JP2003096267A - Roughened surface forming resin composition, and multilayer printed wiring board and prepreg for printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a roughened surface forming resin composition excellent in adhesiveness between a conductor circuit and an interlayer resin insulating layer, less suffering from the occurrence of cracks during heat cycle, and having good flexibility, heat resistance, moisture resistance, electrical properties and flame resistance, and to provide a highly reliable multilayer printed wiring board and a prepreg for a printed wiring board. SOLUTION: The resin composition capable of forming a good roughened surface comprising an epoxy resin and/or a phenol resin as a main component of a matrix comprises crosslinkable phenoxyphosphazene resin powders as an easily dissolved organic filler, in which at least one phosphazene compound (a) selected from the group consisting of a cyclic phenoxyphosphazene and a linear phenoxyphosphazene is the compound crosslinked with at least one crosslinking group (b) selected from an o-phenylene group, a m-phenylene group, a p-phenylene group and a bis-phenylene group, and a free hydroxy group is not included in the molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for forming a roughened surface, a multilayer printed wiring board using the same, and a prepreg for a printed wiring board. Has excellent adhesiveness with
A resin composition for forming a roughened surface, which has few cracks during heat cycle, has good flexibility, and has excellent heat resistance, insulation properties, impact resistance, chemical resistance, moisture resistance, water resistance, and electrical characteristics. And a multilayer printed wiring board using the resin composition and a prepreg for the printed wiring board.

[0002]

2. Description of the Related Art In order to meet the needs for higher performance of electronic equipment, higher integration of LSIs and IC chips has progressed, and accordingly, higher density of conductor circuits of wiring boards for mounting these semiconductor devices, Higher miniaturization is required. In response to such demands, so-called build-up multilayer printed wiring boards, in which conductor circuit layers and interlayer resin insulation layers are alternately laminated, have been attracting attention.

In manufacturing a build-up multilayer printed wiring board, it is important to form a conductor circuit on an interlayer resin insulation layer with high reliability, and in order to meet the demand for higher density, the conductor circuit is required. Miniaturization and thinning of the interlayer resin insulation layer are required. However, when the conductor circuit is miniaturized, the contact area between the interlayer resin insulation layer and the conductor circuit is reduced, which causes a problem of poor adhesion. To solve this, the anchor effect is improved, that is, the interlayer resin insulation layer Efforts have been made for unevenness, that is, for roughening the so-called interlayer resin insulation layer.

Currently, as a method of roughening an interlayer resin insulation layer, a substance that is hardly soluble in a roughening agent such as an acid, an alkali or an oxidizing agent and a substance that is soluble in a roughening agent such as an acid, an alkali or an oxidizing agent are contained in a resin composition for forming a roughened surface. Dispersion is performed, and fine unevenness is formed on the surface due to the difference in solubility. Here, as the substance soluble in the roughening agent, conventionally, inorganic particles, resin particles, metal particles, rubber particles,
Liquid layer particles are used. In particular, from the viewpoint of moisture resistance, chemical resistance and electrical characteristics, attention is paid to organic fillers as heat resistant resin powders.

As the heat-resistant resin powder used for such a purpose, that is, as an organic filler, for example, in JP-B-4-55555, an epoxy resin, a polyester resin, a bismaleimide / triazine resin, and a melamine resin are used. Is proposed. In addition, JP 2000
In JP-A-186217, an elastic resin powder having a carboxyl group and soluble in an oxidizing agent, for example, a carboxylated crosslinked NBR or a carboxylated crosslinked acrylic resin is used, and at the same time roughening, impact resistance and crack resistance. Have been proposed. Also, Japanese Patent Laid-Open No. 2000-15986
Japanese Unexamined Patent Publication (Kokai) No. 4 proposes a roughening method using an alicyclic epoxy resin powder containing an ester bond, which does not require a strong oxidizing agent such as chromic acid. Further, in Japanese Patent Laid-Open No. 2000-208889, a heat-decomposable resin powder, for example, poly (cyanoacrylate) resin is used as an organic filler, and the organic filler is decomposed and vaporized when the interlayer resin insulation layer is heat-cured, A method has been proposed in which voids are generated at the same time as roughening, the dielectric constant of the interlayer resin insulating layer is lowered, and a harmful roughening agent is not used.

On the other hand, electric / electronic equipment members using a printed wiring board are required to have a high degree of flame retardant treatment in order to ensure safety against fire. At the same time, in printed wiring boards, under various conditions, mechanical properties (elongation rate, elastic modulus, peel strength, impact resistance, etc.), electrical characteristics (electrical resistance, dielectric constant, dielectric loss, etc.), thermal It is required to have excellent properties (glass transition point (Tg), expansion coefficient, etc.), water resistance, moisture resistance, chemical resistance and the like.

From this point of view, conventionally, acid,
Mechanical properties such as impact resistance and crack resistance can be obtained by dispersing resin particles or rubber particles, which have been used as substances exhibiting solubility in roughening agents such as alkalis and oxidizing agents, in a resin composition for forming a roughened surface. It also causes deterioration of thermal characteristics and electrical characteristics. Moreover, when inorganic particles or metal particles are used, problems such as deterioration of water resistance, moisture resistance, chemical resistance and electrical characteristics occur, and even if various inorganic particles or organic particles are blended and adjusted, all properties It was difficult to obtain a resin composition for forming a roughened surface sufficient to satisfy the above condition.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and when an interlayer resin insulation layer is formed, a roughened surface can be formed by a roughening treatment, and the adhesiveness to a conductor circuit can be improved. Excellent, less cracking during heat cycle, good flexibility, heat resistance, moisture resistance, electrical characteristics, flame retardant resin composition for forming a roughened surface. is there. Another object of the present invention is to provide a highly reliable multilayer printed wiring board that can meet the demand for higher miniaturization and higher density of conductor circuits by using such a resin composition. . Still another object of the present invention is to use the resin composition as described above, to obtain thermal shock resistance,
Another object of the present invention is to provide a prepreg for a printed wiring board, which is excellent in flexibility, heat resistance, moisture resistance, electric characteristics, flame retardancy and the like.

[0009]

In order to achieve the above object, according to the first aspect of the present invention, an epoxy resin and / or
Alternatively, in a resin composition containing a phenol resin as a main component of a matrix, at least one selected from the group consisting of a cyclic phenoxyphosphazene represented by the following general formula (1) and a linear phenoxyphosphazene represented by the following general formula (2). The phosphazene compound (a) of the species is o-
A compound crosslinked with at least one crosslinkable group (b) selected from the group consisting of a phenylene group, an m-phenylene group, a p-phenylene group and a bisphenylene group represented by the following general formula (3): The phosphazene compound (a) has a structure in which the bridging group (b) is interposed between two oxygen atoms eliminated from the phenyl group, and the phenyl group content is all phenyl groups in the phosphazene compound (a). A resin composition for forming a roughened surface, characterized in that the crosslinked phenoxyphosphazene resin powder having a free hydroxyl group in the molecule is contained as an organic filler in an amount of 50 to 99.9% based on the total number of Will be provided.

[Chemical 2] [In the formula, Ph represents a phenyl group, and X represents a group -N = P.
(OPh) ₃ or a group —N═P (═O) OPh,
Y is a group -P (= O) (OPh) or a group -P (OPh) _3.
The expressed, A is _{-C (CH 3) 2 -,} - SO 2 -, - S-
Or represents -O-, m is an integer of 3 to 25, n is an integer of 3 to 10,000, and a is 0 or 1. ] Preferably, the crosslinked phenoxyphosphazene resin powder is contained in a proportion of 1 to 40 wt% of the entire resin composition. The roughened surface forming resin composition may be in the form of a liquid (paste), or may be in the form of a dry film.

According to the second aspect of the present invention, in a multilayer printed wiring board in which an interlayer resin insulation layer is formed between conductor circuit layers, the interlayer resin insulation layer is formed by using the resin composition. A multilayer printed wiring board characterized by being roughened is also provided. Further, according to a third aspect of the present invention, there is provided a prepreg for a printed wiring board, which is obtained by impregnating a fibrous sheet-shaped substrate with the resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In order to solve the above-mentioned problems, the present inventors have studied a number of heat resistant resin powders, and as a result, a crosslinked phenoxyphosphazene resin powder having a special structure has excellent heat resistance, As a highly soluble organic filler that has a number of excellent properties such as low elastic modulus, low expansion coefficient and low water absorption rate, and is mixed in the roughened surface forming resin composition used as the interlayer resin insulation layer of the multilayer printed wiring board. The inventors have found that it is optimal and have completed the present invention. Further, according to the research conducted by the present inventors, the crosslinked phenoxyphosphazene resin powder having such a special structure imparts a sufficient flame retardant effect to the resin composition in spite of being halogen-free, and as described above. In order to impart excellent properties, a curable resin composition containing the same has been found to be optimal as a resin composition for impregnating a fibrous sheet-like base material used in a prepreg for a printed wiring board.

That is, the resin composition of the present invention is characterized by containing a crosslinked phenoxyphosphazene resin powder as an essential component in a resin composition containing an epoxy resin and / or a phenol resin as a main component of a matrix. The crosslinked phenoxyphosphazene resin contains at least one phosphazene compound (a) selected from the group consisting of the cyclic phenoxyphosphazene represented by the general formula (1) and the linear phenoxyphosphazene represented by the general formula (2). A compound crosslinked with at least one crosslinking group (b) selected from the group consisting of an o-phenylene group, an m-phenylene group, a p-phenylene group and a bisphenylene group represented by the general formula (3). And has a structure in which the bridging group (b) is interposed between two oxygen atoms from which the phenyl group of the phosphazene compound (a) has been eliminated, and the content ratio of the phenyl group in the phosphazene compound (a) is 5 based on the total number of all phenyl groups
It is a crosslinked phenoxyphosphazene resin powder having 0 to 99.9% and having no free hydroxyl group in the molecule.
Since the crosslinked phenoxyphosphazene resin is described in JP-A-2000-256551,
For details, refer to the publication.

The crosslinked phosphazene resin powder used in the present invention has a maximum particle size of 10 μm or less, and an average particle size of 2 μm or less, preferably 0.1 to 1.0 μm. If the average particle size exceeds 2 μm,
It is not preferable because the dispersibility of the resin powder in the composition is reduced. To improve the thermal shock resistance by making the roughened surface fine (fine pattern circuit formation) and fine (sea / island) structure formation, The particle size is desirably 2 μm or less, preferably 1 μm or less, and preferably 0.1 μm or more.

In the present invention, in order to form a favorable roughened surface, the blending ratio of the crosslinked phenoxyphosphazene resin powder needs to be 1 to 40% by weight, preferably 5 to 20% by weight based on the whole resin composition. If the blending ratio of the crosslinked phenoxyphosphazene resin powder is less than 1 wt%, it is difficult to obtain a sufficient roughening effect, while if it exceeds 40 wt%, the glass transition point of the obtained cured coating film is significantly lowered, which is not preferable.

The epoxy resin as the thermosetting resin used in the resin composition of the present invention includes bisphenol A.
Type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, and the like. Examples of the phenol resin include phenol novolac resin, cresol novolac resin, bisphenol A type novolac resin, bisphenol F type novolac resin, and naphthol novolac resin. These thermosetting resins can be used alone or in combination of two or more kinds.

The resin composition of the present invention preferably contains a latent curing catalyst in order to accelerate the thermosetting reaction.
As a latent curing catalyst, an imidazole compound, for example, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2methylimidazole, 2-heptadecylimidazole, 4,5- Diphenyl imidazole, 2-isopropyl imidazole, 2,4-dimethyl imidazole, 2-phenyl-4-methyl imidazole and the like can be mentioned. In addition, imidazoline compounds, for example, 2-methylimidazoline, 2-methyl-4-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-ethylimidazoline, 2-isopurupylimidazoline, 2,4-
Examples thereof include dimethylimidazoline and 2-phenyl-4-methylimidazoline. Also, dicyandiamide,
Examples thereof include organic phosphorus compounds. These latent curing catalysts can be used alone or in combination of two or more. The compounding amount of the latent curing catalyst is sufficient in a usual quantitative ratio, and is generally 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin and / or the phenol resin.

The resin composition of the present invention may contain an inorganic and / or organic filler together with the crosslinked phenoxyphosphazene resin powder in a quantitative ratio that does not impair its effect. Examples of the inorganic filler include barium sulfate, calcium carbonate, barium titanate, silicon oxide, amorphous silica, talc, clay and mica powder, and examples of the organic filler include silicon powder, nylon powder and fluorine powder. . The proportion of these inorganic and / or organic fillers is preferably 50 wt% or less of the total composition.

Further, in the resin composition of the present invention, additives other than the above-mentioned components are added unless the effects of the present invention are impaired.
Colorants may be added. As additives, thickeners such as asbestos, orben, and benton, silicone-based agents,
Fluorine-based defoaming agents, leveling agents and the like can be mentioned, and examples of the coloring agents include phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, titanium oxide, carbon black and the like.

The resin composition of the present invention can be applied to a printed circuit board by various conventionally known methods such as curtain coating, roll coating, spray coating and dip coating, as well as dry film or prepreg. It can be used in the form of Various solvents can be used depending on the method of use and application, but depending on the case, not only a good solvent but also a poor solvent may be used.

Next, a production example of a multilayer printed wiring board using the resin composition of the present invention will be described. First, the resin composition of the present invention is applied onto the insulating base material on which the inner layer conductor circuit is formed by a known method such as a screen printing method, a curtain coating method, a roll coating method, or a spray coating method,
It is dried and cured to form an insulating resin layer. Depending on the coating method, a coating film having a desired film thickness may not be obtained by one coating, but in that case, coating is performed multiple times. When the coating is performed a plurality of times, the resin composition of the present invention may be used alone, or another thermosetting resin composition having good adhesion to copper may be coated on the undercoat, and then the You may make it use the resin composition of this invention for the coating of an upper layer. Further, in the dry curing of the coating film, heat treatment for curing reaction of the epoxy resin or the phenol resin is performed at 130 to 200 ° C. for 15 minutes.
Do ~ 60 minutes.

Through holes and via holes are drilled at predetermined positions of the insulating resin layer thus formed on the inner layer circuit board by a drill, a laser or the like. Then, the surface of the insulating resin layer is treated with a roughening agent to form fine irregularities. At this time, if necessary, before the roughening treatment, physical polishing with a buff may be performed to stabilize the adhesiveness. The surface roughening treatment can be carried out by means such as immersing the substrate on which the insulating resin layer is formed in a solution such as an oxidizing agent or spraying a solution such as an oxidizing agent. Specific examples of the roughening agent include dichromate, permanganate, ozone, oxidizers such as hydrogen peroxide / sulfuric acid and nitric acid, and N.
Organic solvents such as -methyl-2-pyrrolidone, N, N-dimethylformamide and methoxypropanol, alkaline aqueous solutions such as caustic soda and caustic potash, acidic aqueous solutions such as sulfuric acid and hydrochloric acid, and various plasma treatments can be used. Also, these treatments may be used in combination.

Next, a conductor layer is formed by dry plating such as vapor deposition, sputtering, ion plating, or wet plating such as electroless plating and electrolytic plating. At this time, a plating resist having a pattern opposite to that of the conductor layer may be formed on the insulating resin layer, and the conductor layer may be formed only by electroless plating. After the conductor layer is formed in this way, the thermosetting resin is cured by annealing, so that the peel strength of the conductor layer can be further improved. Next, a dry film / plating resist is formed on the conductor layer as required, and a necessary conductor pattern is formed by etching. Furthermore, by repeating these steps several times as needed, a multilayer printed wiring board having a desired number of layers can be obtained.

Next, an example of a method for producing a multilayer printed wiring board by the build-up method using the resin composition of the present invention will be described with reference to FIG. First, the outer layer conductor pattern 8 is formed on both sides of the laminated substrate A in which the inner layer conductor pattern 3 and the resin insulating layer 4 are previously formed on both sides of the insulating substrate 1, and the screen printing method, the spray coating method, and the curtain coating are formed on the outer layer conductor pattern 8. After the resin composition of the present invention is applied by an appropriate method such as a method, the resin insulating layer 9 is formed by heating and curing. Next, a through hole 21 is formed so as to penetrate the resin insulating layer 9 and the laminated substrate A. The through hole 21 can be formed by a suitable means such as a drill, a die punch, or a laser beam. After that, each of the resin insulation layers 9 is roughened by using the above-mentioned roughening agent. For example, when an oxidizing agent is used as the roughening agent, the resin insulating layer 9
Is swelled with an organic solvent, and then roughened with an oxidizing agent. By this roughening treatment, an uneven surface structure can be easily formed on the surface of the resin insulating layer 9 and the through hole 21.

Next, a conductor layer is formed on the surface of the resin insulating layer 9 by electroless plating, electrolytic plating, a combination of electroless plating and electrolytic plating, or the like. At this time, the conductor layer covers not only the surface of the resin insulating layer 9 but also the entire surface inside the through hole 21 and the blind hole. Then, according to a conventional method, a predetermined circuit pattern is formed on the conductor layer on the surface of the resin insulating layer 9, and the outermost layer conductor pattern 10 is formed on both sides as shown in FIG.
To form. At this time, as described above, the through hole 21
A plating layer is also formed on the inner surface of the multilayer printed wiring board so that the connection portion 22 of the outermost layer conductor pattern 10 and the connection portion 3a of the inner layer conductor pattern 3 are electrically connected. , Through hole 20
Is formed. Further, when manufacturing a multilayer printed wiring board, the resin insulating layers and the conductor layers may be further alternately built up.

In the above build-up, an example in which the resin insulating layer and the conductor layer are formed on the laminated substrate has been described, but the present invention is also applicable to the case where a single-sided substrate or a double-sided substrate is used instead of the laminated substrate. It goes without saying that it can be applied. Further, the multilayer printed wiring board is provided with blind via holes for electrically connecting the connection portions of the respective conductor layers, and these blind via holes have substantially the same structure as the through hole 20 and each connection portion. Although the electrical connection between them is intended, the illustration thereof is omitted. Such blind via holes are
It can be opened by a conventionally known ordinary method such as laser light and sand blast, and is not limited to a specific method.

Although one embodiment of the method for producing a multilayer printed wiring board using the resin composition of the present invention has been described above, the method of the present invention is not limited to the above-mentioned production method, and the object of the present invention is not limited to this. Various modifications are possible as long as the above can be achieved. Further, the resin composition of the present invention can be prepared and used in the form of a dry film in advance, or can be prepared and used as a prepreg for press working. For example, it is possible to prepare a prepreg by impregnating a sheet-like base material composed of glass fiber, polyester fiber, aramid fiber or the like, and also on one side or both sides of this prepreg or a laminated plate which is a plurality of heat and pressure-molded articles thereof. It is also possible to produce a metal foil-clad laminate which is obtained by integrating metal foils such as copper foil.

[0027]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to the following Examples. still,
In the following, "part" means "part by mass" unless otherwise specified.

Synthesis Example 1 (Synthesis of a phenoxyphosphazene compound having a crosslinked structure with a p-phenylene group) Phenol 103.5 parts (1.1 mol), sodium hydroxide 44.0 parts (1.1 mol), water 50 A toluene solution of sodium phenolate was prepared by heating and refluxing a mixture of 1 part and 500 ml of toluene and removing only water out of the system. In parallel with the reaction, 16.5 parts (0.15 mol) of hydroquinone, 94.1 parts (1.0 mol) of phenol and 31.1 parts (1.3 mol of lithium hydroxide) were placed in a 2-liter four-necked flask. ), 52 parts of water and 600 ml of torun were charged, heated and refluxed, and only water was removed to the outside of the system to prepare a toluene solution of lithium salt of hydroquinone and phenol. In this toluene solution, dichlorophosphazene oligomer (trimer 62%, tetramer 12%, pentamer and hexamer 11%, heptamer 3%, octamer or more 12%) 1. 0 unit mole (115.9
580 parts of a 20% chlorobenzene solution containing 1 part) was added dropwise with stirring at 30 ° C. or lower, and then the mixture was reacted with stirring at 110 ° C. for 3 hours. Next, the toluene solution of sodium phenolate prepared above was added under stirring, and then the reaction was continued at 110 ° C. for 4 hours. After completion of the reaction, the reaction mixture was washed 3 times with 1.0 liter of 3% aqueous sodium hydroxide solution, then
After washing with 1.0 liter of water three times, the organic layer was concentrated under reduced pressure. The obtained product was heated and vacuum dried at 80 ° C. for 3 hours at 3 mmHg or less to obtain 211 parts of a slightly yellow powder of crosslinked phenoxyphosphazene. The obtained crosslinked phenoxyphosphazene had a composition of 0.04% of hydrolyzed chlorine, a weight average molecular weight (Mw) of 1100, a phosphorus content and a CHN elemental analysis value of approximately [N = P (-O-p-Ph-O).
-) _0.15 (-O-Ph) _1.7 ] was found.

Synthesis Example 2 (Synthesis of a phenoxyphosphazene compound having a crosslinked structure with a 2,2-bis (p-oxyphenyl) isopropylidene group) 65.9 parts (0.7 mol) of phenol and 50 parts of toluene
0 ml was placed in a 1-liter four-necked flask and stirred,
While keeping the internal liquid temperature at 25 ° C, sodium metal 0.6
14.9 parts of 5 gram atom was finely cut and added. After completion of the addition, stirring was continued for 8 hours at 77 to 113 ° C. until the metallic sodium completely disappeared to prepare a sodium phenolate solution. In parallel with the above reaction, bisphenol A
57.1 parts (0.25 mol), phenol 103.5 parts (1.1 mol) and tetrahydrofuran (THF) 80
Add 0 ml to a 3 liter four-necked flask, and stir,
While keeping the internal liquid temperature at 25 ° C. or lower, metallic lithium 1.
11.1 parts of 6 gram atom was finely cut and added. After completion of the addition, stirring was continued for 8 hours at 61 to 68 ° C. until the metallic lithium completely disappeared. Dichlorophosphazene oligomer (concentration: 37%, 313 parts chlorobenzene solution, composition: 75% trimer, tetramer 17)
%, 5 and 6-mer 6%, 7-mer 1%, 8-mer or more 1% mixture) 1.0 unit mol (115.9 parts) was stirred and the internal liquid temperature was kept at 20 ° C. or lower. While maintaining the temperature, the solution was dropped over 1 hour and then reacted at 80 ° C. for 2 hours. Then, with stirring, while maintaining the internal liquid temperature at 20 ° C., a separately prepared sodium phenolate solution was added over 1 hour, and then 8
The reaction was carried out at 0 ° C for 5 hours. After completion of the reaction, the reaction mixture was concentrated to remove THF, and 1 liter of toluene was newly added. This toluene solution was mixed with 1 liter of 2% NaOH 3 times.
After washing twice, then washing three times with 1.0 liter of water,
The organic layer was concentrated under reduced pressure. The obtained product at 80 ° C.,
It was heated and vacuum-dried at 3 mmHg or less for 11 hours to obtain 229 parts of a white powder of crosslinked phenoxyphosphazene. The obtained crosslinked phenoxyphosphazene had a hydrolyzed chlorine content of 0.07.
%, Weight average molecular weight (Mw) 1130, phosphorus content and composition based on CHN elemental analysis values are [N = P (-O-Ph-C
(CH ₃₎ was _{2 -Ph-O-) 0.25 (-O} -Ph) 1.50].

Example 1 Phenolic novolac type epoxy resin 50.0 parts (Japan Epoxy Resin Co., Ltd. Epicoat 154) Biphenol type epoxy resin 50.0 parts (Japan Epoxy Resin Co., Ltd. YX-4000) Phenol novolac resin 61 1 part (MF-1 manufactured by Meiwa Kasei Co., Ltd., -OH equivalent: 107) Epoxy curing agent 0.5 part (Curazole 2MZ-A manufactured by Shikoku Kasei Co., Ltd.) Light calcium carbonate 50.0 parts Crosslinked phenoxyphosphazene 20.0 parts of resin powder (obtained in Synthesis Example 1, average particle size: 2 μm) A varnish made of the above raw materials was prepared, and the varnish was formed into a glass epoxy having a first circuit layer formed by a subtractive method. After coating the copper-clad laminate by screen coating, dry at 110 ° C for 20 minutes, then at 150 ° C. Thirty
It was heat-cured for a minute to prepare a substrate having an insulating resin layer with a thickness of 60 μm formed. The above-mentioned substrate was immersed in a swelling solution (manufactured by Shipley Co., Ltd.) for 10 minutes at 80 ° C., and washed with permanganate-based roughening solution (manufactured by Shipley Co., Ltd.) at 80 ° C. for 2 minutes.
After dipping for 0 minutes, it was washed with water and further dipped in a reducing solution (manufactured by Shipley Co., Ltd.) at 50 ° C. for 5 minutes and then washed with water to roughen the surface of the insulating resin layer. This roughened substrate was immersed in an electroless copper plating solution (manufactured by Shipley Co., Ltd.) at 35 ° C. for 10 minutes to perform electroless copper plating. After washing with water, 100 ℃
After annealing for 30 minutes, the thickness of the plating layer was 0.3 μm. Subsequently, an electrolytic copper plating solution (manufactured by Shipley Co., Ltd.) using a copper sulfate solution was used to make the
An electrolytic copper plating layer having a thickness of 20 μm was formed, and after-baking was performed at 150 ° C. for 60 minutes.

Example 2 A substrate having a copper plating layer was prepared in the same manner as in Example 1 except that the resin composition containing no light calcium carbonate was used.

Example 3 Methyl ethyl ketone was added to the varnish of Example 2 to give a concentration of 5
It was adjusted to be 5 wt%. Next, thickness 0.2mm
Glass woven fabric (manufactured by Nitto Boseki Co., Ltd.) with a varnish solid content of 4
Impregnated so as to be 4.4 wt%, 130-150 ℃
And dried to prepare a prepreg. Six sheets of this prepreg were stacked, sandwiched between polypropylene films having a thickness of 25 μm, and heated and pressed at 170 ° C. for 120 minutes to prepare a laminated plate. Using this laminated plate, a substrate on which a copper plating layer was formed was prepared in the same manner as in Example 1.

Example 4 Bisphenol A type epoxy resin 30.0 parts (YP-50 manufactured by Tohto Kasei Co., Ltd.) Phenol novolac type epoxy resin 30.0 parts (Epicoat 152 manufactured by Japan Epoxy Resin Co., Ltd.) Biphenol type epoxy resin 30.0 parts (YX-4000 manufactured by Japan Epoxy Resins Co., Ltd.) 36.7 parts of phenol novolac resin (HF-1 manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent: 107) Epoxy curing agent 0.5 parts (Shikoku Chemicals) CUREZOL 2MZ-A manufactured by Co., Ltd. Light calcium carbonate 50.0 parts Crosslinked phenoxyphosphazene resin powder 20.0 parts (obtained in Synthesis Example 2, average particle size: 1 μm) A varnish using the above raw materials, It is applied to a PET film with a thickness of 38 μm so that the dry thickness is 60 μm, and an adhesive film is obtained. The same substrate as in Example 1 was laminated on a glass-epoxy copper clad laminate at 70 ° C. with a vacuum laminator, and a copper plating layer was further formed on the substrate.

Comparative Example 1 In Example 1, the amount of light calcium carbonate added was 70%.
As a part, a substrate on which a copper plating layer was formed was prepared in the same manner as in Example 1 except that a resin composition containing no crosslinked phenoxyphosphazene resin powder was used.

Comparative Example 2 Instead of the light calcium carbonate and the crosslinked phenoxyphosphazene resin powder in Example 1, polybutazine rubber (Eporide PB3600 manufactured by Daicel Chemical Industries Ltd.) was used.
Was prepared in the same manner as in Example 1 except that the amount was 20.0 parts.

Comparative Example 3 In Comparative Example 2, light calcium carbonate of 70.
A substrate on which a copper plating layer was formed was prepared in the same manner as in Comparative Example 2 except that 0 part was added.

The compositions of the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 1.

[Table 1]

Test Example Using the substrate on which the copper plating layer formed in Examples 1 to 4 and Comparative Examples 1 to 3 was formed, observation of roughened shape, peel strength, heat cycle test (heat shock resistance), adhesion Tests such as heat resistance test (PCT resistance), insulation resistance, flexibility test and heat resistance test, and the glass transition point (Tg) of the cured product.
Was measured. The results are shown in Table 2.

[Table 2] The properties shown in Table 2 were measured and evaluated as follows.

Roughness: The surface of the insulating resin layer of the produced substrate was observed with an electron microscope at a magnification of 3000 and judged by comparing the eluted portions. The judgment criteria are as follows. ⊚: The unevenness is uniform throughout, and the diameter and depth of the recess are good. ○: The unevenness is obtained, but the diameter and depth of the recess are small.

Peel strength: Measured according to JIS-C6481.

Thermal shock resistance: -5 for the prepared substrate
A cycle of holding at 5 ° C. for 30 minutes and then at + 125 ° C. for 30 minutes was repeated 1000 times, and the degree of crack occurrence in the insulating resin layer was inspected. The judgment criteria are as follows. ◯: No abnormality such as cracks. X: A crack occurred.

PCT resistance: The prepared substrate is kept at 121 ° C.
R. H. After standing still at 100% and 2 atom for 500 hours, the state of peeling of the insulating resin layer was inspected. The judgment criteria are as follows. ○: No abnormality. X: Blistering and peeling occurred.

Insulation resistance: L (line) / S (space)
= 50/50 and 135 ° C, 85% R.S.
H. The resistance value was measured under the measurement condition of DC500V for 1 minute on the test substrate after applying 300V for 15 hours.

Flexibility: Measured by the Erichsen test and judged according to the following criteria. Good: 5 mm or more Poor: 5 mm or less

Solder heat resistance: According to the test method described in JIS C-6481, an operation of applying a rosin flux to the insulating resin layer of the substrate and immersing it in a solder bath at 230 ° C. for 10 seconds is repeated 3 times. The state of the insulating resin layer was evaluated according to the following criteria. Good: No abnormality. Bad: Blisters and peeling occurred.

Glass transition point (Tg): JIS-K71
The measurement was performed according to the regulations of 21.

[0047]

As described above, the resin composition for forming a roughened surface of the present invention, as a filler soluble in the roughening agent,
Since it contains crosslinked phenoxyphosphazene resin powder with a specific structure, it can form a good roughened surface by roughening treatment, and has excellent properties such as adhesion, thermal shock resistance, PCT resistance, and flexural modulus. It is possible to provide a highly reliable printed circuit board which can form an interlayer resin insulation layer having excellent properties and can respond to higher miniaturization and higher density of conductor circuits. Further, the crosslinked phenoxyphosphazene resin powder imparts a sufficient flame retarding effect to the resin composition despite being halogen-free and, in addition, imparts the above-mentioned excellent properties to the resin composition of the present invention. By using it, thermal shock resistance, flexibility, heat resistance, moisture resistance, electrical characteristics,
It is possible to provide a prepreg for a printed wiring board having excellent flame retardancy and the like.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view showing a schematic configuration of a multilayer printed wiring board produced by a build-up method using a resin composition of the present invention.

[Explanation of symbols]

1 Insulation board 3 Inner layer conductor pattern 4,9 Resin insulation layer 8 Outer layer conductor pattern 10 Outermost layer conductor pattern 20 through holes A laminated substrate

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/46 H05K 3/46 T (72) Inventor Naoki Yoneda 388, Okura, Okura, Arakiyama-cho, Hiki-gun, Saitama Prefecture Yo Ink Manufacturing Co., Ltd. Arashiyama Plant (72) Inventor Yuji Tada 463, Kagasuno, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. Tokushima Laboratory Co., Ltd. F Term (reference) 4F072 AA07 AB09 AB28 AD13 AD15 AD16 AD26 AD27 AD28 AF16 AK05 AL13 4J002 BD123 CC041 CC061 CD021 CD041 CD051 CD061 CL003 CP033 CQ012 DE186 DE236 DG046 DJ016 DJ036 DJ046 DJ056 FD013 GF00 GQ00 4J030 CA02 CB43 CB48 CD11 CE02 CG21 5E346 AA12 CC09 HH08 HH13 HH18

Claims (4)

[Claims] 1. A resin composition containing an epoxy resin and / or a phenol resin as a main component of a matrix, which comprises a cyclic phenoxyphosphazene represented by the following general formula (1) and a linear phenoxy group represented by the following general formula (2). At least one phosphazene compound (a) selected from the group consisting of phosphazenes is an o-phenylene group, m-
Phenylene group, p-phenylene group and the following general formula (3)
A compound which is crosslinked by at least one kind of a crosslinkable group (b) selected from the group consisting of bisphenylene groups represented by the following formula, wherein the phenyl group of the phosphazene compound (a) is between two oxygen atoms eliminated. The phenyl group content is 50 to 99.9% based on the total number of all phenyl groups in the phosphazene compound (a), while having a structure in which the crosslinking group (b) is interposed, and is free in the molecule. A resin composition for forming a roughened surface, comprising the crosslinked phenoxyphosphazene resin powder having no hydroxyl group as described above as an organic filler. [Chemical 1] [In the formula, Ph represents a phenyl group, and X represents a group -N = P.
(OPh) ₃ or a group —N═P (═O) OPh,
Y is a group -P (= O) (OPh) or a group -P (OPh) _3.
The expressed, A is _{-C (CH 3) 2 -,} - SO 2 -, - S-
Or represents -O-, m is an integer of 3 to 25, n is an integer of 3 to 10,000, and a is 0 or 1. ] 2. The resin composition according to claim 1, which is in the form of a dry film. 3. In a multilayer printed wiring board in which an interlayer resin insulation layer is formed between conductor circuit layers, the interlayer resin insulation layer is formed by using the resin composition according to claim 1 and is roughened. A multilayer printed wiring board characterized by being processed. 4. A prepreg for a printed wiring board, which is obtained by impregnating a fibrous sheet-like base material with the resin composition according to claim 1.