JP6497639B2 - Thermosetting resin composition, cured product and method for producing modified phenolic resin - Google Patents

Description

  The present invention relates to a thermosetting resin composition, a cured product, and a method for producing a modified phenolic resin.

Thermosetting resin compositions combining an epoxy resin and a phenolic resin (curing agent) can be used in various fields because the cured products of such thermosetting resin compositions are excellent in heat resistance, adhesion, electrical insulation, etc. Is used. For example, a resin composition for printed circuit boards, a resin composition for interlayer insulation materials used for printed circuit boards and copper foils with resin, a resin composition for sealing materials for electronic components, a resist ink, and a conductive paste containing a conductive filler , Paints, adhesives, composite materials, etc.
The degree of integration of semiconductors has been increasing year by year in accordance with Moore's Law. In order to cope with the higher integration of semiconductors, semiconductor packages also have a single-side sealed package such as a ball grid array (hereinafter referred to as BGA) connected by bumps or a stacked structure in addition to a package using a conventional lead frame. Dimension packages have been developed. On the other hand, semiconductor encapsulating materials have been studied for blending thermosetting resin compositions suitable for respective packages, and molding methods have been improved. For example, in a single-side sealed package, since the surface to be sealed is only one side, warping caused by the difference in shrinkage between the substrate side and the sealing material side during molding is a problem, and thermosetting to suppress this There is a need for a functional resin composition.
In order to meet such a demand, various solutions have been studied. For example, the following means are known as one of the solution means. The thermosetting resin composition generally contains various fillers, and a method for suppressing warpage by increasing the amount of filler used is known.
Moreover, the method of raising a crosslinking density by increasing the number of functional groups of the resin component in a thermosetting resin composition is known. For example, a method for suppressing warping by using an epoxy resin or a phenol resin having a triphenylmethane structure, or an epoxy resin or a phenol resin having a tetrakisphenolethane structure has been studied.

As a document showing such means, for example, Patent Document 1 describes reducing the warpage of a package by blending 85 to 95 wt% of an inorganic filler.
Further, for example, Patent Document 2 describes that after forming with a sealing material having a low glass transition temperature, the warpage is suppressed by coating with a sealing material having a high glass transition temperature.
On the other hand, Patent Document 3 is characterized by having a phenolic hydroxyl group in the molecule obtained by reacting a phenolic hydroxyl group of a novolak resin with an equivalent amount or less of glycidyl (meth) acrylate. It is increased by mixing a curable resin composition in which a compound having two or more epoxy groups in the molecule and an aliphatic tertiary amine are mixed with a (meth) acryloylated novolak resin at 50 ° C. or higher and 100 ° C. or lower. It is described to make it viscous.

  Further, in Patent Document 4, there is a need for solving the problem of convex warpage at room temperature, which is opposite to the conventional one, by increasing the area occupied by the semiconductor chip in addition to downsizing and thinning of the single-side sealed package. It is described that it is increasing.

JP 11-1541 A Japanese Patent Laid-Open No. 10-112515 JP 2000-198832 A JP 2012-72209 A

In order to reduce the warpage, there are methods such as reducing the shrinkage rate of the thermosetting resin composition as much as possible, or increasing the rigidity of the thermosetting resin composition to resist the warpage itself.
Under such circumstances, as shown in Patent Documents 1 and 2, the amount of inorganic filler is increased to increase the elastic modulus, or the cured product of the thermosetting resin composition has a low linear expansion coefficient up to the highest possible temperature. In order to obtain the glass region, methods for increasing the glass transition temperature of the cured product have been studied.
However, the methods as disclosed in Patent Documents 1 and 2 are effective for the warp in the concave direction of the chip mounting surface, but have the opposite effect for the warp in the convex direction that occurs in a thin package. That is, it is necessary to increase the shrinkage rate of the thermosetting resin composition in order to offset the warpage of the substrate against the warpage in the convex direction.
Moreover, even if the thermosetting resin composition having a specific configuration described in Patent Document 3 is thickened by mixing in a specific temperature range, the substrate still remains against warping in the convex direction. It is difficult to suppress warpage.

  An object of this invention is to provide the manufacturing method of the thermosetting resin composition from which the hardened | cured material with a high shrinkage rate at the time of hardening is obtained, the hardened | cured material obtained by hardening | curing this, and modified phenol resin.

That is, the present invention is configured as follows.
[1] A thermosetting resin composition comprising a modified phenol resin (A) represented by the general formula (I) obtained by reacting in the presence of an organic phosphorus compound and an epoxy resin (B). The total content of alkali metal and alkaline earth metal in the modified phenol resin (A) is 0.1% by mass or less based on the total amount of the phenol resin (A), and the modified phenol resin ( The content of the amine compound in A) is 0.1% by mass or less with respect to the total amount of the phenol resin (A), and the weight average molecular weight of the modified phenol resin (A) is 250 to 5000. The thermosetting resin composition characterized by the above-mentioned.

(In the formula, R ¹ is a hydrogen atom or a group represented by the following formula (II), and the proportion of R ¹ being a hydrogen atom is 20% or more and less than 80%. R ² and R ³ are each independent. Represents a hydrogen atom or an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 40.)

(In the formula, R ⁴ is a group represented by a hydrogen atom or a methyl group.)
[2] The total content of alkali metal and alkaline earth metal in the thermosetting resin composition is 0.05% by mass or less, and the content of the amine compound in the thermosetting resin composition is The thermosetting resin composition according to [1], which is 0.05% by mass or less.
[3] The content of the modified phenol resin (A) is such that the hydroxyl group of the modified phenol resin (A) is 0.6 equivalent to 1.2 equivalents with respect to 1.0 equivalent of the epoxy group in the epoxy resin (B). The thermosetting resin composition according to [1] or [2], which is in an equivalent range.
[4] The thermosetting resin composition according to any one of [1] to [3], wherein the epoxy resin (B) has a weight average molecular weight of 300 to 5,000.
[5] The thermosetting resin composition according to any one of [1] to [4], including a filler.
[6] A cured product obtained by curing the thermosetting resin composition according to any one of [1] to [5].
[7] The cured product according to [6], which has a shrinkage rate of 0.15% to 0.40%.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the thermosetting resin composition from which the hardened | cured material with a high shrinkage rate at the time of hardening is obtained, hardened | cured material, and a thermosetting resin composition is provided.

<Thermosetting resin composition>
The thermosetting resin composition of the present invention contains a modified phenolic resin (A) and an epoxy resin (B).
The thermosetting resin composition of the present invention may further contain a filler, a compounding agent and the like as long as the effects of the present invention are not impaired.
Hereinafter, the thermosetting resin composition of the present invention will be described in detail.
In addition, the numerical value range shown using "to" in this specification shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.

[Modified phenolic resin (A)]
The modified phenol resin (A) is suitably obtained by reacting a phenol resin and glycidyl (meth) acrylate in the presence of an organic phosphorus compound.

(Phenolic resin)
The phenol resin used in the present invention is not particularly limited, and a known novolak type phenol resin obtained by reacting phenols and aldehydes in the presence of an acidic catalyst can be used.
Specific examples of phenols include, for example, phenol, cresol, ethylphenol, xylenol, butylphenol, octylphenol, nonylphenol, phenylphenol, cyclohexylphenol, trimethylphenol, bisphenol A, catechol, resorcinol, hydroquinone, naphthol, pyrogallol and the like. From the viewpoint of the shrinkage ratio of the resulting thermosetting resin, phenol and cresol are preferable, and ortho-cresol is preferable as cresol.

  Specific examples of aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, hexylaldehyde, benzaldehyde, hydroxybenzaldehyde, dihydroxybenzaldehyde, hydroxymethylbenzaldehyde, glyoxal, crotonaldehyde, glutaraldehyde and the like. From the viewpoint of shrinkage of the resulting thermosetting resin, formaldehyde and benzaldehyde are preferable.

  As the phenol resin, for example, a phenol novolac resin can be used. As the phenol novolak resin, a trade name “Shonol BRG-558” (phenol novolak, manufactured by Showa Denko KK, hydroxyl group equivalent 104 g / eq., “Shonol”) Is a trademark of Showa Denko KK), trade name "Shonol CRG-951" (orthocresol novolak, manufactured by Showa Denko KK, hydroxyl equivalent of 118 g / eq., "Shonol" is a trademark of Showa Denko KK There is).

[Method for producing modified phenolic resin (A)]
The method for producing a modified phenolic resin of the present invention is a method in which a phenolic resin and glycidyl (meth) acrylate are reacted in the presence of an organophosphorus compound to obtain a modified phenolic resin (A) represented by the general formula (I). is there.
In the formula, R ¹ is a hydrogen atom or the following formula (II)
(In the formula, R ⁴ is a group represented by a hydrogen atom or a methyl group.)
The ratio of R ¹ being a hydrogen atom is 20% or more and less than 80%. R ² and R ³ each independently represents a hydrogen atom or an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms. n represents an integer of 0 to 40.

In the general formula of the modified phenolic resin (A), the proportion of n + 2 total R ^{1 s} where R ¹ is a hydrogen atom is 20% or more and less than 80%, preferably 30 to 70%, more preferably 40-60%.
Thermosetting resin containing modified phenolic resin (A) and epoxy resin (B) described later by making the proportion of hydrogen atom of R ¹ in the general formula of modified phenolic resin (A) 20% or more and less than 80% The shrinkage rate at the time of hardening of a composition becomes large.
In said formula (I), R < ² > and R < ³ > represents a hydrogen atom or a C1-C20 aliphatic or aromatic hydrocarbon group each independently.
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a chain-like or branched saturated alkyl group or unsaturated alkyl group, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. . Specific examples include, but are not limited to, a methyl group, an ethyl group, an isopropyl group, an n-octyl group, a vinyl group, and a butenyl group. From the viewpoint of versatility and ease of reaction, a methyl group and an ethyl group are preferable.
Examples of the aromatic hydrocarbon group having 1 to 20 carbon atoms include a phenyl group and a naphthyl group.
From the viewpoints of versatility and ease of reaction, R ² and R ³ are preferably each independently a methyl group or an ethyl group.
In said formula (I), n represents the integer of 0-40, Preferably it is 0-30, More preferably, it is 0-20. When n in the formula (I) is an integer of 0 to 40, the weight average molecular weight of the modified phenol resin (A) can be controlled within a specific range, which is preferable from the viewpoint of fluidity.

Here, the modified phenolic resin (A) can be obtained by reacting a phenolic resin and glycidyl (meth) acrylate under a basic catalyst.
The amount of glycidyl (meth) acrylate used is preferably 20 to 90 mol%, more preferably 30 to 80 mol%, based on the number of moles of hydroxyl groups in the phenol resin. Glycidyl (meth) the amount of acrylate 20 mol% or more, can be adjusted to by 90 mol% or less, a predetermined amount ratio of the hydrogen atoms of R ¹ in the general formula of the modified phenolic resin (A).
Examples of the basic catalyst include alkali (earth) metal hydroxides and organic phosphorus compounds.
However, when alkali (earth) metal hydroxide is used, metal ions remain in the modified phenolic resin. For example, in an electronic material application, there is a possibility that a problem due to mixing of metal ions may occur, so a catalyst removal step is required. In the catalyst removal step, for example, the modified phenolic resin is washed with water a plurality of times, or a salt generated by neutralization with an acid is removed by washing with water. Such a process is not preferable because it generates a large amount of waste water and increases the process time.
When an amine compound is used as the basic catalyst, the amine compound remains in the modified phenol resin. The amine compound acts as a curing agent for the epoxy resin, and the reaction temperature is generally lower than the reaction temperature between the phenol resin and the epoxy resin. This is not preferable because the reaction balance between the modified phenolic resin (A) and the epoxy resin (B) in the subsequent step is lost. For example, when hexamethylenetetramine is used as the amine compound, it is not preferable because the reaction between the modified phenol resin (A) and the epoxy resin (B) becomes insufficient because the modified phenol resins have a function of cross-linking with methylene bonds. .

(Organic phosphorus compounds)
Therefore, in the present invention, an organic phosphorus compound is used as the basic catalyst.
Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetra Examples include phenylphosphonium tetraphenylborate. These may be used alone or in combination of two or more, and triphenylphosphine is preferable in consideration of the properties as a thermosetting resin composition.

The amount of the organic phosphorus compound used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and still more preferably 0.1 parts by mass with respect to 100 parts by mass of the phenol resin. Part to 5 parts by mass.
When the amount of the organic phosphorus compound used is 0.01 parts by mass or more with respect to 100 parts by mass of the phenol resin, the reaction time for obtaining the modified phenol resin (A) can be shortened to a practical range. Moreover, control of the reaction rate of a thermosetting resin composition becomes easy that the usage-amount of an organophosphorus compound is 10 mass parts or less with respect to 100 mass parts of phenol resins.

(Other additives)
A polymerization inhibitor can be added as needed from the viewpoint of the storage stability of the composition. Examples of the polymerization inhibitor include hydroquinone and methylhydroquinone.

The method for reacting the phenol resin with glycidyl (meth) acrylate is not particularly limited. For example, the phenol resin, glycidyl (meth) acrylate and a basic catalyst are charged together and reacted, or the phenol resin and the basic catalyst. And adding glycidyl (meth) acrylate at a predetermined reaction temperature.
At this time, the reaction temperature is preferably 30 ° C to 120 ° C, more preferably 60 ° C to 110 ° C.
When the reaction temperature is 30 ° C. or higher, the progress of the reaction can be hardly delayed. Moreover, the radical polymerization of glycidyl (meth) acrylate can be suppressed because reaction temperature is 120 degrees C or less.
There is no restriction | limiting in particular in reaction time, What is necessary is just to adjust suitably according to the quantity of glycidyl (meth) acrylate and a catalyst, and reaction temperature.
In the reaction, an organic solvent may be used.

(Organic solvent)
Examples of such organic solvents include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butanol, glycols such as ethylene glycol and propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene Glycol ethers such as glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, butylene glycol monopropyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate , Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Esters such as acetate, 1,4-dioxane ethers such etc. alone or can be used in combination of two or more thereof.
The organic solvent is preferably 0 to 1,000 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably about 10 to 50 parts by mass with respect to 100 parts by mass of the phenol resin. Can be used as

The modified phenol obtained by the reaction may remove the organic solvent by distillation after the reaction, or may be washed with water as necessary to remove the catalyst.
Further, unreacted phenols may be removed by distillation under reduced pressure or steam distillation.

The total content of alkali metals and alkaline earth metals or the content of amine compounds in the modified phenolic resin (A) is 0.1% by mass or less, preferably 0.8%, based on the total amount of the phenolic resin (A). It is 05 mass% or less, More preferably, it is 0.01 mass% or less. Although it does not specifically limit as an amine compound, The thing derived from the basic catalyst at the time of obtaining modified phenol resin (A) etc. are mentioned, For example, aromatic amines, such as hexamethylenetetramine, aromatics, such as metaxylenediamine Group amines.
Washing of the modified phenolic resin obtained by the total content of alkali metal, alkaline earth metal or the content of amine compound being 0.1% by mass or less with respect to the total amount of the phenol resin (A) The number of times can be reduced. As a result, the manufacturing process time is shortened, and the balance of the reaction between the modified phenol resin (A) and the epoxy resin (B) in the subsequent process is suppressed.
The total content of alkali metals, alkaline earth metals or amine compounds in the thermosetting resin composition is 0.05% by mass or less with respect to the total amount of the thermosetting resin composition. is there. At this time, when the thermosetting resin composition contains a filler, these do not participate in the curing reaction. Therefore, the alkali metal, the alkali with respect to the amount obtained by removing the filler from the total amount of the thermosetting resin composition. Considered as the total content of earth metals or the content of amine compounds.

  The alkali metal and alkaline earth metal in the modified phenol resin (A) are quantitatively measured using an atomic absorption photometer (AAS). The amine compound in the modified phenolic resin (A) is quantitatively analyzed using a gas chromatograph analyzer (GC). The analysis conditions and the like will be described in detail in the examples.

The weight average molecular weight of the modified phenolic resin (A) is preferably 250 to 5000, more preferably 300 to 4000, and more preferably 400 to 3000 in consideration of the fluidity of the thermosetting resin composition. Is more preferable.
The weight average molecular weight of the resin can be measured, for example, by gel permeation chromatography (GPC). As specific measurement conditions for GPC, for example,
Column: Trade names “KF-801”, “KF-802”, “KF-802”, and “KF-803” (manufactured by Showa Denko KK, Shodex ™ series) were used in a linked manner.
Detector: Trade name “RI-71” (manufactured by Showa Denko KK, differential refractometer “Shodex” (trademark))
Solvent: tetrahydrofuran flow rate: 1 ml / min.

[Epoxy resin (B)]
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 divalent 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, naphtha All novolak 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 novolac type epoxy resin And epoxy resins derived from trivalent or higher valent phenols, epoxy resins modified with organophosphorus compounds, and the like. Among these, triphenylmethane type epoxy resin is preferable. Moreover, these epoxy resins may be used independently and may use 2 or more types together. Among these, bisphenol type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, triphenylmethane type epoxy resins, and biphenyl aralkyl type epoxy resins are preferable, and biphenyl aralkyl type epoxy resins are more preferable.

  The weight average molecular weight of the epoxy resin (B) is preferably 300 to 5000, more preferably 400 to 3500, from the viewpoint of the balance between fluidity and heat resistance of the thermosetting resin composition. More preferably, it is 3000.

  The mixing ratio of the epoxy resin (B) and the phenol resin (A) is such that the hydroxyl group in the phenol resin (A) is preferably 0.6 equivalent to 1.0 equivalent of the epoxy group in the epoxy resin (B). The range is 1.2 equivalents, more preferably 0.7 equivalents to 1.1 equivalents.

In the thermosetting resin composition, a curing accelerator can be appropriately used for the purpose of accelerating the curing reaction.
Examples of the curing accelerator include imidazole compounds, organic phosphorus compounds, Lewis acids and the like. These may be used alone or in combination of two or more.

  Examples of the 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.

The imidazole compound 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 Examples include phenylphosphonium tetraphenylborate.
Of these curing accelerators, triphenylphosphine is preferable.

〔filler〕
The thermosetting resin composition of the present invention preferably contains a filler for the purpose of imparting flame retardancy and suppressing thermal expansion. Specific examples include, 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, hydroxide An inorganic filler such as magnesium can be used.
The fused silica can be used in either crushed or spherical shape, but 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 one. . Furthermore, in order to increase the blending amount of the spherical silica into the thermosetting resin composition, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The desirable range of the blending ratio of the fused silica varies depending on the application and desired characteristics of the thermosetting resin composition. For example, when the thermosetting resin composition is used for semiconductor encapsulant application, the blending ratio of fused silica is higher in view of the linear expansion coefficient and flame retardancy of the cured product of the thermosetting resin composition. Is preferred. Specifically, 50 mass% or more is preferable with respect to the thermosetting resin composition whole quantity, 60 mass% or more is more preferable, More preferably, it is about 70 mass%-about 90 mass%.
Moreover, when using a thermosetting resin composition for uses, such as an electrically conductive paste and an electrically conductive film, electroconductive fillers, such as silver powder and copper powder, can be used as a filler.

In addition, the thermosetting resin composition of the present invention includes various compounding agents such as a thermosetting resin and a thermoplastic resin, a pigment, a silane coupling agent, and a release agent, which are used as a modifier, if necessary. Can be contained.
As the thermosetting resin and the thermoplastic resin used as the modifier, various known ones can be used.
Examples of the thermosetting resin and thermoplastic resin include phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyester resin, polystyrene resin, polyethylene terephthalate resin, and the like. Can be used as long as it does 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.

The thermosetting resin composition containing the modified phenolic resin (A) and the epoxy resin (B) of the present invention gives a cured product having a high shrinkage rate when cured.
When used as a resin composition for an encapsulant for electronic parts, the shrinkage when curing a thermosetting resin composition is preferably 0.15% to 0, particularly from the viewpoint of suppressing the convex warpage of a thin package. .40%, more preferably 0.20% to 0.40%.
In particular, the thermosetting resin composition of the present invention is 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 resin, and a conductive material. Can be suitably used for conductive pastes, paints, adhesives and composite materials containing a conductive filler.

<Hardened product>
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, and for example, the thermosetting resin composition may be heated under the conditions of a heating temperature of 170 ° C. to 250 ° C. and a heating time of 60 minutes to 20 hours. The heating temperature is more preferably 170 ° C to 220 ° C, and further preferably 170 ° C to 200 ° C. The heating time is more preferably 60 minutes to 10 hours, and still more preferably 90 minutes to 8 hours.
In addition, it is preferable to pressure-mold a thermosetting resin composition before manufacture of hardened | cured material. The pressure at the time of pressure molding is preferably 2 to 20 MPa, more preferably 4 to 15 MPa, and still more preferably 5 to 12 MPa. Moreover, the temperature at the time of pressure molding becomes like this. Preferably it is 170-250 degreeC, More preferably, it is 170-220 degreeC, More preferably, it is 170-200 degreeC.

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

Production Example 1 (Synthesis of modified phenolic resin A)
In a flask equipped with a condenser and a stirrer, 104 g of a trade name “Shonol (trademark) BRG-558” (manufactured by Showa Denko KK, hydroxyl group equivalent 104 g / eq.) As phenol novolak resin, 50 g of methyl ethyl ketone, 0.04 g of hydroquinone and 43 g of glycidyl methacrylate was charged and mixed at 60 ° C. until uniform. After cooling to 40 ° C. or lower, 2 g of triphenylphosphine was added. After reacting at 100 ° C. for 5 hours, the distillate was removed from the product under reduced pressure at 120 ° C. and 50 mmHg to obtain 147 g of a light brown lump modified phenolic resin A. The resulting modified phenolic resin A had a softening point of 83 ° C. and a weight average molecular weight of 1900.

Production Examples 2-3 and Comparative Production Examples 2-4
The reaction was performed in the same manner as in Production Example 1 except that the compositions shown in Table 1 were used, and modified phenol resins B to C and J to L shown in Tables 2 and 3 were obtained.

Production Example 4
In a flask equipped with a condenser and a stirrer, 200 g of bisphenol F and 100 g of methyl ethyl ketone were charged and dissolved, then 0.08 g of hydroquinone and 56 g of glycidyl methacrylate were added and mixed until uniform, and then 2 g of triphenylphosphine was added. After reacting at 100 ° C. for 5 hours, the distillate was removed from the product under reduced pressure of 120 ° C. and 50 mmHg to obtain 256 g of a modified phenolic resin D.

Production Example 5
A flask equipped with a condenser and a stirrer was charged with 100 g of orthocresol, 49 g of benzaldehyde and 10 g of paratoluenesulfonic acid, and reacted at 100 ° C. for 8 hours. Next, after neutralization with an aqueous sodium hydroxide solution, washing was performed 5 times with 100 g of pure water to remove salts.
Next, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg, and then dissolved in 39 g of methyl ethyl ketone. Next, 0.04 g of hydroquinone and 19 g of glycidyl methacrylate were charged and mixed until uniform, and then 2 g of triphenylphosphine was added. After reacting at 100 ° C. for 5 hours, the distillate was removed under reduced pressure at 120 ° C. and 50 mmHg to obtain 98 g of a modified phenol resin E.

Production Example 6
A reaction was performed in the same manner as in Production Example 5 except that the composition shown in Table 1 was used.

Production Examples 7 and 8
Resins G and H were obtained by using the composition of Table 1 and carrying out the reaction in the same manner as in Production Example 5 except that the neutralization step was not performed after the first-stage reaction, and washing was performed twice with 100 g of pure water. .

Comparative production example 1
The first-stage reaction was carried out in the same manner as in Production Example 5 to remove the salt and the distillate to obtain a phenol novolac resin, which was designated as Resin I. Reaction with the second stage glycidyl methacrylate is not performed.

BRG-558: Phenol novolac resin, trade name “Shonol (trademark) BRG-558”, manufactured by Showa Denko KK, hydroxyl equivalent 104 g / eq.
CRG-951: orthocresol novolak, trade name “Shonol (trademark) CRG-951”, manufactured by Showa Denko KK, hydroxyl group equivalent 118 g / eq.

The modified phenol resin and the analysis method of the phenol resin are as follows.
(1) Softening point (° C)
The measurement was performed using a gas phase softening point measuring apparatus EX-719PD manufactured by Elex Scientific. The heating rate was 2.5 ° C./min.
(2) Weight average molecular weight It measured by gel permeation chromatography (GPC).
The column configuration was measured by Showa Denko Co., Ltd., trade names “KF-801”, “KF-802”, “KF-802” and “KF-803”, using tetrahydrofuran as a solvent at a flow rate of 1 ml / min. . The detector used was a trade name “RI-71” (manufactured by Showa Denko KK, differential refractometer “Shodex” (trademark)). The molecular weight was calculated in terms of polystyrene.
(3) Ratio of hydrogen atom of R ^{1 in} the general formula of the modified phenolic resin The NMR chart (benzene ring) of the phenolic resin before modification using a nuclear magnetic resonance (NMR) apparatus (manufactured by BRUKER, product name “AVANCE400”) The ratio of the chemical shift of 6.5 to 7.5 ppm derived from the ratio of the chemical shift of 8.0 to 10.0 ppm derived from the phenolic hydroxyl group) and the NMR chart of the modified phenolic resin (same as above), I) R ¹
The percentage of hydrogen was calculated.
(4) The alkali metal and alkaline earth metal in the modified phenol resin (A) were quantitatively measured using an atomic absorption photometer (AAS) (manufactured by Thermo Scientific, product name “iCE3000”).
(5) The amine compound in the modified phenolic resin (A) was quantitatively analyzed using a gas chromatograph (GC) (manufactured by Shimadzu Corporation, product name “GC-8APF”) under the following conditions.
<GC>
Column: Polapack Q column (80-100 mesh)
Carrier gas: Nitrogen Flow rate: 40 ml / min Column temperature: 230 ° C

  The results of each analysis are shown in Tables 2 and 3.

Examples 1 to 15 and Comparative Examples 1 to 6
(Preparation of thermosetting resin composition)
About each of the modified phenolic resin and the phenolic resin obtained in Production Examples 1 to 8 and Comparative Production Examples 1 to 4, the blends shown in Tables 2 and 3 were mixed and melt-kneaded at a temperature of 90 ° C. for 5 minutes, The thermosetting resin compositions of Examples 1 to 15 and Comparative Examples 1 to 5 were obtained.
The components shown in Tables 2 and 3 were blended as follows.
The modified phenolic resin and phenolic resin having the hydroxyl equivalent weight / epoxy radical equivalent ratio shown in Tables 2 and 3 with respect to the epoxy resin (weight average molecular weight 1000) in the amounts shown in Tables 2 and 3 (for example, 10 parts in Example 1). And 0.1 part of triphenylphosphine (curing accelerator) was added to obtain a resin component. Next, fused silica (inorganic filler) is mixed with the resin component so that the content in the composition is 80% by mass, and a two-roll (Nishimura Machinery, NS-155 (S) type) is mixed. And kneading at 100 ° C. for 5 minutes to prepare a thermosetting resin composition.
(Manufacture of cured product)
Mold obtained in accordance with JIS K-6911 (a sample having a circular shape with a diameter of 90 mm, a thickness of 5 mm, and having a convex part with a height of 3 mm in the range of 76 to 80 mm in diameter is obtained from the obtained thermosetting resin composition. ) At 150 ° C. for 40 minutes under a pressure of 10 MPa. Then, it heated at 180 degreeC for 5 hours, the thermosetting resin composition was hardened, and the test piece of hardened | cured material was produced.

About the obtained test piece, the shrinkage rate was evaluated by the following method.
(6) Shrinkage rate It evaluated by the method based on JISK-6911.
Tables 3 and 2 show the measurement results of the shrinkage rates of the test pieces prepared in Examples 1 to 15 and Comparative Examples 1 to 6.

  From Tables 2 and 3, it was confirmed that the cured product (test piece) of the thermosetting resin composition of the present invention expresses a high shrinkage rate. That is, it was found that the shrinkage rate of the test piece of the example was far superior to the cured product obtained using the conventional novolac resin.

Claims (7)

It is a thermosetting resin composition containing a modified phenol resin (A) represented by the general formula (I) obtained by reacting in the presence of an organophosphorus compound, and an epoxy resin (B),
The total content of alkali metal and alkaline earth metal in the modified phenolic resin (A) is 0.1% by mass or less based on the total amount of the phenolic resin (A), and
The content of the amine compound in the modified phenol resin (A) is 0.1% by mass or less based on the total amount of the phenol resin (A),
A thermosetting resin composition, wherein the modified phenolic resin (A) has a weight average molecular weight of 250 to 5,000.

(In the formula, R ¹ is a hydrogen atom or a group represented by the following formula (II), and the proportion of R ¹ being a hydrogen atom is 20% or more and less than 80%. R ² and R ³ are each independent. Represents a hydrogen atom or an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 40.)

(In the formula, R ⁴ is a group represented by a hydrogen atom or a methyl group.) The total content of alkali metal and alkaline earth metal in the thermosetting resin composition is 0.05% by mass or less, and
The thermosetting resin composition according to claim 1, wherein the content of the amine compound in the thermosetting resin composition is 0.05% by mass or less.   The content of the modified phenolic resin (A) is in the range of 0.6 equivalent to 1.2 equivalent of the hydroxyl group of the modified phenolic resin (A) with respect to 1.0 equivalent of the epoxy group in the epoxy resin (B). The thermosetting resin composition according to claim 1 or 2, wherein   The thermosetting resin composition in any one of Claims 1-3 whose weight average molecular weights of the said epoxy resin (B) are 300-5000.   The thermosetting resin composition according to any one of claims 1 to 4, comprising a filler.   Hardened | cured material obtained by hardening | curing the thermosetting resin composition in any one of Claims 1-5.   The hardened | cured material of Claim 6 whose shrinkage rate is 0.15%-0.40%.