JP2022189965A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition that can form an insulation layer between wiring layers that shows low dielectric properties and has excellent insulation reliability.

SOLUTION: One aspect of the present invention is a composition containing a maleimide compound, and a nadiimide compound having a group represented by the formula (1). In the formula (1), R¹¹ is an allyl group, m is 0 or 1.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present disclosure relates to curable compositions.

For the purpose of increasing the density and performance of semiconductor packages, there have been proposed mounting forms in which chips with different performance are mounted together in one package. In this case, high-density interconnection technology between chips, which is excellent in terms of cost, has become important (see, for example, Patent Document 1).

Package technology using organic substrates with high-density wiring and fan-out package technology (FO-WLP: Through Mold Via) with through mold vias (TMV) are used as forms for mounting multiple chips at high density. FanOut-WaferLevel Package), package technology using silicon or glass interposers, package technology using through silicon vias (TSV: Through Silicon Via), package technology using chips embedded in substrates for chip-to-chip transmission, etc. have been proposed. ing.

In particular, when semiconductor chips are mounted on a semiconductor wiring layer and an FO-WLP, a fine wiring layer is required for high-density conduction between the semiconductor chips (see, for example, Patent Document 2). A fine wiring having a line width and a space width of, for example, 5 μm or less is arranged in the wiring layer. The wiring is formed using, for example, a trench method. The trench method is a method of forming a metal layer to be wiring in a trench (groove) formed by a laser or the like on the surface of an insulating layer (inter-wiring insulating layer) formed between wiring layers by plating or the like.

In the wiring interlayer insulating layer, it is necessary to suitably maintain insulation (excellent insulation reliability). For example, in Patent Document 3, for the purpose of providing an inter-wiring insulating layer or the like having good insulation reliability, a curable resin and a curing agent are contained to form an inter-wiring insulating layer in contact with copper wiring. A resin composition is disclosed that is used to

Japanese translation of PCT publication No. 2012-529770 U.S. Patent Application Publication No. 2011/0221071 WO2018/056466

Inter-wiring insulating layers are required to exhibit low dielectric properties (low dielectric constant and dielectric loss tangent) in addition to excellent insulation reliability. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composition capable of forming an inter-wiring insulating layer exhibiting low dielectric properties and excellent insulating reliability.

式（１）中、Ｒ^１１はアリル基を表し、ｍは０又は１を表す。 One aspect of the present invention is a composition containing a maleimide compound and a nadimide compound having a group represented by the following formula (1).

In formula (1), R ¹¹ represents an allyl group and m represents 0 or 1.

式（２）中、Ｒ^１１及びｍは、それぞれ独立に、前記式（１）中のＲ^１１及びｍとそれぞれ同義であり、Ｒ^１２は、２価の有機基を表す。 The nadimide compound may be a compound represented by the following formula (2).

In formula (2), R ¹¹ and m are each independently synonymous with R ¹¹ and m in formula (1) above, and R ¹² represents a divalent organic group.

式（３）中、Ｒ^１２は、前記式（２）中のＲ^１２と同義である。 The nadimide compound may be a compound represented by the following formula (3).

In formula (3), R ¹² has the same definition as R ¹² in formula (2).

A divalent organic group may have an aromatic hydrocarbon group. The divalent organic group may be a divalent hydrocarbon group.

The composition described above may be used to form an insulating layer between wiring layers of a semiconductor package.

According to the present invention, it is possible to form an inter-wiring insulating layer exhibiting low dielectric properties and excellent insulation reliability.

1 is a schematic cross-sectional view showing an embodiment of a semiconductor package; FIG. 2 is a schematic cross-sectional view showing a wiring layer laminate included in the semiconductor package of FIG. 1; FIG.

A composition according to one embodiment contains a maleimide compound and a nadimide compound. This composition is a curable composition that can be cured by heat and/or light. In this composition, a nadimide compound can function as a curing agent.

The composition contains one or more maleimide compounds. The maleimide compound has, for example, at least two maleimide groups represented by the following formula (I).

式中、Ｘは、２価の炭化水素基を含む２価の連結基である。 A maleimide compound is, for example, a compound represented by the following formula (II).

In the formula, X is a divalent linking group containing a divalent hydrocarbon group.

The divalent hydrocarbon group contained in the linking group represented by X may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. The divalent hydrocarbon group may be either linear or cyclic, and the linear divalent hydrocarbon group may be linear or branched. A cyclic unsaturated hydrocarbon group may be an aromatic group. A divalent hydrocarbon group may contain two or more of these groups.

A divalent hydrocarbon group is preferable from the viewpoint of being able to increase the flexibility of the composition and the handleability (tackiness, cracking, powder falling off, etc.) and strength of a film produced from the composition. contains a chain hydrocarbon group, more preferably a chain alkylene group having a main chain of 6 or more carbon atoms.

A chain alkylene group having a main chain of 6 or more carbon atoms is represented by -(CR ^a R ^b ) _m - (m represents an integer of 6 or more, R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having less than m carbon atoms). The carbon number (m) of the main chain of the alkylene group is preferably 4 or more or 6 or more, and preferably 20 or less, 15 or less, or 10 or less.

The number of carbon atoms in the divalent hydrocarbon group is preferably 8 or more and 10 or more from the viewpoints that the molecular structure of the maleimide compound can be easily three-dimensionalized and the free volume of the polymer can be increased to reduce the density, that is, to reduce the dielectric constant. or 15 or more, preferably 300 or less, 250 or less, 200 or less, 100 or less, 70 or less, or 50 or less. The number of carbon atoms in the divalent hydrocarbon group may be preferably 8-300, 8-250, 8-200, or 8-100 from the same viewpoint. The divalent hydrocarbon group is preferably an optionally branched alkylene group having 8 to 300, 8 to 250, 8 to 200 or 8 to 100 carbon atoms, more preferably an alkylene group having 10 to 70 carbon atoms. An optionally branched alkylene group, more preferably an optionally branched alkylene group having 15 to 50 carbon atoms.

式中、Ｒ^１及びＲ^２は、それぞれ独立にアルキレン基を表し、Ｒ^３及びＲ^４は、それぞれ独立にアルキル基を表す。 The divalent hydrocarbon group may be a group represented by the following formula (III) from the viewpoint of more effectively improving high-frequency characteristics and HAST (Highly Accelerated temperature and humidity Stress Test) resistance.

In the formula, R ¹ and R ² each independently represent an alkylene group, and R ³ and R ⁴ each independently represent an alkyl group.

The number of carbon atoms in the alkylene group represented by R ¹ or R ² is preferably 4 to 50, more preferably 5 to 25, still more preferably 6 to 10, from the viewpoint of further improving flexibility and facilitating synthesis. , particularly preferably 7-10. The alkylene group represented by R ¹ and R ² is preferably a chain alkylene group having a main chain of 6 or more carbon atoms as described above.

The number of carbon atoms in the alkyl group represented by R ³ or R ⁴ is preferably 4 to 50, more preferably 5 to 25, still more preferably 6 to 10, from the viewpoint of further improving flexibility and facilitating synthesis. , particularly preferably 7-10.

The maleimide compound preferably has a plurality of divalent hydrocarbon groups from the viewpoint of more effectively enhancing the high-frequency characteristics and elongation. In this case, the plurality of divalent hydrocarbon groups may be the same or different. The maleimide compound preferably has 2 to 40, more preferably 2 to 20, still more preferably 2 to 10 divalent hydrocarbon groups.

Divalent hydrocarbon groups include, for example, nonylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, hexadecylene group, octadecylene group, nonadecylene group, icosylene group, henicosylene group, docosylene group, tricosylene group, tetracosylene group, Alkylene groups such as pentacosylene group, hexacosylene group, heptacosylene group, octacosylene group, nonacosylene group and triacontylene group; arylene groups such as benzylene group, phenylene group and naphthylene group; phenylene methylene group, phenylene ethylene group and benzyl propylene group , a naphthylenemethylene group, an arylenealkylene group such as a naphthyleneethylene group; an arylenedialkylene group such as a phenylenediethylene group, a phenylenediethylene group, and the like.

The linking group represented by X may consist only of the above divalent hydrocarbon groups, or may contain other organic groups in addition to the above divalent hydrocarbon groups. Other organic groups are, for example, divalent organic groups having at least two imide bonds.

式中、Ｒ^５は、４価の有機基を表す。 A divalent organic group having at least two imide bonds may be, for example, a group represented by the following formula (IV).

^In the formula, R5 represents a tetravalent organic group.

The tetravalent organic group represented by ^R5 may be, for example, a hydrocarbon group from the viewpoint of handleability. The number of carbon atoms in the hydrocarbon group may be, for example, 1-100, 2-50 or 4-30.

The hydrocarbon groups may be substituted and may include, for example, substituted or unsubstituted siloxane groups. Examples of siloxane groups include groups derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and the like.

Substituents are, for example, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, alkoxy groups, mercapto groups, cycloalkyl groups, substituted cycloalkyl groups, heterocyclic groups, substituted heterocyclic groups, aryl groups, substituted aryl groups, heteroaryl group, substituted heteroaryl group, aryloxy group, substituted aryloxy group, halogen atom, haloalkyl group, cyano group, nitro group, nitroso group, amino group, amido group, -C(O)H, -C(O)- , —S—, —S(O) ₂ —, —OC(O)—O—, —C(O)—NR ^c , —NR ^c C(O)—N(R ^c ) ₂ , —OC(O )—N(R ^c ) ₂ , acyl group, oxyacyl group, carboxyl group, carbamate group, sulfonyl group, sulfonamide group, sulfuryl group and the like. Here, ^Rc represents a hydrogen atom or an alkyl group. One type or two or more types of these substituents can be selected according to the purpose, application, and the like.

The tetravalent organic group represented by R ⁵ is, for example, a tetravalent residue of an acid anhydride having two or more anhydride rings in one molecule, that is, from an acid anhydride to an acid anhydride group (- It may be a tetravalent group excluding two CO(=O)OC(=O)-). Examples of acid anhydrides include compounds described later.

The organic group represented by R ⁵ is preferably a tetravalent aromatic group, more preferably a residue obtained by removing two acid anhydride groups from pyromellitic anhydride, from the viewpoint of excellent high-frequency characteristics. The divalent organic group having at least two imide bonds is preferably a group represented by formula (V) below.

The divalent organic group having at least two imide bonds may be a group represented by the following formula (VI) or (VII) from the viewpoint of excellent dielectric properties.

The maleimide compound preferably has at least two imides from the viewpoint of excellent high-frequency characteristics and excellent compatibility with other resins when the composition further contains other resins (especially high-molecular-weight thermoplastic elastomer resins). It has a plurality of divalent organic groups with bonds. In this case, the plurality of divalent organic groups may be the same or different. The maleimide compound preferably has 2 to 40, more preferably 2 to 20, still more preferably 2 to 10 such divalent organic groups.

式中、Ｚ^１、Ｚ^２及びＺ^３は、それぞれ独立に上述した２価の炭化水素基を表し、Ｒ^５は式（ＩＶ）中のＲ^５と同義であり、ｎは１～１０の整数を表す。ｎが２以上である場合、複数のＺ^３は、互いに同一であっても異なっていてもよい。 More specifically, in one embodiment, the maleimide compound may be, for example, a compound represented by the following formula (VIII) or a compound represented by the following formula (IX).

In the formula, Z ¹ , Z ² and Z ³ each independently represent a divalent hydrocarbon group as described above, R ⁵ has the same definition as R ⁵ in formula (IV), and n is an integer of 1 to 10 represents When n is 2 or more ^, the plurality of Z3 may be the same or different.

A maleimide compound can be used, for example, by purchasing a commercial product. Commercially available products include, for example, BMI-TMH, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-, which are maleimide compounds represented by formula (VIII). 3000, BMI-3000H, BMI-4000, BMI-5100, BMI-7000, BMI-7000H (all trade names, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (all trade names, manufactured by K-I Kasei Co., Ltd.) and the like. Commercially available products include, for example, SFR2300 (trade name, manufactured by Hitachi Chemical Co., Ltd.), BMI-1500, BMI-1700, BMI-3000, BMI-5000 and BMI-, which are maleimide compounds represented by formula (IX). 9000 (both trade names, manufactured by Designer Molecules Inc. (DMI)) and the like.

The weight average molecular weight Mw of the maleimide compound may be 1,000 or more, 1,500 or more, or 3,000 or more, and may be 30,000 or less, 20,000 or less, or 15,000 or less. The weight average molecular weight Mw of the maleimide compound is preferably 1,000 to 30,000, more preferably 1,500 to 20,000, from the viewpoints of solubility in solvents and compatibility with other components such as monomers and resins.

The weight average molecular weight Mw of the maleimide compound can be measured by a gel permeation chromatography (GPC) method. The measurement conditions of GPC are as follows.
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Guard column and column: TSK Guardcolumn HHR-L + TSKgel G4000HHR + TSKgel G2000HHR [all manufactured by Tosoh Corporation, trade name]
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg/5 mL
Injection volume: 20 μL
Measurement temperature: 40°C

The content of the maleimide compound, based on the total solid content in the composition, may be, for example, 10% by mass or more, 40% by mass or more, or 80% by mass or more, and 99% by mass or less, 95% by mass or less, Or it may be 90% by mass or less.

式（１）中、Ｒ^１１はアリル基を表し、ｍは０又は１を表す。 The composition contains one or more nadimide compounds. A nadimide compound is a compound having a group represented by the following formula (1).

In formula (1), R ¹¹ represents an allyl group and m represents 0 or 1.

式（２）中、Ｒ^１１及びｍは、それぞれ独立に、式（１）中のＲ^１１及びｍとそれぞれ同義であり、Ｒ^１２は、２価の有機基を表す。 The nadimide compound may have one group represented by Formula (1), may have two or more groups, and preferably have two groups. The nadimide compound is preferably a compound represented by the following formula (2).

In formula (2), R ¹¹ and m are each independently synonymous with R ¹¹ and m in formula (1), and R ¹² represents a divalent organic group.

The divalent organic group represented by R ¹² may have an aromatic hydrocarbon group (aromatic ring). An aromatic hydrocarbon group (aromatic ring) may be a benzene residue, a toluene residue, a xylene residue, a naphthalene residue, or the like. The divalent organic group may have a linear, branched or cyclic aliphatic hydrocarbon group. Aliphatic hydrocarbon groups may be linear, branched or cyclic alkyl groups. The divalent organic group may have both the above aromatic hydrocarbon group (aromatic ring) and aliphatic hydrocarbon group.

The divalent organic group represented by R ¹² may be a divalent hydrocarbon group containing only carbon atoms and hydrogen atoms, and a divalent organic group containing other atoms in addition to carbon atoms and hydrogen atoms and preferably a divalent hydrocarbon group.

式中、ｎは１～１０の整数である。 The divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group and may be a divalent aliphatic hydrocarbon group having the structure below.

In the formula, n is an integer of 1-10.

The divalent hydrocarbon group is preferably a divalent hydrocarbon group having an aromatic hydrocarbon group (aromatic ring), more preferably a divalent hydrocarbon group having any of the following structures is.

The divalent organic group containing other atoms may contain, in addition to carbon atoms and hydrogen atoms, one or more of atoms such as nitrogen, oxygen, sulfur and fluorine atoms. Divalent organic groups containing other atoms are preferably divalent hydrocarbon groups having any of the structures below.

式（３）中、Ｒ^１２は、式（２）中のＲ^１２と同義である。 The nadimide compound is preferably a bisallyl nadimide compound represented by the following formula (3) (a compound in which m is 1 in formula (2)).

In formula (3), R ¹² has the same definition as R ¹² in formula (2).

The nadimide compound is more preferably a bisallyl nadimide compound in which R ¹² in formula (3) is a divalent hydrocarbon group having an aromatic hydrocarbon group (aromatic ring), more preferably the following formula It is a bisallyl nadiimide compound represented by (3-1) or (3-2), is excellent in UV curing and compatibility with maleimide compounds, and exhibits low dielectric properties. A bisallylnadiimide compound represented by the following formula (3-1) is more preferable from the viewpoint of formation.

The content of the nadimide compound is preferably 1 part by mass or more, more preferably 10 parts by mass or more, from the viewpoint of sufficiently improving the heat resistance when the total of the maleimide compound and the nadimide compound is 100 parts by mass. , preferably 90 parts by mass or less, more preferably 50 parts by mass or less.

The composition contains a compound having a (meth)acryloyl group (hereinafter also referred to as "(meth)acryloyl compound") from the viewpoint of improving the UV curability of the composition and also improving the compatibility between the maleimide compound and the nadimide compound. may be further included. A coupling agent having a (meth)acryloyl group, which will be described later, is not included in the (meth)acryloyl compound.

(Meth)acryloyl compounds include, for example, tricyclodecanedimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A (meth)acrylate, dipentaerythritol poly(meth)acrylate, It may be ethoxylated isocyanuric acid tri(meth)acrylate, polyethylene glycol di(meth)acrylate, silsesquioxane derivative having (meth)acryloyl group, and the like.

From the viewpoint of excellent heat resistance, the (meth)acryloyl compound is preferably tricyclodecanedimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A (meth)acrylate, or It is a silsesquioxane derivative having a (meth)acryloyl group, and more preferably tricyclodecane dimethanol di(meth)acrylate from the viewpoint of excellent compatibility with the maleimide compound.

The content of the (meth)acryloyl compound is 0.1 parts by mass or more, 2 parts by mass or more, or 5 parts by mass or more when the total of the maleimide compound, the nadimide compound and the (meth)acryloyl compound is 100 parts by mass. may be 98 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less; It is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less. In one embodiment, the composition does not contain a (meth)acryloyl compound from the viewpoint of more preferably forming an inter-wiring insulating layer exhibiting low dielectric properties.

The composition may further contain a radical photopolymerization initiator as a curing agent. The radical photopolymerization initiator may be, for example, an alkylphenone-based radical photopolymerization initiator, an acylphosphine oxide-based radical photopolymerization initiator, or the like.

Alkylphenone-based radical photopolymerization initiators can be purchased, for example, as Irgacure651, Irgacure184, DAROCURE1173, Irgacure2959, Irgacure127, DAROCUREMBF, Irgacure907, Irgacure369, Irgacure379EG manufactured by BASF. The acylphosphine oxide photoradical polymerization initiator can be purchased as Irgacure 819, LUCIRINTPO, etc. manufactured by BASF.

The photo-radical polymerization initiator may be other photo-radical polymerization initiators commercially available as Irgacure 784, Irgacure OXE01, Irgacure OXE02, Irgacure 754, etc. manufactured by BASF.

As the radical photopolymerization initiator, Irgacure907, Irgacure369, Irgacure379EG, IrgacureOXE01, and IrgacureOXE02 are preferably used from the viewpoint of high sensitivity, and Irgacure907, Irgacure379EG, and IrgacureOXE02 are more preferably used from the viewpoint of solubility in solvents. These photo-radical polymerization initiators may be used alone or in combination of two or more, depending on the purpose, application, and the like.

The content of the photoradical polymerization initiator is preferably 0.1 parts by mass or more from the viewpoint of sufficiently curing the curable composition when the total of the maleimide compound and the nadimide compound is 100 parts by mass. It may be 10 parts by mass or less, and more preferably 1 part by mass or more and 6 parts by mass or less from the viewpoint that unreacted substances are less likely to remain.

The composition may further contain a coupling agent. The coupling agent may be, for example, a silane coupling agent. Silane coupling agents may have, for example, vinyl groups, epoxy groups, styryl groups, acryloyl groups, methacryloyl groups, amino groups, ureido groups, isocyanate groups, isocyanurate groups, mercapto groups, and the like.

Silane coupling agents having a vinyl group include KBM-1003 and KBE-1003 (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.; hereinafter the same). Silane coupling agents having an epoxy group include KBM-303, 402, 403, KBE-402, 403, X-12-981S, X-12-984S and the like. Silane coupling agents having a styryl group include KBM-1403 and the like. Silane coupling agents having a methacryloyl group include KBM-502,503, KBE-502,503 and the like. Silane coupling agents having an acryloyl group include KBM-5103, X-12-1048, X-12-1050 and the like. Silane coupling agents having an amino group include KBM-602, 603, 903, 573, 575, KBE-903, 9103P and X-12-972F. Silane coupling agents having a ureido group include KBE-585 and the like. Silane coupling agents having an isocyanate group include KBE-9007, X-12-1159L and the like. Silane coupling agents having an isocyanurate group include KBM-9659 and the like. Silane coupling agents having a mercapto group include KBM-802, 803, X-12-1154, X-12-1156 and the like. These may be used singly or in combination of two or more according to the purpose, application, and the like.

The content of the silane coupling agent is preferably 0.01 part by mass or more from the viewpoint of improving adhesion to glass, silica, etc., when the total of the maleimide compound and the nadimide compound is 100 parts by mass. It may be 5 parts by mass or less, and more preferably 0.1 parts by mass or more, or 2 parts by mass, from the viewpoint that unreacted substances are less likely to remain.

The composition may further contain a thermosetting resin. Examples of thermosetting resins include epoxy resins, phenol resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, A melamine resin etc. are mentioned. However, the thermosetting resin does not include the maleimide compounds and nadimide compounds described above. Thermosetting resins may be used singly or in combination of two or more. From the viewpoint of heat resistance and electrical insulation, the thermosetting resin is preferably an epoxy resin or a cyanate resin.

Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol F novolak type epoxy resin. , stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy Diglycidyl ether compounds of resins, polyfunctional phenols and polycyclic aromatics such as anthracene, and phosphorus-containing epoxy resins obtained by introducing phosphorus compounds into these. Epoxy resins are biphenylaralkyl type epoxy resins or naphthalene type epoxy resins in terms of heat resistance and flame retardancy. These may be used individually by 1 type, or may be used in mixture of 2 or more types.

Examples of cyanate resins include bisphenol-type cyanate resins such as novolak-type cyanate resins, bisphenol-A-type cyanate resins, bisphenol-E-type cyanate resins, tetramethylbisphenol-F-type cyanate resins, and prepolymers obtained by partially triazine-forming these resins. be done. These may be used singly or in combination of two or more. From the viewpoint of heat resistance and flame retardancy, the cyanate resin is preferably a novolac cyanate resin.

The composition may further contain other curing agents in addition to the nadimide compound and the photoradical polymerization initiator as curing agents. Other curing agents include, for example, dicyandiamide, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenylsulfone, phenylenediamine, xylenediamine, and the like. , aliphatic amine compounds such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine. Other curing agents are preferably aromatic amine compounds from the viewpoint of obtaining good reactivity and heat resistance.

When the composition contains a cyanate resin, the composition contains, as a curing agent, for example, polyfunctional phenol compounds such as phenol novolak, cresol novolak, and aminotriazine novolak resins, phthalic anhydride, pyromellitic anhydride, maleic anhydride, Acid anhydrides such as maleic anhydride copolymers may be further contained. These can be used individually by 1 type or in mixture of 2 or more types.

The composition may further contain a filler from the viewpoint of imparting low hygroscopicity and low moisture permeability. The filler may be an inorganic filler made of an inorganic material or an organic filler made of an organic material. These fillers are preferably insulating fillers.

Examples of inorganic fillers include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, crystalline silica, and amorphous Silica, boron nitride, titania, glass, iron oxide, ceramics, and the like. Examples of organic fillers include carbon and rubber fillers. The filler can be used without particular restrictions regardless of its type, shape, and the like.

Different fillers may be used depending on the desired function. For example, the inorganic filler is added for the purpose of imparting thermal conductivity, low thermal expansion, low hygroscopicity, etc. to the wiring interlayer insulating layer. The organic filler is added, for example, for the purpose of imparting toughness and the like to the wiring interlayer insulating layer. The filler should just contain at least one of an inorganic filler and an organic filler. The filler can be used individually by 1 type or in combination of 2 or more types. The filler is preferably an inorganic filler from the viewpoint of being able to impart thermal conductivity, low hygroscopicity, insulating properties, etc., which are required for the wiring interlayer insulating layer. At least one of a silica filler and an alumina filler is more preferable from the viewpoint of imparting adhesive strength.

The average particle size of the filler is, for example, 10 μm or less, and the maximum particle size of the filler is, for example, 30 μm or less. It is preferable that the average particle size of the filler is 5 μm or less and the maximum particle size of the filler is 20 μm or less. When the average particle diameter is 10 μm or less and the maximum particle diameter is 30 μm or less, the effect of improving the fracture toughness of the wiring interlayer insulating layer can be satisfactorily exhibited, and the adhesion strength of the wiring interlayer insulating layer can be reduced and the variation can be suppressed. It is also possible to suppress the surface roughness of the inter-wiring-layer insulating layer and the deterioration of the bonding strength. Although the lower limit of the average particle size and the lower limit of the maximum particle size of the filler are not particularly limited, both may be 0.001 μm or more.

Examples of the method for measuring the average particle size and maximum particle size of the filler include a method of measuring the particle size of about 20 fillers using a scanning electron microscope (SEM). As a measurement method using SEM, for example, a sample is prepared by heat-curing a composition containing a filler (preferably at 150 to 180° C. for 1 to 10 hours), and the central portion of this sample is cut. , a method of observing the cross section with an SEM, and the like. At this time, it is preferable that the existence probability of the filler having a particle diameter of 30 μm or less in the cross section is 80% or more of all the fillers.

The content of the filler is appropriately determined according to the properties or functions to be imparted. The filler content is, for example, preferably 1% to 70% by weight, or 2% to 60% by weight, more preferably 5% to 50% by weight, based on the weight of the composition. By increasing the filler content, it is possible to increase the elastic modulus of the wiring interlayer insulating layer. As a result, dicing properties (cutting properties with a dicer blade), wire bonding properties (ultrasonic efficiency), and adhesive strength during heating can be effectively improved. From the viewpoint of suppressing deterioration of thermocompression bonding properties, the content of the filler is preferably equal to or less than the above upper limit. An optimum filler content may be determined to balance the desired properties. Mixing and kneading of the filler may be carried out by appropriately combining dispersing machines such as ordinary stirrers, kneaders, triple rolls and ball mills.

The composition may further contain an antioxidant from the viewpoint of storage stability, prevention of electromigration, and prevention of corrosion of metal conductor circuits. The antioxidant is not particularly limited, and examples thereof include benzophenone-based, benzoate-based, hindered amine-based, benzotriazole-based, and phenol-based antioxidants. The content of the antioxidant is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin component, from the viewpoint of the effect of addition, heat resistance, cost, and the like.

The composition may further contain a catalyst to further accelerate curing. Catalysts include, for example, peroxides, imidazole compounds, organophosphorus compounds, secondary amines, tertiary amines and quaternary ammonium salts. These may be used individually by 1 type, or may use 2 or more types together. From the viewpoint of reactivity, the catalyst is preferably at least one selected from the group consisting of peroxides, imidazole-based compounds and organophosphorus compounds. Peroxide is more preferable from the viewpoint of contributing to the reaction with.

The composition may further contain a flame retardant. Flame retardants include, but are not limited to, brominated flame retardants, halogen-containing flame retardants such as chlorine flame retardants, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate compounds, red phosphorus, and the like. Nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate, phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene, inorganic flame retardants such as antimony trioxide, etc. mentioned. These flame retardants may be used singly or in combination of two or more.

The composition may further contain an ultraviolet absorber. Examples of the ultraviolet absorber include, but are not particularly limited to, benzotriazole-based ultraviolet absorbers.

The composition may further contain an optical brightener. Examples of fluorescent brightening agents include, but are not limited to, stilbene derivatives.

The composition is preferably in the form of a film from the viewpoint of handleability. The composition may be a varnish (liquid) in which each component is dissolved or uniformly dispersed in a solvent.

The varnish preparation means, conditions, etc. are not particularly limited. For example, after each main component in a predetermined blending amount is sufficiently and uniformly stirred and mixed with a mixer or the like, it is kneaded using a mixing roll, an extruder, a kneader, a roll, an extruder, or the like, and the resulting kneaded product is further cooled. and a method of pulverizing. A kneading method is not particularly limited.

If the composition is a varnish, the solvent can be, for example, an organic solvent. Organic solvents are not particularly limited, but for example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone; aromatic hydrocarbons such as toluene, xylene, mesitylene, limonene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl- It may be a nitrogen-containing compound such as 2-pyrrolidone. These may be used individually by 1 type, and may be used in mixture of 2 or more types. The organic solvent is preferably toluene, xylene, cyclohexanone, cyclopentanone, limonene or mesitylene in terms of solubility, and more preferably cyclopentanone, limonene or mesitylene in terms of low toxicity.

The organic solvent, for example, is preferably used in an amount such that the solid content of the composition in the varnish is 5 to 90% by mass, and from the viewpoint of maintaining good varnish handling properties and application/coating properties, the It is more preferable to use an amount such that the solid content is 10 to 60% by mass.

The cured product of the composition preferably has a moisture absorption rate of 1% by mass or less after being placed in an atmosphere of 130° C. and a relative humidity of 85% for 200 hours. The moisture absorption of the cured product of the composition after being placed in an environment of 130° C. and a relative humidity of 85% for 200 hours can be measured by the method described in Examples.

The concentration of chloride ions in the cured product of the composition is preferably 5 ppm or less from the viewpoint of insulation reliability, and more preferably 3 ppm or less from the viewpoint of suppressing discoloration of copper wiring. The chloride ion concentration can be measured by the following procedure. 1 g of a cured product sample and 10 g of ultrapure water as an extraction liquid are placed in a Teflon (registered trademark) heat-resistant container and heated at 130° C. for 5 hours. The extract is then filtered and then analyzed by ion chromatography. In the obtained chromatogram, the peak detected at the elution time of 0 to 30 minutes is regarded as the total amount of eluate, and the mass of chloride ions in the cured product sample is calculated from the peak area of chloride ions around 9.6 minutes. Ask for The ratio of the obtained mass of chloride ions to the mass of the cured product sample is calculated as the chloride ion concentration (ppm) in the cured product.
The conditions for ion chromatography here are as follows.
・Equipment: Dionex ISC-2000
・Detector: Electrical conductivity detector ・Column: AS20 (4mmφ×200mm)
・Column temperature: 30°C
・Flow rate: 1.0 mL/min ・Injection volume: 25 μL
- Gradient setting: KOH concentration was set to 5 mM at 0 min, 5 mM at 5 min, 30 mM at 15 min, 55 mM at 20 min.

The dielectric constant at 10 GHz of the insulating layer between wiring layers (cured product of the composition) is preferably 3.6 or less, 3.2 or less, or 3.0 or less in terms of suppressing crosstalk between wiring layers. Furthermore, it is more preferably 2.8 or less in that the reliability of electric signals can be improved. The dielectric constant may be 1.0 or greater. The dielectric loss tangent of the wiring interlayer insulating layer (cured product of the composition) at 10 GHz is preferably 0.012 or less, more preferably 0.008 or less, still more preferably 0.005 or less, for example 0.0001 or more. It's okay. The dielectric constant and dielectric loss tangent can be measured by the methods described in Examples.

The glass transition temperature of the cured product of the composition is preferably 120° C. or higher from the viewpoint of suppressing cracks during temperature cycles, and more preferably 140° C. or higher from the viewpoint of relaxing stress on wiring. The glass transition temperature of the cured product of the composition is preferably 240° C. or lower from the viewpoint of enabling lamination at a low temperature, and more preferably 220° C. or lower from the viewpoint of suppressing curing shrinkage. The glass transition temperature of the cured product of the composition can be measured by the method described in Examples.

The elongation at break of the cured product of the composition is preferably 5% or more from the viewpoint of reducing the warpage of the wiring interlayer insulating layer, and more preferably 10% or more from the viewpoint of relaxing the stress on the copper wiring. From the viewpoint of improving the temperature cycle reliability of the wiring layer laminate, it is more preferably 15% or more. The elongation at break may be 200% or less. The elongation at break can be measured by the method described in Examples.

The 5% weight loss temperature of the cured product of the composition is, for example, 300° C. or higher from the viewpoint of heat resistance reliability. The 5% weight loss temperature of the cured product of the composition was determined by using a sample of a 300 μm thick cured product obtained by curing the composition by heating at 180 ° C. for 2 hours. High Tech Science, trade name: TG/DTA6300) can be used for measurement under conditions of a temperature increase rate of 10°C/min and a nitrogen flow of 400 mL/min.

The cured product of the composition may have a storage modulus at 40° C. of 10 MPa to 5 GPa.

Since the composition described above can form an inter-wiring insulating layer exhibiting low dielectric properties and excellent insulation reliability, it is suitably used for an inter-wiring insulating layer of a semiconductor package as described below.

FIG. 1 is a schematic cross-sectional view showing one embodiment of a semiconductor package, and FIG. 2 is a schematic cross-sectional view showing a wiring layer laminate included in the semiconductor package of FIG. As shown in FIG. 1, the semiconductor package 100 includes a substrate 1, a wiring layer laminate 10 provided on the substrate 1, and semiconductor chips 2A and 2B mounted on the wiring layer laminate 10.

The substrate 1 is a sealing body formed by sealing semiconductor chips 2C, 2D and electrodes 5A, 5B with an insulating material 4. As shown in FIG. The semiconductor chips 2C and 2D in the substrate 1 can be connected to an external device through electrodes exposed from the insulating material 4. As shown in FIG. The electrodes 5A and 5B function, for example, as conductive paths for electrically connecting the wiring layer laminate 10 and an external device to each other. The semiconductor chips 2A and 2B are fixed on the wiring layer laminate 10 by corresponding underfills 3A and 3B, respectively, and are electrically connected to each other via surface wiring (not shown) provided in the wiring layer laminate 10. It is Each of the semiconductor chips 2A-2D is electrically connected to one of the wirings in the wiring layer laminate 10. FIG.

Each of the semiconductor chips 2A to 2D is, for example, a graphic processing unit (GPU: Graphic Processing Unit), a volatile memory such as DRAM (Dynamic Random Access Memory) or SRAM (Static Random Access Memory), and a nonvolatile memory such as flash memory. , RF chips, silicon photonics chips, MEMS (Micro Electro Mechanical Systems), sensor chips, and the like. The thickness of the semiconductor chips 2A and 2B may be, for example, 30 μm or more and may be 200 μm or less.

The underfills 3A, 3B are, for example, capillary underfills (CUF), mold underfills (MUF), paste underfills (NCP), film underfills (NCF), or photosensitive underfills. Each of the underfills 3A and 3B is mainly composed of liquid curable resin (for example, epoxy resin). The insulating material 4 is, for example, a curable resin having insulating properties.

As shown in FIG. 2, the wiring layer laminate 10 includes organic insulating layers 21 and 22, copper wires 13 and 14 embedded in the organic insulating layers 21 and 22, and copper wires 13 and 14 and the organic insulating layer 21. , 22, wiring interlayer insulating layers 17 and 18 adjacent to the wiring layers 41 and 42, and organic insulating layers 21 and 22. , and a through wiring 19 passing through the wiring interlayer insulating layers 17 and 18 . Organic insulating layers 21 and 22 and wiring interlayer insulating layers 17 and 18 are alternately laminated on the substrate 11 . A part of the surfaces of the copper wirings 13 and 14 are exposed on one main surface side of the wiring layers 41 and 42, and the wiring interlayer insulating layers 17 and 18 are in contact with the exposed surfaces of the copper wirings 13 and 14, respectively. The wiring interlayer insulating layers 17 and 18 are cured products of the composition described above. The organic insulating layers 21 and 22 can be layers formed from a photosensitive insulating resin. The copper wiring may be exposed on both main surface sides of the wiring layer, and the wiring interlayer insulating layer may be in contact with the surface of the exposed copper wiring.

The substrate 11 is a support that supports the wiring layer laminate 10 . The shape of the substrate 11 in plan view is, for example, circular or rectangular. When circular, substrate 11 has a diameter of, for example, 200 mm to 450 mm. In the case of a rectangular shape, one side of the substrate 11 is, for example, 300 mm to 700 mm.

Substrate 11 may be, for example, a silicon substrate, a glass substrate, or a peelable copper foil. When a silicon substrate, a glass substrate, or the like is used as the substrate 11, a temporary fixing layer (not shown) for temporarily fixing the wiring layer laminate 10 and the substrate 11 may be provided. In this case, the substrate 11 can be easily separated from the wiring layer laminate 10 by removing the temporary fixing layer. A peelable copper foil is a laminate in which a support, a release layer, and a copper foil are laminated in order. In the peelable copper foil, the support corresponds to the substrate 11 and the copper foil can constitute a part of the through wiring 19 .

The organic insulating layer 21 (first organic insulating layer) includes a third organic insulating layer 23 located on the substrate 11 side and a fourth organic insulating layer 24 located on the second organic insulating layer 22 side. I'm in. The first organic insulating layer 21 has a plurality of grooves 21a (first grooves) in which the corresponding copper wirings 13 are arranged. The fourth organic insulating layer 24 is provided with a plurality of openings corresponding to the grooves 21a. The surface of the third organic insulating layer 23 exposed through these openings constitutes the bottom surface of the inner surface of the groove 21a. The side surface of the groove portion 21a is composed of the fourth organic insulating layer 24. As shown in FIG.

The thicknesses of the third organic insulating layer 23 and the fourth organic insulating layer 24 may be, for example, 0.5 μm to 10 μm, respectively. The thickness of the first organic insulating layer 21 may be, for example, 1 μm to 20 μm.

A plurality of grooves 21 a are provided on the surface of the first organic insulating layer 21 opposite to the substrate 11 . Each of the grooves 21a has a substantially rectangular shape in a cross section along a direction perpendicular to the extending direction of the grooves 21a. The inner surface of the groove portion 21a has a side surface and a bottom surface. The plurality of grooves 21a have a predetermined line width L and space width S. As shown in FIG. Line width L and space width S may each independently be, for example, 0.5 μm to 10 μm. The line width L corresponds to the width of the groove portion 21a in the direction orthogonal to the extending direction of the groove portion 21a in plan view. The space width S corresponds to the distance between adjacent grooves 21a. The depth of the groove 21a corresponds to the thickness of the fourth organic insulating layer 24, for example.

The organic insulating layer 22 (second organic insulating layer) is laminated on the first organic insulating layer 21 with the wiring interlayer insulating layer 17 (first wiring interlayer insulating layer) interposed therebetween. The second organic insulating layer 22 has a plurality of grooves 22a (second grooves) in which the corresponding copper wirings 14 are arranged.

The thickness of the second organic insulating layer 22 may be, for example, 1 μm to 10 μm. A portion of the second organic insulating layer 22 is provided with a plurality of openings corresponding to the grooves 22a. The surface of the first wiring interlayer insulating layer 17 exposed through these openings constitutes the bottom surface of the inner surface of the trench 22a. Each side surface of the groove portion 22 a is configured by the second organic insulating layer 22 . The line width and space width of the plurality of grooves 22a match the line width L and space width S of the groove 21a.

The copper wiring 13 is provided in the corresponding groove portion 21a as described above and functions as a conductive path inside the wiring layer laminate 10 . The width of the copper wiring 13 substantially matches the line width L of the groove 21a, and the interval between adjacent copper wirings 13 substantially matches the space width S of the groove 21a. The copper wiring 14 is provided in the corresponding groove portion 22a as described above and functions as a conductive path inside the wiring layer laminate 10 . Therefore, the width of the copper wiring 13 substantially matches the line width of the groove 22a, and the interval between adjacent copper wirings 14 substantially matches the space width of the groove 22a. Copper wiring 14 contains the same metal material as copper wiring 13 .

The barrier metal film 15 (first barrier metal film) is a metal film provided so as to partition the copper wiring 13 and the first organic insulating layer 21 (that is, the inner surface of the trench 21a). The first barrier metal film 15 is a film for preventing diffusion of copper from the copper wiring 13 to the first organic insulating layer 21, and is formed along the inner surface of the trench 21a. Therefore, the first barrier metal film 15 contains a metal material (eg, titanium, chromium, tungsten, palladium, nickel, gold, tantalum, or an alloy containing these) that is difficult to diffuse into the organic insulating layer.

The thickness of the first barrier metal film 15 is less than half the width of the trench 21a and less than the depth of the trench 21a. The thickness of the first barrier metal film 15 may be, for example, 0.001 μm to 0.5 μm from the viewpoint of preventing conduction between the copper wirings 13 and suppressing an increase in resistance of the copper wirings 13 .

The second barrier metal film 16 is a metal film provided so as to partition the copper wiring 14 and the second organic insulating layer 22 (that is, the inner surface of the trench 22a). The second barrier metal film 16 is a film for preventing diffusion of copper from the copper wiring 14 to the second organic insulating layer 22, and is formed along the inner surface of the trench 22a. Therefore, like the first barrier metal film 15, the second barrier metal film 16 contains a metal material that is difficult to diffuse into the organic insulating layer. Similarly to the first barrier metal film 15, the thickness of the second barrier metal film 16 is less than half the width of the groove 22a and less than the depth of the groove 22a. It's okay.

The first wiring interlayer insulation layer 17 is an insulation film for preventing diffusion of copper from the copper wiring 13 to the first organic insulation layer 21 and the second organic insulation layer 22 . The first wiring interlayer insulation layer 17 partitions the copper wiring 13 and the second organic insulation layer 22 between the wiring layer 41 (first wiring layer) and the wiring layer 42 (second wiring layer). is provided as follows. The first wiring interlayer insulating layer 17 is in contact with the surface of the copper wiring 13 exposed on the main surface of the first wiring layer 41 opposite to the substrate 11 . From the viewpoint of making the wiring layer laminate 10 thin, the thickness of the first wiring interlayer insulating layer 17 may be, for example, 50 μm or less.

The second wiring interlayer insulation layer 18 is an insulation film for preventing diffusion of copper from the copper wiring 14 to the second organic insulation layer 22 . The second wiring interlayer insulating layer 18 is provided on the second wiring layer 42 while being in contact with the surface of the copper wiring 14 exposed on the main surface of the second wiring layer 42 opposite to the substrate 11 . . The second wiring interlayer insulating layer 18 contains the same material as the first wiring interlayer insulating layer 17 and has the same characteristics as the first wiring interlayer insulating layer 17 .

The through wiring 19 is a wiring embedded in the via 31 penetrating the wiring layers 41 and 42 and the inter-wiring insulating layers 17 and 18, and functions as a connection terminal to an external device.

The copper wiring in the semiconductor package may be formed by the trench method as described above, or may be formed by SAP (Semi Additive Process) in another embodiment. In any case, the composition described above is suitably used for forming an inter-wiring insulating layer.

The present invention will be described in more detail by the following examples, but the invention is not limited to these examples.

（Ａ－２）：下記式で表されるマレイミド化合物の混合物（大和化成工業株式会社製、商品名：ＢＭＩ－ＴＭＨ）

（ａ－１）：アクリル系エラストマ（日立化成株式会社製、商品名：ＫＨ－ＣＴ－８６５） The following components were used in Examples and Comparative Examples.
(A-1): Maleimide compound represented by the following formula (mixture of n = 1 to 10, weight average molecular weight: about 15000 to 20000, manufactured by Hitachi Chemical Co., Ltd., trade name: SFR2300)

(A-2): A mixture of maleimide compounds represented by the following formula (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-TMH)

(a-1): Acrylic elastomer (manufactured by Hitachi Chemical Co., Ltd., trade name: KH-CT-865)

（Ｂ－２）：下記式（３－２）で表されるナジイミド化合物（丸善石油化学株式会社製、商品名：ＢＡＮＩ－Ｍ）

（ｂ－１）液状エポキシ樹脂(ｊＥＲ８１１、三菱ケミカル株式会社製)とした場合の比較例を追記いたしました。 (B-1): a nadimide compound represented by the following formula (3-1) (manufactured by Maruzen Petrochemical Co., Ltd., trade name: BANI-X)

(B-2): a nadimide compound represented by the following formula (3-2) (manufactured by Maruzen Petrochemical Co., Ltd., trade name: BANI-M)

(b-1) Added a comparative example when using a liquid epoxy resin (jER811, manufactured by Mitsubishi Chemical Corporation).

(C): Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DCP)
(D): Photoradical polymerization initiator (manufactured by BASF, trade name: IrgacureOXE02)
(E): Silane coupling agent having an epoxy group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-12-984S)

<Evaluation of dielectric properties>
A varnish was prepared by mixing each of the above components at the compounding ratio shown in Tables 1 to 3. The produced varnish was spin-coated on a peelable copper foil under the following conditions, and then dried, exposed and baked after exposure to form a resin film. By stacking this multiple times, a resin film having a thickness of about 30 to 100 μm was obtained. After that, it was cured at 220° C. for 2 hours. Subsequently, the copper foil was peeled off, and the copper foil was dissolved and removed with ammonium persulfate to obtain a sample for evaluation.
The conditions for spin coating, drying, exposure, and post-exposure baking were as follows.
- Spin coat conditions Step. 1: 1000 rpm/5 seconds Step. 2: 2000 rpm/30 seconds SLOPE: 5 seconds Drying conditions: 90° C. for 3 minutes Exposure conditions: Exposure amount: 1000 mJ/cm ²
Broadband exposure/post-exposure bake (PEB)
100°C, 1 minute

Dielectric properties (dielectric constant Dk and dielectric loss tangent Df) were measured by the SPDR method using an evaluation sample cut into a predetermined size. An SPDR dielectric resonator manufactured by Agilent Technologies was used as the SPDR, a vector network analyzer E8364B manufactured by Agilent Technologies was used as the measuring instrument, and CPMA-V2 was used as the measurement program. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C.

<Evaluation of insulation reliability (b-HAST resistance)>
The above varnish was applied by spin coating onto the comb-like wiring produced using SAP, followed by drying, exposure, and PEB to produce a sample for evaluation. The conditions for spin coating, drying, exposure, and post-exposure baking were the same as those for the dielectric property evaluation sample. Under conditions of humidity of 85% and 130° C., the comb-shaped wiring was left standing while a voltage of 3.3 V was applied to the fabricated comb-like wiring. The resistance value between the anode and the cathode was measured at scheduled intervals, and the resistance value was 1×10 ⁶ Ω or more for 300 hours or longer. ), and those that did not were evaluated as "B" (no insulation reliability (b-HAST resistance)).

<Measurement of glass transition temperature>
An evaluation sample prepared in the same manner as the dielectric property evaluation sample was cut into a size of 8 mm×3 cm. For this sample, a DMA (dynamic viscoelasticity measurement) device (manufactured by UBM Co., Ltd., product name: Rheogel-E4000) was used, the distance between chucks was 20 mm, the frequency was 10 Hz, the temperature increase rate was 10 ° C./min, and the temperature range was -30. The temperature at which tan δ showed the maximum value measured by the tensile method under conditions of up to 300° C. was recorded as the glass transition temperature (° C.).

<Measurement of coefficient of linear expansion>
An evaluation sample prepared in the same manner as the dielectric property evaluation sample was cut into a size of 4 mm × 3 cm, and a TMA (thermo-mechanical analysis) apparatus (manufactured by Seiko Instruments Inc., trade name: TMA/SS6000) was used. , a linear expansion coefficient α1 (10 ^-6 /K) at 50 ° C. to 70 ° C. and a linear expansion coefficient α2 (10 ^-6 /K) at 200 ° C. to 220 ° C. by a tensile method under a load of 10 mN and the following temperature conditions. was measured.
・Temperature condition 30°C → 200°C (heating rate 10°C/min)
200°C→30°C (temperature drop rate 20°C/min)
30°C → 260°C (heating rate 5°C/min)
260°C→30°C (temperature drop rate 20°C/min)

<Spatter resistance>
A silicon wafer (diameter of 6 inches, thickness of 400 μm) was coated with the above varnish by spin coating and dried by heating at 90° C. for 3 minutes to form a resin film on the silicon wafer. Exposure was performed at 1000 mJ/cm ² using a high-precision parallel exposure machine (trade name: EXM-1172-B-∞ manufactured by ORC Manufacturing Co., Ltd.). Furthermore, after additional heating was performed under the conditions of 100° C./1 minute, the sample was obtained by further heating at 220° C./2 hours.
On the resin film of the obtained sample, a titanium film of 50 nm was formed by sputtering, and then a copper film of 150 nm was formed by sputtering. After cooling, the sample was taken out and the presence or absence of cracks or wrinkles in the sputtered film was observed under a microscope. A film in which cracks or wrinkles were not observed in the sputtered film was evaluated as "A" (with sputter resistance), and a film in which cracks or wrinkles were observed was evaluated as "B" (no sputtering resistance).

<Measurement of moisture absorption rate>
A wafer (diameter of 6 inches, thickness of 400 μm) was coated with the above varnish using a spin coater and dried at 90° C. for 3 minutes to form a resin layer. Samples were prepared by exposure at 1000 mJ/cm ² and curing followed by heating at 220° C./2 hours. This sample was allowed to stand for 200 hours in a constant temperature/humidity chamber (manufactured by Espec Co., Ltd., trade name: EHS-221MD) set at 85% relative humidity and 130°C. Then, after the temperature inside the constant temperature and humidity chamber was lowered to 50° C., the sample was taken out, and part of the resin was scraped off from the silicon wafer. A part of the scraped resin was measured using a simultaneous differential thermogravimetric measurement device (manufactured by Hitachi High-Tech Science Co., Ltd., product name: TG/DTA6300), temperature increase rate: 10 ° C. / min, nitrogen flow: 400 mL / min, Temperature range: Measured under conditions of 25°C to 150°C. On the other hand, a similarly prepared sample was dried at 130° C. for 2 hours, and TG-DTA was measured by the same method. The difference in weight loss rate at 150°C was calculated as the moisture absorption rate.

<Measurement of elongation>
The above varnish was spin-coated on the peelable core and dried. The next exposure was performed through a mask having a length of 30 mm and a width of 5 mm. The resulting sample was developed and then cured at 220°C for 2 hours. Thereafter, a resin film was obtained by etching the copper foil portion in the same manner as described above. The obtained sample was measured for elongation at break with a small desktop tester (manufactured by Shimadzu Corporation, trade name: EZ-S) at a feed rate of 5 mm/min. Since the resin film produced by this method had smooth edges, a higher elongation rate was obtained than a sample cut out using a knife such as a cutter.

<Evaluation of Formability of Fine Wiring>
A varnish was applied to a silicon wafer (diameter of 6 inches, thickness of 400 μm) by spin coating, and dried by heating at 90° C./3 minutes to form a resin film on the silicon wafer. At that time, the spin coating conditions were adjusted so that the film thickness of the resin after drying was 5 μm. Next, Line/Space (L/S (μm/μm)) is 200/200, 100/100, 80/80, 60/60, 50/50, 40/40, 30/30, 20/20, 10 /10, 7/7, 5/5, 4/4, 3/3 and via diameters of 50, 40, 30, 20, 10, 7, 5, 4, 3 μm. Exposure was performed at 1000 mJ/cm ² using a high-precision parallel exposure machine (trade name: EXM-1172-B-∞ manufactured by ORC Manufacturing Co., Ltd.). Furthermore, additional heating was performed under the conditions of 100° C./1 minute to obtain a sample. The resulting sample was immersed in cyclopentanone at room temperature (25° C.) for 60 seconds with shaking, then rinsed with cyclopentanone and then immersed in isopropyl alcohol at room temperature (25° C.) for 5 seconds. After that, the isopropyl alcohol was volatilized by blowing compressed air or the like.
The formation of fine wiring was checked with a metallurgical microscope for the presence or absence of peeling of the resin film from the wafer, cracking of the resin film, roughness at the pattern edge, and residue at the bottom of the pattern after the resin was developed. The minimum L/S and via diameter at which these defects could not be confirmed were regarded as microfabrication.

Tables 1 to 3 show the evaluation results of each characteristic described above.

DESCRIPTION OF SYMBOLS 1... Substrate, 2A-2D... Semiconductor chip, 3A, 3B... Underfill, 4... Insulating material, 10... Wiring layer laminate, 11... Substrate, 13... Copper wiring, 14... Copper wiring, 15, 16... Barrier metal Film 17, 18 Inter-wiring insulating layer 21 Organic insulating layer 21a Groove 22 Organic insulating layer 22a Groove 100 Semiconductor package L Line width S Space width.

Claims (6)

A curable composition containing a maleimide compound and a nadimide compound having a group represented by the following formula (1).

[In formula (1), R ¹¹ represents an allyl group, and m represents 0 or 1. ] The curable composition according to claim 1, wherein the nadimide compound is a compound represented by the following formula (2).

[In Formula (2), R ¹¹ and m are each independently synonymous with R ¹¹ and m in Formula (1), and R ¹² represents a divalent organic group. ] The curable composition according to claim 2, wherein the nadimide compound is a compound represented by the following formula (3).

[In Formula (3), R ¹² has the same definition as R ¹² in Formula (2). ] 4. The curable composition according to claim 2 or 3, wherein said divalent organic group has an aromatic hydrocarbon group. A curable composition according to any one of claims 2 to 4, wherein said divalent organic group is a divalent hydrocarbon group. The curable composition according to any one of claims 1 to 5, which is used for forming an insulating layer between wiring layers in a semiconductor package.

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