JP2005347571A - Printed wiring board, substrate therefor and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printed wiring board in which disconnection of conductor wiring formed from a conductive ink or release from a substrate is sufficiently reduced even when using a printing method such as ink jet printing or offset printing, a method of manufacturing the same, and a substrate to be used for such a printed wiring board. <P>SOLUTION: A method of manufacturing a printed wiring board with conductor wiring formed on a substrate includes a substrate preparation step of preparing a substrate containing a resin composition, in which adhesiveness appears for conductor wiring after the lapse of a predetermined temperature history; a conductive film pattern formation step of forming a conductive film pattern by applying a conductive ink onto a surface of the substrate; and a conductor wiring formation step of imparting adhesiveness to the substrate and transferring the conductive film pattern into conductor wiring, by heating and cooling the substrate and the conductive film pattern based on the predetermined temperature history. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a printed wiring board substrate, a printed wiring board, and a printed wiring board manufacturing method.

  A printed wiring board is manufactured by forming a conductor wiring on a substrate. Conventionally, a subtractive method, which is a kind of photolithography method, has been used as a method of forming the conductor wiring on the substrate. The subtractive method includes, for example, (1) a step of forming a metal layer on one or both sides of the insulating layer of the substrate, (2) a step of forming an etching resist layer on the metal layer, and (3) a photomask on the etching resist layer. A step of exposing the etching resist layer by ultraviolet irradiation or the like after being arranged, (4) a step of removing unnecessary portions of the exposed etching resist layer, (5) a step of removing unnecessary portions of the metal layer by etching, etc. It is a method including many steps.

  The multilayer printed wiring board has conductor wiring on the inner layer in addition to the outer layer of the substrate. For example, a printed wiring board having conductor wiring on one side or both sides obtained by the above method is woven into a glass woven fabric. There is known a structure in which a laminate is formed by press laminating a plurality of sheets through an adhesive layer such as a prepreg. Also, normally, (7) a step of drilling the laminate with a drill or a laser, (8) a step of electrically connecting conductor wirings of different layers by plating the drilled portion, etc. Is given.

  In recent years, a method for forming a conductive film pattern on a substrate by an ink jet printing method in manufacturing a printed wiring board (for example, see Patent Documents 1 and 2) is known. In addition, a method of using an offset printing method for manufacturing a printed wiring board (for example, see Patent Document 3) is also known. In these methods, for example, a conductive wiring pattern can be formed by forming a conductive film pattern made of conductive ink and heating it to convert it into a conductor. Therefore, the manufacturing process is compared with the above subtractive method. Simplification is possible. In addition, there is an advantage that the material use efficiency is very high when forming the conductor wiring. Therefore, when these methods are employed for manufacturing a multilayer printed wiring board composed of a plurality of printed wiring boards, higher cost performance can be exhibited.

JP 2003-80694 A JP 2002-121437 A JP-A-11-58921

  However, in the conventional printed wiring board manufactured using the inkjet printing method including the printed wiring board described in Patent Documents 1 and 2, the present inventors cause disconnection of the conductor wiring or peeling from the substrate. It was easy to find, and the yield of printed wiring boards was reduced, and it was found that there was still room for improvement before practical use.

  Moreover, also when manufacturing a printed wiring board using the offset printing method of patent document 3, the disconnection of the conductive wiring of the obtained printed wiring board or peeling from a board | substrate tends to arise, and the yield of a printed wiring board is produced. It has been found that there is still room for improvement before it can be put into practical use.

  The present invention has been made in view of the above circumstances, and even when a printing method such as an inkjet printing method or an offset printing method is used, the conductor wiring formed from the conductive ink is disconnected or peeled off from the substrate. An object of the present invention is to provide a printed wiring board and a method for manufacturing the same. Moreover, an object of this invention is to provide the board | substrate for printed wiring boards used for this printed wiring board.

  As a result of examining the inkjet printing method or the offset printing method described in Patent Documents 1 to 3 in detail, the present inventors have found that glass and polyimide films used as substrates for conventional printed wiring boards have a substrate and a conductor wiring. It was found that this was the cause of the above problems, and the present invention was completed.

  That is, the printed wiring board manufacturing method of the present invention is a printed wiring board manufacturing method in which a conductor wiring is formed on a substrate, and a resin that exhibits adhesiveness to the conductor wiring after a predetermined temperature history. A substrate preparing step for preparing a substrate containing the composition, a conductive film pattern forming step for forming a conductive film pattern by applying a conductive ink on the surface of the substrate, and the substrate and the conductive layer based on the predetermined temperature history. It is characterized by comprising a conductor wiring forming step of imparting adhesiveness to the substrate by heating and cooling the film pattern and converting the conductive film pattern into a conductor wiring.

  Here, the “predetermined temperature history” includes a temperature increase due to heating and a temperature decrease due to cooling (including natural cooling) in this order. Further, the temperature rise temperature and the temperature fall temperature are set so that the conductive ink can be used as a conductor and the resin composition to be used can exhibit adhesiveness.

  In addition, it is not particularly distinguished whether the “substrate” in this specification is a substrate before or after the predetermined temperature history.

  According to the method for manufacturing a printed wiring board of the present invention, the portion of the substrate to which the conductive ink is applied exhibits adhesiveness in the above-described process, so that the conductor wiring and the substrate are sufficiently bonded to each other. Thereby, even when the conductor wiring is formed using a printing method such as an inkjet printing method or an offset printing method, a printed wiring board in which disconnection of the conductor wiring or peeling from the substrate is sufficiently reduced is obtained. Can do. Furthermore, since the adhesiveness of the substrate is manifested in the conductor wiring forming step, the substrate can be easily handled, and a good conductive film pattern can be formed by a printing method.

  In addition, the printed wiring board substrate of the present invention has a conductive film pattern forming step of forming a conductive film pattern by applying a conductive ink on the surface of the substrate, and the conductive film pattern is converted into a conductor wiring through a predetermined temperature history. A substrate used for a printed wiring board manufactured through a conductor wiring forming step, which contains a resin composition that exhibits adhesion to the conductor wiring when heated and cooled based on the predetermined temperature history It is characterized by that.

  The printed wiring board substrate of the present invention having the above-described characteristics contains a resin composition that exhibits adhesiveness according to the predetermined temperature history, and thus sufficiently with the conductor wiring formed in the conductor wiring forming step. Can be glued. Therefore, when a printed wiring board is manufactured using the printed wiring board substrate of the present invention, even if a printing method such as an inkjet printing method or an offset printing method is used, the conductor wiring formed from the conductive ink is disconnected. Alternatively, a printed wiring board in which peeling from the substrate is sufficiently reduced can be obtained. Furthermore, the printed wiring board substrate of the present invention exhibits excellent handling properties and can form a good conductive film pattern by a printing method because the adhesion of the substrate is manifested in the conductor wiring forming step.

  In the present invention, the resin composition is preferably a thermosetting resin composition that is cured after being melted or softened after the predetermined temperature history.

  In the present invention, whether or not the thermosetting resin composition is cured after being melted or softened after a predetermined temperature history can be determined, for example, by the following method.

  First, a film made of a certain thermosetting resin composition is produced by a bar coating method or the like. Next, the viscosity when this film is heated based on a predetermined temperature history is measured using a flow tester, a rheometer, or the like. Observe the viscosity change at the time of temperature rise, there is a case where a decrease in viscosity due to the melting or softening of the film is observed, and then an increase in viscosity due to the progress of the curing reaction of the film is observed. It can be determined that the thermosetting resin composition is cured after being melted or softened at a predetermined temperature history.

  The board | substrate containing this thermosetting resin composition can express the adhesiveness with respect to conductor wiring more reliably. Thereby, the printed wiring board by which the disconnection of the conductor wiring or peeling from the board | substrate is fully reduced can be obtained more reliably. Furthermore, since a thermosetting resin is used, even when the printed wiring board is reheated, the adhesion between the substrate and the conductor wiring does not become insufficient, and the printed wiring board becomes heat resistant. It will be excellent.

  Moreover, in this invention, it is preferable that the said board | substrate is equipped with a base material and the contact bonding layer provided on this base material, and an contact bonding layer contains the said resin composition.

  By using the substrate having such a configuration, the adhesiveness to the conductor wiring can be expressed more reliably.

  Furthermore, it is preferable that the adhesive layer is formed by volatilizing the solvent of the varnish after applying the varnish containing the resin composition on the substrate.

  In this method, since the thickness of the adhesive layer can be easily adjusted to a desired value, the adhesive layer can exhibit sufficient adhesiveness, and the shape of the adhesive layer is restricted by the substrate. The effect that the curvature of a printed wiring board is reduced is acquired.

  Moreover, in this invention, it is preferable that the said board | substrate is a film-form molded object containing the said resin composition.

  Here, the thickness of the molded body is not particularly limited, but is preferably set as appropriate depending on the use of the finally obtained printed wiring board. Moreover, although it does not specifically limit about a shape, It is preferable that it shape | molds or cuts previously according to the shape of the target printed wiring board.

  By using the substrate having such a configuration, the adhesiveness to the conductor wiring can be expressed more reliably. Furthermore, since it is excellent in flexibility, there is an advantage that it can be bent freely.

  In the present invention, the substrate is preferably a prepreg sheet containing the resin composition.

  By using the substrate having such a configuration, the adhesiveness to the conductor wiring can be expressed more reliably. Furthermore, since the dimensional stability in the surface direction is excellent, there is an advantage that the positional accuracy of the conductor wiring is good.

  In the present invention, the resin composition preferably contains an epoxy resin.

  By using an epoxy resin that is a thermosetting resin, the insulation reliability, connection reliability, and heat resistance of the obtained printed wiring board are further improved.

  Moreover, it is preferable that an epoxy resin contains the compound obtained by glycidyl-etherifying the condensate of a phenol compound and an aldehyde compound. By using such a compound, the connection reliability and heat resistance of the obtained printed wiring board are further improved.

  Furthermore, the resin composition preferably contains a curing agent that cures the epoxy resin.

  By using the curing agent, the epoxy resin is efficiently cured in a short time, so that the conductor wiring and the substrate can be more reliably bonded.

  The curing agent is preferably at least one compound selected from the group consisting of a phenol compound, an amine compound, an acid anhydride, an amide compound, a mercaptan compound, and an imidazole compound.

  Since the epoxy resin is efficiently cured in a short time by using the above curing agent, the conductor wiring and the substrate can be more reliably bonded.

  Furthermore, in this invention, it is preferable that the said resin composition contains a polyamide resin. By using a polyamide resin in combination, a film can be formed.

  Moreover, it is preferable that the said resin composition contains a polyamide-imide resin. By using a polyamideimide resin in combination, excellent heat resistance is imparted, and the connection reliability and heat resistance of the resulting printed wiring board are further improved.

  Furthermore, the polyamide-imide resin is preferably a silicone-modified polyamide-imide resin. Silicone-modified polyamide-imide resin is a resin that combines the excellent heat resistance of polyamide-imide resin and the flexibility of silicone rubber. The wiring board has excellent characteristics such as heat resistance, flexibility, and toughness.

  The printed wiring board of the present invention is obtained by any one of the above-described methods for producing a printed wiring board of the present invention. As a result, the printed wiring board of the present invention sufficiently reduces disconnection of the conductor wiring formed from the conductive ink or peeling from the substrate even when a printing method such as an inkjet printing method or an offset printing method is used. Has been.

  According to the present invention, even when a printing method such as an inkjet printing method or an offset printing method is used, the printed wiring in which disconnection of the conductive wiring formed from the conductive ink or peeling from the substrate is sufficiently reduced. A board and a manufacturing method thereof can be provided. Moreover, according to this invention, the board | substrate for printed wiring boards used for this printed wiring board can be provided.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of a printed wiring board substrate of the present invention. A printed wiring board substrate 1 shown in FIG. 1 includes a base material 10 and an adhesive layer 20 provided on the base material 10.

  In the printed wiring board substrate 1 of the present embodiment, a conductive film pattern forming step of forming a conductive film pattern by applying a conductive ink on the surface of the adhesive layer 20, and the conductive film pattern is solidified through a predetermined temperature history. As a result, a printed wiring board is obtained through a conductor wiring forming process which is converted into a conductor wiring.

  The printed wiring board substrate 1 of the present embodiment includes the conductor wiring formed in the conductor wiring forming step and the printing by providing the adhesive layer 20 that exhibits adhesiveness to the conductor wiring after the predetermined temperature history. The wiring board substrate 1 can be sufficiently adhered to each other. As a result, the printed wiring board obtained has sufficiently reduced disconnection of the conductor wiring or peeling from the substrate.

  Examples of the substrate 10 include organic films, metal foils; plates made of metal, glass, ceramics, etc .; epoxy resins, phenol resins, polyimide resins, polyamide resins, polyamideimide resins, silicone-modified polyamideimide resins, polyester resins, cyanates. Examples thereof include a plate made of a fiber reinforced plastic obtained by combining a resin such as ester resin, BT resin, acrylic resin, melamine resin, urethane resin, alkyd resin with glass woven fabric, glass nonwoven fabric, paper, aramid nonwoven fabric, or the like. These base materials can be appropriately selected according to the desired form of the printed wiring board.

  The adhesive layer 20 contains a resin composition that exhibits adhesiveness to the conductor wiring after the predetermined temperature history. Examples of the resin used in this resin composition include epoxy resin, phenol resin, polyimide resin, polyamide resin, polyamideimide resin, silicone-modified polyamideimide resin, polyester resin, cyanate ester resin, BT resin, acrylic resin, melamine resin, A urethane resin, an alkyd resin, etc. are mentioned. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  In the printed wiring board substrate 1 of the present embodiment, the resin composition is preferably a thermosetting resin composition that is cured after being melted or softened after the predetermined temperature history. In the printed wiring board substrate 1 having the adhesive layer 20 containing such a thermosetting resin composition, the conductor wiring and the substrate can be more reliably bonded.

  Moreover, it is preferable to use a thermosetting resin composition from the viewpoints of insulation reliability, connection reliability, heat resistance, and the like of the printed wiring board.

  The composition of the thermosetting resin composition is not particularly limited as long as it is cured after being melted or softened after passing through the predetermined temperature history. For example, an epoxy resin or a phenol resin as a thermosetting resin as a main agent. The composition containing is mentioned. In the printed wiring board substrate 1 of this embodiment, the thermosetting resin composition preferably contains an epoxy resin as the thermosetting resin.

  When the said thermosetting resin composition contains an epoxy resin, the insulation reliability of the obtained printed wiring board, connection reliability, and heat resistance will improve more.

  Examples of the epoxy resin contained in the thermosetting resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, and aliphatic chain epoxy. Resin, glycidyl ester type epoxy resin; a compound obtained by glycidyl etherification of a condensate of a phenol compound such as phenol, cresol, alkylphenol, catechol, bisphenol F, bisphenol A, bisphenol S and an aldehyde compound such as formaldehyde or salicylaldehyde , Compounds obtained by glycidyl etherification of bifunctional phenols, compounds obtained by glycidyl etherification of bifunctional alcohols, compounds obtained by glycidyl etherification of polyphenols Objects, as well as hydrogenated products or halides of these compounds. The molecular weight of these epoxy resins is not particularly limited. Moreover, said epoxy resin can be used individually by 1 type or in combination of 2 or more types.

  Of the above epoxy resins, from the viewpoint of more reliably obtaining the heat resistance and connection reliability of the printed wiring board, it is preferable to use a compound obtained by glycidyl etherification of a condensate of a phenol compound and an aldehyde compound. Examples of such compounds include o-cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, phenol salicylaldehyde novolak type epoxy resins, and the like. As commercially available products, “YDCN500-10” (trade name, manufactured by Toto Kasei Co., Ltd.), “E-154”, “E-157”, and “E-1032” (Japan Epoxy) Resin Co., Ltd., trade name).

  Moreover, it is preferable that the said thermosetting resin composition used for the board | substrate 1 for printed wiring boards of this embodiment further contains the hardening | curing agent. By using the curing agent, the epoxy resin is efficiently cured in a short time, so that a printed wiring board in which the conductor wiring and the substrate are sufficiently bonded to each other can be obtained more reliably and easily. It does not specifically limit about the kind of hardening | curing agent, According to the kind of thermosetting resin to be used, it can select suitably.

  For example, when an epoxy resin is included in the thermosetting resin composition, amines such as diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, and dicyandiamide are used as the curing agent; Acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, trimellitic anhydride; imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diph Nylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline Imidazoles such as 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; imino groups are masked with acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate, etc. Imidazoles; bisphenol F, bisphenol A, bisphenol S, polyvinylphenol; phenol, cresol, al Condensates of phenolic compounds such as ruphenol, catechol, bisphenol F, bisphenol A, bisphenol S and aldehyde compounds such as formaldehyde and salicylaldehyde and their halides; polyamide resins, polyamideimide resins, silicone modified polyamideimide resins, etc. Of the amide compound. These can be used alone or in combination of two or more.

  In the thermosetting resin composition used for the printed wiring board substrate 1 of the present embodiment, it is preferable to use a polyamide resin among the curing agents. A film can be formed by using an epoxy resin and a polyamide resin in combination.

  Moreover, it is preferable that the said thermosetting resin composition contains a polyamidoimide resin.

  When a polyamideimide resin is used as a curing agent for an epoxy resin, it becomes easier to form a film from the thermosetting resin composition due to the excellent film forming ability of the polyamideimide resin. Thereby, the contact bonding layer 20 can be more easily formed by bonding the film of the said thermosetting resin composition with the base material 10. FIG. Moreover, when using the film of the said thermosetting resin composition as a board | substrate for printed wiring boards, it is especially preferable to use a polyamideimide resin. This will be described later.

  Furthermore, the polyamideimide resin is preferably a silicone-modified polyamideimide resin. Silicone-modified polyamide-imide resin is a resin that combines the excellent heat resistance of polyamide-imide resin and the flexibility of silicone rubber. The wiring board has excellent characteristics such as heat resistance, flexibility, and toughness.

  Examples of the silicone-modified polyamideimide resin include commercially available “KS-6500” (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  Regarding the molecular weights of the polyamide resin, the polyamideimide resin, and the silicone-modified polyamideimide resin, the styrene-converted weight average molecular weight measured by gel per emission chromatography is preferably 20000 or more, and more preferably 40000 or more. By using a material having such a molecular weight, it becomes easier to use the thermosetting resin composition after being formed into a film.

  Moreover, when a hardening | curing agent contains at least 1 sort (s) of a polyamide resin, a polyamideimide resin, and a silicone modified polyamideimide resin, the whole quantity of these resins is 50-98 mass in a thermosetting resin composition. %, And more preferably 70 to 95% by mass. If the blending ratio of the resin is less than 50% by mass in the thermosetting resin composition, the film-forming ability and the heat resistance tend to decrease. On the other hand, if it exceeds 98% by mass, the solvent resistance decreases. Tend to.

  Moreover, you may mix | blend a catalyst, a hardening accelerator, a coupling agent, antioxidant, a filler, etc. with the said thermosetting resin composition as needed.

  The method for forming the adhesive layer 20 of the printed wiring board substrate 1 of the present embodiment is not particularly limited. For example, the adhesive layer 20 can be formed by bonding a film made of the resin composition to the base material 10.

  As a method for obtaining a film of the resin composition, for example, a varnish obtained by dissolving or dispersing the resin composition in a solvent is developed on a PET film to form a coating film, and the solvent is removed from the coating film. The method of peeling the film formed by volatilizing from PET film is mentioned.

  Although it does not specifically limit as a solvent, For example, a dimethylacetamide, N-methylpyrrolidone etc. are mentioned. Moreover, the conditions for volatilizing the solvent are not particularly limited. For example, when the resin composition contains a thermosetting resin, it is preferably dried at a temperature lower than the temperature at which the curing reaction of the resin composition starts.

  Moreover, the film thickness of the film which forms the contact bonding layer 20 is although it does not specifically limit, It is preferable that it is 5-100 micrometers.

  Moreover, as a method of forming the adhesive layer 20 of the printed wiring board substrate 1 of the present embodiment, a varnish in which the resin composition is dissolved or dispersed in a solvent or the like is applied on the substrate 10 and dried. A method of forming the adhesive layer 20 may be used.

  In the printed wiring board substrate 1 of the present embodiment, the adhesive layer 20 volatilizes the step of applying a varnish containing the resin composition on a substrate to form a coating film, and the solvent of the formed coating film. It is preferable that it is formed through the process of making it.

  When the adhesive layer 20 is formed by this method, defects such as voids do not occur at the interface between the base material and the adhesive layer.

  Moreover, the board | substrate for printed wiring boards of this invention may shape | mold the said resin composition in the film form. That is, in the printed wiring board substrate 1 shown in FIG. 1, the substrate 10 is not provided, and the film of the resin composition functions as an adhesive layer and also functions as a printed wiring board substrate. Such a printed wiring board substrate is particularly suitable for use as a flexible printed wiring board.

  Further, the fact that the printed wiring board substrate is a film made of the resin composition is effective particularly when it is desired to reduce the thickness of the printed wiring board.

  Moreover, although it does not specifically limit about the specific thickness of a film, It is preferable to set according to the use of the printed wiring board obtained by finally hardening | curing a film. Usually, it is preferable from the point of handleability that film thickness is the range of 10-150 micrometers. Moreover, although it does not specifically limit about a shape, It is preferable that it shape | molds or cuts previously according to the shape of the target printed wiring board.

  Furthermore, the prepreg sheet containing the said resin composition is mentioned as another suitable embodiment of the board | substrate for printed wiring boards of this invention.

  As such a prepreg sheet, for example, a substrate such as a glass woven fabric, a glass nonwoven fabric, paper, an aramid nonwoven fabric is immersed in a varnish obtained by dissolving or dispersing the resin composition in the solvent, and then a dryer. Examples thereof include a prepreg sheet obtained by volatilizing the solvent with a method such as the above.

  The printed wiring board substrate, which is a prepreg sheet containing the resin composition, can more reliably exhibit adhesiveness to the conductor wiring. Furthermore, since the dimensional stability in the surface direction is excellent, there is an advantage that the positional accuracy of the conductor wiring is good.

  Next, a preferred embodiment of the method for producing a printed wiring board of the present invention will be described.

  The printed wiring board manufacturing method of the present embodiment includes a substrate preparation step for preparing the printed wiring board substrate of the present invention, and a conductive film for forming a conductive film pattern by applying a conductive ink on the surface of the substrate. A film pattern forming process, and a conductor wiring forming process for imparting adhesiveness to the substrate and converting the conductive film pattern into a conductor wiring by heating and cooling the substrate and the conductive film pattern based on the predetermined temperature history; Is provided.

  As described above, the printed wiring board substrate of the present invention contains a resin composition that exhibits adhesiveness to the conductor wiring through the predetermined temperature history. Thereby, the conductor wiring formed at the said conductor wiring formation process fully adhere | attaches with the board | substrate for printed wiring boards. Therefore, the printed wiring board manufacturing method of the present embodiment described above may be caused by disconnection of the conductor wiring formed from the conductive ink or from the substrate even when a printing method such as an inkjet printing method or an offset printing method is used. A printed wiring board in which peeling is sufficiently reduced can be obtained.

  Although it does not specifically limit as a conductive ink used with the manufacturing method of the printed wiring board of this embodiment, What melt | dissolved or disperse | distributed the electroconductive material in the solvent is mentioned.

  Examples of the conductive material include conductive metals such as gold, silver, copper, platinum, palladium, and nickel, fine particles or colloids of various alloys, inorganic conductive fine particles such as carbon black, and conductive polymers. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of the solvent include aliphatic hydrocarbon organic solvents such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, isopentane, isohexane, isooctane, cyclohexane, methylcyclohexane, and cyclopentane; benzene, toluene, o-xylene , M-xylene, p-xylene, ethylbenzene, mesitylene, naphthalene, cyclohexylbenzene, diethylbenzene and other aromatic hydrocarbon solvents; methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate , Ester solvents such as isobutyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone; methanol, ethanol, propanol, isopropanol, sec-butanol Alcohol solvents such as tert-butanol, cyclohexanol and α-terpineol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-hexanone, 2-heptanone and 2-octanone; diethylene glycol ethyl ether; Diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol Sopropyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol-t-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate, triethylene glycol butyl ether acetate, Alkylene glycol solvents such as triethylene glycol-t-butyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, Ether solvents such as til vinyl ether, anisole, butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, dioxane, furan, tetrahydrofuran; N, N-dimethylformamide, N, N-dimethyla Amide solvents such as cetamide and N-methylpyrrolidone; water and the like. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Moreover, binder resin, such as a dispersing agent, a surface treating agent, and an epoxy resin, can be added to a conductive ink as needed.

  In the printed wiring board manufacturing method of the present embodiment, the method for applying the conductive ink to the surface of the substrate is not particularly limited, and examples thereof include printing methods such as an ink jet printing method and an offset printing method.

  In addition, the above-mentioned predetermined temperature history that solidifies the conductive film pattern and converts it into conductive wiring and develops the adhesiveness of the resin composition contained in the printed wiring board substrate of the present invention, The temperature is not particularly limited as long as it includes at least the temperature drop due to cooling (including natural cooling) in this order, and the temperature rise temperature and the temperature fall temperature may be obtained by solidifying the conductive ink into a conductor. It can be set so that the resin composition to be used can develop adhesiveness.

  Specifically, for example, when using the above-mentioned thermosetting resin composition containing an epoxy resin as a resin composition using a silver paste as a conductive ink, the conductive ink can be converted into a conductor, and thermosetting A temperature history in which the resin composition is heated at 150 to 300 ° C., which exceeds the temperature at which the curing reaction starts, for 1 to 2 hours and then cooled to room temperature.

  The temperature at which the thermosetting resin composition starts a curing reaction can be measured by a flow tester, a rheometer, a differential scanning calorimeter, or the like.

  Moreover, it is preferable that the said heating is less than the temperature which the said thermosetting resin composition contained in the printed wiring board board | substrate starts thermal decomposition.

  The temperature at which the thermosetting resin composition starts to decompose can be measured by, for example, a thermogravimetric meter or a differential calorimeter.

  Moreover, when a thermoplastic resin is contained as the resin composition, it is preferable that the temperature rise is not less than the temperature at which the resin composition melts or softens.

  As for the heating means, for example, a method in which the entire substrate on which the conductive film pattern is formed is heated using an oven, a hot plate, or the like.

  In addition, from the viewpoint of preventing oxidation of the conductive material and the substrate, heating is preferably performed under an inert atmosphere such as nitrogen, a reducing atmosphere such as carbon monoxide, or under reduced pressure.

  The preferred embodiments of the printed wiring board substrate, the printed wiring board, and the printed wiring board manufacturing method of the present invention have been described above, but the present invention is not limited to the above embodiment.

  For example, for a printed wiring board substrate having an adhesive layer and a base material, the adhesive layer may be provided on both surfaces of the base material, or when the place where conductor wiring is formed is limited. An adhesive layer may be provided on a part of the material.

  In the printed wiring board of the present invention, since the conductor wiring and the substrate are sufficiently bonded, the problem of disconnection of the conductor wiring or peeling from the substrate is sufficiently reduced, and the printed wiring board is used for an IC card, a mobile phone, and the like. It is useful as a printed wiring board.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Synthesis of polyamide-imide resin]
(Polyamideimide resin 1)
A heat-coolable 500 ml reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and both ends aminated polypropylene glycol (trade name “Jeffamine D-2000”, manufactured by Sun Techno Chemical Co., Ltd.) 19.2 g, 4 , 4'-diaminodicyclohexylmethane (manufactured by Shin Nippon Chemical Co., Ltd., trade name “Wandamine HM”) 8.08 g, trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 19.36 g, N-methylpyrrolidone 244.24 g Then, 32 g of toluene was added, and the mixture was heated to 80 ° C. under a nitrogen stream and dissolved. After confirming dissolution, the reaction solution was heated to 160 ° C. and refluxed for 2 hours. Thereafter, the temperature was raised to 180 ° C. while removing toluene from the reaction system together with the water produced during the reaction, and the mixture was further stirred for 2 hours. Then, after cooling to room temperature, 14.12 g of methylene-4,4′-bis (phenylisocyanate) (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “MILLIONATE MT-F”) was added, and the temperature was increased again to 150 ° C. Warmed and stirred for 2 hours. Then, it cooled to room temperature and obtained the polyamideimide resin solution of 20% of non volatile matters. It was 70400 when the weight average molecular weight of the obtained polyamidoimide resin was measured by the gel per emission chromatography.

(Polyamideimide resin 2)
Both ends of amine-modified polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KF-8010”) 18.7 g in a 500 ml reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, capable of being heated and cooled. , 2-bis (4- (4-aminophenoxy) phenyl) propane (trade name “BAPP” manufactured by Wakayama Seika Kogyo Co., Ltd.), trimellitic anhydride 29.58 g, N-methylpyrrolidone 213 g, toluene 73 g was charged and dissolved by heating to 80 ° C. under a nitrogen stream. After confirming dissolution, the reaction solution was heated to 160 ° C. and refluxed for 2 hours. Thereafter, the temperature was raised to 190 ° C. while removing toluene from the reaction system together with water produced during the reaction, and the mixture was further stirred for 2 hours. Thereafter, after cooling to room temperature, 22.03 g of “MILLIONATE MT-F” was added, and the temperature was raised again to 190 ° C. and stirred for 2 hours. Thereafter, it was cooled to room temperature to obtain a silicone-modified polyamideimide resin solution having a nonvolatile content of 30%. It was 73000 when the weight average molecular weight of the obtained silicone modified polyamideimide resin was measured by gel per emission chromatography.

[Combination of varnish]
(Varnish 1)
It is obtained by dissolving 1.5 g of o-cresol novolak type epoxy resin (trade name “YDCN500-10”, manufactured by Toto Kasei Co., Ltd.) in 31.05 g of dimethylacetamide as a solvent, and further by synthesizing the polyamideimide resin 1 In addition, 67.43 g of the polyamideimide resin solution and 0.01 g of 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved to obtain a varnish having a nonvolatile content of 15%.

  Next, the obtained varnish is spread on a PET film to form a coating film, and the coating film is heated and dried at 130 ° C. for 10 minutes, and then peeled off from the PET film to form a film having a thickness of 100 μm. Obtained. A circular sample having a diameter of 20 mm was cut out from the obtained film, and a stack of five samples was used as a measurement sample. With respect to this measurement sample, the temperature dependence of the viscosity was measured at a heating rate of 5 ° C./min with a rheometer (manufactured by Rheometric, product name “ARES-2KSTD”), and the graph shown in FIG. 2 was obtained. As shown in FIG. 2, the measurement sample had a softening start temperature of 85 ° C. and a curing reaction start temperature of 113 ° C., and it was confirmed that the measurement sample exhibited adhesiveness.

(Varnish 2)
In 53.53 g of dimethylacetamide, 1.5 g of YDCN500-10 was dissolved, and 44.96 g of the silicone-modified polyamideimide resin solution obtained by the synthesis of polyamideimide resin 2 and 0.01 g of 2-ethyl-4-methylimidazole were mixed. As a result, a varnish having a nonvolatile content of 15% was obtained.

  Next, a film was produced from the obtained varnish in the same manner as Varnish 1, and a measurement sample was obtained. About the obtained sample for a measurement, the temperature dependence of a viscosity was measured with the rheometer at the temperature increase rate of 5 degree-C / min, and the graph shown in FIG. 3 was obtained. As shown in FIG. 3, the measurement sample had a softening start temperature of 105 ° C. and a curing reaction start temperature of 135 ° C., and it was confirmed that the measurement sample exhibited adhesiveness.

(Example 1)
Varnish 1 was spread on a PET film, dried by heating at 130 ° C. for 10 minutes, and then peeled from the PET film to obtain a film having a thickness of 50 μm. On the obtained film, a silver paste (trade name “Perfect Silver”, manufactured by Vacuum Metallurgical Co., Ltd.) was used as a conductive ink, and a linear circuit pattern having a width of 150 μm was printed by an ink jet printing method. The printed circuit board was made by converting the linear circuit pattern into a conductor by heating for 1 hour.

  A printed wiring board was prepared in the same manner except that the linear circuit pattern was used as a test pattern, and a tape peeling test was performed on the printed wiring board in accordance with JIS C 5012 8.5. As a result of the test, no peeling of the conductor circuit was observed.

(Example 2)
A glass cloth having a thickness of 30 μm was immersed in the varnish 1, and this was heated and dried at 130 ° C. for 10 minutes to obtain a prepreg sheet having a thickness of 50 μm. Using the perfect silver on the obtained prepreg sheet, a linear circuit pattern with a width of 150 μm is printed by an ink jet printing method, and this is heated at 250 ° C. for 1 hour to convert the linear circuit pattern into a conductor and print wiring. A board was created.

  Moreover, as a result of conducting the tape peeling test in the same manner as in Example 1, no peeling of the conductor circuit was observed.

(Example 3)
Varnish 1 was spread on a glass plate having a thickness of 0.4 mm and dried by heating at 130 ° C. for 10 minutes to obtain a glass plate having an adhesive layer having a thickness of 50 μm on the surface. Using perfect silver on the adhesive layer of the obtained glass plate, a linear circuit pattern with a width of 150 μm was printed by an ink jet printing method, and this was heated at 250 ° C. for 1 hour to convert the linear circuit pattern into a conductor. A printed wiring board was created.

  Moreover, as a result of conducting the tape peeling test in the same manner as in Example 1, no peeling of the conductor circuit was observed.

Example 4
Varnish 2 was spread on a PET film, dried by heating at 130 ° C. for 10 minutes, and then peeled from the PET film to obtain a film having a thickness of 50 μm. On the obtained film, using a perfect silver, a linear circuit pattern having a width of 150 μm was printed by an ink jet printing method, and this was heated at 250 ° C. for 1 hour to convert the linear circuit pattern into a conductor, thereby printing a printed wiring board. It was created.

  Moreover, as a result of conducting the tape peeling test in the same manner as in Example 1, no peeling of the conductor circuit was observed.

(Example 5)
A glass cloth having a thickness of 30 μm was immersed in the varnish 2 and dried by heating at 130 ° C. for 10 minutes to obtain a prepreg sheet having a thickness of 50 μm. Using the perfect silver on the obtained prepreg sheet, a linear circuit pattern with a width of 150 μm is printed by an ink jet printing method, and this is heated at 250 ° C. for 1 hour to convert the linear circuit pattern into a conductor and print wiring. A board was created.

  Moreover, as a result of conducting the tape peeling test in the same manner as in Example 1, no peeling of the conductor circuit was observed.

(Example 6)
Varnish 1 was spread on a glass plate having a thickness of 0.4 mm and dried by heating at 130 ° C. for 10 minutes to obtain a glass plate having an adhesive layer having a thickness of 50 μm on the surface. Using perfect silver on the adhesive layer of the obtained glass plate, a linear circuit pattern with a width of 150 μm was printed by an ink jet printing method, and this was heated at 250 ° C. for 1 hour to convert the linear circuit pattern into a conductor. A printed wiring board was created.

  Moreover, as a result of conducting the tape peeling test in the same manner as in Example 1, no peeling of the conductor circuit was observed.

(Comparative Example 1)
On a polyimide film having a thickness of 50 μm (trade name “UPILEX 50S” manufactured by Ube Industries, Ltd.), a linear circuit pattern having a width of 150 μm was printed by an ink jet printing method using Perfect Silver, and this was printed at 250 ° C. for 1 hour. The printed circuit board was made by converting the linear circuit pattern into a conductor by heating.

  Moreover, as a result of conducting the tape peeling test in the same manner as in Example 1, the conductor circuit was peeled off from the polyimide film.

(Comparative Example 2)
On a glass plate with a thickness of 0.4 mm, using Perfect Silver, a linear circuit pattern with a width of 150 μm is printed by inkjet printing, and this is heated at 250 ° C. for 1 hour to convert the linear circuit pattern into a conductor. A printed wiring board was created.

  Moreover, as a result of conducting the tape peeling test in the same manner as in Example 1, the conductor circuit was peeled off from the glass plate.

  In the printed wiring boards of Examples 1 to 6, it was confirmed that the formed conductor circuit and the substrate were sufficiently adhered by using the substrate having the resin composition exhibiting adhesiveness. On the other hand, in the printed wiring boards of Comparative Examples 1 and 2, adhesion between the formed conductor circuit and the substrate was insufficient.

It is a schematic cross section which shows suitable one Embodiment of the board | substrate for printed wiring boards of this invention. It is a graph which shows the temperature dependence of the viscosity of the film formed from the varnish 1 used in an Example. It is a graph which shows the temperature dependence of the viscosity of the film formed from the varnish 2 used in an Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Board | substrate for printed wiring boards, 10 ... Base material, 20 ... Adhesive layer

Claims (27)

A method of manufacturing a printed wiring board in which conductor wiring is formed on a substrate,
A substrate preparation step of preparing a substrate containing a resin composition that exhibits adhesiveness to the conductor wiring after a predetermined temperature history;
A conductive film pattern forming step of forming a conductive film pattern by applying a conductive ink on the surface of the substrate;
A conductor wiring forming step of imparting adhesiveness to the substrate by heating and cooling the substrate and the conductive film pattern based on the predetermined temperature history, and converting the conductive film pattern into the conductor wiring;
A method for producing a printed wiring board, comprising:   The method for producing a printed wiring board according to claim 1, wherein the resin composition is a thermosetting resin composition that is cured after being melted or softened after the predetermined temperature history. The substrate is
A base material, and an adhesive layer provided on the base material,
The method for manufacturing a printed wiring board according to claim 1, wherein the adhesive layer contains the resin composition. The adhesive layer is
The method for producing a printed wiring board according to claim 3, wherein the varnish containing the resin composition is formed on the substrate by volatilizing a solvent of the varnish. The substrate is
It is a film-form molded object containing the said resin composition, The manufacturing method of the printed wiring board of Claim 1 or 2 characterized by the above-mentioned. The substrate is
It is a prepreg sheet containing the said resin composition, The manufacturing method of the printed wiring board of Claim 1 or 2 characterized by the above-mentioned.   The method for producing a printed wiring board according to any one of claims 1 to 6, wherein the resin composition contains an epoxy resin.   The method for producing a printed wiring board according to claim 7, wherein the epoxy resin contains a compound obtained by glycidyl etherification of a condensate of a phenol compound and an aldehyde compound.   The method for producing a printed wiring board according to claim 7, wherein the resin composition contains a curing agent that cures the epoxy resin.   The printed wiring according to claim 9, wherein the curing agent is at least one compound selected from the group consisting of a phenol compound, an amine compound, an acid anhydride, an amide compound, a mercaptan compound, and an imidazole compound. A manufacturing method of a board.   The said resin composition contains a polyamide resin, The manufacturing method of the printed wiring board as described in any one of Claims 7-10 characterized by the above-mentioned.   The method for manufacturing a printed wiring board according to any one of claims 7 to 11, wherein the resin composition contains a polyamideimide resin.   The method for producing a printed wiring board according to claim 12, wherein the polyamideimide resin is a silicone-modified polyamideimide resin. A conductive film pattern forming step of forming a conductive film pattern by applying a conductive ink on the surface of the substrate;
A conductor wiring forming step in which the conductive film pattern is converted into a conductor wiring through a predetermined temperature history;
The substrate used for a printed wiring board manufactured through
A printed wiring board substrate comprising a resin composition that exhibits adhesiveness to the conductor wiring when heated and cooled based on the predetermined temperature history.   The printed wiring board substrate according to claim 14, wherein the resin composition is a thermosetting resin composition that is cured after being melted or softened after the predetermined temperature history. A base material, and an adhesive layer provided on the base material,
The printed wiring board substrate according to claim 14, wherein the adhesive layer contains the resin composition. The adhesive layer is
The substrate for a printed wiring board according to claim 16, wherein the substrate is formed by volatilizing a solvent of the varnish after applying the varnish containing the resin composition on the base material.   The printed wiring board substrate according to claim 14, wherein the printed wiring board substrate is a film-like molded body containing the resin composition.   The printed wiring board substrate according to claim 14 or 15, wherein the printed wiring board substrate is a prepreg sheet containing the resin composition.   The printed circuit board substrate according to any one of claims 14 to 19, wherein the resin composition contains an epoxy resin.   21. The printed wiring board substrate according to claim 20, wherein the epoxy resin contains a compound obtained by glycidyl etherification of a condensate of a phenol compound and an aldehyde compound.   The printed wiring board substrate according to claim 20 or 21, wherein the resin composition contains a curing agent that cures the epoxy resin.   The printed wiring according to claim 22, wherein the curing agent is at least one compound selected from the group consisting of a phenol compound, an amine compound, an acid anhydride, an amide compound, a mercaptan compound, and an imidazole compound. Board substrate.   The printed resin board substrate according to any one of claims 20 to 23, wherein the resin composition includes a polyamide resin.   The printed wiring board substrate according to any one of claims 20 to 24, wherein the resin composition contains a polyamideimide resin.   The printed wiring board substrate according to claim 25, wherein the polyamide-imide resin is a silicone-modified polyamide-imide resin. A printed wiring board obtained by the method for producing a printed wiring board according to claim 1.

Images