JP3527809B2 - Filling ink for manufacturing through-hole printed wiring board and method for manufacturing through-hole printed wiring board - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hole filling ink used in a process of manufacturing a through hole printed wiring board and a method of manufacturing a through hole printed wiring board using the ink.

[0002]

2. Description of the Related Art A through-hole printed wiring board is one in which wiring circuit conductors formed on both front and back surfaces of an insulating substrate are electrically connected to each other by electrically connecting holes penetrating both of them. Japanese Patent Laid-Open No. 04-6288
As disclosed in JP-A No. 7 and JP-A-55-102290, a step generally called a hole filling method is adopted. That is, first, a hole for a through hole is formed at a desired position of a double-sided copper-clad laminate, and copper is coated on the entire surface of the double-sided copper-clad laminate including a hole wall by electroless plating or a combination of electroless plating and electrolytic plating. A conductive layer made of a plated layer is formed. As a result, a printed wiring board manufacturing panel in which through holes for electrically connecting the front and back wiring circuit conductors are formed can be obtained. Next, a solvent drying type hole filling ink is filled in the through hole and the hole filling ink is cured by volatilization of the solvent, or a radiation curing type hole filling ink is filled in the through hole and the hole is formed. Radiation cure the fill ink. Thereafter, a desired resist pattern is printed on the front and back of the printed wiring board manufacturing panel with an acid-resistant ink, and the acid-resistant ink is cured to form a resist layer. The through-hole printed wiring board is prepared by etching away with an acid etching solution such as ferric iron, and further removing the hole filling ink and the acid resistant ink with an alkaline solution.

Various types of solvent-drying or radiation-curing hole-filling inks used in the above steps have been put to practical use.

However, since the solvent-drying type hole-filling ink generally takes a long time to cure and the volume contraction due to the evaporation of the solvent contained therein is as large as 20 to 50%, the through-hole edge portion of the ink is large. Since the protective action becomes insufficient and that part is etched during etching,
The performance of the manufactured through-hole printed wiring board is likely to deteriorate.

On the other hand, the radiation-curable hole-filling ink has a small problem of volumetric shrinkage due to curing, unlike the solvent-drying type hole-filling ink, but the radiation-curing reaction in the deep part of the through hole is difficult to proceed sufficiently, so that polishing is performed. In the process, the cured surface of the pores was often peeled off, and the uncured resin in the interior was likely to pop out, leading to troubles. As one of the main reasons why the radiation curing reaction in the deep part of the through hole becomes difficult in the conventional hole filling ink,
Rosin-based resins are mixed mainly for the purpose of improving the solubility of the ink cured product in an alkaline solution, and these rosin-based resins are specifically gum rosin of natural resin, wood rosin, chemically modified hydrogenated rosin, and polymerization. Rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin, etc., all of which have a high color tone and thus have low transmittance of radiation such as ultraviolet rays, resulting in insufficient exposure in the deep part of the through hole.
It is considered that the radiation curing reaction does not proceed sufficiently.

In addition, in the hole filling ink, the hole filling ink is generally an inert solid powder in order to improve the polishing property and the removability of the cured product of the hole filling ink from the through hole. It is said that it is preferable to add a filler such as an extender pigment or a coloring pigment. However, in the radiation-curable hole-filling ink using the rosin-based resin as described above, in order to facilitate deep-curing, ultraviolet rays or the like may be used. Since it is necessary to maintain the radiation transparency, a sufficient amount of the inert solid powder cannot be blended, the polishing property is deteriorated, and the cured product of the ink tends to remain on the surface of the panel for producing a printed wiring board. Further, due to insufficient blending of the inert solid powder, even when removing the cured product from the through hole, peeling with an alkaline solution, the removability is poor, and a part of the cured product remains attached to the inner wall of the through hole. , Problems that cause troubles when mounting parts are likely to occur.

As described above, the radiation-curable hole-filling ink has the advantage that the problem of volume shrinkage is smaller than the solvent-drying type hole-filling ink, but it can solve the problem of curability in the deep part of the through hole. It has not yet fully utilized its advantages.

By the way, in recent years, the tendency of forming a fine conductor pattern on a printed wiring board is rapidly progressing, and there is a demand for realization of a high density printed wiring board having a fine conductor pattern having a conductor pattern width of 100 μm or less. It has been strongly recognized that the dry film, which has been conventionally used as an etching resist material for forming a fine and high-density conductor pattern, has problems of adhesion and resolution and cannot sufficiently cope with it. In order to meet this demand, it is considered to use a photo-developable liquid etching resist ink as a material replacing the dry film, and the following method using this is drawing attention.

That is, first, a hole filling ink is filled in a through hole of a printed wiring board manufacturing panel and cured, and a through hole filling step, and an extra hole filling attached to the surface of the printed wiring board manufacturing panel in the through hole filling step. A polishing step of removing the ink and its cured product by polishing,
A photoetchable liquid etching resist ink is applied on the printed wiring board manufacturing panel after the polishing step, preliminarily dried if necessary, and then exposed and developed by radiation such as ultraviolet rays to form a resist layer. A resist forming step, an etching step of forming a conductor pattern on the printed wiring board manufacturing panel by etching after the resist forming step, an etching resist on the surface of the printed wiring board manufacturing panel after the etching step, and holes in through holes This is a method for manufacturing a through-hole printed wiring board, which comprises a peeling step for removing a cured material of a filling ink (hereinafter, referred to as a method for manufacturing a through-hole printed wiring board using a filling ink and a liquid etching resist ink, “hole filling-liquid etching resist”). Law ".).

The hole-filling ink used in the "hole-filling-liquid etching resist method" may be radiation-curing type, heat-drying type or heat-polymerizing type, and any of these hole-filling inks is used in this manufacturing process. There is the following problem in relation to the liquid etching resist ink used. That is, the liquid etching resist ink used in the resist forming step is usually methyl ethyl ketone, ketones such as cyclohexanone, and toluene, aromatic hydrocarbons such as xylene, petroleum-based aromatic solvents, and ethyl acetate, butyl acetate, Since it contains acetic acid esters such as cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and organic solvent-based diluents such as dialkyl glycol ethers, it can be used as a liquid for printed wiring board manufacturing panels. When the etching resist ink is applied, the solvent resistance of the hole-filling ink that has been filled and hardened in advance in the through holes becomes a problem.

For example, in the case of heat-drying type hole filling ink,
Due to poor solvent resistance of filled and dried hole filling ink,
When a liquid etching resist ink is applied to a panel for producing a printed wiring board, the liquid etching resist ink is melted and mixed with the liquid etching resist ink component, and a resist pattern may be removed during development with a weak alkaline solution, or development failure may occur.

Further, the radiation-curable hole-filling ink has a slightly better solvent resistance than the heat-drying hole-filling ink, but the cured product on the surface of the through-hole is still uncured due to insufficient curing depth. The problem of elution to the surface of the part remains. Furthermore, in the manufacture of through-hole wiring boards that require particularly high density and high quality, the surroundings of through-holes caused by the bleeding of additives such as defoaming agents that are compounded in the filling ink to the surface of the cured product. The film thickness of the etching resist layer becomes extremely thin due to the repelling of the liquid etching resist ink at the portions, and therefore, the problem of erosion of the circuit conductor portion to be protected at the time of etching remains at the through hole edge. Therefore, in order to put the "hole filling-liquid etching resist method" using the above liquid etching resist ink into practical use, the problem of insufficient curing depth and the problem of bleeding on the surface of a cured product such as an antifoaming agent are solved. There is a need to.

On the other hand, in the field where the finest and high-density conductor pattern is required, the through holes, and particularly the via holes among them, are miniaturized, and in order to further enhance the effect, no land is formed around the through holes. The demand for so-called landless through holes has become strong, and various methods have been proposed to realize them.

For example, a method as disclosed in Japanese Patent Laid-Open No. 61-85895, that is, after forming a plating resist layer while avoiding a portion to be a landless through hole of a printed wiring board manufacturing panel, the inside of the through hole is formed. There is a so-called "pattern plating method" that forms a metal plating layer that also serves as an etching mask, and a so-called "solder peeling method" that uses solder as a metal plating layer in this "pattern plating method" and finally removes the solder layer. . However, in the case of the "pattern plating method" or the "solder stripping method", there are problems that the process is complicated and the yield is poor due to the line warping of the wiring circuit conductor in the etching process. Further, when the method of forming a landless through hole using a dry film as disclosed in, for example, Japanese Patent Laid-Open No. 62-202587 is used, there is a problem such as poor adhesion to the through hole portion filled with hole filling ink. Therefore, since the etching solution flows around the edge of the through-hole during etching, the edge portion is easily etched and a conduction failure is likely to occur, and landing is difficult. Furthermore, as disclosed in JP-A-58-100493 or JP-A-61-139089, the "hole-filling-liquid etching resist method" using a liquid etching resist ink and a hole filling ink without using a dry film. However, in these cases, when the conventional hole filling ink is used, the curing depth of the hole filling ink is insufficient as described above, the cured product is eluted, and the liquid etching resist ink is repelled by the defoaming agent. Due to such problems, the current situation is that landing has not been sufficiently achieved.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to
Sufficient curing depth can be secured, volume shrinkage is small, and the polishing amount can be improved by increasing the compounding amount of the inert solid powder while maintaining such curing depth, and easily removed by alkaline solution. It is an object of the present invention to provide a hole-filling ink for manufacturing a through-hole printed wiring board which can be used, and a method of manufacturing a through-hole printed wiring board using the same.

Another object of the present invention is that the cured product has good solvent resistance, polishability and removability with an alkaline solution, and the liquid etching resist ink on the surface of the cured product is unlikely to repel. In particular, a hole-filling ink for manufacturing a through-hole printed wiring board and a through-hole printed wiring board using the same, which can easily realize formation of fine and high-density conductor patterns and landless in the "hole-filling-liquid etching resist method". It is to provide a manufacturing method of.

[0017]

The hole-filling ink for producing a through-hole printed wiring board according to the present invention comprises (A) the following general formula [I] and / or [II].

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[In the formula, R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and Y is 1 to 4 carbon atoms.
Alkylene group or a _{- (C n H 2n O)} P -CH 2 - ( wherein, n an integer of 2 to 6, p is an 1-19 integer.)
Represents a group represented by. } 1 to 90% by weight of a monoester compound represented by the formula (B), 0.01 to 20% by weight of a photopolymerization catalyst, and (C) a colorless rosin having a Hazen color tone of 300 or less obtained by hydrogenating a purified rosin, and / Or α, β-unsaturated monocarboxylic acid or α, β-
An unsaturated dicarboxylic acid and a purified rosin are subjected to an addition reaction and further subjected to a hydrogenation reaction to obtain 5 to 40% by weight of a colorless rosin derivative having an acid value of 150 to 500 and a Hazen color tone of 300 or less.

DETAILED DESCRIPTION OF THE INVENTION

Examples of the monoester compound represented by the general formula [I] or [II] used as the component (A) of the hole filling ink of the present invention include, for example, polyvalent carboxylic acids and alcohols having a vinyl unsaturated group. A monoester compound is mentioned.

Examples of the polyvalent carboxylic acid include tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, 3-propyltetrahydrophthalic acid, 4-propyltetrahydrophthalic acid, 3-butyltetrahydrophthalic acid, 4-butyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, Examples thereof include 4-ethylhexahydrophthalic acid, 3-propylhexahydrophthalic acid, 4-propylhexahydrophthalic acid, 3-butylhexahydrophthalic acid and 4-butylhexahydrophthalic acid. Among these, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, and 4-methylhexahydrophthalic acid are among the alkali solutions. It is preferable in that the removability is improved.

As the alcohol having a vinylic unsaturated group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Exemplify vinyl monomers such as hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate and polycaprolactone mono (meth) acrylate. You can

The monoester compound of the above component (A) is
Although it can be produced by various conventional synthetic methods, it can be easily obtained particularly by a ring-opening addition reaction of the above-mentioned polycarboxylic acid anhydride and a vinyl monomer. The content of the component (A) is 1 to 90% by weight with respect to the total amount of the hole filling ink. If it is less than 1% by weight, the removability of the hole filling ink with an alkaline solution is lowered, and if it exceeds 90% by weight. Due to the increased viscosity, it becomes difficult to fill the through hole with the filling ink. From this point, the preferable range of the compounding amount of the component (A) is 1 to 70% by weight, and the optimum range is 5 to 50% by weight.

As the photopolymerization catalyst which is the component (B) of the hole-filling ink of the present invention, for example, a usual compound which generates a radical or a Lewis acid by a photochemical reaction after irradiation with visible light, near ultraviolet light or ultraviolet light is used. However, those having high spectral sensitivity in the ultraviolet region are preferable in consideration of workability and the like.

Examples of the compound which induces a radical polymerization reaction include benzophenones, vicinal ketones such as diacetyl, benzyl, and acyloins such as pivaloin, α-pyridoin, and benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin. Isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and acetophenones, such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, α-pyridylacetophenone, and thioxanthones, such as 2,4-diethyl. Thioxanthone, 2,4-dimethylthioxanthone,
Thioxanthone derivatives such as 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, and 2,4-dipropylthioxanthone, and anthraquinones such as ethylanthraquinone, benzanthraquinone, diaminoanthraquinone, and camphorquinone, 4,4'-
Bis (dimethylamino) benzophenone, dibenzosuberone, 4,4'-diethylisophthalophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, acylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide can be mentioned, and the above compounds can be used alone or as a mixture of two or more kinds.
Of these, benzyl dimethyl ketal, benzophenones, thioxanthone and its derivatives, and anthraquinones are particularly preferable in terms of ensuring a large curing depth in the ultraviolet light region.

As the photopolymerization catalyst for inducing the cationic polymerization reaction, aryldiazonium, diarylhalonium, triphenylphosphonium and dialkyl-4 are used.
-Hydroxysulfonium, dialkyl-4-hydroxydiphenylsulfonium, allene-iron complex and other P
F ₆ ⁻ , As F ₆ ⁻ , BF ₄ ⁻ , Sb F ₆ ⁻ salt and the like can be mentioned.

Further, an amine photopolymerization co-catalyst or the like, which itself is not activated by irradiation of ultraviolet rays, but which accelerates the photopolymerization reaction when used in combination with the photopolymerization catalyst, can also be used. As such photopolymerization co-catalyst, mainly aliphatic,
Aromatic amines are used, such as triethylenetetramine, triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine,
N-methyldiethanolamine, diethylaminoethylmethacrylate, Michler's ketone, 4,4'-diethylaminophenone, ethyl 4-dimethylaminobenzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc. Can be mentioned. Among these, especially Michler's ketone,
4,4′-diethylaminophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-
Aromatic amines such as butoxy) ethyl and isoamyl 4-dimethylaminobenzoate are preferable because they ensure a large curing depth in the ultraviolet light region. Further, as a laser sensitizer, 7-diethylamino-4-methylcoumarin,
Coumarin derivatives such as 4,6-diethyl-7-ethylaminocoumarin, and carbocyanine dye-based and xanthene dye-based compounds can also be used.

The blending amount of the component (B) is 0.01 to 20% by weight based on the whole amount of the filling ink, and this is 0.01
If it is less than 20% by weight, the surface curability of the hole-filling ink during exposure is remarkably lowered, and if it exceeds 20% by weight, the etching resistance is lowered.

Further, the component (C) of the hole filling ink of the present invention
Purified rosin used for the production of colorless rosin and colorless rosin derivatives is gum rosin, wood rosin, or tall containing resin acids such as abietic acid, parastophosphoric acid, neoabietic acid, pimaric acid, isopimaric acid, and dehydroabietic acid. Unpurified rosin such as oil rosin from which unsaponifiable substances are removed. The purification method by removing the unsaponifiable matter is not particularly limited, and for example, known methods such as distillation, recrystallization, and extraction can be used. Among these, the method of obtaining the main fraction by distillation,
It is preferable because it produces excellent colorless rosin and colorless rosin derivatives.

Next, the component (C) of the hole-filling ink of the present invention.
Examples of the α, β-unsaturated monocarboxylic acid used for the production of the colorless rosin derivative include acrylic acid, methacrylic acid, crotonic acid and the like, and examples of the α, β-unsaturated dicarboxylic acid include maleic acid. , Maleic anhydride, fumaric acid and the like. The addition reaction of the α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated dicarboxylic acid with the purified rosin is usually carried out by the Diels-Alder reaction, for example, at 180 to 240 ° C. for 1 to 9 hours, preferably an unsaturated reaction. It is performed under an active gas stream.

The hydrogenation reaction is carried out under known conditions, for example, by heating with a known hydrogenation catalyst such as palladium carbon or rhodium carbon under normal pressure or under pressure. The addition reaction and hydrogenation reaction are not limited to the above methods. As described above, for the colorless rosin derivative used in the present invention, the purified rosin is subjected to an addition reaction with α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated dicarboxylic acid, and further hydrogenated. The colorless rosin can be obtained by simply hydrogenating the purified rosin.

It is necessary to use a colorless rosin or a colorless rosin derivative in the radiation curable hole-filling ink of the present invention.
With rosin-based resins such as rosin-modified maleic acid that have been commonly used in hole filling inks, the color tone is generally as high as about 8 to 12 Gardner color tone, so that the transmission of radiation such as ultraviolet rays is poor, and the depth of the through hole is poor. The reason is that the curability in (2) will occur. On the other hand, the colorless rosin and the colorless rosin derivative used in the hole-filling ink of the present invention are substantially colorless and therefore have good permeability to radiation such as ultraviolet rays and good curability in the deep part of the through hole. And the solvent resistance of the hole-filled ink cured product can be made sufficient. For this purpose, both the colorless rosin and the colorless rosin derivative must have a Hazen color tone of 300 or less.

The acid value of the colorless rosin is usually about 150 to 180, but the acid value of the colorless rosin derivative must be 150 to 500, which is 150.
When it is less than 500, the removability of the cured ink of the hole-filling ink of the present invention with an alkaline solution is deteriorated, and when it exceeds 500, the acid resistance to an etching solution is deteriorated and the protective effect of the through hole during etching is deteriorated. From this point, the particularly preferable range of the acid value is 150 to 400.

As the above-mentioned colorless rosin, for example, Japanese Patent Laid-Open No.
No. 277675 can be used, and examples of commercially available products thereof include Arakawa Chemical Industry Co., Ltd.
Super light color rosin "KR-610" {color tone (Hazen 6
0), acid value 170, softening point 85 ° C.} and the like are known.
As the colorless rosin derivative, for example, JP-A-5-8
The one disclosed in Japanese Patent No. 6334 can be used,
As the commercially available product, for example, ultra-light color rosin “KE-604” manufactured by Arakawa Chemical Industries, Ltd. {color tone (Hazen 50),
Acid number 245, softening point 132 ° C.} and the like are known.

The compounding amount of the component (C) is 5 to 40% by weight based on the total amount of the hole-filling ink, and by mixing this, radiation curing in the deep part of the through hole is possible.
Moreover, it is possible to improve the removability of the cured product of the hole-filling ink with the alkaline solution. If the content is less than 5% by weight, the removability of the cured product of the hole-filling ink with an alkaline solution will not be improved, and if it exceeds 40% by weight, it will be difficult to fill the hole-filling ink into the through holes due to an increase in viscosity. Become.

The hole-filling ink of the present invention may further contain an inert solid powder as the component (D).
Examples of the inert solid powder include talc as an extender pigment and a coloring pigment, silica, aluminum hydroxide, titanium oxide, barium sulfate, kaolin, calcium carbonate, phthalocyanine, etc., and polyethylene, nylon, polyester, etc. as organic polymer fine particles, Further, as the thixotropic agent, Aerosil and the like can be mentioned, but an extender pigment is particularly preferable from the viewpoint of improving the polishing property of the cured ink for filling holes and the removability by an alkaline solution.

In the conventional radiation-curable hole-filling ink, when an inert solid powder is blended, the curability in the deep part of the through-hole is lowered. Therefore, in order to suppress this curability reduction to an allowable range, an extender pigment is actually used. In addition, there was no choice but to mix it in a small amount. However, in the radiation-curable hole-filling ink of the present invention, since colorless rosin or a colorless rosin derivative is used, the transparency of radiation such as ultraviolet rays is good as described above, and an inert solid powder is sufficient to achieve the above effects. It can be compounded to the extent that it can be demonstrated. Therefore, the hole-filling ink of the present invention may contain the component (D) in an amount not exceeding 90% by weight based on the total amount of the hole-filling ink. However, if the blending amount exceeds 90% by weight, it becomes difficult to fill the through-hole with the filling ink due to an increase in viscosity, and insufficient penetration of radiation such as ultraviolet rays into the deep part of the through-hole is likely to occur.

By blending an inert solid powder, the general purpose as a filler is achieved, such as improving the filling property and filling state when the hole filling ink is filled in the through holes. In the invention, further, the polishing property of the cured product after curing the hole-filling ink is improved, and the releasability of the cured product by the alkaline solution is improved, and the cured product of the hole-filling ink is transferred from the through hole to its inner wall in the final peeling step. It is completely removed without remaining, and troubles etc. when mounting parts are prevented.

Due to these properties, the hole-filling ink of the present invention containing the inert solid powder is not suitable for the above-mentioned "hole-filling ink".
A method for manufacturing a through-hole printed wiring board by the "liquid etching resist method", in particular, a through-hole filling step of filling a hole filling ink into a through-hole of a panel for manufacturing a printed wiring board and curing the same, and a printed wiring board in the through-hole filling step. A polishing step of removing excess hole-filling ink adhering to the surface of the manufacturing panel and its cured product by polishing,
After the polishing step, a photo-developable liquid etching resist ink is applied on the printed wiring board manufacturing panel, preliminarily dried if necessary, and then exposed and developed to form a resist layer, and a resist forming step. After the forming step, an etching step of forming a conductor pattern on the printed wiring board manufacturing panel by etching, and after the etching step, the etching resist on the surface of the printed wiring board manufacturing panel and the hole-filled ink cured material in the through holes are removed. It is particularly suitably applied to a method of manufacturing a through-hole printed wiring board, which comprises a peeling step.

By the way, in the conventional hole-filling ink, bubbles are apt to be generated due to the inclusion of air during filling into the through holes, and therefore, a large amount of additives such as an antifoaming agent is usually added. However, since these additives are filled after exposure and bleed on the surface of the cured product, when applied to the above-mentioned manufacturing method, the liquid etching resist ink is repelled in the peripheral portion of the through hole, and the film of the etching resist layer formed is formed. The thickness becomes extremely thin. Therefore, at the edge of the through hole, the portion of the wiring circuit conductor to be protected during etching is likely to be eroded. On the other hand, in the hole-filling ink of the present invention, particularly when the inert solid powder is blended in an amount of 20% by weight or more based on the total amount of the hole-filling ink, a sufficient defoaming effect can be obtained without adding an additive such as a defoaming agent. As a result, the liquid etching resist ink is not repelled. Further, as described above, even if the inert solid powder is blended, a sufficient curing depth can be ensured, so that the cured surface of the hole is not peeled off and the uncured resin inside does not pop out in the polishing step.

Therefore, 20% by weight of inert solid powder
When blended as described above, not only is it suitable for forming a fine and high-density conductor pattern, but also landless through holes can be easily formed. In particular, an inert solid powder of 50 to 90
When compounded in the range of weight%, the cured product is most suitable for forming a landless through hole in combination with the excellent polishing property of the cured product.

The hole-filling ink of the present invention may further contain a vinyl monomer other than the monoester compound of the component (A) for the purpose of adjusting the viscosity, the curing rate and the peeling rate of the ink. Examples of such unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cellosolve (meth) acrylate, methyl cellosolve (meth) acrylate, butyl cellosolve (meth) acrylate, and diethylene glycol mono (meth) acrylate. ) Acrylate, ethyl carbitol (meth) acrylate, methyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentadienyloxy Ethyl (meth) acrylate, vinyl acetate, N-vinylpyrrolidone, (meth) acrylic amide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol mono ( Monofunctional vinyl monomers such as acrylate), polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, and phenylglycidyl ether (meth) acrylic acid adduct, and Examples thereof include bifunctional vinyl monomers such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and polycaprolactone di (meth) acrylate. The content of this component is preferably 50% by weight or less based on the total amount of the filling ink.
If it is used in excess of 0% by weight, the removability with an alkaline solution tends to be lowered.

The hole-filling ink of the present invention includes various additives such as a coupling agent such as a silane coupling agent, an adhesion promoter, a leveling agent, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and tertiary butyl catechol. Further, a polymerization inhibitor such as phenothiazine, and a surfactant or a polymer dispersant for improving dispersion stability may be added.

The hole-filling ink of the present invention is prepared by kneading the above-mentioned respective components and additives by a known method such as using three rolls, a ball mill, a sand mill or a mixer alone or in combination. can do.
The hole-filling ink can be cured by a known exposure method without particular limitation.

FIG. 1 is a sectional view of a principal part of a printed wiring board manufacturing panel showing a specific example of a method of manufacturing a through hole printed wiring board using the hole filling ink of the present invention, and FIG. 2 is a photo-developable liquid etching. FIG. 6 is a cross-sectional view of a main part of a panel for manufacturing a printed wiring board, showing a specific example of a resist forming step by a method of forming a resist layer using resist ink.
FIG. 3 shows a printed wiring board manufacturing panel at the time of forming a resist layer in a landless through hole forming method using a photo-developable liquid etching resist ink. 8A is a cross-sectional view of the main part taken along the line A-A in the previous figure (a), and (c) is a cross-sectional view of the main part taken along the line BB in the previous figure (a). Further, FIG. 4 shows a panel for producing a printed wiring board after the final formation of landless through holes in the method of forming landless through holes using a photo-developable liquid etching resist ink, and (d) is a plan view of its main part, (E) is a cross-sectional view of the main part of the CC line in (d) of the previous figure, and (f) is C- when a conduction failure occurs in the edge portion of the through hole in the (d) of the previous figure.
It is a C line principal part sectional view.

As shown in FIG. 1 (A), an insulating substrate 1 (an insulating substrate is, for example, a paper base phenol resin, a paper base epoxy resin, a paper base polyester resin, a glass base epoxy resin, a glass base material). Synthetic resin substrate such as Teflon resin, glass base polyimide resin or composite resin, or metal-based insulating substrate in which metal such as aluminum or iron is covered with epoxy resin for insulation treatment, or alumina ceramic, low temperature firing It is made of a ceramic substrate such as ceramic or aluminum nitride ceramic.) Conductive metal layers made of copper are formed on both upper and lower surfaces of a laminated plate (for example, a copper clad laminated plate) to pass through at desired positions. A hole for a hole is formed, and for example, by using both electroless plating and electrolytic plating, a copper plating layer 3 or the like is formed on the entire surface of the double-sided copper-clad laminate including the hole wall. Forming a composed conductive layer. Through hole 2 for electrical connection of front and back wiring circuit conductors
A panel for producing a printed wiring board on which is formed is obtained. Incidentally, the printed wiring board manufacturing panel, unlike the above,
First, a hole for a through hole is formed at a desired position of the insulating base material 1, and then a metal conductive layer is formed on the entire surface of the insulating base material including the hole wall by using, for example, electroless plating and electrolytic plating. A metal conductor layer may be formed on both surfaces of an insulating substrate such as a flat plate.

Next, in the through hole filling step, as shown in FIG. 1B, the hole filling ink 4 of the present invention is immersed in the through hole 2 in order to protect the inner wall of the through hole 2 from the etching solution. Filled by a screen printing filling method, a pin filling method, a roll filling method, etc., and subsequently, a panel for producing this printed wiring board is charged with a high pressure mercury lamp, an ultra high pressure mercury lamp,
Using a metal halide lamp, etc., 50 to 20 per side
By exposing both surfaces with a light amount of 00 mJ, the hole-filling ink 4 is cured and the hole-filling ink cured product 4h is obtained. At this time, it is possible to obtain a curing depth of 700 μm or more per side, and the filling rate of the hole-filling ink cured product 4h in the through hole can be maintained at 90 to 100%.

In the polishing step after the through hole filling step, as shown in FIG. 1C, the hole-filling ink cured material 4h on the surface of the copper plating layer 3 is, for example, belt sander polishing, buff polishing or slab polishing. Are removed by mechanical polishing or the like. When the hole-filling ink of the present invention is used, the hole-filling ink 4 and the hole-filling ink cured product 4h are easily removed with a low polishing pressure, and the hole-filling ink cured product 4h in the copper plating layer 3 and the through hole edge portion 2a is removed. No chipping occurs, and the filling rate of the filled ink cured product 4h in the through hole can be maintained at 90 to 100% even after polishing.

In the resist forming step after the polishing step, an etching resist is formed on the surface of the copper plating layer 3. In this resist forming method, a resist pattern is printed by screen printing and cured to form the resist layer. Any of a forming method, a method of forming a resist layer using a photo-developable liquid etching resist ink, a method of using a dry film resist, an electrodeposition resist and the like may be used.

For example, in a resist forming step by a method of forming a resist pattern by screen printing,
As shown in FIG. 1D, a desired etching resist ink pattern layer 5 is printed with an etching resist ink by screen printing on the surface of the copper plating layer 3 after polishing,
After that, the etching resist layer 5h is formed by heat curing or curing by radiation such as ultraviolet rays. When the hole-filling ink of the present invention is used, since the hole-filling ink cured product 4h in the through hole 2 is excellent in flattening, a desired etching resist ink pattern layer 5 is formed in the opening of the through hole 2 and its peripheral portion. Can be printed accurately and uniformly, and a uniform etching resist layer 5h can be formed.

In the resist forming step by the method of forming a resist layer using a photo-developable liquid etching resist ink, first, as shown in FIG. 2 (D'-1), a copper plating layer after polishing is used. 3 An etching resist ink is applied to the surface by a screen printing method, a curtain coating method, a roll coating method, a spin coating method, a dip coating method, a spray method or the like, and if necessary, predried to form an etching resist ink coating film layer 6. It is formed. When the hole-filling ink of the present invention is used, the hole-filling ink cured product 4h in the through-hole 2 is excellent in flattening, so that even at the opening of the through-hole 2, a uniform etching resist is formed as in the other portions. It becomes the ink coating layer 6. Further, in this case, the solvent in the etching resist ink coating layer 6 is unlikely to elute the hole-filling ink cured product 4h in the through hole 2.

Next, as shown in FIG. 2 (D'-2), a pattern mask film 7 depicting a wiring circuit is applied on the etching resist ink coating film layer 6, and ultraviolet rays, visible light, near infrared rays, etc. are applied. Exposure to radiation. The mask film 7 is an etching resist ink coating layer 6
May be placed in an off-contact state. After the exposure of the etching resist ink coating layer 6, the mask film 7 is removed and subsequently developed with a developing solution, so that as shown in FIG. 2 (D'-).
As shown in 3), an etching resist layer 6h having a desired resist pattern is formed. When the hole-filling ink of the present invention is used, the hole-filling ink cured product 4h in the through-hole 2 is excellent in flattening, so that a uniform etching resist layer 6h can be formed.

In the etching step after the resist forming step, as shown in FIG. 1 (E), ferric chloride solution,
The exposed portion of the copper plating layer 3 is removed by etching with an etching solution such as cupric chloride solution, and the copper wiring circuit conductor 8 is formed on the printed wiring board manufacturing panel.

In the final stripping step after the above etching step, as shown in FIG. 1 (F), an inorganic basic substance such as caustic soda, caustic potash, sodium metasilicate, or an organic material such as alkylamine or alkanolamine is used. 1 with an aqueous solution of the basic substance of FIG.
The etching resist layer 5h or 6h and the hole-filled ink cured product 4h shown in (E) are dissolved and removed to obtain the desired through-hole printed wiring board.

A method of forming landless through holes by using a photo-developable liquid etching resist ink will be described. The manufacturing process in that case is the same as the conventional photo-developable liquid etching resist ink. Exactly the same as when manufacturing a through-hole printed wiring board (having lands), except that FIG.
As shown in (a) to (c), the resist pattern of the etching resist layer 6h to be formed has a feature that it does not have a portion corresponding to the through hole land. In particular, as shown in FIG. The width may be narrower than the through hole diameter. In this case, conventionally, the adhesion of the etching resist layer 9 is poor at the portion 9 where the etching resist layer 6h, the copper plating layer 3 and the cured hole filling ink 4h come into contact with each other at the through hole edge portion shown in FIG. And the thickness of the resist film becomes insufficient due to the repelling problem of the liquid etching resist ink, and the finally obtained through hole 2 of the printed wiring board after formation of the landless through hole shown in FIG. , The wiring circuit conductor 8 of the through hole edge portion 2a is shown in FIG.
As shown in (v), it is apt to be corroded by the etching solution to cause defective conduction. On the other hand, when the hole filling ink of the present invention is used, such a problem does not occur, and the through hole edge portion 2a of the through hole 2 after the landless through hole is formed has the wiring circuit conductor 8 as shown in FIG.
No erosion and no problem of poor conduction.

The various conditions and steps in the above manufacturing method are mere examples, and the manufacturing method of the through-hole printed wiring board using the hole filling ink of the present invention is not limited.

[0058]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. All parts and% used below are based on weight.

[Synthesis Example 1] 154 g (1 mol) of hexahydrophthalic anhydride, 116 g (1 mol) of 2-hydroxyethyl acrylate, 0.1 g of N, N-dimethylbenzylamine and 0.1 of hydroquinone monomethyl ether.
g was put in a flask equipped with a stirrer, and reacted for 24 hours at 95 ° C. while blowing air until the peak derived from the acid anhydride in the infrared absorption spectrum disappeared to obtain a monoester compound (A-1).

[Synthesis Example 2] 168 g (1 mol) of 4-methylhexahydrophthalic anhydride, 144 g (1 mol) of 2-hydroxypropyl methacrylate, 0.1 g of N, N-dimethylbenzylamine and 0.3 g of hydroquinone were added. The monoester compound (A-
2) was obtained.

[Synthesis Example 3] 152 g (1 mol) of tetrahydrophthalic anhydride, 116 g (1 mol) of 2-hydroxyethyl acrylate, 0.1 g of N, N-dimethylbenzylamine and 0.3 g of hydroquinone were used as Synthesis Example 1. A similar reaction was performed to obtain a monoester compound (A-3).

[Production of Hole Filling Inks of Examples 1 to 7 and Comparative Examples 1 and 2] Each component was blended based on the blending composition shown in Table 1 below, and each was kneaded by three rolls to prepare the ink composition of the invention. The hole filling inks of Examples 1 to 7 and Comparative Examples 1 and 2 were prepared.

[0063]

[Table 1]

[Production of Through Hole Printed Wiring Board with Land] Glass epoxy double-sided copper clad laminate “R170
5 "{Matsushita Electric Works, Ltd., plate thickness: 1.6 mm, copper thickness: 3
5 μm, substrate size: 330 mm × 330 mm} with 2000 holes with 0.9 mm drill diameter, and 30 μm copper plating layer on the entire surface of double-sided copper clad laminate including hole walls by electroless copper and electrolytic copper plating. It formed and produced the panel for printed wiring board manufacture. Next, Examples 1 to 7 and Comparative Example 1
2A to 2C for each of the hole filling inks of FIGS.
The printed wiring board manufacturing panel is dipped in the hole filling ink and the through holes are filled with the hole filling ink, and then taken out, and the hole filling ink adhered to both sides of the printed wiring board manufacturing panel is urethane squeegee. It was scraped off by. Then, this printed wiring board manufacturing panel was applied with a high-pressure mercury lamp at 1000
mJ (exposure of 1000 m in Comparative Example 2)
Since it hardly cures at J, it was exposed at 2000 mJ),
The hole filling ink was cured from both sides. After that, the hole-filling ink and its cured product adhering to the surface of the printed wiring board manufacturing panel were polished with a load current of 2 A using a belt sander {manufactured by Marugen Ironworks Co., Ltd. (grinding belt = 400)}. , 4-axis double-side polishing machine "IOP-600" {(Ltd.)
Ishii notation}, "CP wheel as a polishing buff
Load current 2 using "VF" (Sumitomo 3M Limited)
It was removed by polishing with A.

Then, using the following two kinds of etching resist inks, through hole printed wiring boards were prepared by the methods described in the following items 1 and 2.

On the panel for producing a printed wiring board after the polishing step, an ultraviolet curable screen printing etching resist ink “PLUS FINE PER-143B-5” according to the steps shown in FIGS. A resist pattern having a land shape (land diameter: 1.35 mm) corresponding to each through hole was printed by means of Kyodo Chemical Co., Ltd.} and cured by exposure to ultraviolet rays to form an etching resist layer. Then, the exposed copper portion is removed by etching with a cupric chloride etching solution at 50 ° C.,
After washing with water, the hole-filled ink cured product and the etching resist layer were removed by spraying with a 3% aqueous sodium hydroxide solution to prepare a through-hole printed wiring board.

The printed wiring board manufacturing panel after the polishing step was subjected to a diluted alkali treatment according to the steps shown in (D′-1) to (D′-3) of FIG. 2 and (E) to (F) of FIG. A liquid-sided etching resist ink that can be photo-developed with a solution, "Ekiresin PER-800 (RB-102)" {manufactured by Kyowa Chemical Industry Co., Ltd.}
Furnace product}, and dried in a far infrared dryer at an ambient temperature of 70 ° C. for 3 minutes. Next, the land shape corresponding to each through hole (land diameter 1.35 m
(2) Simultaneous exposure machine "HMW20" for photoresist exposure by applying a mask film on which a pattern having m) is drawn.
1GX "{made by Oak Manufacturing Co., Ltd.}
It was exposed to J and then developed with a 1% sodium carbonate aqueous solution to form an etching resist layer. Then 50
The exposed copper parts are removed by etching with cupric chloride etching solution at ℃, and after washing with water, the hole-filling ink cured product and the etching resist layer are removed by spraying with a 3% sodium hydroxide aqueous solution to form a through-hole printed wiring board. Created.

Examples 1 to 7 obtained as described above
For the through-hole printed wiring boards according to the hole-filling inks of Comparative Examples 1 and 2, the curing depth of the hole-filling ink and the filling rate of the hole-filling ink cured product in the manufacturing process were measured, and the polishing property in the polishing step was measured. When each test item of the etching suitability when applying the etching resist and the dissolution removal time in the peeling step was tested, Examples 1 to 7 were better than Comparative Examples 1 and 2 as shown in Table 2 below. . On the other hand, in Comparative Example 1, the curing depth at the time of exposure is small, and there are problems such as erosion of the through-hole edge portion due to elution of the solvent, and in Comparative Example 2, almost all of the holes are filled with the ink due to extreme insufficient curing. It was impossible to judge the test items.

The depth of cure is measured by removing the uncured hole-filling ink after the filling of the hole-filling ink and the curing process by photopolymerization, and measuring the thickness of the remaining cured portion with a micrometer. I did.

[0070]

[Table 2]

[Production of Landless Through Hole Printed Wiring Board] Glass epoxy double-sided copper clad laminate “R1705”
{Matsushita Electric Works, Ltd., plate thickness: 1.6 mm, copper thickness: 35 μ
m Substrate size: 330 mm x 330 mm} with 3000 holes for drilling holes with a diameter of 0.3 mm, and 30 μm copper on the entire surface of the double-sided copper clad laminate including the hole walls by electroless copper and electrolytic copper plating A plating layer was formed to produce a printed wiring board manufacturing panel. Next, Examples 1 to 1
7. For each of the hole filling inks of Comparative Example 1, FIG.
According to the steps shown in (C) to (C), the printed wiring board manufacturing panel in which the via through holes are formed as described above is immersed in the hole filling ink, and the hole filling ink is filled into the through holes, and then taken out and printed. The hole filling ink adhering to both sides of the wiring board manufacturing panel was scraped off with a urethane squeegee. Then, this printed wiring board manufacturing panel was applied with a high-pressure mercury lamp at 1000
mJ exposure (in the case of Comparative Example 1, 200
The one by exposure of 0 mJ was also prepared. ), The hole filling ink was cured from both sides. After that, the hole-filling ink and its cured product attached to the surface of the printed wiring board manufacturing panel,
Belt sander {made by Marugen Iron Works Co., Ltd. (Grinding belt = 4
No. 00)} with a load current of 2 A, and a 4-axis double-sided polishing machine "IOP-600" {manufactured by Ishii Notation Co., Ltd.} as a polishing buff "CP Wheel VF" {Sumitomo 3M Ltd. )} And was removed by polishing with a load current of 2A.

After the polishing step, the printed wiring board manufacturing panel was subjected to a diluted alkali treatment according to the steps shown in (D'-1) to (D'-3) of FIG. 2 and (E) to (F) of FIG. Liquid-type etching resist ink "Photoresin PER-800 (RB-102)" (manufactured by Kyowa Chemical Industry Co., Ltd.) that can be photo-developed with a solution is applied by a horizontal double-sided roll coater (manufactured by Furnace Co., Ltd.) and dried with far infrared rays It was dried for 3 minutes at an ambient temperature of 70 ° C. in a machine. Next, a mask film having a pattern in which a portion corresponding to each through hole for a via hole has a stripe shape with a width of 80 μm as shown in FIG. 3A is applied, and a double-sided simultaneous exposure machine “HMW201GX for photoresist exposure” is applied. "{Oak Manufacturing Co., Ltd.}
To 100 mJ, and then developed with a 1% sodium carbonate aqueous solution to form an etching resist layer. Subsequently, the exposed copper portion is removed by etching with a cupric chloride etching solution at 50 ° C., washed with water, and then the hole-filling ink cured product and the etching resist layer are removed by spraying with a 3% aqueous solution of sodium hydroxide to perform a landless process. A through-hole printed wiring board was created.

Examples 1 to 7 obtained as described above
And for the landless via through-hole printed wiring board according to each hole filling ink of Comparative Example 1, the curing depth of the hole filling ink and the filling rate of the hole filling ink cured product in the manufacturing process were measured, and the polishing property in the polishing step was also measured. ,
When the respective test items of the etching suitability when applying the etching resist and the dissolution removal time in the peeling process were tested, Examples 1 to 7 were better than Comparative Example 1 as shown in Table 3 below. On the other hand, in Comparative Example 1, when the exposure amount is 1000 mJ, the liquid etching resist is eluted at the time of application of the ink due to insufficient curing, and erosion is caused by etching, and when the exposure amount is 2000 mJ, the etching resist film at the corners of the through-holes is repelled. It became thick or extremely thin and etching caused erosion.

[0074]

[Table 3]

[0075]

EFFECTS OF THE INVENTION Since the hole-filling ink for producing a through-hole printed wiring board of the present invention is constituted as described above, a sufficient curing depth can be ensured, volume shrinkage is small, and a solvent-resistant cured product of the hole-filling ink. It has excellent properties, through-hole protection, and through-hole edge covering function, and can be easily removed with an alkaline solution.

Further, in the above hole filling ink, the amount of the inert solid powder is increased while maintaining a sufficient curing depth to improve the polishing property in the polishing process and the removability of the cured product of the hole filling ink in the peeling process with the alkaline solution. Can be improved. Furthermore, the method of manufacturing a through-hole printed wiring board by the so-called "hole-filling-liquid etching resist method" using this hole-filling ink and a liquid etching resist ink that can be photo-developed in the resist forming step has no repellency problem. It has excellent characteristics and can realize formation of fine and high-density conductor patterns and landless.

Furthermore, the hole-filling ink of the present invention and the method for manufacturing a through-hole printed wiring board using the same are as follows:
A high-density through-hole printed wiring board having a conductor pattern width of 100 μm or less and a landless can be manufactured at low cost while maintaining high reliability. Further, the through-hole printed wiring board manufactured by these has excellent performance. Such a high-performance landless through-hole printed wiring board has complicated processes such as "pattern plating method", "solder peeling method" or "hole filling method using dry film" which have been conventionally proposed, and cost is low. It was difficult to manufacture by a high manufacturing method.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a principal part of a printed wiring board manufacturing panel showing a specific example of a method of manufacturing a through-hole printed wiring board using the hole filling ink of the present invention.

FIG. 2 is a cross-sectional view of essential parts of a panel for producing a printed wiring board, showing a specific example of a resist forming step by a method of forming a resist layer using a photo-developable liquid etching resist ink.

FIG. 3 shows a panel for producing a printed wiring board at the time of forming a resist layer in a method of forming a landless through hole using a photo-developable liquid etching resist ink, in which (a) is a plan view of relevant parts, and (b). 6A is a cross-sectional view taken along the line AA in FIG. 7B, and FIG. 7C is a cross-sectional view taken along the line BB in FIG.

FIG. 4 shows a panel for producing a printed wiring board after the final formation of landless through holes in a method for forming landless through holes using a photo-developable liquid etching resist ink, in which (d) is a plan view of its main part, (E) is a cross-sectional view of the main part of the C-C line in the previous figure (d), and (f) is a cross-sectional view of the main part of the CC line in the case where a conduction failure occurs in the through-hole edge part in the previous figure (d). .

[Explanation of symbols]

1 Insulating Substrate 2 Through Hole 2a Through Hole Edge Part 3 Copper Plating Layer 4 Hole Filling Ink 4h Hole Filling Ink Cured Material 5 Etching Resist Ink Pattern Layer 5h Etching Resist Layer 6 Etching Resist Ink Coating Layer 6h Etching Resist Layer 7 Mask Film 8 Copper wiring circuit conductor 9 A portion where the etching resist layer, the copper plating layer, and the cured cured hole filling ink come in contact with each other.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-58-202440 (JP, A) JP-A-62-59606 (JP, A) JP-A-64-85265 (JP, A) JP-A-5- 271622 (JP, A) JP 2-143584 (JP, A) JP 3-175691 (JP, A) JP 57-143367 (JP, A) JP 6-338674 (JP, A) Japanese Patent Publication 6-15587 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) H05K 3/02-3/08 H05K 3/40 C08F 6/00-246/00 C08F 299 / 02

Claims (7)

(57) [Claims] 1. (A) The following general formulas [I] and / or [II] [Chemical 2] {In the formula, R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or an alkyl group having 1 to 4 carbon atoms, Y is an alkylene group having 1 to 4 carbon atoms, or-(C _n H _2n O) _P --CH _2- (In the formula, n is 2 to
An integer of 6 and p is an integer of 1 to 19. ) Represents a group represented by. } Monoester compound represented by 1 to 90% by weight, (B) photopolymerization catalyst 0.01 to 20% by weight, and
(C) A colorless rosin having a Hazen color tone of 300 or less and / or α, which is obtained by hydrogenating a purified rosin.
Addition reaction of β-unsaturated monocarboxylic acid or α, β-unsaturated dicarboxylic acid with purified rosin, and hydrogenation reaction to obtain an acid value of 150 to 500 and a Hazen color tone of 300 or less colorless rosin derivative 5 to 40 Filling ink for manufacturing through-hole printed wiring boards, which comprises by weight. 2. (D) 20 to 90% by weight of inert solid powder
The hole-filling ink for producing a through-hole printed wiring board according to claim 1, which comprises: 3. The hole-filling ink for producing a through-hole printed wiring board according to claim 1, which is for a hole-filling liquid etching resist method. 4. A method of manufacturing a through-hole printed wiring board using the filling ink according to claim 1. 5. A method of manufacturing a through-hole printed wiring board using the hole-filling ink according to claim 1, 2 or 3 and a photo-developable liquid etching resist ink. 6. A through hole filling step of filling the through hole of a printed wiring board manufacturing panel with the hole filling ink according to claim 1, 2 or 3 and hardening, and a through printed wiring board manufacturing panel in the through hole filling step. A polishing step of removing excess hole-filling ink and its cured product attached to the surface by polishing, and applying a photo-developable liquid etching resist ink on the printed wiring board manufacturing panel after the polishing step, if necessary. Pre-drying, followed by exposure and development to form a resist layer, a resist forming step, and an etching step of forming a conductor pattern on the printed wiring board manufacturing panel by etching after the resist forming step,
A method of manufacturing a through-hole printed wiring board, comprising an etching resist on the surface of a panel for manufacturing a printed wiring board and a peeling step of removing a cured product of ink filling holes in the through holes after the etching step. 7. A method of manufacturing a landless through-hole printed wiring board using the manufacturing method according to claim 4, 5, or 6.