JP5624288B2 - Manufacturing method of printed wiring board with through hole - Google Patents

Description

  The present invention relates to a method for manufacturing a printed wiring board having a through hole.

  A printed wiring board having a through hole has a hole (through hole 4) formed by electrically connecting wiring circuit conductors formed on both front and back surfaces of an insulating substrate by making the hole penetrating both of them conductive. Is.

  Conventionally, as a method of manufacturing a printed wiring board having a through hole, as disclosed in Patent Document 1, Patent Document 2, Patent Document 3, etc., a through hole and a conductor pattern are generally formed by a process called a hole filling method. And a hole filling dry film tenting method in which a through hole and a conductor pattern are formed by a dry film are used.

  Specifically, a through hole for a through hole is first drilled at a desired location of a double-sided copper-clad laminate, and a double-sided copper-clad laminate including a hole wall is formed by electroless plating or a combination of electroless plating and electrolytic plating. A conductive layer made of a copper plating layer is formed on the entire surface. As a result, a printed wiring board manufacturing panel having through holes for electrical connection between the front and back wiring circuit conductors is obtained.

  Next, the solvent-drying type hole filling ink is filled in the through hole and the hole filling ink is cured by evaporation of the solvent, or the radiation hole type filling ink is filled in the through hole and the hole filling ink is filled. Is cured by radiation.

  Next, after forming an etching resist layer having a desired pattern with a resist material on the front and back of the printed wiring board manufacturing panel after the hole filling ink is cured, the exposed copper portion is made of cupric chloride and ferric chloride. A conductor pattern is formed by etching away with an acidic etching solution such as.

  Next, a printed wiring board having a through hole is produced by removing the hole-filled ink cured product and the etching resist layer with an alkaline aqueous solution.

  However, with the recent trend toward fine conductor patterns on printed wiring boards, the above-mentioned hole filling method or the like can form a fine conductor pattern with a wiring conductor pattern width of 100 μm or less in order to form a fine conductor pattern with sufficient adhesion and solution of the resist layer. There is a problem in terms of image quality, and it has not been fully addressed.

  For this reason, a liquid etching resist ink that can be developed with a photo is used, and the surface of the printed wiring board manufacturing panel and the inside of the through hole are covered with the liquid etching resist ink by immersing the panel for manufacturing the printed wiring board in this. Therefore, a method using this is attracting attention. Examples of such prior art include those disclosed in Patent Literature 4, Patent Literature 5, and the like.

  In these prior arts, there is a problem that ink sink tends to occur at the peripheral edge portion (hole edge) of the through hole, and the resist layer becomes thin at this portion and the resist layer is likely to fall off. In addition, bubbles are likely to be generated in the through hole in the resist layer, and if the bubble layer of the resist layer is broken in the development process or the like, there is a problem that the conductor portion is eroded by the etching solution. Further, there is a problem that the resist layer in the through hole is difficult to peel in the peeling process.

  On the other hand, in the field where the finest and high-density conductor pattern is required, so-called landless through that does not form lands around the through-holes, in particular, the via-through holes, in order to further increase the effect while miniaturizing them. The demand for halls has become stronger, and various methods have been proposed.

  In the landless through hole forming method using a dry film as disclosed in Patent Document 6, etching is performed around the through hole edge during etching due to problems such as poor adhesion to the through hole portion filled with hole filling ink. Since the liquid wraps around, the edge portion is easily etched to easily cause poor conduction, which makes it difficult to achieve landlessness.

  In addition, as disclosed in Patent Document 7 or Patent Document 8, a “hole filling-liquid etching resist method” is proposed in which a liquid etching resist ink and a hole filling ink are used without using a dry film. In these cases, it is necessary to remove the hole-filling ink adhering to the surface of the printed wiring board manufacturing panel by a polishing process, etc., and the generation of scratches on the surface of the printed wiring board manufacturing panel during buffing, printed wiring board manufacturing There is a problem such as a dimensional accuracy error of the panel.

Japanese Patent Laid-Open No. 04-62887 JP-A-55-102290 JP-A-9-249718 JP-A-2005-158907 JP-A-10-13017 Japanese Patent Laid-Open No. 62-202587 JP 58-1000049 A Japanese Patent Laid-Open No. 61-139089

  The present invention has been made in view of the above points, and can prevent the photosensitive resin layer at the hole edge and the resist layer formed from the photosensitive resin layer from falling off. It aims at providing the manufacturing method of the printed wiring board which has a through hole which can maintain sufficient conduction | electrical_connection between.

  In addition, the present invention makes it possible to form a fine resist pattern, miniaturize the conductor wiring, and to easily remove the resist layer on the inner surface of the through hole in the peeling process. It aims at providing the manufacturing method of the printed wiring board which has a hole.

  In the method for producing a printed wiring board with a through hole according to the present invention, a negative photosensitive resin composition is applied to the panel 1 for producing a printed wiring board having a through hole 4 and having a conductor layer 3 formed on the surface. The first photosensitive resin layer forming step for forming the first photosensitive resin layer 5a on the inner surface of the through hole 4 and the surface of the conductor layer 3, and the production of the printed wiring board on which the first photosensitive resin layer 5a is formed The second photosensitive resin layer 5a is formed by further applying a negative photosensitive resin composition to the surface of the panel 1 to form the second photosensitive resin layer 5b. The photosensitive resin layer 5 composed of the second photosensitive resin layer 5b is formed, and the surface of the printed wiring board manufacturing panel 1 is formed of the first photosensitive resin layer 5a and the second photosensitive resin layer 5b and the through holes 4 are formed. Only the first photosensitive resin layer 5a on the inner surface It covers respectively. Next, an exposure process for exposing the surface of the printed wiring board manufacturing panel 1 and the photosensitive resin layer 5 on the inner surface of the through hole 4, and a photosensitive resin layer remaining after removing the unexposed portion of the photosensitive resin layer 5 by development. 5, a developing step for forming a resist layer, an etching step for removing a portion of the conductor layer 3 on the substrate surface not covered with the resist layer by etching to form a conductor wiring, and a peeling for removing the resist layer Through the steps, a printed wiring board with through holes is obtained.

  Therefore, the inner surface of the through hole 4 can be covered with the first photosensitive resin layer 5a, and the second photosensitive resin layer 5b is not formed inside the through hole 4. At the edge), the second photosensitive resin layer 5b is not contracted, and the thickness of the photosensitive resin layer 5 at the hole edge can be kept sufficiently large. For this reason, dropping off of the photosensitive resin layer 5 and the resist layer formed from the photosensitive resin layer 5 at the hole edge can be suppressed, and sufficient conduction between the through hole 4 and the conductor wiring can be maintained. Will be able to.

  In the first photosensitive resin layer forming step, the negative type photosensitive resin is formed on the surface of the printed wiring board with through holes and inside the through holes 4 by dipping the panel 1 for manufacturing a printed wiring board in the negative photosensitive resin composition and then pulling it up. It is preferable to apply a functional resin composition.

  In this case, the negative photosensitive resin composition is allowed to enter the through hole 4 so that the inner surface of the through hole 4 can be easily covered with the first photosensitive resin layer 5a.

  Moreover, in a 2nd photosensitive resin layer formation process, it is preferable to apply | coat a negative photosensitive resin composition to the surface of the panel 1 for printed wiring board manufacture by the roll type coating method.

  In this case, it becomes easy to apply the negative photosensitive resin composition to the surface of the printed wiring board manufacturing panel 1 without entering the through hole 4, and the second photosensitive resin layer 5b is used for manufacturing the printed wiring board. It can be easily formed on the surface of the panel 1 and not formed inside the through hole 4.

  Further, in the method for manufacturing the printed wiring board with through holes, it is preferable to form the landless through holes 4.

  In this case, since sufficient conduction between the through hole 4 and the conductor wiring can be maintained as described above, even if the through hole 4 is the landless through hole 4, the through hole 4 can be maintained. Sufficient conduction between the conductor wiring and the conductor wiring can be maintained.

  The method for producing a printed wiring board with a through hole according to the present invention comprises a carboxyl group having a polymerizable unsaturated bond with respect to a printed wiring board manufacturing panel 1 having a through hole 4 and a conductor layer 3 formed on the surface. A photosensitive resin layer forming step of forming a photosensitive resin layer 5 on the inner surface of the through hole 4 and the surface of the conductor layer 3 by applying a negative photosensitive resin composition containing the containing resin (A), and a printed wiring board; An exposure process for exposing the surface of the manufacturing panel 1 and the photosensitive resin layer 5 on the inner surface of the through-hole 4, and a resist layer in the photosensitive resin layer 5 remaining by removing the unexposed portions of the photosensitive resin layer 5 by development. A developing step for forming a conductor, an etching step for removing a portion of the conductor layer 3 on the substrate surface not covered with the resist layer by etching to form a conductor wiring, and a stripping for removing the resist layer. By going through the process, it may be obtained with through-hole printed wiring board.

  For this reason, it is possible to form a fine resist pattern and miniaturize the conductor wiring, and in the stripping step, the resist layer is swollen without being dissolved in the stripping solution, or is further stripped to be stripped. As a result, the resist layer can be easily removed from the inner surface of the through hole 4.

  Further, the negative photosensitive resin composition comprises (A) a carboxyl group-containing resin having a polymerizable unsaturated bond, (B) an amine compound, (C) a polymerizable unsaturated compound, (D) a photopolymerization initiator, and ( E) It contains water and the content of the carboxyl group-containing resin (A) is preferably 10 to 90% by mass relative to the total amount of the composition.

  In this case, since the negative photosensitive resin composition is water-based, it avoids various problems such as occupational safety and health problems due to volatilization of organic solvents, environmental pollution problems, and risk of fire occurrence. Further, it is advantageous in terms of process operation and working environment because it can be easily exposed, has high sensitivity, is excellent in resistance to etching solution, and can be peeled off.

  The carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A-1) having a polymerizable unsaturated bond, and the carboxyl group-containing resin (A-1) is an ethylenically unsaturated compound having a carboxyl group ( A part of the carboxyl group in the polymer produced by the polymerization reaction of the ethylenically unsaturated compound (b) having no carboxyl group with the ethylenically unsaturated compound (c) having an epoxy group reacts. It is preferable to produce | generate by doing.

  In this case, the carboxyl group-containing resin (A-1) provided with a hydrophilic group and a hydrophobic group functions as a surfactant, and the emulsification and dispersion of the components in the negative photosensitive resin composition are further promoted. High developability is imparted to the negative photosensitive resin composition. Further, since the carboxyl group-containing resin (A-1) has high photoreactivity, particularly excellent developer resistance and etching resistance are imparted to the resist layer.

  The carboxyl group-containing resin (A-1) preferably has an acid value (mg KOH / g) in the range of 20 to 500 and a weight average molecular weight in the range of 10,000 to 100,000.

  In this case, the emulsifying power and dispersing power of the components in the negative photosensitive resin composition by the carboxyl group-containing resin (A-1) are further improved, and polymerizable unsaturated in the negative photosensitive resin composition. The compound (C) and the photopolymerization initiator (D) can be further finely dispersed. Further, the removability of the non-exposed portion after the exposure of the photosensitive resin layer 5 by the developing solution, and the resistance of the resist layer to the developing solution and the etching solution are further improved, so that the resist layer having a fine resist pattern can be obtained. The formation of the resist layer further improves the alkali peelability of the resist layer.

  Moreover, it is also preferable that the carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A-2) having a polymerizable unsaturated bond. This carboxyl group-containing resin (A-2) is a polymer produced by a polymerization reaction between an ethylenically unsaturated compound (d) having an epoxy group and an ethylenically unsaturated compound (e) having no epoxy group. It reacts with the ethylenically unsaturated compound (f) having a carboxyl group and the hydroxyl group produced by this reaction reacts with the acid anhydride (g).

  In this case, the carboxyl group-containing resin (A-2) provided with a hydrophilic group and a hydrophobic group functions as a surfactant, and the emulsification and dispersion of components in the negative photosensitive resin composition are further promoted. High developability is imparted to the negative photosensitive resin composition. Further, since the carboxyl group-containing resin (A-2) has high photoreactivity, particularly excellent developer resistance and etching resistance are imparted to the resist layer.

  The carboxyl group-containing resin (A-2) preferably has an acid value (mg KOH / g) in the range of 20 to 500 and a weight average molecular weight in the range of 1000 to 50000.

  In this case, the emulsifying power and dispersing power of the components in the negative photosensitive resin composition by the carboxyl group-containing resin (A-2) are further improved, and polymerizable unsaturated in the negative photosensitive resin composition. The compound (C) and the photopolymerization initiator (D) can be further finely dispersed. Further, the removability of the non-exposed portion after the exposure of the photosensitive resin layer 5 by the developing solution, and the resistance of the resist layer to the developing solution and the etching solution are further improved, so that the resist layer having a fine resist pattern can be obtained. The formation of the resist layer further improves the alkali peelability of the resist layer.

  Moreover, it is preferable that the said carboxyl group-containing resin (A) is neutralized with the amine compound (B).

  In this case, the water dispersibility or water solubility of the carboxyl group-containing resin (A) in the negative photosensitive resin composition is further improved, and the alkali peelability of the resist layer is further improved. In particular, the resist layer in the through hole can be easily removed.

  The amine compound (B) preferably contains a tertiary amine.

  In this case, the viscosity stability and storage stability of the negative photosensitive resin composition and the storage stability of the photosensitive resin layer 5 are improved.

  Moreover, it is preferable that content of this amine compound (B) is the range of 0.2-1.0 equivalent with respect to 1 mol of carboxyl groups contained in carboxyl group-containing resin (A).

  In this case, the water-dispersibility or water-solubility of the carboxyl group-containing resin (A) in the negative photosensitive resin composition is further improved, and a high alkali peelability is imparted to the resist layer, thereby producing a printed wiring board manufacturing panel. The resist layer on the surface and the through hole can be easily removed.

  Further, the negative photosensitive resin composition may be polymerized in an aqueous solution containing the neutralized carboxyl group-containing resin (A) by neutralizing the carboxyl group-containing resin (A) with the amine compound (B). It is preferably prepared through a step in which the saturated compound (C) and the photopolymerization initiator (D) are added.

  In this case, the water-dispersibility or water-solubility of the carboxyl group-containing resin (A) is improved, the function as a surfactant is also improved, and the emulsifying power and the dispersibility are excellent. The saturated compound (C) and the photopolymerization initiator (D) can be further finely dispersed.

Moreover, it is preferable that the said negative photosensitive resin composition is prepared through the following process (1) to (6).
(1) Step of synthesizing carboxyl group-containing resin (A) in an organic solvent (2) An organic solvent solution of the carboxyl group-containing resin (A) prepared in the step (1) is mixed, and this mixed solution is mixed Step (3) of adding amine compound (B) Step (4) of adding water (E) to this solution while stirring the solution prepared in step (2) (4) Solution prepared in step (3) (5) Step of dissolving the photopolymerization initiator (D) in the polymerizable unsaturated compound (C) (6) Stirring the aqueous solution prepared in the step (4) However, the step of adding the solution prepared in the step (5) to this aqueous solution. In this case, the printed wiring board is finely grounded while reducing occupational safety and health problems, environmental pollution problems, and the risk of fire. Conductor wiring pattern can be formed .

  According to the present invention, dropping of the photosensitive resin layer 5 and the resist layer formed from the photosensitive resin layer 5 at the hole edge can be suppressed, and sufficient conduction between the through hole 4 and the conductor wiring can be achieved. Will be able to maintain.

  In addition, according to the present invention, a fine resist pattern can be formed and the conductor wiring can be miniaturized, and the resist layer can be easily removed on the inner surface of the through hole 4 in the peeling process. become.

It is sectional drawing which shows an example of embodiment of this invention. It is sectional drawing which shows the other example of embodiment of this invention.

  Hereinafter, modes for carrying out the present invention will be described.

[Panel manufacturing process for printed wiring board production]
The printed wiring board manufacturing panel 1 has a structure in which a plurality of conductor layers 3 and an insulating layer 2 interposed between the conductor layers 3 are laminated. This printed wiring board manufacturing panel 1 has a through hole 4 formed by applying a conductor coating 6 to the inner surface of the through hole. The printed wiring board manufacturing panel 1 can be manufactured as follows, for example.

  First, an insulating substrate is prepared. Examples of insulating substrates include paper base phenolic resin, paper base epoxy resin, paper base polyester resin, glass base epoxy resin, glass base Teflon (registered trademark) resin, glass base polyimide resin, composite resin, etc. Synthetic resin substrate formed; metal-based insulating substrate formed by covering a metal such as aluminum or iron with epoxy resin and insulating treatment; ceramic substrate formed from alumina ceramic, low-temperature fired ceramic, aluminum nitride ceramic, etc. Etc.

  Through holes that open on both the upper and lower surfaces are formed in the insulating substrate by laser processing, drilling, or the like.

  Next, a sheet-like conductor layer 3 made of copper or the like is provided on both surfaces of the insulating substrate, and a conductive coating is applied to the inner surface of the through hole. For example, a conductive layer made of a copper plating layer or the like is formed on the entire surface of the laminate including the hole walls of the through holes by using electroless plating and electrolytic plating together.

[First photosensitive resin layer forming step]
After applying a negative photosensitive resin composition to the printed wiring board manufacturing panel 1, the first photosensitive resin layer 5a is formed by drying as necessary.

  The first photosensitive resin layer 5a is formed so as to cover the surface of the printed wiring board manufacturing panel 1 and the inner surface of the through hole 4 as shown in FIG. 1 (a), or further as shown in FIG. 2 (a). In addition, the first photosensitive resin layer 5 a stretches the film inside the through hole 4 to close the through hole 4.

  The method for applying the negative photosensitive resin composition in forming the first photosensitive resin layer 5a is not particularly limited, and examples thereof include a dip coating method (dipping method), a roll coating method, and a spray coating method. In particular, in the case of the dip coating method, the first photosensitive resin layer 5a can be prevented from containing bubbles inside the through hole 4, and the inner surface of the through hole 4 is covered with the negative photosensitive resin composition, or Furthermore, it is easy to close the through hole 4 by stretching a film inside the through hole 4. In this dip coating method, in order to further suppress air bubbles inside the through-hole 4, the printed wiring board manufacturing panel 1 is swung in a negative photosensitive resin composition bath, or printed wiring It is preferable to immerse the panel for panel production 1 in a negative photosensitive resin composition bath while inclining.

  The composition of the negative photosensitive resin composition used for forming the first photosensitive resin layer 5a is not particularly limited, and a negative photosensitive resin composition having an appropriate composition can be used.

[Second photosensitive resin layer forming step]
After the negative photosensitive resin composition is further applied to the printed wiring board manufacturing panel 1 on which the first photosensitive resin layer 5a is formed, the second photosensitive resin layer 5b is formed by drying as necessary. Thus, it is preferable to form the photosensitive resin layer 5 including the first photosensitive resin layer 5a and the second photosensitive resin layer 5b as shown in FIG. 1B or FIG. 2B.

  The second photosensitive resin layer 5b is formed so as to cover the first photosensitive resin layer 5a. Although the application method of the negative photosensitive resin composition in forming the 2nd photosensitive resin layer 5b is not specifically limited, A dip coating method (dipping method), a roll-type coating method, a spray coating method etc. are mentioned.

  The second photosensitive resin layer 5b is formed so as to cover the surface of the first photosensitive resin layer 5a on the upper and lower surfaces of the printed wiring board manufacturing panel 1, and the second photosensitive resin layer is formed inside the through hole 4. It is preferable not to form the layer 5b.

  As shown in FIG. 2, when the inside of the through hole 4 is blocked by the film of the first photosensitive resin layer 5a, the second photosensitive resin layer 5b may not be formed inside the through hole 4. It becomes easy. In this case, when the negative photosensitive resin composition is applied to the printed wiring board manufacturing panel 1 to form the second photosensitive resin layer 5b, the opening of the through hole 4 and the first through hole 4 are closed. The air between the film of the photosensitive resin layer 5a prevents the negative photosensitive resin composition from entering the through hole 4, and the second photosensitive resin layer 5b is not formed on the inner surface of the through hole 4. Can be. In particular, when the second photosensitive resin layer 5b is formed by applying the roll coating method, the formation of the second photosensitive resin layer 5b on the inner surface of the through hole 4 can be sufficiently inhibited.

  In particular, if a double-sided roll coating method in which roll coating is simultaneously applied to the upper and lower surfaces of the printed wiring board manufacturing panel 1, the inside of the through hole 4 is formed by the film of the first photosensitive resin layer 5a as shown in FIG. Even if it is not closed, the rolls on both sides of the through hole 4 are arranged so that air is confined in the through hole 4 and this air prevents the negative photosensitive resin composition from entering the through hole 4. In addition, the second photosensitive resin layer 5 b can be prevented from being formed on the inner surface of the through hole 4.

  If the second photosensitive resin layer 5b is not formed on the inside of the through hole 4 in this way, the second photosensitive resin layer 5b will not be damaged at the peripheral edge (hole edge) of the through hole 4. Therefore, the thickness of the photosensitive resin layer 5 at the hole edge can be kept sufficiently large. For this reason, it is possible to prevent the photosensitive resin layer 5 and the resist layer from dropping off at the hole edge, and maintain sufficient conduction between the through hole 4 and the conductor wiring even when the landless through hole 4 is formed. Will be able to.

  The kind of negative photosensitive resin composition used for formation of the 2nd photosensitive resin layer 5b is not specifically limited, A suitable thing can be used.

  Thus, by forming the photosensitive resin layer 5 through the two-step coating process, the film thickness of the photosensitive resin layer 5 can be appropriately adjusted in the through hole 4 and the surface of the printed wiring board manufacturing panel 1. it can.

[Exposure process]
In the exposure step, the first photosensitive resin layer 5a and the second photosensitive resin layer 5b constituting the photosensitive resin layer 5 are simultaneously exposed through a pattern mask.

  As a pattern mask, a mask in which a desired conductor wiring pattern made of wiring, land, or the like is drawn as an exposed portion that transmits active energy rays and other portions are formed as non-exposed portions that shield active energy rays Photo tools such as films and dry plates are used. When a printed wiring board with a through hole having the landless through hole 4 is manufactured, a conductive wiring pattern having no land is formed as a non-exposed portion on the phototool.

  The phototool is placed in contact with the photosensitive resin layer 5 on both sides of the printed wiring board manufacturing panel 1 or in a state of being separated by a certain distance (off contact), and activated from both sides of the printed wiring board manufacturing panel 1. By irradiating energy rays, the photosensitive resin layer 5 is exposed through a photo tool.

  As the light source used for the exposure, a light source that irradiates an active energy ray capable of reacting the composition is used according to the composition of the negative photosensitive resin composition. Examples of the active energy rays include appropriate active energy rays such as ultraviolet rays, visible light, and near infrared rays, depending on the composition of the negative photosensitive resin composition.

The energy amount of the active energy ray is an appropriate amount for sufficiently reacting the negative photosensitive resin composition. For example, the active energy ray is irradiated from one side of the panel 1 for manufacturing a printed wiring board. The active energy ray is irradiated from both sides of the printed wiring board manufacturing panel 1 with an energy amount of 5 to 2000 mJ / cm ² .

  Note that the exposure method is not limited to the method using the photo tool as described above, and an appropriate method can be adopted. For example, a direct drawing method by laser exposure or the like can be adopted.

[Development process]
By removing the phototool from the exposed printed wiring board manufacturing panel 1 and developing the photosensitive resin layer 5, the unexposed portion of the photosensitive resin layer 5 is removed, and the remaining photosensitive resin layer 5 is removed. A resist layer is formed at the exposed portion. At this time, the resist layer is formed in the shape of a conductor pattern on the surface of the printed wiring board manufacturing panel 1. A resist layer is also formed on the inner surface of the through hole 4.

  In the development process, an appropriate developer according to the type of the negative photosensitive resin composition forming the photosensitive resin layer 5 can be used. Specific examples of the developer include inorganic basic substances such as sodium carbonate, caustic soda, caustic potash, and sodium metasilicate, and aqueous solutions of organic basic substances such as alkylamines and alkanolamines.

[Etching process]
Next, the conductor layer 3 that is not covered with the resist layer is removed by etching. As a result, a conductor circuit having a desired pattern is formed in the remaining portion of the conductor layer 3 on the printed wiring board manufacturing panel 1 and the through hole 4 is formed.

  In the etching process, an appropriate etching solution corresponding to the type of metal constituting the conductor layer 3 can be used. Specific examples of the etching solution include ferric chloride solution and cupric chloride solution.

[Peeling process]
After the etching step, the resist layer is stripped in a stripping step. In the peeling process, as shown in FIG. 2, the resist layer is peeled from the printed wiring board manufacturing panel 1 in which the conductor wiring and the through hole 4 are formed.

  The resist layer is peeled off by treatment with a peeling solution. As the stripping solution, an appropriate stripping solution according to the composition of the negative photosensitive resin composition forming the photosensitive resin layer 5 can be used. Specific examples of the stripping solution include aqueous solutions of inorganic basic substances such as caustic soda, caustic potash and sodium metasilicate, and aqueous solutions of organic basic substances such as alkylamines and alkanolamines.

  In this stripping step, it is preferable that the resist layer is stripped not by being dissolved in the stripping solution but by being swollen by the stripping solution, or by being further broken into pieces by swelling. In this case, the resist layer can be easily peeled even on the inner surface of the through hole 4 where the resist layer tends to remain.

  As described above, a printed wiring board having desired conductor wiring and through holes 4 can be obtained.

[Negative photosensitive resin composition]
Although the negative photosensitive resin composition used for manufacture of a printed wiring board is not specifically limited, As the suitable example, the water-system negative photosensitive resin composition which has the composition shown below is mentioned. . As the negative photosensitive resin composition for forming the first photosensitive resin layer 5a and the second photosensitive resin layer 5b, at least one is preferably an aqueous negative photosensitive resin composition having the following composition. The negative photosensitive resin composition for forming the first photosensitive resin layer 5a and the second photosensitive resin layer 5b is more preferably an aqueous negative photosensitive resin composition having the following composition.

  Since such an aqueous negative photosensitive resin composition is aqueous, various problems such as occupational safety and health problems due to volatilization of organic solvents, environmental pollution problems, and the risk of fire occurrence, etc. This is advantageous in terms of process operation and working environment from the viewpoint that exposure operation is easy, sensitivity is high, etching solution resistance is excellent, and peeling is possible.

  In particular, when this water-based negative photosensitive resin composition is used, it is possible to swell the resist layer without dissolving it in the stripping solution in the stripping step, or to further smash the strip, so that the inner surface of the through hole 4 can be stripped. In this case, the resist layer can be easily removed.

  In the following description, “(meth) acryl” is a general term for “acryl” and “methacryl”. For example, “(meth) acrylic acid” means “acrylic acid” and “methacrylic acid”. Is a generic term.

  This aqueous negative photosensitive resin composition (hereinafter sometimes abbreviated as “composition”) includes a carboxyl group-containing resin (A) having a polymerizable unsaturated bond, an amine compound (B), and a polymerization. An unsaturated compound (C), a photopolymerization initiator (D), and water (E) are contained.

  Hereinafter, each component will be described in detail.

(Carboxyl group-containing resin (A))
Since the carboxyl group-containing resin (A) has a polymerizable unsaturated bond, an unsaturated group is introduced into the aqueous negative photosensitive resin composition. Therefore, when photosensitivity is imparted to the aqueous negative photosensitive resin composition, and the photosensitive resin layer 5 formed from this composition is partially exposed, the non-exposed portion and the exposed portion (resist There is a sufficient difference in solubility, dispersibility, swellability and the like in a developer such as water or a dilute alkaline solution. For this reason, a fine resist pattern can be formed.

  The content of the carboxyl group-containing resin (A) with respect to the total amount of the composition is preferably in the range of 10 to 90% by mass. In this range, excellent exposure developability is imparted to the composition.

  As the carboxyl group-containing resin (A), an appropriate one is used, but it is preferable to contain at least one of the following carboxyl group-containing resin (A-1) and carboxyl group-containing resin (A-2).

  The carboxyl group-containing resin (A-1) is a carboxyl in a polymer produced by a polymerization reaction between an ethylenically unsaturated compound (a) having a carboxyl group and an ethylenically unsaturated compound (b) having no carboxyl group. It produces | generates by making a part of group react with the ethylenically unsaturated compound (c) which has an epoxy group.

  As the ethylenically unsaturated compound (a), an appropriate monomer or prepolymer having a carboxyl group is used. Specific examples of the ethylenically unsaturated compound (a) include, for example, acrylic acid, methacrylic acid, acrylic acid dimer, cinnamic acid, etc .; succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydro anhydride Dibasic acid anhydrides such as phthalic acid, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride and hydroxyethyl (meth) acrylate, hydroxy Propyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate Half esters obtained by reacting a compound having an ethylenically unsaturated group containing one hydroxyl group in one molecule, such as a rate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate; Dibasic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, itaconic acid and the like One ester per molecule such as glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate monoglycidyl ether, etc. Examples thereof include half esters obtained by reacting a compound having an ethylenically unsaturated group containing a poxy group. These compounds are used individually by 1 type, or multiple types are used together.

  As the ethylenically unsaturated compound (b), an appropriate ethylenically unsaturated monomer having no carboxyl group and copolymerizable with the ethylenically unsaturated compound (a) is used. Specific examples of the ethylenically unsaturated compound (b) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) Linear, branched or alicyclic alkyl (meth) acrylates such as acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc .; 2-hydroxyethyl (meth) acrylate Hydroxyalkyl, such as rate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate (Meth) acrylates; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is 2 to 23, for example) mono (meth) acrylates; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, diethylene glycol Ethylene glycol esters such as mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and methoxydiethylene glycol (meth) acrylate (Meth) acrylates and similar propylene glycol-based (meth) acrylates, butylene glycol-based mono (meth) acrylates; dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) Amino group-containing (meth) acrylates such as acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-propyl (meth) acrylamide Acrylamides such as N-tertiary butyl (meth) acrylamide, N-tertiary octyl (meth) acrylamide and diacetone (meth) acrylamide; styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene Ene, α-methylstyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, p -Vinyl aromatic compounds such as vinyl benzyl alcohol; Maleimides such as maleimide, N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; 2- (meth) acrylamide ethanesulfonic acid, 2- (meth) acrylamidepropane Sulfonic acid group-containing (meth) acrylates such as sulfonic acid and 3- (meth) acrylamidepropanesulfonic acid; in addition, glycerol mono (meth) acrylate, vinyl acetate, vinyl ethers, (meth) allyl alcohol, vinylidene cyanide, salt Vinyl, vinylidene chloride, vinyl pyrrolidone, and (meth) acrylonitrile. In addition to these compounds, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) as necessary Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene, etc. A compound (b-2) having two or more ethylenically unsaturated groups in one molecule is also used. These compounds are used individually by 1 type, or multiple types are used together.

  As the ethylenically unsaturated compound (c), an appropriate monomer or prepolymer having an epoxy group is used. Specific examples of the ethylenically unsaturated compound (c) include glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate glycidyl ether, allyl glycidyl ether, epoxidized stearyl acrylate (manufactured by Shin Nippon Rika Co., Ltd .; product number “Rikaresin ESA”) and the like. These compounds are used individually by 1 type, or multiple types are used together. Among these compounds, glycidyl acrylate and glycidyl methacrylate are particularly preferable because they are widely used and easily available.

  The reaction of the ethylenically unsaturated compound (a) and the ethylenically unsaturated compound (b) proceeds by an appropriate polymerization method. As this polymerization method, a known method such as a solution polymerization method may be employed.

  When the solution polymerization method is adopted, a method of heating and stirring in an appropriate organic solvent in which the ethylenically unsaturated compound (a), the ethylenically unsaturated compound (b) and the polymerization initiator are mixed, under a nitrogen atmosphere, An azeotropic polymerization method or the like is employed.

  Examples of the organic solvent include alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, butyl carbitol Examples include acetates such as acetate and propylene glycol monomethyl ether acetate; dialkyl glycol ethers and the like. These solvents are used alone or in combination.

  Examples of the polymerization initiator include hydroperoxides such as diisopropylbenzene hydroperoxide; dialkyl peroxides such as dicumyl peroxide and 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane. Diacyl peroxides such as isobutyryl peroxide; ketone peroxides such as methyl ethyl ketone peroxide; alkyl peresters such as t-butyl peroxybivalate; peroxydicarbonates such as diisopropyl peroxydicarbonate; Examples include azo compounds such as azobisisobutyronitrile. These polymerization initiators are used individually by 1 type, or multiple types are used together. A redox initiator may also be used as the polymerization initiator.

  The ratio of the ethylenically unsaturated compound (a) to the ethylenically unsaturated compound (b) is appropriately adjusted, but the molar ratio of the former to the latter is preferably in the range of 10:90 to 90:10.

  The reaction between a part of the carboxyl groups in the polymer of the ethylenically unsaturated compound (a) and the ethylenically unsaturated compound (b) and the ethylenically unsaturated compound (c) proceeds by an appropriate method. As this method, a known method can be adopted. For example, a thermal polymerization inhibitor and a catalyst are added to an organic solvent solution containing a polymer of an ethylenically unsaturated compound (a) and an ethylenically unsaturated compound (b) produced by the above solution polymerization method, While stirring and mixing the organic solvent solution, a part of the carboxyl group in the polymer can be reacted with the ethylenically unsaturated compound (c) by heating by an ordinary method. As the thermal polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, or the like is used. As the catalyst, tertiary amines such as dimethylbenzylamine and triethylamine; quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride; triphenylstibine and the like are used. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

  The amount of ethylenically unsaturated compound (c) used is ethylenically unsaturated with respect to 1 mol of carboxyl groups present in the polymer of ethylenically unsaturated compound (a) and ethylenically unsaturated compound (b). The amount of the epoxy group present in the compound (c) is preferably in the range of 0.1 to 0.8 mol, more preferably in the range of 0.3 to 0.6 mol. Within this range, particularly excellent developability with a developer (water or dilute alkaline solution) is imparted to the non-exposed portion of the photosensitive resin layer 5 formed from the composition, and the exposed portion (resist layer) of this coating film. Particularly excellent developer resistance is imparted.

  The acid value of this carboxyl group-containing resin (A-1) is preferably in the range of 20 to 500, more preferably in the range of 50 to 200. Moreover, the weight average molecular weight of this carboxyl group-containing resin (A-1) is preferably in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 50,000.

  When the acid value of the carboxyl group-containing resin (A-1) is too small, the carboxyl group-containing resin (A-1) is sufficient even if the carboxyl group-containing resin (A-1) is neutralized with the amine compound (B). Therefore, it is difficult to remove the non-exposed portion of the photosensitive resin layer 5 with a developing solution or to peel the resist layer with an alkaline solution. On the other hand, when this acid value is too large, the water solubility of the carboxyl group-containing resin (A-1) neutralized with the amine compound (B) becomes too high, and the resist resistance to developing solution and etching resistance of the resist layer is increased. May not be sufficiently obtained, and as a result, it may be difficult to form a fine resist pattern.

  Moreover, when the weight average molecular weight of carboxyl group-containing resin (A-1) is too small, tackiness arises in the photosensitive resin layer 5, and the handleability at the time of exposure etc. of the board | substrate with which the photosensitive resin layer 5 was formed was carried out. There is a risk that the resist layer may be deteriorated, and the resist solution resistance and etching solution resistance of the resist layer may not be sufficiently obtained. On the other hand, when the weight average molecular weight is too large, the viscosity of the composition becomes excessively high, and it becomes difficult for the carboxyl group-containing resin (A-1) to be finely dispersed in the composition. There is a risk that it is difficult to form a fine resist pattern.

  The acid value of the carboxyl group-containing resin (A-1) depends on the type of raw material used for the synthesis of the carboxyl group-containing resin (A-1), and the ethylenically unsaturated compound (a) and the ethylenically unsaturated compound By adjusting the ratio of the amount used with (b) and the amount of ethylenically unsaturated compound (c) used for the polymer of ethylenically unsaturated compound (a) and ethylenically unsaturated compound (b), Adjust as appropriate.

  The weight average molecular weight of the carboxyl group-containing resin (A-1) depends on the type of raw materials used for the synthesis of the carboxyl group-containing resin (A-1), the reaction conditions, and the like, and the ethylenically unsaturated compound (a). It adjusts suitably by preparing the usage-amount of the polymerization initiator etc. which are used for the polymerization reaction of an ethylenically unsaturated compound (b).

  The carboxyl group-containing resin (A-2) is a polymer in a polymer produced by a polymerization reaction between an ethylenically unsaturated compound (d) having an epoxy group and an ethylenically unsaturated compound (e) having no epoxy group. An epoxy group reacts with an ethylenically unsaturated compound (f) having a carboxyl group, and a hydroxyl group produced by this reaction reacts with an acid anhydride (g).

  As the ethylenically unsaturated compound (d), an appropriate monomer or prepolymer having an epoxy group is used. Specific examples of the ethylenically unsaturated compound (d) include the same compounds as the above specific examples of the ethylenically unsaturated compound (c) used for the synthesis of the carboxyl group-containing resin (A-1). . These compounds are used individually by 1 type, or multiple types are used together. Among these compounds, glycidyl acrylate and glycidyl methacrylate are particularly preferable because they are widely used and easily available.

  As the ethylenically unsaturated compound (e), an appropriate ethylenically unsaturated monomer having no epoxy group and copolymerizable with the ethylenically unsaturated compound (d) is used. Specific examples of the ethylenically unsaturated compound (e) include the same compounds as the above specific examples of the ethylenically unsaturated compound (b) used for the synthesis of the carboxyl group-containing resin (A-1). . These compounds are used individually by 1 type, or multiple types are used together.

  As the ethylenically unsaturated compound (f), an appropriate monomer or prepolymer having a carboxyl group is used. Specific examples of the ethylenically unsaturated compound (f) include the same compounds as the above specific examples of the ethylenically unsaturated compound (a) used for the synthesis of the carboxyl group-containing resin (A-1). . These compounds are used individually by 1 type, or multiple types are used together.

  An appropriate compound is used as the acid anhydride (g). Specific examples of the acid anhydride (g) include succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Dibasic acid anhydrides such as acid, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, Examples of the acid anhydride include tribasic acids or more such as cyclohexanetricarboxylic acid anhydride. These compounds are used individually by 1 type, or multiple types are used together.

  The reaction of the ethylenically unsaturated compound (d) and the ethylenically unsaturated compound (e) proceeds by an appropriate polymerization method. As this polymerization method, a known method such as a solution polymerization method may be employed. For example, the same technique as in the case of the reaction of the ethylenically unsaturated compound (a) and the ethylenically unsaturated compound (b) can be employed.

  The ratio of the ethylenically unsaturated compound (d) and the ethylenically unsaturated compound (e) is adjusted as appropriate, but the ethylenically unsaturated compound (d) and the ethylenically unsaturated compound (e) are not mixed with the ethylenically unsaturated compound (e). It is preferable that the ratio of the saturated compound (e) exceeds 0 mol% and is 90 mol% or less.

  The reaction between the epoxy group in the polymer of the ethylenically unsaturated compound (d) and the ethylenically unsaturated compound (e) and the ethylenically unsaturated compound (f) proceeds by an appropriate method. As this method, a known method can be adopted. For example, the same technique as in the case of the reaction between the polymer of the ethylenically unsaturated compound (a) and the ethylenically unsaturated compound (b) and the ethylenically unsaturated compound (c) may be employed.

  The amount of the ethylenically unsaturated compound (f) used is ethylenically unsaturated with respect to 1 mol of the epoxy group present in the polymer of the ethylenically unsaturated compound (d) and the ethylenically unsaturated compound (e). The amount of the carboxyl group present in the compound (f) is preferably in the range of 0.7 to 1.2 mol, more preferably in the range of 0.9 to 1.1 mol. In this range, the residual amount of epoxy groups in the carboxyl group-containing resin (A-2) is particularly reduced. For this reason, the thermosetting reaction of the carboxyl group-containing resin (A-2) in the composition is suppressed under weak heat drying conditions (for example, heat drying conditions in the preliminary drying step). For this reason, the thermosetting of the photosensitive resin layer 5 is suppressed, and the developability fall of this photosensitive resin layer 5 is suppressed. In addition, the remaining unreacted ethylenically unsaturated compound (f) in the composition is also suppressed.

  The amount of acid anhydride (g) used is produced by the reaction of the epoxy group in the polymer of ethylenically unsaturated compound (d) and ethylenically unsaturated compound (e) with ethylenically unsaturated compound (f). The amount is preferably in the range of 0.1 to 0.8 mol, more preferably in the range of 0.3 to 0.6 mol, relative to 1 mol of the hydroxyl group. Within this range, the carboxyl group-containing resin (A-2) gives particularly excellent developability to the non-exposed portion of the photosensitive resin layer 5 and also gives particularly excellent developer resistance to the resist layer.

  The acid value of this carboxyl group-containing resin (A-2) is preferably in the range of 20 to 500, more preferably in the range of 50 to 200. The weight average molecular weight of the carboxyl group-containing resin (A-2) is preferably in the range of 1000 to 50000, and more preferably in the range of 5000 to 20000.

  When the acid value of the carboxyl group-containing resin (A-2) is too small, the carboxyl group-containing resin (A-2) is sufficient even if the carboxyl group-containing resin (A-2) is neutralized with the amine compound (B). Therefore, it is difficult to remove the non-exposed portion of the photosensitive resin layer 5 with a developing solution or to peel the resist layer with an alkaline solution. On the other hand, when this acid value is too large, the water solubility of the carboxyl group-containing resin (A-2) neutralized with the amine compound (B) becomes too high, and the resist resistance of the resist layer to developer and etching resistance May not be sufficiently obtained, and as a result, it may be difficult to form a fine resist pattern.

  In addition, when the weight average molecular weight of the carboxyl group-containing resin (A-2) is too small, the tackiness of the photosensitive resin layer is increased, and the handling property of the substrate on which the photosensitive resin layer 5 is formed during exposure is increased. There is a risk that the resist layer may be deteriorated, and the resist solution resistance and etching solution resistance of the resist layer may not be sufficiently obtained. On the other hand, when the weight average molecular weight is too large, the viscosity of the composition becomes excessively high, and it becomes difficult to finely disperse the carboxyl group-containing resin (A-2) in the composition. There is a possibility that the formation of the pattern becomes difficult.

  When the carboxyl group-containing resin (A) contains at least one of the carboxyl group-containing resin (A-1) and the carboxyl group-containing resin (A-2), the carboxyl group-containing resin in the carboxyl group-containing resin (A) The content of (A-1) is preferably in the range of 50 to 100% by mass, and the content of the carboxyl group-containing resin (A-2) in the carboxyl group-containing resin (A) is in the range of 50 to 100% by mass. preferable. When the carboxyl group-containing resin (A) contains both the carboxyl group-containing resin (A-1) and the carboxyl group-containing resin (A-2), the carboxyl group-containing resin in the carboxyl group-containing resin (A) The total content of (A-1) and the carboxyl group-containing resin (A-2) is preferably in the range of 50 to 100% by mass. When the carboxyl group-containing resin (A) thus contains at least one of the carboxyl group-containing resin (A-1) and the carboxyl group-containing resin (A-2), the carboxyl group-containing resin (A-1) and the carboxyl group Since the group-containing resin (A-2) has high photoreactivity, the resist layer is provided with particularly excellent developer resistance, and a carboxyl group-containing resin (A-) having a hydrophilic group and a hydrophobic group. 1) and carboxyl group-containing resin (A-2) function as a surfactant, and the emulsification and dispersion of components in the composition are further promoted, and the polymerizable unsaturated compound (C) and photopolymerization start in the composition The agent (D) is finely dispersed. At this time, the polymerizable unsaturated compound (C) and the photopolymerization initiator (D) are dispersed in the form of fine particles in the composition.

(Amine compound (B))
An appropriate compound is used as the amine compound (B). Specific examples of the amine compound (B) include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine; triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine, Examples include alkylamines such as diisobutylamine; alkylalkanolamines such as dimethylaminoethanol and diethylaminoethanol; alicyclic amines such as cyclohexylamine; and organic amines such as tetramethylammonium hydroxide. These compounds are used alone or in combination of two or more. Of these compounds, tertiary amines such as triethanolamine, triethylamine, dimethylaminoethanol, and diethylaminoethanol are preferably used.

  The content of the amine compound (B) in the composition is such that the equivalent of the amine compound (B) to 1 mol of the carboxyl group contained in the carboxyl group-containing resin (A) in the composition is 0.2 to 1. The amount is preferably in the range of 0. If the equivalent of the amine compound (B) is less than 0.2, the water solubility of the composition may be lowered and the storage stability may be lowered. Further, the alkali peelability may be lowered, and the panel surface for producing a printed wiring board. There is a possibility that the resist layer in the through hole cannot be removed. On the other hand, if this equivalent exceeds 1.0, the resist layer is not sufficiently provided with developer resistance, and it may be difficult to form a fine pattern. Moreover, the content of the amine compound with respect to the total amount of the composition is preferably in the range of 1 to 20% by mass. If this content is less than 1% by mass, the water-solubility of the composition may be lowered and the storage stability may be lowered. Further, the alkali peelability may be lowered, and the printed wiring board manufacturing panel surface and the through hole may be reduced. There is a possibility that the resist layer cannot be removed. On the other hand, if the content exceeds 20% by mass, the developer resistance of the resist layer may be lowered, and it may be difficult to form a fine pattern.

(Polymerizable unsaturated compound (C))
An appropriate compound is used as the polymerizable unsaturated compound (C). Specific examples of the polymerizable unsaturated compound (C) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene And the like (D-1) having two or more ethylenically unsaturated groups in one molecule. These compounds are used alone or in combination of two or more.

  The content of the polymerizable unsaturated compound (C) with respect to the total amount of the composition is preferably in the range of 1 to 20% by mass. If the content is less than 1% by mass, the photopolymerizability of the composition is lowered, and it may be difficult to form a resist pattern. Moreover, when this content exceeds 20 mass%, tackiness will arise in the photosensitive resin layer 5, and there exists a possibility that the handleability at the time of exposure of the board | substrate with which the photosensitive resin layer 5 was formed may worsen.

(Photopolymerization initiator (D))
An appropriate compound is used as the photopolymerization initiator (D). Specific examples of the photopolymerization initiator (D) include benzoin and its alkyl ethers; acetophenones such as acetophenone and benzyldimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone, 2,4 -Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4-diisopropylthioxanthone; Benzophenones such as benzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; and 2,4-diisopropylxanthone Xanthones; α-hydroxyketones such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-pro Those containing a nitrogen atom of a non like; and (2,4,6-trimethylbenzoyl) such as diphenyl phosphine oxide, and a photopolymerization initiator for UV curing. Moreover, visible light sclerosis | hardenability and near-infrared curability may be provided to a composition by using photoinitiator (D) for visible light or near-infrared exposure. These compounds are used alone or in combination of two or more.

  Further, in the composition, in addition to the photopolymerization initiator (D), tertiary amines such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethylbenzoate, etc. These known photopolymerization accelerators and sensitizers may be contained. Further, a coumarin derivative such as 7-diethylamino-4-methylcoumarin may be contained in the composition as a sensitizer for laser exposure, for example.

  The content of the photopolymerization initiator (D) in the composition is appropriately adjusted. In order to improve the photocurability imparted to the composition and the physical properties imparted to the resist layer in a well-balanced manner, the composition The content of the photopolymerization initiator (D) with respect to the total amount of the product is preferably in the range of 0.1 to 10% by mass.

(Water (E))
Water (E) is an essential component in the composition. Although content of water (E) in a composition is adjusted suitably, it is preferred that content of water (E) to the composition whole quantity is the range of 30-70 mass%. In this range, the advantages of making the composition water-based, that is, occupational health and safety, environmental pollution, fire caused by volatilization of the organic solvent in the process in which the photosensitive resin layer 5 is formed after the composition is applied to the substrate. Reduction of problems such as prevention can be sufficiently achieved.

(Other ingredients)
The composition may contain other components as long as the object of the present invention is not adversely affected.

  For example, the composition may contain a solvent such as an organic solvent other than water. The content of the solvent is preferably 5% by mass or less based on the total amount of the composition.

  As this solvent, not only a solvent that is easily soluble in water, but also an organic solvent that is hardly soluble or insoluble in water can be used. Specific examples of usable organic solvents include ethanol, propanol, 2-propanol, butanol, 2-butanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, trimethylolpropane, Linear, branched, secondary or polyhydric alcohols such as neopentyl glycol, glycerin, 1,2,4-butanetriol, 1,2-butanediol, 1,4-butanediol, diacetone alcohol; ethylene glycol Ethylene glycol alkyl ethers such as monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; diethylene glycol monomethyl ether, diethylene group Polyethylene glycol alkyl ethers such as coal monoethyl ether and triethylene glycol monomethyl ether; propylene glycol alkyl ethers such as propylene glycol monomethyl ether, polypropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol Acetic esters such as monomethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, glycerol monoacetate, glycerol diacetate; lactates such as ethyl lactate and butyl lactate; diethyl adipate, dibutyl adipate, etc. Adipic acid esters; phthalic acid Phthal esters such as ethyl and dibutyl phthalate; Dialkyl glycol ethers such as diethylene glycol diethyl ether; Ketones such as methyl ethyl ketone, cyclohexanone and isophorone; Aromatic hydrocarbons such as toluene and xylene; Swazol series (Maruzen Petrochemical Co., Ltd.) Manufactured), Solvesso series (manufactured by Exxon Chemical Co., Ltd.) and the like, and petroleum-based aromatic mixed solvents; n-hexane, cyclohexane, tetrahydrofuran and the like. These solvents are used alone or in combination of two or more.

  Further, the composition may contain a polymer compound into which a photoreactive group other than the above essential components is introduced. Specific examples of the polymer compound include (meth) acrylic acid ester copolymer having an ethylenically unsaturated group introduced, (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-acrylic acid ester. Copolymers, polymers such as styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid resins; bisphenol A type epoxy resins with added (meth) acrylic acid, phenol novolac type Examples include an epoxy resin, a cresol novolac type epoxy resin, an alicyclic epoxy resin; a resin obtained by further adding a saturated or unsaturated polybasic acid anhydride to the resin; an emulsion of the resin or the like.

  In the composition, for the purpose of adjusting coating properties and other purposes, leveling agents such as silicone, (meth) acrylate copolymer, and fluorosurfactant as necessary; thixotropic agents such as aerosil; hydroquinone Polymerization inhibitors such as hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine; antihalation agents; flame retardants; plating resistance improvers; antifoaming agents; antioxidants; pigment wetting agents; Dyes; various additives such as natural or synthetic rubber powders may be contained. Further, the composition may contain a surfactant, a polymer dispersant and the like in order to improve dispersion stability.

  Moreover, an inert solid powder may be contained in the composition. Specific examples of the inert solid powder include extender pigments or colored pigments such as talc, silica, aluminum hydroxide, titanium oxide, barium sulfate, kaolin, calcium carbonate, and phthalocyanine; fine organic polymer particles such as polyethylene, nylon, and polyester; Examples include thixotropic agents such as Aerosil. In particular, when an extender is contained in the composition, it is preferable in that the peelability when the resist layer is peeled off with an alkaline solution is improved.

[Production of water-based negative photosensitive resin composition]
A water-based negative photosensitive resin composition is manufactured by mix | blending and mixing each said component. In the production of this composition, the carboxyl group-containing resin (A) is neutralized with the amine compound (B), and then the polymerizable unsaturated compound (C) is added to the aqueous solution containing the neutralized carboxyl group-containing resin (A). ) And a photopolymerization initiator (D) are preferably added.

  More specifically, the aqueous negative photosensitive resin composition is preferably produced through the following steps (1) to (6).

  Step (1); First, a carboxyl group-containing resin (A) is synthesized by a method such as the solution polymerization method described above.

  Step (2): An organic solvent solution of the carboxyl group-containing resin (A) prepared in Step (1) is mixed to prepare a mixed solution, and a predetermined amount of the amine compound (B) is added to the mixed solution.

  Step (3): While stirring the solution prepared in Step (2), water (E) is added to this solution.

  Step (4): The organic solvent is removed from the solution prepared in Step (3) by distillation to prepare an aqueous solution containing the carboxyl group-containing resin (A) neutralized with the amine compound (B). The conditions for distillation under reduced pressure are appropriately adjusted so that the organic solvent is sufficiently removed and a predetermined amount of water (E) is contained in the aqueous solution. For example, using an oil rotary vacuum pump, The vacuum distillation can be carried out.

  Step (5): Separately from the preparation of the aqueous solution in steps (1) to (4), a solution in which the photopolymerization initiator (D) is dissolved in the polymerizable unsaturated compound (C) is prepared.

  Step (6): The aqueous negative photosensitive resin composition is produced by adding the solution prepared in Step (5) to this aqueous solution while stirring the aqueous solution prepared in Step (4) at high speed. The

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not limited to these Examples. The “parts” and “%” shown below are all based on mass.

  Moreover, the weight average molecular weight was measured on condition of the following using the GPC measuring apparatus (SHODEX SYSTEM11) by Showa Denko KK.

-Column: SHODEX KF-800P, KF-805, KF-803, KF-801 in series-Moving bed: THF (tetrahydrofuran)
・ Flow rate: 1 ml
-Column temperature: 45 ° C
・ Detector: RI
Conversion: Polystyrene [Synthesis Example 1]
(Copolymerization reaction)
In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution and a stirrer, 25 parts of methacrylic acid, 105 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, 20 parts of styrene, 0.5 part of lauryl mercaptan 2,2′-azobis (2,4-dimethylvaleronitrile) 4 parts and ethanol 200 parts were added, heated in a nitrogen stream and polymerized at 65 ° C. for 5 hours to obtain a copolymer solution.

(Addition reaction)
To the above copolymer solution, 0.05 part of hydroquinone, 29 parts of glycidyl methacrylate and 0.2 part of dimethylbenzylamine are added, and an addition reaction is performed at 75 ° C. for 24 hours, and the weight average molecular weight is 15000 and the acid value is 20. A group-containing resin solution was obtained.

(Preparation of aqueous dispersion)
To the above solution, 6 parts of diethylethanolamine was added and stirred, 360 parts of ion-exchanged water was added, and the mixture was further stirred for 30 minutes to obtain a uniform solution. This solution was distilled under reduced pressure at 40 ° C. for 3 hours using an evaporator to remove ethanol, which is an organic solvent, to obtain an aqueous dispersion (A-1-1) of a carboxyl group-containing resin. The neutralization rate of the carboxyl group-containing resin with diethylethanolamine is 60%, and the resin solid content of the aqueous dispersion (A-1-1) is 60% by mass. Moreover, when this water dispersion (A-1-1) was measured with the gas chromatography, the content rate of the organic solvent (ethanol) was 1.1 mass%.

[Synthesis Examples 2 to 6]
In Synthesis Example 1, the raw material components and the amounts used thereof were changed as shown in Table 1, and the rest of the procedure was the same as in Synthesis Example 1 except that water of the carboxyl group-containing resin having the weight average molecular weight and acid value shown in Table 1 was used. Dispersions (A-1-2) to (A-1-6) were prepared. Table 1 shows the resin solid content of these aqueous dispersions (A-1-2) to (A-1-6), the neutralization rate of the carboxyl group-containing resin, and the organic solvent content.

[Synthesis Example 7]
(Copolymerization reaction)
In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution and a stirrer, 10 parts of methyl methacrylate, 10 parts of styrene, 180 parts of glycidyl methacrylate, 1.5 parts of lauryl mercaptan, 2,2′-azobis 5 parts of (2,4-dimethylvaleronitrile) and 200 parts of methyl ethyl ketone were added, heated in a nitrogen stream, and polymerized at 65 ° C. for 5 hours to obtain a copolymer solution.

(Addition reaction)
To this copolymer solution, 0.05 part of hydroquinone, 91 parts of acrylic acid, and 0.2 part of dimethylbenzylamine were added, followed by an addition reaction at 75 ° C. for 24 hours, followed by 102 parts of trimellitic anhydride, and 75 The mixture was reacted at 0 ° C. for 8 hours to obtain a carboxyl group-containing resin solution having a weight average molecular weight of 3000 and an acid value of 150.

(Preparation of aqueous dispersion)
To this carboxyl group-containing resin solution, 54 parts of triethylamine was added and stirred, and 301 parts of ion-exchanged water was added and stirred for another 30 minutes to obtain a uniform solution. This solution was distilled under reduced pressure at 40 ° C. for 3 hours using an evaporator to remove methyl ethyl ketone, which is an organic solvent, to obtain an aqueous dispersion (A-2-1) of a carboxyl group-containing resin. The neutralization rate of the carboxyl group-containing resin with triethylamine is 50%, and the resin solid content of the aqueous dispersion (A-2-1) is 60% by mass. Moreover, when this water dispersion (A-2-1) was measured with the gas chromatography, the content rate of the organic solvent (methyl ethyl ketone) was 0.01 mass%.

[Synthesis Examples 8 to 12]
In Synthesis Example 7, the raw material components and the amounts used thereof were changed as shown in Table 1, and the rest was the same as in Synthesis Example 1, except that the water of the carboxyl group-containing resin having the weight average molecular weight and acid value shown in Table 1 was used. Dispersions (A-2-2) to (A-2-6) were prepared. Table 1 shows the resin solid contents of these aqueous dispersions (A-2-2) to (A-2-6), the neutralization rate of the carboxyl group-containing resin, and the organic solvent content.

  The details of each component in Table 1 are as follows.

MAA: methacrylic acid AA: acrylic acid MMA: methyl methacrylate BMA: n-butyl methacrylate HEMA: hydroxyethyl methacrylate DEAA: N, N-diethylacrylamide EGDA: tetraethylene glycol diacrylate GMA: glycidyl methacrylate ABN-V: 2, 2 ′ -Azobis (2,4-dimethylvaleronitrile) (polymerization initiator manufactured by Nippon Finechem Co., Ltd., trade name ABN-V)
MEK: methyl ethyl ketone HQ: hydroquinone DMBA: dimethylbenzylamine SA: succinic anhydride.

[Preparation of photosensitive resin composition]
While maintaining the aqueous dispersion of the carboxyl group-containing resin obtained in each of the above synthesis examples at 60 ° C. and stirring with a homomixer, the polymerizable unsaturated compounds shown in Table 2 in this aqueous dispersion of the carboxyl group-containing resin After adding a photopolymerization initiator, a dye and an additive, an aqueous negative photosensitive resin composition was prepared by stirring for 30 minutes.

  Details of each component in Table 2 are as follows.

Polymerizable unsaturated compound A: trimethylolpropane EO modified (3 mol) triacrylate Polymerized unsaturated compound B: pentaerythritol EO modified (4 mol) tetraacrylate Photopolymerization initiator A: 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one Photopolymerization initiator B: 2,4-diethylthioxanthone Photopolymerization initiator C: (2,4,6-trimethylbenzoyl) diphenylphosphine oxide Dye: Dainippon Colorant manufactured by Ink Chemical Industry Co., Ltd. (trade name Disperse Blue Uni 614)
Additive A: A surface conditioner (trade name BYK-348) manufactured by Big Chemie.

[Examples 1-14, Comparative Examples 1-4]
Glass epoxy double-sided copper-clad laminate ("R1705" manufactured by Panasonic Electric Works Co., Ltd .; plate thickness 1.6mm; copper thickness 18μm; substrate size 330mm x 330mm) 1000 holes with drill diameter 0.9mm, drill diameter 0.4mm A 20 μm copper plating layer was formed on the entire surface of the double-sided copper-clad laminate including the hole walls by electroless copper and electrolytic copper plating to produce a printed wiring board manufacturing panel 1.

  As for the photosensitive resin compositions for forming the first photosensitive resin layer 5a and the second photosensitive resin layer 5b for each example and comparative example, the first photosensitive film composition and the first photosensitive resin composition shown in Table 3, respectively. A combination of two photosensitive coating compositions was selected, and a photosensitive resin layer 5 was provided on the printed wiring board manufacturing panel 1. At this time, except for Comparative Examples 3 and 4, first, the printed wiring board manufacturing panel 1 was first dipped in the first photosensitive coating composition, then pulled up, and dried in a dryer at 100 ° C. for 20 minutes to obtain the first photosensitive property. Resin layer 5a was formed. Subsequently, except for Comparative Examples 1 and 2, the second photosensitive film composition was applied to the printed wiring board manufacturing panel 1 with an inclined double-sided roll coater (“NR-5000” manufactured by Satsuma Communication Industrial Co., Ltd.) and dried. The second photosensitive resin layer 5b was formed by drying at 100 ° C. for 10 minutes using a machine.

  A mask film having a pattern corresponding to each through-hole 4 is applied to the printed wiring board manufacturing panel 1 provided with the photosensitive resin layer 5, and a reduced pressure contact type double-side exposure machine “ORC HMW680GW” manufactured by Oak Manufacturing Co., Ltd. Then, exposure was performed by irradiating with ultraviolet rays having a light amount shown in Table 3 (exposure step). At this time, by using two types of mask films, a printed wiring board with a through hole having a land and a printed wiring board with a landless through hole were produced.

  For the production of a printed wiring board with through holes having lands, a pattern having a land diameter of 1.35 mm in a hole having a drill diameter of 0.9 mm, and a pattern having a land diameter of 0.85 mm in a hole having a drill diameter of 0.4 mm, respectively. The drawn mask film with a pattern width of 100 μm was used. For the production of a printed wiring board with landless through-holes, a mask film having a pattern with a pattern width of 100 μm and having no lands was used.

  In addition, the exposure amount of ultraviolet rays shown in Table 3 is obtained by directly applying an exposure test mask “Step Tablet PHOTEC 21-stage” manufactured by Hitachi Chemical Co., Ltd. to the photosensitive resin layer 5 formed under the same conditions as described above, and adhesion under reduced pressure. The exposure amount of the ultraviolet rays is such that the remaining step level becomes 7 when the ultraviolet ray is irradiated in this state and subsequently developed using a 1% sodium carbonate aqueous solution as a developer. This exposure amount is a value derived for each negative photosensitive resin composition by a preliminary test.

  The exposed photosensitive resin layer 5 was developed with a 1% aqueous sodium carbonate solution at 30 ° C. to form a resist layer (etching resist layer) (developing step).

  Subsequently, etching was performed using a cupric chloride etchant at 50 ° C., and the copper foil exposed from the resist layer was removed (etching step).

  After this printed wiring board manufacturing panel 1 was washed with water, the resist layer was removed by spraying a 3% aqueous sodium hydroxide solution at 40 ° C. with a spray (peeling step).

  This produced the printed wiring board with a through hole.

(Pencil hardness)
The pencil hardness of the photosensitive resin layer 5 (dry film) before exposure was measured according to JIS K-5600-5-4-1999 using Mitsubishi High Uni (manufactured by Mitsubishi Pencil Co., Ltd.).

(Adhesion)
In accordance with the test method of JIS D 0202, cross-cuts are put in a grid pattern on the photosensitive resin layer 5 (dried film) before exposure, and then the state of peeling after a peeling test with a cellophane adhesive tape is visually observed. Evaluation was made according to the following criteria.
A: No peeling occurred at the crosscut portion.
○: Partial peeling occurred at the crosscut portion when the tape was peeled off.
X: Swelling or peeling occurred in the photosensitive resin layer 5 without performing a cross-cut test.

(Tackiness)
The photosensitive resin layers 5 (dry coatings) are brought into contact with each other before being exposed to each other, and the substrate is placed at 25 ° C. in a state in which a load of 98 kPa (1 kg / cm ² ) is applied in the stacking direction of the substrates. , And left in a 55% RH atmosphere for 1 week. After the treatment, the substrates were separated from each other, and the appearance of the photosensitive resin layer 5 of the substrate was observed with a 100-fold microscope, and peeling of the photosensitive resin layer 5 and abnormality of the surface state were confirmed. Based on the results, the tackiness of the photosensitive resin layer 5 was evaluated according to the following criteria.
(Double-circle): The photosensitive resin layer 5 does not peel and a contact trace is not recognized.
○: A contact mark is observed on the surface of the photosensitive resin layer 5.
X: Peeling occurs in the photosensitive resin layer 5.

(Resolution)
The appearance of the conductor wiring formed on the printed wiring board was observed, and the resolution was evaluated according to the following criteria.
A: The conductor wiring has a clear pattern shape.
◯: The conductor wiring has a pattern shape, but a part of the conductor wiring is missing.
X: The conductor wiring does not have a pattern shape.

(Etching solution resistance in printed wiring boards with through holes with lands)
The resist layer after the etching process was observed, and the etching resistance (acid resistance) was evaluated according to the following criteria.
A: No erosion is observed in the conductor wiring and the through hole 4.
○: No erosion was observed in the conductor wiring, but slight erosion was observed in the through hole 4.
X: Erosion is observed in the conductor wiring and the through hole 4.

(Etching solution resistance in printed wiring boards with landless through holes)
The resist layer after the etching process was observed, and the etching resistance (acid resistance) was evaluated according to the following criteria.
(Double-circle): The erosion was not recognized by the through-hole 4 edge and the land dress was formed.
○: Slight erosion is observed at the edge of the through hole 4.
X: Erosion is observed at the edge of the through hole 4 and the conductor wiring is disconnected.

(Alkali peelability)
The substrate surface and the through hole 4 after the peeling process were observed, and the alkali peelability of the resist layer was evaluated according to the following criteria.
(Double-circle): Resist layer remains in the through hole 4 on the substrate.
○: Resist layer remaining on the substrate is not observed, but a slight residue is observed in the through hole 4.
X: The resist layer remains in the through hole 4 on the substrate without being removed.

  Table 3 shows the results of the above evaluation tests.

DESCRIPTION OF SYMBOLS 1 Panel for printed wiring board manufacture 3 Conductor layer 4 Through hole 5 Photosensitive resin layer 5a 1st photosensitive resin layer 5b 2nd photosensitive resin layer

Claims (11)

Pulled after the conductive layer was formed printed wiring board manufacturing panel was immersed in the negative photosensitive resin composition containing a carboxyl group-containing resin (A) having a polymerizable unsaturated bond to the surface and having a through hole The first photosensitive resin layer which forms a first photosensitive resin layer on the inner surface of the through hole and the surface of the conductor layer by applying a negative photosensitive resin composition on the surface of the printed wiring board with through hole and inside the through hole A negative photosensitive resin composition comprising a forming step and a carboxyl group-containing resin (A) further having a polymerizable unsaturated bond on the surface of the panel for manufacturing a printed wiring board on which the first photosensitive resin layer is formed. by going through the second photosensitive resin layer forming step of forming a second photosensitive resin layer by applying a roll coating method, a photosensitive consisting first photosensitive resin layer and second photosensitive resin layer The printed wiring board surface of the manufacturing panel to form the resin layer between the first photosensitive resin layer and second photosensitive resin layer, the inner surface of the through hole is only the first photosensitive resin layer, covering respectively,
Next, an exposure process of exposing the surface of the printed wiring board manufacturing panel and the photosensitive resin layer on the inner surface of the through hole, and a resist layer in the photosensitive resin layer remaining by removing the unexposed portion of the photosensitive resin layer by development A developing step for forming a conductive layer, an etching step for removing a portion of the conductive layer on the substrate surface not covered with the resist layer by etching to form a conductor wiring and a landless through hole, and the resist layer is removed. A manufacturing method of a printed wiring board with a through hole characterized by going through a peeling process. The negative photosensitive resin composition is
(A) a carboxyl group-containing resin having a polymerizable unsaturated bond,
(B) an amine compound,
(C) a polymerizable unsaturated compound,
(D) contains a photopolymerization initiator and (E) water,
Production method with the through hole printed wiring board according to claim 1, wherein the content of the carboxyl resin (A) is 10 to 90 wt% based on the total amount of the composition. The carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A-1) having a polymerizable unsaturated bond,
The carboxyl group-containing resin (A-1) is a polymer in a polymer produced by a polymerization reaction between an ethylenically unsaturated compound (a) having a carboxyl group and an ethylenically unsaturated compound (b) having no carboxyl group. The method for producing a printed wiring board with a through hole according to claim 2 , wherein a part of the carboxyl group and the ethylenically unsaturated compound (c) having an epoxy group are reacted with each other. 4. The printed wiring board with through holes according to claim 3 , wherein the carboxyl group-containing resin (A-1) has an acid value in the range of 20 to 500 and a weight average molecular weight in the range of 10,000 to 100,000. Method. The carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A-2) having a polymerizable unsaturated bond,
The carboxyl group-containing resin (A-2) is a polymer produced by a polymerization reaction between an ethylenically unsaturated compound (d) having an epoxy group and an ethylenically unsaturated compound (e) having no epoxy group. The epoxy group of the present invention reacts with the ethylenically unsaturated compound (f) having a carboxyl group, and the hydroxyl group produced by this reaction reacts with the acid anhydride (g). The manufacturing method of the printed wiring board with a through hole as described in any one of 2 thru | or 4 . 6. The printed wiring board with through holes according to claim 5 , wherein the carboxyl group-containing resin (A-2) has an acid value in the range of 20 to 500 and a weight average molecular weight in the range of 1000 to 50000. Method. The method for producing a printed wiring board with through holes according to any one of claims 2 to 6 , wherein the carboxyl group-containing resin (A) is neutralized with an amine compound (B). The said amine compound (B) contains a tertiary amine, The manufacturing method of the printed wiring board with a through hole as described in any one of Claim 2 thru | or 7 characterized by the above-mentioned. Claim 2 in which the content of the amine compound (B) is, with respect to a carboxyl group to 1 mole of the contained in the carboxyl group-containing resin (A), the characterized in that it is in the range of 0.2 to 1.0 equivalents of The manufacturing method of the printed wiring board with a through-hole as described in any one of thru | or 8 . The negative photosensitive resin composition is prepared by neutralizing the carboxyl group-containing resin (A) with an amine compound (B), and an aqueous solution containing the neutralized carboxyl group-containing resin (A). The printed wiring board with a through hole according to any one of claims 2 to 9 , wherein the printed wiring board is prepared through a process in which (C) and a photopolymerization initiator (D) are added. Method. The printed wiring with a through hole according to any one of claims 2 to 10 , wherein the negative photosensitive resin composition is prepared through the following steps (1) to (6). A manufacturing method of a board.
(1) A step of synthesizing a carboxyl group-containing resin (A) in an organic solvent (2) An organic solvent solution of the carboxyl group-containing resin (A) prepared in the step (1) is mixed, and this mixed solution is mixed Step of adding amine compound (B) (3) Step of adding water (E) to this solution while stirring the solution prepared in step (2) (4) Solution prepared in step (3) (5) Step of dissolving the photopolymerization initiator (D) in the polymerizable unsaturated compound (C) (6) The aqueous solution prepared in the step (4) is stirred. While adding the solution prepared in step (5) to the aqueous solution.

Images