TW201527400A - Thermosetting resin composition and cured product - Google Patents

Abstract

To provide a thermosetting resin composition that, after cured, can yield a cured product having both excellent heat resistance and flame retardancy, and to provide a cured product having both excellent heat resistance and flame retardancy. A thermosetting resin composition, which includes a nitrogen-containing phenol-based resin (A) and an epoxy resin (B), wherein the nitrogen-containing phenol-based resin (A) is obtained by reacting (A-1) a dimethylol body of a nitrogen-containing compound with (A-2) a phenolic hydroxyl group-containing compound containing at least two phenolic hydroxyl groups in one molecule and having a hydroxyl equivalent of 100 g/eq. or more.

Description

Thermosetting resin composition and cured product

The present invention relates to a thermosetting resin composition and a cured product.

The thermosetting resin composition in which the epoxy resin and the phenol resin (hardener) are combined is used because the cured product of the thermosetting resin composition is excellent in heat resistance, adhesion, electrical insulation, and the like. In various fields. For example, a resin composition for a printed circuit board, a resin composition for an interlayer insulating material used for a printed circuit board and a copper foil with a resin, a resin composition for a sealing material for an electronic component, a resist ink, and a conductive filler Conductive paste, coating, adhesive, composite materials, etc.

For example, a semiconductor sealing material such as a resin composition for a sealing material has a demand for miniaturization, thinning, and miniaturization of the product, and a higher cured product (molded article) is required for the thermosetting resin composition. Heat resistance, improvement of flame retardancy, etc.

For this requirement, various solutions are explored. As one of the means for solving this problem, for example, a means as described below is known. A thermosetting resin composition is generally known to contain various fillers and to increase the use of a filler. the amount.

As means for improving the heat resistance of the cured product, a method of increasing the crosslinking density by increasing the number of functional groups of the resin component in the thermosetting resin composition is known. For example, it has been proposed to improve heat resistance by using an epoxy resin or a phenol resin having a triphenylmethane structure or an epoxy resin or a phenol resin having a nonylphenol ethane structure.

As a document showing such a means, for example, Patent Document 1 discloses that an epoxy resin having a triphenylmethane structure and a phenol resin having a triphenylmethane structure are used as a main component, and further, crystallinity is further described. An invention in which an epoxy resin is partially blended.

For example, Patent Document 2 describes an invention in which a phenol resin is used as a curing agent for an epoxy resin, and the phenol resin is a phenol resin having a nonylphenol ethane structure as a condensate of a phenol and a dialdehyde.

In addition, for example, Patent Document 3 discloses a cured product which is excellent in heat resistance and flame retardancy by a thermosetting resin composition containing a nitrogen-containing phenol resin and an epoxy resin.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3365725

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-48959

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-266403

Although the flame retardancy of the cured product is easily increased by increasing the filling amount in the thermosetting resin composition, on the other hand, the fluidity of the thermosetting resin composition is lowered to form the cured product. The problem of deterioration. Therefore, the low melt viscosity of the resin component is required at the same time.

When the number of functional groups of the resin component in the thermosetting resin composition is increased, the heat resistance of the cured product is likely to increase, but the fluidity of the resin component tends to decrease as the number of functional groups increases.

Under the circumstances, as shown in Patent Documents 1 and 2, a method of combining the heat resistance of the cured product with the fluidity of the resin was examined.

However, the resin composition obtained by the method described in Patent Document 1 is excellent in fluidity, but the heat resistance of the cured product is lowered by blending the crystalline epoxy resin.

The phenol resin described in Patent Document 2 imparts fluidity by increasing the ratio of a substance which is condensed to 3 mol or less with respect to the dialdehyde type 1 moler. Therefore, although the fluidity is improved, the heat resistance of the cured product is not sufficient.

Further, the resin composition described in Patent Document 3 is excellent in flame retardancy, but further improvement in heat resistance is required.

An object of the present invention is to provide a thermosetting resin composition which can obtain a cured product having excellent heat resistance and flame retardancy after curing, and a cured product which has excellent heat resistance and flame retardancy.

That is, the present invention is constructed in the following manner.

(1) A thermosetting resin composition comprising a nitrogen-containing phenol resin (A) and an epoxy resin (B), wherein the nitrogen-containing phenol resin (A) is a (A-1) nitrogen-containing compound The dihydroxymethyl group is obtained by reacting a phenolic hydroxyl group-containing compound having two or more phenolic hydroxyl groups in the (A-2) molecule and having a hydroxyl group equivalent of 100 g/eq. or more.

(2) The thermosetting resin composition of (1), wherein the (A-2) phenolic hydroxyl group-containing compound is a group of a compound having two hydroxyphenyl groups in the molecule and a phenol resin. At least one of the selected ones.

(3) The thermosetting resin composition according to (2), wherein the compound having two hydroxyphenyl groups in the molecule is composed of bisphenol A, bisphenol F, bisphenol S, and bisphenol Z. At least one selected from the group.

(4) The thermosetting resin composition according to (2) or (3), wherein the phenol resin has a weight average molecular weight of 200 to 5,000.

(5) The thermosetting resin composition according to any one of (1) to (4) wherein the nitrogen-containing compound is a cyclic urea compound.

(6) The thermosetting resin composition according to (5), wherein the cyclic urea compound is derived from ethylene urea, acryl urea, intramethylene urea, cyanuric acid, and violuric acid. At least one selected from the group.

(7) The thermosetting resin composition according to any one of (1) to (6) wherein the hydroxyl group equivalent of the nitrogen-containing phenol resin (A) is epoxy with respect to the epoxy resin (B). The base is 1.0 equivalent and is from 0.6 equivalents to 1.2 equivalents.

(A) The thermosetting resin composition of any one of (1) to (7), wherein the hydroxyl group equivalent of the compound (A-2) having a phenolic hydroxyl group is 100g/eq.~200g/eq.

(9) The thermosetting resin composition according to any one of (1) to (8) wherein the nitrogen-containing phenol resin (A) has a weight average molecular weight of 500 to 5,000.

(10) The thermosetting resin composition according to any one of (1) to (9) wherein the epoxy resin (B) has a weight average molecular weight of 300 to 5,000.

(11) The thermosetting resin composition according to any one of (1) to (10), which contains a filler.

(12) A cured product obtained by curing the thermosetting resin composition according to any one of (1) to (11).

According to the present invention, it is possible to provide a thermosetting resin composition which can obtain a cured product having excellent heat resistance and flame retardancy after curing, and a cured product which has excellent heat resistance and flame retardancy.

<Thermosetting resin composition>

The thermosetting resin composition of the present invention comprises a nitrogen-containing phenol resin (A) and an epoxy resin (B), wherein the nitrogen-containing phenol resin (A) is a compound of (A-1) nitrogen-containing compound A methylol group and a compound containing two or more phenolic hydroxyl groups in the (A-2) molecule and having a hydroxyl group equivalent of 100 g/eq. or more are reacted.

The thermosetting resin composition of the present invention may further contain a filler, a dopant, and the like within the limits of not impairing the effects of the present invention.

Hereinafter, the thermosetting resin composition of the present invention will be described in detail.

In addition, the numerical range represented by "~" in this specification is a range which shows the numerical value of the minimum value and the maximum value after the "~".

[Nitrogen-containing phenol resin (A)]

The nitrogen-containing phenol resin (A) contains (A-1) a nitrogen-containing compound and a (A-2) 1 molecule having two or more phenolic hydroxyl groups, and a hydroxyl equivalent of 100 g/eq. The above phenolic hydroxyl group-containing compound is reacted.

By obtaining a nitrogen-containing phenol resin (A) by reacting (A-1) a nitrogen-containing compound of a nitrogen-containing compound with (A-2) a phenolic hydroxyl group-containing compound, heat resistance and heat resistance can be obtained. A nitrogen-containing phenol resin excellent in flame retardancy.

1. (A-1) a dihydroxymethyl group of a nitrogen-containing compound

The nitrogen-containing compound may be a compound containing at least one nitrogen atom in the molecule.

For example, a nitrile compound such as acetonitrile or benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamine)ethanol, pyridine, quinoline or α -Methylpyridine, 2,4,6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine, 2,2,5,5, tetramethylpyrrolidine, N,N,N', An amine compound such as N'-tetramethylethylenediamine, aniline or dimethylaniline, formamide, trimethylamine hexamethylphosphate, N,N,N',N',N"-pentamethyl- N'-β-dimethylaminomethyl Amidoxime compound such as triammonium phosphate, octamethylpyrophosphate or guanamine, N,N,N',N'-tetramethylurea, dimethylol urea [1,3-bis(hydroxymethyl)urea An amide compound such as a urea compound such as ethylene urea (2-imidazolidinone), an isocyanate compound such as phenyl isocyanate or tolyl isocyanate, or an azo compound such as azobenzene.

Among the above, the nitrogen-containing compound is preferably a urea compound. Further, the urea compound may be linear or cyclic, but is preferably a cyclic urea compound from the viewpoint of compatibility with a phenolic hydroxyl group-containing compound.

Examples of the cyclic urea compound include ethylene urea (2-imidazolidinone), propylene urea (tetrahydro-2-pyrimidinone), carbendazim (2,5-imidazolidindione), and cyanuric acid. Acid [1,3,5-triazine-2,4,6(1H,3H,5H)-trione], and uric acid [5-(hydroxyimino)pyrimidine-2,4,6 (1H At least one selected from the group consisting of 3H, 5H)-trione]. However, the cyclic urea compound used in the present invention is not limited thereto.

The dihydroxymethyl group of the nitrogen-containing compound is a compound obtained by extracting a hydrogen atom from two nitrogen-containing compounds and then bonding a methylol group (-CH ₂ -OH). For example, in the case of using a cyclic urea compound as a nitrogen-containing compound, a bifunctional compound which can react with a molecule of the formaldehyde-based compound 2 with respect to one molecule of the cyclic urea compound can be mentioned. Here, the formaldehyde-based compound means a compound having one formazan group (-CHO).

The bonding position of the methylol group to the nitrogen-containing compound is not particularly limited, but the dihydroxymethyl group of the nitrogen-containing compound is preferably substituted with a secondary amine nitrogen atom bonded to the nitrogen-containing compound (-NH-). a hydrogen atom, and a structure in which a methylol group is bonded.

In the case of a dihydroxymethyl group of a nitrogen-containing compound, for example, a cyclic urea compound is used as the nitrogen-containing compound, specifically, dimethylol ethylene urea [1,3-bis(hydroxymethyl group) is exemplified. )-2-imidazolidinone], dimethylol propylene urea [1,3-bis(hydroxymethyl)-2-pyrimidinone], dimethylol carbendazim [1,3-bis (hydroxyl) ,2,5-imidazolidindione], dimethylol cyanuric acid [1,3-bis(hydroxymethyl)-1,3,5-triazine-2,4,6 (1H, 3H,5H)-Trione], and Dimethylol-Usuluic Acid [1,3-bis(hydroxymethyl)-5-(hydroxyimino)pyrimidine-2,4,6(1H,3H,5H )-trione] and so on.

The dihydroxymethyl group of the nitrogen-containing compound may be used alone or in combination of two or more.

The dihydroxymethyl group of the nitrogen-containing compound can be obtained, for example, by subjecting a nitrogen-containing compound to an addition reaction with a formaldehyde-based compound. In this addition reaction, it is preferred to use 2.0 mol to 2.1 mol of a formaldehyde-based compound with respect to 1.0 mol of the nitrogen-containing compound. Formaldehyde compounds, for example, formaldehyde, polyoxymethylene, and trisole can be used. (Sanformaldehyde) and so on.

The above addition reaction can be carried out in the presence of a solvent containing at least one of water and an organic solvent, without a catalyst, or in the presence of a basic catalyst.

The reaction temperature is preferably from 45 ° C to 80 ° C, more preferably from 45 ° C to 70 ° C, still more preferably from 45 ° C to 50 ° C. The reaction time is preferably from 1 hour to 10 hours, more preferably from 1 hour to 6 hours, still more preferably from 1 hour to 4 hours.

By allowing the reaction temperature to be 45 ° C or higher, the reaction can be easily carried out to efficiently obtain a dihydroxymethyl group of a nitrogen-containing compound. Further, by setting the reaction temperature to 80 ° C or lower, the reaction can be easily controlled, and side reactions are less likely to occur. The addition reaction is fully advanced by a reaction time of 1 hour or more. OK, and the reaction is roughly completed within 10 hours.

The organic solvent to be used for the reaction of the nitrogen-containing compound and the formaldehyde-based compound may, for example, be an alcohol such as methanol or ethanol, a glycol such as ethylene glycol or propylene glycol, or acetone or methyl ethyl ketone. Esters such as ketones, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, 1,4-dioxane, etc. Ethers, acetic acid, dimethyl hydrazine, and the like.

The solvent may be used singly or in combination of two or more. The amount of the solvent to be used is preferably more than 0 parts by mass and 1,000 parts by mass, more preferably from 10 parts by mass to 100 parts by mass, per 100 parts by mass of the nitrogen-containing compound.

The basic catalyst used in the above addition reaction can be suitably used for the purpose of promoting the reaction.

Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydride chloride, magnesium hydroxide, trimethylamine, triethylamine, and tributylamine. In the case where the thermosetting resin composition of the present invention and the cured product thereof are used as a member requiring electrical insulation such as a semiconductor sealing material, it is preferred that after the reaction is completed, the product is neutralized with an acid. Water is washed, etc., and the catalyst is removed from the product.

The amount of the basic catalyst used is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 0.2 part by mass to 15 parts by mass, per 100 parts by mass of the nitrogen-containing compound.

2. (A-2) a compound containing a phenolic hydroxyl group

The phenolic hydroxyl group-containing compound contained in the thermosetting resin composition of the present invention contains two or more phenolic hydroxyl groups in one molecule, and has a hydroxyl group equivalent of 100 g/eq. or more. If the number of phenolic hydroxyl groups in one molecule is less than two, the Tg of the cured product may be lowered, and if the hydroxyl equivalent is less than 100 g/eq., the density of the hydroxyl group in one molecule is increased. The influence of the intermolecular hydrogen bond is increased, and as a result, the melt viscosity of the phenolic hydroxyl group-containing compound is increased, which is not preferable.

Examples of the phenolic hydroxyl group-containing compound include a compound having two hydroxyphenyl groups in a molecule such as bisphenol A, bisphenol F, bisphenol S or bisphenol Z, a phenol novolac resin, and a cresol novolak resin. Various phenol resins such as phenol aralkyl resin, biphenyl aralkyl resin, naphthol novolak resin, and naphthol aralkyl resin.

The phenolic hydroxyl group-containing compound may be used singly or in combination of two or more.

The phenolic hydroxyl group-containing compound is preferably a compound having two hydroxyphenyl groups in the molecule, more preferably at least 1 selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, and bisphenol Z. Kind.

The hydroxyl equivalent of the phenolic hydroxyl group-containing compound is preferably 200 g/eq. or less, more preferably 150 g/eq. or less, still more preferably 130 g/eq. or less from the viewpoint of improving the heat resistance of the cured product.

In the case of using a phenol resin as the phenolic hydroxyl group-containing compound, the weight average molecular weight of the phenol resin is preferably from 200 to 5,000 from the viewpoint of balance between fluidity and heat resistance of the thermosetting resin composition. More preferably 250~4000, and even more preferably 300~4000.

The weight average molecular weight of the resin can be determined, for example, by gel permeation chromatography (GPC). Specific measurement conditions of GPC include, for example:

Pipe column: trade name "KF-801+KF-802+KF-802+KF-803" (Showa Denko Co., Ltd., Shodex (registered trademark) series)

Detector: "RI-71" (Showa Refractometer "Shodex" (registered trademark))

Solvent: tetrahydrofuran

Flow rate: 1ml/min

Wait.

The nitrogen-containing phenol resin (A) of the present invention can be obtained by subjecting a (A-1) nitrogen-containing compound to a dihydroxymethyl group to a condensation reaction with (A-2) a phenolic hydroxyl group-containing compound.

In the condensation reaction, it is preferred to use 1.0 mol to 4.0 mol of the (A-2) phenolic hydroxyl group-containing compound to condense with (A-1) a nitrogen-containing compound of 1.0 mol. reaction. The amount of the (A-2) phenolic hydroxyl group-containing compound is more preferably from 2.0 mol to 4.0 mol, and even more preferably 2.0, to 1.0 mol of the (A-1) nitrogen-containing compound. Moer ~ 3.5 Moh.

The condensation reaction is preferably carried out in the presence of a solvent containing at least one of water and an organic solvent in the presence of an acid catalyst.

The reaction temperature is preferably from 70 ° C to 150 ° C, more preferably from 80 ° C to 120 ° C, still more preferably from 90 ° C to 110 ° C. The reaction time is preferably from 1 hour to 10 hours, more preferably from 1 hour to 7 hours, still more preferably from 1 hour to 5 hours. By allowing the reaction temperature to be 70 ° C or higher, the reaction can be easily carried out, and the nitrogen-containing phenol resin (A) can be efficiently obtained. In addition, by setting the reaction temperature to 150 ° C Down, it is easy to control the reaction, and it is not easy to cause side reactions. The addition reaction was sufficiently carried out by a reaction time of 1 hour or more, and the reaction was substantially completed within 10 hours.

The acid catalyst is not particularly limited as long as it is used in the production of a general novolak resin, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and oxalic acid. The acid catalyst system may be used alone or in combination of two or more.

In the above-mentioned acid catalyst, oxalic acid which is decomposed by heating is particularly preferable. The amount of the acid catalyst to be used is preferably 0.001 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass to 8 parts by mass, per 100 parts by mass of the dihydroxymethyl group of the (A-1) nitrogen-containing compound. More preferably, it is 0.1 mass part - 5 mass parts.

After the reaction of the condensation reaction, the product may be washed with water, heated and decompressed, and the condensed water and the unreacted phenolic hydroxyl group-containing compound may be removed. The product, that is, the nitrogen-containing phenol resin (A), can be obtained as a solid having a softening point, and can be dissolved in an organic solvent as needed to prepare a resin solution.

The softening point of the nitrogen-containing phenol resin (A) is preferably from 70 ° C to 94 ° C, more preferably from 75 ° C to 93 ° C, still more preferably from 81 ° C to 92 ° C.

Further, the melt viscosity of the nitrogen-containing phenol resin (A) at 150 ° C is preferably from 200 mPa ‧ to 800 mPa ‧ , more preferably from 240 mPa ‧ to 700 mPa ‧ , and even more preferably from 280 mPa ‧ to 650 mPa ‧ s .

The weight average molecular weight of the nitrogen-containing phenol resin (A) is preferably from the viewpoint of balance between fluidity and heat resistance of the thermosetting resin composition. 500~5000, more preferably 600~3500, and even better 700~3000.

In addition, the content of the thermosetting resin composition of the nitrogen-containing phenol resin (A) is preferably 2.5% by mass based on the total mass of the thermosetting resin composition from the viewpoint of heat resistance and flame retardancy. ~13% by mass, more preferably 4.0% by mass to 10% by mass, still more preferably 4.0% by mass to 9.0% by mass.

[Epoxy Resin (B)]

The epoxy resin used in the present invention is not particularly limited, and a known epoxy resin can be used. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and resorcinol type epoxy resin. , hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxy naphthalene type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, etc. Epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene- Phenol-modified epoxy resin, phenol aralkyl epoxy resin, biphenyl aralkyl epoxy resin, naphthol novolac epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol Co-phenolic varnish type epoxy resin, naphthol-cresol co-retort phenolic epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin epoxy resin, biphenyl modified novolak epoxy resin, etc. An epoxy resin derived from a ternary or higher phenol, an epoxy resin modified by an organic phosphorus compound, or the like. Among them, a triphenylmethane type epoxy resin is preferred. Further, these epoxy resins may be used singly or in combination of two or more. Among these, bisphenol epoxy resin and phenol are preferred. A novolak type epoxy resin, a cresol novolac type epoxy resin, a triphenylmethane type epoxy resin, and more preferably a triphenylmethane type epoxy resin.

The weight average molecular weight of the epoxy resin (B) is preferably from 300 to 5,000, more preferably from 400 to 3,500, still more preferably from the viewpoint of balance between fluidity and heat resistance of the thermosetting resin composition. ~3000.

The mixing ratio of the epoxy resin (B) to the phenol resin (A) is preferably from 0.6 equivalents to 1.2 equivalents per 100 equivalents of the epoxy group in the epoxy resin (B) to the hydroxyl group in the phenol resin (A). The range is more preferably in the range of 0.7 equivalents to 1.1 equivalents.

In the thermosetting resin composition, a hardening accelerator may be suitably used for the purpose of promoting the curing reaction.

Examples of the curing accelerator include an imidazole compound, an organic phosphorus compound, a secondary amine compound, a tertiary amine compound, an organic acid metal salt such as tin octylate, a Lewis acid, an amine salt, and the like. These may be used alone or in combination of two or more.

Examples of the imidazole-based compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl- 2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazole Porphyrin, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethyl Imidazolinium, 2-phenyl-4-methylimidazoline and the like.

The imidazole compound can be masked by a masking agent.

Examples of the masking agent include acrylonitrile, phenyl diisocyanate, and o Amine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate, and the like.

Examples of the organophosphorus compound include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, and tri Cyclohexylphosphine, triphenylphosphine/triphenylborane complex, tetraphenylphosphonium tetraphenyl borate, and the like.

Examples of the second-order amine compound include morpholine, piperidine, pyrrolidine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dibenzylamine, and Cyclohexylamine, N-alkylarylamine, piperazine, diallylamine, thiazoline, thiomorpholine and the like.

Examples of the tertiary amine compound include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-cis (diaminomethyl)phenol.

Among these hardening accelerators, triphenylphosphine is preferred.

In the thermosetting resin composition of the present invention, it is preferred to blend a filler for the purpose of imparting flame retardancy, suppressing thermal expansion, and the like. Specific examples include, for example, molten cerium oxide, crystalline cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, zirconia, forsterite (Fosterite). An inorganic filler such as talc, spinel, titanium oxide, aluminum hydroxide or magnesium hydroxide.

The molten cerium oxide can be used in any of a crushing state and a spherical shape. However, in order to increase the amount of molten cerium oxide to be added and to suppress an increase in the melt viscosity of the molding material, it is preferred to use a spherical shape. Further, in order to increase the blending amount of the spherical cerium oxide to the thermosetting resin composition, it is preferred to appropriately adjust the particle size distribution of the spherical cerium oxide. Fusion of molten cerium oxide The preferred range of the ratio varies depending on the applicable use of the thermosetting resin composition and the desired characteristics. For example, when the thermosetting resin composition is used for a semiconductor sealing material, the blending ratio of the molten cerium oxide is higher in view of the linear expansion coefficient or flame retardancy of the cured product of the thermosetting resin composition. It is better. Specifically, the total amount of the thermosetting resin composition is preferably 65% by mass or more, and more preferably about 80% by mass to 90% by mass.

In addition, when the thermosetting resin composition is used for a conductive paste or a conductive film, a conductive filler such as silver powder or copper powder can be used as the filler.

In addition, the thermosetting resin composition of the present invention may contain various thermosetting resins, thermoplastic resins, pigments, decane coupling agents, and release agents, which are used as modifiers, as needed.

As the thermosetting resin and the thermoplastic resin used as the modifier, various known ones can be used.

The thermosetting resin and the thermoplastic resin can be used, for example, in a range that does not impair the effects of the present invention, using a phenoxy resin, a polyamide resin, a polyimine resin, a polyether quinone resin, and a poly Ether oxime resin, polyphenylene ether resin, polyphenylene sulfide resin polyester resin, polystyrene resin, polyethylene terephthalate resin, and the like.

Examples of the decane coupling agent include a decane coupling agent such as an amino decane compound, a vinyl decane compound, a styrene decane compound, or a methacryl decane compound.

Further, the release agent may be exemplified by stearic acid, zinc stearate, and stearic acid. Calcium, aluminum stearate, magnesium stearate, and palm wax.

The thermosetting resin composition of the present invention containing the nitrogen-containing phenol resin (A) and the epoxy resin (B) excellent in heat resistance and flame retardancy is excellent in fluidity and can be obtained by curing to obtain heat resistance. And hardened materials with excellent flame retardancy.

In particular, the thermosetting resin composition of the present invention can be suitably used for a resin composition for a sealing material for an electronic component, a resin composition for a printed circuit board, and a resin for an interlayer insulating material used for a printed circuit board and a copper foil with a resin. A composition, a conductive paste containing a conductive filler, a coating material, an adhesive, and a composite material. When the thermosetting resin composition of the present invention is used, a cured product excellent in flame retardancy can be obtained without further using a halogen-based flame retardant. Therefore, the thermosetting resin composition of the present invention is also useful as an environmentally compatible epoxy resin composition.

<hardened matter>

The cured product of the present invention is obtained by curing the thermosetting resin composition of the present invention.

The curing method of the thermosetting resin composition is not particularly limited. For example, the thermosetting resin composition may be heated under the conditions of a heating temperature of 170 to 250 ° C and a heating time of 60 to 20 hours. The heating temperature is preferably from 170 ° C to 220 ° C, more preferably from 170 ° C to 200 ° C. The heating time is preferably from 60 minutes to 10 hours, more preferably from 90 minutes to 8 hours.

The cured product of the present invention is obtained by curing the thermosetting resin composition of the present invention, and therefore has a high glass transition temperature and excellent heat resistance. different. Further, the cured product of the present invention is excellent in flame retardancy and can have both heat resistance and flame retardancy.

The glass transition temperature of the cured product of the present invention is preferably from 150 ° C to 230 ° C, more preferably from 170 ° C to 220 ° C, still more preferably from 190 ° C to 215 ° C.

Further, the cured product of the present invention has a bending strength measured by a method according to JIS K-6911, preferably from 125 MPa to 180 MPa, more preferably from 130 MPa to 170 MPa, still more preferably from 135 MPa to 160 MPa. For the bending strength, for example, a test piece having a length of 90 mm, a height of 4 mm, and a width of 10 mm may be used, and the measurement may be performed at a distance of 64 mm between the fulcrums.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto, and the "%" in the examples and comparative examples is a quality standard.

Production Example 1 (Synthesis of Nitrogen-containing Phenol Resin A)

In a flask equipped with a cooling tube and a stirrer, 100 g of ethylene urea (1.16 mol) and 8 g of a 25% aqueous sodium hydroxide solution were charged, and after the reaction liquid was heated to 50 ° C, it took 1 hour to add 37% formaldehyde to 188 g (2.32 mol). The ear) was dropped into the reaction solution. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and then 6 g of phosphoric acid was added to the reaction liquid for neutralization, thereby obtaining a dihydroxymethyl group of ethylene urea [1,3-bis(hydroxymethyl)-2-imidazolidinium. ketone].

Next, in the flask, bisphenol A (hydroxy equivalent: 114 g/eq.) 663 g (2.9 mol) and 1.5 g oxalic acid. After the reaction was carried out at a reflux temperature for 3 hours, the product was washed four times with 100 g of pure water to remove the catalyst and the salt from the product. Then, the distillate was removed from the product under reduced pressure of 150 ° C and 50 mmHg to obtain 750 g of a pale brown phenol resin A. The obtained nitrogen-containing phenol resin A had a softening point of 83 ° C and a weight average molecular weight of 600.

Production Example 2 (Synthesis of Nitrogen-containing Phenol Resin B)

In the synthesis of the nitrogen-containing phenol resin A, the reaction was carried out in the same manner as in Production Example 1, except that 581 g (2.91 mol) of bisphenol F (hydroxyl equivalent: 100 g/eq.) was used instead of bisphenol A. And 680 g of the nitrogen-containing phenol resin B was obtained. The obtained nitrogen-containing phenol resin B had a softening point of 86 ° C and a weight average molecular weight of 750.

Production Example 3 (Synthesis of Nitrogen-containing Phenol Resin C)

In the synthesis of the nitrogen-containing phenol resin A, 465 g (2.33 mol) of bisphenol F and 116 g of phenol novolac resin (Shonol (registered trademark) BRG-556, weight, used in place of bisphenol A, were used. The reaction was carried out in the same manner as in Production Example 1 except that the average molecular weight was 1,000 and the hydroxyl group equivalent was 103 g/eq.), and 686 g of a nitrogen-containing phenol resin C was obtained. The obtained nitrogen-containing phenol resin C had a softening point of 90 ° C and a weight average molecular weight of 1,200.

Production Example 4 (Synthesis of Nitrogen-containing Phenol Resin D)

In a flask equipped with a cooling tube and a stirrer, 100 g (1 mol) and 8 g of a 25% aqueous sodium hydroxide solution were placed in a flask equipped with a cooling tube and a stirrer, and the reaction liquid was heated to 50 ° C, and then 172 g of 37% formaldehyde was consumed for 1 hour. 2 moles were dropped into the reaction solution. Thereafter, the reaction was carried out at 50 ° C for 3 hours, and then 6 g of phosphoric acid was added to the reaction liquid to carry out neutralization, whereby a dihydroxymethyl group [1,3-bis(hydroxymethyl)-2] of carbendazim was obtained. 5-imidazolidindione].

Next, 582 g (2.55 mol) of bisphenol A and 1.5 g of oxalic acid were added to the flask. After the reaction was carried out at a reflux temperature for 3 hours, the product was washed four times with 100 g of pure water to remove the catalyst and the salt from the product. Then, the distillate was removed from the product under reduced pressure of 150 ° C and 50 mmHg to obtain 686 g of a nitrogen-containing phenol resin D in a pale brown mass. The obtained nitrogen-containing phenol resin D had a softening point of 89 ° C and a weight average molecular weight of 1,000.

Production Example 5 (nitrogen-containing phenol resin E; synthesis of comparative resin)

In a flask equipped with a cooling tube and a stirrer, 100 g of ethylene urea and 8 g of a 25% aqueous sodium hydroxide solution were charged, and after the reaction liquid was heated to 50 ° C, 188 g of 37% formaldehyde was dropped into the reaction liquid over 1 hour. Thereafter, the reaction was carried out at 50 ° C for 2 hours, and then 6 g of phosphoric acid was added to the reaction liquid for neutralization, thereby obtaining a dihydroxymethyl group of ethylene urea [1,3-bis(hydroxymethyl)-2-imidazolidinium. ketone].

Next, 328 g of phenol (hydroxyl equivalent: 94 g/eq.) and 1.5 g of oxalic acid were added to the flask, and the reaction was carried out at reflux temperature for 4 hours. Then, the unreacted phenol is removed from the product under a reduced pressure of 180 ° C and 50 mmHg, and 288 g of a nitrogen-containing phenol resin E having a softening point of 80 ° C and a weight average molecular weight of 400 was obtained.

Production Example 6 (nitrogen-containing phenol resin F; synthesis of comparative resin)

Into a flask equipped with a cooling tube and a stirrer, 100 g of phenol, 65 g of salicylaldehyde, and 1 g of p-toluenesulfonic acid were charged, and the reaction was carried out at 100 ° C for 8 hours. Next, the product was washed four times with 100 g of pure water, and the catalyst was removed from the product. Then, the distillate was removed from the resultant under a reduced pressure of 180 ° C and 50 mmHg to obtain 96 g of a phenol resin F. The obtained phenol resin F had a softening point of 128 ° C and a weight average molecular weight of 700.

Production Example 7 (phenol resin G; synthesis of comparative resin)

In a flask equipped with a cooling tube and a stirrer, 100 g of phenol, 60 g of 37% formaldehyde, and 1 g of oxalic acid were charged, and the reaction was carried out at 100 ° C for 5 hours. Then, the distillate was removed from the reaction liquid under a reduced pressure of 180 ° C and 50 mmHg to obtain 84 g of a phenol resin G. The obtained phenol resin G had a softening point of 95 ° C and a weight average molecular weight of 1,600.

The characteristic values of the nitrogen-containing phenol resins A to E and the phenol resins F to G obtained in Production Examples 1 to 7 are shown in Table 1. The analysis method of the resin is as follows.

(1) Softening point (°C)

The measurement was carried out using a gas phase softening point measuring device EX-719PD manufactured by ELEX Scientific Co., Ltd. The heating rate was set to 2.5 ° C / min.

(2) Melt viscosity (mPa‧s)

The melt viscosity of the resin at 150 ° C was measured using an ICI viscosity meter manufactured by Research equip.

Use cone and plate: 19.5 , 0-40

(3) Weight average molecular weight

The column structure was carried out by KF-801+KF-802+KF-802+KF-803 (trade name) manufactured by Showa Denko Co., Ltd., and measured using a tetrahydrofuran as a solvent at a flow rate of 1 ml/min. For the detector, the product name "RI-71" [Showa Refractometer "Shodex" (registered trademark)] was used. The molecular weight is calculated in terms of polystyrene.

As is clear from Table 1, the nitrogen-containing phenol resins A to D used in the present invention have lower softening points and melt viscosities than the phenol resins F and G, and are similar to the conventional nitrogen-containing phenol resin E. This tendency is also the same when considering the fluidity of the thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 which will be described later.

Examples 1 to 7, and Comparative Examples 1 to 3 (Modulation of thermosetting resin composition)

The nitrogen-containing phenol resin and the phenol resin obtained in Production Examples 1 to 7 were mixed and blended by the blending shown in Table 2, and Examples 1 to 7 and Comparative Examples 1 to 3 were obtained. A thermosetting resin composition.

The blending of the components shown in Table 2 was carried out as follows.

For the epoxy resin (weight average molecular weight: 1000) in the amount shown in Table 2 (for example, 10 g in Example 1), the resin A to G having the hydroxyl equivalent/epoxy equivalent ratio described in Table 2 was mixed, and 0.1 g of triphenylphosphine (hardening accelerator) was added to obtain a resin component. Then, molten cerium oxide (inorganic filler) was mixed in the resin component so that the content of the composition was 80%, and a two-roll mill (NS-155(S) manufactured by NISHIMURA MACHINERY Co., Ltd.) was used. The mixture was kneaded at 100 ° C for 5 minutes to prepare a thermosetting resin composition.

(Manufacture of hardened material)

The obtained thermosetting resin composition was subjected to press molding under the conditions of a mold at 150 ° C for 30 minutes and a pressure of 30 kg / cm ² . Thereafter, the film was heated at 180 ° C for 5 hours to cure the thermosetting resin composition, thereby preparing a test piece of a cured product.

With respect to the obtained test piece, the glass transition temperature, the bending strength, and the flame retardancy were evaluated by the following methods.

(3) Glass transition temperature (Tg)

The glass transition temperature was measured by the TMA method (Thermo Mechanical Analysis method) using SCI Corporation and SSC/5200. The heating rate was set to 10 ° C / min.

(4) bending strength

The measurement was carried out in accordance with the method of JIS K-6911. The shape of the test piece was measured by a length of 90 mm × a height of 4 mm × a width of 10 mm, and a distance of 64 mm between the fulcrums.

(5) Flame retardancy

The test piece of the following shape was used for evaluation of flame retardancy. The test method was carried out in accordance with the JIS K6911B method according to the UL specification (Underwriters Laboratories).

Test piece: 5 lengths 130mm × width 13mm × height 2mm

Number of trials: n=5

Test method: A methane gas cylinder was used, and the flame height of the burner was adjusted to a blue flame of 19 mm, and the flame was held in contact with the flame for 10 seconds at the center of the lower end of the test piece which was held vertically by the jig. (The burner is at the lower end of the test piece with a spacing of 9.5 mm.) After the flame is touched, the burner is tested. The test piece was removed and the burning time was measured. Immediately after the combustion was stopped, the flame was again brought into contact with the same portion of the test piece, and after 10 seconds, it was removed, and the burning time was measured.

The flame retardancy of the test piece was evaluated based on the following criteria in terms of counting the respective burning times (evaluation 1) after 10 times of contact with the flame and the total time (evaluation 2) of the total burning time. Among the results of the evaluation of the two viewpoints, the one with the poor result was expressed as the result of the flame retardancy evaluation of the test piece. For example, in the evaluation 1, all of the burning times counted 10 times are all within 10 seconds, and in the evaluation 2, when the total burning time counted 10 times is 50 seconds or less, it is displayed as "in Table 2". V-0". In addition, the results of at least one of Evaluation 1 and Evaluation 2 are self-contained, and are shown in Table 2 as "self-destructive".

In addition, the flame retardancy of the test piece was carried out twice in a single test piece, and this was carried out five times (n=5).

(Evaluation 1)

. Burning time is all within 10 seconds: V-0

. Burning time (all 10 times each) more than 10 seconds, less than 30 seconds: V-1

. Burning time (all 10 times each) 31 seconds or more: self-contained (assessment 2 basis)

. Counting 10 times of burning time totals less than 50 seconds: V-0 level

. Counting 10 times of burning time totals more than 50 seconds, less than 250 seconds: V-1 level

. Counting 10 times of burning time for more than 250 seconds: self-destructive

The measurement results of the glass transition temperature, the bending strength, and the flame retardancy of the test pieces produced in Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Table 2.

From Table 2, it was confirmed that the cured product (test piece) of the thermosetting resin composition of the present invention exhibits a high glass transition temperature and high flame retardancy. That is, it is understood that the flame retardancy of the test piece of the example is much better than that of the cured product obtained by using the resins F and G which are conventional novolak resins. In addition, it is also known that the glass transition temperature of the test piece of the example is much higher than the value of the cured product obtained by using the resin E as a conventional novolak resin, and exhibits high heat resistance.

That is, the thermosetting resin composition of the present invention can maintain good fluidity, and the cured product thereof has both good heat resistance and flame retardancy.

[Industrial availability]

The cured product obtained by the thermosetting resin composition of the present invention has excellent heat resistance and flame retardancy. Therefore, the thermosetting resin composition of the present invention can be suitably used for a resin composition for a sealing material for an electronic component, a resin composition for a printed substrate, and an interlayer for use in a printed substrate and a copper foil with a resin. A resin composition for an insulating material, a conductive paste containing a conductive filler, a coating material, an adhesive, a composite material, and the like.

Claims (12)

A thermosetting resin composition comprising a nitrogen-containing phenol resin (A) and an epoxy resin (B), wherein the nitrogen-containing phenol resin (A) is a dihydroxy group of (A-1) a nitrogen-containing compound A methyl group or a compound containing a phenolic hydroxyl group having two or more phenolic hydroxyl groups in the (A-2) molecule and having a hydroxyl group equivalent of 100 g/eq. or more is reacted. The thermosetting resin composition of claim 1, wherein the (A-2) phenolic hydroxyl group-containing compound is at least selected from the group consisting of a compound having two hydroxyphenyl groups in the molecule and a phenol resin. 1 species. The thermosetting resin composition of claim 2, wherein the compound having two hydroxyphenyl groups in the molecule is selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, and bisphenol Z. At least one of them. The thermosetting resin composition of claim 2 or 3, wherein the phenol resin has a weight average molecular weight of 200 to 5,000. The thermosetting resin composition according to any one of claims 1 to 3, wherein the nitrogen-containing compound is a cyclic urea compound. The thermosetting resin composition of claim 5, wherein the cyclic urea compound is a group of ethylene urea, acryl urea, carbendazim, cyanuric acid, and violuric acid. At least one of the selected ones. The thermosetting resin composition according to any one of claims 1 to 3, wherein the hydroxyl group equivalent of the nitrogen-containing phenol resin (A) is 1.0 equivalent of the epoxy group of the epoxy resin (B). 0.6 equivalents to 1.2 equivalents. The thermosetting resin composition according to any one of claims 1 to 3, wherein the phenolic hydroxyl group-containing compound (A-2) has a hydroxyl group equivalent of from 100 g/eq. to 200 g/eq. The thermosetting resin composition according to any one of claims 1 to 3, wherein the nitrogen-containing phenol resin (A) has a weight average molecular weight of 500 to 5,000. The thermosetting resin composition according to any one of claims 1 to 3, wherein the epoxy resin (B) has a weight average molecular weight of 300 to 5,000. The thermosetting resin composition according to any one of claims 1 to 3, which comprises a filler. A cured product obtained by hardening a thermosetting resin composition according to any one of claims 1 to 11.