JP2002201364A - Flame-retardant resin composition and build-up substrate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is free from a halogen, has flame retardancy, and exhibits alkali resistance. SOLUTION: This flame-retardant resin composition comprises a main resin component, a flame retardant, and a curing agent is characterized in that the flame retardant is (2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10- oxidediglycidyl ether or its polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition and a build-up substrate on which an insulating layer is formed using the flame-retardant resin composition.

[0002]

2. Description of the Related Art In recent years, thermosetting resins such as epoxy resins and polyimide resins have been widely used in the manufacture of electronic equipment parts. Various properties are generally required for thermosetting resin compositions used in electronic device parts depending on their functions and applications, and one such property is flame retardancy. Here, the term "flame retardancy" refers to the degree of difficulty in burning of the resin composition. From the viewpoint of fire safety, it can be said that flame retardancy is one of the important characteristics of the resin composition.

On the other hand, in recent years, along with demands for miniaturization, high performance, and low price of electronic devices, in addition to miniaturization of electronic circuits on printed circuit boards and high-density mounting of electronic components, printing 2. Description of the Related Art Multi-layer wiring adopting a build-up structure in a substrate is progressing. In a substrate having such a build-up structure, a thermosetting resin is employed for the insulating film. Here, the insulating film in the build-up substrate is a film formed between layers of an electronic circuit, and is formed over substantially the entire surface except for a portion (via hole) connecting the upper electronic circuit and the lower electronic circuit. Is what is done. Also from the viewpoint of fire safety, high flame retardancy is required for the resin composition used for such an insulating film.

As means for imparting flame retardancy to a resin composition, there are generally two modes.
One of them is to use a halide, and use a halogen-based resin such as vinyl chloride or fluorocarbon resin in combination with the resin material of the main component, or use a low molecular weight resin such as paraffin chloride or tetrachlorophthalic acid. Addition of a halogen compound imparts flame retardancy to the resin composition. However, such a resin composition containing a halide has a problem in that toxic substances such as hydrogen halide are generated during combustion.

[0005] The other uses a phosphoric acid compound, such as a phosphate ester such as triphenyl phosphate and cresyl diphenyl phosphate;
9,10-Dihydro-9-oxa-10-phosphaphenanthrene-1 disclosed in JP-A-122489.
Addition of 0-oxide or the like to the resin material as a main component imparts flame retardancy to the resin composition. According to the resin composition containing such a phosphoric acid compound, the problem of toxicity unlike the above-mentioned resin composition containing a halide does not occur.

[0006]

However, phosphate esters such as triphenyl phosphate and cresyl diphenyl phosphate do not form a covalent bond with the resin skeleton and exist as single molecules in the cured resin composition. . Therefore, when these are used as a flame retardant, these components bleed out from the resin body at a high temperature, and the breaking strength and the breaking elongation of the resin body decrease. Further, the plasticity of these components tends to lower the glass transition point of the resin composition. Furthermore, low-molecular-weight phosphate compounds also have the disadvantage of low resistance to alkalis and acids. Therefore, for example, when using a resin composition to which a phosphoric acid ester compound is added as an insulating film forming material of a build-up substrate, a desmear process in which an alkali solution or an acid solution is used in the manufacturing process of the build-up substrate, or roughening. During the process, phosphate ester compounds are decomposed and
The problem of elution occurs.

On the other hand, 9,10-dihydro-9-oxa-
Since 10-phosphaphenanthrene-10-oxide has some reactivity with an epoxy group, for example, when an epoxy resin is used as a main resin component, a part thereof is:
It can form a covalent bond with the resin skeleton and be incorporated into the resin skeleton. The phosphate compound incorporated in the resin skeleton does not cause the above-mentioned problems observed in low-molecular-weight phosphate esters. However, 9,10-dihydro-9-oxa-
The reactivity of 10-phosphaphenanthrene-10-oxide with epoxy resins is lower than common epoxy curing agents. Therefore, for example, when this flame retardant is used to improve the flame retardancy of the epoxy resin composition, the reaction between the epoxy resin and the epoxy curing agent precedes the reaction between the epoxy resin and the flame retardant. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-
The oxide remains in the composition as a monomolecular component. As a result, 9,10-dihydro-9-
Even with the use of oxa-10-phosphaphenanthrene-10-oxide, the same problems as those found in low molecular weight phosphate esters still occur due to the effects of unreacted components that are not incorporated into the resin skeleton.

The present invention has been conceived under such circumstances, and eliminates or reduces the problem of bleed-out, and has excellent resistance to alkali solutions and acid solutions.
Further, it is an object of the present invention to provide a flame-retardant resin composition having excellent breaking strength and breaking elongation of a cured product.

[0009]

In order to solve the above-mentioned problems, the present invention takes the following technical means. That is, the flame retardant resin composition provided by the present invention contains a main resin component, a flame retardant, and a curing agent, and the flame retardant is
(2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide diglycidyl ether or a polymer containing the same.

Here, (2,5-dihydroxyphenyl)
-10H-9-oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether is (2,5
-Dihydroxyphenyl) -10H-9-oxa-10
Phosphaphenanthrene-10-oxide has 2
A diglycidyl adduct to two phenolic hydroxyl groups, the structure of which is shown in Formula 1 below. When the present ether is used as a polymer, a homopolymer of the present ether can be used, or a copolymer with another monomer unit can be used. As for the polymer, the structure of the homopolymer is shown in the following formula 2 as an example.

[0011]

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[0012]

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As shown in the above equation 1, (2,5
-Dihydroxyphenyl) -10H-9-oxa-10
-Phosphaphenanthrene-10-oxide diglycidyl ether is a so-called bifunctional glycidyl ether type epoxy resin having two epoxy rings in one molecule. Although the terminal structure of the polymer represented by the above formula 2 is omitted, like the monomer represented by the above formula 1, each terminal structure has one epoxy ring. That is, the polymer is also a bifunctional glycidyl ether type epoxy resin. Therefore, if these are added to the main resin component of the resin composition, after the polymerization reaction is started by the initiator or the like, they exhibit the same degree of reactivity as other ordinary epoxy resins. Promotes a polymerization reaction or a crosslinking reaction. As a result, almost all of the (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether or the polymer containing the same added to the resin composition is: It will be incorporated into the resin skeleton of the main resin component as a flame retardant.

The structure of (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether used as a flame retardant in the present invention or a polymer containing the same is as follows:
Even after these are incorporated into the resin skeleton of the main resin component, high flame retardancy can be exhibited.

Further, since almost all of the flame retardant of the present invention is incorporated into the resin skeleton of the main resin component, the occurrence of bleed-out, which is observed when a conventional phosphate compound is used as the flame retardant, Problems such as a decrease in breaking strength and breaking elongation and a decrease in alkali resistance can be eliminated or reduced.

When the (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether polymer is used as the flame retardant, the following advantages can be further obtained. .
Since a certain amount of crosslinked chains is secured, the mechanical properties of the cured product of the resin composition such as breaking strength and elongation at break are improved, and the cured product of the resin composition is adjusted by adjusting the length of the crosslinked chains. Breaking strength and elongation at break can be adjusted appropriately,
In addition, since the polymer is a polymer, the phosphorus concentration in the resin composition can be easily increased, so that the flame retardancy of the resin composition is easily improved.

From the viewpoint of satisfactorily exhibiting the function as a flame retardant, a flame retardant, that is, (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether or a mixture containing the same. The amount of the polymer to be added is preferably in a range such that 0.5 to 5 parts by weight of phosphorus is contained with respect to 100 parts by weight of the resin composition according to the present invention.

When (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether polymer is used as the flame retardant, the degree of polymerization is considered from the viewpoint of breaking strength. Two
It is preferred to use 20 oligomers. To prepare the polymer, for example, (2,5-dihydroxyphenyl)
-10H-9-oxa-10-phosphaphenanthrene-10-oxide diglycidyl ether and a polymerization initiator may be dissolved in an organic solvent, and this may be heated and stirred at 90 to 140 ° C. Such organic solvents include, for example, ethylene glycol monoethers, acetates,
Cyclohexane can be used. As the polymerization initiator, tertiary amines, imidazoles, and Lewis acids can be used.

As the tertiary amine, for example, 2,4,6-
Tris (dimethylaminomethyl) phenol, benzyldimethylamine and the like.

Examples of the imidazoles include 2-methyl-4-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1
-Cyanoethyl-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole and the like can be mentioned.

Examples of the Lewis acid include monoethylamine boron trifluoride adduct, piperazine boron trifluoride adduct, and the like.

The polymerization initiators exemplified may be used alone or in combination of two or more.
Tris (dimethylaminomethyl) phenol is preferably used.

As the main resin component of the flame-retardant resin composition according to the present invention, any of a thermosetting resin and a thermoplastic resin can be used. An epoxy resin which is a thermosetting resin is preferably used. As the epoxy resin, alicyclic type, glycidyl ether type, glycidyl ester type,
And glycidylamine type can be used.

Examples of the alicyclic epoxy resin include alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxycarboxylate, and vinylcyclohexene dioxide.

Examples of the glycidyl ether type epoxy resin include bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F type,
Examples include bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenol novolak type, cresol novolak type, DPP novolak type, tris-hydroxyphenylmethane type, and tetraphenylolethane type.

Examples of the glycidyl ester type epoxy resin include those produced by condensing a carboxylic acid such as a phthalic acid derivative or a synthetic fatty acid with epichlorohydrin (ECH).

As the glycidylamine type epoxy resin, for example, tetraglycidyldiaminodiphenylmethane (TGDDM), triglycidyldiisocyanate (T
GIC), hydantoin type, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRA
DD), aminophenol type, aniline type, and toluidine type.

The exemplified epoxy resins may be used alone or in combination of two or more. Particularly, three or more epoxy resins in one molecule such as a phenol novolak type epoxy resin and a cresol novolak type epoxy resin may be used. A polyfunctional epoxy resin having the following epoxy group is preferably used. From the viewpoint of improving heat resistance, the main resin component preferably contains a phenol novolak epoxy resin or a cresol novolak epoxy resin. Further, from the viewpoint of lowering the modulus of elasticity, for example, a rubber-modified epoxy as shown in the following formula 3 may be included.

[0029]

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The curing agent in the flame-retardant resin composition of the present invention is appropriately selected in consideration of the type of the main resin component, the curing temperature, and the like. For example, a polyphenol-based curing agent, an acid anhydride, an amine-based compound, Imidazoles and cationic polymerization catalysts can be used. In addition, even when a thermoplastic resin is used as the main resin component, the thermosetting resin (2,5-dihydroxyphenyl) -10H-9-
In order to cure oxa-10-phosphaphenanthrene-10-oxide diglycidyl ether or a polymer containing the same, a curing agent is required in the resin composition of the present invention.

Examples of the polyphenol-based curing agent include novolak-type phenolic resins, novolak-type p-xylyl-modified phenolic resins, cresol novolaks, phenolic polymers, and resol-type phenolic resins.

Examples of the acid anhydride include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride,
Methylhymic anhydride, hexahydrophthalic anhydride,
Examples include trialkyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, and nadic anhydride.

Examples of the amine compound include aliphatic polyamine compounds such as triethylenetetraamine, m-xylenediamine, bis (4-amino-3-methylcyclohexyl) methane, m-phenylenediamine, 4,4'-
Examples include aromatic amine compounds such as diaminodiphenylene sulfone, and tertiary amine compounds such as benzyldimethylamine and dimethylaminomethylphenol.

Examples of imidazoles include 2-methyl-4-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1
-Cyanoethyl-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole and the like can be mentioned.

Examples of the cationic polymerization catalyst include benzylsulfonium salts, benzylammonium salts, hydrazinium salts, aryldiazonium salts and the like.

The above-mentioned curing agents may be used alone or in combination of two or more. However, from the viewpoint of high heat resistance after curing, novolak-type phenol resins and novolak-type p-xylyl-modified phenol resins are used. It is preferably used. With respect to the amount of the curing agent to be added, an appropriate amount of the polyphenol, the acid anhydride, and the amine compound is used so as to be suitable for a reactive group such as an epoxy group of the main resin component. Further, the imidazoles and the cationic polymerization catalyst can homopolymerize the main resin component. When only the imidazoles are used, the addition amount is 0.5 to 5 parts by weight based on 100 parts by weight of the main resin component. When only the cationic polymerization catalyst is used, the addition amount is in the range of 0.1 to 1 part by weight based on 100 parts by weight of the main resin component.

When the reactivity of the curing agent itself is poor in the resin composition of the present invention, a curing accelerator may be further added in addition to the curing agent in order to increase the reactivity of the curing agent. . The addition amount of the curing accelerator is, for example, in the range of 0.1 to 1 part by weight with respect to 100 parts by weight of the main resin component in consideration of the viscosity and the like of the resin composition as a whole while ensuring the purpose of addition. It is said.

The curing accelerator used in the present invention includes, for example, imidazoles and organic phosphines. As mentioned above, imidazoles themselves can also function as a curing agent. Therefore, if the amount of the curing accelerator added is large, a situation may occur in which the addition of the curing accelerator can be the simultaneous addition of the curing agent. In such a case, as long as the addition of the curing accelerator contributes to the improvement of the reactivity of another type of curing agent, it is to be considered as a curing accelerator.

Accordingly, examples of imidazoles include 2-methyl-4-ethylimidazole and 1-methyl-2-ethylimidazole listed in the description of the curing agent.

On the other hand, the organic phosphines include, for example, triphenylphosphine, trimetatrilephosphine,
Tetraphenylphosphonium tetraphenylborate,
Alternatively, triphenylphosphine triphenylborane and the like can be mentioned.

As the curing accelerator, in addition to imidazoles and organic phosphines, diazabicycloundecene, diazabicycloundecene toluenesulfonate, diazabicycloundecene octylate and the like can be used. it can. Further, the curing accelerator exemplified above,
They may be used alone or in combination.

An inorganic filler may be added to the resin composition of the present invention from various viewpoints such as reducing the coefficient of thermal expansion after curing of the resin composition of the present invention and increasing the rigidity. In order to sufficiently obtain such effects, the amount of the inorganic filler is preferably in the range of 5 to 50 parts by weight based on 100 parts by weight of the main resin component. The average particle size of the inorganic filler is preferably 5 μm or less, particularly preferably 1 μm or less. Here, examples of the inorganic filler used in the resin composition of the present invention include aluminum hydroxide, magnesium hydroxide, colloidal silica, Aerosil, and nitride (such as aluminum nitride and boron nitride).

In the resin composition of the present invention, a coupling agent may be further added. The coupling agent has a function of increasing the dispersibility of the inorganic filler in a non-cured state of the resin composition and lowering the viscosity of the resin composition. In addition, since the coupling agent has a function of increasing the affinity between the organic material and the inorganic material, if a coupling agent is added to the resin composition, in the cured state of the resin composition, an inorganic filler and Compatibility with main resin components such as epoxy resin is enhanced.

In order to sufficiently obtain such effects, the amount of the coupling agent is preferably in the range of 0.05 to 1 part by weight based on 100 parts by weight of the main resin component. The coupling agent may be added directly to the resin component to act on the inorganic filler, or the inorganic filler before being added to the resin component may be subjected to a surface treatment in advance. Here, as the coupling agent used in the resin composition of the present invention, a silane coupling agent and a titanate coupling agent can be used.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, or γ-mercaptopropyl Trimethoxysilane.

Examples of titanate-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate,
Isopropyl tris (dioctyl pyrophosphate)
Titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldi Methacryl isostearyl titanate, isopropyl isostearyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate,
Isopropyl tricumylphenyl titanate or isopropyl tri (N-aminoethyl-aminoethyl)
Titanate and the like can be mentioned.

The exemplified silane coupling agents and titanate coupling agents may be used alone or in combination of two or more.

Further, a coloring pigment such as phthalocyanine, an antifoaming agent composed of silicone and a fluorine compound, a leveling agent, an antioxidant, and the like may be added to the resin composition of the present invention.

Examples of the solvent for appropriately coexisting the above components include organic solvents such as ketones, esters, toluene, xylene, ethylene glycol monoethers, acetates and cyclohexanone. However, when a liquid component is used as the composition of the present invention before the curing, a solvent may not be used in some cases.

[0050]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for forming a multilayer circuit board having a build-up structure using the resin composition of the present invention will be described below. However, the following description exemplifies a mode of use of the resin composition of the present invention, and should not be limited to this.

First, a varnish of the resin composition of the present invention is applied on a printed circuit board with a thickness of 30 μm to form a film. For application and film formation, methods such as screen printing, curtain coating, roll coating, spin coating, and a doctor blade method can be adopted. Next, the insulating film thus formed on the substrate is heated at a temperature of 100 to 200 ° C. for 30 to 1 hour.
Heat for 20 minutes. This heat treatment is performed mainly for the purpose of improving the heat resistance of the insulating film. Next, a laser beam having an appropriate exposure amount is applied to a predetermined via hole forming portion in the film, that is, a portion for forming a via hole for connection with an upper electronic circuit to be formed in a later step. Thereby, a predetermined number of via holes are formed in the insulating film. As a laser beam, a gaseous carbonate laser, an excimer laser, a YAG laser, or the like can be used.

Next, an alkaline solution such as an aqueous solution of permanganate is applied to etch the surface of the film.
Thereby, a plurality of small holes are formed on the film surface including the via hole wall surface, and the film surface is roughened. At this time, a desmear process for removing smear generated at the time of forming a via hole is performed simultaneously. Next, a conductor pattern is formed by a subtractive method, a semi-additive method, or the like. In the subtractive method, a conductor pattern is formed by performing electroless plating and plating on the film surface and then performing patterning. In the semi-additive method, a conductor pattern is formed by performing patterning after applying electroless plating and a resist, and then stripping the resist after performing the electrolytic plating.

On the thus formed conductor pattern, the steps from the application of the varnish of the resin composition to the formation of the conductor pattern are repeated a predetermined number of times, whereby a multilayer circuit board comprising an insulating film and a conductor pattern is formed. Can be produced.

Next, examples of the present invention will be described together with comparative examples, but it goes without saying that the technical idea of the present invention is not limited to these examples.

Example 1 (Preparation of Flame Retardant Solution) (2,5)
-Dihydroxyphenyl) -10H-9-oxa-10
-Phosphaphenanthrene-10-oxide diglycidyl ether in an amount of 30 parts by weight, and 2,4,4 as a polymerization initiator
6-tris (dimethylaminomethyl) phenol 0.2
Parts by weight, and dissolved in 30 parts by weight of propylene glycol monomethyl ether as a solvent, while stirring this,
Heated at 80 ° C. for 4 hours. Then, it was left at 4 ° C. for 1 hour. It is contained in the flame retardant solution thus prepared (2,5
-Dihydroxyphenyl) -10H-9-oxa-10
The number average molecular weight of the polymer of -phosphaphenanthrene-10-oxide diglycidyl ether was measured by gel permeation chromatography (GPC), and compared with the value of the average molecular weight measured before the reaction, thereby obtaining the polymer of the present invention. The average degree of polymerization was found to be about 5.

(Preparation of Flame Retardant Resin Composition) To 60.2 parts by weight of the flame retardant solution prepared as described above, 15 parts by weight of methyl ethyl ketone (MEK) was added and stirred. Cresol novolak epoxy (trade name: EOCN1020, manufactured by Nippon Kayaku) 40 as an ingredient
30 parts by weight of novolak-type phenol (trade name: PSM-4300, manufactured by Gunei Chemical) as a curing agent and novolak-type p-xylyl-modified phenol (trade name:
Xyloc XLC-LL, manufactured by Mitsui Chemicals) 40 parts by weight, 2-methyl-4-ethyl-imidazole (manufactured by Shikoku Chemicals) 1 part by weight as a curing accelerator, aluminum hydroxide (trade name: H-32, Showa) as an inorganic filler A flame-retardant resin composition was prepared by adding and mixing 15 parts by weight (made by Denko) and 5 parts by weight of silica powder (trade name: AEROSIL200, manufactured by Nippon Aerosil Co., Ltd.).

(Measurement of peel strength) The flame-retardant resin composition prepared as described above was applied to a copper foil provided on a glass epoxy substrate by a doctor blade method.
The coating was applied at a thickness of 0 μm, and this was first dried by heating at 120 ° C. for 20 minutes, then dried by heating at 170 ° C. for 60 minutes, and then allowed to cool to room temperature to form a resin film. The resin film was thus formed 6
The substrates are pretreated by immersion in a swelling liquid (trade name: MLB211, manufactured by Shipley) at 60 ° C. for 10 minutes, and then by a roughening liquid (trade name: MLB213, manufactured by Shipley) at 70 ° C.
Oxidation treatment by immersion for 0 minutes, and then a neutralizing solution (trade name: M
(LB216-2, manufactured by Shipley) at 60 ° C. for 10 minutes for neutralization. Subsequently, the insulating film is subjected to electroless copper plating and electrolytic copper plating, and a 25 μm
A conductor layer having a thickness of With respect to the joint between the resin film thus formed and the conductor layer, the peel strength was measured by a 90-degree bending tensile tester.

Table 1 shows the results. The average peel strength at the joint surface between the resin film and the conductor layer by the resin composition of this example was 0.90 kg / cm.

(Measurement of Rupture Strength and Rupture Elongation) The flame-retardant resin composition prepared as described above was applied on an aluminum plate by a doctor blade method, and this was first heated to 120 ° C.
For 20 minutes, and then cured by heating and drying at 170 ° C. for 60 minutes. The cured resin film was peeled off to form a film having a thickness of 70 μm. The tensile strength and elongation at break of the six films thus prepared were measured by a tensile break tester (RSA-II, manufactured by Rheometrics).

Table 1 shows the results. The breaking strength of the film having a thickness of 70 μm was 70 MPa on average, and the elongation at break was 12% on average.

(Extraction of Phosphorus Compound) A film was prepared by the same method as that used in the measurement of the breaking strength and the breaking elongation described above, and this film was washed with water exhibiting almost the same alkalinity as the electroless plating solution. Sodium oxide aqueous solution (concentration: 5
g / l) 500 ml. After immersion for 24 hours, the concentration of the phosphorus-containing compound extracted into the alkaline aqueous solution was analyzed by plasma emission analysis.

Table 1 shows the results. The concentration of the phosphorus compound in the aqueous alkali solution was less than 10 μg / g, indicating that the amount of extraction was small.

(Flame Retardancy Test) A 0.4 mm thick halogen-free core substrate (trade name: TLC-) obtained by subjecting the flame retardant resin composition prepared as described above to an etching treatment on a copper foil.
W-555, manufactured by Toshiba Corporation)
For 20 minutes, and then cured by heating and drying at 170 ° C. for 60 minutes. The cured resin composition was allowed to cool to form a resin film having a thickness of 70 μm. Two substrates (125 mm x 13 mm) on which a resin film is formed in this way
Was evaluated for flame retardancy according to the UL94 flame retardancy test.

Table 1 shows the results. The flame retardancy of the resin film formed as described above was equivalent to V0, and it was found that the resin composition of this example had high flame retardancy.

[0065]

[Table 1]

Example 2 (Preparation of Flame Retardant Resin Composition) A flame retardant solution was prepared in the same manner as in Example 1, and 15 parts by weight of methyl ethyl ketone (MEK) was added to 60.2 parts by weight of the flame retardant solution. After adding and stirring the mixture, phenyl epoxy (formula 4 below) (trade name: NC-3000P,
40 parts by weight of Nippon Kayaku Co., Ltd. and 10 parts by weight of trifunctional epoxy (formula 5 below) (trade name: VG3101, manufactured by Mitsui Chemicals), and a novolac phenol (trade name: P) as a curing agent
30 parts by weight of SM-4300, manufactured by Gunei Chemical) and 30 parts by weight of novolak-type p-xylyl-modified phenol novolak (trade name: Xyloc XLC-LL, manufactured by Mitsui Chemicals), 2-methyl-4-ethyl- as a curing accelerator 1 part by weight of imidazole (manufactured by Shikoku Chemicals), aluminum hydroxide (trade name: H-32, manufactured by Showa Denko) 1 as an inorganic filler
5 parts by weight and silica powder (trade name: AEROSIL20)
0, manufactured by Nippon Aerosil Co., Ltd.) to prepare a flame-retardant resin composition.

[0067]

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[0068]

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(Measurement of Peel Strength) Using the resin composition prepared as described above, six glass epoxy substrates were coated on a copper foil provided on a substrate in the same manner as in Example 1. After a resin film was formed and immersed sequentially in a swelling solution, a roughening solution, and a neutralizing solution, electroless copper plating and electrolytic copper plating were performed to form a conductor layer having a thickness of 25 μm on the resin film. With respect to the joint between the resin film thus formed and the conductor layer, the peel strength was measured by a 90-degree bending tensile tester. Table 1 shows the results. The peel strength at the joint surface between the resin film and the conductor layer by the resin composition of this example was 0.90 kg / cm, which was the same as in Example 1.

(Measurement of Breaking Strength and Elongation at Break) Using the flame-retardant resin composition prepared as described above, four films having a thickness of 70 μm were prepared in the same manner as in Example 1. Then, the breaking strength and the breaking elongation of these films were measured by a tensile tester. Table 1 shows the results. The breaking strength of the film having a thickness of 70 μm was 75 MPa on average, and the elongation at break was 9% on average. From these results, it was found that the resin composition according to the present example was obtained in Example 1.
It can be understood that the resin composition has increased rigidity as compared with the resin composition of (1).

(Extraction of Phosphorus Compound) The flame-retardant resin composition prepared as described above was analyzed in the same manner as in Example 1 for the concentration of the phosphorus-containing compound extracted into the aqueous alkali solution. Table 1 shows the results. The concentration of the phosphorus compound in the aqueous alkali solution is less than 10 μg / g;
It was found that the amount of extraction was small.

(Flame Retardancy Test) The flame retardancy of the flame retardant resin composition prepared as described above was evaluated in the same manner as in Example 1 according to the UL94 flame retardancy test. Table 1 shows the results. The flame retardancy of the resin film formed as described above was equivalent to V0, and it was found that the resin composition of this example had high flame retardancy.

Comparative Example 1 (Preparation of Flame Retardant Resin Composition) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene
32 parts by weight of 10-oxide (trade name: HCA-HQ, manufactured by Sanko Co., Ltd.), 35 parts by weight of cresol novolak epoxy (trade name: EOCN1020, manufactured by Nippon Kayaku) as main resin components, and biphenyl type epoxy (trade name: NC)
-3000P, manufactured by Nippon Kayaku) 50 parts by weight and 15 parts by weight of trifunctional epoxy (trade name: VG3101, manufactured by Mitsui Chemicals)
Novolak type phenol (PSM-430) as a curing agent
0, manufactured by Gunei Chemical Co., Ltd.) and novolak-type p-xylyl-modified phenol (trade name: Xyloc XLC-L)
L, manufactured by Mitsui Chemicals, Inc.), 20 parts by weight, 2-methyl-4-ethyl-imidazole (trade name: 2E4M) as a curing accelerator
Z, Shikoku Chemicals) 1 part by weight, aluminum hydroxide (trade name: H-32, manufactured by Showa Denko) 15 parts by weight as inorganic filler and silica powder (trade name: AEROSIL, manufactured by Nippon Aerosil Co., Ltd.) 5 parts by weight Was mixed with a solvent composed of 35 parts by weight of propylene glycol monoether and 15 parts by weight of MEK to prepare a resin composition as a comparative example.

(Measurement of Peel Strength) Using the resin composition prepared as described above, six glass epoxy substrates were coated on a copper foil provided on a substrate in the same manner as in Example 1. After a resin film was formed and immersed sequentially in a swelling solution, a roughening solution, and a neutralizing solution, electroless copper plating and electrolytic copper plating were performed to form a conductor layer having a thickness of 25 μm on the resin film. With respect to the joint between the resin film thus formed and the conductor layer, the peel strength was measured by a 90-degree bending tensile tester. Table 1 shows the results. The average peel strength at the joint surface between the resin film and the conductor layer of the resin composition of this comparative example was 0.60 kg / cm, which was lower than that of the resin compositions of Examples 1 and 2.

(Measurement of Breaking Strength and Elongation at Break) Using the resin composition of this comparative example, four films having a thickness of 70 μm were prepared in the same manner as in Example 1. Then, the breaking strength and the breaking elongation of these films were measured by a tensile tester. Table 1 shows the results. The breaking strength of the film is 60 MPa on average, and the breaking elongation is 3 on average.
%Met. From these results, it can be understood that the resin composition according to the present comparative example is lower in both the breaking strength and the breaking elongation as compared with the resin compositions of Example 1 and Example 2.

(Extraction of Phosphorus Compound) The resin composition according to this comparative example was analyzed for the concentration of the phosphorus-containing compound extracted into the aqueous alkali solution by the same method as in Example 1. Table 1 shows the results. The concentration of the phosphorus compound in the aqueous alkali solution was about 70 μg / g, and it was found that the amount of extraction was larger than in Examples 1 and 2.

[0077]

The resin composition of the present invention exhibits high flame retardancy equivalent to V0 in a UL94 flame retardancy test. Because it is halogen-free, it has excellent safety. Further, the elongation at break, which is an important property in manufacturing a build-up substrate, shows a high value of 5% or more. Further, when the insulating film of the build-up substrate is formed using the flame-retardant resin composition of the present invention to exhibit alkali resistance, elution to an alkaline processing solution such as an electroless copper plating solution used in a wiring forming process is performed. Is less.

[0078]

[Supplementary Note] Finally, the constitution of the present invention and its variations are listed below as supplementary notes.

(Supplementary Note 1) A main resin component, a flame retardant,
A flame retardant resin composition containing a curing agent, wherein the flame retardant is (2,5-dihydroxyphenyl) -10H-9-
A flame-retardant resin composition, which is oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether. (Supplementary Note 2) A flame-retardant resin composition containing a main resin component, a flame retardant, and a curing agent, wherein the flame retardant is (2,5)
-Dihydroxyphenyl) -10H-9-oxa-10
-A flame-retardant resin composition, which is a polymer containing phosphaphenanthrene-10-oxide diglycidyl ether. (Supplementary Note 3) The flame retardant according to Supplementary Note 2, wherein the polymer is a homopolymer of (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether. Resin composition. (Supplementary Note 4) The above (2,5-dihydroxyphenyl)-
10H-9-oxa-10-phosphaphenanthrene-
The flame retardant resin composition according to claim 3, wherein the degree of polymerization of the 10-oxide diglycidyl ether homopolymer is from 2 to 20. (Supplementary Note 5) The flame-retardant resin composition according to any one of Supplementary Notes 2 to 4, wherein the polymer is a polymer having a tertiary amine as a polymerization initiator. (Supplementary note 6) The flame-retardant resin composition according to supplementary note 5, wherein the tertiary amine is 2,4,6-tris (dimethylaminomethyl) phenol and / or benzyldimethylamine. (Supplementary Note 7) The flame retardant is the flame retardant fat composition 100
7. The flame-retardant resin composition according to any one of supplementary notes 1 to 6, wherein the composition is added so that 0.5 to 5 parts by weight of phosphorus is contained with respect to parts by weight. (Supplementary Note 8) The flame-retardant resin composition according to any one of Supplementary Notes 1 to 7, wherein the main resin composition is a polyfunctional epoxy resin having three or more epoxy groups in one molecule. (Supplementary Note 9) The main resin composition is selected from the group consisting of phenol novolak epoxy, cresol novolac epoxy, bisphenol A epoxy, bisphenol F epoxy, bisphenol S epoxy, and biphenyl epoxy. 8. The flame-retardant resin composition according to any one of items 1 to 7. (Supplementary Note 10) The flame-retardant resin composition according to any one of Supplementary Notes 1 to 9, wherein the main resin composition contains a rubber-modified epoxy. (Supplementary Note 11) The flame-retardant resin composition according to any one of Supplementary Notes 1 to 10, wherein the curing agent is a novolak-type phenol resin and / or a novolak-type p-xylyl-modified phenol resin. (Supplementary Note 12) Further, 2-methyl-4 is used as a curing accelerator.
12. The flame-retardant resin composition according to any one of supplementary notes 1 to 11, comprising -ethyl-imidazole. (Supplementary Note 13) Supplementary notes 1 to 1 further containing an inorganic filler
3. The flame-retardant resin composition according to any one of 2. (Supplementary Note 14) The amount of the inorganic filler to be added is 5 to 50 parts by weight based on 100 parts by weight of the main resin component.
14. The flame-retardant resin composition according to supplementary note 13. (Supplementary note 15) The flame-retardant resin composition according to Supplementary note 13 or 14, wherein the inorganic filler is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, and silica. (Supplementary Note 16) The flame-retardant resin composition according to any one of Supplementary Notes 13 to 15, wherein the inorganic filler has an average particle size of 5 µm or less. (Supplementary Note 17) A build-up substrate on which an insulating layer is formed using the flame-retardant resin composition according to any one of Supplementary Notes 1 to 16.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H05K 3/46 H05K 3/46 TF term (Reference) 4J002 AA00W AA01W AA02W CC03Y CC07Y CD00W CD02W CD03W CD05W CD06W CD08W CD11X CD13W CH06X FD13X FD14Y GQ00 GQ01 4J036 AA01 AA04 AA05 AC01 AC20 AD01 AD08 AF01 AF06 AF07 AG00 AH00 FB07 FB08 JA08 5E346 AA12 AA15 BB01 CC09 DD03 DD22 EE31 FF04 GG15 GG19 HH16

Claims (5)

[Claims] 1. A flame-retardant resin composition comprising a main resin component, a flame retardant, and a curing agent, wherein the flame retardant is (2,5-dihydroxyphenyl) -1.
0H-9-oxa-10-phosphaphenanthrene-1
A flame-retardant resin composition, which is 0-oxide diglycidyl ether. 2. A flame-retardant resin composition comprising a main resin component, a flame retardant, and a curing agent, wherein the flame retardant is (2,5-dihydroxyphenyl) -1.
0H-9-oxa-10-phosphaphenanthrene-1
A flame-retardant resin composition, which is a polymer containing 0-oxide diglycidyl ether. 3. The above polymer is a homopolymer having a degree of polymerization of 2 to 20 with (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxidediglycidyl ether. The flame-retardant resin composition according to claim 2. 4. The flame-retardant resin composition according to claim 2, wherein the curing agent contains a novolak-type phenol resin and / or a novolak-type p-xylyl-modified phenol resin. 5. A build-up substrate on which an insulating layer is formed using the flame-retardant resin composition according to claim 1.