TW200942095A - Resist ink and method for manufacturing multilayer printed wiring board - Google Patents

Abstract

Disclosed is a resist ink having improved heat resistance and crack resistance. Also disclosed is a method for manufacturing a multilayer printed wiring board having a partially exposed inner layer, wherein the resist ink is used. Specifically disclosed is a resist ink containing at least one member selected from the group consisting of tetracarboxylic acids, tetracarboxylic acid dianhydrides and half esterified tetracarboxylic acid dianhydrides, a polyhydric alcohol having three or more hydroxyl groups in a molecule, and a filler. The resist ink is soluble in an alkaline solution.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist ink for exposing a portion of an inner layer in a manufacturing step of a multilayer printed wiring board, and using the resist ink A method of manufacturing a multilayer printed wiring board in which an exposed region is formed on one of the inner layers. [Prior Art] In recent years, in order to meet the requirements of small size, light weight, and high functionality of electronic equipment, multi-layer printed wiring boards have gradually required different structural layers. For example, in order to increase the degree of freedom in machine design, there is a rigid flexible printed wiring board (flex-ngld printed wiring) that uses a flexible substrate cable to connect multiple layers of rigidity without a connector. The substrates are mutually connected to form an integrated structure. In addition, it is required to have a low profile as a packaging application, and it is required to mount a partial shape of a semiconductor element & a so-called empty 15 (coffee) structure. Further, the recent rigid-flexible composite printed wiring board has a tendency to use not only a flexible portion as a rigid substrate but also a hard wire, and also actively use it as a component mounting portion or an LCD module. LCD connection or connector connection. In a conventional rigid-flexible composite printed wiring board, a flexible substrate having a wiring pattern formed on one surface or both surfaces of an insulating film such as a polyimide film is formed by performing an insulating coating (cover layer or the like). And as part of the rigid part 'prepreg and (4), or an insulating sheet with copper foil. 200942095 At this time, the entire surface of the flexible portion is covered by the cover layer and serves as a cable connecting the rigid portions. On the other hand, a rigid flexible composite printed wiring board using a flexible portion as a connector connecting portion is provided with a flexible terminal portion protruding from one side of the rigid portion. Such a terminal portion is not covered by the film of the cover layer, but exposes the wiring pattern of the flexible substrate. A rigid-flexible composite printed wiring board as a component mounting portion or an LCD connecting portion is used. In the manufacturing step, the wiring pattern of the flexible substrate must be partially exposed. The wiring pattern exposed in this manner must be The reliability of the function as a component mounting portion, an LCD connecting portion, and a connector connecting portion is higher. The method for producing a rigid-flexible composite printed wiring board has, for example, a method of laminating a bonding sheet or a prepreg having an opening portion corresponding to a portion corresponding to a flexible portion in advance on a flexible substrate, and Further, a copper clad or a copper foil of a glass epoxy resin is laminated on the bonding sheet or the prepreg to form a rigid portion in which a prepreg or the like is laminated, and the opening portion is formed. A laminated prepreg and a flexible portion composed only of a flexible substrate. In this method, when the bonding sheet, the prepreg, the copper foil, or the like is laminated, heating and pressurization are performed. Therefore, it is unavoidable that the resin constituting the bonding sheet or the prepreg flows out to the opening. That is, this method causes the resin constituting the bonding sheet or the prepreg to flow out to the flexible portion. In particular, when the wiring pattern is exposed to the flexible portion, the wiring pattern portion adheres to the resin to cause electrical defects. 200942095 A method of preventing resin from flowing into a flexible portion, for example, has the method described in Patent Document 1 below. In the patent document, a rigid/leafable composite printed wiring board is described, which is formed by screen printing, and is formed in a flexible portion of a rigid/lead composite printed squall plate corresponding to a predetermined portion of the bending. And the portion other than the curved pre-bending portion is multi-layered to form a rigid portion. In the case of forming a heat-resistant film by the flexible portion, it is possible to prevent the resin in the prepreg from flowing into a predetermined portion to be bent when the multilayer is formed.

However, the rigid-flexible composite printed wiring board is not formed with a wiring pattern in advance in the curved portion, and is a physical peeling method in which the heat-resistant film is peeled off. In the method of manufacturing such a rigid-flexible composite printed wiring board, after the rigid portion is formed, the heat-resistant film and the adjacent prepreg enter each other, so that the heat-resistant film is extremely difficult to be peeled off, and the prepreg is formed. The boundary of the heat-resistant film may cause damage or cracking in the insulating layer, and it is impossible to avoid the above-mentioned situation from being completely peeled off. In addition, the method for producing the rigid/flexible composite printed wiring board is a method which physically removes the heat-resistant film, and is therefore cumbersome. Further, when the method for manufacturing a rigid-flexible composite printed wiring board is applied to a wiring pattern in a curved portion, the heat-resistant film is laminated by a high temperature and a high pressure, unlike a flat surface in which a wiring pattern is not formed. It is firmly attached to the unevenness formed by the wiring pattern. Therefore, it is very difficult to peel off the heat resistant film without damaging the wiring pattern and leaving no residue between the wiring patterns. In addition, the multilayer printed wiring board which exposes the inner layer is not limited to the 5 200942095 rigid-flexible composite printed wiring board. For the rigid multilayer substrate, there is also a method for exposing the inner layer (for example, refer to Patent Document 2, Patent Literature). 3). These techniques are performed after the prepreg or the like is laminated, and the prepreg or the like is cut to the internal circuit to be exposed by the hole expanding process, whereby the internal circuit is exposed, and the procedure becomes complicated. JP-A-2003-179361, JP-A-2003-179361, JP-A-2003-179361A SUMMARY OF INVENTION [Reference] In the method for producing a flexible composite printed wiring board, a method is considered in which an ink layer is formed by printing of an alkali-soluble ink at substantially the same thickness as the prepreg, instead of forming a predetermined portion of the f-curve by screen printing. A heat resistant film is formed by laminating a prepreg around the ink layer. According to this method, by the presence of the ink layer at the predetermined portion of the bending, it is possible to prevent the resin constituting the prepreg from flowing into the predetermined portion of the bend when the volume layer is prepreged. Further, according to the method, when the resist used in forming the outer layer pattern is removed by using an alkaline solution, since the ink layer can be dissolved and removed by using an alkaline solution, the ink layer is not formed at a predetermined portion of the bend. Residue. Further, since the physical layer is not peeled off, the ink layer can be removed without causing damage or breakage of the insulating layer, whereby the flexible portion can be formed. An ink for an electronic material which is soluble in an alkaline solution, and is known as a so-called ink for plating resist, a 200942095 ink for plugging holes for protecting a through hole from an etching liquid, and a resist for printing type. Etching resist, etc. These inks are printed thinner at a thickness of 20 m or less, and are dried and hardened in a shorter period of time after i5 (rc below), and then supplied to the plating step or the remaining step. In the manufacturing step of the rigid-flexible composite printed wiring board, the ink layer for forming the wrapable portion must be formed to have the same thickness as the prepreg in order to prevent the resin of the prepreg from flowing into the exchangeable portion. This is a thick film printing of 50/zm or more equivalent to a commercially available prepreg. In addition, in the step of laminating a prepreg, the heating and pressing conditions are about i 8 ,, and the time is also 1 hour. Therefore, it is necessary to make the ink after the thick film is formed, and the ten-k heating and pressing conditions have a cracking property, and the heat resistance of the ink itself is not melted, flowed, or pyrolyzed, and even after heating and pressurization, Maintain sufficient solubility. The commercially available alkali-soluble inks are not problematic in normal use, but they are often resistant to cracking after thick film formation, and there is almost no heat resistance. Commercially available test When the ink is used for the formation of the flexible portion of the rigid-flexible composite printed wiring board, in most cases, cracks may occur when printing, drying, and hardening are performed at the same thickness as the insulating layer such as the flexible layer. Or the ink is modified or decomposed by the heating of the laminate of the prepreg and the a force, which may be accompanied by cracking, or may be lost due to fusion to the substrate. The present invention is complicated by such a situation. The purpose of the present invention is to provide a resist ink which has sufficient crack resistance even when formed into a thick crucible and which does not lose alkali solubility even when heated and pressurized; and an inner layer using the resist 200942095 ink A method for producing a partially exposed multilayer printed wiring board. The anti-silver agent ink of the present invention is characterized in that it contains at least one of tetrahistreic acid, tetrarexic acid anhydride, and tetrabasic acid dianhydride half ester, one molecule a polyol having three or more hydroxyl groups and a filler; and soluble in an alkaline solution. Further, the method for producing a first multilayer printed wiring board according to the present invention is characterized in that the second insulating layer is insulated A wiring pattern is formed on at least one surface, and the resist ink of the present invention is applied to one portion of the first insulating layer to form an ink layer, and the ink layer is formed on the ink layer forming side of the first insulating layer. Forming a second insulating layer from the second insulating layer, forming a metal layer on the second insulating layer, patterning the metal layer to form a second wiring pattern, and then dissolving and removing the above by using an inert solution In the ink layer ', one of the first insulating layers is partially exposed. The second multilayer printed wiring board manufacturing method according to the present invention is characterized in that a wiring pattern is formed on at least one side of the flexible second insulating layer. The anti-surname ink of the present invention is coated on a portion of the cover layer on the side of the wiring pattern forming side of the second insulating layer to form an ink layer on the cover layer, and the ink layer is formed on the cover layer. The insulating layer is exposed to form a second insulating layer, and a metal layer is formed on the second insulating layer, and the metal layer is patterned to form a second wiring pattern, and then alkaline is used. Removing the liquid to dissolve the ink layer, so that a portion of the cover layer is exposed. The resist ink of the present invention contains at least one of a tetracarboxylic acid, a tetracarboxylic dianhydride, and a half esterified product of tetracarboxylic acid dianhydride, and has a hydroxyl group having a solid of 200942095 or more in i molecules, and The filler can be carried out by reacting at least one of a tetraester of a tetracarboxylic acid, a tetracarboxylic dianhydride, and a tetracarboxylic dianhydride with a polyol having three or more hydroxyl groups in one molecule. Three-dimensional cross-linking 'generates a polyester polycarboxylic acid polymer having a higher acid value. Therefore, 'when the ink layer is formed on the first insulating layer using the resist ink', the resist ink is heated and added The polymer formed after pressing has a high acid value, so it is soluble in the test solution, and has heat resistance by two-dimensional cross-linking. In addition, since the polymer is very rich in flexibility, it is even thick. Further, the film is also sufficiently resistant to cracking. Further, the method for producing the second multilayer printed wiring board of the present invention is formed by using the resist ink on a part of the first insulating layer or a part of the cover layer. Ink layer, thus forming When the second insulating layer is heated and pressurized to form a layer after the ink layer, the ink layer has flexibility and heat resistance. Therefore, the "ink layer is not broken by pressurization" and does not melt and flow by heating. When heating and pressurizing the second insulating layer, even if the resin of the second insulating layer is melted and flows, the resin can be reliably prevented by the ink layer. Further, the method of manufacturing the multilayer printed wiring board is heated. After the pressurization, the ink layer does not lose the solubility to the alkaline solution, so the ink solution can be dissolved and completely removed by the test solution. Therefore, the residue of the ink-free layer can be produced, and the first insulating layer can be used. A multilayer printed wiring board in which a part or a part of a cover layer is partially exposed. [Embodiment] Hereinafter, a method of manufacturing a multilayer printed with a 200942095 wire plate according to the present invention will be described in detail with reference to the drawings. In the first embodiment of the method for producing the first multilayer printed wiring board of the present invention, the double-sided multilayer printed wiring board (hereinafter only A method of manufacturing a multilayer printed wiring board is described. However, before the description of the manufacturing method, a multilayer printed wiring board manufactured by the manufacturing method will be described. As shown in FIG. 1, the multilayer printed wiring board i is The first wiring pattern 3 is formed on one surface 2a of the core substrate 2 as the first insulating layer, and the second insulating layer 4 formed of the first prepreg layer 4 having the adhesion and insulating properties is laminated thereon. Then, the second wiring pattern 5 is formed on the second insulating layer 4. The third wiring pattern 6 is formed on the other surface 2b of the core substrate 2, and the second pre-layer and the insulating layer are laminated thereon. The third insulating layer 7 formed by the dip layer is further formed with the fourth wiring pattern 8 on the third insulating layer 7. In the multilayer printed wiring board, the core substrate 2 is formed to electrically connect the first wiring pattern 3 A channel ("&) 2c with the third wiring pattern 6. Further, in the multilayer printed wiring board, a via 9 and a through hole 1 are formed, and the via 9 is electrically connected to the second wiring pattern 3 and the second wiring pattern 5'. The first wiring pattern 3, the second wiring pattern 5, the 帛3 wiring pattern 6, and the fourth wiring pattern 8. The multilayer printed wiring board i has an exposed region u on the core substrate 2 including a portion 4 of the ith wiring pattern 3, thereby exposing the knives including the first wiring pattern 3 of the core substrate Formed by. Therefore, in the multilayer printed wiring board ι, the exposed area 200942095 is formed in a concave shape. For example, when electronic components are mounted on the ith wiring pattern 3 in the exposed area, low profile can be achieved. Such a multilayer printed wiring board 1 can be manufactured in the following manner. First, as shown in Fig. 2, a core substrate 2 provided with steel rafts 12 on both sides is prepared. The core substrate 2 has excellent heat resistance, mechanical strength, and electrical characteristics. For example, a resin such as polyacrylonitrile, epoxy resin, or fat can be used. Next, as shown in FIG. 3, a method of forming the first "wire pattern 3, the third wiring pattern 6, and the channel & channel 2c for electrically connecting the ? wiring pattern 3 and the third wiring pattern 6 is formed, for example, The other side 2b' of the core substrate 2 of 2 is formed by laser-forming the copper drop 12 of the portion of the channel 2c with the core substrate 2; a method of opening the hole; and a copper box which is formed by etching to form the channel 2. 12, after removing, the method of opening the core substrate 2 by means of #射, etc.; for the entire surface of the hole formed by the methods, using the electroless ore method or the electrolytic bell copper method to carry out the ore In addition, the channel 2c' may be plated with copper after forming a through hole by a drill or the like, and a through hole may be formed. Secondly, a copper foil on the channel and the second wiring pattern 3 is formed. A resist is formed on the 12 so that the formed via 2c is not etched, for example, by a subtractive method (substractive (10)), the copper drop 12 disposed on one side 2a of the core substrate 2 is left, thereby forming the ith wiring. Similarly, the third wiring pattern 6 of the pattern 3 is reduced by, for example, The copper foil 12 provided on the other surface 2b of the core substrate 2$ is etched, and the same is applied to the exposed region 11 where the second wiring pattern 3 is exposed as shown in FIG. The details are as described below for the alkali-soluble resist 200942095 ink of the present invention to form the ink layer 13. The ink layer 13 is an anti-(iv) ink of the present invention by a printing method such as screen printing or spray film printing. It is printed on the exposed region 11' and dried and hardened under appropriate conditions. As shown in Fig. 5, the ink layer 13 is laminated with the i-th pre-layered on the first wiring pattern 3 in the next step. The ink of the ink layer 13 is formed by the substantially same thickness of the dip layer 4, and the alkali-soluble resist ink of the present invention is used. Here, the ink is alkali-soluble, meaning that the ink is soluble not only before hardening. An alkaline solution, which is also soluble in an alkaline solution after hardening, preferably means not dissolved in a weakly alkaline solution used to develop a dry film resist, but soluble in the dried to remove hardening An alkaline solution of a film resist. ◎ Specifically The resist ink of the present invention contains at least one of a tetracarboxylic acid, a tetracarboxylic dianhydride, and a half esterified product t of a tetracarboxylic dianhydride, and has 2 (f) or more of a transbasic polyol in a molecule, and is filled. And at least one of a semi-esterified product of a tetracarboxylic acid, a tetracarboxylic dianhydride, and a tetracarboxylic dianhydride, and 3 of the i molecules, by the resist ink. More than one hydroxyl group polyol reacts to perform three-dimensional cross-linking to obtain a polyester polycarboxylic acid polymer having a higher acid value, so that the cured product of the resist ink has the following characteristics: soluble in alkaline Since the solution has heat resistance and is very flexible, it does not cause bending even if it is a thick film. Further, by containing a filler, the shape of the layer can be favorably maintained and the heat resistance can be further improved. . Specifically, as the tetracarboxylic dianhydride, any of those known as a raw material for epoxy hardener or polyimine synthesis can be used. Four-acidic acid II 12 200942095 Anhydride 'for example' can be cited as diterpenic acid di-xanthene, 3,3,4,4-diphenyltetracarboxylic acid di-xanthene, 3,3,4,4-benzophenone tetracarboxylic dianhydride , Oxygen_4,4·diphthalic acid dixanthine: ethyl ethyl trimellitic acid dianhydride, 2,2·bis(4)(3,4-dicoylphenoxy)benzene) , W'4-butadiene tetracarboxylic acid dioxane, and 5_(2,5-dioxotetrahydro-3·furanyl)_3_methyl_3_cyclohexene decanedicarboxylic anhydride, etc. Among them: use - or mix a variety of uses. Among these, it is preferably 3, 3, 4, 4_ two, formic acid two-needle, oxygen-4,4·diphthalic dianhydride, and exoethyl double

Benzene*-formic acid mono-anhydride, butane tetracarboxylic acid dianhydride, especially preferably diethylidene dipyridyl acid dihepatic acid. For example, the tetracarboxylic acid which can form an acid dianhydride in the molecule can be obtained by reacting the above tetracarboxylic acid dianhydride with water to ring the anhydride group. The half esterified product of the tetracarboxylic dianhydride can be obtained by subjecting the above tetracarboxylic dianhydride to an alcohol to open the ring of the acid anhydride group. A semi-esterified product of a tetracarboxylic acid monoanhydride can be produced by a general method, for example, a tetracarboxylic dianhydride and a half esterifying agent can be obtained at a temperature of from room temperature to 12 Torr and in the presence of a catalyst. The alcohol is reacted to produce. For the catalyst, for example, a tertiary amine such as triethylamine or tributylamine; a quaternary ammonium salt such as benzyl-methyl vaporized acid or benzyltrimethylammonium bromide; 2_曱基咪坐, 2 Imidazole such as undecylimidazole, it dimethylimidazole, 2-ethyl-4-indolyl imidazole, 2-pyrylene imidazole, 2-phenylidene-4-methylimidazole, benzylidene-2-methylimidazole class. The semi-acetalizing agent' may be any one if it is an alcohol, and it is preferred to use a low molecular weight alcohol. As the low molecular weight alcohol, methanol, ethanol, n-propanol, isopropanol, n-butanol, allyl alcohol, propargyl alcohol or the like can be used. Among them, 13 200942095 methanol or ethanol is particularly preferable. The alcohol of the esterifying agent is set to water, and the acid can be formed in the molecule. The half of the manufacturing method of the semi-esterified product of the above-mentioned four-deoxyanhydride can be made into the ink, and all of the four can be contained. The carboxylic acid, the tetra-acid di-hepatic acid, the four-poisoned two-pin half, and the compound may also contain one or more of these, when used as an early liquid type anti-(four) antimony ink, due to acid sf and plural The reaction of alcohol can also be carried out at room temperature, thus extending the concept of PGt life

In the case, it is preferred to use a semi-acetate of tetracarboxylic acid or tetracarboxylic acid. It can also be used together with a semi-esterified product of tetracarboxylic acid, tetra-retensive dianhydride and tetra-salination dianhydride to use a bis-carboxylic acid anhydride, a half ester of a dicarboxylic anhydride, a dicarboxylic acid, a tricarboxylic anhydride. And a half esterified product of a tricarboxylic anhydride. As the dicarboxylic acid, for example, a dicarboxylic acid which can form an acid anhydride in the molecule can be used, and more specifically, cis-butane dicarboxylic acid, phthalic acid or the like can be used. 2. Two reductive acid needles, maleic anhydride, phthalic anhydride, etc., half ester of dicarboxylic anhydride

As the compound, a half-δ derivative of cis-butane (tetra), a half esterified product of phthalic acid liver, or the like can be used. Further, 'tricarboxylic acid, acid', more specifically, trimellitic acid liver or the like, a semi-esterified product of phthalic anhydride, etc. when a ditacky acid, a carboxylic acid, a tricarboxylic anhydride is added, for example, an acid anhydride can be formed in the molecule. Tricarboxylic acid uses trimellitic acid or the like. The tricarboxylic acid anhydride can be used as a semi-esterified product of a dicarboxylic acid anhydride, and when a semi-esterified product of a trimellitic anhydride, a half ester of a dicarboxylic anhydride, and a semi-esterified product of a tribasic acid anhydride can be used, if sj is excessively added, The three-dimensional crosslink density after curing of the ink of the agent is reduced by 14 200942095, which results in a decrease in heat resistance of the ink layer 13 'and thus is not good. a content of a carboxylic acid e ❹ dicarboxylic acid, a dicarboxylic acid anhydride, a half esterified product of a dicarboxylic acid anhydride, and a half esterified product of a tricarboxylic acid, a tricarboxylic acid anhydride, and a tricarboxylic acid anhydride, and a tetracarboxylic acid, a tetracarboxylic dianhydride, and The semi-esterified product of tetracarboxylic dianhydride is called tetracarboxylic acid, and the semi-esterified product of di-oroxic acid, di-theorereic anhydride and di-anhydride is called didecanoic acid, and the semi-ester of tri-, tricarboxylic anhydride and tricarboxylic anhydride When the compound is called a tricarboxylic acid, the total amount of the acid anhydride group in the anhydride state of the carboxylic acid and the tricarboxylic acid is relative to the anhydride state of the tetracarboxylic acid (that is, the state before the acid anhydride is opened by the acid and the alcohol). The molar ratio of the base is preferably 1: 〇~1 : 〇2. A polyhydric alcohol having three or more hydroxyl groups in one molecule of the reaction of the tetracarboxylic acid, the tetracarboxylic dianhydride, or the semi-esterified tetracarboxylic dianhydride may be, for example, glycerin, diglycerin, polyglycerin or red. Polyols such as decyl alcohol, pentaerythritol, trimethyl ketone, etc., which are polymerized on these alcohols to form epoxy epoxies, propylene propylene and the like (iv) polyhydric alcohols; Two (four) cool bonds of polyester polyols; and ε-caprolactone henry polyols. In the case of heat resistance from the viewpoint of heat resistance, the lactone polyol is preferably a polycaptan filler, preferably an inorganic material, for example, preferably a stone. Synthetic mica, hydrazine, magnesium hydroxide ^ cut, slippery acid, oxygen (four), barium sulfate, and magnesium oxide, ^, rabbit acid town, hydroxide New Zealand.隹 is a oxidized stone, a tetracarboxylic acid in a resist ink, at least one of a tetra-half vinegar, and a polyhydric alcohol having at least one of the solid elements of the tetramethyl phthalate. The better fit is as follows. When the tetracarboxylic acid, the tetracarboxylic dianhydride, and the semi-esterified product of the tetracarboxylic acid two-needle are called tetracarboxylic acids, they are blended into the state of the tetracarboxylic acid needle (that is, the state before the acid anhydride is opened by water and alcohol). The total amount of the anhydride group under the polyol is preferably in the range of 〇6:1~1: 0.6, more preferably 〇8:1~1: 〇8. When the compounding ratio is outside the range, when the printing is performed, drying or hardening, the unreacted material remains in a large amount, and the heat resistance is easily impaired.

The preferred content of the filler is in the range of 〇 8 to 5 相对 with respect to the weight i of the polyol. When the content of the filler is less than 丨8 with respect to the weight of the polyol, the heat resistance of the ink layer 13 is easily impaired, and when it is more than 5 Å, the ink layer 13 lacks crack resistance, and the ink layer is additionally provided. When 丨3 is dissolved in the test solution and removed, it is easy to produce a residue of the filler. Further, in addition to the use of a filler in the resist ink, a shake densification imparting agent of Ai(sil) (Aen) sil), a cerevisiae, a gas-based leveling agent, a cyanine blue, an ugly green, or the like may be suitably used. Additives such as colorants such as cerium oxide. Further, from the viewpoint of protecting the wiring pattern, it is preferable that the resist A ink contains a metal deactivator or an antioxidant. As the metal deactivator, it is possible to use a thiol such as 2-mercaptoimidazole; benzotriazole, methylbenzotriazole, ortho-benzylidene-based amine 2,4_3. Sitting on the three saliva; and n, n double [3_(3,5-second-butyl hydroxyphenyl) propyl fluorenyl] hydrazine, bismuth dibenzoic acid bis (2 phenoxy propyl hydrazinyl) and the like . Antioxidants can use block

Ph gangsters or hindered amines. The metal deactivator or the right oxidizing agent may suitably contain an amount which exhibits the effect of the above, and the ink weight is preferably about 0.1 to 5 wt% with respect to a 16 200942095. Further, the resist ink may additionally contain an alkali-soluble resin. By including the resin in the ink, the formed ink layer 13 can be used to impart flexibility. As the resin, an acrylic resin containing a monomer having a carboxyl group as a copolymerization component, a copolymer of a polyvinyl phenol resin and an acrylic resin, or a phen 〇 nov〇iak resin, such as acrylic acid or mercaptoacrylic acid, may be used. And a styrene-maleic acid copolymer or the like. Ο

The epoxy resin of the present invention may also contain an epoxy resin to the extent that the solubility is not impaired, as needed. Examples of the epoxy resin to be used include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac, a polyglycidyl ether obtained by a reaction of a cresol novolak type with epichlorohydrin, and the like. And an alicyclic diglycidyl ether such as an aliphatic epoxy resin such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or diethylene glycol diglycidyl ether, or cyclohexane dimethanol diglycidyl ether Compounds, etc. A solvent may be contained in the resist ink as needed. The solvent is preferably one which does not increase the viscosity due to volatilization during the operation and does not increase the drying after printing, and preferably has a boiling point of about 13 (rc~23〇t) and is not a primary alcohol. The resist ink can be produced by mixing the above components by a general method. π The resist ink of the present invention is printed on the exposed region (1) by screen printing or the like by heating in a box or the like to be dried and cured. As shown in the figure, the ink layer 13 can be formed. In the ink layer 13, at least one of the tetracarboxylic acid, the tetracarboxylic acid-hepatic acid, the tetraacetic acid and the semi-acetic acid of the Sf acid, and the polyol will be printed on the anti-surname of 17 200942095 The heat of the agent ink reacts with heat during drying and hardening to form a three-dimensionally crosslinked polyester polycarboxylic acid polymer. The polyester polycarboxylic acid polymer is a three-dimensionally crosslinked polymer having a very high acid value. Therefore, the obtained ink layer 13 has sufficient heat resistance and alkali solubility. Moreover, since it is very flexible, it can prevent bending cracks even if it is a thick film having a thickness substantially the same as that of the first prepreg layer 4. Produced so that The first wiring pattern 3 is protected. Next, as shown in FIG. 5, the i-th prepreg layer 4 is formed so that the ink layer 3 faces the outer side on the surface of the ink layer 13 on the core substrate 2. That is, the first prepreg layer 4 is formed such that the ink layer 13 is exposed from the first prepreg layer 4. Specifically, an ink layer is not formed on one surface 2a of the core substrate 2 on which the ink layer 13 is formed. In the portion of the first prepreg layer 4, the second prepreg layer 7 is provided on the entire surface 2b of the core substrate 2, and the second prepreg layer 7 is laminated on the first prepreg layer 4.

A film is used instead of the prepreg, and as a function of the insulating layer, a thermoplastic resin film or the like can also be used. If it is laminated on the core substrate 2, it can be used as an insulating layer. 18 200942095 Next, as shown in FIG. 5, a steel foil 14 as a second wiring pattern 5 is provided on the first prepreg layer 4, and a second pre-preparation is provided. A copper foil crucible 5 as a fourth wiring pattern 8 is provided on the dip layer 7. Further, in the method of manufacturing the multilayer printed wiring board, a copper-clad insulating substrate to which a copper foil is attached may be used instead of the first prepreg layer 4, the copper foil 14, and the second prepreg layer 7 and copper. Foil 15. At this time, the region corresponding to the ink layer 13 of the copper-clad insulating substrate is previously opened. Then, the first prepreg layer 4, the second pre-and/or layer 7 and the copper foils 14 and 15 are heated by the laminating press, and are pressed toward the core substrate 2 side, thereby being semi-hardened. The first prepreg layer 4 and the second prepreg layer 7 are melted, flowed, and then hardened, and the layers are then integrated, thereby forming a layered body 16 composed of a multilayer structure as shown in Fig. 6 .

In this case, even if the second prepreg layer 4 is melted and flows during heating and pressurization, it can be formed of the above-described resist ink, has heat resistance, is very flexible, and does not cause bending cracks. The ink; | 13, prevents the resin constituting the first prepreg layer 4 from flowing into the exposed region 丨i, thereby preventing the first exposure! The wiring pattern 3 adheres to the resin, or the exposed area n is returned to the y and the through hole ι from the drink as shown in Fig. 7 . Through-form formation: using a drill or laser processing, forming the copper box 14 of the second wiring pattern 5 up to the first "self-line pattern: using an electroless ore method or an electrolysis (four) method The copper plating is performed on the surface. The through hole 10 can be formed by using 200942095 to form a fourth wiring pattern 8 by using a drill or by laser processing 'forming the copper foil 14 from the second wiring pattern 5 to be formed. The through hole ' of the copper foil 15 removes the burr remaining in the through hole, and the entire surface of the through hole is plated with copper by a copperless method or an electrolytic copper plating method. Next, as shown in FIG. The second wiring pattern 5 and the fourth wiring pattern 8 are formed by a subtractive method. Specifically, first, the dry film resists 17 and 18 are formed on the entire surface of the copper foil 14 and the copper foil 15, in order to form The wiring pattern is used to expose the dry film resists 17, 18. The desired dry film resist is dissolved and removed by a solution such as sodium hydrogencarbonate, and then the gas is used. Iron or vaporized copper solution is etched by a general method to thereby form a second wiring pattern Case 5 and the fourth wiring pattern 8. When the copper foil 14 on the ink layer 13 is dissolved and removed, the ink layer 13 remains, so that the second wiring pattern 3 formed in the exposed region u can be protected from the second wiring pattern 3. The influence of the etching solution of the wet etching. Next, the dry film resists 17, 18 on the second wiring pattern 5 and the fourth wiring pattern 8 are removed by an alkaline solution such as sodium hydroxide, and are also made alkaline. The solution dissolves and removes the ink layer 13, thereby obtaining a multilayer printed wiring board of FIG. 1 in which one of the core substrate 2 is divided and a portion of the first wiring pattern 3 is exposed to the outside in the exposed region. When this step cannot be completely removed In the case of the ink layer 13, it may be additionally impregnated with an alkaline solution to completely remove the ink layer 13. The alkaline layer is used to dissolve and remove the ink layer 13 in the above manner without peeling by hand or by physical means. To remove, the ink layer 13 can be easily and completely removed. Further, the removal of the dry film resists 17, U and the removal of the ink layer 13 can also be carried out in different steps. 200942095 Multilayer printing as described above Wiring board 1 In the method, the ink layer 13 is formed in the exposed region 11 where the first wiring pattern 3 is exposed by the resist ink of the present invention. Thereby, even the second prepreg layer 4 is heated and added to the core substrate 2. The ink layer 13 can also maintain the shape by laminating and laminating.

❹ It does not lose alkali solubility, has heat resistance, and is very flexible. Even if it is formed into a thick film having substantially the same thickness as that of the first prepreg layer 4, it does not cause bending cracks. Therefore, even if the i-th prepreg layer 4 is laminated on the core substrate 2 and then heated and pressurized, the ink layer 13 can be used to prevent the resin constituting the first prepreg layer 4 from flowing into the exposed region! Therefore, the ith wiring pattern 3 can be protected and electrical defects can be prevented. Further, in the method of manufacturing the multilayer printed wiring board 1, since the first wiring pattern 3 is formed in the exposed region 11, the exposed region u becomes uneven, and the ink layer 13 is pressed against the exposed region by lamination pressing. On the uneven surface, the ink layer U is in close contact with the exposed region U, but the ink layer 13 can be dissolved and completely removed by an alkaline solution. Therefore, it is possible to prevent the residue of the ink layer 13 from occurring between the first wiring pattern 3 or the first wiring pattern 3, and the exposed region η and the first wiring pattern 3 can be protected even if the exposed region 11 has a fine shape. In the manufacturing method of the multilayer printed wiring & 1 , the ink layer 13 is dissolved and removed by alkali; therefore, the second insulating insulating ST surface adjacent to the second insulating layer can be prevented from being damaged or peeled off, and adjacent to the exposed region 11 2. The end surface on the exposed side of the rim edge layer 4 is flat. As shown in FIG. 9, the multilayer printed wiring board 1 obtained from the first wiring pattern 3 is a connection terminal on which the electronic component 19 is mounted in the exposed region 1 1 . 21 200942095 At this time, the plurality of layers in the exposed region 11 have portions of the second wiring pattern 5, and electronic components are mounted on the wiring pattern 3 to achieve low profile. Since the thickness of the printed wiring board 1 is smaller than that of the printed wiring board 1 , it does not become too high even at the height of the first 19 ′. Further, in the multilayer printed wiring board i , the wiring pattern may not be formed in the exposed region 11 . Only the core substrate 2 is exposed. Further, in the above-mentioned multi-layer printed wiring board 1, it is attached to the phantom and the wing #. τ You set the wiring pattern on both sides of the substrate 2

However, the present invention is not limited thereto, and the wiring pattern may be provided only on one surface 2a of the core substrate 2. Further, in the multilayer printed wiring board i, the second insulating layer 4 and the second wiring pattern 5 are formed on the inner surface 2a of the core substrate 2, but the insulating layer and the wiring pattern may be further formed to form three or more layers. Layer. Similarly, an insulating layer and a wiring pattern may be further formed on the other surface 2b of the core substrate 2 to form a three-layer multilayer printed wiring board. [In the case of the core substrate 2, one side and the other side of the core substrate 2 are further formed. When the insulating layer and the wiring pattern are formed in three or more layers, not only the wiring pattern on the core substrate 2 but also the other wiring patterns located inside can be exposed.

Next, in the second embodiment, the following description will be specifically described. The use of a resist ink, such as the multilayer printed wiring board 2 shown in FIG. 10, is formed not only on the side of the core substrate 2 but also on the side 2b side. The area 21 is exposed. In the multilayer printed wiring board 2, the same components as those of the above-described multi-layer printed wiring board are denoted by the same reference numerals, and detailed description thereof will be omitted. In the multilayer printed wiring board 20 formed in the multilayer printed wiring board 20, the first insulating layer 4 of the first prepreg layer 22 200942095 is not laminated in the exposed region 11' provided on the side of the core substrate 2 surface 2a, thereby making the first wiring One of the patterns 3 is partially exposed, and the exposed area 21 on the other side 2b side of the core base cylinder, 0 咏 2 is not laminated with the third layer formed by the second pre-, Mudi/history layer. The insulating layer 7 is partially exposed to the third wiring pattern 6. Wrong way, the manufacturing method of the multilayer printed wiring board 2G,

In the same manner as in the method of manufacturing the wiring board 1, after the first wiring pattern 3 and the third wiring pattern 6 are formed, as shown in FIG. 11, the ink layer 13 is formed on the surface of the core substrate 2 on the surface 2a, and is formed on the other surface. Ink layer u. The ink layers 13 and 22 are formed to have substantially the same thickness as the fourth and fourth prepreg layers 4 and 7, respectively. At this time, since the ink layers 3 and 22 are formed by the resist ink of the present invention described above, even if the thickness is substantially the same as the thickness of the second prepreg layer 4 and the second prepreg layer 7, It also prevents the occurrence of bending cracks. Next, the ink layers U, 22 are formed such that the ink layers 13, 22 are inserted at positions corresponding to the respective ink layers 13, 22 from the i-th and second prepreg layers [7]. The first pre-, the body layer 4, and the second prepreg layer 7 of the openings 4a and 7a are provided on the first wiring pattern 3 and the third wiring pattern 6, and steel is provided on each of the prepreg layers 4 and 7.羯 14, 15 Further, in the same manner as the method of manufacturing the multilayer printed wiring board 1, the integrated multilayered laminate 23 shown in Fig. 12 is produced by heating and pressurization. In the case of μ, since the ink layers 13 and 22 have heat resistance, they do not melt and flow, and since they have flexibility, cracks do not occur. By this, it is possible to prevent the resin from flowing into the respective exposed regions u, 21 〇 23 200942095 from the first prepreg layer 4 and the second prepreg layer 7 . Next, as shown in FIG. 13 , similarly to the method of manufacturing the multilayer printed wiring board 上述The via hole 10 and the channel 9 are formed, and the second wiring pattern 5 and the fourth wiring pattern 8 are formed by etching the copper pigs 14, 15. Then, when the dry film resists 17 and 18 used for forming the second wiring pattern 5 and the fourth wiring pattern 8 are removed by the "alkaline solution", the ink layers 13 and 22 formed in the exposed regions 11 and 21 are also It is dissolved and removed. When the second wiring pattern 5 and the fourth wiring pattern 8 are formed, the ink layers 13 and 22 are formed in the exposed regions 11 and 21, whereby the ith wiring pattern 3 and the third wiring pattern 6 exposed by the exposed regions 11 and 21 can be protected. Protected from etchant. Further, since the oil ink layers 13 and 22 are formed by the above-described resist ink, even if heating and pressurization are carried out in the laminating step, alkali solubility is not lost, and it can be surely removed by an alkaline solution. . In the method of manufacturing the multilayer printed wiring board 20 as described above, the resist ink of the present invention can be used to form the first exposed surface on both sides 2a and 2b of the core substrate 2 by using the resist ink of the present invention. The exposed region 11 of the wiring pattern 3 and the exposed region 21 of the third wiring pattern 6 are exposed. Both of the exposed region 11 and the exposed region 21 can obtain the same effects as the above-described method of manufacturing the multilayer printed wiring board 1. Next, a third embodiment will be specifically described for the method of manufacturing the multilayer printed wiring board 30 shown in Fig. 14 using ink. In the multilayer printed wiring board 30, the first wiring pattern 32 is formed on one surface 31a of the core substrate 31 as the second insulating layer, and the second insulating layer 33 is laminated, and the second insulating layer 33 protects the first! The wiring pattern 32 and the adjacent first wiring patterns 3 2 are insulated from each other and have an adhesive property; the second insulating layer 33 layer-the third insulating wiring pattern 34' is laminated with the third insulating layer adjacent to the second insulating layer 33' at 24 200942095 The wiring pattern 34 protects the second wiring pattern 34' and forms a hearing edge on the third insulating layer 35, and has an adhesive property; and at this point, a third wiring pattern is formed. The fourth substrate of the core substrate 31, the other side 31b, and the fourth wiring pattern 37 are laminated to protect the fourth wiring pattern 37 and the adjacent wiring patterns 37 are insulated from each other. The layer 38 forms the fifth wiring pattern 39 on the fourth overlayer protection layer < layer 38, and Φ / 〇 the wiring pattern 39, and the adjacent fifth wiring pattern is matched with the pattern 41. Further, in the multilayer printed wiring board 30, the core is electrically connected to the wiring (four) 32 and the fourth wiring pattern W channel 31c, and the first wiring _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The fifth wiring is connected to the channel 43 of the external wiring 6th wiring pattern 41, and the first wiring system 32, the second wiring pattern 34, the third wiring pattern 36, the fourth wiring pattern 37, and the fifth _. fifth wiring are electrically connected. The pattern 39 and the through hole 44 of the sixth wiring pattern 41. In the multilayer printed wiring board 3, not only one portion of the first wiring pattern formed on the core substrate 31 but also the third insulating region 46 is formed in the third insulating region 46. One of the second wiring patterns 34 on the layer 35 is partially exposed. The multilayer printed wiring board 30 can be manufactured as follows. First, as shown in Fig. 15, a multilayer printed wiring board having a first exposed region 45 is manufactured. The above-described multilayer printed wiring board is manufactured in the same manner, and detailed description thereof will be omitted. 25 200942095 Next, as shown in FIG. 16, the resist ink of the present invention is printed by screen printing or the like. The exposed area 45 and the second exposed area are young to form the ink layer 47. When the second prepreg layer 35 is heated and pressed in the subsequent step to laminate, the ink layer 47 prevents the second insulating layer 33 from being hardened. The resin of the resin and the second prepreg layer 35 flows into the first exposed region 45 in which the first wiring pattern 32 is exposed and the second exposed region 46 in which the second wiring pattern 34 is exposed. Therefore, 'the ink layer 47 is as shown in FIG. Opening with the second insulating layer 33 The depth in the portion 33a and the thickness of the second prepreg layer 35 laminated on the i-th prepreg layer 33 in the next step are substantially the same thickness, and are formed around the opening 33a of the second insulating layer 33 and 2. The exposed region 46. The ink layer 47 is formed by the resist ink of the present invention, and therefore, even if it is formed to have substantially the same thickness as the total thickness of the first prepreg layer 33 and the second prepreg 35, Next, as shown in FIG. 17, the second prepreg layer 35 as the third insulating layer is provided on the second insulating layer 33 so that the ink layer 47 faces the outside. The second prepreg layer 35 is provided so that the layer 47 is exposed from the second prepreg layer 35. More specifically, the second prepreg layer 35 having the opening portion 35a of the size in which the ink layer 47 can be inserted is used. The ink layer 47 is provided so as to be exposed from the opening 35a. Further, the second prepreg layer 35 is provided with a copper drop 48 for forming the third wiring pattern 36. On the other hand, the fourth insulating layer 38 is provided. a fourth prepreg layer 40 as a fifth insulating layer, and is provided thereon for forming a sixth wiring pattern The copper box 49 of the case 41. The second prepreg layer 35, the fourth prepreg layer 40, and the steel foils 48 and 49 are directed toward the core substrate 31, and are pressurized while being heated, so that the laminates 26 200942095 are formed. When the heating and pressurization are performed, the ink (4) is formed by the second ==, and even if the second insulating layer 3 is melted, the immersion layer 35 is melted, and the ink layer 47 is not formed by the ink layer 47. Heat resistance, so oily, so it will not be produced, and because the ink layer 47 has softness

33 and the second prepreg layer can prevent the formation of the $2 insulating layer exposed region 46, and the first exposed region 45 and the second image of the τρ are formed in the first exposed region 45. "The second wiring diagram of the second exposed region 46 is formed in the second exposed region 46. The grease is blocked: the first exposed region 45 and the second exposed region 46 are formed into a channel, and the multilayer printed wiring is reversed. In the same manner as in the manufacturing method, when the fourth wiring ', the third wiring pattern 41 and the sixth wiring pattern 41 are formed by the subtraction method 3 wiring pattern 36 and the sixth wiring pattern 4 in the form of the fourth opening 48 and the through hole 44, Since the ink layer 47 remains, it is possible to protect the first wiring pattern 32 formed in the first exposed region 45 and the second wiring pattern 34 formed in the second exposed region 46 from the liquid of the wet etching. The human-used person removes the dry film resist used in forming the third wiring pattern 36 and the sixth wiring pattern 41 by using an alkaline solution such as sodium hydroxide, and also dissolves and removes the ink layer 47 by using an alkaline solution. As shown in FIG. 14 , the multilayer printed wiring board 3 露出 in which the first wiring pattern 32 is exposed in the first exposed region 45 and the second wiring pattern 34 is exposed in the second exposed region 46 can be obtained. When the ink layer 47 is formed by the anti-money ink of the present invention, 27 200942095 does not lose alkali solubility after heating and pressurization in the lamination step, and can be surely passed through the alkaline solution. And removed. In the method of manufacturing the multilayer printed wiring board 30, the ink layer 47 is formed on the core substrate 31 and the second insulating layer 33, so that the first layer formed on the core substrate 31 and the second insulating layer 33 can be different. Since the wiring pattern 32 and the second wiring pattern 34 are exposed in the same step, the manufacturing steps can be simplified. Further, the manufacturing method of the multilayer printed wiring board 30 is performed by using the resist ink of the present invention in the i-th exposed region 45 and the second exposed region 4 (the ink layer 47 is formed, even on the core substrate 31). The second prepreg layer 33 and the second prepreg layer 35 are heated and pressurized to be laminated, and the ink layer can maintain its shape, does not lose alkali solubility, has heat resistance, and is very flexible, so even The i-th prepreg layer 33 and the second prepreg layer 35 are formed to have substantially the same thickness, and no bending cracks are formed. Therefore, the i-th pre-dip (four) 33 and the second prepreg I 35 are laminated on the core. In the case of the substrate 31, the resin constituting the first prepreg layer μ and the second prepreg layer 35 can be prevented from flowing into the exposed regions 45 and 46 by the ink layer 47, so that the first protection layer can be protected.

The wiring pattern 32 and the second wiring pattern 34' can prevent electrical defects from occurring. Nai, the 琢 层 layer is brushed with the green plate 30 of the ancient ' '' ^ ^ ^ ^ ^, the method of production, not by physical means to remove the ink layer 47, but dissolves the ink layer 47, so it can be prevented The first green region 32 and the second wiring pattern 34 which are exposed in the first exposed region 45 and the second exposed region 46 are damaged, and the second insulating layer 3 3 is removed, and the third insulating layer 35 is peeled off. The second insulating layer 33 adjacent to the second exposed region "and the second insulating layer 33 or the third exposed portion of the third insulating layer 35 is flat on the side of the 20094595 region 45 and the second exposed region 46. Further, the multilayer printing is performed. In the manufacturing method of the wiring board 3, the second wiring pattern 34 is formed in the second exposed region by the formation of the second wiring pattern 32 in the second exposed region, and the wiring layer 34 is formed to be four-convex, and the ink layer 47 is formed by lamination. Squeeze on the 帛! Exposed area cedar and the second exposed area "the uneven surface, the ink layer 47 will be the same! The exposed region 45 and the second exposed region 46 are in close contact with each other, but the ink layer 47 can be completely removed by the alkaline solution.

e The residue of the ink layer 47 between the first wiring pattern 32 or the second wiring pattern 34, between the second wiring patterns 32, or between the second wiring patterns 34 can be prevented. Next, in the fourth embodiment, a method of manufacturing the rigid-flexible composite printed wiring board 50 shown in Fig. 18 using the ink of the present invention will be described. The flexible flexible portion 51' connects the i-th rigid portion 52 and the second rigid portion 53. The handleable portion 51 forms a first wiring pattern 55 electrically connecting the first rigid portion 52 and the second rigid portion 53 to one surface 54a of the flexible substrate 54 having a flexible insulating substrate, and protects the first wiring portion 55. In the first wiring pattern 55, the first cover film 56 that insulates the adjacent first wiring patterns 55 and the second cover film 57 are formed on the other surface 54b'. The flexible portion 51 has a region 58 on the one surface 54a side of the flexible substrate 54 that exposes the first cover film 56 without laminating the first prepreg layer 60, and faces the region 58 on the other surface 54b. The side has a region 59 in which the second cover film 57 is exposed without laminating the second prepreg layer 63. The first rigid portion 52 laminates the first wiring pattern 55, the first coating film 56, and the second prepreg layer 29, 200942095 second insulating layer 60, and second wiring pattern formed on one surface 54a of the flexible substrate 54. 61. Further, the j-th rigid portion 52 laminates the third wiring pattern 62, the second coating film 57, the third insulating layer 63 formed of the second prepreg layer, and the fourth wiring pattern on the other surface 54b of the flexible substrate 54. 64. In the first rigid portion 52, a channel 65 for electrically connecting the first wiring pattern 55 and the third wiring pattern 62 is formed on the flexible substrate M, and a channel 66 for electrically connecting the first wiring pattern 55 and the second wiring pattern 61 is formed. Further, the first rigid portion 52 has an exposed region 67 in which the i-th wiring pattern 55 is exposed. Similarly to the first rigid portion 52, the second rigid portion 53 laminates the i-th wiring pattern 55, the i-th cover film%, and the second insulation formed by the first prepreg layer on one surface 54a of the flexible substrate 150. The layer 6A and the second wiring pattern 61 are laminated on the other surface 54b with the third wiring pattern 62, the second coating film 57, the third insulating layer 由 formed by the second prepreg layer, and the first The line pattern 64 is formed with a through hole 6 that electrically connects the first wiring pattern 55, the second wiring pattern 61, the third wiring pattern 62, and the fourth wiring pattern to the second rigid portion 53. The rigid flexible composite printed wiring board 50 can be manufactured by the following means. First, as shown in Fig. 19, in the same manner as the above-described method of manufacturing the multilayer printed wiring board 1, a flexible substrate having steel foil on both sides is prepared to form a channel Μ, and then one side 54a of the flexible substrate 54 is formed. The first wiring pattern 55' is formed by the subtractive method to form the third wiring pattern 62 on the other surface. On the other hand, as shown in Fig. 20, the first cover film having the opening portion is deposited in a region corresponding to the exposed region 67 by pressing or the like. On the other surface 54b, the cover film 57 of the second 30 200942095 is also laminated by pressing or the like. Next, as shown in Fig. 21, 9 is formed in and around the opening portion 56a of the i-th cover film 56 corresponding to the exposed region Ο. The thickness of the first ink layer 69 around the opening is substantially the same as the thickness of the first pre-sublayer 60 of the first coating film 56. Further, the area on the i-th cover film 56 corresponding to the region 58 of the un-layered i-th prepreg layer (9) is also larger than the thickness of the i-th prepreg layer 6〇.

The same thickness is formed by the second oil (four) by screen printing or the like: the second cover film 57 is in the region corresponding to the region where the second prepreg layer 63 is not laminated, and is laminated on the second cover film. The thickness of the second prepreg layer 63 on 57 is substantially the same as the thickness of the third ink layer 71. In this case, the thickness is substantially the same as the total thickness of the first cover film 56 and the first prepreg layer 6G. In the ink layer 69, even if the second ink layer and the third ink layer 71 are formed to have substantially the same thickness as the i-th prepreg layer 60 and the second prepreg layer 63, the resist ink may be used. In the first cover film 56, the first ink layer 69 and the second ink layer 70 are faced to the outside, and the first prepreg layer 6 is provided. The first prepreg layer 6 is formed on the first cover film 56 so that the first ink layer 69 and the second ink layer 70 are exposed from the prepreg layer 60. More specifically, the first cover film 56 is formed on the first cover film 56. The first prepreg in which the openings 6〇a and 6〇b are formed at positions corresponding to the first ink layer 69 and the second ink layer 7〇 is provided. In the second coating film 57, a second prepreg layer 31 200942095 63 having an opening 63a formed at a position corresponding to the third > ink layer 71 is provided on the second coating film 57, whereby the third ink is formed. The layer 71 faces the outer second prepreg layer 63. The copper pores 72 forming the second wiring pattern 61 are provided on the first prepreg layer 60, the i-th ink layer 69, and the second ink layer 7〇, and 2 The prepreg layer 63帛3 The ink layer 71 is provided with a copper foil 73 on which the fourth wiring pattern 64 is formed. First, 'the same as the manufacturing method of the multilayer printed wiring board 1 described above, the pressure is applied, and the laminate is pressed and laminated. As shown in Fig. 23, the laminated body 74 is formed. © When the heating and pressurization are performed, even if the tree (four) forming the first prepreg layer 60 and the second prepreg layer 63 is melted and flows, the second ink layer 69, Since the second ink layer 7 and the third ink layer 71 have heat resistance, they do not melt and flow, and since they have flexibility, cracks are not generated by heating and pressurization, thereby preventing formation of the first prepreg. The tree layer of the bulk layer and the second prepreg layer 63 flows into the regions 58, 59 or the exposed region 67, thereby preventing the exposed i-th line The resin 55 is adhered to the case 55, or the region 58, or the exposed region π is blocked by the resin. ❹ Next, the channel u and the via hole Η - 2 shown in Fig. 24 of the multilayer printed wiring board i are formed on the laminated body 74. 66 and the through hole. Forming the first: the second wiring pattern 61 is formed by the subtraction method 72, and the fourth wiring pattern 64 is formed on the steel by the subtractive method. The second se* line is formed. When the pattern 61 is formed, the first ink layer 69' is formed in the region 67. Thus, the first wiring pattern 55 emerging from the exposed region can be protected from the etching liquid. Next, when the resist used in forming the second wiring _ Η and the 32 nd 200942095 4 wiring pattern 64 is removed by using the test solution, m indicates the first ink layer 9 and the third ink layer 70 and the third ink. The layer 71 is also dissolved by the test solution. ☆ The first ink layer 69, the second ink layer 70, and the third ink layer 71 are caused by '. Since the ink of the present invention is formed, even if it is heated and pressurized in the lamination step, the solubility is not lost. By removing the anti-surname agent, showing the ink layer

69. The second ink layer 70 and the third ink layer 71 can be manufactured as follows. As shown in FIG. 18, the region 58 and the unstacked layer of the first pre-cooling layer 60 are not laminated. The area of the second prepreg layer 63 = the flexibility of the unpreposed first prepreg layer 60 and the second prepreg layer 63 = 51, and the first prepreg layer 6 and the first layer are laminated via the flexible portion 51 The pre-existing layer 63 has an exposed region in which the i-th wiring pattern 55 is exposed, and the first rigid portion 52 and the second rigid portion 53 are connected. The exposed region 67 of the first rigid portion 52 formed by the method for manufacturing the rigid-flexible composite printed wiring board 5 () is exposed in the inner 3 first wiring pattern 55, so that the exposed region 67 can be used as an electron The connection terminal of the part. Further, in the 'flexible portion 51, since the prepreg layer is not laminated, the bovine 63 is maintained, so that the flexibility can be maintained, and the j-th wiring pattern 55 is covered by the first cover film 56 and the second cover film 57. Flexible line is used. In the manufacturing method of the rigid-flexible composite printed wiring board 5, the resist ink of the present invention is used in the region 58, 59 S, nr \ λ* 2 ink, and the third ink layer 71. Therefore, when the laminated body 74 is formed, the first prepreg layer 60 and the second prepreg layer 63 are heated and pressurized, and the second ink layer 70 and the third ink layer 71 can maintain their shape. Resistance 33 200942095 Thermal property is very flexible and does not cause bending cracks, so that the resin inflow region and region 59 ′ constituting the first prepreg layer 60 and the second prepreg layer 63 can be prevented from being formed in the flexible portion 51. The flexibility of the flexible substrate 5 is maintained. In addition, the anti-sludge ink of the present invention is also used to form the first! The ink layer 69' can thereby prevent the resin of the first prepreg layer 6 from flowing into the exposed region 67. Therefore, in the exposed region 67, the resin can be prevented from adhering to the exposed second line pattern 55, whereby the occurrence of electrical defects can be prevented. In addition, in the manufacturing method of the rigid-flexible composite printed wiring board 5, the test solution is used to dissolve and remove the first! The ink layer 69, the second ink layer %, and the third ink layer 71 are not removed by physical means, so that the first ink layer 69, the second ink layer 70, and the third ink layer 71 can be removed without Damage to the first wiring pattern exposed in the exposed region 67 of the first rigid portion 52,

Alternatively, the i-th cover film 56, the second cover film 57, the second insulating layer 6A, and the third insulating layer 63 are peeled off. Further, an end surface of the second insulating layer 60 adjacent to the region 58, an end surface of the third insulating layer 63 adjacent to the region 59, and an end surface of the i-th cover film 56 adjacent to the exposed region 67 and the second insulating layer 6 The end faces become flat. In addition, in the manufacturing method of the rigid-flexible composite printed wiring board 5, the exposed region 67 is uneven by the formation of the first wiring pattern 55, so that the first ink layer 69 is pressed by lamination pressing. In the uneven surface of the exposed region 67, the first ink layer 69 is adhered to the exposed region 67, but the ink layer 69 can be completely removed by dissolution in an alkaline solution, so that the first wiring pattern 55 can be prevented or the first layer can be prevented. The wiring pattern 55 produces the first! Residue of ink layer 69. Further, 'the second ink layer 70 and the third ink layer? ! It is also dissolved in the alkaline solution. In addition, the occurrence of the residue of the second ink layer 70 and the third ink layer 71 due to the region 58 and the region 59 is prevented, and the flexibility of the flexible portion 5 is lowered. In the above-described rigid-flexible composite printed wiring board 50, the exposed region 67 in which the first wiring pattern 55 is exposed is formed in the first rigid portion 52. However, the exposed region 67 may not be formed in the first rigid portion 52. On the other hand, the rigid-flex composite printed wiring board of the flexible portion 51 is formed by the region 58 and the region 59 by the method of the present invention. Next, as a fifth embodiment, a multilayer printed wiring board 80 as shown in Fig. 26 ® can be manufactured using ink. The multilayer printed wiring board 80 is provided with a rigid portion 81 such as an electronic component, and the rigid portion 8 1 The flexible terminal portions 82 and 83 projecting from both sides are formed. In the multilayer printed wiring board 8A, the flexible terminal portions 82, 83 are electrically connected to connectors of other electronic components, and the electronic components mounted on the rigid portion 81 are electrically connected to other electronic components. Fig. 27 is a sectional view showing a line segment X-X in Fig. 26. In the rigid portion 81, the first wiring pattern 85 is formed on the flexible substrate 84, and the cover film 86 for protecting the first wiring pattern 85 and insulating the first wiring pattern 85 from each other is laminated on the flexible substrate 13 84. An insulating layer 87 formed of a prepreg layer is laminated on the cover film 86, and a second wiring pattern 88 is formed thereon. As shown in Fig. 26, the surface of the rigid portion 81 is covered with the solder resist 89 except for the electronic component mounting region 90 where the second wiring pattern 88 is used as a terminal. The flexible terminal portions 82 and 83 also have the first wiring pattern 85 formed on the flexible substrate 84. However, the cover film 86 and the insulating layer formed of the prepreg layer are not laminated on the 帛1 wiring pattern 85. 87 ' Thereby, a portion exposing the first 35 200942095 wiring pattern 85 can be formed. Here, the first wiring pattern 85 and the second wiring pattern 88 must be electrically connected by via holes or vias, but are omitted here. Further, the flexible terminal portion 亦 is also the same as the flexible terminal portion 82. Therefore, the drawings are omitted. The structure of the flexible terminal portion 82 of the multilayer printed wiring board 80 can be specifically formed by forming a first wiring pattern 85 not only over the product portion 92 but also over the product outer portion 93 as shown in FIG. The exposed area 9 is stamped by taking z_z as a cut surface. The structure of Fig. 28 can be produced by using the above-described resist ink in the same manner as the method of forming the exposed region 67 described in the fourth embodiment, and the same effect can be obtained. Further, in the multilayer printed wiring board 80, it is also possible to manufacture a wiring board having a plurality of rigid portions and connecting the rigid portions with a flexible cable portion. EXAMPLES Hereinafter, examples and comparative examples of resist inks will be described. (1) Preparation of resist ink First, the semi-esterified solution of the tetracarboxylic acid di-hepatic acid used in the production of the resist ink, the alkali-soluble resin solution 丨, and the alkali-soluble resin solution 2 will be described. The semi-esterified solution 1 of tetracarboxylic dianhydride was obtained by adding 15 g of dipropylene glycol dimethyl ether and imidazole manufactured by Shikoku Chemicals Co., Ltd. to a flask equipped with a stirrer of 0.51. Name: 2E4Mz) 1.875g, stir until the imidazole dissolves. Then, methanol 41 41 liters was placed, and an anhydride equivalent of 2 〇 5 of 36 manufactured by New Japan Physicochemical Co., Ltd. was added. 200942095 Ethyl bis(trimellitic acid) dianhydride (trade name: TMEG200) i5〇g, The mixture was stirred at room temperature for 24 hours to cause a reaction, thereby obtaining a half ester of tetracarboxylic acid dihepatic acid. After the reaction, when the formed substance was analyzed by infrared spectroscopy (IR), it was confirmed that the absorption by the acid anhydride group (1785 cm-1) completely disappeared. The half esterified solution of the tetracarboxylic dianhydride solution 2 was obtained by adding propylene glycol monobutyl ether 15 〇g and imidazole manufactured by Shikoku Chemicals Co., Ltd. to a flask equipped with a stirrer 0.51 (trade name: 2E4MZ). 3.75g, and stir until the imidazole dissolves. Then, 'methanol 35 〇 8 g, and put into the ampoule equivalent of 2 〇 5 of the ethyl bismuth (p-dicarboxylic acid) needle (trade name: TMEG200) I50g manufactured by New Japan Physicochemical Co., Ltd. The mixture was allowed to react at room temperature for 48 hours to obtain a half esterified solution 2 of tetracarboxylic dianhydride. When the substance formed after the reaction was analyzed by infrared spectroscopy (IR), it was confirmed that the absorption (1785 cm·1) caused by the acid anhydride group completely disappeared. The solvent-soluble resin solution 1 was obtained by adding 1 g of diethylene glycol dimethyl ether to a flask equipped with a scrambler of 0.51, and a carboxyl group-containing acrylic acid manufactured by Toagosei Co., Ltd. 150 g of a resin (trade name: ARUFON UC3000) was stirred at room temperature for 24 hours to be dissolved. The alkali-soluble resin solution 2 was obtained by adding propylene glycol ethyl ether acetate 15 〇g to a flask equipped with a stirrer of 0.51, and a polyvinyl phenol resin manufactured by Maruzen Petrochemical Co., Ltd. (trade name) :MARUKA LYNCUR S 2P) l50g, which was sonicated at room temperature for 24 hours to dissolve. The tetracarboxylic acid dihepatic half-esterified solution 1 and 2, the test-soluble tree 37 200942095 fat solution 1, the alkali-soluble resin solution 2, and the materials shown in Table 1 below were used according to the composition shown in Table 1. The resist inks A to 实施 of the examples and the resist inks I to L of the comparative examples were produced by dispersing and mixing the planetary stirring type mixer. [Table 1] Material composition (parts by weight) Comparative Example Ink A Ink B Ink C Ink D Ink E Ink F Ink G Ink Ink I Ink J Ink Ink L PLACCEL308 100 100 100 100 100 100 100 100 _ 100 _ PLACCEL205 _ - • - _ - _ 100 _ . Alkali-soluble resin solution 1 140 - 140 140 - - - 140 140 140 - Alkali-soluble resin solution 2 - 120 168 Semi-ester compound solution 1 156.9 156.9 _ . _ 156.9 133.4 110.9 167.5 156.9 _ Semi-ester compound solution 2 . _ 163.4 _ _ _ _ _ - TMEG200 72.4 EPICLON Β-4400 • - 46.6 . _ _ • _ _ • Dipropylene glycol dioxime ether 72.4 Propylene glycol monobutyl ether 25 Adekastab CDA-1 5.9 5.4 5.8 4.0 4.4 4.2 3.8 3.6 4.9 2.7 1.8 1.8 Higilite H-42M 320 290 320 220 250 230 210 200 320 100 100 The molar ratio of the hydroxyl group of the polyol to the anhydride group 1:1 1:1 1:1 1:1 1:1 1 :1 1 : 0.85 1 : 0.7 1:1 1:1 - -

38 200942095 In Table 1, 'TMEG2 00 is a new type of ethyl bis(p-dihexanoic acid) manufactured by New Japan Physical and Chemical Co., Ltd. EPICLON B-4400 is a 5-(2,5·dioxotetrahydro-3-(furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylate manufactured by Dainippon Ink Chemical Industry Co., Ltd. Anhydride. PLACCEL308 is manufactured by Daisel Chemical Industry Co., Ltd. and has a base price of 197 6 [K〇Hmg/g] and an average amount of 850 of polyhexyl glycerol (molecular weight "ο). PLACCEL205 is a subsidiary of Daisel Chemical Industry Co., Ltd. The company produces a polycaprolactone diterpene alcohol having a hydroxyl group of 197.6 [KOH mg/g] and an average molecular weight of 85. HigiHte H-42M is an aluminum hydroxide fine particle manufactured by Showa Denko Co., Ltd., which is a filler. The average particle size of the filler is 丨〇"Claw. Adekastab CDA-i metal deactivator, 3-(N-o-hydroxyphenyl)amino group], 2,4· (3) Production of printed sample and mounted sample (2-1) Printed sample Using the resist inks A to H of the examples shown in Table 1 and the resist ink of the comparative example! ~L, manufacturing samples Α~sample L is used as a printed sample. Samples A to L are produced in the following manner: Ube Kosei Co., Ltd., which has a thickness of 25 bismuth on both sides of polyimide and has a thickness of 9/zm. Two-sided copper-clad flexible substrate (trade name: Upiseru N) is cut into 15〇xl20mm The size of the ink is printed on the one side of the single-sided side in an area of 7〇χ4〇匪, and the anti-smudge inks A to L are screen-printed by using a hot air oven of a temperature of 15 generations to dry for 4G minutes to form an ink printing unit. / Ink layer) The thickness of the ink printed portion of each sample after drying and hardening was 70 #m by selecting printing conditions. 39 200942095 (2_2) Mounting samples using the anti-contact agent ink of the examples shown in Table 1 A to H and the resist inks I to L of the comparative example, the sample Μ to the sample X were prepared as a mounting sample. Sample X-type preparation: an opening of 70 lx4 G lmm was punched in the same portion as the ink printing portion by punching in advance. a prepreg of a glass cloth substrate impregnated with epoxy resin having the same size as the flexible substrate and having a thickness of 7 μm, and preparing the same sample as the sample A to the sample H of (2-1); The glass cloth substrate prepreg impregnated with the epoxy tree mooncake layer is laminated (I"叩) without overlapping the ink printing portion. 1 and 9, 9 layers of electrolytic copper with a thickness of 12 " m are used as an outer layer in a vacuum, a hot plate temperature of 18 generations, a pressure of 4Gkg/cm2 for a few hours of pressing, and the integration of the layers, Then, using 48 C of vaporized copper residual liquid, w 〇" 5 MPa of the jet pressure, the entire copper layer is etched and removed, and the glass cloth substrate prepreg impregnated with the epoxy resin and the ink printing portion are exposed. Thereby a mounting sample is made. (3) Evaluation (3 -1) Viscosity evaluation of the printing surface According to the adhesion of the absorbent cotton on the printing surface when the absorbent surface of the sample σσ A to the sample 1 was wiped, the sample A to the sample L were evaluated according to the following criteria. The stickyness of the printed surface. 〇: The case where the absorbent cotton is not attached to the printing surface X: The case where the absorbent cotton is attached to the printing surface The evaluation results are shown in Table 2 below. The ideal use in practice is to evaluate the leader. 200942095 [Table 2] This test compares the sample evaluation sample sample sample sample sample sample sample sample sample sample ABCDEFG Η I j Κ L using ink ink ink ink ink ink ink ink ink ink ink ABCDEFG Η I j Κ L Printing surface viscosity 〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇 〇〇❹ According to the results shown in Table 2, in the sample j, since the ink using the polyol having two hydroxyl groups is used, the polyol does not The half esterified product of tetracarboxylic dianhydride is three-dimensionally crosslinked to form a viscous film. Further, in the sample J, since the ink j containing no filler was used, it became a film having a slight viscosity. Take this sample! In the sample j, if the ink surface is wiped with absorbent cotton, the absorbent cotton adheres to the ink printing portion. On the other hand, in Samples A to H using the ink of the embodiment of the present invention, since a polyol having three radicals is used, the polyol reacts with the tetrahedral dihepatic half ester to form a three-dimensional crosslinked product. The polyester polycarboxylic acid polymer can reduce the viscosity of the ink surface. Further, by containing a filler, the viscosity of the ink surface can be eliminated without adhering to the absorbent cotton. (3_2) Evaluation in actual use Using sample Μ to sample X prepared as a sample for mounting, a. heat resistance (flow state of prepreg and ink), b. bending resistance, c . Evaluation of alkali solubility, d. etching resistance. The results of the evaluation are shown in Table 3 under 41 200942095. a. Evaluation of heat resistance The appearance of the sample Μ to the sample X was observed, and the flow state of the prepreg and the ink was observed and judged according to the following criteria. ◎: The boundary between the ink and the prepreg is clear, and the boundary at the time of printing is maintained. 边界: The boundary between the ink and the prepreg is clear, but it is slightly skewed compared with the printing △: the ink oozes out to the boundary of the prepreg In the case of a more skewed condition ❹ X: In the case where a large amount of ink flows into or under the prepreg, it is preferable to evaluate it to be 〇 or more. b. Evaluation of the curvature of the curved crack The sample M to the sample 评价 was evaluated according to the following criteria, based on the diameter of the circle in which the crack was generated when the printing surface was turned outward. 〇: Even if it is bent at 180 degrees, cracks do not occur. △: The case where the diameter of the arc is 5 mm or less and cracks occur. X: The case where the diameter of the arc is 30 mm or less and cracks occur ❹ XX : Slightly bent In the case where the crack is actually used, it is preferable to evaluate it as Δ or more. c. Evaluation of solubility test The printed surface of the sample M to the sample was exposed to a 2 wt% aqueous solution of 3 wt% of sodium hydroxide for 2 minutes at a spray pressure of 0.15 MPa, and evaluated according to the dissolution state of the ink according to the following criteria. . 〇: The case where the printed layer is completely dissolved and removed in 1 minute. 42 200942095 △: The case where the printed layer is completely dissolved and removed in 2 minutes X: The case where there is still a residue in 2 minutes is actually used. . d. Evaluation of the etching property The surface of the sample M to the sample was exposed to a 48 C vaporized copper-based etching solution for 1 minute at a jet pressure of M5 MPa, and then washed with water and then impregnated at 5 G ° Ct 3 wt%. In the sodium hydroxide to remove the ink layer,

The degree of the (4) liquid entrapment button of the copper box under the ink layer was observed and evaluated according to the following criteria. 〇·The situation is completely uneroded △•Slightly invading the button x·Severe intrusion situation In actual use, it is ideal. [table 3]

-~~_ The invention--- Evaluation sample sample Sample sample Sample Sample Sample Sample Sample -------___ Μ N 0 PRT JL VW Product X Use ink Ink Ink Ink Ink Ink Ink Ink and ink oil ABCD Ε FG Η I Τ κ 箄Τ, human fat for a long time by 墨 〇〇 ◎ ◎ ◎ Δ Δ XXX △ bending crack resistance 〇 〇Λ 〇〇〇Λ Λ Λ 〇 XX test solubility '--- 〇〇〇Δ 〇〇〇〇〇〇Δ X Last name tolerance----, 〇〇〇〇〇〇〇〇Δ △ XX 43 200942095 According to the results shown in Table 3, the sample of the comparative example is used The ink is used in the polyol having two hydroxyl groups, so that it does not cross-link with the semi-S bismuth of the tetracarboxylic dianhydride, and the heat does not increase, the ink melts and flows due to heat, and it cannot Obtained etching resistance. Further, in the sample v, since the ink J containing no filler was used, the heat resistance was not improved, and the oil: melted and flowed by heat, and the etching property was not obtained. The sample is composed of an alkali-soluble resin and a filler, and does not contain tetracrylic acid or a vertical hemi-acetate or a polyol, so that a three-dimensionally crosslinked polyacetal polycarboxylic acid polymer is not formed, resulting in failure to obtain heat resistance. And the flexibility, the bending crackability is deteriorated, and the etching property is also deteriorated. In addition, the turtles in the ink printing section of the samples w and x were severely cracked. With respect to the samples U to X of the sample, the sample of the ink of the example was used, and the sample T contained a half ester of tetracarboxylic dianhydride or tetracarboxylic dianhydride and a polyol having three hydroxyl groups. A semi-esterified product of a tetracarboxylic dianhydride or a tetracarboxylic dianhydride is reacted with a polyhydric alcohol to form a three-dimensionally crosslinked polyester polycarboxylic acid polymer, which additionally contains a filler, whereby it is not melted by heat. It is also heat-resistant, and it can also obtain softness, prevent the occurrence of cracks, and obtain a ruthlessness. According to the above, it is understood that the resist ink of the present invention has excellent heat resistance, flex cracking resistance, etching resistance, and alkali solubility, so that the resist ink can be easily used to expose one of the inner layer or the lower layer. Multilayer printed wiring board. In particular, if the resist ink of the present invention is printed in an exposed region where the inner layer of the multilayer printed wiring board is exposed, and then the prepreg is laminated, the resin constituting the prepreg is heated and pressurized even when the prepreg is laminated. 44 200942095 also does not flow into the exposed area, and can also protect the wiring pattern located in the exposed area from the etching liquid when forming the wiring pattern of the outer layer, and finally can also remove the resist ink used when forming the wiring pattern. Since the resist ink is completely removed by the alkaline solution, the multilayer printed wiring board in which the inner layer is partially exposed can be easily manufactured. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a multilayer printed wiring board according to a first embodiment of the present invention, which is produced by applying the multilayer printed wiring board of the present invention. Fig. 2 is a cross-sectional view showing the state of a double-sided copper-clad core substrate. Fig. 3 is a cross-sectional view showing a state in which a second wiring pattern wiring pattern is formed on a core substrate. Fig. 4 is a cross-sectional view showing a state in which an ink layer is formed in an exposed region. Fig. 5' is a cross-sectional view showing a state in which a prepreg layer and a copper foil are placed on a core substrate. 6, the state in which the core substrate, the prepreg layer, and the copper foil are laminated is integrated into the surface. Fig. 7 is a cross-sectional view showing a state in which a channel and a through hole are formed. Fig. 8 is a cross-sectional view showing a state in which a wiring pattern of an outer layer is formed. Fig. 9 is a cross-sectional view showing a state in which an electronic component is mounted on a wiring pattern formed in an exposed region. Fig. 1 is a cross-sectional view showing a multilayer printed wiring board of a second embodiment produced by applying the multilayer printed wiring board of the present invention. 45 200942095 is a cross-sectional view showing a state in which an ink layer is formed in an exposed region in the method of manufacturing a multilayer printed wiring board according to the second embodiment. Fig. 12 is a cross-sectional view showing a state in which a core substrate, a prepreg layer, and a copper foil are laminated in a method of manufacturing a multilayer printed wiring board according to the second embodiment. Fig. 13 is a cross-sectional view showing a state in which a wiring pattern of an outer layer is formed in the method of manufacturing a multilayer printed wiring board according to the second embodiment. Fig. 14 is a cross-sectional view showing a multilayer printed wiring board according to a third embodiment of the present invention, which is manufactured by the method for producing a multilayer printed wiring board of the present invention. [Fig. 15] Fig. 15 is a cross-sectional view showing a state in which a first exposed region is exposed in a method of manufacturing a multilayer printed wiring board according to a third embodiment. Fig. 16 is a cross-sectional view showing a state in which an ink layer is formed in the first exposed region and the second exposed region in the method of manufacturing the multilayer printed wiring board of the third embodiment. Fig. 17' is a cross-sectional view showing a state in which a laminate is formed in the same production method. Fig. 18 is a cross-sectional view showing a rigid-flexible composite printed wiring board according to a fourth embodiment manufactured by the method of manufacturing a multilayer printed wiring board of the present invention. Fig. 19 is a cross-sectional view showing a state in which the first wiring pattern and the third wiring pattern are formed on the flexible substrate in the method of manufacturing the multilayer printed wiring board according to the fourth embodiment. Fig. 20 is a cross-sectional view showing a state in which a first cover film and a second cover film 46 200942095 are laminated on a flexible substrate in the method of manufacturing a multilayer printed wiring board according to the fourth embodiment. Fig. 21 is a cross-sectional view showing a state in which the first to third ink layers are formed on the flexible substrate in the method of manufacturing the multilayer printed wiring board of the fourth embodiment. Fig. 22 is a cross-sectional view showing a state in which a cover film, a prepreg layer, and a copper foil are placed on a flexible substrate in the method of manufacturing a multilayer printed wiring board according to the fourth embodiment. Fig. 23 is a cross-sectional view showing a state in which a flexible substrate, a cover film, a prepreg layer, and a copper foil are laminated in a manufacturing method of the multilayer printed wiring board according to the fourth embodiment. Fig. 24 is a cross-sectional view showing a state in which a channel and a through hole are formed in the method of manufacturing a multilayer printed wiring board according to the fourth embodiment. Fig. 25 is a cross-sectional view showing a state in which a wiring pattern of an outer layer is formed in the method of manufacturing a multilayer printed wiring board according to the fourth embodiment. Fig. 26 is a plan view showing a multilayer printed wiring board according to a fifth embodiment manufactured by the method for producing a multilayer printed wiring board of the present invention. Refer to Fig. 27' for a section of the line segment χ_χ in Fig. 26. Fig. 28 is a cross-sectional view showing a state before the stamping of the flexible terminal portion in the manufacture of the multilayer printed wiring board of the fifth embodiment. [Main component symbol description] 1 Multi-layer printed wiring board 2 First insulating layer (core substrate) 2a One side of the core substrate 47 200942095 2b The other side of the core substrate 2c Channel 3 First wiring pattern 4 Second insulating layer (first pre- Bundle layer) 4a Opening portion 5 of the first prepreg layer Second wiring pattern 6 Third wiring pattern 7 Third insulating layer (second prepreg layer) 7a Opening portion of the second prepreg layer 第 8 Fourth wiring pattern 9 Channel 10 through hole 11 exposed area

12 Copper H 13 Ink layer 14 Copper foil 15 Copper crucible ❹ 16 Laminated body 17 Dry film resist 18 Dry film resist 19 Electronic parts 20 Multi-layer printed wiring board 21 Exposed area 22 Ink layer 48 200942095

23 30 31 31a 31b 31c 32 33 33a 34 35 35a 36 37 38 39 40 41 42 43 44 45 46 47 Multilayer laminated multilayer printed wiring board 1st insulating layer (core substrate) One side of one core substrate of the core substrate First wiring pattern second insulating layer (first prepreg layer) First prepreg layer opening second wiring pattern third insulating layer (second prepreg layer) second prepreg layer opening third wiring pattern Fourth wiring pattern fourth insulating layer (third prepreg layer) fifth wiring pattern fifth insulating layer (fourth prepreg layer) sixth wiring pattern channel passage through hole first exposed region second exposed region ink layer 49 200942095 48 Copper foil 49 Copper foil 50 Rigid-flexible composite printed wiring board 51 Flexible portion 52 of rigid-flexible composite printed wiring board 50 First rigid portion 53 of rigid-flexible composite printed wiring board 50 Rigidity-flexibility The second rigid portion 54 of the composite printed wiring board 50. The first insulating layer (flexible substrate) 54a One side of the flexible substrate 54b The other side of the flexible substrate © 55 First wiring pattern 56 First covering film 56a 1 cover film opening portion 57 second cover Film 58 region 59 region 60 second insulating layer (first prepreg layer) 60a opening portion of first prepreg layer © 60b opening portion 60c of first prepreg layer opening portion 61 of first prepreg layer second wiring pattern 62 third wiring pattern 63 third insulating layer (second prepreg layer) 63a opening portion 64 fourth wiring pattern 50 200942095 65 channel 66 channel 67 exposed region 68 through hole 69 ink layer 70 ink layer 71 ink layer 72 copper foil

73 copper foil 74 laminated body 80 multilayer printed wiring board 81 rigid portion 82 of multilayer printed wiring board 80 flexible terminal portion 83 of multilayer printed wiring board 80 flexible terminal portion 84 of multilayer printed wiring board 80 flexible substrate 85 First wiring pattern 86 Cover film 87 Insulation layer (prepreg layer) 88 Second wiring pattern 89 Solder resist 90 Electronic component mounting region 91 Exposure region 92 Product portion 93 Product exterior 51

Claims (1)

200942095 VII. Patent application scope: 1. A etchant ink, characterized in that it comprises: a half ester of tetrazoic acid, tetracarboxylic dianhydride and tetracarboxylic dianhydride, which has one molecule in the genus More than three hydroxyl polyols, and a filler; and soluble in an alkaline solution. 2. A method of producing a multilayer printed wiring board, comprising: forming a wiring pattern on at least one surface of a first insulating layer, and coating a resist ink of claim 1 in a portion of the first insulating layer; And forming an ink layer on the ink layer forming side of the i-th insulating layer, forming a second insulating layer so that the ink layer is exposed from the second insulating layer, and forming the second insulating layer on the second insulating layer In the metal layer, after the metal layer is patterned to form a second wiring pattern, the ink layer is dissolved and removed by an alkaline solution to expose one of the first insulating layers. 3. The method for producing a multilayer printed wiring board according to the second aspect of the invention, wherein the ink layer and the resist provided to form the wiring pattern are simultaneously removed by an alkaline solution. 4. The method of manufacturing a multilayer printed wiring board according to claim 2 or 3, wherein a wiring pattern is formed on a portion of the first insulating layer in a region exposed by removing the ink layer. 5. The method of manufacturing a multilayer printed wiring board according to claim 2, wherein the second insulating layer and the metal layer are formed as follows: a surface is disposed in such a manner that the ink layer is exposed A prepreg on the ink layer forming side of the first insulating layer, and a metal foil provided on the prepreg 52 200942095. The heating is performed by heating 1 ', thereby laminating the layer. 6. The method of manufacturing a multilayer printed wiring board according to claim 2, wherein the second insulating layer and the metal layer are formed as follows: on the ink layer forming side of the first insulating layer On the surface, an insulating substrate to which a metal case is attached is provided so that the ink layer is exposed, and the film is heated while being heated, thereby integrating the layers. A method of manufacturing a multilayer printed wiring board in which a part of the second insulating layer is exposed by the method of the second application of the second insulating layer. 8. The method of manufacturing a multilayer printed wiring board according to claim 2, 3 or 7 wherein the i-th insulating layer has a chargeability, and after forming a wiring pattern on the first insulating layer, forming the ink layer Previously, at least a portion of the second insulating layer is covered with a cover layer in addition to the exposed portion of the second insulating layer. 9. The manufacturing method of the multilayer printed wiring board according to item 8 of the patent application scope, wherein the second ink layer is formed by the resist ink of the patent scope of the coating on the cover layer The second ink layer is formed by exposing the second ink layer on the cover layer to the second insulating layer together with the ink layer on the first insulating layer, and the second ink layer on the cover layer is insulated from the first ink layer. The ink layers on the layer are dissolved together with an alkaline solution to partially expose one of the cover layers. 10. A method of producing a multilayer printed wiring board, wherein a wiring pattern is formed on at least one surface of a flexible first insulating layer, and a coating layer is provided on a surface on a side of a wiring pattern formation of the second insulating layer; The cover layer is coated with a resist ink of the first application of the patent application, forming an ink layer, and the second insulating layer is formed on the cover layer so that the ink layer is exposed from the second insulating layer. A metal layer is formed on the second insulating layer, and the metal layer is patterned to form a second wiring pattern, and then the ink layer is dissolved and removed in an alkaline solution to expose one of the coating layers. Eight, schema · (such as the next page) 54