JP2013237780A - Phenol compound, method for producing the same, resin composition and electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenol compound which enables a resin composition to be formed, the resin composition having a long pot life, showing good fluidity when filled into a narrow gap, having a low curing temperature, reducing thermal stress applied to a semiconductor element after curing, and having a high glass transition temperature, and to provided a resin composition including the phenol compound, and an electronic component device using the resin composition.SOLUTION: A phenol compound is represented by general formula (I), wherein Rto Rand Rto Reach independently denote H or a 1-18C hydrocarbon group, two adjacent groups selected from Rto Rand Rto Rmay bond to each other to form a ring, and n denotes a number of ≥0.

Description

  The present invention relates to a phenol compound, a production method thereof, a resin composition, and an electronic component device.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin compositions have been widely used. This is because the epoxy resin is excellent in the balance of various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. An epoxy resin composition is widely used as a sealing material in an electronic component device mounted with bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package).

  In an electronic component device (flip chip) in which a semiconductor element is directly bump-connected to a wiring board using ceramic, glass / epoxy resin, glass / imide resin, or polyimide film as a substrate, the bump-connected semiconductor element and wiring board An epoxy resin composition is used as an underfill material that fills the gap. These epoxy resin compositions play an important role in protecting electronic component devices from temperature and humidity and mechanical external force.

  When flip chip mounting is performed, the element and the substrate have different coefficients of thermal expansion, and thermal stress is generated at the joint. For this reason, ensuring connection reliability is an important issue. Further, since the circuit forming surface of the bare chip is not sufficiently protected, moisture and ionic impurities are likely to enter. Therefore, ensuring moisture resistance reliability is also an important issue. Further, a fillet is formed on the side surface of the chip for chip protection, but cracks may occur in the resin due to thermal stress caused by a difference in thermal expansion between the underfill material and the chip. As a result, the chip may be destroyed. Depending on the selection of the underfill material, the connection may not be sufficiently protected when subjected to repeated thermal shocks in a temperature cycle test or the like. For this reason, the joint portion may be fatigued at low cycles. In addition, if there is a void in the underfill material, the protection of the bump may be insufficient. For this reason, the joint portion may similarly undergo fatigue failure at a low cycle.

  Under the above circumstances, an epoxy resin composition for sealing excellent in moisture-resistant adhesive strength and low-stress property, and an electronic component device having high reliability (moisture resistance and thermal shock resistance) including an element sealed thereby It has been demanded. For example, Patent Document 1 discloses (A) a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) an elastomer, (D) an epoxy resin composition for sealing containing a surfactant, and An electronic component device including an element sealed with the sealing epoxy resin composition is disclosed.

Japanese Patent No. 3716237

  With recent high integration and multi-functionality of semiconductor elements, the chip size is increasing. On the other hand, bumps have been reduced in diameter, pitch, and gap by increasing the number of pins. In addition, with the miniaturization of on-board equipment, the chip is becoming thinner. For this reason, it is becoming increasingly difficult to ensure high reliability, particularly low warpage of electronic component devices, simply by adding an elastomer and a surfactant to the epoxy resin composition. It has been found that curing at low temperatures is effective for achieving low warpage. However, the method of Patent Document 1 has a drawback that the gel time at low temperature (the time until the epoxy resin loses fluidity and becomes a gel state) is long.

  As a method of shortening the gel time at a low temperature, there is a method of using a phenol resin as a curing agent. However, the conventional epoxy resin composition containing a liquid phenol resin has a drawback of low heat resistance (glass transition temperature).

  The present invention has been made in view of such circumstances, has a long pot life, good fluidity when filling a narrow gap, low curing temperature, and reduced thermal stress applied to the semiconductor element after curing. And a phenol compound capable of forming a resin composition having a high glass transition temperature. It is another object of the present invention to provide a resin composition containing the phenol compound and an electronic component device having high reliability (low warpage, moisture resistance, temperature cycle resistance) sealed by the resin composition.

  As a result of intensive studies, the present inventors have found a specific phenol compound and a resin composition containing the phenol compound as a curing agent. More specifically, the present invention relates to the following.

<1> A phenol compound represented by the following general formula (I).

In formula, R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. n represents a number of 0 or more.

<2> The phenol compound according to <1> represented by the following general formula (II).

In formula, R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. n represents a number of 0 or more.

<3> The phenol compound according to <1> represented by the following general formula (III).

In formula, R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. n represents a number of 0 or more. )

<4> A compound having a structure represented by the following general formula (VI) is obtained by reacting a phenol compound represented by the following general formula (IV) with at least one allyl halide represented by the following general formula (V). Process,
Obtaining a compound having the structure represented by the following general formula (VII) by Claisen rearrangement from the compound having the structure represented by the general formula (VI);
Reacting the compound having the structure represented by (VII) with at least one selected from the group consisting of a compound having the structure represented by the following general formula (VIII) and a multimer thereof, Obtaining a compound having a structure represented by general formula (II) or general formula (III);
The manufacturing method of the phenol compound of any one of <1>-<3> containing this.

R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > in General formula (IV)-General formula (VIII) represents a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. X represents a halogen atom.

<5> A resin composition comprising the phenol compound according to any one of <1> to <3> and a thermosetting resin.

<6> The resin composition according to <5>, wherein the thermosetting resin is liquid at 25 ° C.

<7> The resin composition according to <5> or <6>, wherein the thermosetting resin contains an epoxy resin.

<8> The resin composition according to any one of <5> to <7>, further containing a curing accelerator.

<9> The resin composition according to any one of <5> to <8>, further containing an inorganic filler.

<10> The resin composition according to <9>, wherein the content of the inorganic filler is 50% by mass or more and 80% by mass or less of the entire resin composition.

<11> a substrate having a circuit on its surface;
A semiconductor element having on its surface electrodes electrically connected to the circuit of the substrate via bumps;
An electronic component device comprising: a cured product of the resin composition according to any one of <5> to <10>, which fills a gap between the semiconductor element and the substrate.

  According to the present invention, a resin having a long pot life, good fluidity when filling a narrow gap, a low curing temperature, a reduced thermal stress applied to a semiconductor element after curing, and a high glass transition temperature. A phenolic compound capable of forming a composition is provided. The present invention can further provide a resin composition containing the phenol compound and a highly reliable electronic component device sealed thereby (low warpage, moisture resistance, temperature cycle resistance).

2 is a ¹ H NMR spectrum of Compound 1 synthesized in Synthesis Example 1. 2 is a ¹ H NMR spectrum of Compound 2 synthesized in Synthesis Example 2. 2 is a ¹ H NMR spectrum of Compound 3 synthesized in Synthesis Example 3. 2 is a ¹ H NMR spectrum of Compound 4 synthesized in Synthesis Example 4. 2 is a ¹ H NMR spectrum of Compound 5 synthesized in Synthesis Example 5. 2 is a ¹ H NMR spectrum of Compound 6 synthesized in Synthesis Example 6. 2 is a ¹ H NMR spectrum of Compound 7 synthesized in Synthesis Example 7.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.
Further, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .

<Phenol compound>
The phenol compound of the present invention has a structure represented by the following general formula (I). Hereinafter, the phenol compound of the present invention may be referred to as a specific phenol compound.

In formula, R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. n represents a number of 0 or more. n is preferably 0 to 20 and more preferably 0 to 10 from the viewpoint of low viscosity. If ^{R 1 ~R 8, R 11 ~R} 15 there are two or more, respectively, two or more ^{R 1 ~R 8, R 11 ~R} 15 may be the same or different.

When the phenol compound of the present invention has the above-described structure, it is considered that the resin composition has a low viscosity before curing and the cured product has a high Tg. This is thought to be due to the high density of phenolic hydroxyl groups and the introduction of alkenyl groups.

Specific examples of the hydrocarbon group include a linear or branched alkyl group, a cycloalkyl group, a linear or branched alkenyl group, a cycloalkenyl group, and an aryl group.
Among them, the hydrocarbon group is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a linear or branched chain having 2 to 18 carbon atoms from the viewpoint of pot life. A chain alkenyl group, a cycloalkenyl group having 3 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms are preferable, a linear or branched alkyl group having 1 to 12 carbon atoms, and 3 carbon atoms. More preferably a cycloalkyl group having 12 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. A linear or branched alkyl group having 1 to 6 is more preferable.

R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ are each independently preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, from the viewpoint of low viscosity. 6 is more preferably a linear or branched alkyl group, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or a methyl group. .

  The specific phenol compound is preferably a phenol compound represented by the following general formula (II) or (III) from the viewpoint of reactivity, and more preferably a phenol compound represented by the following general formula (III) from the viewpoint of low viscosity. .

In general formula (II) or general formula (III), R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. n represents a number of 0 or more. n is preferably 0 to 20 and more preferably 0 to 10 from the viewpoint of low viscosity. ^{R 1 ~R 8, R 11 ~R} 15 is respectively the same meaning as ^{R 1 ~R 8, R 11 ~R} 15 in formula (I), preferable embodiments thereof are also the same.

<Method for producing phenolic compound>
The manufacturing method of a specific phenol compound is not specifically limited.
For example, a phenolic hydroxyl group of a phenol compound represented by the following general formula (IV) is reacted with at least one allyl halide represented by the following general formula (V) to form a β-alkenyl ether, and the following general formula (VI) Obtaining a compound having the structure shown;
Obtaining a compound having the structure represented by the following general formula (VII) by Claisen rearrangement from the compound having the structure represented by the general formula (VI);
The compound having the structure represented by the above (VII) is reacted with at least one selected from the group consisting of a compound having the structure represented by the following general formula (VIII) and a multimer thereof in the general formula (I) And obtaining a compound having the structure shown.

In the formula, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

In formula, R < ¹ > -R < ⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁵ may be bonded to each other to form a ring. X is selected from halogen atoms. Specific examples of X include halogen atoms such as chlorine atom, bromine atom, fluorine atom and iodine atom. From the viewpoint of reactivity, a bromine atom is preferable.

In formula, R < ¹ > -R < ⁶ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently.

In formula, R < ¹ > -R < ⁶ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently.

In formula, R < ⁷ > -R < ⁸ > shows a hydrogen atom or a C1-C18 hydrocarbon group. Specific examples of the hydrocarbon group include the same specific examples as in the general formula (I).

^{R 1 ~R 8, R 11 ~R} 15 in the general formula (IV) ~ the general formula (VIII) are respectively synonymous with ^{R 1 ~R 8, R 11 ~R} 15 in the general formula (I), the preferred embodiment also It is the same.

  In the step of reacting the phenol compound represented by the general formula (IV) and at least one allyl halide represented by the general formula (V), a solvent may be used. The solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as tetrahydrofuran, non-aqueous solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide. Examples include protic polar solvents, alcohol solvents such as methanol, ethanol and isopropanol, and water.

  The reaction conditions are not particularly limited as long as the reaction proceeds to obtain a product. The reaction temperature can be, for example, room temperature to 200 ° C. Although reaction time will not be restricted to this if reaction is achieved, For example, it can be set as 1 hour-100 hours. The product may be purified as necessary after the reaction. Examples of purification methods include a method of removing the solvent after removing unnecessary components such as by-products and catalysts, a method of filtering the solid precipitated by cooling, a method of filtering the solid deposited by pouring into a poor solvent, etc. Is mentioned.

  As needed, you may use the compound which accelerates | stimulates at least 1 sort (s) of the phenolic hydroxyl group of the phenol compound shown by the said general formula (IV), and the compound shown by general formula (V). The compound that promotes the reaction is not particularly limited as long as the reaction is promoted. Examples thereof include inorganic acids, organic acids, inorganic bases, organic bases, onium salts, compounds described later used as curing accelerators, known compounds that promote the reaction between hydroxyl groups and hydrocarbon halides, and the like. Among these, an inorganic base is preferable from the viewpoint of promoting the reaction, and potassium carbonate is preferable.

  The compound represented by the following general formula (VII) by Claisen rearrangement from the compound represented by the above general formula (VI) generated by the reaction of the phenol compound represented by the above general formula (IV) and the allyl halide represented by the above general formula (V). In the step of obtaining a compound having a structure, a solvent may or may not be used. When a solvent is used, the solvent is not particularly limited, but a solvent having a boiling point of 100 ° C. or higher is preferable. For example, ketone solvents such as methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene, xylene and dimethylnaphthalene, aprotic polarities such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone A solvent, water, etc. are mentioned.

  The reaction conditions are not particularly limited as long as the reaction proceeds to obtain a product. The reaction temperature can be, for example, 100 to 250 ° C. Although reaction time will not be restricted to this if reaction is achieved, For example, it can be 10 minutes-300 minutes. The product may be purified as necessary after the reaction. Examples of the purification method include a method of distilling off the solvent in the case of using a solvent, a method of filtering a solid precipitated by cooling, a method of filtering a solid deposited by pouring into a poor solvent, and the like.

  The compound represented by the above general formula (VII) obtained by Claisen rearrangement from the compound represented by the above general formula (VI) is reacted with the compound represented by the above general formula (VIII) or a multimer thereof. In the step of obtaining the compound represented by the formula (I), a solvent may be used. The solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as tetrahydrofuran, non-aqueous solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide. Examples include protic polar solvents, alcohol solvents such as methanol, ethanol and isopropanol, and water.

  The reaction conditions are not particularly limited as long as the reaction proceeds to obtain a product. The reaction temperature can be, for example, room temperature to 200 ° C. Although reaction time will not be restricted to this if reaction is achieved, For example, it can be 10 minutes-48 hours. The product may be purified as necessary after the reaction. As a purification method, if necessary after the reaction, after removing unnecessary components such as by-products and catalysts, a method of distilling off the solvent, a method of filtering a solid precipitated by cooling, and depositing into a poor solvent for precipitation For example, a method of filtering the obtained solid may be used.

  If necessary, a compound that promotes the reaction between the general formula (VII) and the compound represented by the general formula (VIII) or a multimer thereof may be used. The compound that promotes the reaction is not particularly limited as long as the reaction can be promoted. Examples thereof include known compounds such as inorganic acids, organic acids, inorganic bases, organic bases, onium salts and the like. Among these, an inorganic acid or an organic acid is preferable from the viewpoint of promoting the reaction. Examples of the inorganic acid include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid and the like. Examples of organic acids include, but are not limited to, oxalic acid, acetic acid, adipic acid, succinic acid, glutaric acid, benzoic acid, and the like.

<Resin composition>
The resin composition of the present invention contains a specific phenol compound and a thermosetting resin. By containing a specific phenol compound, the pot life is long, the fluidity when filling a narrow gap is good, the curing temperature is low, the thermal stress applied to the semiconductor element after curing is reduced, and the glass transition temperature is further increased. A high resin composition can be obtained. Hereinafter, each component of the resin composition of this invention is demonstrated.

(A) Thermosetting resin The resin composition of the present invention contains at least one thermosetting resin. The thermosetting resin is preferably liquid at normal temperature (25 ° C.) from the viewpoint of workability.

  In the present invention, the fact that the thermosetting resin is liquid means that it is liquid in an uncured state. In this specification, being liquid means that the viscosity at 25 ° C. is 1000 Pa · s or less. The viscosity of the thermosetting resin at 25 ° C. is measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm).

  Although the kind in particular of thermosetting resin is not restrict | limited, An epoxy resin, maleimide resin, and cyanate resin can be mentioned. Among these, an epoxy resin is preferable from the viewpoint of reliability, and an epoxy resin having two or more epoxy groups in one molecule is more preferable. In particular, from the viewpoint of workability, a liquid epoxy resin that is liquid at normal temperature (25 ° C.) is preferable.

  As an epoxy resin, the epoxy resin generally used for the epoxy resin composition can be used. As epoxy resins that can be used in the present invention, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, hydrogenated bisphenol A and other bisphenol type epoxy resins, orthocresol novolac type epoxy resins and other phenolic compounds and aldehyde compounds are condensed. Or epoxy resin obtained by epoxidizing novolak resin obtained by co-condensation, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, p-aminophenol, diaminodiphenylmethane, isocyanuric Glycidylamine type epoxy resin obtained by reaction of amine compound such as acid and epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid An alicyclic epoxy resin. These epoxy resins may be used alone or in combination of two or more.

  The epoxy resin is preferably at least one selected from bisphenol-type epoxy resins and glycidylamine-type epoxy resins from the viewpoint of fluidity when filling the resin composition. From the viewpoint of heat resistance, adhesiveness and fluidity of the resin composition, it is preferable to use a bisphenol type epoxy resin and a glycidylamine type epoxy resin in combination.

  The epoxy equivalent of the epoxy resin is not particularly limited. Especially, it is preferable that it is 50-5000 from the viewpoint of Tg of hardened | cured material, It is more preferable that it is 70-1000, More preferably, it is 70-500.

  The purity of the epoxy resin, particularly the amount of hydrolyzable chlorine, is preferable because it is related to corrosion of aluminum wiring on an IC or other device. In order to obtain a resin composition excellent in moisture resistance, the amount of hydrolyzable chlorine is preferably 500 ppm or less. Here, the amount of hydrolyzable chlorine is a value obtained by dissolving 1 g of the epoxy resin of the sample in 30 ml of dioxane, adding 5 ml of 1M-KOH methanol solution, heating and refluxing for 30 minutes, and then by potentiometric titration. It is.

  When the resin composition of this invention contains a liquid epoxy resin as a thermosetting resin, a liquid epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more type. In order to exhibit the performance, the content of the liquid epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more in the total amount of the epoxy resin. preferable.

  When the resin composition of the present invention includes an epoxy resin as a thermosetting resin, the resin composition may include a solid epoxy resin as long as the effects of the present invention are achieved. From the viewpoint of fluidity at the time of molding, the content of the solid epoxy resin is preferably 70% by mass or less, more preferably 50% by mass or less, and more preferably 30% by mass or less in the total amount of the epoxy resin. Is more preferable.

  The content of the thermosetting resin in the total amount of the resin composition of the present invention is preferably 5% by mass to 100% by mass from the viewpoint of viscosity, fillability and strength, and is 10% by mass to 100% by mass. Is more preferable.

(B) Curing Agent The resin composition of the present invention contains at least one specific phenol compound as a curing agent.
The resin composition of the present invention may be used in combination with other curing agents other than the specific phenol compound as long as the effects of the present invention are achieved. The other curing agent is not particularly limited as long as it is a compound that can cure the thermosetting resin. For example, phenol compounds such as phenol resin; amine compounds such as diamine and polyamine; organic anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; carboxylic acid compounds such as dicarboxylic acid and polycarboxylic acid . These other curing agents may be used alone or in combination of two or more.

  Among the other curing agents, it is preferable to use a phenol compound having two or more phenolic hydroxyl groups in one molecule. Specific examples of the phenol compound include the following compounds.

Phenol compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol;
At least one selected from phenolic compounds such as phenol, cresol, o-allylphenol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. A novolak-type phenolic resin obtained by condensation or cocondensation of a seed with an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, hydroxybenzaldehyde under an acidic catalyst;

Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from at least one selected from phenol compounds and naphthol compounds and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc .;
Paraxylylene or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
A dicyclopentadiene type phenol resin and a dicyclopentadiene type naphthol resin synthesized by copolymerization from at least one selected from a phenol compound and a naphthol compound and dicyclopentadiene;

Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
Triphenylmethane phenol resin;
A phenol resin obtained by copolymerizing two or more of the above resins.
The said phenol compound may be used independently or may be used in combination of 2 or more type.

  When the specific phenol compound and other curing agent are used in combination, the content of the specific phenol compound is preferably 30% by mass or more in the total amount of the curing agent in order to exert its performance, and is 50% by mass or more. More preferably.

  The equivalent ratio of the epoxy resin and the curing agent containing the specific phenol compound is not particularly limited. In order to suppress the amount of each unreacted component, the curing agent is preferably 0.5 equivalents or more and 2.0 equivalents or less, and 0.7 equivalents or more and 1.4 equivalents or less with respect to 1.0 equivalent of the epoxy resin. More preferably, it is 0.8 or more and 1.2 equivalent or less.

(C) Hardening accelerator The resin composition of this invention may contain at least 1 sort (s) of a hardening accelerator as needed. The curing accelerator is not particularly limited. Specific examples of the curing accelerator include the following compounds.

Cycloamidine compounds such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, and other diazabicycloalkenes and derivatives thereof, and phenol novolacs thereof salt;
These compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl. Intramolecular polarization formed by adding a quinone compound such as -1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, or a compound having a π bond such as diazophenylmethane. Having a compound;
Tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and derivatives thereof;

Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole;
Tetra-substituted phosphonium tetra-substituted borate salts such as tetraphenyl phosphonium tetraphenyl borate, tetraphenyl boron salts such as 2-ethyl-4-methylimidazole tetraphenyl borate, N-methylmorpholine tetraphenyl borate;

  Triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, Organic phosphine compounds such as tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, or Complexes of these organic phosphine compounds with organic borons;

  The above organic phosphines, maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5 Intramolecular polarization formed by adding a quinone compound such as methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane. A compound having:

  The above organic phosphines, 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2- Iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2, Reaction with halogenated phenol compounds such as 6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl And a compound having intramolecular polarization obtained by dehydrohalogenation (JP 2004-156A). See JP 36); and the like.

  When the curing accelerator is used in combination, from the viewpoint of fluidity, after reacting a compound having an intramolecular polarization formed by adding a compound having a π bond with an organic phosphine, an organic phosphine and a halogenated phenol compound. A compound having intramolecular polarization obtained through a dehydrohalogenation step is preferred. From the viewpoint of curability, a compound having intramolecular polarization obtained through a dehydrohalogenation step after reacting an organic phosphine with a halogenated phenol compound is preferable. In particular, a phosphonium compound represented by the following general formula (IX) or an intermolecular salt thereof is preferable.

(In General Formula (IX), each R ⁹ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all are the same or different. Two or more R ⁹ may be bonded to each other to form a cyclic structure.
R ¹⁰ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group and an organic group having 1 to 18 carbon atoms which may have a substituent, and all may be the same or different. Two or more R ¹⁰ may be bonded to each other to form a cyclic structure.
Y ⁻ is a functional group having a structure in which one proton is eliminated from a functional group having 0 to 18 carbon atoms having one or more releasable protons (H ⁺ ). The functional group may be bonded to one or more R ¹⁰ to form a cyclic structure. )

In the general formula (IX), the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent represented by R ⁹ includes the following aliphatic hydrocarbon group, alicyclic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned.
Fats such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, allyl, vinyl, etc. Group hydrocarbon group;
An aliphatic hydrocarbon group substituted with an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an amino group, a halogen atom, or the like;

Cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other alicyclic hydrocarbon groups; alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, halogen atoms, etc. are substituted Alicyclic hydrocarbon groups;
Aromatic hydrocarbon groups such as phenyl and tolyl groups;
Alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group and tert-butylphenyl group; alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group and tert-butoxyphenyl group;
Furthermore, an alkyl group-substituted aryl group substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like, or an alkoxy group-substituted aryl group.

Wherein R ⁹ may be 2 or more R ⁹ are bonded to each other to form a cyclic structure, two or three R ⁹ are attached form a respective bivalent or trivalent hydrocarbon group as a whole May be.
Examples of the divalent or trivalent hydrocarbon group include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene that can be bonded to a P atom to form a cyclic structure, alkenylene groups such as ethenylene, propenylene, and butenylene groups, methylene Examples thereof include an aralkylene group such as a phenylene group and an arylene group such as phenylene, naphthylene, and anthracenylene. These divalent or trivalent hydrocarbon groups may be substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

R ⁹ is preferably a monovalent substituent selected from the group consisting of an alkyl group and an aryl group. Among these, from the viewpoint of easy availability of raw materials, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p -Hydroxyphenyl group, m-hydroxyphenyl group, o-hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2 -Hydroxy naphthyl) group, unsubstituted aryl group such as 1- (4-hydroxy naphthyl) group or aryl group substituted with at least one selected from alkyl group, alkoxy group and hydroxyl group, methyl group, ethyl group, propyl group, Chain or cyclic such as isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group Substituents selected from alkyl group is more preferable.

R ⁹ is a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p-hydroxyphenyl group, m-hydroxy. Phenyl group, o-hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2-hydroxynaphthyl) group, 1- More preferably, it is an unsubstituted aryl group such as a (4-hydroxynaphthyl) group or an aryl group substituted with at least one selected from an alkyl group, an alkoxy group and a hydroxyl group.

In the general formula (IX), the organic group having 1 to 18 carbon atoms which may have a substituent represented by R ¹⁰ includes an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an aliphatic carbonization. Hydrogen oxy group, alicyclic hydrocarbon oxy group, aromatic hydrocarbon oxy group, aliphatic hydrocarbon carbonyl group, alicyclic hydrocarbon carbonyl group, aromatic hydrocarbon carbonyl group, aliphatic hydrocarbon oxycarbonyl group, fat Examples thereof include a cyclic hydrocarbon oxycarbonyl group, an aromatic hydrocarbon oxycarbonyl group, an aliphatic hydrocarbon carbonyloxy group, an alicyclic hydrocarbon carbonyloxy group, and an aromatic hydrocarbon carbonyloxy group.

Specific examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group include the specific examples given for R ⁹ above. .

  Specific examples of the aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms which may have a substituent, an alicyclic hydrocarbon oxy group, and an aromatic hydrocarbon oxy group include a methoxy group, an ethoxy group, and a propoxy group. Aliphatic hydrocarbon oxy groups such as isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, allyloxy group and vinyloxy group; alicyclic rings such as cyclopropyloxy group, cyclohexyloxy group and cyclopentyloxy group Hydrocarbon oxy group; aromatic hydrocarbon oxy group such as phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group; and alkyl group, alkoxy group, aryl group, aryloxy group , The above aliphatic hydrocarbon oxy groups substituted by amino groups, halogen atoms, etc. Alicyclic hydrocarbon group and an aromatic hydrocarbon-oxy group.

  Specific examples of the optionally substituted aliphatic hydrocarbon carbonyl group having 1 to 18 carbon atoms, alicyclic hydrocarbon carbonyl group, and aromatic hydrocarbon carbonyl group include formyl group, acetyl group, ethylcarbonyl An alicyclic hydrocarbon carbonyl group such as an aliphatic hydrocarbon carbonyl group such as a group, butyryl group or allylcarbonyl, a cyclohexylcarbonyl group; an aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group or a methylphenylcarbonyl group; and an alkyl group, Examples thereof include the above-mentioned aliphatic hydrocarbon carbonyl group, alicyclic hydrocarbon carbonyl group, aromatic hydrocarbon carbonyl group substituted with an alkoxy group, aryl group, aryloxy group, amino group, halogen atom and the like.

  Specific examples of the optionally substituted aliphatic hydrocarbon oxycarbonyl group having 1 to 18 carbon atoms, alicyclic hydrocarbon oxycarbonyl group, and aromatic hydrocarbon oxycarbonyl group include methoxycarbonyl group, ethoxy Aliphatic hydrocarbon oxycarbonyl groups such as carbonyl group, butoxycarbonyl group and allyloxycarbonyl group; Alicyclic hydrocarbon oxycarbonyl groups such as cyclohexyloxycarbonyl group; Aromatic hydrocarbon oxy such as phenoxycarbonyl group and methylphenoxycarbonyl group A carbonyl group; and the above-mentioned aliphatic hydrocarbon oxycarbonyl group, alicyclic hydrocarbon oxycarbonyl group, aromatic hydrocarbon oxycarbonyl group substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, or halogen atom Etc.

  Specific examples of the aliphatic hydrocarbon carbonyloxy group having 1 to 18 carbon atoms which may have a substituent, an alicyclic hydrocarbon carbonyloxy group, and an aromatic hydrocarbon carbonyloxy group include a methylcarbonyloxy group, Aliphatic hydrocarbon carbonyloxy groups such as ethylcarbonyloxy group, butylcarbonyloxy group and allylcarbonyloxy group; Alicyclic hydrocarbon carbonyloxy groups such as cyclohexylcarbonyloxy group; phenylcarbonyloxy group, methylphenylcarbonyloxy group and the like And the above aliphatic hydrocarbon carbonyloxy group substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen atom, etc., alicyclic hydrocarbon carbonyloxy group, Aromatic hydrocarbon carbonyloxy group, etc. And the like.

Wherein R ¹⁰ may form a cyclic structure 2 or more R ¹⁰ are bonded to each other, two to four of R ¹⁰ is bonded, form respective divalent to tetravalent organic group as a whole Also good.
Examples of the divalent to tetravalent organic group include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene that can form a cyclic structure; alkenyl groups such as ethenyl, propenyl, and butenyl groups; aralkylene groups such as a methylenephenylene group; And arylene groups such as phenylene, naphthylene, anthracenylene, etc .; these alkylene groups, alkenyl groups, aralkylene groups, groups in which an oxy group or dioxy group is bonded to the arylene group; and the like. These divalent to tetravalent organic groups may be substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

R ¹⁰ is preferably a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, from the viewpoint of availability of raw materials, unsubstituted aryl groups or alkyl groups such as hydrogen atoms, hydroxyl groups, phenyl groups, p-tolyl groups, m-tolyl groups, o-tolyl groups, p-methoxyphenyl groups, etc. Aryl groups substituted with at least one selected from alkoxy groups and hydroxyl groups, and methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, tert-butyl groups, octyl groups, cyclohexyl groups, etc. A substituent selected from a chain or cyclic alkyl group is more preferable. When two or more R ¹⁰ are bonded to each other to form a cyclic structure, a benzene ring to which R ¹⁰ is bonded together with a 1- (2-hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) group, and the like. Organic groups that form ring aromatic groups are preferred.

In the general formula (IX), as an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms and having one or more releasable protons (H ⁺ ) represented by Y ⁻ , a hydroxyl group, A group in which a proton is eliminated from a monovalent organic group in which a hydrogen atom is bonded to a group 16 atom such as a mercapto group or a hydroseleno group, a carboxyl group, a carboxymethyl group, a carboxyethyl group, a carboxyphenyl group, a carboxynaphthyl group, etc. A group in which a carboxylic acid proton is eliminated from a monovalent organic group having 1 to 18 carbon atoms having a carboxyl group, a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, a hydroxythienyl group, a hydroxypyridyl group From a monovalent organic group having 1 to 18 carbon atoms having a phenolic hydroxyl group such as There desorbed group and the like.

Y ⁻ may combine with one or more R ¹⁰ to form a cyclic structure. For example, Y ⁻ is a divalent group that forms a group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as a 2- (6-hydroxynaphthyl) group together with a benzene ring to which Y ⁻ is bonded. It may be an organic group.
Among them, Y ^- is oxygen anion proton from the hydroxyl group is eliminated, or hydroxyphenyl group, hydroxyphenyl methyl group, hydroxynaphthyl group, hydroxy furyl group, hydroxy thienyl group, a proton from the phenolic hydroxyl group such as hydroxyethyl pyridyl group de A monovalent organic group having a separated oxygen anion is preferable.
When Y ⁻ is bonded to one or more R ¹⁰ to form a cyclic structure, for example, Y ⁻ is a 2-(-6-hydroxynaphthyl) group together with a benzene ring to which it is bonded. A group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as

  The intermolecular salt of the phosphonium compound represented by the general formula (IX) is not particularly limited. For example, a compound having a phenolic hydroxyl group such as a phosphonium compound represented by the formula (IX), phenol, naphthol, a compound exemplified above as a phenol compound having two or more phenolic hydroxyl groups in the molecule, triphenylsilanol, diphenyl Examples thereof include compounds having silanol groups such as silanediol and trimethylsilanol, organic acids such as oxalic acid, acetic acid and benzoic acid, and intermolecular salt compounds with inorganic acids such as hydrochloric acid, hydrogen bromide, sulfuric acid and nitric acid.

  The content of the curing accelerator in the resin composition of the present invention is not particularly limited as long as a curing acceleration effect is achieved. From the viewpoint of improvement in curability and fluidity at the time of moisture absorption of the resin composition, it is preferable to contain a total of 0.01 to 10 parts by mass of a curing accelerator with respect to a total of 100 parts by mass of the thermosetting resin. It is more preferable to contain 0.1-7.0 mass parts. When the content of the curing accelerator is less than 0.01 parts by mass, it may be difficult to cure the resin composition in a short time. If it exceeds 10 parts by mass, the resin composition may be cured too fast to obtain a good molded product.

(D) Inorganic filler It is preferable that the resin composition of this invention contains at least 1 sort (s) of (D) inorganic filler from viewpoints, such as reduction of a thermal expansion coefficient. Examples of inorganic fillers include silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fosterite, Examples thereof include powders such as steatite, spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. These inorganic fillers may be used alone or in combination of two or more. Of these, fused silica is preferred, and spherical silica is more preferred from the viewpoint of fluidity and permeability into the fine gaps of the resin composition.

The volume average particle diameter of the inorganic filler is preferably in the range of 0.1 μm to 20 μm, more preferably in the range of 0.3 μm to 10 μm, and still more preferably in the range of 0.5 μm to 5 μm. Particularly in the case of spherical silica, a range of 0.1 μm to 10 μm is preferable, a volume average particle size of 0.3 μm to 5 μm is more preferable, and a range of 0.5 μm to 3 μm is more preferable. When the volume average particle size of the inorganic filler is 0.1 μm or more, the dispersibility in the liquid resin is excellent, the thixotropic property is hardly imparted to the resin composition, and the effect of excellent flow characteristics is easily obtained. When the volume average particle size of the inorganic filler is 10 μm or less, the sedimentation of the inorganic filler in the resin composition can be reduced, and the permeability and fluidity of the resin composition into the fine gaps are improved, resulting in voids and unfilled particles. There is a tendency to prevent the occurrence of filling.
The volume average particle diameter of the inorganic filler can be measured by a laser diffraction method.

  The content of the inorganic filler is preferably 50% by mass to 80% by mass, more preferably 55% by mass to 75% by mass, and more preferably 60% by mass to 70% by mass in the total amount of the resin composition. More preferably, it is as follows. When the content of the inorganic filler is 50% by mass or more, an effect of reducing the thermal expansion coefficient is easily obtained. When the content of the inorganic filler is 80% by mass or less, an increase in the viscosity of the resin composition is suppressed, and fluidity / penetration and dispensing properties tend to be good.

(E) Other additives The resin composition of the present invention may contain additives in addition to the above components. Examples of the additive include a flexible agent, a silicone-modified epoxy resin, a coupling agent, an ion trapping agent, an anion exchanger, a dye, a colorant such as carbon black, a diluent, a leveling agent, and an antifoaming agent.

  The resin composition of the present invention may contain a flexible agent from the viewpoint of improving thermal shock resistance and reducing stress on the semiconductor element. The flexible agent is not particularly limited, but rubber particles are preferable. Examples of the rubber particles include rubber particles such as silicone rubber particles, styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic rubber (AR). Silicone rubber particles are preferred from the viewpoints of low viscosity, low stress and adhesiveness. From the viewpoint of heat resistance and moisture resistance of the resin composition, rubber particles made of acrylic rubber are preferable, and core-shell type acrylic polymers, that is, core-shell type acrylic rubber particles are more preferable.

  Silicone rubber particles include silicone rubber particles obtained by crosslinking polyorganosiloxanes such as linear polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane, silicone rubber particles coated with silicone resin on the surface, and epoxy groups on the surface. Examples thereof include modified silicone rubber particles, core-shell polymer particles comprising a core of solid silicone particles obtained by emulsion polymerization and a shell of an organic polymer such as an acrylic resin.

  The shape of the silicone rubber particles may be amorphous or spherical. In order to keep the viscosity affecting the moldability of the resin composition low, it is preferable to use spherical silicone rubber particles. Spherical silicone rubber particles are commercially available from Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., and the like.

  The volume average particle size of the silicone rubber particles is preferably 0.001 μm or more and 100 μm or less, more preferably 0.01 μm or more and 50 μm or less, from the viewpoint of improving thermal shock resistance and reducing stress on the semiconductor element. And more preferably 0.05 μm or more and 10 μm or less.

  When the resin composition of the present invention contains rubber particles, the content of the rubber particles in the total amount of the resin composition is 0.1% by mass to 20% by mass from the viewpoints of low viscosity, low stress, and adhesiveness. Is preferable, and it is more preferable that it is 0.5 mass%-10 mass%.

  The resin composition of the present invention may contain a silicone-modified epoxy resin having an effect as a surfactant. The silicone-modified epoxy resin can be obtained as a reaction product of an organosiloxane having a functional group that reacts with an epoxy group and an epoxy resin. The silicone-modified epoxy resin is preferably liquid at normal temperature. Examples of the organosiloxane having a functional group that reacts with an epoxy group include dimethylsiloxane, diphenylsiloxane, and methylphenylsiloxane having one or more functional groups such as amino group, carboxyl group, hydroxyl group, phenolic hydroxyl group, and mercapto group in one molecule. Is mentioned.

  The weight average molecular weight of the organosiloxane is preferably 500 or more and 5000 or less from the viewpoint of obtaining appropriate compatibility with the resin system. When the weight average molecular weight is 500 or more, the resin system is appropriately compatible with each other and the effect as an additive tends to be appropriately exhibited. When the weight average molecular weight is 5000 or less, it is possible to suppress incompatibility with the resin system, and it is possible to suppress the silicone-modified epoxy resin from being separated or exuded during molding, and excellent in adhesiveness and appearance. There is a tendency.

  The epoxy resin for obtaining the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin system of the resin composition of the present invention, and an epoxy resin generally used for the epoxy resin composition is used. be able to. For example, phenol and aldehyde such as glycidyl ether type epoxy resin, orthocresol novolak type epoxy resin obtained by reaction of phenol such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and epichlorohydrin. Novolak type epoxy resin obtained by epoxidizing novolak resin obtained by condensation or co-condensation with glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diaminodiphenylmethane, isocyanuric acid, etc. Glycidylamine type epoxy resin obtained by reaction of polyamine with epichlorohydrin, linear aliphatic epoxy obtained by oxidizing olefinic bonds with peracid such as peracetic acid Resin, alicyclic epoxy resin. These epoxy resins may be used alone or in combination of two or more. The epoxy resin is preferably liquid at normal temperature.

  When the resin composition of the present invention contains a silicone-modified epoxy resin, the content of the silicone-modified epoxy resin in the total amount of the resin composition is preferably 0.01% by mass or more and 1.5% by mass or less. More preferably, the content is from 1% by mass to 1% by mass. When the content is 0.01% by mass or more, a sufficient addition effect tends to be obtained. When the content is 1.5% by mass or less, the occurrence of bleeding from the surface of the cured product at the time of curing can be prevented, and a decrease in adhesive strength tends to be prevented. As long as the effect of the present invention is obtained, an additive having an effect as a surfactant can be contained in addition to the silicone-modified epoxy resin.

  In the resin composition of the present invention, a coupling agent may be used from the viewpoint of strengthening the interfacial adhesion between the resin and the inorganic filler or the resin and the component of the electronic component. There is no restriction | limiting in particular in a coupling agent, A conventionally well-known thing can be used. For example, silane compounds having primary, secondary and / or tertiary amino groups, epoxy silanes, mercapto silanes, alkyl silanes, ureido silanes, vinyl silane and other silane compounds, titanium compounds, aluminum chelates, aluminum / zirconium compounds Compound etc. are mentioned. Specific examples of the coupling agent include the following compounds. A coupling agent may be used individually by 1 type, or may be used in combination of 2 or more types.

  Vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ -Aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxysilane, γ- (N, N -Diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N-ethyl) anilinopropyltrimethoxy Silane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) aminopropyltriethoxysilane, γ- ( N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) amino Propylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropylmethyldimethoxysilane Lan, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, Silane coupling agents such as methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane,

  Isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltris (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1 -Butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, Isopropyl isostearoyl diacryl titanate, isopropyl tris (diocti Phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate coupling agents such as titanates.

  When the resin composition of the present invention contains a coupling agent, the content of the coupling agent in the total amount of the resin composition is 0.1% by mass to 5% by mass from the viewpoint of low viscosity and adhesiveness. Preferably, it is 0.2 mass%-4 mass%.

The resin composition of the present invention contains an ion trap agent represented by the following general formula (1) or (2) from the viewpoint of improving migration resistance, moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. Also good.
Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (1)
(0 <x ≦ 0.5, m is a positive number)
BiO _x (OH) _y (NO ₃ ) _Z (2)
(0.9 ≦ x ≦ 1.1, 0.6 ≦ y ≦ 0.8, 0.2 ≦ z ≦ 0.4)

The content of the ion trapping agent is preferably 0.1% by mass or more and 3.0% by mass or less, and more preferably 0.3% by mass or more and 1.5% by mass or less with respect to the entire resin composition. . The volume average particle size of the ion trapping agent is preferably 0.1 μm or more and 3.0 μm or less, and the maximum particle size is preferably 10 μm or less.
The compound of general formula (1) is available as a commercial product (trade name DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.). The compound of the general formula (2) is available as a commercial product (trade name IXE500, manufactured by Toagosei Co., Ltd.).

  The resin composition of the present invention may contain a colorant such as carbon black for the purpose of coloring the resin composition. When the resin composition of the present invention contains a colorant, the content of the colorant in the total amount of the resin composition is preferably 0.01% by mass to 3% by mass from the viewpoint of colorability and electrical characteristics. It is more preferable that it is 0.05 mass%-1.5 mass%.

  The resin composition of the present invention may contain an anion exchanger from the viewpoint of reliability. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. For example, hydrous oxides such as magnesium, aluminum, titanium, zirconium, and antimony can be used. An anion exchanger can be used individually or in combination of 2 or more types.

  The method for preparing the resin composition of the present invention is not particularly limited as long as the above components can be uniformly dispersed and mixed. As a general method, there may be mentioned a method of obtaining a resin composition by mixing and kneading a predetermined amount of components using a screening machine, a mixing roll, a planetary mixer or the like, and defoaming as necessary.

The viscosity at 25 ° C. of the resin composition of the present invention is preferably 0.01 Pa · s to 1000 Pa · s, more preferably 0.1 Pa · s to 200 Pa · s from the viewpoint of filling properties. -More preferably, it is s-50Pa.s.
The viscosity at 25 ° C. of the resin composition is measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm).

<Electronic component device>
An electronic component device of the present invention includes a substrate having a circuit on the surface, a semiconductor element having an electrode electrically connected to the circuit of the substrate through a bump, and a gap between the semiconductor element and the substrate. And a cured product of the resin composition of the present invention filled.
The electronic component device of the present invention exhibits excellent low warpage, moisture resistance, and temperature cycle resistance by filling the space between the semiconductor element and the substrate with the resin composition of the present invention.

  Examples of the method for filling the resin composition of the present invention between the semiconductor element and the substrate include a dispensing method, a casting method, and a printing method.

When filling the resin composition of the present invention between the semiconductor element and the substrate, it is preferably performed at 70 ° C. to 150 ° C. for 0.1 minute to 10 minutes from the viewpoint of filling property and curing reaction control, and 80 ° C. More preferably, it is performed at ˜120 ° C. for 0.3 minutes to 5 minutes.
When the resin composition of the present invention is cured after filling, it is preferably performed at a temperature of 100 ° C. to 200 ° C., from 120 ° C. to 180 ° C. for 30 minutes from the viewpoint of warpage, reaction rate, and stability of the entire electronic component. More preferably, it is performed for 360 minutes.
Although the board | substrate used for the said electronic component apparatus is not specifically limited, From a viewpoint of curvature and stress, an organic substrate is preferable.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
A 2000 ml separable flask was charged with hydroquinone 100 g (0.908 mol), allyl bromide 329.6 g, (2.725 mol), potassium carbonate 376.6 g (2.725 mol), and ethanol 300 ml, and the mixture was heated to reflux for 24 hours. The reaction solution was transferred to a separatory funnel, 500 ml of toluene and 300 ml of distilled water were added, and the aqueous layer was removed. Subsequently, the organic layer was washed with 100 ml of 1 mol / l NaOH aqueous solution and washed twice with 300 ml of distilled water. The organic layer after washing was placed under reduced pressure with an aspirator, and the solvent was removed at 100 to 120 ° C. to obtain 113 g (yield 65%) of hydroquinone diallyl ether (Compound 1). ¹ H NMR of the obtained Compound 1 was measured by the following method. The results are shown in FIG.

(Measurement method of ¹ H NMR)
About 10 mg of a sample was dissolved in about 1 ml of heavy acetone to form a solution, and the solution was put into a φ5 mm sample tube and measured using AV-300M manufactured by Bruker BioSpin. The shift value was based on CHD ₂ C (═O) CD ₃ (2.04 ppm) contained in a trace amount in the solvent.

100 g of the obtained hydroquinone diallyl ether was placed in a 200 ml four-necked flask and heated at 180 ° C. for 2 hours to cause Claisen rearrangement (Compound 2). ¹ H NMR of compound 2 obtained by the Claisen rearrangement was measured by the above method. The results are shown in FIG.

Thereafter, 12.0 g of paraaldehyde, 80 ml of ethanol, and 1.8 g of concentrated hydrochloric acid were added and heated to reflux for 3 hours. The reaction solution was transferred to a separatory funnel, 100 ml of toluene and 100 ml of distilled water were added, and the aqueous layer was removed.
Subsequently, the organic layer was washed twice with 100 ml of distilled water. The organic layer after washing is placed under reduced pressure with an aspirator, the solvent is removed at 80 to 100 ° C., and the general formula (II) (R ^{1 to} R ⁷ and R ^{11 to} R ¹⁵ are hydrogen atoms, and R ⁸ is methyl. 78 g of a semi-solid phenol compound (compound 3) presumed to have the structure represented by (group) as a main component was obtained. The hydroxyl equivalent was measured by the method of JIS K 0070 and found to be 130. ¹ H NMR of the obtained compound 3 was measured by the above method. The results are shown in FIG.

(Synthesis Example 2)
A 2000 ml separable flask was charged with 100 g (0.908 mol) of resorcin, 329.6 g of allyl bromide (2.725 mol), 376.6 g (2.725 mol) of potassium carbonate, and 300 ml of ethanol, and heated under reflux for 24 hours. The reaction solution was transferred to a separatory funnel, 500 ml of toluene and 300 ml of distilled water were added, and the aqueous layer was removed. Subsequently, the organic layer was washed with 100 ml of 1N NaOH aqueous solution and twice with 300 ml of distilled water. The organic layer after washing was placed under reduced pressure with an aspirator, and the solvent was removed at 100 to 120 ° C. Then, the organic layer was placed under reduced pressure with a vacuum pump and distilled at 130 ° C. to obtain 82 g (yield 47%) of resorcin diallyl ether (compound 4). ¹ H NMR of the obtained compound 4 was measured by the above method. The results are shown in FIG.

40 g of the obtained resorcin diallyl ether was placed in a 100 ml four-necked flask and heated at 180 ° C. for 2 hours to cause Claisen rearrangement (Compound 5). ¹ H NMR of compound 5 obtained by the Claisen rearrangement was measured by the above method. The results are shown in FIG.

Thereafter, 4.8 g of paraaldehyde, 40 ml of ethanol, and 2 g of oxalic acid were put into a four-necked flask and heated to reflux for 5 hours. The reaction solution was placed under reduced pressure with an aspirator, and the solvent was removed at 80 to 100 ° C. Subsequently, heating is performed at 130 ° C. for 1 hour to decompose oxalic acid, and a structure represented by general formula (III) (R ^{1 to} R ⁷ , R ^{11 to} R ¹⁵ are hydrogen atoms, and R ⁸ is a methyl group) is mainly used. 41 g of a liquid phenol compound (compound 6) estimated to be a component was obtained. It was 133 as a result of measuring a hydroxyl equivalent by the method of JISK0070. ¹ H NMR of the obtained compound 6 was measured by the above method. The results are shown in FIG.

(Synthesis Example 3)
40 g of resorcin diallyl ether obtained in Synthesis Example 2 was placed in a 100 ml four-necked flask and heated at 180 ° C. for 2 hours to cause Claisen rearrangement. Thereafter, 9.4 g of a 35% formaldehyde aqueous solution, 40 ml of ethanol, and 2 g of oxalic acid were added and heated to reflux for 5 hours. The reaction solution was placed under reduced pressure with an aspirator, and the solvent was removed at 80 to 100 ° C. Subsequently, the mixture is heated at 130 ° C. for 1 hour to decompose oxalic acid, and is assumed to have a structure represented by the general formula (III) (R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ are hydrogen atoms) as a main component. 39 g of the phenol compound (Compound 7) was obtained. It was 127 as a result of measuring a hydroxyl equivalent by the method of JISK0070. ¹ H NMR of the obtained compound 7 was measured by the above method. The results are shown in FIG.

(Examples 1-3, Comparative Examples 1-2)
The following components were blended so as to have the composition shown in Table 1 below, and kneaded and dispersed with a three roll and vacuum crusher to prepare resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2. The units in Table 1 are parts by mass unless otherwise specified. “-” Indicates that the compound was not blended.

(A) Thermosetting resin Liquid epoxy 1: Epoxy equivalent 160 liquid diepoxy resin obtained by epoxidizing bisphenol F (trade name jER806, manufactured by Mitsubishi Chemical Corporation)
Liquid epoxy 2: Trifunctional liquid epoxy resin having an epoxy equivalent of 95 obtained by epoxidizing aminophenol (trade name jER630, manufactured by Mitsubishi Chemical Corporation)
(B) Curing agent Phenol compound 1: Compound having a hydroxyl equivalent of 130 obtained in Synthesis Example 1 Phenol compound 2: Compound having a hydroxyl equivalent of 133 obtained in Synthesis Example 2 Phenol compound 3: Compound having a hydroxyl equivalent of 127 obtained in Synthesis Example 3 Liquid aromatic amine (comparative example): diethyltoluenediamine having an active hydrogen equivalent of 45 (trade name jER Cure W, manufactured by Mitsubishi Chemical Corporation)
Phenol resin (comparative example): Allylated phenol novolac resin having a hydroxyl group equivalent of 141 (trade name MEH-8000H, manufactured by Meiwa Kasei Co., Ltd.)
(C) Curing accelerator Curing accelerator 1: Addition reaction product of triphenylphosphine and 1,4-benzoquinone (D) Inorganic filler Silica: Spherical fused silica (E) additive having a volume average particle diameter of 1 μm Silicone rubber particles : Dimethyl-type solid silicone rubber particles whose surface is modified with an epoxy group, volume average particle diameter 2 μm, spherical silane coupling agent: γ-glycidoxypropyltrimethoxysilane colorant (carbon black, trade name MA-100, Mitsubishi Chemical Co., Ltd.)
Ion trap agent (Bismuth ion trap agent, trade name IXE-500, manufactured by Toagosei Co., Ltd.)

  The evaluation results of the obtained resin composition are shown in Table 2. Various characteristics and impregnation time of the epoxy resin composition, observation of voids, and evaluation of reliability were performed by the following methods and conditions.

The electronic component device used for the evaluation of reliability was manufactured with the following materials and conditions. The gap between the semiconductor element and the substrate was 50 μm.
Semiconductor element Size: 20 x 20 x 0.55 tmm, Circuit: Aluminum daisy chain connection, Passivation: Polyimide film (trade name HD4000, manufactured by Hitachi Chemical DuPont Microsystems)
Bump Solder ball (Sn—Ag—Cu), diameter: 80 μm, 7,744 pin, bump pitch: 190 μm
Substrate Product name FR-5, manufactured by Hitachi Chemical Co., Ltd., solder resist: SR7200, size: 60 × 60 × 0.8 tmm

  The electronic component device was produced by underfilling the resin composition in the gap between the chip and the substrate by a dispense method and curing at 130 ° C. or 165 ° C. for 2 hours.

(1) Viscosity (initial viscosity)
Within 2 hours after preparing the resin composition, the viscosity at 25 ° C. was measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm).

(2) Pot life (viscosity increase rate over time)
The resin composition was allowed to stand at 25 ° C. for 24 hours, and the viscosity at 25 ° C. was measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm) (viscosity after standing). The pot life (%) was calculated by ((viscosity after standing) − (initial viscosity)) / (initial viscosity) × 100.
In addition, when it was gelled after being left for 24 hours, measurement was impossible.

(3) Gel time (time until epoxy resin loses fluidity and becomes gel state)
Using a gelation tester, about 3 ml of the resin composition was dropped on a hot plate at 165 ° C. or 130 ° C., and then visually observed, and the time from loss of fluidity to gelation was measured as gel time.

(4) Glass transition temperature (Tg)
The resin composition was cured at a curing temperature of 130 ° C. or 165 ° C. for 2 hours to prepare a test piece (3 mm × 3 mm × 20 mm).
The glass transition temperature of the test piece was measured using a thermomechanical analyzer (trade name TMAQ400, manufactured by TA Instruments) under the conditions of a load of 15 g, a measurement temperature of 0 ° C. to 200 ° C., and a temperature increase rate of 10 ° C./min. It was measured.

(5) Adhesive strength / Adhesive strength to silicon nitride (SiN) A test piece made of a cured product of a resin composition having a diameter of 3 mm and a height of 3 mm was prepared on the surface of a wafer with SiN film (manufactured by Sumitomo Corporation Kyushu Co., Ltd.). Using a bond strength tester (trade name Bond Tester DS100, manufactured by DAGE), shear strength was applied under the conditions of a head speed of 50 μm / sec and 25 ° C., and the strength at which the test piece peels from the wafer with the P-SiN film was measured. did. The measurement was performed immediately after the preparation of the test piece and after the test piece was treated for 200 hours under 130 ° C. and 85% RH HAST (Highly Accelerated Temperature and Humidity Stress Test) conditions.
-Adhesive strength with respect to polyimide (PI) A test piece made of a cured product of a resin composition having a diameter of 3 mm and a height of 3 mm was prepared on the surface of a photosensitive polyimide film (trade name HD4100, manufactured by Hitachi Chemical DuPont Microsystems). Using a bonding strength tester (trade name Bond Tester DS100, manufactured by DAGE), shear strength was applied under the conditions of a head speed of 50 μm / sec and 25 ° C., and the strength at which the test piece peeled from the photosensitive polyimide was measured. The measurement was performed immediately after the preparation of the test piece and after the test piece was treated for 200 hours under HAST conditions of 130 ° C. and 85% RH.

(6) Impregnation time The electronic component device is placed on a hot plate heated to 110 ° C., and a resin composition (about 1 ml) is dropped onto the side surface (one side) of the chip using a dispenser, and the resin composition is formed up to the opposite side surface. The time until the object penetrated was measured.

(7) Void Observation The inside of the electronic component device produced by underfilling the resin composition was observed with an ultrasonic flaw detector (trade name AT-5500, manufactured by Hitachi Construction Machinery Co., Ltd.) to examine the presence or absence of voids.

(8) Chip warpage The amount of warpage (μm) on the chip diagonal line of an electronic component device produced by underfilling a resin composition was measured at a room temperature (25 ° C.) with a surface roughness measuring instrument (trade name Surfcoder SE-2300). , Manufactured by Kosaka Laboratory).

(9) Temperature cycle resistance The electronic component device produced by underfilling the resin composition was subjected to a continuity test after being subjected to 1000 cycles in a heat cycle of −55 ° C. to 125 ° C. for 30 minutes and 2000 cycles, respectively. went. The disconnection defect of the aluminum wiring and the pad was examined, and the evaluation was performed based on the number of defective packages / number of evaluation packages.

(10) Moisture resistance An electronic component device produced by underfilling the resin composition was treated for 200 hours under HAST conditions of 130 ° C. and 85% RH. Then, the presence or absence of disconnection of the aluminum wiring and the pad was confirmed by a continuity test, and the evaluation was performed by the number of defective packages / the number of evaluation packages.

  In Comparative Example 1 in which a liquid aromatic amine was used instead of the phenol compound of the present invention as a curing agent, the gel time was long and the curability was insufficient. In addition, voids were generated when the semiconductor device was manufactured. This is due to the long gel time. Furthermore, the temperature cycling resistance and moisture resistance of the semiconductor device are inferior, and the temperature cycling resistance is particularly inferior. This is due to the low adhesive strength of the cured product when cured at 130 ° C.

  In Comparative Example 2 using a phenol resin instead of the phenol compound of the present invention as a curing agent, although the gel time is short, the Tg of the cured product is low, and even when cured at 165 ° C., the Tg is insufficient, The temperature cycle was significantly reduced.

  In Examples 1 to 3 using the phenolic compound of the present invention as a curing agent, the gel time was shorter than that of Comparative Examples 1 and 2, and the low temperature curability was good. Further, no void was generated when the semiconductor device was manufactured. The adhesive strength of the cured product was also high, and the temperature cycle resistance and moisture resistance were also good. In particular, the temperature cycle resistance and moisture resistance of the semiconductor device when cured at 130 ° C. were as good as when cured at 165 ° C. This is due to the high adhesive strength of the cured product when cured at 130 ° C. In addition, it is possible to reduce the amount of chip warpage by lowering the curing temperature.

Claims (11)

A phenol compound represented by the following general formula (I).

In formula, R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. n represents a number of 0 or more. The phenol compound of Claim 1 shown by the following general formula (II).

In formula, R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. n represents a number of 0 or more. The phenol compound of Claim 1 shown by the following general formula (III).

In formula, R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > shows a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. n represents a number of 0 or more. ) A step of reacting a phenol compound represented by the following general formula (IV) with at least one allyl halide represented by the following general formula (V) to obtain a compound having a structure represented by the following general formula (VI);
Obtaining a compound having the structure represented by the following general formula (VII) by Claisen rearrangement from the compound having the structure represented by the general formula (VI);
Reacting the compound having the structure represented by (VII) with at least one selected from the group consisting of a compound having the structure represented by the following general formula (VIII) and a multimer thereof, Obtaining a compound having a structure represented by general formula (II) or general formula (III);
The manufacturing method of the phenol compound of any one of Claims 1-3 containing this.





R < ¹ > -R < ⁸ >, R < ¹¹ > -R < ¹⁵ > in General formula (IV)-General formula (VIII) represents a hydrogen atom or a C1-C18 hydrocarbon group each independently. Two adjacent groups selected from R ^{1 to} R ⁸ and R ^{11 to} R ¹⁵ may be bonded to each other to form a ring. X represents a halogen atom.   The resin composition containing the phenolic compound as described in any one of Claims 1-3, and a thermosetting resin.   The resin composition according to claim 5, wherein the thermosetting resin is liquid at 25 ° C.   The resin composition according to claim 5 or 6, wherein the thermosetting resin contains an epoxy resin.   Furthermore, the resin composition of any one of Claims 5-7 containing a hardening accelerator.   Furthermore, the resin composition of any one of Claims 5-8 containing an inorganic filler. The resin composition according to claim 9, wherein the content of the inorganic filler is 50% by mass or more and 80% by mass or less of the entire resin composition. A substrate having a circuit on its surface;
A semiconductor element having on its surface electrodes electrically connected to the circuit of the substrate via bumps;
The electronic component apparatus which has the hardened | cured material of the resin composition of any one of Claims 5-10 which has filled the clearance gap between the said semiconductor element and the said board | substrate.