JP2010056135A - Phenolic resin composition for wiring coating, printed circuit board using the same, and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenolic resin composition for wiring coating of a printed circuit board, which suppresses cracking and migration of a coating resin layer. <P>SOLUTION: The present invention relates to: the phenolic resin composition for wiring coating of the printed circuit board, comprising a phenolic resin and layered silicate intercalated with at least one organic cation selected from a group of RNH<SB>3</SB><SP>+</SP>(R: alkyl group being ≥15C of a chain), R<SB>2</SB>NH<SB>2</SB><SP>+</SP>(R: hydrocarbon group), R<SB>3</SB>NH<SP>+</SP>(R: hydrocarbon group), NR<SB>4</SB><SP>+</SP>(at least one of four Rs being an alkyl group ≥10C of a chain), ammonium containing 1 to 4 hydrocarbon groups having aromatic hydrocarbon, and ammonium containing 1 to 4 hydrocarbon groups having a heterocycle; and the printed circuit board using the same, and a method of manufacturing the same. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a phenol resin composition for wiring coating, a printed circuit board using the same, and a method for producing the same.

Conventionally, it has been proposed to use a composition containing an inorganic compound such as a thermoplastic resin and a layered silicate as a cover layer for metal wiring formed by screen printing or ink jet printing on a substrate. (For example, Patent Document 1).
In addition, it has been proposed to use an exterior resin containing an inorganic filler (for example, clay) for an electronic component (for example, Patent Document 2).

JP 2006-57099 A JP 2002-252150 A

However, when the exterior resin layer is applied to a metal wiring using a composition containing a thermoplastic resin and a layered silicate (clay), conditions at the time of manufacture (for example, heating during mixing and film formation, The inventors of the present application have found that the orientation (morphology) is changed by dissolution with a solvent, heating for solvent removal, etc.), and an exterior resin layer having a certain orientation cannot be produced and migration is likely to occur. It was.
In addition, the orientation of the thermoplastic resin can be determined to some extent by controlling the structure of the thermoplastic resin and the like. For this reason, it is possible to use either a single clay or an intercalated clay (hereinafter referred to as “clay etc.”) and blend the thermoplastic resin with clay etc. for the thermoplastic resin. it can.
On the other hand, by polymerizing a composition in which a clay alone or intercalated clay is added to a thermosetting resin (thermosetting monomer), the formation of the polymer and the delamination of the clay and the like proceed simultaneously, so that the exterior resin When forming a layer, since the matrix made of thermosetting resin forms a three-dimensional network structure, it is possible to suppress migration even if clay or the like that can be used for thermoplastic resin is simply used for thermosetting resin. The inventor has found that this is not possible.
Furthermore, the anode which has the exterior resin layer (the exterior resin layer was produced by one coating) obtained from the composition containing 100 mass parts of phenol resins as a thermosetting resin, and 2 mass parts of clay single-piece | units. Using the apparatus shown in FIG. 2 and applied potential −1.5 V vs. The inventors of the present application have found that short-circuiting occurs in only 160 seconds after the start of measurement when observing migration by QCM under SCE conditions.
This is probably because fine cracks occurred in the exterior resin layer and migration could not be suppressed.
Then, an object of this invention is to provide the phenol resin composition for wiring coatings of a printed circuit board which can suppress generation | occurrence | production of a crack and migration in an exterior resin layer.

As a result of intensive studies to solve the above problems, the present inventor has found that a phenol resin, RNH ₃ ⁺ (R: an alkyl group having 15 or more carbon atoms in the chain), R ₂ NH ₂ ⁺ (R: hydrocarbon) Group), R ₃ NH ⁺ (R: hydrocarbon group), NR ₄ ⁺ (at least one of the four R is an alkyl group having 10 or more carbon atoms in the chain), a hydrocarbon having an aromatic hydrocarbon A layered silicate intercalated with at least one organic cation selected from the group consisting of ammonium containing 1 to 4 groups and ammonium containing 1 to 4 hydrocarbon groups having a heterocyclic ring It was found that the composition to be used becomes a phenol resin composition for wiring coating of a printed circuit board capable of suppressing the occurrence of cracks and migration in the exterior resin layer.
Further, the wiring board includes a substrate, a plurality of wirings provided on the substrate, and an exterior resin layer that coats at least a space between the wirings, and the exterior resin layer uses the above-described phenol resin composition for wiring coating. The printed circuit board obtained in this way was found to be able to suppress cracks in the exterior resin layer.
Further, a printing process for printing a plurality of wirings on a substrate, a coating process for applying the phenol resin composition for wiring coating, at least between the wirings after the printing process, and after the coating process are obtained. The present invention has been completed by finding that a printed circuit board capable of suppressing cracks and migration in the exterior resin layer can be obtained according to the manufacturing method having a heating step of heating the substrate.

That is, this invention provides the following 1-5.
1. Phenolic resin,
RNH ₃ ⁺ (R: alkyl group having carbon atoms is 15 or more ^{_{chains), R 2 NH 2 + (}} R: hydrocarbon ^{_{group), R 3 NH + (R}} : hydrocarbon group), NR ₄ ⁺ ₍₄ At least one of the R is an alkyl group having 10 or more carbon atoms in the chain), an ammonium containing 1 to 4 hydrocarbon groups having an aromatic hydrocarbon, and a hydrocarbon group having a heterocyclic ring 1 to A phenolic resin composition for wiring coating of a printed circuit board, comprising a layered silicate intercalated with at least one organic cation selected from the group consisting of four ammonium.
2. 2. The phenol resin composition for wiring coating according to 1 above, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite and saponite.
3. 3. The phenol resin composition for wiring coating according to 1 or 2, wherein the amount of the layered silicate is 0.1 to 10 parts by mass with respect to 100 parts by mass of the phenol resin.
4). A substrate and a plurality of wirings provided on the substrate;
An exterior resin layer that coats at least between the wires;
The printed circuit board by which the said exterior resin layer is obtained using the phenol resin composition for wiring coating in any one of said 1-3.
5). A printing process for printing a plurality of wirings on a substrate;
After the printing step, between at least the wiring, an application step of applying the phenol resin composition for wiring coating according to any one of the above 1-3,
A printed circuit board manufacturing method comprising: a heating step of heating the obtained substrate after the coating step.

The phenol resin composition for wiring coating of the present invention can suppress the occurrence of cracks and migration in the exterior resin layer.
Moreover, the printed circuit board of this invention can suppress generation | occurrence | production of a crack and migration in an exterior resin layer.
Moreover, according to the method for manufacturing a printed circuit board of the present invention, it is possible to obtain a printed circuit board capable of suppressing the occurrence of cracks and migration in the exterior resin layer.

The present invention will be described in detail below.
First, the printed circuit board of the present invention will be described below.
The printed circuit board of the present invention includes a substrate, a plurality of wirings provided on the substrate,
An exterior resin layer that coats at least between the wires;
The said exterior resin layer is a board | substrate obtained using the phenol resin composition for wiring coatings of this invention.

The printed circuit board of the present invention will be described below with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 1 is a cross-sectional view schematically showing an example of the printed circuit board of the present invention.
In FIG. 1, a printed circuit board 100 of the present invention includes a substrate 103, a plurality of wirings 105 and 106 on the substrate 103, and an exterior resin layer 107.

The wiring 105 and the wiring 106 are adjacent to each other and have different potentials. Two or more wirings may be used.
The exterior resin layer is coated at least between the wirings. The exterior resin layer can coat the surface of the wiring. In FIG. 1, the exterior resin layer 107 coats the entire surfaces of and between the wirings 105 and 106 (not shown).

About the printed circuit board of the present invention, as its manufacturing method,
A printing process for printing a plurality of wirings on a substrate;
After the printing step, at least between the wiring, an application step of applying the phenolic resin composition for wiring coating of the present invention,
A method for producing a printed circuit board having a heating step of heating the obtained substrate after the coating step is preferably mentioned.

A method for manufacturing a printed circuit board according to the present invention will be described below with reference to FIG.
First, in the printing process, a plurality of wirings 105 and 106 are printed on the substrate 103.
The material of the substrate 103 used when manufacturing the printed circuit board of the present invention is not particularly limited. For example, a polyimide resin, a polyamideimide resin, an acrylic resin, a polyether nitrile resin, a polyether sulfone resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, and a polyvinyl chloride resin can be used.

The material of the wirings 105 and 106 used when manufacturing the printed circuit board of the present invention is not particularly limited. Examples include metals such as silver, copper, tin, nickel, bismuth, zinc, gold, lead, and indium. The metals can be used alone or in combination of two or more.
The method for printing the wirings 105 and 106 on the substrate 103 is not particularly limited. For example, screen printing, inkjet printing, etc. are mentioned.
After the printing process, a substrate having a plurality of wirings is obtained.

An application | coating process is a process of apply | coating the phenol resin composition for wiring coatings of this invention at least between the said wiring after a printing process.
The phenol resin composition for wiring coating used in the production of the printed circuit board of the present invention will be described below.
The phenolic resin composition for wiring coating used in the production of the printed circuit board of the present invention is the phenolic resin composition for wiring coating of the present invention. Hereinafter, the phenol resin composition for wiring coating of the present invention may be referred to as “the phenol resin composition of the present invention”.

The phenolic resin composition of the present invention is
Phenolic resin,
RNH ₃ ⁺ (R: alkyl group having carbon atoms is 15 or more ^{_{chains), R 2 NH 2 + (}} R: hydrocarbon ^{_{group), R 3 NH + (R}} : hydrocarbon group), NR ₄ ⁺ ₍₄ At least one of the R is an alkyl group having 10 or more carbon atoms in the chain), an ammonium containing 1 to 4 hydrocarbon groups having an aromatic hydrocarbon, and a hydrocarbon group having a heterocyclic ring 1 to A phenolic resin composition for wiring coating of a printed circuit board, comprising a layered silicate intercalated with at least one organic cation selected from the group consisting of four ammonium.

  The phenol resin used in the phenol resin composition of the present invention is not particularly limited. For example, a conventionally well-known thing (For example, an acid type, a novolak type, etc.) is mentioned.

The layered silicate will be described below.
The layered silicate used in the phenolic resin composition of the present invention includes RNH ₃ ⁺ (R: an alkyl group having 15 or more carbon atoms in the chain), R ₂ NH ₂ ⁺ (R: a hydrocarbon group), R ₃ NH ⁺ (R: hydrocarbon group), NR ₄ ⁺ (at least one of the four Rs is an alkyl group having 10 or more carbon atoms in the chain), 1 hydrocarbon group having an aromatic hydrocarbon It is intercalated by at least one organic cation selected from the group consisting of ammonium containing ˜4 and ammonium containing 1-4 hydrocarbon groups having a heterocyclic ring.
The layered silicate contained in the phenol resin composition of the present invention is intercalated (intercalated) with an organic cation.

  The layered silicate used in the intercalation (hereinafter referred to as “raw material layered silicate”) is not particularly limited. For example, montmorillonite, hectorite (trade name Laponite, etc.), saponite (trade name, smecton, etc.), smectite such as beidellite; kaolinite; pyrophynite; vermiculite; mica; Of these, montmorillonite, hectorite, and saponite are preferable from the viewpoint of further suppressing crack generation and migration in the exterior resin layer and being excellent in solubility in water. The raw material layered silicate may be either a natural product or a synthetic product.

Organic cations, RNH ₃ ⁺ (R: alkyl group having carbon atoms is 15 or more ^{_{chains), R 2 NH 2 + (}} R: hydrocarbon ^{_{group), R 3 NH + (R}} : hydrocarbon group), NR ₄ ⁺ (at least one of four Rs is an alkyl group having 10 or more carbon atoms in the chain), ammonium containing 1 to 4 hydrocarbon groups having an aromatic hydrocarbon, and a hydrocarbon having a heterocyclic ring It is at least one selected from the group consisting of ammonium containing 1 to 4 groups.

In RNH ₃ ⁺ , R is an alkyl group having 15 or more carbon atoms in the chain.
In the present invention, the number of carbon atoms in the chain means the number of carbon atoms in the skeleton of the alkyl group. The same applies hereinafter.
R is linear or branched. In the case where R is linear or branched, the number of carbon atoms in the R chain (skeleton) is 15 or more, and from the viewpoint that crack generation and migration in the exterior resin layer can be further suppressed. The number of carbon atoms is preferably 15-20. When R is branched, the hydrocarbon group as the side chain is not particularly limited.
Examples of R include a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and a nonadecyl group. Especially, an octadecyl group is preferable from a viewpoint that generation | occurrence | production of a crack and a migration in an exterior resin layer can be suppressed more.

In R ₂ NH ₂ ⁺ , R is a hydrocarbon group. R may be the same or different.
The hydrocarbon group is not particularly limited. For example, a C1-C20 alkyl group, an aromatic group, and these combinations are mentioned.
Examples of R ₂ NH ₂ ⁺ include diphenylammonium.

In R ₃ NH ⁺ , R is a hydrocarbon group. R may be the same or different. The hydrocarbon group is as defined above.
Examples of R ₃ NH ⁺ include dimethylbenzylammonium.

In NR ₄ ⁺ , at least one of the four R's is an alkyl group having 10 or more carbon atoms in the chain. R is linear or branched. From the viewpoint that generation of cracks and migration in the exterior resin layer can be further suppressed, the number of carbon atoms in the chain is preferably 10-20. When R is branched, the hydrocarbon group as the side chain is not particularly limited.
Examples of R include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and an octadecyl group. Among these, a dodecyl group and an octadecyl group are preferable from the viewpoint that generation of cracks and migration in the exterior resin layer can be further suppressed.
When the alkyl group having 10 or more carbon atoms in the chain is bonded to 1 to 3 nitrogen atoms, the remaining hydrocarbon groups bonded to the ammonium nitrogen atom are not particularly limited. For example, C1-C9 alkyl groups, such as a methyl group, an ethyl group, and a hexyl group, are mentioned.
Examples of NR ₄ ⁺ include dodecyltrimethylammonium, dodecyltriethylammonium, and octadecyltrimethylammonium.

In the ammonium containing 1 to 4 hydrocarbon groups having an aromatic hydrocarbon, examples of the hydrocarbon group having an aromatic hydrocarbon include an aromatic hydrocarbon group and an aralkyl group. Specific examples include aromatic hydrocarbon groups such as phenyl and naphthyl groups; and aralkyl groups such as benzyl and phenethyl groups.
When ammonium contains 1 to 3 hydrocarbon groups having an aromatic hydrocarbon, a hydrogen atom or a hydrocarbon group can be bonded to the nitrogen atom of ammonium. The hydrocarbon group that can be bonded to the nitrogen atom of ammonium is not particularly limited. For example, an alkyl group having 1 or more carbon atoms such as a methyl group, an ethyl group, and a hexyl group can be given.
Ammonium containing 1 to 4 hydrocarbon groups having aromatic hydrocarbons is 1 hydrocarbon group having aromatic hydrocarbons from the viewpoint that crack generation and migration in the exterior resin layer can be further suppressed. Preferred are ammonium containing 1 and 3 hydrogen atoms, and ammonium containing 1 hydrocarbon group having an aromatic hydrocarbon and 3 alkyl groups.
Examples of ammonium containing one hydrocarbon group having an aromatic hydrocarbon and three hydrogen atoms include phenylammonium, naphthylammonium, benzylammonium, and phenethylammonium.
Examples of ammonium containing one hydrocarbon group having an aromatic hydrocarbon and three alkyl groups include phenyltrimethylammonium, naphthyltrimethylammonium, benzyltrimethylammonium, and phenethyltrimethylammonium.

In the ammonium containing 1 to 4 hydrocarbon groups having a heterocyclic ring, the heterocyclic ring is not particularly limited. Examples thereof include a 5- to 7-membered ring having a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom, and a condensed system. The heterocycle can be attached to the ammonium nitrogen atom via an alkyl group. Specific examples of the heterocyclic ring include a pyrrole ring, a furan ring, and a thiophene ring.
When ammonium contains 1 to 3 hydrocarbon groups having a heterocyclic ring, a hydrogen atom or a hydrocarbon group can be bonded to the nitrogen atom of ammonium. The hydrocarbon group that can be bonded to the nitrogen atom of ammonium is not particularly limited. For example, an alkyl group having 1 or more carbon atoms such as a methyl group or an ethyl group can be used.

  The organic cation is preferably octadecylammonium, benzylammonium, dodecyltrimethylammonium, or benzyltrimethylammonium from the viewpoint that generation of cracks and migration in the exterior resin layer can be further suppressed.

The combination of the raw material layered silicate and the organic cation is at least one selected from the group consisting of montmorillonite, hectorite and saponite, from the viewpoint that crack generation and migration in the exterior resin layer can be further suppressed. And a combination with at least one selected from the group consisting of octadecylammonium, benzylammonium, dodecyltrimethylammonium and benzyltrimethylammonium.
The layered silicates can be used alone or in combination of two or more.
The layered silicate is not particularly limited for its production. For example, it can be produced by mixing a raw material layered silicate and an organic cation salt (for example, an organic cation hydrochloride) in an aqueous solution under heating conditions of 80 ° C.
The amount of the organic cation salt used when producing the layered silicate can further suppress the occurrence of cracks and migration in the exterior resin layer, and is excellent in adhesion to wiring and base materials (PET, etc.) From a viewpoint, it is preferable that it is 0.01-1.00 mol with respect to 100 grams of raw material layered silicate, and it is more preferable that it is 0.1-0.2 mol.

  The amount of the layered silicate is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the phenol resin from the viewpoint that the occurrence of cracks and migration in the exterior resin layer can be further suppressed. 0.1 to 2 parts by mass is more preferable.

  The phenol resin composition of this invention can contain an additive in the range which does not impair the objective and effect of this invention. Examples of the additive include an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, an antistatic agent, an antifogging agent, a filler, a softener, a plasticizer, and a colorant. .

  The phenol resin composition of the present invention is not particularly limited for its production. For example, it can be obtained by mixing a phenol resin, a layered silicate, and an additive that can be used as required.

  In the method for producing a printed circuit board of the present invention, the method for applying the phenol resin composition of the present invention to wiring is not particularly limited. For example, a screen printing method, an inkjet printing method, a dipping method, a spin coating method, and the like can be given.

Next, the board | substrate obtained in the heating process is heated after the application | coating process in the manufacturing method of the printed circuit board of this invention.
The heating temperature is preferably 100 to 200 ° C. from the viewpoint that generation of cracks and migration in the exterior resin layer can be further suppressed.
The heating method is not particularly limited. For example, the substrate can be heated using an oven such as a muffle furnace.
In the heating step, the phenol resin composition of the present invention is cured, and the layered silicate can be peeled off to form an exterior resin layer dispersed in a three-dimensional matrix of phenol resin.
After the heating, the printed circuit board of the present invention can be obtained by cooling.

The printed circuit board of the present invention uses a phenol resin composition of the present invention as a composition for forming an exterior resin layer, whereby a high applied potential [−1.5 to −2.0 V vs. Even when SCE (saturated calomel electrode)] is applied, cracks in the exterior resin layer are unlikely to occur, migration can be suppressed, and the exterior resin layer can have insulating properties.
Moreover, the manufacturing method of the printed circuit board of this invention uses the phenol resin composition of this invention, and the orientation of the phenol resin and layered silicate in an exterior resin layer changes with heating, a solvent, etc. Therefore, a printed circuit board having stable quality (for example, mechanical strength and migration suppressing effect) can be easily manufactured.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Anode (1) Anode The anode used in the examples of the present invention will be described below with reference to the accompanying drawings.
FIG. 3 is a front view schematically showing the anode used in the example of the present invention.
In FIG. 3, the anode 300 has silver wiring 305 on a PET film substrate 303. Reference numeral 307 denotes an exterior resin layer, and the exterior resin layer 307 covers the substrate 303 and the wiring 305.
4 is a cross-sectional view of the anode 300 shown in FIG.
In FIG. 4, the anode 400 has a wiring 405 disposed on a substrate 403, and an exterior resin layer 407 coats the wiring 405.
The thickness L of the exterior resin layer 407 (from the surface of the substrate 403 to the surface of the exterior resin layer 407) was about 20 μm.
(2) Fabrication of anode A wiring 305 was printed by a screen printing method using a silver paste on a PET film substrate 303, and then a composition obtained by the following method by a hand-printed screen printing method was used as the silver of the portion 307. The wiring part was coated once, heated at 150 ° C. for 1 hour and cooled to form an exterior resin layer 307, and an anode 300 was produced. The obtained anode 300 was used as the anode (counter electrode) of the potentiostat.

2. Evaluation (Electrochemical behavior of coating resin containing organic ammonium hybrid clay)
-Apparatus used to measure metal deposition using an electrochemical QCM (Quarts Crystal Microbalance) In an embodiment of the present invention, used to measure metal deposition using an electrochemical QCM. The apparatus will be described below with reference to the accompanying drawings.
FIG. 2 is a schematic diagram schematically showing an apparatus used for measuring metal deposition using electrochemical QCM in an embodiment of the present invention.
In FIG. 2, the apparatus 200 includes a potentiostat 203, a QCM 205, and a water tank 207. The potentiostat 203 includes an anode 209 as a counter electrode, a cathode 205 using QCM as a working electrode, and a reference electrode 211. The anode 209 and the reference electrode 211 are electrically connected to the potentiostat 203. The cathode 205 has a gold vapor deposition portion 215 on the substrate 213, and is electrically connected to the potentiostat 203 in the gold vapor deposition portion 215. The cathode 205 is electrically connected to the QCM controller 217.
The anode 209 is curved by applying a force in the direction of the arrow 221 to such an extent that the surface (not shown) of the exterior resin layer 219 is in contact with the gold vapor deposition portion 215.
The inside of the water tank 207 is filled with a 0.1 mM aqueous solution 223 containing TEACIO ₄ (compound name: tetraethylammonium perchlorate) as a supporting salt, and the cathode 205, the anode 209, and the reference electrode 211 are added to the aqueous solution 223. It has been done.
A current flows from the power source of the potentiostat 203 in the direction of the arrow 225, and a voltage is applied to the cathode 205 by the potentiostat 203 so that the potential with respect to the reference electrode 211 is always equal.
When a crack (not shown) is generated in the curved exterior resin layer 219, silver ions are eluted from the crack and reduced on the gold vapor deposition portion 215 to become silver (not shown).
If a metal (here, silver, not shown) adheres on the gold vapor deposition part 215, a resonance frequency deviation will fall according to the mass. The fluctuation of the resonance frequency deviation is detected by the QCM controller 217.
In the embodiment of the present invention, an electrochemical system: HZ-3000 (made by Hokuto Denko) is used as the potentiostat 203, the anode prepared as described above is used as the anode 209, and gold having a resonance frequency of 6 MHz is used as the cathode 205. A vapor-deposited AT cut crystal QCM (manufactured by Hokuto Denko) was used, and an Ag / AgCl wire was used as the reference electrode 211.
By this experiment, it can be confirmed whether or not the anode 209 originally has a crack (before the experiment).
Measurement Using the apparatus shown in FIG. 2 and the anode shown in FIG. 3, the applied potential at the potentiostat 203: −1.5 V vs. Frequency deviation / Δf was measured as SCE. The results are shown in FIG. FIG. 6 is a graph showing a QCM measurement result (time-resonance frequency deviation relationship).

3. Preparation of salt of organic cation (1) Compound 2a
Compound 1a (0.1 g) was reacted in a 1 mol / L aqueous hydrochloric acid solution (10 ml) to produce compound 2a.
(2) Compound 2b
Compound 1b (0.1 g) was reacted in a 1 mol / L hydrochloric acid aqueous solution (10 ml) to produce compound 2b.
(3) Compound 2c
Compound 1c (0.1 g) was reacted in a 1 mol / L aqueous hydrochloric acid solution (10 ml) to produce compound 2c.
The structure of each compound is shown in FIG.
FIG. 5 is a chemical formula showing the structures of organic cation salts (2a to 2e) and the production of organic cation salts (2a to 2c) used in Examples.

4). Production of Layered Silicate (1) Layered Silicate (Organic Hybrid Clay) Hectorite (trade name Laponite, manufactured by Sakai Kogyo Co., Ltd.) was used as the layered silicate before intercalation.
As the organic cation salt, compounds 2a, 2b and 2c obtained as described above, compound 2d (manufactured by Tokyo Chemical Industry Co., Ltd.) and compound 2e (manufactured by Tokyo Chemical Industry Co., Ltd.) were used. The structures of compounds 2d and 2e are shown in FIG.
The organic cation was intercalated in hectorite using 0.15 mol of compound 2b (octadecyl ammonium chloride) per 100 grams of hectorite.
Moreover, 0.15 mol of compound 2a was used for 100 g of hectorite, and an organic cation was intercalated in hectorite. For compound 2c, compound 2d, and compound 2e, 0.15 mol of compound 2c, compound 2d, and compound 2e were used per 100 g of hectorite, and organic cations were intercalated into hectorite.
The intercalation method followed the method described in the literature (see Macromolecules 1997, 30, 6334).
The layered silicate obtained using Compound 2b is referred to as Layered Silicate 1.
The layered silicate obtained using Compound 2e is referred to as Layered Silicate 2.
The layered silicate obtained using Compound 2d is referred to as Layered Silicate 3.
The layered silicate obtained using Compound 2c is referred to as Layered Silicate 4.
The layered silicate obtained using Compound 2a is referred to as Layered Silicate 5.

(2) Analysis of layered silicate In order to clarify the presence or absence of intercalation of various organic cations into the layered silicate, IR measurement was performed. The measurement was performed by preparing a pellet obtained by diffusing organic hybrid clay in KBr and measuring the total reflection.
In hectorite reacted with dodecylammonium, octadecylammonium and n-dodecyltrimethylammonium, an absorption spectrum due to CH stretching vibration appeared in the region of 3000 to 2840 cm ⁻¹ . This indicates that the above ammonium is intercalated in the clay.
However, in the sample reacted with benzyltrimethylammonium and benzylammonium, no clear absorption band due to CH stretching vibration or phenyl ring could be confirmed.
In IR measurement, UV measurement was performed for the purpose of clarifying the presence or absence of intercalation of benzyltrimethylammonium and benzylammonium that could not be recognized as intercalation. Sample in which only clay (hectorite) is dissolved in water, sample in which benzyltrimethylammonium chloride is dissolved in water, sample in which benzylamine is dissolved in water, sample in which benzyltrimethylammonium hybrid clay is dissolved in water, benzylammonium hybrid in water The UV spectrum of the sample in which clay was dissolved was measured.
In the spectrum in which only clay is dissolved in water, a characteristic absorption band does not appear, but in the spectrum of the clay reacted with benzyltrimethylammonium chloride, an absorption band (about 260 nm) derived from the phenyl ring appears.
Therefore, it was clarified that benzyltrimethylammonium and benzylammonium were intercalated in the clay.

5). Example (1) Example 1
2 parts by mass of layered silicate 1 was added to 100 parts by mass of phenol resin (trade name Phenolite 5010, Dainippon Ink and Chemicals, Inc.) and mixed to obtain a composition. The resulting composition is referred to as Composition 1.
(2) Example 2
A composition was obtained in the same manner as in Example 1 except that the layered silicate 1 was replaced with the layered silicate 2. The resulting composition is designated as Composition 2.
(3) Example 3
A composition was obtained in the same manner as in Example 1 except that the layered silicate 1 was replaced with the layered silicate 3. The resulting composition is designated as Composition 3.
(4) Example 4
A composition was obtained in the same manner as in Example 1 except that the layered silicate 1 was replaced with the layered silicate 4. The resulting composition is designated as Composition 4.
(5) Comparative Example 1
A composition was obtained in the same manner as in Example 1 except that the layered silicate 1 was replaced with the layered silicate 5. The obtained composition is designated as Composition 5.
(6) Comparative Example 2
A composition was obtained in the same manner as in Example 1 except that non-intercalated hectorite was used instead of intercalated hectorite. The obtained composition is designated as Composition 6.

As is clear from the results shown in FIG. 6, Examples 1 to 4 (samples coated with a phenol resin containing an organic ammonium hybrid clay) are not intercalated in Comparative Example 1 in which the organic cation is dodecyl ammonium. Compared with Comparative Example 2 using the layered silicate, the resonance frequency deviation was maintained for a long time. This is presumably because the compatibility with the phenol resin was improved by intercalating the organic substance into the clay, and crack formation in the phenol resin was suppressed. In other words, as a result of detailed examination of the molecular structure of the organic ammonium to be hybridized, it was found that migration is strongly suppressed when organic ammonium having a long carbon chain is intercalated (octadecyl ammonium: carbon chain 18 and dodecyl ammonium: carbon Comparison with chain 12). This is probably because the longer the carbon chain that is a hydrophobic part that does not interact with the clay layer, the stronger the vdw interaction with the phenol resin is induced and the more the compatibility is increased.
On the other hand, when an amine having a phenyl ring in the carbon chain portion is used, a π-π interaction that is stronger than the vdw interaction is induced between the phenyl ring that is the basic skeleton of the phenol resin, Even if there are few carbon chains, compatibility with a phenol resin can be expected. Actually, when benzylammonium was used, it was found that migration was suppressed over a long period of time despite the fact that the number of carbons was smaller than that of dodecylammonium.
Next, quaternary ammonium was examined. The structure of the cation part of quaternary ammonium has a bulky steric structure compared to other ammonium. Therefore, after ion exchange for inorganic ions existing between clay layers, the cation portion is expected to be present in the surface layer portion compared to inorganic ions. For this reason, it can be inferred that the hydrophobic portion exists at a distance from the clay. Based on this assumption, when long-chain quaternary ammonium is hybridized, the hydrophobic portion around the clay and the phenol resin should induce a large intermolecular interaction compared to other organic hybrid clays. Actually, when benzyltrimethylammonium or n-dodecyltrimethylammonium was used, migration was strongly suppressed as expected, and in particular, n-dodecyltrimethylammonium showed the best migration suppressing ability. From these results, we succeeded in suppressing migration by improving the functionality of the phenolic resin as the compatibility of the organic ammonium hybrid clay and the phenolic resin improved.
As mentioned above, the clay which modified the organic residue was synthesized, and the electrochemical behavior of the resin containing it was clarified. That is, the present inventors have found that a phenol resin containing an organic hybrid clay is less susceptible to cracking and suppresses migration over a long period of time compared to a resin containing solid clay or a resin containing no clay. As a result of detailed examination of the molecular structure of the organic ammonium to be hybridized, it was found that long-chain quaternary ammonium (such as n-dodecyltrimethylammonium) functions effectively in suppressing migration of silver wiring coated with phenol resin.
In addition, when the precipitation state of the metal (for example, silver) by migration in Examples 1 to 4 was observed, the metal precipitation occurred at a position unrelated to the bending of the anode.
According to the present invention, by clarifying the interaction between a phenol resin and an inorganic filler (clay), which are widely used as a binder for silver paste, it is difficult to crack and has an ability to suppress migration and an exterior resin containing an organic hybrid clay Could be developed.

FIG. 1 is a cross-sectional view schematically showing an example of the printed circuit board of the present invention. FIG. 2 is a schematic diagram schematically showing an apparatus used for measuring metal deposition using electrochemical QCM in an embodiment of the present invention. FIG. 3 is a front view schematically showing the anode used in the example of the present invention. 4 is a cross-sectional view of the anode 300 shown in FIG. FIG. 5 is a chemical formula showing the structures of organic cation salts (2a to 2e) and the production of organic cation salts (2a to 2c) used in Examples. FIG. 6 is a graph showing the QCM measurement result (time-resonance frequency deviation relationship).

Explanation of symbols

100 Printed Circuit Board of the Present Invention 103 Substrate 105, 106 Wiring 107 Exterior Resin Layer 200 Device 203 Potentiostat 205 QCM (Cathode) 207 Water Tank 209 Anode 211 Reference Electrode 213 Substrate 215 Gold Deposition Unit 217 QCM Controller 219 Exterior Resin Layer 221 225 Arrow 223 Aqueous solution 300, 400 Anode 303, 403 Substrate 305, 405 Wiring 307, 407 Exterior resin layer L Thickness of exterior resin layer 307 (from the surface of substrate 303 to the surface of exterior resin layer 307)

Claims (5)

Phenolic resin,
RNH ₃ ⁺ (R: alkyl group having 15 or more carbon atoms in the chain), R ₂ NH ₂ ⁺ (R: hydrocarbon group), R ₃ NH ⁺ (R: hydrocarbon group), NR ₄ ⁺ (4 At least one of the R is an alkyl group having 10 or more carbon atoms in the chain), an ammonium containing 1 to 4 hydrocarbon groups having an aromatic hydrocarbon, and a hydrocarbon group having a heterocyclic ring 1 to A phenolic resin composition for wiring coating of a printed circuit board, comprising a layered silicate intercalated with at least one organic cation selected from the group consisting of four ammonium.   The phenol resin composition for wiring coating according to claim 1, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite and saponite.   The phenol resin composition for wiring coating according to claim 1 or 2, wherein the amount of the layered silicate is 0.1 to 10 parts by mass with respect to 100 parts by mass of the phenol resin.   The wiring coating according to claim 1, further comprising: a substrate, a plurality of wirings provided on the substrate, and an exterior resin layer that coats at least a space between the wirings. Printed circuit board obtained by using the phenol resin composition. A printing process for printing a plurality of wirings on a substrate;
The application | coating process which apply | coats the phenol resin composition for wiring coating in any one of Claims 1-3 between the said wiring after the said printing process,
A printed circuit board manufacturing method comprising: a heating step of heating the obtained substrate after the coating step.

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