JP5845528B2 - Phenol resin composition and thermosetting resin composition - Google Patents

Description

  The present invention provides a phenolic resin as an epoxy resin curing agent that gives a thermosetting resin composition having good fluidity and gives a cured product having excellent heat resistance and moisture resistance, and thermosetting containing the phenolic resin. The present invention relates to a resin composition.

Thermosetting resin compositions combining an epoxy resin and a phenol resin (curing agent) are used in various fields because the cured product is excellent in heat resistance, adhesion, electrical insulation and the like. For example, resin compositions for printed circuit boards, resin compositions for interlayer insulation materials used for printed circuit boards and resin-coated copper foils, resin compositions for electronic parts sealing materials, resist inks, conductive pastes (contains conductive fillers) Used in paints, adhesives, composite materials, etc.
In particular, there is an increasing need for miniaturization, thinning, and miniaturization of products for semiconductor encapsulants, and even for the thermosetting resin composition, further heat resistance and moisture resistance of the cured product (molded product). There is a demand for improvements in heat resistance and flame retardancy, and reduction in coefficient of linear expansion.
One solution is to increase the amount of filler used. Increasing the amount of filler makes it possible to reduce the coefficient of linear expansion of the molded product, reduce the moisture absorption rate, and improve flame retardancy. However, since the problem that moldability deteriorates arises, it is necessary to simultaneously lower the melt viscosity of the resin component.
As a means for improving the heat resistance of the cured product, there is a method of increasing the crosslinking density by increasing the number of functional groups of the resin component. Therefore, improvement in heat resistance has been studied by using an epoxy resin having a triphenylmethane structure, a phenol resin, an epoxy resin having a tetrakisphenolethane structure, or a phenol resin. However, since the fluidity of the resin decreases as the number of functional groups increases, methods for achieving both the heat resistance of the cured product and the fluidity of the resin have been studied (see Patent Documents 1 and 2).

Patent Document 1 describes an invention in which an epoxy resin having a triphenylmethane structure and a phenol resin having a triphenylmethane structure are the main components and a crystalline epoxy resin is partly blended. Although the resin composition thus obtained is excellent in fluidity, the heat resistance of the cured product is lowered by blending the crystalline epoxy resin.
On the other hand, Patent Document 2 describes an invention in which a phenol resin containing a phenol resin having a tetrakisphenolethane structure, which is a condensate of phenols and dialdehydes, is used as a curing agent for an epoxy resin. However, since the phenol resin described in Patent Document 2 imparts fluidity by increasing the ratio of a substance in which phenols are condensed to 3 moles or less with respect to 1 mole of dialdehydes, fluidity is improved. However, the heat resistance of the cured product is insufficient.

Japanese Patent No. 3365725 JP 2001-48959 A

  The present invention has been made on the basis of the above circumstances, and provides an epoxy resin curing that provides a thermosetting resin composition having good fluidity and a cured product having excellent heat resistance and moisture resistance. It is an object of the present invention to provide a phenol resin which is an agent and a thermosetting resin composition containing the phenol resin.

In the present invention, the above-mentioned problem is caused by reacting a phenolic hydroxyl group-containing compound obtained by reacting an all-phenolic phenolic hydroxyl group with acetone under acidic conditions, a dimethylol body of a nitrogen-containing compound, and a phenol. It is based on what was found to be achieved by the thermosetting resin composition which used the phenol resin composition containing the nitrogen-containing phenol resin obtained as an essential component as an epoxy resin hardening | curing agent.
That is, the present invention has the following configuration.
(1) (A) 50 to 90% by mass of a phenolic hydroxyl group-containing compound having a structure represented by the following formula (II) in the total phenol resin, and (B) a methylene bond between the nitrogen-containing compound and phenols A phenol resin comprising 10 to 50% by mass of a nitrogen-containing phenol resin having a structure alternately repeated through a total phenol resin.

(In formula (II), R ₁ and R ₂ may be the same or different; R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; j and k are integers of 1 or 2; And l and m represent an integer of 0 to 2.)
(2) The phenol resin composition according to (1), wherein the structure of the formula (II) is a structure represented by the following formula (III).

( 3 ) The phenol resin composition according to the above (1) or (2), wherein the nitrogen-containing compound is one or more compounds selected from ethylene urea, propylene urea, hydantoin, cyanuric acid, and pyorlic acid.
( 4 ) A thermosetting resin composition comprising the phenol resin composition according to any one of (1) to ( 3 ) and an epoxy resin.
( 5 ) The thermosetting resin composition according to (4), wherein the phenol resin is 0.6 to 1.2 equivalents relative to 1.0 equivalent of epoxy resin.
( 6 ) The thermosetting resin composition according to the above ( 4 ) or ( 5 ), which contains a filler.
( 7 ) Hardened | cured material of the thermosetting resin composition in any one of said ( 4 )-( 6 ).

The phenolic resin of the present invention is obtained by mixing a nitrogen-containing phenolic resin with a crystalline phenolic hydroxyl group-containing compound capable of giving a cured epoxy resin having excellent heat resistance and moisture resistance.
As a result, according to the present invention, a phenol resin which is an epoxy resin curing agent which gives a thermosetting resin composition having good fluidity and gives a cured product having excellent heat resistance and moisture resistance, and the phenol resin The thermosetting resin composition containing can be provided.

The present invention will be described in detail below.
The phenolic resin of the present invention is a nitrogen-containing phenolic resin (A) obtained by reacting a phenolic hydroxyl group-containing compound (A) obtained by reacting phenols and acetone under acidic conditions, a dimethylol body of a nitrogen-containing compound, and phenols ( B) is contained as an essential component.

Here, the phenol refers to a compound represented by the following formula (I).

(In formula (I), R ₁ is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a condensed ring together with a benzene ring of phenol, or 7 to 10 carbon atoms. And i represents an integer of 0 to 3.)

  Examples of the phenolic hydroxyl group-containing compound (A) obtained by reacting phenols with acetone under acidic conditions include compounds having an oxyflavan structure represented by the following formula (II).

(In formula (II), R ₂ and R ₃ may be the same or different, R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, j and k are integers of 1 or 2; And l and m represent an integer of 0 to 2.)

  The phenols used in the synthesis of the phenolic hydroxyl group-containing compound may be those used in the production of general phenol resins, such as phenol, orthocresol, metacresol, paracresol, orthoethylphenol, meta Ethylphenol, paraethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,5-xylenol, 2,6-xylenol, orthobutylphenol, metabutylphenol, parabutylphenol, orthooctylphenol, meta Octylphenol, paraoctylphenol, orthononylphenol, methanonylphenol, paranonylphenol, orthophenylphenol, metaphenylphenol, paraphenylphenol, orthosi B hexyl phenol, meta-cyclohexyl phenol, p-cyclohexyl phenol, catechol, resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, hydroquinone, can be used alone or in combination. Of these, resorcinol is preferred from the viewpoint of excellent reactivity with acetone.

  The amount of acetone used is preferably 15 to 250 parts by weight, preferably 25 to 150 parts by weight, based on 100 parts by weight of phenols.

  Any acidic catalyst may be used as long as it is used for the production of general novolak resins. Examples thereof include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and oxalic acid. Can be used. The usage-amount of an acidic catalyst is 0.001-10 mass parts with respect to 100 mass parts of phenols, Preferably it is 0.01-8 mass parts, More preferably, 0.1-5 mass parts can be used suitably. .

  The reaction method of phenols and acetone is not particularly limited, and is a method in which phenols, acetone and a catalyst are charged in a lump or reacted, or phenols and a catalyst are charged and reacted in advance at a predetermined temperature, and then acetone is dropped. The method of reacting. There is no restriction | limiting in particular also in reaction time, What is necessary is just to adjust with the quantity of acetone and a catalyst, and reaction temperature. After the reaction, unreacted acetone and condensed water may be removed by distillation, or if necessary, the remaining catalyst and unreacted phenols may be removed by washing with water. Further, unreacted phenols may be removed by distillation under reduced pressure or steam distillation.

  When resorcinol is used as the phenol, the resulting phenolic hydroxyl group-containing compound contains a structure represented by the following formula (III), and when the purity is high, it becomes a crystal having a melting point exceeding 200 ° C. On the other hand, when the dimer or more is increased, the melting point becomes 200 ° C. or less, but the flowability as an epoxy resin compound becomes extremely poor because the melt viscosity is high.

Nitrogen-containing phenol resin (B) obtained by reacting a dimethylol body of a nitrogen-containing compound and phenols is mixed with the phenolic hydroxyl group-containing compound (A) to suppress crystallization, and for semiconductor encapsulant Sufficient fluidity can be imparted.
The nitrogen-containing compound is preferably a cyclic ureido in terms of compatibility with the phenolic hydroxyl group-containing compound, for example, one or more compounds selected from ethylene urea, propylene urea, hydantoin, cyanuric acid, and pyorlic acid, It is not limited to these. The dimethylol body of the nitrogen-containing compound is preferably a bifunctional compound that can react with two molecules of a formaldehyde compound with respect to one molecule of cyclic ureido, and specifically, dimethylol ethylene urea and dimethylol propylene urea. Dimethylol hydantoin, dimethylol cyanuric acid, and dimethylol pyoruric acid. These may be used alone or in combination of two or more.

A dimethylol form of a nitrogen-containing compound can be obtained by addition reaction of a nitrogen-containing compound and a formaldehyde compound. In this reaction, 2.0 to 2.1 mol of a formaldehyde compound is preferable with respect to 1.0 mol of the nitrogen-containing compound. As the formaldehyde-based compound, formalin, paraformaldehyde, or trioxane (metaformaldehyde) can be used.
The reaction is preferably carried out in the presence of water or an organic solvent, without a catalyst, or in the presence of a basic catalyst. The reaction temperature is 45 ° C. to 80 ° C. or less, preferably 45 ° C. to 70 ° C. or less, more preferably 45 ° C. to 50 ° C. or less, and preferably about 1 to 10 hours. When the reaction temperature is less than 45 ° C, the reaction is slow and not efficient. On the other hand, when the reaction temperature exceeds 80 ° C., it is difficult to control the reaction and a side reaction may occur, which is not preferable.

  Organic solvents used in the reaction include water, alcohols such as methanol and ethanol, glycols such as ethylene glycol and propylene glycol, ketones such as acetone and methyl ethyl ketone, ethyl acetate, propyl acetate, butyl acetate, and ethylene glycol monomethyl. Esters such as ether acetate and propylene glycol monomethyl ether acetate, ethers such as tetrahydrofuran and 1,4-dioxane, acetic acid, N, N-dimethylformamide, dimethyl sulfoxide, etc. are used alone or in combination of two or more. It is possible to use 0 to 1,000 parts by mass, preferably about 10 to 100 parts by mass with respect to 100 parts by mass of the nitrogen-containing compound, if necessary.

  As the basic catalyst used in the reaction, for example, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, trimethylamine, triethylamine, tributylamine and the like can be appropriately used for the purpose of promoting the reaction. . When electrical insulation such as a semiconductor encapsulant is required, it is preferable to remove the catalyst by neutralizing with an acid after completion of the reaction and then washing with water.

The nitrogen-containing phenol resin (B) is obtained by subjecting a dimethylol body of a nitrogen-containing compound and a phenol to a condensation reaction. In this reaction, it is preferable to carry out a condensation reaction of 1.0 to 3.0 mol of phenols with 1.0 mol of a dimethylol body of a nitrogen-containing compound.
The phenols used here may be those used in the production of general phenol resins, and the above phenols may be used alone or in combination of two or more.

  The reaction is preferably carried out in the presence of an acid catalyst in the presence of water or an organic solvent. The reaction temperature is 70 ° C. to 150 ° C. or less, preferably 80 ° C. to 120 ° C. or less, more preferably 90 ° C. to 110 ° C. or less, and preferably about 1 to 10 hours. When the reaction temperature is less than 70 ° C., the reaction is slow and not efficient. On the other hand, when the reaction temperature exceeds 150 ° C., it is difficult to control the reaction and a side reaction may occur, which is not preferable.

  Any acid catalyst may be used as long as it is used for the production of general novolak resins. Examples thereof include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, oxalic acid, and the like. Can be used. In particular, oxalic acid that decomposes by heating is preferable. The amount of the acid catalyst used is suitably 0.001 to 10 parts by mass, preferably 0.01 to 8 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the dimethylol body of the nitrogen-containing compound. can do.

  After the reaction, it can be washed with water as necessary, and heated under reduced pressure to remove condensed water and unreacted phenols. The resin can also be obtained as a solid resin having a softening point, and if necessary, can be dissolved in an organic solvent to form a resin solution.

  The nitrogen-containing phenol resin (B) of the present invention can be obtained by the above-described method, but after obtaining a dimethylol body of a nitrogen-containing compound, the nitrogen-containing compound and the phenols react with this to form a methylene bond. Thus, an oligomer having a structure alternately repeated is obtained.

In the phenol resin of the present invention, the phenolic hydroxyl group-containing compound (A) is contained in the total phenol resin in an amount of 50 to 90% by mass, and the nitrogen-containing phenol resin obtained by reacting a dimethylol body of a nitrogen-containing compound with a phenol. It is preferable that 10-50 mass% of (B) is included in the total phenol resin. If the content of the phenolic hydroxyl group-containing compound exceeds 90% by mass, the softening point of the phenol resin becomes too high, which is not preferable. On the other hand, when the content of the phenolic hydroxyl group-containing compound is less than 50% by mass or the content of the nitrogen-containing phenol resin exceeds 50% by mass, the heat resistance of the cured product of the thermosetting resin composition (epoxy resin composition). Is not preferable because it becomes insufficient. Moreover, if content of nitrogen-containing phenol resin is less than 10 mass%, since the effect which suppresses crystallization of a phenolic hydroxyl-containing compound becomes inadequate, it is unpreferable.
In the phenol resin of the present invention, if the phenolic hydroxyl group-containing compound and the nitrogen-containing phenol resin are within the above ranges, a phenol novolak resin, a cresol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a naphthol novolak resin, a naphthol aralkyl resin, etc. Of course, other phenol resins can be used in combination.

  In the phenol resin of the present invention, the phenolic hydroxyl group-containing compound (A) and the nitrogen-containing phenol resin (B) can be blended separately, but the phenolic hydroxyl group-containing compound has a high melting point / softening point. It is preferable to use in a form in which the organic solvent is removed after mixing and dissolving in an organic solvent in advance. In that case, it is preferable to adjust the blending ratio of the phenolic hydroxyl group-containing compound, the nitrogen-containing phenol resin and the other phenol resin so that the resulting mixture (phenol resin) has a softening point of 125 ° C. or lower. When the softening point of the phenol resin exceeds 125 ° C., the fluidity of the thermosetting resin composition, which is a mixture with the epoxy resin, is not preferable.

  It does not specifically limit as an epoxy resin used by this invention, A well-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, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type Epoxy resins derived from dihydric phenols such as epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane Type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, na Tall novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolak type epoxy resin Examples thereof include epoxy resins derived from trivalent or higher-valent phenols such as resins, and epoxy resins modified with organic phosphorus compounds. Among these, triphenylmethane type epoxy resin is preferable. Moreover, these epoxy resins may be used independently and may use 2 or more types together.

The mixing ratio of the epoxy resin and the phenol resin is such that the phenol resin is in the range of 0.6 to 1.2 equivalents, preferably in the range of 0.7 to 1.1 equivalents, relative to 1.0 equivalent of the epoxy resin.
In this thermosetting resin composition, a curing accelerator can be appropriately used for the purpose of accelerating the curing reaction.
Examples of such curing accelerators include organic acid metal salts such as imidazole, organic phosphorus compounds, secondary and tertiary amines, tin octylate, Lewis acids, amine complex salts, and the like. Alternatively, two or more kinds can be used in combination.

  Among the above, imidazole compounds 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-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2- Phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline and the like can be mentioned.

These imidazole compounds may be masked with a masking agent.
Examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate.

  Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetra And phenylphosphonium tetraphenylborate.

Secondary amine compounds include morpholine, piperidine, pyrrolidine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, N-alkylarylamine, piperazine, diallylamine, thiazoline, thiol. Examples include morpholine.
Examples of the tertiary amine compound include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, and 2,4,6-tris (diaminomethyl) phenol.

  In addition, the thermosetting resin composition of the present invention includes various kinds of fillers, thermosetting resins and thermoplastic resins used as modifiers, pigments, silane coupling agents, mold release agents, and the like as necessary. These compounding agents can be added depending on the purpose.

  Among these, for example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, aluminum hydroxide And inorganic fillers such as magnesium hydroxide. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The desired range varies depending on the application and desired properties, but for example, when used for semiconductor encapsulant applications, it is preferable to use a higher coefficient in view of the linear expansion coefficient and flame retardancy. It is preferably 65% by mass or more, particularly preferably about 80 to 90% by mass. Moreover, when using for uses, such as an electrically conductive paste and an electrically conductive film, electrically conductive fillers, such as silver powder and copper powder, can be used.

  Various known thermosetting and thermoplastic resins used as the modifier can be used. For example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether Resins, polyphenylene sulfide resins, polyester resins, polystyrene resins, polyethylene terephthalate resins, and the like can be used as long as they do not impair the effects of the present invention.

Examples of the silane coupling agent include silane coupling agents such as amino silane compounds, vinyl silane compounds, styrene silane compounds, and methacryl silane compounds.
Examples of the mold release agent include stearic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, and carnauba wax.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these, "part" and "%" in an Example and a comparative example are mass references | standards.

Example 1 (Synthesis of phenol resin)
A flask equipped with a condenser and a stirrer was charged with 100 g of resorcinol, 26 g of acetone, and 0.1 g of paratoluenesulfonic acid, and reacted at 80 ° C. for 2 hours. Next, 26 g of acetone was added and reacted at 80 ° C. for 2 hours. Subsequently, it was washed 4 times with 100 g of pure water to remove the catalyst and unreacted resorcinol. Subsequently, the distillate was removed under reduced pressure at 150 ° C. and 50 mmHg to obtain 76 g of white crystalline phenol resin A-1. The melting point of the obtained phenol resin A-1 was 200 ° C. 76 g of phenol resin A-1 was dissolved in 95 g of acetone, and then nitrogen-containing phenol resin B-1 (made by Showa Denko), which is a nitrogen-containing phenol resin using dimethylolethyleneurea as the nitrogen-containing compound and phenol as the phenol. 19 g of Shounol BRM-5622, softening point 82 ° C., hydroxyl equivalent 160) were charged and dissolved. Next, the distillate was removed under reduced pressure at 150 ° C. and 50 mmHg to obtain 95 g of a light brown lump phenol resin AN1. The obtained phenol resin AN1 had a softening point of 112 ° C.

Example 2 (Synthesis of phenol resin)
The reaction was performed in the same manner as in Example 1 except that 57 g of phenol resin A-1 and 38 g of nitrogen-containing phenol resin B-1 were used, and 95 g of phenol resin AN2 was obtained. The resulting phenol resin AN2 had a softening point of 94 ° C.

Example 3 (Synthesis of phenol resin)
A flask equipped with a condenser and a stirrer was charged with 100 g of resorcinol, 65 g of acetone, and 0.1 g of paratoluenesulfonic acid, and reacted at 90 ° C. for 5 hours. Subsequently, it was washed 4 times with 100 g of pure water to remove the catalyst and unreacted resorcinol. Subsequently, the distillate was removed under reduced pressure at 150 ° C. and 50 mmHg to obtain 94 g of a light brown lump-like phenol resin A-2. The softening point of the obtained phenol resin A-2 was 119 ° C. 76 g of phenol resin A-2 was dissolved in 95 g of acetone, and then 19 g of nitrogen-containing phenol resin B-1 was charged and dissolved. Subsequently, the distillate was removed under reduced pressure at 150 ° C. and 50 mmHg to obtain 95 g of a light brown lump-like phenol resin BN1. The softening point of the obtained phenol resin BN1 was 104 ° C.

Example 4 (Synthesis of phenol resin)
The reaction was performed in the same manner as in Example 3 except that 57 g of phenol resin A-2 and 38 g of nitrogen-containing phenol resin B-1 were used, and 95 g of phenol resin BN2 was obtained. The softening point of the obtained phenol resin BN2 was 90 ° C.

Example 5 (Synthesis of phenol resin)
A flask equipped with a condenser and a stirrer was charged with 70 g of resorcinol, 30 g of phenol, 68 g of acetone, and 0.1 g of paratoluenesulfonic acid, and reacted at 90 ° C. for 5 hours. Subsequently, it was washed 4 times with 100 g of pure water to remove the catalyst and unreacted resorcinol. Next, the distillate was removed under reduced pressure at 150 ° C. and 50 mmHg to obtain 89 g of a light brown lump-like phenol resin A-3. The resulting phenol resin C had a softening point of 111 ° C. 89 g of phenol resin A-3 was dissolved in 95 g of acetone, and then 19 g of nitrogen-containing phenol resin B-1 was charged and dissolved. Subsequently, the distillate was removed under reduced pressure at 150 ° C. and 50 mmHg to obtain 95 g of a light brown lump phenol resin CN. The softening point of the obtained phenol resin CN was 99 ° C.

Comparative Example 1 (Synthesis of phenol resin)
A flask equipped with a condenser and a stirrer was charged with 100 g of phenol, 65 g of salicylaldehyde, and 1 g of paratoluenesulfonic acid, and reacted at 100 ° C. for 8 hours. Next, the catalyst was removed by washing 4 times with 100 g of pure water. Subsequently, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 96 g of phenol resin D. The obtained phenol resin D had a softening point of 128 ° C.

Comparative Example 2 (Synthesis of phenol resin)
A flask equipped with a condenser and a stirrer was charged with 100 g of phenol, 60 g of 37% formalin, and 1 g of oxalic acid. After reacting at 100 ° C. for 5 hours, the distillate was removed under reduced pressure of 180 ° C. and 50 mmHg, and phenol resin E84 g Got. The softening point of the obtained phenol resin E was 95 ° C.

Table 1 shows the characteristic values of the phenol resins obtained in Examples 1 to 5 and the phenol resins obtained in Comparative Examples 1 and 2. The analysis method of resin is as follows.
(1) Softening point (° C)
Measurement was performed at a temperature increase rate of 2.5 ° C./min using an EX-719 gas phase softening point measuring apparatus EX-719PD.
(2) Melt viscosity (mPa · s)
The measurement was performed at 150 ° C. using an ICI viscometer manufactured by Research Equip.

  From Table 1, it can be seen that the phenol resin of the present invention is excellent in fluidity when compared with the triphenylmethane type phenol resin of Comparative Example 1 which is an epoxy resin curing agent that gives a cured product having excellent heat resistance.

Examples 6 to 14, Comparative Examples 3 and 4 (Preparation of thermosetting resin composition)
About each of the phenol resin obtained in Examples 1-5 and the phenol resin obtained in Comparative Examples 1 and 2, it melt-kneaded with the mixing | blending shown in Table 2, and heat of Examples 6-14 and Comparative Examples 3 and 4 A curable resin composition was obtained.
The formulation in Table 2 was performed as follows.
The composition is mainly composed of 10 parts of epoxy resin and a resin component obtained by mixing 0.1 parts of triphenylphosphine (curing accelerator) with a hydroxyl group equivalent phenol resin in the ratio shown in Table 2. A thermosetting resin composition was prepared by mixing fused silica (inorganic filler) so that the content was 80%.

The obtained thermosetting resin composition is pressure-molded in a mold at 150 ° C. for 30 minutes at a pressure of 30 kg / cm ² . Then, it hardened | cured after 180 degreeC-5 hours, and the test piece was created.

The glass transition temperature, the water absorption rate and the bending strength of the obtained test piece were evaluated by the following methods.
(3) Glass transition temperature Glass transition temperature was measured by TMA method using SSC / 5200 manufactured by SII. The heating rate was 10 ° C./min.
(4) Water absorption rate Using a unsaturated high acceleration life test apparatus PC-422R8 manufactured by Hirayama Seisakusho Co., Ltd., the weight increase rate after holding at a temperature of 121 ° C. and a humidity of 100% for 20 hours was measured.
(5) Bending strength It measured by the method based on JISK-6911.
Table 2 shows the measurement results of glass transition temperature, water absorption, and bending strength for Examples 6 to 14 and Comparative Examples 3 and 4.

In the composition of Table 2, the following were used as the epoxy resin, triphenylphosphine, and fused silica.
Epoxy resin: manufactured by Mitsubishi Chemical Corporation, resin H (triphenylmethane type epoxy resin), trade name 1032H60
Triphenylphosphine: Wako Pure Chemical Industries, Ltd. Fused silica: Tatsumori Co., Ltd., trade name: MSR-2212

  From Table 2, the hardened | cured material of the thermosetting resin composition of this invention can express a high glass transition temperature, and can suppress a water absorption rate low. That is, it can be seen that the water absorption is much lower than the conventional novolac resins of phenol resins D and E, and the glass transition temperature, the linear expansion coefficient and the like exhibit the same physical properties as those of the conventional novolac resins.

  As described above, according to the present invention, a phenol resin which is an epoxy resin curing agent which gives a thermosetting resin composition having good fluidity and gives a cured product having excellent heat resistance and moisture resistance, and heat containing the phenol resin It has become possible to provide a curable resin composition.

  The thermosetting resin composition of the present invention has good fluidity, and the cured product has good heat resistance, moisture resistance, mechanical properties, electrical insulation, adhesion to metal, and the like. Therefore, specifically, a resin composition for an electronic component sealing material, 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 conductive paste (conductive filler) Containment), paints, adhesives and composite materials.

Claims (7)

(A) A phenolic hydroxyl group-containing compound having a structure represented by the following formula (II) is contained in the composition in an amount of 50 to 90% by mass, and (B) a nitrogen-containing compound and phenols are alternately connected via a methylene bond. A phenol resin composition comprising 10 to 50% by mass of a nitrogen-containing phenol resin having a repeated structure in the composition.

(In formula (II), R ₁ and R ₂ may be the same or different; R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; j and k are integers of 1 or 2; And l and m represent an integer of 0 to 2.) The phenol resin composition according to claim 1, wherein the structure of the formula (II) is a structure represented by the following formula (III).
  3. The phenol resin composition according to claim 1, wherein the nitrogen-containing compound is at least one compound selected from ethylene urea, propylene urea, hydantoin, cyanuric acid, and pyorlic acid. The thermosetting resin composition containing the phenol resin composition and epoxy resin in any one of Claims 1-3 . The thermosetting resin composition according to claim 4 , wherein the phenol resin composition is 0.6 to 1.2 equivalents relative to 1.0 equivalent of epoxy resin. The thermosetting resin composition according to claim 4 or 5 , comprising a filler. Cured thermosetting resin composition according to any one of claims 4-6.