Source: http://www.google.com/patents/US5795618?dq=6,073,142
Timestamp: 2014-03-08 23:48:59
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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', 'in fine']

Patent US5795618 - Polymerizable adhesive (comprising cured amino resin powder) for print ed ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsThere 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/US5795618?utm_source=gb-gplus-sharePatent US5795618 - Polymerizable adhesive (comprising cured amino resin powder) for print ed circuit boardAdvanced Patent SearchPublication numberUS5795618 APublication typeGrantApplication numberUS 08/470,801Publication dateAug 18, 1998Filing dateJun 6, 1995Priority dateJul 23, 1991Fee statusPaidAlso published asDE4224070A1, US5344893, US5447996, US5688583, US5741575Publication number08470801, 470801, US 5795618 A, US 5795618A, US-A-5795618, US5795618 A, US5795618AInventorsMotoo Asai, Chie OnishiOriginal AssigneeIbiden Co., LtdExport CitationBiBTeX, EndNote, RefManPatent Citations (20), Non-Patent Citations (4), Referenced by (1), Classifications (46), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetPolymerizable adhesive (comprising cured amino resin powder) for print ed circuit boardUS 5795618 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 method of producing printed circuit boards by forming electroless plated conductor circuits through an adhesive layer formed on a substrate, which comprises:(1) forming onto a substrate an adhesive layer of an adhesive, wherein the adhesive is produced by dispersing a cured fine powder of amino resin which is soluble in an acid or an oxidizing agent into an uncured resin matrix, said uncured resin matrix being curable into a heat-resistant resin matrix which is insoluble in the acid or the oxidizing agent; (2) roughening a surface of said adhesive layer with the acid or the oxidizing agent; and (3) subjecting the roughened adhesive layer to electroless plating to form a conductor circuit. 2. The method according to claim 1, wherein said adhesive layer is formed on said substrate by applying said adhesive onto said substrate and then drying and curing it.
3. The method according to claim 1, wherein said adhesive layer is formed on said substrate by placing a sheet of adhesive on said substrate and then heating under pressure.
4. The method according to claim 1, wherein said adhesive layer is formed on said substrate by placing a prepreg adhesive on said substrate and then heating under pressure.
5. The method according to claim 1, wherein a substrate provided with a conductor circuit is used as said substrate.
6. The method according to claim 1, wherein said amino resin fine powder is dispersed into said heat-resistant resin matrix in an amount of 10-100 parts by weight per 100 parts by weight as a solid content of said matrix.
7. The method according to claim 1, wherein said amino resin fine powder is at least one member selected from the group consisting of melamine resin, urea resin, and guanamine resin.
8. The method according to claim 1, wherein said heat-resistant resin matrix is a thermosetting heat-resistant resin or a photosensitive heat-resistant resin.
9. The method according to claim 1, wherein said uncured resin matrix comprises an uncured polyfimctional resin having at least one epoxy group and an imidazole curing agent.
10. The method according to claim 9, wherein said uncured resin matrix comprises a mixture of a thermosetting heat-resistant resin comprised of said uncured polyfunctional resin having at least one epoxy group and 2-10 wt % as a solid content of said imidazole curing agent.
11. The method according to claim 1, wherein said uncured resin matrix comprises at least one photosensitive heat resistant resin selected from the group consisting of uncured polyfunctional resin having at least one epoxy group and uncured polyfunctional resin containing an acryl group.
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
Further, the melamine resin as a molding material generally has a molar ratio of formaldehyde to melamine within a range of about 1:2-1:3. Particularly, as the molar ratio becomes higher, the molded product having a higher hardness is produced. Therefore, melamine and formaldehyde are reacted within the above molar ratio range at 80 while maintaining neutral or slight alkaline condition with ammonia or the like, and then the resulting syrup is added with a base material such as rayon, pulp cloth piece, asbestos, fiber or the like, which is dried and pulverized and added with pigment, releasing agent, curing agent and the like and finely pulverized to form a molding material. Moreover, the molding material is sufficiently cured by heating under pressure without adding the curing agent, but a curing agent such as citric acid, phthalic acid, organic carboxylic acid ester or the like is generally used.
Such a thermosetting heat-resistant resin matrix is a mixture of uncured polyfunctional resin having at least one epoxy group or uncured difunctional epoxy resin as a thermosetting heat-resistant resin and an imidazole series curing agent.
The thermosetting heat-resistant resin matrix is preferably a mixture of a thermosetting heat-resistant resin consisting of 20-100 wt % of the uncured polyfunctional resin having at least one epoxy group and 80-0 wt % of the uncured difunctional epoxy resin as a solid content and 2-10 wt % as a solid content of the imidazole series curing agent. When the solid content of the polyfunctional resin is less than 20 wt %, the hardness of the adhesive lowers and also the resistance to chemicals lowers.
Furthermore, as the photosensitve heat-resistant resin matrix, there are used at least one photosensitive heat-resistant resin selected from uncured polyfunctional resin having at least one epoxy group, resin having uncured polyfunctional acryl group and uncured polyfunctional acrylic resin, or a mixed resin of the above resin and at least one of difunctional epoxy resin and difunctional acrylic resin.
The photosensitive heat-resistant resin matrix is preferably a mixture of 20-100 wt % as a solid content of at least one photsensitive heat-resistant resin selected from the uncured polyfunctional resin having at least one epoxy group, the resin having uncured polyfunctional acryl group and the uncured polyfunctional acrylic resin and 80-0 wt % as a solid content of at least one of the uncured difunctional epoxy resin and the uncured difunctional acrylic resin. When the solid content of the polyfunctional resin is less than 20 wt %, the hardness of the adhesive lowers and also the resistance to chemicals lowers.
As shown in FIG. 6a, the sheet-shaped adhesive may be formed by applying an adhesive solution, which is obtained by dispersing the cured amino resin fine powder into the heat-resistant resin matrix being hardly soluble in acid or oxidizing agent when being subjected to a curing treatment, onto a base film by means of a roll coater, a doctor bar or the like and then drying and curing in a drying furnace at 60 an adhesive layer of a semi-cured state.
In this case, the thickness of the adhesive layer on the base film is adjusted to 25-70 μm by gap of the doctor bar. Since the sheet-shaped adhesive is wound on a roll, a protection film (cover film) is formed on the adhesive layer to protect the adhesive layer of the semi-cured state.
In the production of the sheet-shaped adhesive, a mixture of a resin having a high molecular weight (hereinafter shown by R) and a resin having a low molecular weight (hereinafter shown by r) is used as the heat-resistant resin constituting the heat-resistant resin matrix. Preferably, the molecular weight M of the resin R is 2,000&lt;M≦100,000, particularly 2,000≦M≦5,000, and the molecular weight m of the resin r is 200&lt;m≦2,000, particularly 300≦m≦1,000, and the mixing ratio by weight is 0.2.ltoreq.r/(r+R)≦0.8. Furthermore, in order that the melting point of the resin mixture is not lower than room temperature, it is favorable that the melting point of the resin R is within a range of 50 resin r is within a range of not lower than 10 50
As shown in FIG. 12a, the prepreg-like adhesive may be formed by immersing a fibrous substrate for impregnation into an adhesive solution, which is obtained by dispersing the cured amino resin fine powder into the heat-resistant resin matrix being hardly soluble in acid or oxidizing agent when being subjected to a curing treatment, or applying the adhesive solution onto the fibrous substrate for impregnation by means of a roll coater, a doctor bar or the like and then drying and curing in a drying furnace at 60 a semi-cured state.
In the method using the sheet-shaped adhesive, the sheet-shaped adhesive having the adhesive layer of the semi-cured state after the peeling of the protection film is piled onto the insulation substrate having a surface roughness of Rmax=about 2 μm or the substrate having the conductor circuit so as to face the adhesive layer to the substrate and then lamination cured or pressed under heating at 40 under 40 kg/cm.sup.2 and thereafter the base film is removed to form an adhesive layer for electroless plating.
In the method using the prepreg-like adhesive, the prepreg-like adhesive having the adhesive layer of the semi-cured state is laminated on the insulation substrate having a surface roughness of Rmax=about 2 μm or the substrate having the conductor circuit and then lamination cured or pressed under heating at 40 form an adhesive layer for electroless plating.
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 minutes and then added with 109 parts by weight of methanol.
(4) The mixed resin powder was placed in a mold heated at 150 and held under a pressure of 250 kg/cm.sup.2 for 60 minutes to obtain a shaped body. Moreover, the mold was opened during the molding to escape gas.
(6) Separately, 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 above fine powder having a particle size of 0.5 μm and 30 parts by weight of the above fine powder having a particle size of 5.5 μm, which was kneaded through three rolls and further added with butylcellosolve acetate to prepare an adhesive solution having a solid content of 75%. The viscosity of the solution was measured by means of a digital viscometer made by Tokyo Keiki Co., Ltd. at 20 JIS K7117 to be 5.2 Pa rpm, and the value of SVI (thixotropy) was 2
(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 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 (CrO.sub.3) at 70 adhesive layer 2, further immersed in a neutral solution (made by Shipley) and washed with water. A paladium 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 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   70-72pH                    12.4______________________________________
EXAMPLE 2 (1) A suspension obtained by dispersing 200 g of melamine resin particles (average particle size 3.9 μm) prepare 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 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.
(2) A mixture of 50 parts by weight of the false particles prepared in the above item (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.) was added with butyl carbitol and adjusted in a homodisper dispersing machine to prepare an adhesive solution having a solid content of 80%. The viscosity of this solution was 5.8 Pa and the value of SVI (thixotropy) was 2.9.
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 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.
(2) A mixture of 50 parts by weight of the agglomerate particles prepare in the above item (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 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) was added with butyl carbitol to prepare an adhesive solution having a solid content of 80%. The viscosity of this solution was 5.4 Pa Pa
(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 μmm, 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 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 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 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 nonconductor 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).
(2) 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.), 15 parts by weight of diallyl terephthalate, 4 parts by weight of 2-methyl-1- 4-(methylthio)phenyl!-2-morpholinopropanone-1 (made by Ciba Geigy), 4 parts by weight of an imidazole curing agent (made by Shikoku Kasei Co., Ltd.) 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 butyl cellosolve, which was stirred in a homodizer agitator. Then, the mixture was kneaded through three rolls to prepare a photosensitive adhesive layer having a solid content of 70%. This solution had viscosities of 5.0 Pa rpm and a SVI value of 2
(3) The adhesive solution of the photosensitive resin composition prepared in the above item (2) was applied onto the substrate 1 of the above item (1) by means of a roll coater, which was left to stand at a horizontal state for 20 minutes and dried at 70 adhesive layer 2 having a thickness of about 50 μm (see FIGS. 4b, 4c).
(4) A photomask film printed with black circles of 100 μm in diameter was closed onto the substrate 1 treated in the item (3) and exposed to a super-high vapor pressure mercury lamp at 500 mj/cm.sup.2 Then, it was developed with 1,1,1-trichloroethane through ultrasonic treatment to form opening s as via holes of 100 μm in diameter on the substrate 1, which was then exposed to a super-high vapor pressure mercury lamp at about 3000 mj/cm.sup.2 and heat-treated at 100 150 openings 7 corresponding to the photomask film and having excellent size accuracy (see FIG. 4d).
(5) The substrate 1 treated in the item (4) was immersed in an aqueous solution of 500 g/l chromic acid (CrO.sub.3) as an oxidizing agent at 70 2, which was 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 2 on the substrate 1 to activate the surface of the adhesive layer 2, which was immersed in an electroless plating solution having the same composition as shown in Table 1 for 11 hours to form an electroless plated copper film 6 having a thickness of 25 μm (see FIGS. 4d, 4e).
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 rpm and 2.6 Pa viscometer made by Tokyo Keiki Co., Ltd. at 20 according to JIS K7117 and an SVI value (thixotropy) of 2
(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 having a thickness of about 50 μm (see FIGS. 5b, 5c).
(3) The substrate 1 provided with the adhesive layer 2 was immersed in an aqueous solution of 500 g/l chromic acid (CrO.sub.3) as an oxidizing agent to roughen the surface of the adhesive layer 2, which was immersed in a neutral solution (made by Shipley) and washed with water. Further, openings 7 for via hole were formed through laser (see FIG. 5d), and a paradium catalyst (made by Shipley) was applied to the roughened adhesive layer on the substrate 1 to activate the surface of the adhesive layer 2.
(4) The substrate 1 was heat-treated at 120 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 value of 2
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 and 2.6 Pa
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 orthocresolnovolac 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 value of 2
EXAMPLE 9 This example was fundamentally 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 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 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 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 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 urea and dimethylol urea.
(4) This example was fundamentally the same as in Example 1 except that the urea resin fine powder obtained in the above items (1)-(3) was used as the amino resin fine powder. Moreover, the adhesive solution had viscosities of 5.0 Pa by means of a digital viscometer made by Tokyo Keiki Co., Ltd. at 20
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 bisphenol-A type epoxy resin (made by Yuka Shell Co., Ltd.: molecular weight=900, mp=64 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 by means of a digital viscometer at 20 to JIS K7117.
(2) The adhesive solution was applied to a PET (polyethylene terephthalate) film 14 coated at its surface with silicon coat through a doctor blade 16 and dried in an IR furnace 15 at 80 B-stage (semi-cured state) and further a cover film 11 of polyethylene (for protecting the surface of the adhesive) was laminated thereon to prepare a sheet-shaped adhesive (see FIG. 6a).
(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 kg/cm.sup.2 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 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, 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 thereto. This solution had viscosities of 2.6 Pa Pa
(2) The adhesive was applied to a polyethylene film 11 provided with a silicon coating by means of a roll coater and dried by heating at 120 7a, 7b).
EXAMPLE 18 (1) An adhesive solution having a solid content of 50% was prepared by adding 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 phenol-novolac type epoxy resin (made by Yuka Shell Co., Ltd.: molecular weight=700, mp=40 epoxy resin (made by Yuka Shell Co., Ltd.: molecular weight=500, mp=25 by Shikoku Kasei Co., Ltd.) and adjusting in a homodisper dispersing machine. The viscosity of this solution was 0.1 Pa
(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 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, 80 parts by weight of special functional epoxy resin (made by Nihon Kayaku Co., Ltd.: molecular weight=3200, mp=60 epoxy resin (made by Yuka Shell Co., Ltd.: molecular weight=500, mp=25 Shikoku Kasei Co., Ltd.) in butyl carbitol. The viscosity of this solution was 0.3 Pa
(2) The adhesive solution was applied to a commercially available prepreg 13 by means of a doctor blade 16 and dried at 100 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).
(3) While peeling off the cover film 11, 5 commercially available prepregs and the sheet-shaped adhesive were piled one upon the other so as to contact with the adhesive layer 2, which was pressed at 150 50 kg/cm.sup.2 for 200 minutes and thereafter the PET film 14 was peeled off to obtain the substrate 1 provided at both surfaces with the adhesive layers 2 (see FIGS. 9b, 9c).
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 parts by weight of novolac type polyfunctional epoxy resin (molecular weight=500, mp=35 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 0.1 Pa 20
EXAMPLE 21 (1) 80 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
(3) Then, the -sheet-shaped photosensitive adhesive of the item (2) was piled on the substrate 1 provided with first circuit layer 4 prepare in the same manner as in the item (1) of Example 4 and heated at 80 C. under a pressure of 3 kg/cm.sup.2 to form an adhesive layer 2 (see FIGS. 10b, 10c).
(4) A photomask film printed by black circles of 100 μm in diameter was closed to the substrate 1 treated in the above item (3) and exposed to a super-high vapor pressure mercury lamp at 500 mj/cm.sup.2. This was subjected to ultrasonic developing treatment with 1,1,1-trichloroethane to form opening for via hole of 100 μm in diameter on the circuit board 1', which was further exposed to a super-high vapor pressure mercury lamp at about 3000 mj/cm.sup.2 and heated at 100 further at 150 provided with openings 7 corresponding to the photomask film and having excellent size accuracy (see FIG. 10d).
(5) The substrate 1 treated in the item (4) was immersed in an aqueous solution of 500 g/l chromic acid (CrO.sub.3) as an oxidizing agent at 70 2, which was 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. 10d).
(6) The substrate 1 was heat-treated at 120 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 Pa
(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 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 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 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 20
(2) Then, the adhesive solution was applied to a Tedolar film 12 provided with silicon coating and dried by heating at 80 to prepare a photosensitive sheet-shaped adhesive.
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-morpholinopropanone-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 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 0.1 Pa viscometer at 20
EXAMPLE 25 This example was fundamentally the same as in Example 21 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 phtoinitiator (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 viscometer at 20
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 ih 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 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 resin liquid.
(3) This example was fundamentally the same as in Example 16 except that the guanamine resin fine powder obtained in the above items (1), (2) was used as the amino resin fine powder. Moreover, the viscosity of the adhesive solution was 5.0 Pa digital viscometer at 20
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 measured by means of a digital viscometer at 200 according to JIS K7117.
(2) The adhesive solution was passed through an apparatus consisting of immersion, squeezing, drying and cutting to prepare a prepreg-like adhesive. That is, a galls cloth 18 was immersed in the adhesive solution 17 placed in a tank capable of being stirred under ultrasonic state, squeezed out between squeeze rolls, dried in an IR furnace 15 at 100 (see FIG. 12a).
(3) Glass epoxy prepregs were sandwiched between the prepreg-like adhesives prepared in the item (2) as an outermost layer so as to have a thickness of 1.6 mm, which was treated at 100 for 1 minute and pressed at 100 kg/cm.sup.2 for 20 minutes and then cured at 150 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 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
(2) The adhesive solution was applied onto a glass epoxy prepreg by means of a roll coater, which was left to stand at a horizontal state for 20 minutes and dried at 70 provided with an adhesive layer 2 of 45 μm in thickness (see FIG. 13a).
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 a 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 by means of a digital viscometer at 20 to JIS K7117.
(3) The prepreg-like adhesive of the item (2) was piled on the substrate 1 provided with a first circuit layer 4 in the same manner as in the item (1) of Example 4 and pressed by heating to form an adhesive layer 2 (see FIG. 14b). (4) A both-sided printed circuit board was manufactured by subjecting the substrate 1 provided with the adhesive layer 2 to the same treatment as in the items (4)-(6) of Example 3 (see FIG. 14).
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 60 rpm as measured by means of a digital viscometer at 20 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 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 by means of a digital viscometer at 20 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 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 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 rpm and 0.5 Pa
EXAMPLE 39 (1) Urea, isothiourea and formalin were mixed at a molar ratio of 1:1:2 and cocondensed by heating at 80 cocondensed resin fine powder.
(2) This example was fundamentally the same as in Example 32 except that the urea-thiourea cocondensed resin fine powder obtained in the item (1) was used as the amino resin fine powder. Moreover, the viscosity of the solution was 0.05 Pa viscometer at 20
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 Pa
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 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 Pa
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 Pa
TABLE 2______________________________________Peeling     Electrical                Solubilitystrength    ensulating         Impurity                                 of(kg/cm)     quality  Hardness  influence                                 melamine______________________________________Example 1      1.9     &#9711;                    60      &#9711;                                   300 2      1.8     &#9711;                    50      &#9711;                                   350 3      1.8     &#9711;                    60      &#9711;                                   250 4      1.9     &#9711;                    55      &#9711;                                   220 5      1.8     &#9711;                    52      &#9711;                                   300 6      1.8     &#9711;                    61      &#9711;                                   310 7      1.8     &#9711;                    60      &#9711;                                   310 8      1.9     &#9711;                    61      &#9711;                                   290 9      1.8     &#9711;                    61      &#9711;                                   29010      1.8     &#9711;                    62      &#9711;                                   30011      1.8     &#9711;                    60      &#9711;                                   30012      1.9     &#9711;                    61      &#9711;                                   30013      1.8     &#9711;                    61      &#9711;                                   29014      1.9     &#9711;                    60      &#9711;                                   31015      1.8     &#9711;                    60      &#9711;                                   30016      2.2     &#9711;                    61      &#9711;                                   30117      1.9     &#9711;                    65      &#9711;                                   20018      2.0     &#9711;                    62      &#9711;                                   30019      2.1     &#9711;                    60      &#9711;                                   30020      2.0     &#9711;                    60      &#9711;                                   31021      2.1     &#9711;                    61      &#9711;                                   31022      1.9     &#9711;                    63      &#9711;                                   25523      2.1     &#9711;                    60      &#9711;                                   30024      2.1     &#9711;                    62      &#9711;                                   31025      2.0     &#9711;                    60      &#9711;                                   30026      2.0     &#9711;                    60      &#9711;                                   31027      2.1     &#9711;                    61      &#9711;                                   31028      1.8     &#9711;                    62      &#9711;                                   31029      1.9     &#9711;                    60      &#9711;                                   31030      1.9     &#9711;                    60      &#9711;                                   30031      2.0     &#9711;    &#9711;32      1.8     &#9711;                    61      &#9711;                                   30133      1.8     &#9711;                    55      &#9711;                                   35534      1.9     &#9711;                    58      &#9711;                                   30035      1.9     &#9711;                    57      &#9711;                                   22036      1.9     &#9711;                    55      &#9711;                                   30037      1.7     &#9711;                    60      &#9711;                                   34038      1.9     &#9711;                    55      &#9711;                                   23039      2.0     &#9711;                    61      &#9711;                                   30040      1.9     &#9711;                    60      &#9711;                                   30041      1.8     &#9711;                    65      &#9711;                                   30042      1.8     &#9711;                    65      &#9711;                                   20043      1.9     &#9711;                    60      &#9711;                                   30044      1.8     &#9711;                    65      &#9711;                                   30045      1.8     &#9711;                    60      &#9711;                                   305ComparativeExample 1      1.5     X        35      X       10 2      0.1     X        35      X       10 3      1.5     X        35      X       10 4      0.1     X        35      X       10______________________________________
The surface resistivity in the adhesive-layer is unchangeable as compared with the initial value even after the adhesive layer is immersed in a boiling water of 100 abnormal change even after the circuit board is closed to a hot plate of 300
Adjustment: hardness was adjusted to a value of 100.+-.1 by using a glass plate and then to the indication value by using the aluminum alloy standard piece.
Measurement: hardness was measured by heating the substrate at 150 C. and holding this temperature for 5 minutes.
Test piece: printed circuit board having a comb pattern of LS=50/50 μm
Measurement: the board was placed in a thermo-hygrostat at a temperature of 85.+-.1.degree. 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.
Recently, high densification or high speed access of calculating function in electronic equipments such as large-size computer or the like is advanced with the progress of electronic technique. As a result, high densification and high reliability through fine pattern are lately required even in printed circuit board and LSI mounted print circuit board. Particularly, multilayer printed circuit boards having a plurality of printed circuit layers are lately spotlighted in accordance with high densification and high-speed access.
In the production of the printed circuit board, there has hitherto been known a so-called etched toil method in which a copper foil is laminated onto a substrate and subjected to a photoetching to form a conductor circuit as a method for the formation of conductor circuit. According to this method, the conductor circuit having an excellent adhesion property to the substrate can be formed, but there is a serious drawback that it is difficult to obtain a fine pattern of a high accuracy by etching because the thickness of the copper foil is thick. Furthermore, the production steps become complicated and also the production efficiency is poor.
Na.sup.+ +Cl.sup.- +H.sub.2 O&#8594;NaOH+HCl              (1)
Cu+2NaOH&#8594;Cu(OH).sub.2 +2Na.sup.+                    ( 2)
Cu+2HCl&#8594;CuCl.sub.2 +2H.sup.+                        ( 3)
According to a third aspect of the invention, there is the provision of a method of producing printed circuit boards by forming electroless plated conductor circuits through an adhesive layer formed on a substrate, which comprises the steps of :
The heat-resistant resin matrix is a thermosetting heat-resistant resin or a photosensitive heat-resistant resin. The thermosetting heat-resistant resin matrix is a mixture of an uncured polyfunctional resin having at least one epoxy group or an uncured difunctional epoxy resin and an imidazole series curing agent. The photosensitive heat-resistant resin matrix is at least one phtosensitive heat-resistant resin selected from uncured polyfunctional resin having at least one epoxy group, uncured polyfunctional resin containing an acryl group and uncured polyfunctional acrylic resin, or a mixture of the above resin and at least one photosensitive heat-resistant resin selected from difunctional epoxy resin and difunctional acrylic resin.
Preferably, the thermosetting heat-resistant resin matrix is a mixture of 98-90 wt % of the thermosetting heat-resistant resin consisting of 20-100 wt % as a solid content of the uncured polyfunctional resin having at least one epoxy group and 80-0 wt % as a solid content of the uncured difunctional epoxy resin and 2-10 wt % as a solid content of the imidazole series curing agent. On the other hand, the photosensitive heat-resistant resin matrix is a mixture of 20-100 wt % as a solid content of at least one resin selected from the uncured polyfunctional resin having at least one epoxy group, uncured polyfunctional resin containing an acryl group and uncured polyfunctional acrylic resin and 80-0 wt % as a solid content of at least one resin selected from the uncured difunctional epoxy resin and uncured difunctional acrylic resin.
In the printed circuit board and the method of producing the same according to the invention, the adhesive layer is an adhesive layer formed by application, a sheet-shaped adhesive layer or a prepreglike adhesive layer. As the substrate, use may be made of a substrate provided with conductor circuit.
This application is a division of application Ser. No. 08/248,209, filed May 24, 1994, now U.S Pat. No. 5,447,996, which is a division of application Ser. No. 07/913,935, filed Jul. 17, 1992, now U.S. Pat. No. 5,344,893.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3989767 *Feb 28, 1975Nov 2, 1976Dainippon Ink & Chemicals, IncorporatedPowder coating resin compositions of glycidyl copolymers having an internal flowing agentUS3993549 *Jul 12, 1974Nov 23, 1976W. R. Grace & Co.Curable solid adducts of polyene-polythiol compositions with ureaUS4093674 *Nov 5, 1975Jun 6, 1978Nippon Paint Co., Ltd.Powder coating compositionUS4151220 *Feb 17, 1977Apr 24, 1979Maruzen Oil Co., Ltd.Powder coating compositionUS4152477 *Jan 17, 1977May 1, 1979Matsushita Electric Industrial Co., Ltd.Printed circuit board and method for making the sameUS4496415 *Apr 8, 1982Jan 29, 1985Westinghouse Electric Corp.Method for impregnating resin powder directly into a laminate lay upUS4504607 *Jul 22, 1982Mar 12, 1985Kollmorgen Technologies CorporationEpoxy resin coating composition for printed circuit boardsUS4752499 *May 8, 1986Jun 21, 1988Ibiden Co. Ltd.Adhesive for electroless plating and method of preparation of circuit board using this adhesiveUS5021472 *May 25, 1989Jun 4, 1991Ibiden Co. Ltd.Adhesive for electroless plating and method of preparation of circuit board using this adhesiveUS5039762 *Jan 24, 1989Aug 13, 1991Monsanto CompanyHybrid amino resin compositionsUS5055321 *Apr 28, 1989Oct 8, 1991Ibiden Co., Ltd.Adhesive for electroless plating, printed circuit boards and method of producing the sameUS5106937 *Oct 23, 1990Apr 21, 1992Mitsui Toatsu Chemicals, Inc.Thermosetting resin from penta arylene bis maleimideUS5106945 *Sep 4, 1990Apr 21, 1992Monsanto CompanyPolyglycidamide-poly(meth)-acryloyl-polyamine compositionsUS5137936 *Jul 26, 1990Aug 11, 1992Matsushita Electric Industrial Co., Ltd.Method for packaging electronic parts and adhesive for use in said methodJPH02182731A * Title not availableJPH02188992A * Title not availableJPS5196872A * Title not availableJPS53140344A * Title not availableJPS61276875A * Title not availableJPS63126297A * Title not available* Cited by examinerNon-Patent CitationsReference1"Resin Technique for Coating", Kogyo Chosakai Publishing Co., Ltd., p. 272, 1986. (Japanese).2Moore, J.A., Editor, "Macromolecular Synthese", Method for the Preparation of Macromolecules, Collective vol. 1, pp. 257-264, 1977.3 *Moore, J.A., Editor, Macromolecular Synthese , Method for the Preparation of Macromolecules , Collective vol. 1, pp. 257 264, 1977.4 *Resin Technique for Coating , Kogyo Chosakai Publishing Co., Ltd., p. 272, 1986. (Japanese).* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS6248428Apr 15, 1998Jun 19, 2001Ibiden Co., Ltd.Adhesive for electroless plating, raw material composition for preparing adhesive for electroless plating and printed wiring boardClassifications U.S. Classification427/97.5, 427/98.8, 427/99.5, 427/306International ClassificationH05K3/42, C09J7/00, C08L63/00, H01B3/40, H05K3/18, H05K3/00, C08G59/38, H05K3/46, C09J163/00, C08G59/18, H05K3/38Cooperative ClassificationY10S428/901, Y10S525/934, Y10S525/935, H05K3/184, H01B3/40, H05K2201/0212, C08G59/18, C08G59/38, C09J7/00, H05K2203/0796, H05K3/4644, C09J163/00, H05K2201/0154, H05K3/387, H05K2203/066, H05K3/0035, H05K3/4661, H05K2203/0789, C08L63/00, H05K2203/0143, H05K3/426, H05K2203/0773, H05K3/181European ClassificationC09J163/00, C09J7/00, C08L63/00, C08G59/38, H05K3/38D2, H01B3/40, C08G59/18, H05K3/46C5Legal EventsDateCodeEventDescriptionJan 29, 2010FPAYFee paymentYear of fee payment: 12Jan 27, 2006FPAYFee paymentYear of fee payment: 8Dec 31, 2001FPAYFee paymentYear of fee payment: 4RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google