 55% was obtained by dissolving 100 parts by weight of acrylic resin (made by Shin Nakamura Kagaku Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm, kneading through three rolls and further adding butylcellosolve acetate.
EXAMPLE 31 (1) Formalin was mixed with guanamine at a molar ratio of 1.2-1.6 to 1, adjusted to pH=6.5 and reacted at 60� C. to obtain a transparent resin liquid.
EXAMPLE 32 (1) An adhesive solution having a solid content of 60% was prepared by dissolving 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate to form a resin matrix composition, mixing 100 parts by weight as a solid content of the composition with 15 parts by weight of melamine resin fine powder having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm, which were obtained by the same method as in the items (1)-(5) of Example 1, in a ball mill, kneading in a pearl mill and further adding methyl ethyl ketone. The viscosity of the solution was 0.05 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
(3) Glass epoxy prepregs were sandwiched between the prepreg-1 like adhesives prepared in the item (2) as an outermost layer so as to have a thickness 1.6 mm, which was treated at 100� C. under a contact pressure for 1 minute and pressed at 100� C. under a pressure of 50 kg/cm2 for 20 minutes and then cured at 150� C. for 3 hours to form an adhesive layer 2 onto a substrate 1 (see FIG. 12b).
EXAMPLE 33 (1) An adhesive solution was prepared by adding methyl ethyl ketone to a mixture of 50 parts by weight of false particles prepared in the same manner as in the item (1) of Example 2, 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 30 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) so as to have a solid content of 30% and then kneading in a pearl mill. The viscosity of the solution was 0.06 Pa.s at 60 rpm.
EXAMPLE 34 (1) An adhesive solution having a solid content of 65% was prepared by adding butylcellosolve acetate to a mixture of 50 parts by weight of false particles prepared in the same manner as in the item (1) of Example 3, 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 20 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.), kneading through three rolls, stirring in a homodisper agitator and further adding butylcellosolve acetate. The viscosity of the solution was 0.04 Pa.s at 60 rpm.
EXAMPLE 35 (1) An adhesive solution having a solid content of 55% was prepared by dissolving a mixture of 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in methyl ethyl ketone, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of melamine resin fine powder (made by Honen Co., Ltd.) having a particle size of 0.5 μm and 30 parts by weight of the melamine resin fine powder having a particle size of 5.5 μm in a ball mill and further adding methyl ethyl ketone. The viscosity of the solution was 0.05 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
EXAMPLE 36 (1) An adhesive solution having a solid content of 80% was prepared by dissolving a mixture of 60 parts by weight of cresol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in methylcellosolve, mixing 100 parts by weight as a solid content of the resulting composition with 50 parts by weight of melamine resin fine powder (made by Honen Co., Ltd.: particle size 3 μm) pulverized in a ball mill, kneading through three rolls and further adding methylcellosolve. The viscosity of the solution was 0.04 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
(2) The adhesive solution was applied to a glass epoxy prepreg by means of a doctor bar and then dried at 80� C. to obtain a preprag-like adhesive provided with an adhesive layer 2 having a thickness of 50 μm.
EXAMPLE 37 This example was fundamentally the same as in Example 32 except that the adhesive solution having a solid content of 40% was obtained by dissolving 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in methyl ethyl ketone, mixing 100 parts by weight as a solid content of the resulting composition with 50 parts by weight of hollow melamine resin fine powder (made by Honen Co., Ltd.), kneading in a pearl mill and further adding methyl ethyl ketone. Moreover, the viscosity of the solution was 0.05 Pa.s at 60 rpm as measured by means of a digital viscometer at 20� C. for 60 seconds according to JIS K7117.
EXAMPLE 38 This example was fundamentally the same as in Example 32 except that the adhesive solution having a solid content of 55% was obtained by dissolving 60 parts by weight of phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.), 40 parts by weight of bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.) and 5 parts by weight of an imidazole curing agent (made by Shikoku Kaset Co., Ltd.) in methyl ethyl ketone, mixing 100 parts by weight as a solid content of the resulting composition with 50 parts by weight of false particles prepared in the same manner as in the item (1) of Example 3, kneading in a ball mill and further adding methyl ethyl ketone. Moreover, the solution had viscosities of 0.6 Pa.s at 6 rpm and 0.5 Pa.s at 60 rpm and an SVI value (thixotropy) of 1.2.
EXAMPLE 39 (1) Urea, isothiourea and formalin were mixed at a molar ratio of 1:1:2 and cocondensed by heating at 80� C. to obtain urea-thiourea cocondensed resin fine powder.
EXAMPLE 40 (1) An adhesive solution A was prepared by the same treatment as in the items (1)-(6) of Example 1 (except that the curing agent was not used).
EXAMPLE 41 A multilayer printed circuit board was manufactured by using the same adhesive solution as in Example 40 in the same manner as in Example 5. The properties of the resulting board were the same as in Example 5.
EXAMPLE 42 A printed circuit board was manufactured by using the same adhesive solution as in Example 40 in the same manner as in Example 32. The properties of the resulting board were the same as in Example 32.
EXAMPLE 43 This example was fundamentally the same as in Example 1 except that the adhesive solution having a solid content of 75% was obtained by dissolving 100 parts by weight of nonflammable novolac type epoxy resin (made by Nihon Kayaku Co., Ltd.) and 7 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of the resin particles obtained in the items (1)-(6) of Example 1 having a particle size of 0.5 μm and 30 parts by weight of the above resin particles having a particle size of 5-5 μm, kneading through three rolls and further adding butylcellosolve acetate. Moreover, the solution had viscosities of 5.2 Pa.s at 6 rpm and 2.5 Pa.s at 60 rpm and an SVI value (thixotropy) of 2.0.
EXAMPLE 44 This example was fundamentally the same as in Example 5 except that the adhesive solution having a solid content of 75% was obtained by dissolving 100 parts by. weight of nonflammable novolac type epoxy resin (made by Nihon Kayaku Co., Ltd.) and 7 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of the resin particles obtained in the items (1)-(6) of Example 1 having a particle size of 0.5 μm and 30 parts by weight or the above resin particles having a particle size of 5.5 μm, kneading through three rolls and further adding butylcellosolve acetate. Moreover, the solution had viscosities of 5.2 Pa.s at 6 rpm and 2.5 Pa.s at 60 rpm and an SVI value (thixotropy) of 2.0.
EXAMPLE 45 This example was fundamentally the same as in Example 32 except that the adhesive solution having a solid content of 75% was obtained by dissolving 100 parts by weight of nonflammable novolac type epoxy resin (made by Nihon Kayaku Co., Ltd.) and 7 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) in butylcellosolve acetate, mixing 100 parts by weight as a solid content of the resulting composition with 15 parts by weight of the resin particles obtained in the items (1)-(6) of Example 1 having a particle size of 0.5 μm and 30 parts by weight of the above resin particles having a particle size of 5.5 μm, kneading through three rolls and further adding butylcellosolve acetate. Moreover, the solution had viscosities of 5.2 Pa.s at 6 rpm and 2.5 Pa.s at 60 rpm and an SVI value (thixotropy) of 2.0.
Comparative Example 1 A printed circuit board was produced in the same manner as in Example 1 except that an epoxy resin cured by a dicyano series curing agent was used as a heat-resistant resin fine powder.
Comparative Example 2 A printed circuit board was produced in the same manner as in Example 4 except that an epoxy resin cured by a dicyano series curing agent was used as a heat-resistant resin fine powder.
Comparative Example 3 A printed circuit board was produced in the same manner as in Example 14 except that an epoxy resin cured by anhydrous pyromellitic acid was used as a heat-resistant resin fine powder.
Comparative Example 4 A printed circuit board was produced in the same manner as in Example 27 except that an epoxy resin cured by anhydrous trimellitic acid was used as a heat-resistant resin fine powder.
Measurement: the board was placed in a thermo-hygrostat at a temperature of 85��1� C. and a relative humidity of 85-90% and left to stand while applying a voltage of 30 V. The presence or absence of migration was measured after 1000 hours.
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Ltd.A solder resist comprises an acrylate of novolac type epoxy resin and an imidazole curing agent, has a specific viscosity adjusted with glycol ether comprising diethylene glycol dimethyl ether or dimethyl ether of triethylene glycolUS6217988Nov 2, 1999Apr 17, 2001Ibiden Co., Ltd.Multilayer printed circuit board, method of producing multilayer printed circuit board and resin fillerUS6248428Apr 15, 1998Jun 19, 2001Ibiden Co., Ltd.Adhesive formed by dispersing cured heat-resistant resin particles of specified size soluble in acid or oxidizing agent into uncured heat-resistant resin matrix hardly soluble in acid or oxidizing agent through curing treatmentUS6251502Jul 20, 1999Jun 26, 2001Ibiden Co., Ltd.Multilayer printed circuit board, method of producing multilayer printed circuit board and resin fillerUS6261671 *Apr 15, 1998Jul 17, 2001Ibiden Co., Ltd.Curing heat resistant resinUS6441314 *Mar 23, 2001Aug 27, 2002Shinko Electric Industries Co., Inc.Multilayered substrate for semiconductor deviceUS6680440 *Feb 23, 1998Jan 20, 2004International Business Machines CorporationUsing permanent plating resist, which is not degraded by conventional baths, to protect substrate areas, including metallized features on substrate, from deposition of metal during platingUS6710260 *Mar 29, 2000Mar 23, 2004Victor Company Of Japan, Ltd.Printed circuit board and manufacturing method of the printed circuit boardUS6809935 *Oct 10, 2000Oct 26, 2004Megic CorporationThermally compliant PCB substrate for the application of chip scale packagesUS6931724Jul 30, 2002Aug 23, 2005Shinko Electric Industries Co., Ltd.Insulated multilayered substrate having connecting leads for mounting a semiconductor element thereonUS7230188 *Sep 14, 1999Jun 12, 2007Ibiden Co., Ltd.Printed wiring board and its manufacturing methodUS7514779 *Dec 31, 2002Apr 7, 2009Ibiden Co., Ltd.Multilayer build-up wiring boardUS7624502 *Jan 21, 2005Dec 1, 2009Panasonic CorporationMethod for producing circuit-forming board and material for producing circuit-forming boardUS7691189Apr 17, 2007Apr 6, 2010Ibiden Co., Ltd.electroless plating solution comprising aqueous solution of 0.025-0.25 mol/L basic compound, 0.03-0.15 mol/L reducing agent, 0.02-0.06 mol/L copper ion, 0.05-0.3 mol/L tartaric acid; nickel ion formed from nickel chloride or nickel sulfate; reducing agent comprises formaldehyde or hydrazine; uniformityUS7763809Aug 18, 2004Jul 27, 2010Shink Electric Industries Co., Inc.Multilayered substrate for semiconductor device and method of manufacturing sameUS7827680Jan 6, 2004Nov 9, 2010Ibiden Co., Ltd.Electroplating process of electroplating an elecrically conductive sustrateUS7847318Mar 17, 2009Dec 7, 2010Ibiden Co., Ltd.Multilayer build-up wiring board including a chip mount regionUS20120152595 *Nov 10, 2011Jun 21, 2012Samsung Electro-Mechanics Co., Ltd.Multilayer printed circuit board and method of manufacturing the sameUS20130220683 *Jun 29, 2012Aug 29, 2013Zhen Ding Technology Co., Ltd.Printed circuit board and method for manufacturing printed circuit board* Cited by examinerClassifications U.S. Classification428/209, 428/210, 428/901, 361/748, 361/749International ClassificationC08G59/38, C08G59/18, H01B3/40, C08L63/00, H05K3/46, C09J7/00, H05K3/42, H05K3/00, C09J163/00, H05K3/38, H05K3/18Cooperative ClassificationY10S525/935, Y10S428/901, Y10S525/934, H05K3/0035, C09J163/00, H05K2201/0212, C08G59/38, C08L63/00, H05K2203/0773, H05K2203/0796, H05K2203/0789, H01B3/40, H05K3/4661, H05K3/181, C09J7/00, H05K3/387, H05K3/426, H05K2201/0154, H05K2203/066, H05K2203/0143, H05K3/4644, H05K3/184, C08G59/18European ClassificationC09J163/00, C08L63/00, C09J7/00, H05K3/46C5, H01B3/40, C08G59/18, C08G59/38, H05K3/38D2Legal EventsDateCodeEventDescriptionSep 23, 2009FPAYFee paymentYear of fee payment: 12Sep 23, 2005FPAYFee paymentYear of fee payment: 8Jun 1, 2004CCCertificate of correctionNov 26, 2002CCCertificate of correctionSep 25, 2001FPAYFee paymentYear of fee payment: 4Aug 3, 1999CCCertificate of correctionRotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google