JPH10126055A - Manufacture of printed wiring board having through hole - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the expansion, etc., of hole-filling ink of ultraviolet curing type by preparing the ink by mixing the resulted product of a reaction between a colorless rosin derivative having a specific acid value and Hazen color tone and an ethylenic unsaturated monomer having only one epoxy group in the molecule, a photopolymerization catalyst, and inert solid powder with each other. SOLUTION: Ultraviolet curing hole filling ink 4 containing the resulted product of a reaction between a colorless rosin derivative having an acid value of >=150 and a Hazen color tone of <=300 and an ethylenic unsaturated monomer having only one epoxy group in the molecule, a photopolymerization catalyst, and inert solid powder is formed. After the through holes 2 of an insulating substrate 1 are filled with the ink 4, the ink 4 is cured to become a cured material 4h by exposing both surfaces of the substrate 1. The filling rates of the through holes 2 with the cured material 4h can be maintained within the range of 90-100%. Since both the ink 4 and cured material 4h do not expand, crack, nor foam, the expansion, etc., of the ink 4 and cured material 4h can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a printed wiring board with through holes using an ultraviolet curing ink for filling holes and a liquid etching resist ink.

[0002]

2. Description of the Related Art With the progress of finer and higher-density conductor patterns on printed wiring boards, a method of manufacturing a printed wiring board with through holes is a so-called "hole filling" using a conventional screen printing type etching resist and a hole filling ink. For example, Japanese Patent Application Laid-Open No. 58-100493.
As disclosed in Japanese Unexamined Patent Publication (Kokai) No. Sho 61-139089, etc., a production method using a hole filling ink and a developable liquid etching resist ink (hereinafter referred to as "hole filling
"Liquid etching resist method". ) Is drawing attention. As the filling ink used in the “filling-liquid etching resist method”, an ultraviolet curing type ink is particularly preferably used because the time required for curing is short and the volume shrinkage during curing is small.

[0003] Usually, ultraviolet curing type hole filling inks include:
Although an ethylenically unsaturated monomer is contained as a UV-curable component, it is not possible to sufficiently impart the removal property of the cured product of the ink for filling holes with an alkaline solution. Therefore, conventionally, a method of improving the removability with an alkali solution by incorporating a highly acid-soluble resin such as a rosin having a high acid value into the ink has been adopted.

[0004]

However, such an alkali-soluble resin inherently does not have ultraviolet curability, and thus rather hinders the curing of the filling ink. Also,
Since the alkali-soluble resin has poor compatibility with the ethylenically unsaturated monomer, it becomes non-uniform when filled in the through-hole and cured by ultraviolet rays. For this reason, when the ink filled in the through holes is cured by ultraviolet rays, the heat rays generated from the lamp of the ultraviolet irradiator cause partial vaporization of the ink components, etc. There are problems such as that the cured product of the hole filling ink becomes a porous foam.

[0005] In addition, rosins are blended in the conventional filling ink for the main purpose of improving the solubility of the cured filling ink in an alkaline solution. However, these are generally high in color tone and have low ultraviolet transmittance. Therefore, the exposure amount is insufficient at the deep part of the through hole filled with the filling ink, and the poor curing of the deep part causes the peeling of the surface of the cured filling material in the polishing process or the popping out of the uncured resin inside the cured filling material from the deep curing failure. The problem was easy to happen.

[0006] Further, since the ultraviolet transmittance is low as described above, only a small amount of an inert solid powder such as a pigment having a property of lowering the ultraviolet transmittance can be blended. It is desirable that the inert solid powder be blended in a sufficient amount because it has the property of improving the polishing properties of the cured ink of the pore filling ink and the releasability with an alkaline solution. Due to these problems, at present, the features of the "fill-in-the-liquid etching resist method", in which the conductor pattern can be miniaturized and densified, cannot be fully exhibited.

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and it is possible to prevent swelling or rupture of a cured product of a filled ink, and the cured product of a filled ink does not become a porous foam. In addition, it is possible to prevent peeling of the surface of the cured filling material in the polishing process, and to prevent uncured resin from jumping out of the cured filling material in the polishing step. It is an object of the present invention to provide a method for manufacturing a printed wiring board with through holes, which can improve the properties and the releasability by an alkali solution.

[0008]

According to a first aspect of the present invention, there is provided a method for producing a printed wiring board having a through hole, comprising a colorless rosin derivative having an acid value of 150 or more and a Hazen color tone of 300 or less, and one compound per molecule. A reaction product (A-1) obtained by reacting an ethylenically unsaturated monomer having only an epoxy group, a photopolymerization catalyst (B), and an inert solid powder (C). A through-hole filling step of preparing an ultraviolet-curing type filling ink 4 and filling the through-hole 2 of the printed wiring board manufacturing panel 10 with the filling ink 4 and curing the same, and a printed wiring board manufacturing process through a through-hole filling step Polishing step of removing excess hole filling ink 4 and its cured product 4h attached to the surface of panel 10 for polishing, and printed wiring board manufacturing panel 10 after the polishing step.
A resist forming step of applying a developable liquid etching resist ink to the top, then exposing and developing to form an etching resist layer 6h, and after the resist forming step, etching is performed on the printed wiring board manufacturing panel 10 by etching. An etching step for forming a conductor pattern, and a peeling step for removing the etching resist layer 6h on the surface of the printed wiring board manufacturing panel 10 and the cured ink filling material 4h in the through hole 2 after the etching step. A uniform curing reaction is enabled by using a reaction product (A-1) having good UV transmittance, in which an ethylenically unsaturated group is introduced into a colorless rosin derivative, and a deep portion of the through-hole 2 is formed. UV curable pore filling obtained by improving the curability at room temperature and sufficiently blending the inert solid powder (C) By using the ink 4, - fine conductor pattern "filling liquid etching resist method" is inherent, but to sufficiently exhibit the advantage that it is possible density.

According to a second aspect of the present invention, there is provided a method for manufacturing a printed wiring board having a through-hole according to the first aspect, further comprising a colorless rosin derivative having an acid value of 150 or more and a Hazen color tone of 300 or less. The reaction product obtained by reacting an ethylenically unsaturated monomer having only one epoxy group therein is 1 to 79.99% by weight, and the photopolymerization catalyst is 0.01 to 20% by weight. , 20 to 90 inert solid powders
% By weight to prepare a UV-curable ink for filling holes.

According to a third aspect of the present invention, there is provided a method for manufacturing a printed wiring board having a through hole, wherein a colorless rosin derivative having an acid value of 150 or more and a Hazen color tone of 300 or less and only one epoxy group in a molecule. Reaction product obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting an ethylenically unsaturated monomer having the same (A-2)
, A photopolymerization catalyst (B), and an inert solid powder (C) to prepare an ultraviolet-curable ink 4 for filling the pores, and apply the filling ink 4 to the through-holes of the panel 10 for manufacturing a printed wiring board. 2, a through-hole filling step of filling and curing, and a polishing step of removing excess hole filling ink 4 attached to the surface of the printed wiring board manufacturing panel 10 and the cured product 4h thereof by polishing in the through-hole filling step. A resist forming step of applying a developable liquid etching resist ink 6 on the printed wiring board manufacturing panel 10 after the polishing step, and then exposing and developing to form an etching resist layer 6h; An etching step of forming a conductor pattern on the printed wiring board manufacturing panel 10 by etching, and a printed wiring board Hole filling ink cured product of the etching resist layer 6 and the through hole 2 of the surface of the use panel 10 4
and a peeling step of removing h, wherein an ethylenically unsaturated group is introduced into the colorless rosin derivative, and an acid value is adjusted by reacting with a polybasic acid anhydride. By using the reaction product (A-2) having a good quality, a uniform curing reaction is enabled, the curability in the deep part of the through hole 2 is improved, and the inert solid powder (C) is sufficiently mixed. By using the obtained ultraviolet-curing type hole filling ink 4, it is possible to sufficiently exhibit the feature that the "filling-liquid etching resist method" inherently enables finer and higher density conductive patterns.

According to a fourth aspect of the present invention, there is provided a method for manufacturing a printed wiring board with through holes according to the third aspect, wherein the colorless rosin derivative having an acid value of 150 or more and a Hazen color tone of 300 or less and a molecule. A reaction product obtained by reacting an ethylenically unsaturated monomer having only one epoxy group therein with a polybasic acid anhydride is used in an amount of 1 to 79.99 wt. % Of the photopolymerization catalyst, 0.01 to 20% by weight, and 20 to 90% of the inert solid powder.
% By weight to prepare a UV-curable ink for filling holes.

According to a fifth aspect of the present invention, there is provided a method for manufacturing a printed wiring board with through holes according to any one of the first to fourth aspects, further comprising the step of hydrogenating purified rosin as the colorless rosin derivative. Acid value 160 obtained by
185 to an acid value of 150 to 400 obtained by subjecting a colorless rosin derivative to an addition reaction product of an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated dicarboxylic acid with purified rosin to a hydrogenation reaction. It is characterized by using at least one of a colorless rosin derivative.

According to a sixth aspect of the present invention, there is provided a method of manufacturing a printed wiring board with through holes according to any one of the first to fifth aspects, wherein the through hole 2 is a landless through hole. It is a feature.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The reaction product (A-1) used in the ultraviolet-curing type filling ink for producing a printed wiring board with through holes according to claim 1 of the present invention contains a colorless rosin derivative and a compound in the molecule. It is obtained by reacting with an ethylenically unsaturated monomer having only one epoxy group.

Examples of the colorless rosin derivative as a raw material of the reaction product (A-1) include abietic acid, parastolic acid,
Neoabietic acid, pimaric acid, isopimaric acid, gum rosin containing resin acids such as dehydroabietic acid as a main component, wood rosin, tall oil rosin, or those obtained by chemically treating general rosin such as purified rosin, for example, Hydrogenated rosin, disproportionated rosin, purified disproportionated rosin, disproportionated rosin or purified disproportionated rosin obtained by dehydrogenation reaction using a dehydrogenation catalyst, polymerized rosin, acrylated rosin Rosin, fumaric acid-added rosin, maleic acid-added rosin, rosin-modified maleic resin, rosin-modified phenol resin, etc., having a Hazen color tone of 300 or less. In general, rosin and rosin derivatives have a Gardner color tone of about 7 to 10, and even a light color such as purified rosin or hydrogenated rosin has a Gardner color tone of about 6, but the colorless rosin derivative of the present invention has a color higher than these. It must be thin and have a Hazen tone of 300 or less (Gardner tone 1 corresponds to Hazen tone 400).

By using a colorless rosin derivative having a Hazen color tone of 300 or less as described above, the hole filling ink can be made to have good ultraviolet transmittance.
The curing property of the hole-filling ink in the deep portion of the through-hole is improved when cured by ultraviolet light, and the polishing process causes problems such as peeling of the surface of the cured material of the hole-filled ink and popping out of the uncured resin inside the cured material of the hole-filled ink. Can be prevented. In addition, the cured product of the ink for filling pores has particularly good etching solution resistance.

The colorless rosin derivative used in the present invention must have an acid value of 150 or more. If the acid value is less than 150, the removability of the cured product of the pore-filling ink used in the present invention with an alkaline solution is reduced. The colorless rosin derivative can be used if its acid value is 150 or more, but is preferably 500 or less from the viewpoint of availability. On the other hand, when the acid value exceeds 500, the acid resistance of the cured product of the filled-in ink to the etchant decreases, and the metal conductor layer in the through-hole portion is eroded at the time of etching. The acid value of the colorless rosin derivative is preferably 500 or less even in consideration of this point. Particularly preferred acid value range of the colorless rosin derivative is 150 to 400.

Examples of the above colorless rosin derivative include an acid value of 160 to 185 obtained by hydrogenating purified rosin.
And a colorless rosin derivative having a Hazen color tone of 300 or less (1)
Can be mentioned. Here, the purified rosin is an unpurified rosin or an unpurified rosin such as gum rosin, wood rosin, tall oil rosin or the like, which is mainly composed of resin acids such as abietic acid, parastolic acid, neoabietic acid, pimaric acid, isopimaric acid, and dehydroabietic acid. It refers to a product obtained by removing unsaponifiable substances and the like from disproportionated rosin. 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 methods, a method of obtaining a main fraction by distillation is described. It is preferable in that it produces an excellent colorless rosin derivative.
In the case of purified disproportionated rosin, it may be one which has been further dehydrogenated using a dehydrogenation catalyst after purification. The hydrogenation reaction is carried out under known conditions, for example, by heating with a known hydrogenation catalyst such as palladium carbon, rhodium carbon or the like under normal pressure or under pressure, but is not particularly limited to this method. It is best to add an organic phosphorus compound such as triphenyl phosphite after the hydrogenation reaction, and further heat if necessary.

The colorless rosin derivative (1) having an acid value of 160 to 185 and a Hazen color tone of 300 or less obtained by hydrogenating this purified rosin is described in, for example,
-277675 can be used, and a super-light rosin “KR-6” manufactured by Arakawa Chemical Industries, Ltd. can be used.
10 "(trade name color tone (Hazen 60), acid value 170,
(Softening point of 85 ° C.) corresponds to this.

Examples of the colorless rosin derivative other than the above include, for example, α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid.
A colorless rosin derivative (2) having an acid value of 150 to 400 and a Hazen color tone of 300 or less obtained by hydrogenating an addition reaction product of β-unsaturated dicarboxylic acid and purified rosin can be exemplified. As the purified rosin, the same as the purified rosin of the colorless rosin derivative (1) can be used. Examples of the α, β-unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and the like. Examples of the α, β-unsaturated dicarboxylic acid include maleic acid, maleic anhydride, fumaric acid and the like.

The above α, β-unsaturated monocarboxylic acid and / or
Alternatively, the addition reaction between the α, β-unsaturated dicarboxylic acid and the purified rosin is usually carried out by a Diels-Alder reaction, for example, at 180 to 240 ° C. for 1 to 9 hours, preferably in an inert 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 at normal pressure or under pressure. Incidentally, the addition reaction and the hydrogenation reaction are not limited to the above methods.

An acid value of 150 to 40 obtained by hydrogenating an addition reaction product of α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated dicarboxylic acid with purified rosin.
As the colorless rosin derivative (2) having 0 and a Hazen color tone of 300 or less, for example, the one disclosed in Example 1 of JP-A-5-86334 using acrylic acid as an α, β-unsaturated monocarboxylic acid is used. Ultra light rosin “KE-604” (trade name, color tone (Hazen 50), acid value 245, softening point 13) manufactured by Arakawa Chemical Industry Co., Ltd.
2 ° C.) corresponds to this.

The ethylenically unsaturated monomer, which is a raw material of the reaction product (A-1), has only one epoxy group in the molecule.
It is used for the purpose of imparting curability by ultraviolet rays to 1). Examples of the ethylenically unsaturated monomer having only one epoxy group in the molecule include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate and (3,4-epoxycyclohexyl) methyl (meth) ) Epoxycyclohexyl derivatives of (meth) acrylic acid such as acrylate and (meth) acrylic acid
And alicyclic epoxy derivatives and epoxidized stearyl acrylate. These can be used alone or in combination.

Among them, acrylates are better than methacrylates in terms of reactivity, and particularly, addition reaction with rosins is easy and industrially easily available (3) Most suitable are epoxycyclohexyl derivatives of (meth) acrylic acid such as 2,4-epoxycyclohexyl) methyl (meth) acrylate.

In the reaction product (A-1), the reaction between the colorless rosin derivative and an ethylenically unsaturated monomer having only one epoxy group in the molecule can be carried out by a known method. For example, a colorless rosin derivative and (3,4-
Taking the reaction of epoxycyclohexyl) methyl (meth) acrylate as an example, a tertiary amine such as benzyldimethylamine or triethylamine as a thermal polymerization inhibitor and a tertiary amine such as benzyldimethylamine or triethylamine as a catalyst; Ammonium chloride, quaternary ammonium salts such as methyltriethylammonium chloride or triphenylstibine and the like are added and mixed by stirring, and preferably 60 to 150 ° C, particularly preferably 80 to 120 ° C, according to a conventional method.
At a reaction temperature of

In this case, in order to uniformly mix the components to be used for the reaction and the like, low boiling points such as ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, cyclohexane and the like, which are inert to the reaction, are used as the reaction solvent for each of the above components. The reaction may be carried out by adding a solvent, and after the completion of the reaction, these solvents may be distilled off. Further, in the case where the ethylenically unsaturated monomer (D) described later is blended as an optional component into the ultraviolet curing type hole filling ink used in the present invention, the ethylenically unsaturated monomer (D) is used in the present invention. Those inert to the reaction, such as methyl carbitol (meth) acrylate,
Butyl carbitol (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, N , N-dimethyl (meth) acrylamide or the like, or a mixture thereof, is used as a reaction solvent in the present reaction to distill the ethylenically unsaturated monomer (D) in the obtained reaction product solution. Without removing, it can also be used for the preparation of ink as it is.

At the time of the synthesis reaction of the above reaction product (A-1), the ethylenically unsaturated monomer having only one epoxy group in the molecule is substituted with the carboxyl group in the colorless rosin derivative having the above acid value. Reacts with. In this case, the amount of the ethylenically unsaturated monomer having only one epoxy group in the molecule is 0.05 mol or more per equivalent of the carboxyl group of the colorless rosin derivative and the reaction product after the reaction is formed. It must be an amount that allows the residual acid value of the product (A-1) to be 70 or more.

When the amount of the ethylenically unsaturated monomer having only one epoxy group in the molecule is less than 0.05 mol, the reaction product of an unsaturated bond having reactivity with ultraviolet rays is used. (A-1) Insufficiency in the amount introduced into the ink makes it impossible to effectively prevent swelling, rupture, and foaming of the cured product of the filled pore ink. When the residual acid value is less than 70, the solubility of the reaction product (A-1) in an alkali solution is insufficient, and the removability of the pore-filling ink and the cured product of the pore-filling ink used in the present invention by an alkaline solution is not sufficient. Will be enough. Particularly, from the viewpoint of the removability by the alkaline solution, the amount of the ethylenically unsaturated monomer having only one epoxy group in the molecule is such that the residual acid value of the reaction product (A-1) is 100 or more. Preferably, the amount is such that

The various conditions, steps, and the like in the method for producing the component (A-1) are illustrative, and do not limit the production method. The amount of the reaction product (A-1) is 1 to 79.99% by weight based on the total amount of the hole filling ink. If the amount is less than 1% by weight, the removability of the hole filling ink by an alkaline solution is reduced. If it exceeds 0.99% by weight, it becomes difficult to fill the through-holes with the ink for filling holes due to an increase in viscosity. From this point, a particularly preferred range of the amount of the reaction product (A-1) is 5 to 50% by weight.

The photopolymerization catalyst (B) used in the ultraviolet-curable ink for filling a hole in a printed wiring board having through holes according to the present invention is, for example, a radical or a radical produced by a photochemical reaction after irradiation with visible, near-ultraviolet or ultraviolet light. Normal compounds that generate Lewis acids can be used,
Considering workability and the like, those having high spectral sensitivity in the ultraviolet region are preferable.

Compounds which induce a radical polymerization reaction include benzophenones, vicinal ketones such as diacetyl, benzyl, α-pyridyl and acyloins such as pivaloin, α-pyridin and benzoins such as benzoin, benzoin methyl ether and benzoin ethyl ether , Benzoin isopropyl ether,
Benzoin isobutyl ether, benzyl dimethyl ketal, and acetophenones such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, and thioxanthones, such as 2,4-diethylthioxanthone;
2,4-dimethylthioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4
Thioxanthone derivatives such as 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. Among these, benzyldimethyl ketal, benzophenones, thioxanthone and its derivatives, and anthraquinones are particularly preferable in terms of securing a large curing depth in the ultraviolet region.

As the photopolymerization catalyst for inducing the cationic polymerization reaction, aryldiazonium, diarylhalonium, triphenylphosphonium, dialkyl-4
- hydroxy sulfonium, dialkyl-4-hydroxy-diphenyl sulfonium, Allen - PF _6, such as iron complex
^{_{-, AsF 6 -, BF 4}} -, SbF 6 - can be exemplified salts.

Further, although the photopolymerization catalyst itself is not activated by irradiation with ultraviolet light, an amine-based photopolymerization co-catalyst which promotes a photopolymerization reaction when used in combination with a photopolymerization catalyst can also be used. As such a photopolymerization promoter, mainly aliphatic,
Aromatic amines are used, for example, triethylenetetramine, triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine,
N-methyldiethanolamine, diethylaminoethyl methacrylate, Michler's ketone, 4,4'-diethylaminophenone, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), 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 preferred from the viewpoint of securing a large curing depth in the ultraviolet region.

The blending amount of the photopolymerization catalyst (B) is 0.01 to 20% by weight based on the total amount of the ink for filling pores,
If it is less than 1%, the surface curability of the hole-filling ink at the time of exposure is remarkably reduced. The inert solid powder (C) used in the ultraviolet curing type filling ink for producing a printed wiring board with a through hole according to the present invention has a filling property and a filling state when the filling ink is filled in the through hole. In addition to improving the polishing property, the polishing property of the cured product of the hole-filling ink and the releasability with an alkaline solution are improved. Examples of the inert solid powder (C) include talc, silica, aluminum hydroxide, titanium oxide, barium sulfate, and the like as extender and color pigment.
Examples include kaolin, calcium carbonate, phthalocyanine, and the like, organic polymer fine particles such as polyethylene, nylon, and polyester, and thixotropic agents such as Aerosil.

Since the above-mentioned reaction product (A-1) is used in the ultraviolet curing type hole filling ink of the present invention, the inert solid powder (C) is used in an amount of 20% by weight in the total amount of the hole filling ink.
Even in the case of blending as described above, the ultraviolet ray easily reaches the deep part of the through hole filled with the hole filling ink. Therefore, the curability of the ink for filling the hole in the deep part of the through hole becomes good, and the surface of the hardened material is peeled off in the polishing step, which often occurs at the time of poor hardening in the deep part, and the uncured resin inside the filled hardened material pops out. There is no problem. For this reason,
The intrinsic purpose of the inert solid powder, in which the abrasion property of the cured ink filled material becomes particularly good and the releasability of the cured material by an alkaline solution is improved, and the cured ink filled material is not chipped, In the final peeling step, the cured product of the filling ink is completely removed from the through-hole without remaining on the inner wall, and trouble at the time of mounting components is prevented.

However, if the amount of the inert powder exceeds 90% by weight in the total amount of the filling ink, the viscosity increases, so that it is difficult to fill the filling hole with the filling ink, and it is difficult to fill the deep part of the through hole. Insufficient transmittance of ultraviolet light easily occurs. Further, in the conventional hole filling ink, a large amount of an additive such as an antifoaming agent is blended in order to prevent the generation of bubbles due to the trapping of air when filling the through holes. However, since these additives bleed to the surface of the filled or cured material after exposure, when a liquid resist ink or the like is applied on the cured material of the filling hole filling ink filled in the through hole, it may be around the through hole. Repelling of the liquid etching resist ink occurs, and the thickness of the formed etching resist layer becomes extremely thin. For this reason, at the edge of the through-hole, the portion of the wiring circuit conductor to be protected at the time of etching is likely to be eroded. On the other hand, in the filling ink of the present invention, in particular, the inert solid powder (C) can be blended in an amount of 20% by weight or more based on the whole amount of the filling ink, so that an additive such as an antifoaming agent is not blended. A sufficient defoaming effect can be obtained, and repelling of the liquid etching resist ink or the like does not occur.

In addition, 20% by weight of the inert solid powder (C)
When compounded as described above, from the various advantages described above, not only is preferably used in the method of the present invention for producing a printed wiring board with through holes by “fill-in-liquid etching resist method”, but also a fine and high-density conductor pattern is formed. It is particularly suitable for the production of printed wiring boards with landless through-holes, especially when the inert solid powder is blended in the range of 30 to 90% by weight, and the printed wiring with landless through-holes by the "fill-in-liquid etching resist method" It is optimal for the production of boards.

Further, the ultraviolet curing type hole filling ink for manufacturing a printed wiring board with through holes according to claim 1 of the present invention contains the above component (A) for the purpose of adjusting the viscosity, curing speed and peeling speed of the ink. Ethylenically unsaturated monomers (D) other than the ethylenically unsaturated monomers used in -1) can be added. Examples of such unsaturated compounds include 2-hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, cellosolve (meth) acrylate, methyl cellosolve (meth) acrylate, butyl cellosolve (meth) acrylate, carbitol (meth) acrylate, methyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, phenoxy Ethyl (meth) acrylate,
Dicyclopentadienyl (meth) acrylate, dicyclopentadienyloxyethyl (meth) acrylate,
Vinyl acetate, N-vinylpyrrolidone, (meth) acrylamide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polycaprolactone mono Monofunctional ethylenically unsaturated monomers such as (meth) acrylate and phenylglycidyl ether (meth) acrylic acid adduct, and polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polybutylene glycol di (meth) ) Acrylate, morpholine (meth) acrylate, N, N-dimethyl (meth) acrylamide,
Examples include bifunctional ethylenically unsaturated monomers such as polycaprolactone di (meth) acrylate. It is preferable that the compounding amount of the component (D) is 50% by weight or less in the total amount of the filling ink. If the amount exceeds 50% by weight, the removability with an alkaline solution tends to be reduced.

Further, the ultraviolet curing type hole filling ink for manufacturing a printed wiring board with through holes according to the first aspect of the present invention may further contain various additives (E) and the like. Examples thereof include various additives such as a coupling agent, an adhesion-imparting agent, and a leveling agent, and polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine.

The ultraviolet curing type filling ink for producing a printed wiring board with through holes according to claim 1 of the present invention comprises the reaction product (A-1), the photopolymerization catalyst (B) and an inert solid powder. (C) and kneading the ethylenically unsaturated monomer (D) and various additives (E) by a known method such as using a three-roll, ball mill, sand mill or mixer alone or in combination. Can be prepared.

Next, a method of manufacturing a printed wiring board with through holes according to the present invention using the above-mentioned ultraviolet curing type filling ink will be described. In the manufacturing process of the “filling hole—liquid etching resist method” of the manufacturing method of the printed wiring board with the through hole of the present invention, the above-described ultraviolet curing type hole filling ink is filled in the through hole of the printed wiring board manufacturing panel and cured. A through-hole filling step, a polishing step of removing excess hole filling ink attached to the surface of the printed wiring board manufacturing panel and a cured product thereof by polishing in the through hole filling step, and a printed wiring board manufacturing step after the polishing step. A developable liquid etching resist ink is applied to the surface of the panel, pre-dried if necessary, then exposed and developed to form an etching resist layer, and printed wiring is formed by etching after the resist forming step. After the etching step of forming a conductor pattern on the surface of the panel for panel production, and after the etching step It is made of a hole filling peeling process for removing the ink cured product of the etching resist and the through hole of the printed wiring board surface of the manufacturing panel.

FIG. 1 is a sectional view of a main part showing a specific example of a method of manufacturing a printed wiring board having through holes having lands according to the present invention. As shown in FIG. 1A, an insulating substrate 1 (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 Teflon resin, Synthetic resin substrate such as glass base polyimide resin or composite resin,
Alternatively, a metal-based insulating substrate in which a metal such as aluminum or iron is covered with an epoxy resin or the like and subjected to an insulation treatment, or a ceramic insulating substrate such as an alumina ceramic, a low-temperature fired ceramic, or an aluminum nitride ceramic is used. ), Through holes are formed at desired locations on a laminate (eg, a copper-clad laminate, etc.) obtained by forming a conductive metal layer made of copper on both upper and lower surfaces, for example, a combination of electroless plating and electrolytic plating. Thus, a conductive layer including the copper plating layer 3 and the like is formed on the entire surface of the double-sided copper-clad laminate including the hole walls. As a result, a printed wiring board manufacturing panel 10 in which the through holes 2 for electrically connecting the front and back wiring circuit conductors are formed is obtained. The printed wiring board manufacturing panel 1
As 0, a hole for a through hole is first 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, for example, a combination of electroless plating and electrolytic plating. In this case, a metal conductor layer may be formed on both surfaces of an insulating substrate such as a substrate obtained by the above method.

Next, in the through-hole filling step, as shown in FIG. 1B, the above-mentioned ultraviolet curing type hole filling ink 4 is immersed in the through-hole 2 in order to protect the inner wall from the etching solution. Filling is performed by a filling method, a screen printing filling method, a pin filling method, a roll filling method, and the like. Subsequently, the printed wiring board manufacturing panel 10 is subjected to 50 to 2000 mJ per side using a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, or the like. By exposing both surfaces with the light amount of, the filling ink 4 is cured to form a cured filling ink 4h. At this time, it is possible to obtain a curing depth of 700 μm or more per one side, and the filling rate of the filled ink cured material 4h in the through hole 2 can be maintained at 90 to 100%. In addition, the swelling of the hole-filled ink cured product 4h,
Rupture or foaming of the hole-filled cured ink 4h does not occur. The hole filling ink 4 can be cured by a known exposure method without any particular limitation.

In the polishing step after the through-hole filling step, as shown in FIG. 1C, the cured product 4h of the ink filling the surface of the copper plating layer 3 is subjected to, for example, belt sander polishing, buff polishing or slab polishing. Is removed by mechanical polishing or the like. In this case, by applying the above-mentioned ultraviolet curing type hole filling ink 4, the uncured hole filling ink 4 and the cured material 4h of the hole filling ink are easily removed with a low polishing pressure. Also,
As described above, since the hole-filled ink cured product 4h itself swells, and there is no portion that ruptures or foams the hole-filled ink cured material 4h, the hole-filled ink is cured at the copper plating layer 3 and the through-hole edge 2a. No chipping of the object 4h occurs, and even after polishing, the surface of the cured ink filling material 4h in the through hole 2 is smooth and the filling rate is 90%.
１００100%.

In a resist forming step after the above-mentioned polishing step, an etching resist layer 6h is formed on the surface of the copper plating layer 3 using a developable liquid etching resist ink. In this case, first, FIG. As shown, the surface of the polished copper plating layer 3 is coated with an etching resist ink by a screen printing method, a curtain coating method, a roll coating method, a spin coating method, a dip coating method, a spraying method, or the like. After drying, the etching resist ink coating film layer 6 is formed. In this case, the use of the above-mentioned ultraviolet curing type hole filling ink 4 is excellent in flattening the cured hole filling ink 4h in the through hole 2, so that the opening portion of the through hole 2 is the same as other portions. The etching resist ink coating layer 6 has a uniform thickness. Further, in this case, the solvent in the through-hole 2 due to the solvent in the etching resist ink coating film layer 6 hardly elutes the cured material 4h for filling the hole. Next, FIG.
As shown in (e), a pattern mask film 7 depicting a wiring circuit is applied on the etching resist ink coating layer 6, and is exposed to radiation such as ultraviolet light, visible light, and near infrared light. Incidentally, the mask film 7 may be arranged in an off-contact state with respect to the etching resist ink coating layer 6. After the exposure of the etching resist ink coating film layer 6, the mask film 7 is removed and subsequently developed with a developing solution to form an etching resist layer 6h having a desired resist pattern as shown in FIG. 1 (f). You. When the ultraviolet curing type filling ink of the present invention is applied, since the cured filling material 4h in the through hole 2 is excellent in flattening, the etching resist layer 6h having a uniform thickness is formed. It is possible.

In the etching step after the resist forming step, as shown in FIG.
The exposed portion of the copper plating layer is removed by etching with an etching solution such as a cupric chloride solution, and a copper wiring circuit conductor (including lands) 8 having a desired conductor pattern is formed on the printed wiring board manufacturing panel 10. . After the etching step, in a final stripping step, as shown in FIG. 1H, an inorganic basic substance such as caustic soda, caustic potash, sodium metasilicate, or an organic basic substance such as alkylamine, alkanolamine, etc. 1h, the etching resist layer 6h and the cured ink 4h for filling holes shown in FIG. 1 (i) are dissolved and removed, and the intended printed wiring board with through holes is obtained.

Next, a method of manufacturing a printed wiring board having landless through holes will be described. FIG. 2 shows an etching resist layer 6 in a landless through-hole forming process according to the method of manufacturing a printed wiring board with through-holes of the present invention.
It is the top view and principal part sectional drawing which show the example at the time when h was formed, and the part of the landless through-hole 2 finally formed.

The manufacturing process in this case is exactly the same as that for manufacturing a printed wiring board with through holes having ordinary lands by using the above-mentioned developable liquid etching resist ink. However, as shown in FIG.
The feature is that the etching resist coating layer 6 (and the etching resist layer 6h) of the resist pattern to be formed does not have a portion corresponding to the through-hole land. Further, this state is shown in FIG.
FIG. 2B shows the cross section B, and FIG.

In this case, conventionally, at the edge 9 of the through hole 2 shown in FIG. 2 (b), a portion 9 where the etching resist layer 6h and the copper plating layer 3 and the cured ink for filling the filled hole 4h contact each other 9 In addition, poor adhesion of the etching resist layer 6h is likely to occur due to poor smoothness of the hole filling ink cured product 4h and the like, and the thickness of the etching resist coating layer 6 becomes insufficient due to the problem of repelling the liquid etching resist ink. As shown in FIG. 3C, the state of the cross section C of the landless through-hole portion on the surface of the printed wiring board is the wiring circuit conductor 8 at the edge of the through-hole 2.
Are easily eroded by the etchant, causing poor conduction.

On the other hand, when the ultraviolet curing type hole filling ink of the present invention is used, the edge portion of the finally formed landless through-hole 2 without such a problem is formed as shown in FIG.
As shown in FIG. 3B, the state of the cross section C in FIG. 3A is such that there is no erosion of the wiring circuit conductor 8 and no problem of poor conduction occurs. As described above, in the present invention, the ultraviolet-curable filling ink containing the reaction product (A-1) in which the ethylenically unsaturated monomer is added to the colorless rosin derivative is used. The curability of the ink is improved and filled into the through-holes, and when cured by ultraviolet light, it becomes a sufficiently uniform state and swells the cured ink for filling the holes,
It can solve the problem of rupture or foaming of the cured product.

The various conditions, steps, and the like in the above manufacturing method are merely examples, and do not limit the method for manufacturing a printed wiring board with through holes of the present invention. The above-mentioned ultraviolet curing type hole filling ink is used not only in the method of manufacturing a printed wiring board with through holes according to the present invention, but also with a printed wiring having through holes by a conventional "hole filling method" using a screen printing type etching resist. Needless to say, it can be suitably used for manufacturing a plate.

Next, a method for manufacturing a printed wiring board with through holes according to claim 2 of the present invention will be described. According to the method for producing a printed wiring board with through holes according to claim 2 of the present invention, an acid value of 150 is used in place of the reaction product (A-1) used in the ultraviolet-curable ink for filling holes of claim 1.
A reaction product obtained by reacting a colorless rosin derivative having a Hazen color tone of 300 or less with an ethylenically unsaturated monomer having only one epoxy group in the molecule (claim 1)
(Corresponding to the reaction product (A-1) of Example 1) with a polybasic anhydride to prepare a UV-curable ink for filling pores using the reaction product (A-2) obtained. Have The method for producing a printed wiring board with through holes according to claim 2 of the present invention is directed to a reaction product (A-
Except that the reaction product (A-2) is used instead of 1), the method can be carried out in the same manner as in the method of manufacturing a printed wiring board with through holes according to claim 1.

The amount of the reaction product (A-2) is 1 to 79.99% by weight in the total amount of the ink for filling pores,
If the amount is less than 7% by weight, the removability of the pore-filling ink by the alkali solution is reduced. If the amount exceeds 79.99% by weight, the filling of the through-hole with the hole-filling ink becomes difficult due to an increase in viscosity. From this viewpoint, a particularly preferred range of the amount of the reaction product (A-2) is 5 to 50% by weight.

The reaction product (A-2) is composed of at least one of the colorless rosin derivatives (1) and (2) and the ethylenically unsaturated monomer having only one epoxy group in the molecule (reaction product). (A-1) is obtained by reacting a reaction product of the compound (A-1) with a polybasic acid anhydride. The polybasic acid anhydride is mainly used for adjusting the acid value of the reaction product (A-2).

When a colorless rosin derivative is reacted with an ethylenically unsaturated monomer having only one epoxy group in the molecule, the residual amount of carboxyl groups derived from rosins decreases. Therefore, the acid value of the reaction product (A-2) is adjusted by introducing a carboxyl group by adding a polybasic acid anhydride to the hydroxyl group derived from the reaction between the carboxyl group and the epoxy group of the colorless rosin derivative. You do it.

In this case, since (A-2) introduces a sufficient amount of ethylenically unsaturated groups while maintaining a large acid value, the uniform and good ultraviolet curability of the pore-filling ink and the cured product thereof can be obtained. It can also have alkali peelability. Examples of polybasic acid anhydrides include phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid,
-Methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, 3-propyltetrahydrophthalic acid, 4-propyltetrahydrophthalic acid, 3-butyltetrahydrophthalic acid, 4-butyltetrahydrophthalic acid, hexahydro Phthalic acid, 3
-Methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, 3-propylhexahydrophthalic acid, 4-propylhexahydrophthalic acid, 3-butyl Hexahydrophthalic acid and 4-butylhexahydrophthalic acid, nadic acid, methylnadic acid, succinic acid,
Anhydrides such as dotesylsuccinic acid, chlorendic acid, pyromellitic acid, benzophenonetetracarboxylic acid, ethylene glycol bis (anhydrotrimate), methylcyclohexenetetracarboxylic acid, trimellitic acid, and polyazeleic acid can be exemplified. . In addition, among these, especially tetrahydrophthalic acid, trimellitic acid,
Nadic acid and succinic acid are preferred from the viewpoint of improving the removability of the pore-filling ink used in the present invention and the cured product thereof with an alkaline solution.

The reaction product (A-2) can be produced by a two-stage reaction. In the first step reaction, first, a colorless rosin derivative is reacted with an ethylenically unsaturated monomer having only one epoxy group in a molecule. This reaction can be carried out in the same manner as in the production of (A-1). In this case, the amount of the ethylenically unsaturated monomer having only one epoxy group in the molecule is 0 per equivalent of the carboxyl group of the colorless rosin derivative as in the case of the reaction product (A-1). Must be greater than or equal to .05 moles. However, since a carboxyl group is introduced by adding a polybasic acid anhydride in the second step reaction after this reaction, the acid value of the product of the first step reaction may be less than 70. This is different from the case of producing the reaction product (A-1).

The second stage reaction for producing the reaction product (A-2) is a process in which after the first stage reaction, a polybasic acid anhydride is added to the reaction system to react with the product of the first stage reaction. is there. The second-stage reaction can be performed using a known method. For example, a polybasic acid anhydride is added to the reaction system after the first-stage reaction,
Stir and mix, preferably by 60-150 ° C. by a conventional method,
The reaction is particularly preferably performed at a reaction temperature of 80 to 120 ° C. At this time, a thermal polymerization inhibitor, a catalyst and the like may be newly added.

The reaction product (A-
The residual acid value of 2) must be 70 or more. When the residual acid value is less than 70, the solubility of the reaction product (A-2) in an alkali solution is insufficient, and the removability of the pore-filling ink and the cured product of the pore-filling ink used in the present invention is insufficient. Becomes In particular, from the viewpoint of the removability with the alkaline solution, the amount of the ethylenically unsaturated monomer having only one epoxy group in the molecule is such that the residual acid value of the reaction product (A-2) is 100%. It is preferable that the amount is such as to be as described above.

[0060]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. All parts and percentages used below are based on weight. [Synthesis Example 1] Ultra-light rosin “KE-604” (trade name)
376.0 g of a colorless rosin derivative manufactured by Arakawa Chemical Industry Co., Ltd., Hazen color tone 50, acid value 245, softening point 132 ° C.) and 100.0 g of phenoxyethyl acrylate were put into a flask equipped with a stirrer, dissolved sufficiently, and glycidyl methacrylate was added. 71.0 g was added, and 0.1 g of N, N-dimethylbenzylamine and 0.1 g of hydroquinone monomethyl ether were added thereto. The mixture was allowed to react at 95 ° C. for 24 hours while blowing air, and a peak derived from an epoxy group in an infrared absorption spectrum was obtained. Was confirmed to have disappeared. The reaction product solution obtained as a phenoxyethyl acrylate solution was designated as (A-1-1). Reaction product solution (A-1-
The acid value of the reaction product in 1) was 167. The acid value was measured for the solution (A-1-1), and the acid value of the reaction product was determined by conversion.

[Synthesis Example 2] Ultra-light rosin “KR-61”
0 "(trade name, colorless rosin derivative manufactured by Arakawa Chemical Industry Co., Ltd., Hazen color tone 60, acid value 170, softening point 85 ° C) 3
06.0 g and 100.0 g of ethyl acetate were placed in a flask equipped with a stirrer and dissolved sufficiently.
0 (trade name, (3,4-epoxycyclohexyl) methyl acrylate, manufactured by Daicel Chemical Industries, Ltd.).
2 g, N, N-dimethylbenzylamine 0.1 g and hydroquinone monomethyl ether 0.1 g
Was added thereto, and the mixture was allowed to react at 95 ° C. for 24 hours while blowing air. It was confirmed that the peak derived from the epoxy group in the infrared absorption spectrum had disappeared. After completion of the reaction, 100.0 g of phenoxyethyl acrylate was added, and the mixture was cooled, and then ethyl acetate was distilled off under reduced pressure. The reaction product solution obtained as a phenoxyethyl acrylate solution was subjected to (A-1-2)
And The acid value of the reaction product in the reaction product solution (A-1-2) was 120. In addition, the acid value measurement was performed using (A-1-
2) For the solution, the acid value of the reaction product was determined in conversion.

[Synthesis Example 3] Ultra-light rosin “KE-60”
No. 4 "(trade name, colorless rosin derivative manufactured by Arakawa Chemical Industries, Ltd., Hazen color tone 50, acid value 245, softening point 132 ° C)
376.0 g and 100.0 g of ethyl acetate were placed in a flask equipped with a stirrer and dissolved sufficiently.
00 (trade name, manufactured by Daicel Chemical Industries, Ltd. (3,4-
Epoxycyclohexyl) methyl acrylate))
8.0 g was charged, and N, N-dimethylbenzylamine was added in an amount of 0.1 g.
1 g and 0.1 g of hydroquinone monomethyl ether were added, and the mixture was reacted at 95 ° C. for 24 hours while blowing in air, and it was confirmed that the peak derived from the epoxy group in the infrared absorption spectrum had disappeared. Thereafter, 82.0 g of nadic anhydride was added to the system and reacted at 95 ° C. for 8 hours while blowing air. After completion of the reaction, 100.0 g of phenoxyethyl acrylate was added and the mixture was cooled, and then ethyl acetate was distilled off under reduced pressure. The reaction product solution obtained as a phenoxyethyl acrylate solution was designated as (A-2-1). The acid value of the reaction product in the reaction product solution (A-2-1) was 185. The acid value was measured for the solution (A-2-1), and the acid value of the reaction product was determined in terms of conversion.

[Synthesis Example 4] Ultra-light rosin “KR-61”
0 "(trade name, colorless rosin derivative manufactured by Arakawa Chemical Industry Co., Ltd., Hazen color tone 60, acid value 170, softening point 85 ° C) 3
06.0 g and 100.0 g of ethyl acetate were placed in a flask equipped with a stirrer and dissolved sufficiently.
0 (trade name: (3,4-epoxycyclohexyl) methyl acrylate manufactured by Daicel Chemical Industries, Ltd.)
6.0 g, N, N-dimethylbenzylamine 0.1 g and hydroquinone monomethyl ether 0.1
g was added thereto, and the mixture was reacted at 95 ° C. for 24 hours while blowing air thereinto, and it was confirmed that the peak derived from the epoxy group in the infrared absorption spectrum had disappeared. Thereafter, 192.0 g of trimellitic anhydride was added to the system, and while blowing air, 9
The reaction was performed at 5 ° C. for 8 hours. After completion of the reaction, 100.0 g of phenoxyethyl acrylate was added and the mixture was cooled, and then ethyl acetate was distilled off under reduced pressure. The reaction product solution obtained as a phenoxyethyl acrylate solution was subjected to (A-2-
2). The acid value of the reaction product in the reaction product solution (A-2-2) was 150. In addition, the acid value measurement was performed according to (A-2).
-2) For the solution, the acid value of the reaction product was determined by conversion.

Synthesis Example 5 Hexahydrophthalic anhydride 154.0 g, 2-hydroxyethyl acrylate 11
6.0 g, 0.1 g of N, N-dimethylbenzylamine and 0.1 g of hydroquinone monomethyl ether are placed in a flask equipped with a stirrer, and the peak derived from the acid anhydride in the infrared absorption spectrum disappears at 95 ° C. while blowing air. To obtain a monoester compound (F).

[Manufacture of Filling Ink] Each component was blended based on the composition shown in Table 1 and kneaded by three rolls, respectively, and the filling inks (I) to (I) used in Examples and Comparative Examples of the present invention were used. (X) was prepared.

[0066]

[Table 1]

(Examples 1 to 8 and Comparative Examples 1 and 2) Glass epoxy double-sided copper-clad laminate “R1705” (trade name, Matsushita Electric Works, Ltd., plate thickness 1.6 mm, copper thickness 35 μm, substrate size 330 mm × 330 mm) Drill diameter 0.9m
5,000 holes were formed, and a 30 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 10.

Next, using the hole filling inks (I) to (X) shown in Table 1, the printed wiring board manufacturing panel 10 was filled with the hole filling ink 4 in accordance with the steps shown in FIGS. After filling the inside of the through hole 2 with the filling ink 4, it was taken out, and the filling ink 4 attached to both surfaces of the printed wiring board manufacturing panel 10 was scraped off with a urethane squeegee.

Subsequently, the printed wiring board manufacturing panel 1
No. 0 was exposed at 1000 mJ per side using a high-pressure mercury lamp (in Comparative Example 2, exposure was performed at 2000 mJ because it hardly cures at 1000 mJ), and the hole filling ink 4 was cured from both sides. Then, the hole filling ink 4 and the cured product 4h adhering to the surface of the printed wiring board manufacturing panel 10 are subjected to a load current of 2A using a belt sander (grinding belt = No. 400) manufactured by Marugen Ironworks Co., Ltd. And a four-axis double-side polishing machine "IOP-600" (trade name, manufactured by Ishii Co., Ltd.) using "CP Wheel VF" (trade name, manufactured by Sumitomo 3M Limited) as a polishing buff. It was removed by polishing at a load current of 2A.

After the polishing step, the printed wiring board manufacturing panel 10 is provided with a liquid etching resist ink 6 "Ekiresin PER-800 (RB) which can be developed with a dilute alkaline solution, according to the steps shown in FIGS. 1 (d) to 1 (h). -10
2) ”(trade name, manufactured by Yoyo Kagaku Kogyo Co., Ltd.) using a horizontal double-sided roll coater manufactured by Furness Co., Ltd.
Drying was performed for 3 minutes at an ambient temperature of 70 ° C. using a far infrared dryer.

Next, a mask film 7 on which a pattern having a land shape (land diameter 1.35 mm) corresponding to each through hole 2 is drawn is applied thereto, and a double-sided simultaneous exposure machine “HMW201GX” for photoresist exposure (commercially available) (Oak Manufacturing Co., Ltd.) at a light intensity of 100 mJ, and then developed with a 1% aqueous sodium carbonate solution to form an etching resist layer 6h. Then, at 50 ° C
The exposed copper portion is removed by etching with a cupric chloride etching solution, and after washing with water, the above-mentioned cured ink 4h and the etching resist layer 6h are removed by spraying a 3% aqueous solution of sodium hydroxide to form a through hole having a land. A printed wiring board with holes was made.

With respect to the printed wiring boards with through holes obtained in Examples 1 to 8 and Comparative Examples 1 and 2 obtained as described above, the curing depth of the hole filling ink 4 and the cured product 4 h of the hole filling ink in the manufacturing process. And the test items such as the polishing property in the polishing step, the appropriateness of the etching when applying the etching resist, and the dissolution and removal time in the stripping step were tested. Table 2 shows the results.
In addition, the measurement of the curing depth is performed by removing the uncured pore-filling ink after the filling and curing treatment (irradiation of ultraviolet light only on one side) with the pore-filling ink, and actually measuring the thickness of the remaining cured portion with a micrometer. It was done by doing.

[0073]

[Table 2]

As shown in Table 2, Examples 1 to 5 were better in all test results than Comparative Examples 1 and 2. On the other hand, in Comparative Example 1, the curing depth at the time of exposure was small, and there were difficulties such as erosion of the through-hole edge portion due to the elution of the solvent. The test item could not be determined. (Examples 9 to 16 and Comparative Examples 3 and 4) Glass epoxy double-sided copper-clad laminate “R1705” (trade name, manufactured by Matsushita Electric Works, Ltd., plate thickness 1.6 mm, copper thickness 35 μm)
(330 mm x 330 mm), 5,000 holes for via holes with a drill diameter of 0.3 mm are drilled, and 3 holes are formed on the entire surface of the double-sided copper-clad laminate including the hole walls by electroless copper and electrolytic copper plating.
A printed wiring board manufacturing panel 10 was formed by forming a copper plating layer of 0 μm.

Next, using each of the hole filling inks (I) to (X) shown in Table 1, according to the steps shown in FIGS. 1A to 1C, a print in which a via-through hole is formed as described above. The printed circuit board manufacturing panel 10 is immersed in the hole filling ink 4 and taken out after filling the through hole 2 with the hole filling ink.
The hole-filling ink 4 attached to both surfaces was scraped off with a urethane squeegee.

Subsequently, the printed wiring board manufacturing panel 10 was exposed at 1000 mJ per side using a high-pressure mercury lamp (in the case of Comparative Example 4, exposure was performed at 2000 mJ per side). Cured. Thereafter, the hole filling ink 4 attached to the surface of the printed wiring board manufacturing panel 10 and the cured product 4h thereof are supplied to
Belt sander manufactured by Marugen Iron Works (grinding belt = 400
) And a 4-axis double-side polishing machine "IOP-600" (trade name, manufactured by Ishii Notation).
Then, using a "CP Wheel VF" (trade name, manufactured by Sumitomo 3M Limited) as a polishing buff, the substrate was polished at a load current of 2 A, and removed.

After the above-mentioned polishing step, a liquid etching resist ink 6 “Ekiresin PER-800 (RB-102)” (product) which can be developed with a dilute alkaline solution is applied to the panel for manufacturing a printed wiring board according to the step shown in FIG. Was applied by a horizontal double-sided roll coater manufactured by Furness Co., Ltd., and dried at 70 ° C. for 3 minutes with a far-infrared dryer. Next, a mask film 7 in which a portion corresponding to each via hole through hole has a stripe-shaped pattern having a width of 80 μm as shown in FIG. 2A is applied, and a double-sided simultaneous exposure machine “HMW201GX” for photoresist exposure is applied. (Trade name, manufactured by Oak Manufacturing Co., Ltd.) at a light intensity of 100 mJ, and then developed with a 1% aqueous sodium carbonate solution to form an etching resist layer 6h. Subsequently, the copper exposed portion is removed by etching with a cupric chloride etching solution at 50 ° C.
After washing with water, the above-mentioned cured ink 4 h and the etching resist layer 6 h were removed by spraying a 3% aqueous sodium hydroxide solution to prepare a printed wiring board with a landless via through hole.

With respect to the printed wiring boards having the landless via-through holes of Examples 9 to 16 and Comparative Examples 3 and 4 obtained as described above, the curing depth of the filling ink and the curing of the filling ink during the manufacturing process. In addition to measuring the filling rate of the object, each test item of the polishing property in the polishing step, the appropriateness of the etching when applying the etching resist, and the dissolution and removal time in the stripping step was tested. Table 3 shows the results. In addition, the measurement of the curing depth is performed by removing the uncured pore-filling ink after the filling and curing treatment (irradiation of ultraviolet light only on one side) with the pore-filling ink, and actually measuring the thickness of the remaining cured portion with a micrometer. It was done by doing.

[0079]

[Table 3]

As shown in Table 3, Examples 9 to 16 were better in all the tests than Comparative Examples 3 and 4.
On the other hand, with respect to Comparative Example 3, when 1000 mJ was insufficiently cured, it was eluted during application of the liquid etching resist ink, eroded by etching, and the exposure amount was 2000 mJ.
In Comparative Example 4 of J, the thickness of the etching resist at the corners of the through-hole became extremely thin due to repelling, and erosion occurred by etching.

[0081]

As described above, the invention according to claim 1 of the present invention comprises a colorless rosin derivative having an acid value of 150 or more and a Hazen color tone of 300 or less and an ethylenic compound having only one epoxy group in the molecule. A reaction product obtained by reacting with an unsaturated monomer, a photopolymerization catalyst, and an inert solid powder are contained to prepare an ultraviolet-curable ink for filling holes, and the filled ink is used for a printed wiring board. A through-hole filling step of filling and curing through holes of a manufacturing panel, and a polishing step of removing excess hole filling ink attached to the surface of a printed wiring board manufacturing panel and a cured product thereof by polishing during the through hole filling step. Applying a developable liquid etching resist ink to the surface of the printed wiring board manufacturing panel after the polishing step, and then exposing and developing to form an etching resist layer A resist forming step, an etching step of forming a conductor pattern on the surface of the printed wiring board manufacturing panel by etching after the resist forming step, and an etching resist layer and a through hole formed on the surface of the printed wiring board manufacturing panel after the etching step. And a peeling step of removing the cured filling material of the filling material, so that it is possible to prevent swelling or rupture of the cured filling material from the ink and to prevent the cured filling material from becoming a porous foam. It is also possible to prevent peeling of the surface of the cured filling material in the polishing step and to prevent uncured resin from jumping out of the cured filling material in the polishing step. It can improve the releasability with an alkali solution. Therefore, the through hole has good covering and there is no problem of erosion due to etching, and the conductivity between the landless through hole and the conductor pattern is good and there is no problem such as disconnection.

The invention according to claim 2 of the present invention relates to a colorless rosin derivative having an acid value of 150 or more and a Hazen color tone of 300 or less and an ethylenically unsaturated monomer having only one epoxy group in the molecule. And 1-79.99% by weight of a reaction product obtained by reacting
0% by weight and 20 to 90% by weight of an inert solid powder to prepare an ultraviolet-curable ink for filling holes.
It is possible to prevent swelling or rupture of the filled-in ink cured product, to prevent the filled-in ink cured product from becoming a porous foam, and to use the cured-filled ink in the polishing process. It is possible to prevent peeling of the surface and jumping out of the uncured resin inside the cured product of the hole-filling ink, and it is possible to further improve the polishing property of the cured product of the hole-filling ink and the releasability with an alkaline solution.
Therefore, the through hole has good covering and there is no problem of erosion due to etching, and the conductivity between the landless through hole and the conductor pattern is good and there is no problem such as disconnection.

The invention according to claim 3 of the present invention relates to a colorless rosin derivative having an acid value of 150 or more and a Hazen color tone of 300 or less and an ethylenically unsaturated monomer having only one epoxy group in the molecule. And a reaction product obtained by further reacting a polybasic acid anhydride with a reaction product obtained by reacting the same with a photopolymerization catalyst and an inert solid powder to form an ultraviolet-curable ink for filling pores. A through-hole filling step of preparing and filling this through-hole filling ink into through-holes of a printed wiring board manufacturing panel, and an excess of filling ink attached to the surface of the printed wiring board manufacturing panel in the through-hole filling step. A polishing step of removing the cured product by polishing, and applying a developable liquid etching resist ink to the surface of the printed wiring board manufacturing panel after the polishing step. A resist forming step of developing and forming an etching resist layer; an etching step of forming a conductive pattern on the surface of the printed wiring board manufacturing panel by etching after the resist forming step; and a printed wiring board manufacturing panel after the etching step And an exfoliation step for removing the cured ink in the through-hole in the through-hole, so that blistering and rupture of the cured ink in the through-hole can be prevented and the cured ink in the filled hole can be prevented. Can be prevented from becoming a porous foam, and it is also possible to prevent the peeling of the surface of the cured ink of the filling material in the polishing step and the protrusion of the uncured resin inside the cured product of the filling ink, Further, it can improve the polishing property of the cured product of the hole-filling ink and the releasability with an alkali solution. Therefore, the through hole has good covering and there is no problem of erosion due to etching, and the conductivity between the landless through hole and the conductor pattern is good and there is no problem such as disconnection.

The invention according to claim 4 of the present invention relates to a colorless rosin derivative having an acid value of 150 or more and a Hazen color tone of 300 or less and an ethylenically unsaturated monomer having only one epoxy group in the molecule. And a reaction product obtained by further reacting a polybasic acid anhydride with a reaction product obtained by reacting
Since the ultraviolet curing type filling ink is prepared by containing 20% by weight and 20 to 90% by weight of the inert solid powder, it is possible to prevent swelling or rupture of the cured filling material. At the same time, it is possible to prevent the cured product of the filled-in ink from becoming a porous foam, and to remove the surface of the cured product of the filled-in ink during the polishing process and to jump out of the uncured resin inside the cured product of the filled-in ink. This can improve the polishing property of the cured product of the ink for filling holes and the releasability of the cured product with an alkaline solution. Therefore, the through hole has good covering and there is no problem of erosion due to etching, and the conductivity between the landless through hole and the conductor pattern is good and there is no problem such as disconnection.

The invention according to claim 5 of the present invention is characterized in that, as the colorless rosin derivative, a colorless rosin derivative having an acid value of 160 to 185 obtained by hydrogenating purified rosin, and an α, β-unsaturated Carboxylic acids and / or α, β-
Since at least one of a colorless rosin derivative having an acid value of 150 to 400 obtained by subjecting an addition reaction product of an unsaturated dicarboxylic acid and purified rosin to a hydrogenation reaction is used, the swelling or rupture of the cured product of the filled pore ink is prevented. In addition, it is possible to prevent the cured product of the hole-filling ink from becoming a porous foam, and to peel off the surface of the cured product of the hole-filled ink in the polishing step and to remove the inside of the cured product of the hole-filled ink. This can prevent the cured resin from jumping out, and can further improve the polishing property of the cured product of the ink for filling holes and the releasability with an alkaline solution. Therefore, the through hole has good covering and there is no problem of erosion due to etching, and the conductivity between the landless through hole and the conductor pattern is good and there is no problem such as disconnection.

In the invention according to claim 6 of the present invention, since the through hole is a landless through hole,
It is possible to prevent swelling or rupture of the filled-in ink cured product, to prevent the filled-in ink cured product from becoming a porous foam, and to use the cured-filled ink in the polishing process. It is possible to prevent peeling of the surface and jumping out of the uncured resin inside the cured product of the hole-filling ink, and it is possible to further improve the polishing property of the cured product of the hole-filling ink and the releasability with an alkaline solution.
Therefore, the through hole has good covering and there is no problem of erosion due to etching, and the conductivity between the landless through hole and the conductor pattern is good and there is no problem such as disconnection.

[Brief description of the drawings]

FIGS. 1A to 1H are cross-sectional views illustrating an example of an embodiment of the present invention.

2A is a plan view of another embodiment of the present invention, FIG. 2B is a sectional view taken along line AA in FIG. 2A, and FIG. 2C is a sectional view taken along line BB in FIG. is there.

3A is a plan view of a printed wiring board having a landless through hole manufactured by the present invention, FIG. 3B is a cross-sectional view taken along line CC of FIG. 3A, and FIG. 3C is a conventional example. It is sectional drawing of a printed wiring board.

[Explanation of symbols]

 Reference Signs List 2 through hole 4 hole filling ink 4h hole filling ink cured product 6h etching resist layer 10 panel for manufacturing printed wiring board

Claims (6)

[Claims] 1. An acid value of 150 or more and a Hazen color tone of 30 or more.
Contains a reaction product obtained by reacting a colorless rosin derivative of 0 or less with an ethylenically unsaturated monomer having only one epoxy group in a molecule, a photopolymerization catalyst, and an inert solid powder. To prepare a UV-curable filling ink, and fill the through-hole of the printed wiring board manufacturing panel with the filling ink and harden the through-hole filling step,
Polishing process to remove excess hole filling ink and its hardened material attached to the surface of printed wiring board manufacturing panel by polishing in through hole filling process, and developable on printed wiring board manufacturing panel surface after polishing process Forming a resist pattern by applying an appropriate liquid etching resist ink, and then exposing and developing to form an etching resist layer; and an etching step of forming a conductor pattern on the surface of a printed wiring board manufacturing panel by etching after the resist forming step. And a stripping step of removing an etched resist layer on the surface of the panel for manufacturing a printed wiring board and a cured ink filling the through-holes in the through-holes after the etching step. . 2. An acid value of 150 or more and a Hazen color tone of 30 or more.
0 to 99.99% by weight of a reaction product obtained by reacting a colorless rosin derivative of 0 or less with an ethylenically unsaturated monomer having only one epoxy group in the molecule, 0.01 to 20% by weight and 20 to 20% of the inert solid powder
The method for producing a printed wiring board with through-holes according to claim 1, wherein an ultraviolet-curable ink for filling holes is prepared by adding 90% by weight. 3. An acid value of 150 or more and a Hazen color tone of 30
A reaction product obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a colorless rosin derivative of 0 or less with an ethylenically unsaturated monomer having only one epoxy group in the molecule Product, a photopolymerization catalyst, and an inert solid powder to prepare an ultraviolet-curable ink for filling the pores,
A through-hole filling step of filling and curing the through-hole filling ink into the through-holes of the panel for manufacturing a printed wiring board, and excess filling ink adhered to the surface of the panel for manufacturing a printed wiring board in the through-hole filling step and curing the same. A polishing step of removing the object by polishing, and applying a developable liquid etching resist ink on the surface of the printed wiring board manufacturing panel after the polishing step, and then exposing and developing to form a resist forming an etching resist layer An etching step of forming a conductive pattern on the surface of the printed wiring board manufacturing panel by etching after the resist forming step, and an etching resist layer on the surface of the printed wiring board manufacturing panel and a hole in the through hole after the etching step. A peeling step of removing a cured ink filling material. Method for producing Lumpur with the printed wiring board. 4. An acid value of 150 or more and a Hazen color tone of 30
A reaction product obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a colorless rosin derivative of 0 or less with an ethylenically unsaturated monomer having only one epoxy group in the molecule 1 to 79.99% by weight, a photopolymerization catalyst in an amount of 0.01 to 20% by weight,
The method for producing a printed wiring board with through holes according to claim 3, wherein an ultraviolet-curable ink for filling the hole is prepared by adding about 90% by weight. 5. A colorless rosin derivative having an acid value of 160 to 185 obtained by subjecting purified rosin to a hydrogenation reaction, and an α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated. An acid value of 150 to 40 obtained by hydrogenating an addition reaction product of dicarboxylic acid and purified rosin.
5. The method for producing a printed wiring board with through holes according to claim 1, wherein at least one of the colorless rosin derivative of No. 0 is used. 6. The method according to claim 1, wherein the through hole is a landless through hole.