CN117043135A

CN117043135A - Diester compound

Info

Publication number: CN117043135A
Application number: CN202280022688.6A
Authority: CN
Inventors: 小椋一郎; 佐藤直哉
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2021-03-23
Filing date: 2022-03-18
Publication date: 2023-11-10
Also published as: JP2024124452A; WO2022202703A1; TW202302515A; JPWO2022202703A1; KR20230159431A; JP7513195B2

Abstract

The present invention provides a diester compound having a low viscosity, which gives a resin composition having excellent fluidity when combined with a crosslinkable resin. The diester compound is represented by the following formula (X).(wherein X is _core Represents a divalent aliphatic group, X ¹ _end And X ² _end Each independently represents an aromatic ring optionally having a substituent, and X ¹ _end And X ² _end At least one of them is an aromatic ring having 1 or more groups selected from an unsaturated aliphatic hydrocarbon group, a halogen atom, an alkyl group, and an aryl group as a substituent).

Description

Diester compound

Technical Field

The present invention relates to a diester compound. Further, the present invention relates to a resin crosslinking agent, a resin composition, a resin sheet, a prepreg, a cured product, a semiconductor chip package, a printed wiring board, and a semiconductor device each obtained by using the diester compound.

Background

Resin compositions containing a crosslinkable resin such as an epoxy resin and a crosslinking agent (curing agent) thereof provide cured products excellent in insulation, heat resistance, adhesion and the like, and therefore have been widely used as electronic component materials for semiconductor packages, printed wiring boards and the like.

On the other hand, in high-speed communications such as the 5 th generation mobile communication system (5G), transmission loss during operation in a high-frequency environment is a problem. Therefore, an insulating material having excellent dielectric characteristics (low dielectric constant, low dielectric loss tangent) is demanded. In addition, with further miniaturization, high integration, and multifunction of electronic devices, there have been advances in reducing the diameter of bumps (bumps), narrowing the pitch, and narrowing the gap (narrow gap) due to the multiple stitch. As a result, the flow path of the sealing material at the time of seal molding becomes more complicated, and further excellent fluidity is required for the semiconductor sealing material, and the crosslinking agent used is also required to have a low viscosity.

As a resin material excellent in dielectric characteristics, for example, patent document 1 discloses an active ester resin as a reactant of an aromatic diacid chloride and an aromatic hydroxy compound as a crosslinking agent of an epoxy resin.

Prior art literature

Patent literature

Patent document 1: international publication No. 2018/235424.

Disclosure of Invention

Problems to be solved by the invention

The active ester resin described in patent document 1 has superior dielectric characteristics to conventional phenolic crosslinking agents and the like, but there is room for improvement in terms of lowering viscosity, and fluidity of a resin composition containing the active ester resin and the crosslinkable resin is not satisfactory.

In addition, there are cases where a resin composition having a high content of an inorganic filler is used from the viewpoints of obtaining a cured product having a low dielectric loss tangent, improving heat resistance and moisture resistance after seal molding, achieving low warpage in seal molding of a large area such as in Wafer Level Packaging (WLP), and achieving good heat dissipation in a high heat generating device such as a power semiconductor, but in such cases, there are problems that flow marks (flow marks) are easily generated and unfilled portions are easily generated due to deterioration of fluidity at molding temperature.

The present invention addresses the problem of providing a diester compound having a low viscosity, which gives a resin composition having excellent fluidity when combined with a crosslinkable resin.

Means for solving the problems

Conventionally, when an ester compound is used as a crosslinking agent for a crosslinkable resin, in order to exhibit crosslinking characteristics, the ester compound is considered to be limited to a compound having an aromatic carbon-ester bond-aromatic carbon structure as described in patent document 1 as an ester bond (ester bond). However, as a result of intensive studies, the present inventors have found that even in the structure of aliphatic carbon-ester bond-aromatic carbon, the ester bond portion having the structure of aliphatic carbon-C (=o) -O-aromatic carbon exhibits crosslinking characteristics. In addition, in the course of examining a diester compound having the structure of aliphatic carbon-C (=o) -O-aromatic carbon, it was found that the above problems could be solved by using a diester compound having the following constitution, and the present invention was completed.

Namely, the present invention includes the following.

[1] A diester compound represented by the following formula (X),

[ chemical formula 1]

(in the formula (I),

X _core represents a divalent aliphatic group, and is represented by the formula,

X ¹ _end and X ² _end Each independently represents an optionally substituted group An aromatic ring, and X ¹ _end And X ² _end At least one of them is an aromatic ring having 1 or more groups selected from unsaturated aliphatic hydrocarbon groups, halogen atoms, alkyl groups, and aryl groups as substituents. )

[2]According to [1]]The diester compound, wherein, at X _core The number of carbon atoms of the divalent aliphatic group is 6 or more.

[3]According to [1]]Or [2 ]]The diester compound, wherein, at X _core In (2), the divalent aliphatic group is an alkylene group.

[4]According to [1]]～[3]The diester compound according to any one of the above, wherein X ¹ _end And X ² _end Both of them are aromatic rings having an unsaturated aliphatic hydrocarbon group as a substituent.

[5]According to [1]]～[4]The diester compound according to any one of the above, wherein, in X ¹ _end And X ² _end Wherein the unsaturated aliphatic hydrocarbon group is an allyl group.

[6]According to [1]]～[5]The diester compound according to any one of the above, wherein, in X ¹ _end And X ² _end Wherein the aromatic ring is an aromatic carbocyclic ring having 6 to 14 carbon atoms.

[7] The diester compound according to any one of [1] to [6], wherein the diester compound is in a liquid state at 25 ℃.

[8] The diester compound according to any of [1] to [7], wherein the viscosity at 25℃is 300 mPas or less.

[9] A resin crosslinking agent comprising a diester compound represented by the following formula (X),

[ chemical formula 2]

(in the formula (I),

X ¹ _end and X ² _end Each independently represents an aromatic ring optionally having a substituent. )

[10] The resin crosslinking agent according to [9], wherein the diester compound is any one of [1] to [8 ].

[11] A resin composition comprising a diester compound (X) and a crosslinkable resin (Y),

the diester compound (X) is represented by the following formula (X),

[ chemical formula 3]

(in the formula (I),

[12] The resin composition according to [11], wherein the diester compound (X) is any one of [1] to [8 ].

[13] The resin composition according to [11] or [12], wherein the crosslinkable resin (Y) is 1 or more kinds of resins selected from the group consisting of thermosetting resins and radical-polymerizable resins.

[14] The resin composition according to any one of [11] to [13], further comprising an inorganic filler.

[15] The resin composition according to any one of [11] to [14], wherein an organic solvent is further contained.

[16] The resin composition according to any one of [11] to [15], which is used for sealing a semiconductor.

[17] The resin composition according to any one of [11] to [15], which is used for an insulating layer of a printed wiring board.

[18] A resin sheet comprising a support and a layer of the resin composition according to any one of [11] to [17] provided on the support.

[19] A prepreg formed by impregnating a sheet-like fibrous base with the resin composition according to any one of [11] to [17 ].

[20] The cured product of a resin composition according to any one of [11] to [17 ].

[21] A semiconductor chip package comprising a sealing layer formed of a cured product of the resin composition according to any one of [11] to [16 ].

[22] The semiconductor chip package according to [21], which is a Fan-Out (Fan-Out) package.

[23] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [11] to [15] and [17 ].

[24] A semiconductor device comprising the semiconductor chip package of [21] or [22], or the printed wiring board of [23 ].

Effects of the invention

According to the present invention, a diester compound having a low viscosity which gives a resin composition having excellent fluidity when combined with a crosslinkable resin can be provided.

According to the diester compound of the present invention, even when the content of the inorganic filler is high, a resin composition exhibiting good fluidity at molding temperature can be provided.

Drawings

FIG. 1a shows a GPC chart of a diester compound (A) in example 1;

FIG. 1b shows an IR chart of a diester compound (A) in example 1;

FIG. 2a shows a GPC chart of a diester compound (B) in example 2;

FIG. 2B shows an IR chart of the diester compound (B) in example 2;

FIG. 3a shows a GPC chart of a diester compound (C) in example 3;

FIG. 3b shows an IR chart of a diester compound (C) in example 3;

FIG. 4a shows a GPC chart of a diester compound (D) in example 4;

FIG. 4b shows an IR chart of a diester compound (D) in example 4;

FIG. 5a shows a GPC chart of a diester compound (E) in example 5;

FIG. 5b shows an IR chart of a diester compound (E) in example 5;

FIG. 6a shows a GPC chart of a diester compound (F) in comparative example 1;

FIG. 6b shows an IR chart of the diester compound (F) in comparative example 1.

Detailed Description

Description of the terms

In the present specification, the term "optionally substituted" with respect to a compound or a group means both of the case where a hydrogen atom of the compound or the group is unsubstituted and the case where a part or all of hydrogen atoms of the compound or the group are substituted with substituents.

In the present specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkenyl group (alklyene group), a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a 1-valent heterocyclic group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, and an oxo group. Aliphatic hydrocarbon groups having an unsaturated bond such as alkenyl, alkynyl, alkenyl, cycloalkenyl are also collectively referred to as "unsaturated aliphatic hydrocarbon groups".

Examples of the halogen atom which can be used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group which can be used as a substituent may be any of a linear or branched one. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 14, still more preferably 1 to 12, still more preferably 1 to 6, particularly preferably 1 to 3. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

The alkenyl group which can be used as a substituent may be any of straight-chain or branched-chain alkenyl groups. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 14, still more preferably 2 to 12, still more preferably 2 to 6, particularly preferably 2 or 3. Examples of the alkenyl group include vinyl, allyl, 1-propenyl, butenyl, sec-butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl.

The alkynyl group which can be used as a substituent may be any of straight-chain or branched-chain alkynyl groups. The number of carbon atoms of the alkynyl group is preferably 2 to 20, more preferably 2 to 14, still more preferably 2 to 12, still more preferably 2 to 6, particularly preferably 2 or 3. Examples of the alkynyl group include an ethynyl group, propynyl group, butynyl group, sec-butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, and decynyl group.

The alkenyl group which can be used as a substituent may be any of linear or branched, and the number of double bonds is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2. The number of carbon atoms of the alkenyl group is preferably 3 to 20, more preferably 3 to 14, still more preferably 3 to 12, still more preferably 3 to 6.

The number of carbon atoms of the cycloalkyl group which can be used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The number of carbon atoms of the cycloalkenyl group which can be used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

The alkoxy group which can be used as a substituent may be any of a straight chain and a branched chain. The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6. Examples of the alkoxy group include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy.

The number of carbon atoms of the cycloalkyloxy group which can be used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyloxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group and cyclohexyloxy group.

Aryl groups that can be used as substituents are those obtained by removing 1 hydrogen atom on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms of the aryl group which can be used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. Examples of the aryl group include phenyl, naphthyl, and anthracenyl.

The number of carbon atoms of the aryloxy group which can be used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. Examples of the aryloxy group which can be used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

The number of carbon atoms of the arylalkyl group which can be used as a substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, still more preferably 7 to 11. Examples of the arylalkyl group include: phenyl-C ₁ ～C ₁₂ Alkyl, naphthyl-C ₁ ～C ₁₂ Alkyl and anthryl-C ₁ ～C ₁₂ An alkyl group.

The number of carbon atoms of the arylalkoxy group which can be used as a substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, still more preferably 7 to 11. Examples of the arylalkoxy group include: phenyl-C ₁ ～C ₁₂ Alkoxy and naphthyl-C ₁ ～C ₁₂ An alkoxy group.

The heterocyclic group having 1-valence which can be used as a substituent means a group obtained by removing 1 hydrogen atom from a heterocycle of a heterocyclic compound. The number of carbon atoms of the 1-valent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, and still more preferably 3 to 9. The 1-valent heterocyclic group also includes a 1-valent aromatic heterocyclic group (heteroaryl group). Examples of the 1-valent heterocycle include: thienyl, pyrrolyl, furyl (furanyl), furyl (furyl), pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidinyl, quinolinyl, and isoquinolinyl.

The alkylidene group which can be used as a substituent means a group obtained by removing 2 hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms of the alkylidene group is preferably 1 to 20, more preferably 1 to 14, still more preferably 1 to 12, still more preferably 1 to 6, particularly preferably 1 to 3. Examples of the alkylidene group include: methylene, ethylidene, propylidene, isopropylidene, butylidene, zhong Dingcha, isobutylidene, tert-butylidene, pentylidene, hexylidene, heptylidene, octylidene, nonylidene, decylidene.

Acyl groups which may be used as substituents refer to the formula: -C (=o) -R (wherein R is alkyl or aryl). The alkyl group represented by R may be any of linear or branched. Examples of the aryl group represented by R include phenyl, naphthyl and anthracenyl. The number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 13, and still more preferably 2 to 7. Examples of the acyl group include acetyl, propionyl, butyryl, isobutyryl, pivaloyl and benzoyl.

Acyloxy groups which may be used as substituents are those of the formula: -O-C (=o) -R (wherein R is alkyl or aryl). The alkyl group represented by R may be any of linear or branched. Examples of the aryl group represented by R include phenyl, naphthyl and anthracenyl. The number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and still more preferably 2 to 7. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.

The above substituent may further have a substituent (hereinafter, sometimes referred to as "secondary substituent"). The secondary substituent may be the same as the above substituent unless otherwise specified.

In the present specification, the term "aliphatic group" refers to a group obtained by removing 1 or more hydrogen atoms bonded to aliphatic carbon of an aliphatic compound. Specifically, the monovalent aliphatic group is a group obtained by removing 1 hydrogen atom bonded to an aliphatic carbon of an aliphatic compound, and the divalent aliphatic group is a group obtained by removing 2 hydrogen atoms bonded to an aliphatic carbon of an aliphatic compound. Examples of the divalent aliphatic group include: an alkylene group optionally having a substituent, a cycloalkylene group optionally having a substituent, an alkenylene group optionally having a substituent, or a cycloalkenyl group optionally having a substituent. In the present specification, unless otherwise specified, the number of carbon atoms of the aliphatic group is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, 4 or more, 5 or more, or 6 or more, preferably 50 or less, more preferably 40 or less, further preferably 30 or less, 20 or less, 18 or less, 16 or less, 14 or 12 or less. The number of carbon atoms does not include a substituent.

In the present specification, the term "aromatic ring" refers to a ring in which the number of electrons included in the pi-electron system on the ring is 4p+2 (p is a natural number) in accordance with the Huckel's rule, and includes single-ring aromatic rings and condensed aromatic rings formed by condensing 2 or more single-ring aromatic rings. The aromatic ring may be an aromatic carbocyclic ring having only carbon atoms as ring-forming atoms, or an aromatic heterocyclic ring having not only carbon atoms but also hetero atoms such as oxygen atoms, nitrogen atoms, sulfur atoms, and the like as ring-forming atoms. In the present specification, unless otherwise specified, the number of carbon atoms of the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, still more preferably 6 or more, and the upper limit thereof is preferably 24 or less, more preferably 18 or less or 14 or less, still more preferably 10 or less. The number of carbon atoms does not include a substituent. Examples of the aromatic ring include: a monocyclic aromatic ring such as a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring; fused aromatic rings formed by fusing 2 or more monocyclic aromatic rings, such as naphthalene ring, anthracene ring, phenanthrene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzimidazole ring, indazole ring, benzoxazole ring, benzisoxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, acridine ring, quinazoline ring, cinnoline ring, and phthalazine ring.

The present invention will be described in detail based on preferred embodiments of the present invention. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented within the scope not exceeding the scope of the claims and equivalents thereof.

[ diester Compound ]

The diester compound of the present invention is characterized by comprising:

a nuclear unit formed from a divalent aliphatic group, and

first and second end capping units bonded to the core unit via an ester linkage,

the first and second capping units are each independently an aromatic ring optionally having substituents.

In the diester compound of the present invention, the core unit and the end-capping unit are bonded (bonded) via an ester bond (-C (=O) -O-). Specifically, the carbonyl group (—c (=o) -) is bonded to the core unit, and the oxy group (—o-) is bonded to the end-capping unit, and the core unit and the end-capping unit are bonded via an ester bond. Thus, the diester compound of the present invention has a structure of aliphatic carbon-C (=o) -O-aromatic carbon as an ester bond. As described later, the present invention is based on the finding that the ester bond having the structure of aliphatic carbon-C (=o) -O-aromatic carbon exhibits crosslinking properties, and is based on the finding that the present invention was not predicted from the conventional technical knowledge.

Thus, the core unit is denoted as X _core The first and second capping units are denoted as X respectively ¹ _end And X ² _end In this case, the diester compound of the present invention can be represented by the following formula (X).

[ chemical formula 4]

(in the formula (I),

X ¹ _end and X ² _end Each independently represents an aromatic ring optionally having a substituent. ).

-nuclear unit (X) _core )-

Nuclear unit X _core Formed from divalent aliphatic groups.

By having a core unit formed of a divalent aliphatic group, the diester compound of the present invention can exhibit low viscosity characteristics. In addition, when combined with a crosslinkable resin, a cured product having high toughness and flexibility can be obtained.

When an ester compound is used as a crosslinking agent for a crosslinkable resin, an active ester bond should be formed in order to exhibit crosslinking properties, and it is considered that the ester bond portion needs to have an aromatic carbon-C (=o) -O-aromatic carbon structure. In contrast, the diester compound of the present invention containing a nuclear unit formed of a divalent aliphatic group has a structure of aliphatic carbon-C (=o) -O-aromatic carbon. The present inventors have found that a diester compound having the above-mentioned specific ester bond structure functions as a crosslinking agent for a crosslinkable resin while exhibiting good low viscosity characteristics.

From the viewpoint of achieving a diester compound of lower viscosity, the core unit X _core The number of carbon atoms of the medium divalent aliphatic group is preferably 4 or more, more preferably 6 or more or 8 or more. Thus, in a preferred embodiment, the core unit X _core The number of carbon atoms of the divalent aliphatic group is 6 or more. The upper limit of the number of carbon atoms of the divalent aliphatic group is not particularly limited and can be appropriately determined from the foregoing range. The number of carbon atoms does not include a substituent.

From the viewpoint of achieving a diester compound of lower viscosity, the core unit X _core The divalent aliphatic group is preferably an alkylene group optionally having a substituent, or an alkenylene group optionally having a substituent, and particularly preferably an alkylene group optionally having a substituent. The alkylene group in the core unit may be any of linear or branched. Thus, in a preferred embodiment, the core unit X _core The medium divalent aliphatic group beingAn alkylene group.

The alkylene group and the alkenylene group in the core unit may have substituents as described above. Among them, the substituent is preferably 1 or more selected from halogen atoms, alkyl groups and alkenyl groups, more preferably 1 or more selected from fluorine atoms and alkyl groups having 1 to 6 carbon atoms.

-first and second end-capping units (X ¹ _end And X ² _end )-

First and second end capping units X ¹ _end And X ² _end Each independently is an aromatic ring optionally having a substituent.

The diester compound of the present invention can be used as a crosslinking agent for a crosslinkable resin in a resin composition by having an aromatic ring optionally having a substituent as the first and second end capping units.

From the viewpoint of further enjoying the effects of the present invention, the end-capping unit X ¹ _end And X ² _end The aromatic ring is preferably an aromatic carbocyclic ring. The number of carbon atoms of the aromatic carbocyclic ring is preferably 6 to 14, more preferably 6 to 10. Thus, in a preferred embodiment, the end-capping unit is an aromatic carbocyclic ring having 6 to 14 carbon atoms.

The aromatic ring in the capping unit may have substituents as described above. Among them, from the viewpoint of realizing a diester compound having a lower viscosity, 1 or more selected from the group consisting of an unsaturated aliphatic hydrocarbon group, a halogen atom, an alkyl group, and an aryl group is preferable, and 1 or more selected from the group consisting of an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms is more preferable. When the aromatic ring in the end capping unit has a substituent, it may be the first and second end capping units X ¹ _end And X ² _end Only one of (2) may have a substituent, or both may have a substituent. In one embodiment, the first and second end capping units X ¹ _end And X ² _end At least one of them is an aromatic ring having a substituent, and in a preferred embodiment, the first and secondSecond end capping unit X ¹ _end And X ² _end At least one of them is an aromatic ring having 1 or more groups selected from unsaturated aliphatic hydrocarbon groups, halogen atoms, alkyl groups, and aryl groups as substituents. X is X ¹ _end And X ² _end When the aromatic ring has no substituent, the crystallinity is strong, and the aromatic ring tends to be hardly liquid at ordinary temperature. On the other hand, X ¹ _end And X ² _end When the aromatic ring has a substituent, the crystallinity is weak, and the aromatic ring is easily liquid at ordinary temperature, and is excellent in fluidity and handleability.

Wherein the first and second end capping units X ¹ _end And X ² _end In the case where at least one of them is an aromatic ring having an unsaturated aliphatic hydrocarbon group as a substituent, a diester compound having particularly low viscosity can be obtained, and is therefore preferable. Thus, in a preferred embodiment, the first and second end capping units X ¹ _end And X ² _end At least one of them is an aromatic ring having an unsaturated aliphatic hydrocarbon group as a substituent. When both the first and second end capping units are aromatic rings having an unsaturated aliphatic hydrocarbon group as a substituent, a diester compound having particularly low viscosity, for example, liquid at ordinary temperature (25 ℃) can be realized. In the present specification, the term "liquid at ordinary temperature (25 ℃) as used in reference to the diester compound means that the diester compound has a viscosity of 3,000 mPas or less at 25 ℃. Thus, in a preferred embodiment, the first and second end capping units X ¹ _end And X ² _end Both of them are aromatic rings having an unsaturated aliphatic hydrocarbon group as a substituent.

From the viewpoint of realizing a diester compound having a further low viscosity, the number of carbon atoms of the unsaturated aliphatic hydrocarbon group which the aromatic ring in the end-capping unit may have as a substituent is preferably 2 to 20, more preferably 2 to 14, 2 to 12, 2 to 10 or 2 to 6. From the viewpoint of achieving a diester compound having a further low viscosity, the unsaturated aliphatic hydrocarbon group is preferably an alkenyl group or an alkynyl group, and more preferably an alkenyl group. Wherein the aromatic ring in the end-capping unit may be taken asThe unsaturated aliphatic hydrocarbon group of the substituent is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and still more preferably an allyl group. Thus, in a preferred embodiment, the end-capping unit X ¹ _end And X ² _end The unsaturated aliphatic hydrocarbon group which the aromatic ring may have as a substituent is an allyl group.

In one embodiment, the diester compound of the present invention is represented by the following formula (X1).

[ chemical formula 5]

(in the formula (I),

X _core represents a nuclear unit formed by a divalent aliphatic group,

the rings Ar each independently represent an aromatic ring,

R ¹ each independently represents an unsaturated aliphatic hydrocarbon group,

R ² Each of which independently represents a substituent,

n11 and n12 each independently represent an integer of 0 to 2,

when the number of the substitutable hydrogen atoms of the ring Ar is set to p, m11 and m12 represent integers satisfying 0.ltoreq.m11.ltoreq.p-n 11 and 0.ltoreq.m12.ltoreq.p-n 12. ).

In the formula (X1), X _core Represents a nuclear unit formed from a divalent aliphatic group. As to the core unit, including preferred examples thereof, as described above. In a preferred embodiment, X _core The divalent aliphatic group having 6 or more carbon atoms is more preferably an alkylene group having 6 or more carbon atoms which may have a substituent. Preferred examples of substituents are also described above.

In the formula (X1), the rings Ar each independently represent an aromatic ring. The aromatic ring corresponds to the aromatic ring in the first and second end capping units, including preferred examples thereof, as described above. In a preferred embodiment, each ring Ar is independently an aromatic carbocyclic ring having 6 to 14 carbon atoms, more preferably a benzene ring or naphthalene ring.

In the formula (X1), R ¹ Each independently represents an unsaturated aliphatic hydrocarbon group. R is R ¹ The unsaturated aliphatic hydrocarbon group which may be substituted corresponding to the aromatic ring in the first and second end capping units, including preferred examples thereof, are as described above. In a preferred embodiment, R ¹ Each independently is an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 20 carbon atoms (preferably 2 to 10 or 2 to 6 carbon atoms), or an alkynyl group having 2 to 20 carbon atoms (preferably 2 to 10 or 2 to 6 carbon atoms), and still more preferably an allyl group.

In the formula (X1), R ² Each independently represents a substituent. R is R ² Substituents corresponding to the aromatic ring in the first and second end capping units may have, including preferred examples thereof, as described above. In a preferred embodiment, R ² Each independently selected from a halogen atom, an alkyl group, and an aryl group, more preferably selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

In the formula (X1), n11 and n12 each independently represent an integer of 0 to 2. As described with respect to the first and second end capping units, from the viewpoint of realizing a diester compound having particularly low viscosity, at least one of n11 and n12 is preferably 1 or more. In a preferred embodiment, n11 and n12 are each independently 1 or 2, more preferably both n11 and n12 are 1.

When n11 or n12 is 1 or more, R ¹ The bonding position with respect to the ring Ar is not particularly limited, but from the viewpoint of realizing a diester compound having a lower viscosity, the relationship of the bonding position with the oxo group of the ester bond is preferably ortho-or meta-position, more preferably ortho-position.

In the formula (X1), when the number of the substitutable hydrogen atoms of the ring Ar is set to p, m11 and m12 represent integers satisfying 0.ltoreq.m11.ltoreq.p-n 11 and 0.ltoreq.m12.ltoreq.p-n 12. The number p of substitutable hydrogen atoms of the ring Ar does not include a binding site with an oxygen group of an ester bond. For example, when ring Ar is a benzene ring, the number p of substitutable hydrogen atoms is 5, and when ring Ar is a naphthalene ring, the number p of substitutable hydrogen atoms is 7.

In a preferred embodiment, the diester compound of the present invention is represented by the following formula (X2) or the following formula (X3).

[ chemical formula 6]

(in the formula (I),

X _core 、R ¹ r is R ² As described in the foregoing description of the invention,

n21 and n22 each independently represent an integer of 0 to 2,

m21 and m22 represent integers satisfying 0.ltoreq.m21.ltoreq.m21 (5-n 21) and 0.ltoreq.m22.ltoreq.m22 (5-n 22).

[ chemical formula 7]

(in the formula (I),

n31 and n32 each independently represent an integer of 0 to 2,

m31 and m32 represent integers satisfying 0.ltoreq.m31.ltoreq.m31 (7-n 31) and 0.ltoreq.m32.ltoreq.m32 (7-n 32).

X is either formula (X2) or formula (X3) _core 、R ¹ R is R ² As already mentioned above, their preferred examples are also as already described above.

In the formula (X2), n21 and n22 each independently represent an integer of 0 to 2. From the viewpoint of realizing a diester compound having particularly low viscosity, at least one of n21 and n22 is preferably 1 or more. In a preferred embodiment, n21 and n22 are each independently 1 or 2, more preferably both n21 and n22 are 1.

When n21 or n22 is 1 or more, R ¹ The bonding position to the benzene ring is not particularly limited, but from the viewpoint of realizing a diester compound having a lower viscosity, the relationship between the bonding position to the oxo group of the ester bond is preferably ortho-position or meta-position, and more preferably ortho-position.

In the formula (X2), m21 and m22 represent integers satisfying 0.ltoreq.m21.ltoreq.5-n 21 and 0.ltoreq.m22.ltoreq.5-n 22.

In the formula (X3), n31 and n32 each independently represent an integer of 0 to 2. From the viewpoint of realizing a diester compound having particularly low viscosity, at least one of n31 and n32 is preferably 1 or more. In a preferred embodiment, n31 and n32 are each independently 1 or 2, more preferably both n31 and n32 are 1.

When n31 or n32 is 1 or more, R ¹ The bonding position with respect to the naphthalene ring is not particularly limited, but from the viewpoint of realizing a diester compound having a lower viscosity, the relationship between the bonding position with the oxo group of the ester bond is preferably ortho-position or meta-position, and more preferably ortho-position.

In the formula (X3), m31 and m32 represent integers satisfying 0.ltoreq.m31.ltoreq.7-n 31 and 0.ltoreq.m32.ltoreq.7-n 32.

In a preferred embodiment, in formula (X2),

i)X _core is an alkylene group having 6 or more carbon atoms which may be substituted,

ii) (a) at least one of n21 and n22 is 1 or 2, R ¹ Each independently represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, m21 and m22 are each independently an integer of 0 to 2, and R ² Each independently selected from halogen atoms, alkyl groups, and aryl groups; or (b) n21 and n22 are 0, m21 and m22 are each independently an integer of 0 to 5, and R ² Each independently selected from the group consisting of halogen atoms, alkyl groups, and aryl groups.

In a more preferred embodiment, in formula (X2),

i)X _core an alkylene group having 6 or more carbon atoms which optionally has 1 or more substituents selected from the group consisting of a halogen atom, an alkyl group and an alkenyl group,

ii) (a) at least one of n21 and n22 is 1 or 2, R ¹ Each independently is an alkenyl group having 2 to 10 carbon atoms, m21 and m22 are each independently an integer of 0 to 2, and R ² Each independently selected from halogen atoms, alkyl groups, and aryl groups; or (b) n21 and n22 are 0, m21 and m22 are each independently an integer of 0 to 5, and R ² Each independently selected from halogenA prime atom, an alkyl group, and an aryl group.

In a preferred embodiment, in formula (X3),

ii) (a) at least one of n31 and n32 is 1 or 2, R ¹ Each independently represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, m31 and m32 are each independently an integer of 0 to 2, and R ² Each independently selected from halogen atoms, alkyl groups, and aryl groups; or (b) n31 and n32 are 0, m31 and m32 are each independently an integer of 0 to 7, and R ² Each independently selected from the group consisting of halogen atoms, alkyl groups, and aryl groups.

In a more preferred embodiment, in formula (X3),

ii) (a) at least one of n31 and n32 is 1 or 2, R ¹ Each independently is an alkenyl group having 2 to 10 carbon atoms, m31 and m32 are each independently an integer of 0 to 2, and R ² Each independently selected from halogen atoms, alkyl groups, and aryl groups; or (b) n31 and n32 are 0, m31 and m32 are each independently an integer of 0 to 7, and R ² Each independently selected from the group consisting of halogen atoms, alkyl groups, and aryl groups.

In the diester compound of the present invention, the equivalent weight of the oxycarbonyl group (active ester equivalent weight) is preferably 150g/eq. Or more, more preferably 160g/eq. Or more, still more preferably 180g/eq. Or more, and 200g/eq. Or more. The upper limit of the equivalent of the oxycarbonyl group may be, for example, 1000g/eq. Or less, 750g/eq. Or less, 700g/eq. Or less, 600g/eq. Or 500g/eq. Or less.

The molecular weight (number average molecular weight Mn when having a distribution) of the diester compound of the present invention is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1400 or less, 1200 or less, or 1000 or less, from the viewpoint of being blended into a resin composition as a crosslinking agent for a crosslinkable resin. The lower limit of the molecular weight is not particularly limited, and may be 300 or more, 320 or more, for example. The molecular weight can be measured by Gel Permeation Chromatography (GPC) as a value in terms of polystyrene.

An example of the synthesis procedure of the diester compound of the present invention is shown below.

In one embodiment, the diester compound of the present invention is obtained by subjecting the following (a) and (B) to a condensation reaction:

(A) A divalent aliphatic carboxylic acid compound or a divalent aliphatic carboxylic acid halide (carboxylic acid halide) compound,

(B) Optionally substituted 1-valent aromatic hydroxy compound.

Divalent aliphatic carboxylic acid (acid chloride) compounds

(A) The component (C) is a divalent aliphatic carboxylic acid compound or a divalent aliphatic carboxylic acid halide compound, and is represented by the following formula (X4).

[ chemical formula 8]

(wherein X is _core As described above, Z represents a hydroxyl group or a halogen atom. ).

As the component (A), according to the target nuclear unit X _core Any divalent aliphatic carboxylic acid (acid halide) compound may be used. X is X _core For example as described above. For example, target core unit X _core In the case of a linear alkylene group having 6 carbon atoms, suberic acid (acid chloride) may be used, and in the case of a linear alkylene group having 8 carbon atoms, sebacic acid (acid chloride) may be used.

- (B) 1-valent aromatic hydroxy compound optionally having substituent

(B) The component (A) is a 1-valent aromatic hydroxyl compound optionally having a substituent, and is represented by the following formula (X5).

[ chemical formula 9]

(in the formula (I),

rings Ar, R ¹ R is R ² As described in the foregoing description of the invention,

n represents an integer of 0 to 2,

when the number of substitutable hydrogen atoms of the ring Ar is set to p, m represents an integer satisfying 0.ltoreq.m.ltoreq.p-n. ).

As the component (B), any aromatic monohydric alcohol may be used depending on the intended end-capping unit. Rings Ar, R ¹ R is R ² As described above. For example, as the aromatic monohydric alcohol, when the target end-capping unit is a benzene ring having 1 alkenyl group having 2 to 6 carbon atoms as a substituent, n is 1 and R is used ¹ Phenol compounds having an alkenyl group having 2 to 6 carbon atoms, for example, vinylphenol, allylphenol, 1-propenylphenol, butenylphenol, pentenylphenol, hexenylphenol and the like may be used. In addition, when the target end-capping unit is a benzene ring having a fluorine atom as a substituent, m is 1 to 5 and R is used ² Phenol compounds which are fluorine atoms, for example, pentafluorophenol, tetrafluorophenol, trifluorophenol and the like may be used.

The condensation reaction may be carried out in a solvent-free system without using a solvent, or may be carried out in an organic solvent system using an organic solvent. Examples of the organic solvent used in the condensation reaction include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; a carbitol-based solvent such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. The organic solvent may be used alone or in combination of 1 or more than 2.

In the condensation reaction, a base may be used. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide (caustic soda) and potassium hydroxide; tertiary amines such as triethylamine, pyridine and N, N-dimethyl-4-aminopyridine (DMAP). The alkali may be used alone or in combination of 1 or more than 2.

Condensing agents and phase transfer catalysts may also be used in the condensation reaction. Any condensing agent or phase transfer catalyst known in the art that can be used in the esterification reaction can be used.

The reaction temperature in the condensation reaction is not particularly limited as long as the condensation reaction proceeds, and may be, for example, in the range of 0 to 80 ℃. The reaction time in the condensation reaction is not particularly limited as long as the structure of the target diester compound can be achieved, and may be, for example, in the range of 30 minutes to 8 hours.

After the condensation reaction, the diester compound may be purified. For example, after the condensation reaction, purification steps such as washing with water and fine filtration may be performed to remove by-product salts and an excessive amount of the starting material from the system. Specifically, after the condensation reaction, water in an amount necessary to dissolve the byproduct salt is added, and the mixture is left to stand for separation, and the aqueous layer is discarded. Further, if necessary, acid is added to neutralize the mixture, and washing with water is repeated. Then, the diester compound can be obtained by subjecting the diester compound to a dehydration step by chemical or azeotropic distillation, followed by fine filtration to remove impurities and purification, and then, if necessary, distillation of the organic solvent. The solvent may be used directly in the resin composition without completely removing the organic solvent.

The diester compound of the present invention exhibits such a feature as low viscosity. For example, as described in the column below (viscosity measurement conditions at heating), the viscosity of the diester compound of the present invention at 75 ℃ may be preferably 1000mpa·s or less, more preferably 500mpa·s or less, still more preferably 300mpa·s or less, 200mpa·s or less, 150mpa·s or less, 100mpa·s or less, 80mpa·s or less, 60mpa·s or 50mpa·s or less, when measured with a vibration viscometer.

In a preferred embodiment in which at least one (preferably both) of the first and second end capping units is an aromatic ring having an unsaturated aliphatic hydrocarbon group as a substituent, particularly low viscosity can be exhibited. In one preferred embodiment, the diester compound of the present invention is in a liquid state at ordinary temperature (25 ℃). For example, as described in the column below (viscosity measurement conditions), the diester compound of the present invention may have a viscosity of preferably 2000 mPas or less, more preferably 1500 mPas or less, still more preferably 1000 mPas or less, 800 mPas or less, 600 mPas or less, 500 mPas or less, or 400 mPas or less at 25℃when measured by an E-type viscometer (100 rpm). In a particularly preferred embodiment in which both the first and second end-capping units are aromatic rings having an unsaturated aliphatic hydrocarbon group as a substituent, the diester compound of the present invention can exhibit a lower viscosity, for example, a viscosity of 300mpa·s or less, 250mpa·s or less, 200mpa·s or less, 150mpa·s or less at 25 ℃. Therefore, in a preferred embodiment, the diester compound of the present invention has a viscosity of 300mpa·s or less at 25 ℃.

The diester compound of the present invention can provide a resin composition having excellent fluidity in combination with a crosslinkable resin, while maintaining the advantages of an ester compound such as a cured product exhibiting excellent dielectric characteristics in combination with a crosslinkable resin, and can provide a resin composition having low viscosity and excellent fluidity in combination with a crosslinkable resin, and can suppress occurrence of flow marks and unfilled portions during molding such as seal molding. In addition, the diester compound of the present invention can give a cured product having a high toughness and flexibility in combination with the crosslinkable resin. In addition, even when the content of the inorganic filler is high, a resin composition exhibiting good fluidity at molding temperature can be provided, and a cured product having excellent heat resistance, moisture resistance, lower dielectric loss tangent, low warpage and good heat dissipation can be obtained. Accordingly, in a preferred embodiment, the diester compound of the present invention may be suitably used as a resin crosslinking agent.

[ resin composition ]

The diester compound of the present invention can be used to produce a resin composition. The invention also provides the resin composition.

The resin composition of the present invention is characterized by comprising a diester compound (X) which is the diester compound of the present invention, that is, a diester compound represented by the above formula (X), and a crosslinkable resin (Y).

The details of the diester compound (X) represented by the preferred examples of the core unit, the first and second end capping units and the preferred modes of the general formula are as described in the column [ diester compound ].

In the resin composition of the present invention, the type of the crosslinkable resin (Y) is not particularly limited as long as it can be crosslinked in combination with the diester compound (X). The crosslinkable resin (Y) is preferably 1 or more selected from the group consisting of thermosetting resins and radical polymerizable resins, from the viewpoint of providing a cured product exhibiting excellent dielectric characteristics in combination with the diester compound (X) and exhibiting good flowability at the time of molding.

As the thermosetting resin and the radical polymerizable resin, a known resin used for forming an insulating layer of a printed wiring board and a semiconductor chip package can be used. Hereinafter, a thermosetting resin and a radical-polymerizable resin which can be used as the crosslinkable resin (Y) will be described.

Examples of the thermosetting resin include epoxy resin, benzocyclobutene resin, epoxy acrylate resin, urethane acrylate resin, polyurethane resin, cyanate resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, phenolic resin, melamine resin, silicone resin, and phenoxy resin. The thermosetting resin may be used alone or in combination of 1 or more than 2. Among them, the crosslinkable resin (Y) preferably contains an epoxy resin, from the viewpoint of exhibiting good fluidity at the time of molding and giving excellent dielectric characteristics after curing in combination with the diester compound (X).

The epoxy resin is not particularly limited as long as it has 1 or more (preferably 2 or more) epoxy groups in 1 molecule. Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac (phenol novolac) type epoxy resin, tert-butyl catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac (cresol novolac) type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene skeleton type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic type epoxy resin, spiro ring-containing epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like. According to the resin composition of the present invention containing the diester compound (X), the resin composition can exhibit good fluidity at the time of molding and can give excellent dielectric characteristics after curing, regardless of the kind of the epoxy resin.

The epoxy resin may be classified into an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter referred to as "solid epoxy resin"), and the resin composition of the present invention may contain only the liquid epoxy resin, only the solid epoxy resin, or both the liquid epoxy resin and the solid epoxy resin in combination as the crosslinkable resin (Y). When the liquid epoxy resin and the solid epoxy resin are contained in combination, the compounding ratio (liquid: solid) may be 20:1 to 1:20 (preferably 10:1 to 1:10, more preferably 3:1 to 1:3).

The epoxy equivalent of the epoxy resin is preferably 50g/eq to 2000g/eq, more preferably 60g/eq to 1000g/eq, still more preferably 80g/eq to 500g/eq. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy group, and can be measured in accordance with JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The Mw of the epoxy resin can be measured by GPC as a value in terms of polystyrene.

The radical polymerizable resin is not particularly limited as long as it has 1 or more (preferably 2 or more) radical polymerizable unsaturated groups in 1 molecule. Examples of the radical polymerizable resin include resins having 1 or more radical polymerizable unsaturated groups selected from the group consisting of maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryl groups, methacryl groups, fumaryl groups, and maleimide groups. Among them, the crosslinkable resin (Y) preferably contains 1 or more kinds selected from maleimide resins, (meth) acrylic resins and styrene-based resins, from the viewpoint of exhibiting good fluidity at the time of molding and giving excellent dielectric characteristics after curing in combination with the diester compound (X).

The maleimide resin is not particularly limited in kind as long as it has 1 or more (preferably 2 or more) maleimide groups (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl) in 1 molecule. Examples of the maleimide resin include "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700" and "BMI-689" (all manufactured by design molecule (Designer Molecules)) which contain an aliphatic skeleton having 36 carbon atoms derived from dimer diamine; maleimide resins containing an indane skeleton described in Japanese patent application laid-open technical bulletin No. 2020-500211; "MIR-3000-70MT" (manufactured by Japanese chemical Co., ltd.), "BMI-4000" (manufactured by Dai chemical Co., ltd.), "BMI-80" (manufactured by KI chemical Co., ltd.) and the like.

The (meth) acrylic resin is not particularly limited as long as it has 1 or more (meth) acryloyl groups (preferably 2 or more) in 1 molecule. Here, the term "(meth) acryl" is a generic term for acryl and methacryl. Examples of THE methacrylic resin include (meth) acrylic resins such as "A-DOG" (manufactured by Xinzhou chemical industry Co., ltd.), "DCP-A" (manufactured by Kagaku chemical Co., ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" (manufactured by Nippon chemical Co., ltd.).

The styrene-based resin is not particularly limited as long as it has 1 or more (preferably 2 or more) styryl groups or vinylphenyl groups in 1 molecule. Examples of the styrene-based resin include "OPE-2St", "OPE-2St1200", "OPE-2St 2200" (all manufactured by Mitsubishi gas chemical corporation) and the like.

The resin composition of the present invention may contain, as the crosslinkable resin (Y), only a thermosetting resin, only a radical polymerizable resin, or a combination of a thermosetting resin and a radical polymerizable resin.

In the resin composition of the present invention, the mass ratio ((X)/(Y)) of the diester compound (X) to the crosslinkable resin (Y) may be preferably 0.8 or more, more preferably 0.9 or more, 1 or more, 1.1 or more, or 1.2 or more. The upper limit of the mass ratio ((X)/(Y)) may be, for example, 2 or less, 1.9 or less, 1.8 or less, or the like. Accordingly, in one embodiment, the mass ratio ((X)/(Y)) of the diester compound (X) to the crosslinkable resin (Y) is 0.8 to 2.0.

The resin composition of the present invention may further comprise an inorganic filler. By containing the inorganic filler, the coefficient of linear thermal expansion and the dielectric loss tangent can be further reduced. In addition, by containing an inorganic filler having a high thermal conductivity, a cured product excellent in heat dissipation can be realized.

Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate, and the like, and may be selected according to the specific application. The inorganic filler may be used alone or in combination of at least 2 kinds. Examples of the commercial products of the inorganic filler include "UFP-30" (manufactured by electrochemical chemical industry Co., ltd.); "YC100C", "YA050C-MJE", "YA010C", "SC2500SQ", "SC4050-SX", "SO-C4", "SO-C2", "SO-C1", "SC-C2" (all manufactured by Yakuma Co., ltd.); "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N" (manufactured by Denka Co., ltd.), and "DAW-0525" (manufactured by DENKA Co., ltd.).

The average particle diameter of the inorganic filler may be appropriately determined according to the specific application. For example, in the case of forming an interlayer insulating layer of a printed wiring board or a rewiring forming layer of a semiconductor chip package, the average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less, from the viewpoint of low roughness of the surface of a cured product (insulating layer) and easiness of forming fine wirings. In the case of forming the sealing layer of the semiconductor chip package, the average particle diameter of the inorganic filler is preferably 15 μm or less, more preferably 14 μm or less, and even more preferably 12 μm or less, 10 μm or less, or 8 μm or less, from the viewpoint of improving the fluidity at the time of sealing molding. The lower limit of the average particle diameter is not particularly limited and may be determined according to the specific application, and may be, for example, 0.01 μm or more, 0.02 μm or more, 0.03 μm or more, 0.05 μm or more, or 0.1 μm or more. The average particle size of the inorganic filler material can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, it can be determined by: the particle size distribution of the inorganic filler was prepared based on volume by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was used as the average particle size. For the measurement sample, a product obtained by dispersing an inorganic filler in water by ultrasonic waves can be preferably used. As the laser diffraction scattering particle size distribution measuring apparatus, LA-950 manufactured by horiba, inc. can be used.

The inorganic filler is preferably one having improved moisture resistance and dispersibility by surface-treating with a surface-treating agent such as an aminosilane-based coupling agent, an ureido silane-based coupling agent, an epoxy silane-based coupling agent, a mercapto silane-based coupling agent, a vinyl silane-based coupling agent, a styryl silane-based coupling agent, an acrylate silane-based coupling agent, an isocyanate silane-based coupling agent, a thioether silane-based coupling agent, an organosilane-nitrogen compound, or a titanate-based coupling agent.

When the resin composition of the present invention contains an inorganic filler, the content of the inorganic filler in the resin composition can be determined according to the characteristics required for the resin composition, and when the nonvolatile content in the resin composition is set to 100 mass%, for example, 5 mass% or more, 10 mass% or more, preferably 30 mass% or more, more preferably 40 mass% or more, and even more preferably 50 mass% or more. The resin composition of the present invention comprising the diester compound (X) having a core unit formed of a divalent aliphatic group can further increase the content of the inorganic filler while ensuring good fluidity at the time of molding. The content of the inorganic filler in the resin composition may be increased to 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, or 80 mass% or more, for example. Thus, the resin composition of the present invention can realize a cured product having particularly low dielectric loss tangent, excellent heat resistance, moisture resistance and low warpage, and high heat dissipation properties, depending on the type of inorganic filler, while satisfying the narrow gap filling property. The upper limit of the content of the inorganic filler in the resin composition is not particularly limited, and may be, for example, 95 mass% or less, 90 mass% or less, or the like.

The resin composition of the present invention may further contain a resin crosslinking agent other than the diester compound (X).

Examples of the resin crosslinking agent other than the diester compound (X) include phenolic curing agents such as "TD2090", "TD2131" (manufactured by DIC corporation), "MEH-7600", "MEH-7851", "MEH-8000H" (manufactured by Ming and Chemicals corporation), "NHN", "CBN", "GPH-65", "GPH-103" (manufactured by Japanese chemical Co.), and "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" (manufactured by Niday iron chemical Co., ltd.), "LA7052", "LA7054", "LA3018", "LA1356" (manufactured by DIC corporation); benzoxazine-based crosslinking agents such as "F-a", "P-d" (manufactured by Sichuangji chemical Co., ltd.), "HFB2006M" (manufactured by Showa polymer Co., ltd.); anhydride-based crosslinking agents such as methyl hexahydrophthalic anhydride, methyl nadic anhydride, and hydrogenated methyl nadic anhydride; cyanate-based crosslinking agents such as PT30, PT60, and BA230S75 (manufactured by Lonza Japan Co., ltd.); benzoxazine-based crosslinking agents, and the like.

When the resin composition of the present invention contains a resin crosslinking agent other than the diester compound (X), the content of the resin crosslinking agent in the resin composition may be determined according to the characteristics required for the resin composition, and the content of the non-volatile component in the resin composition may be preferably 40 mass% or less, more preferably 20 mass% or less, still more preferably 10 mass% or less, and the lower limit may be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, or the like, based on 100 mass% of the resin composition.

The resin composition of the present invention may further comprise a crosslinking accelerator. By including the crosslinking accelerator, the crosslinking time and the crosslinking temperature can be effectively adjusted.

Examples of the crosslinking accelerator include organic phosphine compounds such as "TPP", "TPP-K", "TPP-S", "TPTP-S" (manufactured by North chemical industry Co., ltd.); imidazole compounds such as "CUREZOL 2MZ", "2E4MZ", "Cl1Z-CN", "Cl1Z-CNS", "Cl1Z-A", "2MZ-OK", "2MA-OK", "2PHZ" (manufactured by four chemical industries, inc.); amine adduct compounds such as NOVACURE (manufactured by Asahi chemical industry Co., ltd.), fujicure (manufactured by Fuji chemical industry Co., ltd.); amine compounds such as 1, 8-diazabicyclo [5,4,0] undecene-7, 4-dimethylaminopyridine, benzyl dimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 4-dimethylaminopyridine; organometallic complexes or salts of cobalt, copper, zinc, iron, nickel, manganese, tin, and the like.

When the resin composition of the present invention contains a crosslinking accelerator, the content of the crosslinking accelerator in the resin composition may be determined according to the characteristics required for the resin composition, and the content of the nonvolatile component in the resin composition may be preferably 10 mass% or less, more preferably 5 mass% or less, still more preferably 1 mass% or less, and the lower limit may be 0.001 mass% or more, 0.01 mass% or more, 0.05 mass% or more, or the like, based on 100 mass% of the resin composition.

The resin composition of the present invention may further contain any additive. Examples of such additives include: organic fillers such as rubber particles; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polysulfone resin, polyether sulfone resin, polyphenylene oxide resin, polyether ether ketone resin, and polyester resin; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; an antifoaming agent such as an organosilicon antifoaming agent, an acrylic antifoaming agent, a fluorine antifoaming agent, and a vinyl resin antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; an adhesion improver such as urea silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol antioxidants; fluorescent whitening agents such as stilbene derivatives; a surfactant such as a fluorine-based surfactant and an organosilicon-based surfactant; flame retardants such as phosphorus flame retardants (for example, phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (for example, melamine sulfate), halogen flame retardants, and inorganic flame retardants (for example, antimony trioxide); a dispersant such as a phosphate dispersant, a polyoxyalkylene dispersant, an alkyne dispersant, a silicone dispersant, an anionic dispersant, and a cationic dispersant; and stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. The content of the additive may be determined according to the characteristics required for the resin composition.

The resin composition of the present invention may further contain an organic solvent as a volatile component. Examples of the organic solvent include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, carbinol acetate (ethyl diglycol acetate), γ -butyrolactone, methyl methoxypropionate, and the like; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvent may be used alone or in combination of 1 or more than 2.

When the resin composition of the present invention contains an organic solvent, the content of the organic solvent in the resin composition may be determined according to the characteristics required for the resin composition, and when the total content of the components in the resin composition is 100% by mass, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less may be used.

Here, in order to reduce the viscosity of the resin composition, an organic solvent is added as a diluent to prepare the resin composition. When the insulating layer of the semiconductor chip package or the printed wiring board is formed using the resin composition, the following problems occur: void (void) is generated in the film forming step or the seal molding step; or, a large-sized waste apparatus is required because of the organic solvent; alternatively, an organic solvent remains in the obtained insulating layer; etc. In contrast, the resin composition of the present invention containing the diester compound (X) having a core unit formed of a divalent aliphatic group is preferable because it can exhibit good fluidity during molding even when the content of the organic solvent is low or when the organic solvent is not contained. The content of the organic solvent in the resin composition of the present invention may be reduced to less than 10 mass%, 8 mass% or less, 6 mass% or less, 5 mass% or less, 4 mass% or less, 2 mass% or less, 1 mass% or less, or 0.5 mass% or less, for example (solvent-free system).

The resin composition of the present invention can be prepared by: the essential components of the above components are appropriately mixed, and kneaded or mixed by a kneading mechanism such as a three-roll mill, a ball mill, a bead mill, a sand mill, or a stirring mechanism such as a super mixer or a planetary mixer, as required.

The resin composition of the present invention comprising the diester compound (X) and the crosslinkable resin (Y) in combination exhibits good flowability at the time of molding and can bring about excellent dielectric characteristics after curing.

In one embodiment, the cured product of the resin composition of the present invention has a characteristic of low dielectric constant (Dk). For example, as described in the [ dielectric properties ] column described below, when measured at 5.8GHz and 23 ℃, the dielectric constant (Dk) of the cured product of the resin composition of the present invention may preferably be 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, 2.9 or less, or 2.8 or less.

In one embodiment, the cured product of the resin composition of the present invention has a characteristic of low dielectric loss tangent (Df). For example, as described in the [ dielectric properties ] column described below, when measured at 5.8GHz and 23 ℃, the dielectric loss tangent (Df) of the cured product of the resin composition of the present invention may preferably be 0.01 or less, 0.008 or less, 0.007 or less, 0.006 or less, 0.005 or less, or 0.004 or less.

In one embodiment, the cured product of the resin composition of the present invention has a characteristic of high thermal conductivity. For example, as described in the [ thermal conductivity ] column below, when measured by the planar heat source method (Hot Disk), the thermal conductivity of the cured product of the resin composition of the present invention may be preferably 2.5W/mK or more, 2.6W/mK or more, 2.8W/mK or more, 3W/mK or more, 3.1W/mK or more, or 3.2W/mK or more.

The resin composition of the present invention can be suitably used as a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor). The resin composition of the present invention can be suitably used as a resin composition for a rewiring forming layer (a resin composition for a rewiring forming layer) as an insulating layer for forming a rewiring layer in a semiconductor chip package. The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for an insulating layer of a printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for an insulating layer of a printed wiring board). The resin composition of the present invention can be suitably used also in the case where a printed wiring board is a circuit board with built-in components. The resin composition of the present invention can be widely used for applications requiring a resin composition, such as a sheet-like laminate material such as a resin sheet or a prepreg, a solder resist, an underfill material, a die bonding material, a hole-filling resin, and a component-embedding resin.

[ sheet laminate (resin sheet, prepreg) ]

The resin composition of the present invention may be used as it is or in the form of a sheet laminate containing the resin composition.

As the sheet-like laminate, a resin sheet and a prepreg shown below are preferable.

In one embodiment, the resin sheet includes a support and a layer of a resin composition (hereinafter simply referred to as "resin composition layer") provided on the support, and is characterized in that the resin composition layer is formed of the resin composition of the present invention.

The preferable value of the thickness of the resin composition layer varies depending on the application, and can be appropriately determined according to the application. For example, from the viewpoint of reduction in thickness of a printed wiring board or a semiconductor chip package, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, 60 μm or less, or 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be generally 1 μm or more, 5 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film formed of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic polymers such as Polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

The surface of the support to be bonded to the resin composition layer may be subjected to a matting treatment, a corona treatment, or an antistatic treatment. Further, as the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support having a release layer includes, for example, 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available ones can be used, and examples thereof include "SK-1", "AL-5", "AL-7" made by Leideke corporation, which are PET films having a release layer containing an alkyd-based release agent as a main component, and "Miller T60" made by Toli corporation, and "Purex" made by Di people corporation, and "Unipel" made by UNITKA corporation, you Niji.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In the case of using the support with a release layer, the thickness of the entire support with a release layer is preferably in the above range.

As the support, a metal foil with a support substrate formed by bonding a releasable support substrate to a thin metal foil may also be used. In one embodiment, a metal foil with a support substrate includes a support substrate, a release layer disposed on the support substrate, and a metal foil disposed on the release layer. In the case of using a metal foil with a supporting substrate as a support, a resin composition layer is provided on the metal foil.

In the metal foil with the support substrate, the material of the support substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, and the like. When a copper foil is used as a supporting substrate, it may be an electrolytic copper foil or a rolled copper foil. The release layer is not particularly limited as long as the metal foil can be released from the support base material, and examples thereof include an alloy layer of an element selected from Cr, ni, co, fe, mo, ti, W, P; an organic coating, and the like.

Among the metal foils with the supporting substrate, copper foil and copper alloy foil are preferable as the material of the metal foil.

In the metal foil with the support substrate, the thickness of the support substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, and more preferably in the range of 10 μm to 100 μm. The thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

In one embodiment, the resin sheet may further include an optional layer as needed. Examples of the optional layer include a protective film provided on a surface of the resin composition layer that is not bonded to the support (i.e., a surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust or the like to the surface of the resin composition layer or damage to the surface of the resin composition layer can be suppressed.

The resin sheet can be manufactured, for example, by: the resin composition layer is formed by directly applying a liquid resin composition to a support using a die coater or the like, or by preparing a resin varnish in which the resin composition is dissolved in an organic solvent, applying the resin varnish to the support using a die coater or the like, and drying the resin varnish.

The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of 1 or more than 2.

Drying can be performed by a known method such as heating and blowing hot air. The drying conditions are not particularly limited, and the drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. Although the boiling point of the organic solvent varies depending on the resin composition or the resin varnish, for example, in the case of using a resin composition or a resin varnish containing 30 to 60 mass% of the organic solvent, the resin composition layer may be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.

The resin sheet may be wound into a roll for storage. In the case where the resin sheet has a protective film, the protective film can be peeled off for use.

In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous base material with the resin composition of the present invention.

The sheet-like fibrous base material used for the prepreg is not particularly limited, and a sheet-like fibrous base material commonly used as a base material for the prepreg, such as glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, and the like, can be used. The thickness of the sheet-like fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, particularly preferably 20 μm or less, from the viewpoint of thinning of the printed wiring board and the semiconductor chip package. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited. Typically 10 μm or more.

The prepreg can be produced by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet described above.

The sheet-like laminate of the present invention can be suitably used for sealing a semiconductor chip (for semiconductor sealing), and can be suitably used for a rewiring-forming layer as an insulating layer for forming a rewiring layer. The sheet-like laminate of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an insulating layer of a printed wiring board).

[ semiconductor chip Package ]

The semiconductor chip package of the present invention comprises a sealing layer formed of a cured product of the resin composition of the present invention. As described above, the semiconductor chip package of the present invention may further include an insulating layer (rewiring forming layer) formed from the cured product of the resin composition of the present invention for forming a rewiring layer.

The semiconductor chip package can be manufactured, for example, by a method comprising the steps (1) to (6) below using the resin composition and the resin sheet of the present invention. The resin composition and the resin sheet of the present invention may be used for forming the sealing layer in the step (3) or the rewiring-forming layer in the step (5). Hereinafter, an example of forming a sealing layer and a rewiring forming layer using a resin composition or a resin sheet is shown, but a technique of forming a sealing layer and a rewiring forming layer of a semiconductor chip package is known, and a person skilled in the art can manufacture a semiconductor package using the resin composition or the resin sheet of the present invention according to a known technique.

(1) A step of laminating a temporary fixing film on the base material,

(2) A step of temporarily fixing the semiconductor chip on the temporary fixing film,

(3) A step of forming a sealing layer on the semiconductor chip,

(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip,

(5) A step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and

(6) And forming a rewiring layer as a conductor layer on the rewiring layer.

Procedure (1)

The material used in the base material is not particularly limited. As the substrate, a silicon wafer is exemplified; a glass wafer; a glass substrate; metal substrates such as copper, titanium, stainless steel, and cold rolled steel Sheet (SPCC); a substrate (for example, an FR-4 substrate) obtained by impregnating glass fibers with an epoxy resin or the like and thermally curing the glass fibers; a substrate formed of bismaleimide triazine resin (BT resin), and the like.

The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in the step (4) and the semiconductor chip can be temporarily fixed. The temporary fixing film may be commercially available. As a commercial product, there may be mentioned REVALPHA manufactured by Nito electric company.

Procedure (2)

The semiconductor chip is temporarily fixed to the temporary fixing film so that the electrode pad surface thereof is bonded to the temporary fixing film. The temporary fixing of the semiconductor chip can be performed by using a known device such as a flip chip bonder (flip chip bonder) or a die bonder (die bonder). The layout and the number of the semiconductor chips to be arranged may be appropriately set according to the shape and size of the temporary fixing film, the number of the target semiconductor packages to be produced, and the like, and for example, the temporary fixing may be performed in a matrix of a plurality of rows and a plurality of columns.

Procedure (3)

The resin composition of the present invention is applied to a semiconductor chip, or alternatively, a resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip and cured (e.g., thermally cured) to form a sealing layer.

By using the resin composition of the present invention containing the diester compound (X) having a core unit formed of a divalent aliphatic group, good fluidity is exhibited at the time of seal molding, both in the case of directly coating the resin composition and in the case of laminating the resin composition layers in the form of a resin sheet.

For example, when the resin sheet is used, the lamination of the semiconductor chip and the resin sheet can be performed by heat-pressing the resin sheet against the semiconductor chip from the support side after removing the protective film of the resin sheet. As a member for thermocompression bonding the resin sheet to the semiconductor chip (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS end plate or the like), a metal roller (SUS roller) or the like can be cited. It is preferable that the heat pressure bonding member is not directly pressed against the resin sheet but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the semiconductor chip. The lamination of the semiconductor chip and the resin sheet can be performed by a vacuum lamination method, and the lamination conditions are the same as those described later with respect to the method for manufacturing a printed wiring board, and the preferable ranges are also the same.

After lamination, the resin composition is thermally cured to form a sealing layer. The heat curing conditions are the same as those described later with respect to the method of manufacturing a printed wiring board.

The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or may be peeled off before the resin sheet is laminated on the semiconductor chip.

In the case of forming the sealing layer by applying the resin composition of the present invention, the application conditions may be the same as those in the case of forming the resin composition layer described in relation to the resin sheet of the present invention. By using the resin composition of the present invention, good fluidity can be achieved at the coating/molding temperature.

Procedure (4)

The method of peeling the base material and the temporary fixing film may be appropriately changed depending on the material of the temporary fixing film, and examples thereof include a method of peeling the temporary fixing film by heating and foaming (or expanding) the temporary fixing film, a method of peeling the temporary fixing film by irradiating ultraviolet rays from the base material side and the temporary fixing film by lowering the adhesive force thereof.

In the method of peeling the temporary fixing film by heating and foaming (or expanding) the temporary fixing film, the heating condition is usually 100 to 250 ℃ for 1 to 90 seconds or 5 to 15 minutes. In the method of peeling the temporary fixing film by irradiating ultraviolet rays from the substrate side with reduced adhesive force, the irradiation amount of ultraviolet rays is usually 10mJ/cm ² ～1000mJ/cm ² 。

Procedure (5)

The material for forming the rewiring forming layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring forming layer (insulating layer) is formed, and a photosensitive resin or a thermosetting resin is preferable from the viewpoint of ease of manufacturing the semiconductor chip package. The resin composition and the resin sheet of the present invention can be used to form a rewiring-forming layer.

After the formation of the rewiring formation layer, a via hole (via) may be formed in the rewiring formation layer in order to connect the semiconductor chip and a conductor layer described later. The via hole may be formed by a known method according to a material of the rewiring formation layer.

Procedure (6)

The material of the conductor layer formed on the rewiring forming layer is not particularly limited. In a preferred embodiment, the conductor layer comprises 1 or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include a layer formed of an alloy of 2 or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of pattern formation, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, and still more preferably a single metal layer of copper is preferable.

The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more single metal layers or alloy layers each made of a different metal or alloy are stacked. In the case where the conductor layer has a multilayer structure, the layer to be connected to the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer is generally 1 μm to 35 μm, preferably 1 μm to 20 μm, depending on the design of the desired semiconductor chip package.

In one embodiment, the conductor layer may be formed by plating. For example, the conductor layer having a desired wiring pattern can be formed by plating the surface of the rewiring forming layer by a conventionally known technique such as a half-addition method or a full-addition method, and it is preferable to form the conductor layer by a half-addition method from the viewpoint of ease of production. Hereinafter, an example of forming a conductor layer by a half-additive method is shown.

First, a plating seed layer is formed on the surface of the rewiring forming layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, which exposes a portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer (re-wiring layer) having a desired wiring pattern can be formed.

The step (5) and the step (6) may be repeated, and a conductor layer (rewiring layer) and a rewiring layer (insulating layer) may be alternately stacked.

In manufacturing the semiconductor chip package, the steps of (7) forming a solder resist layer on the conductor layer (rewiring layer), (8) forming bumps, and (9) dicing the plurality of semiconductor chip packages into individual semiconductor chip packages and singulating the individual semiconductor chip packages may be further performed. These processes may be performed according to various methods known to those skilled in the art that may be used in the manufacture of semiconductor chip packages.

The above method comprises providing a semiconductor Chip, forming a rewiring layer on the electrode pad surface, i.e. Chip-on-Chip (Chip-1) ^st ) An example of the case where the manufacturing method is performed. In addition to the chip-on-first method described above, the semiconductor chip package of the present invention may also utilize a rewiring layer-on-first (RDL-1) ^st ) Is manufactured by a method, wherein the rewiring layer is assembled in advance (RDL-1) ^st ) The method comprises providing a rewiring layer, and sealing the semiconductor chip on the rewiring layer with the electrode pad surface electrically connected to the rewiring layerThe method. The resin composition and resin sheet of the present invention having excellent narrow gap filling properties are Chip-1 ^st The construction method is RDL-1 ^st The method can realize the semiconductor chip package with extremely low transmission loss required for 5G application.

By forming a sealing layer and a rewiring forming layer using the resin composition and the resin sheet of the present invention which exhibit good fluidity at the time of molding and bring about excellent dielectric characteristics after curing, a semiconductor chip package with little transmission loss can be realized while suppressing occurrence of flow marks, unfilled portions and warpage regardless of whether the semiconductor package is a Fan-In type package or a Fan-Out type package. In one embodiment, the semiconductor chip package of the present invention is a Fan-Out (Fan-Out) package. The resin composition and the resin sheet of the present invention are applicable to both fan-out panel level package (FOPLP) and fan-out wafer level package (FOWLP). In one embodiment, the semiconductor package of the present invention is a fan-out panel level package (FOPLP). In another embodiment, the semiconductor package of the present invention is a fan-out wafer level package (FOWLP).

[ printed wiring Board ]

The printed wiring board of the present invention comprises an insulating layer formed of a cured product of the resin composition of the present invention.

The printed wiring board can be manufactured, for example, by using the resin sheet described above and using a method comprising the steps (I) and (II) described below,

(I) Laminating the resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate

(II) a step of forming an insulating layer by curing (e.g., thermally curing) the resin composition layer.

The "inner substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, in the production of a printed wiring board, an intermediate product to be further formed with an insulating layer and/or a conductor layer is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer board having a component embedded therein may be used.

Lamination of the inner substrate and the resin sheet can be performed by, for example, thermally pressing the resin sheet against the inner substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS end plate or the like), a metal roller (SUS roller) or the like can be cited. The heat and pressure bonding member may be directly pressed against the resin sheet or may be pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by vacuum lamination. In the vacuum lamination method, the thermocompression bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the thermocompression bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the thermocompression bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. Lamination may preferably be performed under reduced pressure of 26.7hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurized laminators manufactured by the company name machine, vacuum applicators (vacuum applicator) manufactured by Nikko-Materials, batch vacuum pressurized laminators, and the like.

After lamination, the laminated resin sheets are smoothed by pressing the thermocompression bonding member from the support body side at normal pressure (atmospheric pressure), for example. The pressing conditions for the smoothing treatment may be set to the same conditions as those for the above-described lamination of the heat press-bonding. The smoothing treatment can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the commercially available vacuum laminator described above.

The support may be removed between the step (I) and the step (II), or may be removed after the step (II). In the case of using a metal foil as the support, the conductor layer may be formed using the metal foil without peeling the support. In the case of using a metal foil with a support substrate as a support, the support substrate (and the release layer) may be peeled off. Also, the conductor layer may be formed using a metal foil.

In the step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing condition of the resin composition layer is not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition, etc., and in one embodiment, the curing temperature is preferably 120 to 250 ℃, more preferably 150 to 240 ℃, still more preferably 180 to 230 ℃. The curing time may be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and still more preferably 15 minutes to 120 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes at a temperature of 50 ℃ to 120 ℃, preferably 60 ℃ to 115 ℃, more preferably 70 ℃ to 110 ℃ before the resin composition layer is thermally cured.

In the case of manufacturing a printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) can be performed according to various methods known to those skilled in the art for use in the production of printed wiring boards. In the case where the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or between the step (IV) and the step (V). Further, the insulating layer and the conductor layer in the steps (I) to (V) may be repeatedly formed as necessary to form a multilayer wiring board.

In other embodiments, the printed wiring board of the present invention may be manufactured using the prepreg described above. The production method is basically the same as in the case of using a resin sheet.

The step (III) is a step of forming a hole in the insulating layer, whereby a through hole, a through hole (through hole), or the like can be formed in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed wiring board.

The step (IV) is a step of roughening the insulating layer. In this step (IV), the removal of the contaminants (decontamination) is also generally performed. The step and condition of the roughening treatment are not particularly limited, and known steps and conditions generally used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.

The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Anmei Japanese Co., ltd. The swelling treatment with the swelling liquid is not particularly limited, and for example, the insulating layer may be immersed in the swelling liquid at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to a proper level, it is preferable to impregnate the insulating layer in a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Anmeite Japan Co., ltd.

The neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction Solution Securiganth P" manufactured by ameter japan.

The neutralization solution-based treatment can be performed by immersing the treated surface, on which the roughening treatment by the oxidizing agent is completed, in the neutralization solution at 30 to 80 ℃ for 5 to 30 minutes. In view of handling properties, it is preferable to impregnate the object subjected to the roughening treatment by the oxidizing agent in a neutralizing liquid at 40 to 70 ℃ for 5 to 20 minutes.

The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The step (V) may be performed in the same manner as the step (6) described with respect to the method for manufacturing the semiconductor chip package.

The thickness of the conductor layer is usually 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the design of the desired printed wiring board.

The conductor layer may also be formed using a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the step (I) and the step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described in relation to the step (I). Next, step (II) is performed to form an insulating layer. Then, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method using a metal foil on the insulating layer.

The metal foil can be produced by a known method such as electrolysis or rolling. Examples of the commercial products of the metal foil include HLP foil manufactured by JX Nitshi metal Co., ltd., JXUT-III foil, 3EC-III foil manufactured by Mitsui metal mine Co., ltd., TP-III foil, and the like.

Alternatively, in the case of using a metal foil, a metal foil with a supporting substrate, as a support for the resin sheet, the conductor layer may be formed using the metal foil, as described above.

[ semiconductor device ]

The semiconductor device of the present invention comprises a layer formed of a cured product of the resin composition of the present invention. The semiconductor device of the present invention can be manufactured using the semiconductor chip package or the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices that can be used in electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, aircraft, and the like).

Examples

Example 1 Synthesis of diester Compound (A)

In a 2 liter four-necked round bottom flask equipped with a stirrer, a thermometer, a dropping funnel, and a nitrogen inlet, 268g (2.00 mol) of allylphenol, 239g (1.00 mol) of sebacoyl chloride (sebacoyl chloride), and 500g of methyl isobutyl ketone were weighed, and the temperature was raised to 30℃while stirring to uniformly dissolve the contents. To this was added dropwise 231g (2.20 moles) of triethylamine. In the case of dropwise addition of triethylamine, dropwise addition was started at a temperature of 30℃of the content, and dropwise addition was performed for 1 hour while paying attention to heat generation so that the liquid temperature became 60 to 70℃after completion of dropwise addition. Further, stirring was continued at 60 to 70℃for 1 hour, and then 200g of distilled water was added thereto to completely dissolve the by-product organic salt. Then, the liquid was transferred to a separating funnel, and the lower layer (aqueous layer) was left to stand for liquid separation. Then, 200g of distilled water and 10g of disodium phosphate were added thereto, and the mixture was shaken vigorously, left to stand for separation, and the lower layer (aqueous layer) was discarded. Further, washing with 200g of distilled water was repeated 3 times. Adding a proper amount of magnesium sulfate (dehydrating agent) into the reaction liquid after water washing, carrying out vigorous shaking for dehydration, and carrying out precise filtration on the dehydrated reaction liquid. Finally, 405g of the diester compound (A) was obtained as a liquid compound by distilling and recovering the reaction solvent (maximum temperature: 120 ℃ C.) from the filtrate under reduced pressure using a rotary evaporator or the like under high vacuum.

The viscosity of the obtained diester compound (a) was measured using an E-type viscometer (viscosity at 25 ℃) and a vibration viscometer (viscosity at 75 ℃) based on the following measurement conditions. The diester compound (A) had a viscosity of 72 mPas at 25℃and a viscosity of 12 mPas at 75 ℃.

(conditions for measuring viscosity)

Measurement device: e-type viscometer (RE-80U manufactured by DONGMAO Co., ltd.)

Cone plate (cone-plate): radius 24mm, angle 1.34 °

Rotational speed: 100rpm

Temperature: 25 ℃.

(conditions for measuring viscosity at heating)

Measurement device: vibration viscometer (manufactured by Sekonic corporation "VM-10A-L")

Temperature: 75 ℃.

Further, the obtained diester compound (a) was measured by Gel Permeation Chromatography (GPC) and infrared spectroscopy (IR). GPC diagrams and IR diagrams of the compounds are shown in FIG. 1a and FIG. 1b, respectively. In addition, in the mass spectrum, a spectrum of m/z=434 corresponding to the molecular weight of the target substance was observed. As a result, it was confirmed that the obtained diester compound (a) was a compound having the target molecular structure shown below.

[ chemical formula 10]

Example 2 Synthesis of diester Compound (B)

In the same manner as in example 1 except that 188g (2.00 mol) of phenol was used instead of allylphenol, 325g of diester compound (B) was obtained as a solid compound.

The melting point of the diester compound (B) obtained was 60 ℃. Further, as a result of measuring the viscosity using a vibration viscometer in the same manner as in example 1, the viscosity of the compound at 75℃was 17 mPas. GPC diagrams and IR diagrams of the compounds are shown in FIG. 2a and FIG. 2b, respectively. In addition, in the mass spectrum, a spectrum corresponding to m/z=354 of the molecular weight of the target substance was observed. As a result, it was confirmed that the obtained diester compound (B) was a compound having the target molecular structure shown below.

[ chemical formula 11]

Example 3 Synthesis of diester Compound (C)

370g of a diester compound (C) was obtained as a liquid compound in the same manner as in example 1, except that 211g (1.00 mol) of octanoyl chloride (Suberoyl Chloride) was used instead of sebacoyl chloride.

The obtained diester compound (C) was measured for viscosity by using an E-type viscometer and a vibration viscometer in the same manner as in example 1, and as a result, the viscosity at 25℃was 68 mPas and the viscosity at 75℃was 12 mPas. GPC diagrams and IR diagrams of the compounds are shown in FIG. 3a and FIG. 3b, respectively. In addition, in the mass spectrum, a spectrum of m/z=406 corresponding to the molecular weight of the target substance was observed. As a result, it was confirmed that the obtained diester compound (C) was a compound having the target molecular structure shown below.

[ chemical formula 12]

Example 4 Synthesis of diester Compound (D)

In the same manner as in example 1 except that 288g (2.00 mol) of 1-naphthol was used instead of allylphenol, 418g of diester compound (D) was obtained as a solid compound.

The melting point of the diester compound (D) obtained was 68 ℃. Further, as a result of measuring the viscosity using a vibration viscometer in the same manner as in example 1, the viscosity of the compound at 75℃was 76 mPas. GPC diagrams and IR diagrams of the compounds are shown in FIG. 4a and FIG. 4b, respectively. In addition, in the mass spectrum, a spectrum of m/z=454 corresponding to the molecular weight of the target substance was observed. As a result, the obtained diester compound (D) is a compound having the target molecular structure shown below.

[ chemical formula 13]

Example 5 Synthesis of diester Compound (E)

In the same manner as in example 1 except that 368g (2.00 mol) of pentafluorophenol was used instead of allylphenol, 505g of diester compound (E) was obtained as a solid compound.

The melting point of the diester compound (E) obtained was 61 ℃. Further, as a result of measuring the viscosity using a vibration viscometer in the same manner as in example 1, the viscosity at 75℃was 19 mPas. GPC diagrams and IR diagrams of the compounds are shown in FIG. 5a and FIG. 5b, respectively. In addition, in the mass spectrum, a spectrum of m/z=534 corresponding to the molecular weight of the target substance was observed. As a result, the obtained diester compound (E) is a compound having the target molecular structure shown below.

[ chemical formula 14]

Comparative example 1 Synthesis of diester Compound (F)

In the same manner as in example 1 except that 203g (1.00 mol) of isophthaloyl dichloride was used instead of sebacoyl dichloride, 240g of diester compound (F) was obtained as a liquid compound.

The obtained diester compound (F) was measured for viscosity by using an E-type viscometer and a vibration viscometer in the same manner as in example 1, and as a result, the viscosity at 25℃was 6000 mPas and the viscosity at 75℃was 85 mPas. GPC diagrams and IR diagrams of the compounds are shown in FIG. 6a and FIG. 6b, respectively. In addition, in the mass spectrum, a spectrum of m/z=398 corresponding to the molecular weight of the target substance was observed. As a result, it was confirmed that the obtained diester compound (F) was a compound having the molecular structure shown below.

[ chemical formula 15]

Examples 6 to 20 and comparative examples 2 to 4 >, respectively

(1) Preparation of resin composition

Resin compositions were prepared using the synthesized diester compounds (a) to (F) and stirring and mixing the diester compounds (a) to (F) while heating the diester compounds to 80 ℃.

(2) Production of cured product

The prepared resin composition was cast by being poured into a gap between 2 glass plates, and cured by heating at 180℃for 90 minutes using a heat-cycle oven to obtain a cured product having a thickness of about 1 mm.

The obtained cured product and resin composition were used to conduct evaluation tests according to the following points. The results are shown in tables 1 to 3.

[ dielectric Property ]

The cured product was cut into test pieces having a width of 2mm and a length of 80mm, and the relative permittivity and dielectric loss tangent were measured at a measurement frequency of 5.8GHz and at 23℃by a cavity perturbation method using a cavity perturbation method permittivity measuring apparatus (CP 521, manufactured by Kato applied electronic development Co., ltd.) and a network analyzer (E8362B, manufactured by Agilent technologies Co.). For each cured product, 2 test pieces were measured (n=2), and an average value was calculated.

[ evaluation of toughness ]

Cutting the cured product into test pieces with a width of 30mm and a length of 80mm, and visually checking the state when the test pieces are folded in half by 180 degrees in the longitudinal direction;

and (2) the following steps: no cracking or breaking was observed in the cured product

X: cracks and damages were observed in the cured product.

[ coefficient of thermal conductivity ]

Each resin composition was put into a predetermined container, and heated at 180℃for 90 minutes using a thermal cycle oven to be cured, whereby a cylindrical cured product having a thickness of 10 mm. Times.a diameter of. Phi.36 mm was produced. The thermal conductivity of the obtained cylindrical cured product was measured by a planar heat source method (Hot Disk) using a thermophysical measuring apparatus (TPS-2500 ", manufactured by Kyoto electronic industries, ltd.) under a constant temperature environment of a measurement temperature of 25℃and 40% RH.

TABLE 1

(Table 1)

Epoxy resin: phenol novolac type epoxy resin (manufactured by Nissan chemical materials Co., ltd.)

"Epotohto" YDPN-638, epoxy equivalent 177 g/eq.)

DAMPs: 4-dimethylaminopyridine

TABLE 2

(Table 2)

"Epotohto YPN-638", epoxy equivalent 177 g/eq.)

Inorganic filler a: silica (obtained by surface treatment of aminosilane-based coupling agent, obtained by "SC4050-SX", manufactured by Yaku Mar Co., ltd., average particle size of 1.0 μm)

DAMPs: 4-dimethylaminopyridine

TABLE 3

(Table 3)

"Epotohto YPN-638", epoxy equivalent 177 g/eq.)

Inorganic filler B: alumina (DAW-0525, manufactured by DENKA Co., ltd., average particle size of 5.3 μm)

DAMPs: 4-dimethylaminopyridine

Claims

1. A diester compound represented by the following formula (X),

in the method, in the process of the invention,

X ¹ _end and X ² _end Each independently represents an aromatic ring optionally having a substituent, and X ¹ _end And X ² _end At least one of them is an aromatic ring having 1 or more groups selected from an unsaturated aliphatic hydrocarbon group, a halogen atom, an alkyl group and an aryl group as a substituent.

2. The diester compound according to claim 1, wherein, in X _core The number of carbon atoms of the divalent aliphatic group is 6 or more.

3. The diester compound according to claim 1 or 2, wherein, in X _core In (2), the divalent aliphatic group is an alkylene group.

4. A diester compound according to any one of claims 1 to 3, wherein X ¹ _end And X ² _end Both of them are aromatic rings having an unsaturated aliphatic hydrocarbon group as a substituent.

5. The di-esterification according to any one of claims 1 to 4A compound, wherein, at X ¹ _end And X ² _end Wherein the unsaturated aliphatic hydrocarbon group is an allyl group.

6. The diester compound according to any one of claims 1 to 5, wherein, in X ¹ _end And X ² _end Wherein the aromatic ring is an aromatic carbocyclic ring having 6 to 14 carbon atoms.

7. The diester compound according to any one of claims 1 to 6, wherein the diester compound is in a liquid state at 25 ℃.

8. The diester compound according to any of claims 1 to 7, wherein the viscosity at 25 ℃ is 300 mPa-s or less.

9. A resin crosslinking agent comprising a diester compound represented by the following formula (X),

in the method, in the process of the invention,

X ¹ _end and X ² _end Each independently represents an aromatic ring optionally having a substituent.

10. The resin crosslinking agent according to claim 9, wherein the diester compound is the diester compound according to any one of claims 1 to 8.

11. A resin composition comprising a diester compound (X) and a crosslinkable resin (Y),

wherein the diester compound (X) is represented by the following formula (X),

in the method, in the process of the invention,

12. The resin composition according to claim 11, wherein the diester compound (X) is the diester compound according to any one of claims 1 to 8.

13. The resin composition according to claim 11 or 12, wherein the crosslinkable resin (Y) is 1 or more kinds of resins selected from the group consisting of thermosetting resins and radical-polymerizable resins.

14. The resin composition according to any one of claims 11 to 13, further comprising an inorganic filler material.

15. The resin composition according to any one of claims 11 to 14, further comprising an organic solvent.

16. The resin composition according to any one of claims 11 to 15, which is used for sealing a semiconductor.

17. The resin composition according to any one of claims 11 to 15, which is used for an insulating layer of a printed wiring board.

18. A resin sheet, comprising:

support body

A layer of the resin composition according to any one of claims 11 to 17 provided on the support.

19. A prepreg comprising a sheet-like fibrous base impregnated with the resin composition according to any one of claims 11 to 17.

20. A cured product of the resin composition according to any one of claims 11 to 17.

21. A semiconductor chip package comprising a sealing layer formed of a cured product of the resin composition according to any one of claims 11 to 16.

22. The semiconductor chip package of claim 21, which is a Fan-Out (Fan-Out) package.

23. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 11 to 15 and 17.

24. A semiconductor device comprising the semiconductor chip package according to claim 21 or 22, or the printed wiring board according to claim 23.