TW202334294A - Film-like underfill material, resin composition for film-like underfill material, method for preparing semiconductor chip with resin composition layer using film-like underfill material, method for preparing mounting board for semiconductor chip with resin composition layer, and method of manufacturing semiconductor device - Google Patents

Abstract

An object of the invention is to provide a film-like underfill material that contains: a resin composition layer containing a thermosetting resin (A) and a visible light absorber (B), and a backing film, wherein the light transmittance of the film-like underfill material at a wavelength of 600 nm is within a range from 20 to 90%, and the difference between the light transmittance of the backing film at a wavelength of 600 nm and the light transmittance of the film-like underfill material at a wavelength of 600 nm is within a range from 2 to 80%.

Description

Film-like underfill material, resin composition for film-like underfill material, and method for manufacturing semiconductor wafer provided with resin composition layer using film-like underfill material, for mounting semiconductor wafer provided with resin composition layer Method for manufacturing substrate and method for manufacturing semiconductor device

The present invention relates to an underfill material and a resin composition. Specifically, it relates to a semiconductor wafer provided with a resin composition layer, a semiconductor wafer mounting substrate provided with a resin composition layer, and a film-like bottom that can be used in a semiconductor device. Filling materials, resin compositions for film-like underfill materials, methods for manufacturing semiconductor wafers provided with resin composition layers using film-like underfill materials, and production of semiconductor wafer mounting substrates provided with resin composition layers Methods, and methods of manufacturing semiconductor devices.

Conventionally, as semiconductor devices have been miniaturized and improved in performance, flip-chip mounting has been used as a method of mounting a semiconductor wafer (hereinafter sometimes abbreviated as "wafer") on a semiconductor wafer mounting substrate (hereinafter sometimes abbreviated as "substrate"). method has attracted attention. In flip-chip mounting, generally speaking, after the chip and the substrate are bonded, an underfill material is filled in the gap between the chip and the substrate and hardened. In addition, there is also a method in which the wafer or the substrate is filled with an underfill material (also called a pre-coated underfill material), and then the wafer, the underfill material, and the substrate are bonded.

In recent years, as for underfill materials, the demand for film-like underfill materials has been gradually increasing, such as for use as precoated underfill materials. Examples of such film-like underfill materials include underfill materials whose main resin contains radically polymerizable monomers, resins that are transparent and undergo cross-linking reactions, compounds with flux activity, inorganic fillers, etc. technologies such as thin films for semiconductors (see, for example, Patent Documents 1 and 2 below). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2015-503220 [Patent Document 2] Japanese Patent Application Publication No. 2009-239128

[Problem to be solved by the invention]

Semiconductor wafers and the like are provided with alignment marks, also called alignment marks, on their surfaces. The marks are recognized and positioned using cameras and the like, and the semiconductor wafers and the like are mounted on substrates and the like. The visibility of such calibration marks is also affected by the production yield of semiconductor wafers provided with the resin composition layer, etc. Therefore, in recent years, studies have been conducted to improve the visibility of calibration marks, such as the invention described in Patent Document 2. technology.

On the other hand, in order to improve the visibility of the calibration mark, it is considered to increase the light transmittance of the resin composition layer. However, as a result of increasing the light transmittance of the resin composition layer, the light transmittance of the resin composition becomes too high, and the light transmittance of the resin composition layer is different from the light transmittance of the base film used for the underfill material. If the difference in transmittance becomes small, it will be difficult to visually determine whether the resin composition layer exists on the front or back of the base film, and the operability of NCF and the work efficiency of NCF placement will be significantly reduced. In summary, there is a demand for the development of a film-like underfill material that has excellent operability and can easily and accurately mount a semiconductor wafer provided with a resin composition layer.

In order to solve the above-mentioned problems, the object of the present invention is to provide a film-like underfill material that can easily and accurately mount an object on which a resin composition layer is laminated, and a film-like underfill material used in the production of the film-like underfill material. A resin composition, a method of manufacturing a semiconductor wafer provided with a resin composition layer using a film-like underfill material, a method of manufacturing a semiconductor wafer mounting substrate provided with a resin composition layer, and a method of manufacturing a semiconductor device. [Means to solve the problem]

The present inventors conducted in-depth research in order to solve the above-mentioned problems of the conventional technology. As a result, they found that a specific resin composition can solve the above-mentioned problems, and finally completed the present invention.

That is, the present invention includes the following contents. <1> A film-like underfill material, containing: a resin composition layer containing a thermosetting resin (A) and a visible light absorber (B), and a base film; the film-like underfill material transmits light at a wavelength of 600 nm The ratio is 20 to 90%, and the difference between the light transmittance of the base film at a wavelength of 600 nm and the light transmittance of the film-like underfill material at a wavelength of 600 nm is 2 to 80%. <2> The film-like underfill material according to the above <1>, wherein the thickness of the resin composition layer is in the range of 5 to 500 μm. <3> The film-like underfill material according to the above <1> or the above <2>, wherein the visible light absorber (B) is at least one selected from the group consisting of organic dyes, organic pigments, and combinations thereof. 1 species. <4> The film-like underfill material according to any one of the above <1> to the above <3>, wherein the visible light absorber (B) contains a quinone-based, aminoketone-based, cationic-based, Cyanine series, phthalocyanine series, quinacridone series, diaryl/triarylmethane series, fulgide, azo series, squarylium series, oxonol series, sub-series At least one compound selected from the group consisting of benzyl, nitro, nitroso, thiazole, indigoid, and combinations thereof. <5> The film-like underfill material according to any one of the above <1> to the above <4>, wherein the visible light absorber (B) contains a quinone series, an aminoketone series, and a combination thereof. At least one compound from the group of combinations. <6> The film-like underfill material according to any one of the above <1> to the above <5>, wherein the thermosetting resin (A) contains a maleimide compound, citracinol At least one kind from the group consisting of imine compounds and combinations thereof. <7> The film-like underfill material according to the above <6>, wherein the maleimide compound contains a 2,2'-bis{4-(4-maleiminophenoxy group) )phenyl}propane, 1,2-bis(maleimino)ethane, 1,4-bis(maleimino)butane, 1,6-bis(maleimino) )Hexane, N,N'-1,3-phenylenedismaleimide, N,N'-1,4-phenylenedismaleimide, N-phenylmaleimide Amine, a maleimide compound represented by the following formula (3), a bismaleimine compound containing a structural unit represented by the following formula (4) and a maleimide group at both ends, the following formula (5 ), at least one of the group consisting of a maleimine compound represented by the following formula (6), a maleimine compound represented by the following formula (7), and a combination thereof . [Chemical 1] In formula (3), n3 represents an integer from 1 to 30. [Chemicalization 2] In formula (4), R ¹¹ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ¹² represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ¹³ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. n ⁵ represents an integer from 1 to 10. [Chemical 3] In formula (5), R ₈ each independently represents a hydrogen atom, a methyl group, or an ethyl group. R ₉ each independently represents a hydrogen atom or a methyl group. [Chemical 4] In formula (6), R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. n4 represents an integer from 1 to 10. [Chemistry 5] In formula (7), R ¹⁰ each independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more. <8> The film-like underfill material according to the above <7>, wherein the maleimide compound contains a group selected from the group consisting of 2,2'-bis{4-(4-maleiminophenoxy) ) phenyl}propane, the maleimide compound represented by the aforementioned formula (3), the bismaleimide compound containing the structural unit represented by the aforementioned formula (4) and maleimide groups at both ends, In the group of the maleimine compound represented by the aforementioned formula (5), the maleimide compound represented by the aforementioned formula (6), the maleimine compound represented by the aforementioned formula (7), and combinations thereof At least 1 of them. <9> The film-like underfill material according to any one of the above <1> to the above <8>, further containing an inorganic filler (C). <10> The film-like underfill material according to the above <9>, wherein the average particle diameter of the inorganic filler (C) is 400 nm or less. <11> The film-like underfill material according to the above <9> or the above <10>, wherein the inorganic filler (C) contains silicon dioxide, aluminum hydroxide, alumina, and boehmite. ), at least one of the group consisting of boron nitride, aluminum nitride, magnesium oxide, magnesium hydroxide, and combinations thereof. <12> The film-like underfill material according to any one of the above <9> to the above <11>, wherein the content of the above-mentioned inorganic filler (C) is relative to the total amount of the above-mentioned thermosetting resin (A). The amount is 100 parts by mass, which is 10 to 500 parts by mass. <13> The film-like underfill material according to the above <9>, wherein the average particle diameter of the inorganic filler (C) is 400 nm or less, and the inorganic filler (C) contains a compound selected from the group consisting of silica, hydroxide and At least one of the group consisting of aluminum, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, magnesium hydroxide, and combinations thereof, the content of the aforementioned inorganic filler (C) relative to the aforementioned heat The total amount of the curable resin (A) is 10 to 500 parts by mass per 100 parts by mass. <14> The film-like underfill material according to any one of the above <1> to the above <13>, further containing a flux activator (D). <15> The film-like underfill material according to the above <14>, wherein the flux activator (D) contains a rosin-based resin. <16> The film-like underfill material according to any one of the above <1> to the above <15>, further containing a curing catalyst (E). <17> The film-like underfill material according to the above <16>, wherein the curing catalyst (E) contains at least one selected from the group consisting of organic peroxides, imidazole compounds, and combinations thereof. <18> The film-like underfill material according to any one of the above <1> to the above <17>, further containing a hardener (F). <19> The film-like underfill material according to the above <18>, wherein the hardener (F) contains an amino tris-novolak resin. <20> A resin composition for film-like underfill materials, containing: a thermosetting resin (A), and a visible light absorber (B). <21> A method of manufacturing a semiconductor wafer provided with a resin composition layer, using the film-like underfill material described in any one of the above <1> to the above <19>. <22> A method of manufacturing a semiconductor wafer mounting substrate provided with a resin composition layer, using the film-like underfill material described in any one of the above <1> to the above <19>. <23> A method of manufacturing a semiconductor device using the film-like underfill material described in any one of the above <1> to the above <19>. [Effects of the invention]

According to the present invention, it is possible to provide a film-like underfill material that is excellent in workability and can easily and accurately mount an object on which a resin composition layer is laminated, and a film-like underfill material used in the production of the film-like underfill material. A resin composition, a method of manufacturing a semiconductor wafer provided with a resin composition layer using a film-like underfill material, a method of manufacturing a semiconductor wafer mounting substrate provided with a resin composition layer, and a method of manufacturing a semiconductor device.

Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described. In addition, the following embodiment is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment.

In addition, in this embodiment, "(meth)acryloxy" means both "acryloxy" and its corresponding "methacryloxy", and "(meth)acrylonitrile" means both "acrylonitrile" and its corresponding "methacrylonitrile", "(meth)acrylic acid" means both "acrylic acid" and its corresponding "methacrylic acid", "(meth)acrylic acid" "(Meth)acrylate" means both "acrylate" and its corresponding "methacrylate", "(meth)allyl" means "allyl" and its corresponding "methyl Allyl" both. In addition, unless otherwise specified, "~" in this specification means that the values at both ends are included as the upper limit and the lower limit, and the upper limit and the lower limit are set in the same unit.

"Film-like underfill material" The film-like underfill material of this embodiment (hereinafter sometimes referred to as "underfill material") is a film containing a resin composition layer containing a thermosetting resin (A) and a visible light absorber (B), and a base film -like underfill material, wherein the light transmittance of the aforementioned film-like underfill material at a wavelength of 600 nm is 20 to 90%, and the light transmittance of the aforementioned base film at a wavelength of 600 nm is consistent with the light transmittance of the aforementioned film-like underfill material at a wavelength of 600 nm. The difference in light transmittance is 2~80%.

In this embodiment, the "film-like underfill material" refers to a laminate including a base film and a resin composition layer, which is laminated on a semiconductor wafer (hereinafter sometimes abbreviated as "wafer") After waiting for the object, the base film is peeled off from the resin composition layer, and the "resin composition layer" is filled with a so-called underfill material between the chip and the substrate. In addition, the resin composition layer is a non-conductive film, also called Non Conductive Film (NCF). In addition, the resin composition layer in this embodiment can be produced using a resin composition for film-like underfill materials (hereinafter sometimes simply referred to as "resin composition") of this embodiment which will be described later.

The underfill material of this embodiment has a base film and a resin composition layer provided on the base film. For example, the resin composition layer may be one in which a resin composition in an uncured state (A-stage) is applied to a base film and then converted into a semi-cured state (B-stage). In addition, in this embodiment, the uncured state (A stage) refers to the state in which the resin composition is hardly cured and has not gelled. The resin composition before coating on the base film is, for example, a mixture of the constituent components of the resin composition (which may or may not contain a solvent), or a varnish obtained by dissolving or dispersing the mixture in a solvent, and is unhardened. Status (A-level). In addition, the semi-hardened state (B stage) means that the components contained in the resin composition layer have not yet actively started to react (harden), but the resin composition layer is in a dry state, that is, the solvent is evaporated by heating to the point where it is non-adhesive. The state to this extent also includes a state in which the solvent is simply volatilized without heating and hardening.

(light transmittance) Since the underfill material of this embodiment has a light transmittance of 600 nm in wavelength (hereinafter sometimes referred to as "light transmittance of the underfill material") of 20 to 90%, the film-like underfill material The light transmittance of the resin composition layer at a wavelength of 600nm can also be set in the range of 20 to 90%. Therefore, using a camera or the like, when placed on a semiconductor wafer, the calibration mark provided on the surface of the wafer or the like can be accurately and quickly recognized through the resin composition layer. Thereby, when the semiconductor chip provided with the resin composition layer is mounted on a substrate or the like, it can be easily and accurately placed on an object. In addition, during the manufacturing process of the underfill material, foreign matter may sometimes be mixed between the base film and the resin composition layer or within the resin composition. The presence of such foreign matter may also affect the performance of the underfill material such as film-forming properties and insulation reliability of the resin composition layer. Therefore, in order to ensure the performance of the underfill material, foreign matter inspection using a defect inspection machine or the like is often performed after the underfill material is produced. On the other hand, the foreign matter inspection is preferably carried out directly in the state of the underfill material, that is, in the state of the laminate of the base film and the resin composition layer. In addition, the foreign matter inspection performed by the inspection machine usually requires a certain degree of transmittance for the underfill material. The light transmittance of the underfill material of this embodiment falls within the range of 20 to 90%, so the above foreign matter inspection can be performed.

The light transmittance of the underfill material in this embodiment is preferably 40 to 90%, more preferably 50 to 90%, from the viewpoint of being compatible with a camera with a small light intensity and further improving the accuracy of the foreign matter inspection.

In the underfill material of this embodiment, the light transmittance of the base film at a wavelength of 600 nm (hereinafter sometimes referred to as the "light transmittance of the base film") is not particularly limited, but it is considered to further improve the accuracy of the foreign matter inspection. From the perspective of perspective, it should be 20~90%, and 40~90% is better. Also not particularly limited, the light transmittance of the resin composition layer (NCF) at a wavelength of 600 nm (hereinafter sometimes referred to as "the light transmittance of the resin composition layer") is considered to be compatible with a camera with a small amount of light, and further improves the above-mentioned foreign matter inspection. From the perspective of accuracy, it should be 20~90%, and 40~90% is better.

The light transmittance of the underfill material, the base film, and the resin composition layer can be measured, for example, by the method described in the Examples described below. Specifically, a spectrophotometer can be used, and the value measured at room temperature (25°C) is adopted. again. The light transmittance of each underfill material, base film, and NCF can be determined by, for example, making a sample of 5 cm in width x 5 cm in length, and measuring the average value of any point on the sample (such as the average of 5 points, etc.). In addition, since the underfill material of this embodiment is based on the light transmittance at each wavelength of 600 nm, it can be widely used in various calibration mark recognition devices such as cameras that are easy to obtain and have high versatility.

(The difference between the light transmittance of the base film and the light transmittance of the underfill material) In the underfill material of this embodiment, the resin composition layer contains a visible light absorber (B), and the difference between the light transmittance of the base film at a wavelength of 600 nm and the light transmittance of the underfill material at a wavelength of 600 nm is 2 to 80 %. In this way, when there is a difference between the light transmittance of the base film at a wavelength of 600 nm and the light transmittance of the underfill material at a wavelength of 600 nm, there will be a difference in the light transmittance of the base film and the resin composition layer, which can be identified with the naked eye. The base film surface and the resin composition layer of the film can be easily identified, which means the visibility is excellent. This eliminates the need for time-consuming identification of the base film surface and the resin composition layer, improves the operability of the underfill material, and can be easily placed on a target wafer or the like. In this embodiment, the difference between the light transmittance of the base film and the light transmittance of the underfill material is preferably 5 to 80%, and particularly preferably 10 to 80%, from the viewpoint of better visibility.

The difference between the light transmittance of the base film at a wavelength of 600nm [T ¹ ] and the underfill material at a wavelength of 600nm [T ⁰ ] is |T ¹ -T ⁰ |, and the absolute value of their difference is used as the basis. Make judgments.

In addition, in this embodiment, the laminated structure of the underfill material is not particularly limited as long as the light transmittance of the underfill material and the difference between the light transmittance and the light transmittance of the base film satisfy the above-mentioned relationship. For example, it may also be There is an intermediate layer between the base film and the resin composition layer. Examples of the intermediate layer include a release layer provided on a base film and the like. For example, when the base film is a film with a release layer, after the base film is peeled off, the release layer will be peeled off together with the base film, so the overall transmittance of the "base film with a release layer" can be regarded as The above-mentioned "light transmittance of the base film".

〈Substrate film〉 The base film is not particularly limited, and a polymer film can be used. Examples of materials for the polymer film include: polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polyvinyl chloride, polyvinylidene chloride; , polyethylene, polypropylene, polybutylene, polybutadiene, ethylene-propylene copolymer, polymethylpentene, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer and other vinyl resins; poly Urethane resin; polyimide resin; polyamide resin, etc. As the base film, a film containing these resins and a release film in which a release agent is coated on the surface of these films can be used. Among them, films containing one or more resins selected from polyester resins, polyimide resins, and polyamide resins, or films whose surfaces are coated with a release agent are preferred. A release film is a film containing polyethylene terephthalate, which is a type of polyester resin, or a release film in which a release agent is coated on the surface of a film containing polyethylene terephthalate. Film is better.

The thickness of the base film is not particularly limited. From the perspective of achieving the above-mentioned light transmittance, it can be adjusted appropriately. However, the thickness of the base film can be adjusted appropriately to facilitate the production of the underfill material, such as the coating thickness when applying the resin composition to the base film. From the viewpoint of good stability and good transportability of the underfill material, 10~100μm is suitable. In addition, the lower limit of the thickness of the base film is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 25 μm or more, from the viewpoint of ensuring sufficient throughput when manufacturing the underfill material. The upper limit of the thickness of the base film is preferably 100 μm, considering the fact that the base film does not ultimately exist as a component of the semiconductor device and will be peeled off during the process, and the manufacturing cost of the underfill material. or below, preferably 80 μm or below, further preferably 50 μm or below.

<Resin composition layer> The resin composition layer contains a thermosetting resin (A) and a visible light absorber (B). The resin composition layer may also contain one selected from the group consisting of inorganic filler (C), flux activator (D), hardening catalyst (E), hardener (F), and combinations thereof as needed. above. In this embodiment, the resin composition layer can be formed using a resin composition for a film-like underfill material containing at least a thermosetting resin (A) and a visible light absorber (B). In addition, the resin composition for film-like underfill materials may also contain an inorganic filler (C), a flux activator (D), a curing catalyst (E), a hardener (F), and More than one type in the group composed of its combination.

The underfill material of this embodiment is suitable for use as a precoated underfill material. As mentioned above, the resin composition layer is preferably in a semi-hardened state (B-stage). In this embodiment, the minimum melt viscosity in the semi-hardened state (B stage) can usually be set to 50,000 Pa･s or less. Moreover, the lower limit of the minimum melt viscosity can be set to 10 Pa･s or more, for example.

In this embodiment, the minimum melt viscosity of the resin composition layer can be measured by the following method. That is, a laminator can be used to laminate the resin composition layers to obtain a resin sheet with a thickness of about 0.4 to 0.6 mm. This resin sheet can be used as a sample and a rheometer (HAAKEMARS60 (trade name) manufactured by Thermo Fisher Scientific) can be used. ) to determine the minimum melt viscosity. In this measurement, a disposable parallel plate with a plate diameter of 8 mm can be used to measure the resin in the range of 40°C to 300°C under the conditions of a heating rate of 10°C/minute, a frequency of 10.0rad/second, and a strain of 0.1%. The value after the lowest melt viscosity of the sheet is regarded as the lowest melt viscosity of the resin composition layer.

The method of forming the resin composition layer on the base film to produce the underfill material of this embodiment is not particularly limited. Examples of such a manufacturing method include: coating a varnish obtained by dissolving or dispersing a resin composition containing a thermosetting resin (A) and a visible light absorber (B) in an organic solvent on the surface of a base film, and heating and / Or a method of drying under reduced pressure, removing the solvent, solidifying the resin composition, and forming a resin composition layer. The drying conditions are not particularly limited. The content ratio of the organic solvent to the resin composition layer is usually 10 parts by mass or less, preferably 5 parts by mass or less, relative to the total mass of the resin composition layer (100 parts by mass). Allow to dry. The conditions for achieving this drying vary depending on the type and blending amount of the organic solvent in the varnish. For example, when a varnish containing 10 to 200 parts by mass of methyl ethyl ketone relative to 100 parts by mass of the total amount of thermosetting resin (A) is dried under 1 atmosphere under heating conditions of 90 to 160°C for 2 to 15 minutes, it is approximate standards.

The thickness of the resin composition layer in the underfill material of this embodiment is a transmittance that can achieve the light transmittance of the above-mentioned underfill material, etc., although it also depends on the content of the visible light absorber (B) described below. However, considering the viewpoint that the resin composition layer can more effectively remove volatile components of lower molecular weight during drying, and that the resin composition layer can more effectively and reliably perform its function as an underfill material, the range of 5 to 500 μm is preferably 5. The range of ~100μm is even better, and the range of 5~50μm is particularly good.

[Thermosetting resin (A)] The resin composition layer contains thermosetting resin (A). As long as the thermosetting resin (A) has a transmittance that can achieve the light transmittance of the underfill material and the like and is a thermosetting resin, a known one can be appropriately used. The type of thermosetting resin (A) is not particularly limited, and examples thereof include maleimide compounds, citraconidine compounds, epoxy resins, oxetane resins, phenolic resins, (methyl) Acrylate resins, unsaturated polyester resins, diallyl phthalate resins, etc., preferably include those selected from the group consisting of maleimide compounds, citraconitrile imine compounds, and combinations thereof At least 1 species. It is preferable that the thermosetting resin (A) does not exhibit reactivity with the flux activator (D) described below. Moreover, the thermosetting resin (A) can be used individually by 1 type or in mixture of 2 or more types.

The thermosetting resin (A) can be used in combination with a higher molecular weight compound (A1) and a lower molecular weight compound (A2). For example, if a compound (A1) with a relatively high molecular weight is used, the stress generated during hardening shrinkage during semiconductor chip mounting or thermal curing (post-curing) can be relaxed. Furthermore, for example, if a compound (A2) with a lower molecular weight is used, the crosslinking density can be improved during semiconductor wafer mounting or post-curing.

In addition, the thermosetting resin (A) may be used in combination with a maleimide compound (AA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less, and a maleimide compound (AA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less. Amine compound (AB-1), and at least one or more of the group of combinations thereof; and a maleimide compound (AA-2) with a weight average molecular weight of 300 or more and less than 3,000, and a maleimide compound (AA-2) selected by weight At least one of the group of citraconitrile imine compounds (AB-2) with an average molecular weight of 300 or more and less than 3,000 and/or their combinations. The compound (A1) preferably contains the maleimide compound (AA-1) from the viewpoint of obtaining further excellent low void properties and chip adhesion. In addition, the compound (A2) preferably contains the maleimide compound (AA-2) from the viewpoint of obtaining further excellent low void properties and wafer adhesion properties.

The weight average molecular weight of the maleimide compound (AA-1) is preferably 3,200 or more and 8,000 or less, and 3,300 or more and 6,000 or less, in order to obtain further excellent low voids and wafer adhesion. good. From the viewpoint of achieving further excellent low voids and wafer adhesion, the weight average molecular weight of the nicotinamide compound (AB-1) is preferably 3,200 or more and 8,000 or less, and 3,300 or more and 6,000 or less. good. The maleimide compound (AA-2) has a weight average molecular weight of 350 or more and 2,800 or less, and preferably 400 or more and 2,500 or less, in order to obtain further excellent low voids and wafer adhesion. good. From the viewpoint of achieving further excellent low voids and wafer adhesion, the weight average molecular weight of the citraconidine compound (AB-2) is preferably 350 or more and 2,800 or less, and 400 or more and 2,500 or less. good.

(maleimide compound) Compared with epoxy resins and the like, maleimide compounds are less likely to react significantly with the flux activator during storage or due to heat treatment, and the flux activator is less likely to be deactivated. The maleimide compound is not particularly limited as long as it is a resin or compound having one or more maleimide groups in the molecule. One type of maleimide compound may be used, or two or more types may be mixed and used. Examples of such maleimide compounds include: N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 4, 4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4- Maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenyl bismaleimide Amine, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis(4-(4-maleiminophenoxy)-phenyl)propane, 3,3 -Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6 -Bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsine bismaleimide Amine, 1,3-bis(3-maleiminophenoxy)benzene, 1,3-bis(4-maleiminophenoxy)benzene, polyphenylmethanemaleamide Amine, novolak resin type maleimide compound, biphenyl aralkyl type maleimide compound, 2,2-bis(4-(4-maleiminophenoxy)phenyl) Propane, 1,2-bis(maleimino)ethane, 1,4-bis(maleimino)butane, 1,6-bis(maleimino)hexane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-phenylmaleimide, the following formula (3) A maleimide compound represented by the following formula (4), a bismaleimine compound containing a maleimide group at both ends of the molecular chain and a structural unit represented by the following formula (4), the following formula (5) A maleimine compound represented by the following formula (6), a maleimine compound represented by the following formula (7), etc. The thermosetting resin (A) may be contained in the form of a prepolymer obtained by polymerizing a maleimide compound, a prepolymer obtained by polymerizing other compounds such as a maleimide compound and an amine compound, etc. In the resin composition of this embodiment.

The maleimide compound is not particularly limited. From the viewpoint of obtaining better solubility in organic solvents, it is preferable to include a maleimide compound selected from the group consisting of 2,2'-bis{4-(4-maleiminophenoxy). )phenyl}propane, 1,2-bis(maleimino)ethane, 1,4-bis(maleimino)butane, 1,6-bis(maleimino) )Hexane, N,N'-1,3-phenylenedismaleimide, N,N'-1,4-phenylenedismaleimide, N-phenylmaleimide Amine, a maleimide compound represented by the following formula (3), a bismaleimine compound containing a structural unit represented by the following formula (4) and a maleimide group at both ends, the following formula (5 ), at least one of the group consisting of a maleimine compound represented by the following formula (6), a maleimine compound represented by the following formula (7), and a combination thereof , containing a maleimide compound selected from 2,2'-bis{4-(4-maleimidophenoxy)phenyl}propane and represented by the following formula (3), containing the following formula (4 ) and a bismaleimine compound containing a maleimide group at both ends, a maleimine compound represented by the following formula (5), and a maleimide compound represented by the following formula (6) At least one kind from the group consisting of an amine compound, a maleimide compound represented by the following formula (7), and a combination thereof is more preferred.

[Chemical 6]

In formula (3), n3 represents an integer from 1 to 30.

[Chemical 7]

In formula (4), R ¹¹ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ¹² represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ¹³ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. n ⁵ represents an integer from 1 to 10. In addition, the detailed description of the structural unit represented by Formula (4) will be mentioned later.

[Chemical 8]

In formula (5), R ₈ each independently represents a hydrogen atom, a methyl group, or an ethyl group. R ₉ each independently represents a hydrogen atom or a methyl group.

[Chemical 9]

In formula (6), R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. n4 represents an integer from 1 to 10. R ¹⁰ is preferably a hydrogen atom.

[Chemical 10]

In the formula (7), R ¹⁰ each independently represents a hydrogen atom or a methyl group, and n 2 represents an integer of 1 or more, preferably an integer of 1 to 10.

Next, the structure of a bismaleimide compound containing a structural unit represented by formula (4) and maleimide groups at both ends of the molecular chain will be described.

The bismaleimide compound may have a plurality of structural units represented by formula (4). In this case, R ¹¹ , R ¹² , and R ¹³ in the plurality of structural units represented by formula (4) may be the same or each of them may be the same. Different. In addition, the bismaleimide compound may be R ¹¹ , R ¹² , and R ¹³ in the structural unit represented by the formula (4), and the bismaleimine compound may be a structural unit represented by the formula (4). At least one of the numerical values is a mixture of different compounds.

In the structural unit represented by formula (4) of the bismaleimide compound, R ¹¹ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkylene group having 2 to 16 carbon atoms. Like alkenyl. R ¹¹ Considering that the resin composition has an ideal viscosity during chip mounting and can ideally control the increase in melt viscosity during mounting, it is appropriate to use a straight-chain or branched alkylene group and a straight-chain alkylene group. The foundation is better.

The carbon number of the alkylene group is preferably 2 to 14, and more preferably 4 to 12, from the viewpoint that the resin composition has a more ideal viscosity during chip mounting and can more ideally control the increase in melt viscosity during mounting. . Examples of linear or branched alkylene groups include methylene, ethylene, propylene, 2,2-dimethylpropylene, butyl, pentyl, hexylene, and heptyl. Base, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Neopentyl, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptyl, dimethylheptyl, trimethylhexylene Heptyl, tetramethylheptyl, ethylheptyl, methyloctyl, methylnonyl, methyldecyl, methylundecyl, methyldodecyl, methyl Tridecyl, methyltetradecyl, and methylpentadecyl.

The carbon number of the alkylene group is preferably 2 to 14, and 4 to 12 is more preferred from the viewpoint that the resin composition has a more ideal viscosity during chip mounting and can more ideally control the increase in melt viscosity during mounting. . Examples of linear or branched alkenylene groups include: vinylene group, 1-methyl vinylene group, allylethylene group, propenylene group, isopropenyl group, 1-butenyl group, and 2-ethylene group. Butenyl, 1-pentenyl, 2-pentenyl, isopentenyl, cyclopentenyl, cyclohexenyl, and dicyclopentadienyl, etc.

In the structural unit represented by formula (4), R ¹² represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ¹² takes into consideration the fact that the resin composition has an ideal viscosity during chip mounting and can ideally control the increase in melt viscosity during mounting. It is preferable to use a straight-chain or branched alkylene group and a straight-chain alkylene group. The foundation is better.

The carbon number of the alkylene group is preferably 2 to 14, and more preferably 4 to 12, from the viewpoint that the resin composition has a more ideal viscosity during chip mounting and can more ideally control the increase in melt viscosity during mounting. . For the linear or branched alkylene group, refer to the aforementioned R ¹¹ .

The carbon number of the alkylene group is preferably 2 to 14, and 4 to 12 is more preferred from the viewpoint that the resin composition has a more ideal viscosity during chip mounting and can more ideally control the increase in melt viscosity during mounting. . For the linear or branched alkenylene group, refer to the aforementioned R ¹¹ .

In the structural unit represented by formula (4), R ¹¹ and R ¹² may be the same or different, but are preferably the same from the viewpoint that the bismaleimide compound can be synthesized more easily.

In the structural unit represented by formula (4), R ¹³ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched olefin having 2 to 16 carbon atoms. base. R ¹³ Considering that the resin composition has an ideal viscosity during chip mounting and can ideally control the increase in melt viscosity during mounting, it is appropriate to independently form a hydrogen atom or a linear or branched chain with carbon numbers from 1 to 16. -like alkyl group, among R ¹³ , 1 to 5 groups (R ¹³ ) are linear or branched alkyl groups with 1 to 16 carbon atoms, and the remaining groups (R ¹³ ) are preferably hydrogen atoms, Among R ¹³ , groups 1 to 3 (R ¹³ ) are linear or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R ¹³ ) are preferably hydrogen atoms.

The carbon number of the alkyl group is preferably 2 to 14, and more preferably 4 to 12, from the viewpoint that the resin composition has a more ideal viscosity during chip mounting and can more ideally control the increase in melt viscosity during mounting. Examples of linear or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tertiary butyl base, n-pentyl, 2-pentyl, tertiary pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl , n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl.

The carbon number of the alkenyl group is preferably 2 to 14, and more preferably 4 to 12, from the viewpoint that the resin composition has a more ideal viscosity during chip mounting and can more ideally control the increase in melt viscosity during mounting. Examples of linear or branched alkenyl groups include vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2- Nonenyl.

In the structural unit represented by formula (4), n ⁵ represents an integer from 1 to 10.

The bismaleimide compound has maleimide groups at both ends of the molecular chain. Both ends mean the ends on both sides of the molecular chain of the bismaleimine compound. For example, when the structural unit represented by formula (4) is located at the end of the molecular chain of the bismaleimine compound, it means R ¹¹ The terminal of the molecular chain has a maleimine group, or the terminal of the molecular chain of the N atom of the maleimine ring has a maleimine group, or the terminals of both sides have maleimine groups. . The bismaleimide compound may have a maleimide group other than both ends of the molecular chain. The maleimide group is represented by the following formula (8), and the N atom is bonded to the molecular chain of the bismaleimine compound. In addition, the maleimine groups bonded to the bismaleimine compound may all be the same or different, but the maleimine groups at both ends of the molecular chain are preferably the same.

[Chemical 11]

In formula (8), R ₁₁ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. From the viewpoint of more ideal reaction with the resin (A), R ₁₁ is preferably both hydrogen atoms. The number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of more ideal reaction with the resin (A). For linear or branched alkyl groups, refer to the aforementioned R ¹³ .

Examples of such bismaleimide compounds include maleimide compounds represented by the following formula (9). One of these compounds may be used alone, or two or more compounds having different repeating numbers of a in formula (9) may be appropriately mixed and used.

[Chemical 12]

In formula (9), a represents an integer from 1 to 10. a Considering that the resin composition has a more ideal viscosity during chip mounting and can more ideally control the increase in melt viscosity during mounting, an integer between 1 and 6 is appropriate. The maleimide compound represented by formula (9) may also be a mixture of different compounds.

The maleimide compound (AA-1) is preferably a maleimide compound represented by the aforementioned formula (3), and a maleimide compound represented by the aforementioned formula (3), from the viewpoint of obtaining further excellent low void properties and wafer adhesion properties. (4) The structural units shown and bismaleimide compounds containing maleimide groups at both ends of the molecular chain.

The maleimide compound (AA-2) is preferably a maleimide compound represented by the aforementioned formula (5), and the aforementioned formula ( 6) represents the maleimide compound.

Commercially available maleimide compounds can also be used. Examples of 2,2'-bis(4-(4-maleiminophenoxy)phenyl)propane include: K･I Chemical Co., Ltd. BMI-80 (trade name) made by the company. Examples of the maleimide compound represented by the formula (3) include: BMI-1000P (trade name) manufactured by K･I Chemical Co., Ltd., n3=14 (average value) in the formula (3), weight average molecular weight: 3,700 ), BMI-650P manufactured by K･I Chemical Co., Ltd. (trade name, n3=9 (average value) in formula (3)), BMI-250P manufactured by K･I Chemical Co., Ltd. (trade name, formula n3=3~8 (average value) in (3)), CUA-4 manufactured by K･I Chemical Co., Ltd. (trade name, n3=1 in formula (3)), etc. Examples of bismaleimide compounds containing a structural unit represented by formula (4) and maleimide groups at both ends of the molecular chain include: MIZ-001 (trade name, containing Maleimide compound represented by formula (9), weight average molecular weight: 3,900). Examples of the maleimide compound represented by formula (5) include: BMI-70 (trade name; bis-(3-ethyl-5-methyl-4-maleimide) manufactured by KI Chemical Co., Ltd. Aminophenyl)methane, molecular weight: 550). Examples of the maleimide compound represented by the formula (6) include: MIR-3000-70MT (trade name) manufactured by Nippon Kayaku Co., Ltd., ^R10 in the formula (6) are all hydrogen atoms, and are n4-based Mixture of 1 to 10, weight average molecular weight: 1,050). Examples of the maleimide compound represented by the formula (7) include BMI-2300 (trade name) manufactured by Daiwa Chemical Industry Co., Ltd.

(citraconimine compound) The citraconimine compound is not particularly limited, and examples thereof include: phthaloconimide, resorcinolimide, p-phenylinodimenide, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl -4-citraconyl iminophenyl)methane, bis(3-ethyl-5-methyl-4-citraconyl iminophenyl)methane, bis(3,5-diethyl-4 -citraconidinylphenyl)methane, 1,3-xylylenebis(citraconidinyl)methane, N-[3-bis(trimethylsilyl)amino-1-propyl]citron Considimine, N-[3-bis(triethylsilyl)amino-1-propyl]citraconidimine, N-[3-bis(triphenylsilyl)amino-1- Propyl]citraconimide, N,N'-(isoxylyldimide)dinitraconidimine, and N-[3-(methylenesuccinimidemethyl)benzylcitraconimide Citraconidimine compound, a citraconidimine compound represented by the following formula (10), a biscitraconidimine compound containing a structural unit represented by the aforementioned formula (4), and a citraconidimine compound having citraconidimine groups at both ends of the molecular chain , a citracenyl imine compound represented by the following formula (11), and a citracenyl imine compound represented by the following formula (12). In addition, the bismaleimide compound may refer to the aforementioned bismaleimide compound. Detailed description of the structure of formula (4) is as mentioned above. Regarding the citraconitrile imine group, it is in the aforementioned formula (8). At least one group in R ₁₁ is a methyl group. Otherwise, please refer to The structure of formula (8). One type of citraconidine compound may be used, or two or more types may be mixed and used.

Among the above-mentioned citraconidine compounds, it is preferable to contain citraconidine compounds represented by the following formula (10) from the viewpoint of obtaining better solubility in organic solvents and obtaining further excellent low void properties and wafer adhesion properties. A citraconimine compound, a biscitraconidimine compound containing a structural unit represented by the aforementioned formula (4) and a citraconidimine group at both ends of the molecular chain, and a citraconidimine compound represented by the following formula (11) An amine compound, and a citraconitrile imine compound represented by the following formula (12).

The citracaniline compound (AB-1) is preferably a citracaniline compound represented by the following formula (10) from the viewpoint of obtaining further excellent low voids and wafer adhesion properties, and a compound containing the aforementioned formula (4) The structural units shown and biscitraconide imine compounds containing citraconide imine groups at both ends of the molecular chain.

[Chemical 13]

In formula (10), n ⁶ represents an integer from 1 to 30.

The citracaniline compound (AB-2) is preferably a citracaniline compound represented by the following formula (11), and the following formula ( 12) represents the citraconitrile imine compound.

[Chemical 14]

In formula (11), R ₈ each independently represents a hydrogen atom, a methyl group, or an ethyl group. R ₉ each independently represents a hydrogen atom or a methyl group. [Chemical 15]

In the formula (12), R ¹⁰ each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 or more, preferably an integer of 1 to 10. R ¹⁰ is preferably a hydrogen atom.

The content (total amount) of the thermosetting resin (A) in the resin composition layer is not particularly limited. Considering the hardenability and manufacturability of the underfill material and the strength of the resin composition layer, the content (total amount) of the thermosetting resin (A) is determined based on the total amount of the resin components. 100 parts by mass is preferably at least 25 parts by mass, more preferably at least 40 parts by mass, and even more preferably at least 50 parts by mass. The upper limit of the content (total amount) of the thermosetting resin (A) is not particularly limited, but it is preferably 100 parts by mass or less, more preferably 95 parts by mass or less, and 90 parts by mass or less based on 100 parts by mass in total of the resin components. Even better. In addition, the "resin component" here refers to a thermosetting resin (A), a resin used as a hardener (F), and a flux activator (D) when these resins are used, and does not contain a visible light absorber. (B), the concept of hardening catalyst (E), etc.

When the thermosetting resin (A) contains the compound (A1) and the compound (A2), from the viewpoint of obtaining further excellent low void properties and die adhesion, the content of the compound (A1) is smaller than that of the compound (A1) and the compound (A2). The total 100 parts by mass of the compound (A2) is preferably 40 to 90 parts by mass, more preferably 42 to 85 parts by mass, and still more preferably 45 to 80 parts by mass. Moreover, the content of compound (A2) is preferably 10 to 60 parts by mass, more preferably 15 to 58 parts by mass, and more preferably 20 to 55 parts by mass based on 100 parts by mass of the total of compound (A1) and compound (A2). good.

When the thermosetting resin (A) contains a maleimide compound (AA-1) and a maleimide compound (AA-2), it is considered that further excellent low voids and die adhesion can be obtained. , the content of the maleimide compound (AA-1) is preferably 40 to 90 parts by mass, preferably 42 to 85 parts by mass relative to 100 parts by mass of the total of the compound (AA-1) and the compound (AA-2). Best, 45 to 80 parts by mass is even better. Moreover, the content of the maleimide compound (AA-2) is preferably 10 to 60 parts by mass, or 15 to 58 parts by mass relative to 100 parts by mass of the total of the compound (AA-1) and the compound (AA-2). Even better, 20 to 55 parts by mass is still better.

When the thermosetting resin (A) contains a citracaniline compound (AB-1) and a citracaniline compound (AB-2), it is considered that further excellent low voids and chip adhesion can be obtained. , the content of the nicotinamide compound (AB-1) is preferably 40 to 90 parts by mass, preferably 42 to 85 parts by mass relative to the total of 100 parts by mass of the compound (AB-1) and the compound (AB-2). The best is 45 to 80 parts by mass. Moreover, the content of the citraconidine compound (AB-2) is preferably 10 to 60 parts by mass, or 15 to 58 parts by mass relative to 100 parts by mass of the total of the compound (AB-1) and the compound (AB-2). Even better, 20 to 55 parts by mass is still better.

[Visible light absorber (B)] The resin composition layer contains a visible light absorber (B). The underfill material of this embodiment can be made into an underfill material by selecting the type of visible light absorber (B) contained in the resin composition layer and adjusting the content of the visible light absorber (B) and the film thickness of the resin composition layer. And the light transmittance of the resin composition layer is controlled within the desired range. For example, in order to adjust the light transmittance of the resin composition layer, it is also possible to consider using larger inorganic particles such as silica with an average particle diameter exceeding 400 nm. However, inorganic particles with larger particle sizes tend to settle during storage, and the varnish is stored Stability will be reduced. Therefore, especially when using an inorganic filler (C) with an average particle diameter of 400 nm or less, it is advantageous from the viewpoint of the storage stability of the varnish, etc., to use a visible light absorber (B) to adjust the light transmittance of the resin composition layer. .

The visible light absorber (B) is not particularly limited as long as it is a material that can absorb visible light. From the viewpoint of light absorption efficiency and suppression of reaction with other components such as the thermosetting resin (A), for example, a material selected from the group consisting of organic dyes, At least one of the group consisting of organic pigments and combinations thereof.

The organic dyes and organic pigments are not particularly limited and can be used, for example, selected from the group consisting of quinone series, aminoketone series, cationic series, cyanine series, phthalocyanine series, quinacridone series, diaryl/triarylmethane series, and phthalocyanine series. Acid anhydride (fulgide), azo series, squarylium series, oxonol series, benzylidene series, nitro series, nitroso series, thiazole series, indigoid series, and the like At least one compound from the group of combinations is preferably selected from the group consisting of quinones, aminoketones, and combinations thereof from the viewpoint of inhibiting the reaction with other components such as the thermosetting resin (A). At least one of the compounds.

(organic dyes) Specific examples of organic dyes are not particularly limited, and examples include the following azo dyes, mordant dyes, reactive dyes, and acid dyes. The organic dye in this embodiment is preferably a black dye among the following from the viewpoint of a wide absorption wavelength range. Kayaset Black A-N Direct Brilliant Pink B(C.I.Direct Red9) Kayarus Light Red F5G(C.I.Direct Red225) Direct Light Rose FR(C.I.Direct Red227) Sumilight Supra Turquoise Blue G(C.I.Direct Blue86) Direct Supra Blue FFRL(C.I.Direct Blue108) Kayarus Cupro Green G(C.I.Direct Green59) Direct Fast Black B(C.I.Direct Black22) Sunchromine Yellow MR(C.I.Mordant Yellow3) Chrome Yellow AS(C.I.Mordant Yellow5) Chrome Yellow 3R(C.I.Mordant Yellow8) Chrome Yellow PG(C.I.Mordant Yellow23) Chrome Orange FL(C.I.Mordant Orange29) Chrome Red B conc.(C.I.Mordant Red7) Chrome Red 5G(C.I.Mordant Red19) Sunchromine Brilliant Violet R conc.(C.I.Mordant Violet1：1) Chrome Fine Violet R(C.I.Mordant Violet1) Chrome Cyanine BXS(C.I.Mordant Blue1) Mordant Blue B 120%(C.I.Mordant Blue13) Chrome Cyanine BLA(C.I.Mordant Blue29) Mordant Green L(C.I.Mordant Green17) Chrome Green 3B-N(C.I.Mordant Green28) Mordant Brown KS(C.I.Mordant Brown15) Chrome Brown LE(C.I.Mordant Brown19) Chrome Brown RH(C.I.Mordant Brown33) Chrome Black P2B(C.I.Mordant Black7) Chrome Black PLW(C.I.Mordant Black9) Chrome Black ET-1(C.I.Mordant Black11)

Chrome Navy CR 158%(C.I.Mordant Black17) Chrome Light Gray G(C.I.Mordant Black38) Chrome Bordeaux FB Alizarine Chrome Brilliant Blue BL Chrome Blue 2G Sumifix Yellow GR 150%(C.I Reactive Yellow15) Lanasol Yellow 4G(C.I Reactive Yellow39) Sumifix Golden Yellow GG(A) 150%(C.I Reactive Yellow76) Kayacion Yellow E-S4R(C.I Reactive Yellow84) Novacron Yellow P-6GS gran(C.I Reactive Yellow95) Kayacion Yellow E-SNA(C.I Reactive Yellow102) Kayacion Yellow E-SN4G(C.I Reactive Yellow105) Drimarene Yellow K-2R CDG(C.I Reactive Yellow125) Sumifix Supra Yellow 3RF 150% gran(C.I Reactive Yellow145) Sumifix Supra Brilliant Yellow 3GF 150% gr(C.I Reactive Yellow167) Novacron Yellow C-R(C.I Reactive Yellow168) Novcron Yellow C-5G(C.I Reactive Yellow175) Kayacion Yellow CF-3RJ 150 Kayacion Yellow E-CM Procion Orange PX-RN(C.I.Reactive Orange5) Remazol Brilliant Orange 3R Special(C.I.Reactive Orange16) Levafix Yellow E-3RL gran(C.I.Reactive Orange30) Levafix Orange E-3GA gran(C.I.Reactive Orange64) Remazol Golden Yellow RNL gran 150%(C.I.Reactive Orange107) Drimaren Rubinol X3LR CDG(C.I.Reactive Red55) Brilliant Red G SPL(C.I.Reactive Red112) Brilliant Red 7BF Liq 25%(C.I.Reactive Red114) Lanasol Red 2G(C.I.Reactive Red116) Levafix Scarlet E-2GA gran(C.I.Reactive Red124) Levafix Brilliant Red E-4BA gran(C.I.Reactive Red158)

Levafix Brilliant Red E-6BA gran(C.I.Reactive Red159) Remazol Brilliant Red F3B gran(C.I.Reactive Red180) Supra Brilliant Red 3BF 150% gran(C.I.Reactive Red195) Remazol Red RB 133%(C.I.Reactive Red198) Supra Scarlet 2GF 150G(C.I.Reactive Red222) Novacron Red P-6B Gran. 150% Novacron Red C-2G Kayacion Violet A-3R(C.I.Reactive Violet1) Remazol Brill. Violet 5R(C.I.Reactive Violet5) Drimaren Violet K-2RL CDG(C.I.Reactive Violet33) Remazol Brill. Blue RN(C.I.Reactive Blue19) Sumifix Turquoise Blue G(N) conc.(C.I.Reactive Blue21) Novacron Blue P-3R IN(C.I.Reactive Blue49) Lanasol Blue 3R(C.I.Reactive Blue50) Drimarene Blue X-3LR CDG(C.I.Reactive Blue52) Lanasol Blue 3G(C.I.Reactive Blue69) Novacron Turquoise P-GR 150%(C.I.Reactive Blue72) Drimarene Navy X-RBL CDG(C.I.Reactive Blue79) Lanasol Blue 8G-01 150%(C.I.Reactive Blue185) Drimarene Blue K-2RL CDG(C.I.Reactive Blue209) Sumifix Supra Blue BRF 150% gran.(C.I.Reactive Blue221) Sumifix Supra Navy Blue BF gran.(C.I.Reactive Blue222) Sumifix Supra Turquoise Blue BGF(N)(C.I.Reactive Blue231) Novacron Blue C-R(C.I.Reactive Blue235) Kayacion Blue CF-GJ 150 Kayacion Blue CF-BL Kayacin Marine E-CM Kayacion Navy E-CM Sumifix Supra Navy Blue 3GF 150% granLevafix Brown E-2R gran(C.I.Reactive Brown19) Novacron Brown P-6R Gran. 150 Remazol Black B-N 150%(C.I.Reactive Black5)

Remazol Black RL 133%(C.I.Reactive Black31) Remazol Deep Black N 150%(C.I.Reactive Black31) Acid Quinoline Yellow WS H/C(C.I.Acid Yellow3) Kayacyl Yellow GG 80(C.I.Acid Yellow17) Tartrazine NS conc(C.I.Acid Yellow23) Suminol Fast Yellow R conc.(C.I.Acid Yellow25) Kayanol Milling Yellow O(C.I.Acid Yellow38) Suminol Milling Yellow MR(C.I.Acid Yellow42) Aminyl Yellow E-3GL(C.I.Acid Yellow49) Suminol Fast Yellow G (B)(C.I.Acid Yellow61) Erionyl Yellow B-4G(C.I.Acid Yellow79) Kayanol Yellow N5G(C.I.Acid Yellow110) Lanyl Yellow G ex cc(C.I.Acid Yellow116) Kayakalan Yellow GL 143(C.I.Acid Yellow121) Kayanol Milling Yellow 5GW(C.I.Acid Yellow127) Lanacron Yellow N-2GL KWL(C.I.Acid Yellow129) Erionyl Golden Yellow M-R-02(C.I.Acid Yellow151) Tectilon Yellow 2G 200%(C.I.Acid Yellow169) Lanacron Yellow S-2G-01 KWL(C.I.Acid Yellow220) Telon Yellow RLN micro(C.I.Acid Yellow230) Tectilon Yellow 3R 200%(C.I.Acid Yellow246) Chuganol Fast Yellow 5GL(C.I.Acid Yellow40：1) Solar Orange(C.I.Acid Orange7) Solar Light Orange GX(C.I.Acid Orange10) Chuganol Milling Brown 5R(C.I.Acid Orange51) Chuganol Milling OrangeSG(C.I.Acid Orange56) Kayanol Yellow N3R(C.I.Acid Orange67) Aminyl Yellow E-3RL(C.I.Acid Orange67) Lanyl Orange R 200%(C.I.Acid Orange88) Chuganol Milling Orange GSN 150%(C.I.Acid Orange95) Suminol Milling Orange GN(N)(C.I.Acid Orange95) Isolan Orange K-RLS(C.I.Acid Orange107) Telon Orange AGT 01(C.I.Acid Orange116) Lanyl Orange 2R e/c(C.I.Acid Orange120) Supralan Orange S-RL(C.I.Acid Orange166) Lanasyn Yellow M-2RL 180(C.I.Acid Orange180) Nylosan Orange NRL 250(C.I.Acid Orange250)

Lanasyn Orange M-RL p Silk Scarlet(C.I.Acid Red9) Brilliant Scarlet 3R conc.(C.I.Acid Red18) Acid Rhodamine G Conc(C.I.Acid Red50) Acid Rhodamine B Conc(C.I.Acid Red52) Chugacid Red FCH(C.I.Acid Red73) Chugacid Rubinol 3B 200%(C.I.Acid Red80) Rocceline NS conc. 120%(C.I.Acid Red88) Chuganol Anthracene Red G(C.I.Acid Red97) Suminol Fast Red G (B)(C.I.Acid Red118) Suminol Milling Brilliant Red 3BN (N) conc.(C.I.Acid Red131) Lanyl Red GG(C.I.Acid Red211) Lanyl Red B(C.I.Acid Red215) Lanasyn Bordeaux M-RLA200(C.I.Acid Red217) Suminol Milling Brilliant Red B conc. N(C.I.Acid Red249) Aminyl Red E-3BL(C.I.Acid Red257) Telon Red M-BL(C.I.Acid Red260) Chugai Aminol Fast Pink R(C.I.Acid Red289) Nylosan Red N-2RBL SGR(C.I.Acid Red336) Telon Red FRL micro(C.I.Acid Red337) Lanasyn Red M-G(C.I.Acid Red399) Kayakalan Red BL Nylosan Red EBL SGR 180 Kayanol Milling Red BW Kayanol Milling Violet FBW(C.I.Acid Violet48) Erionyl Red B-10B-01(C.I.Acid Violet54) Chugai Aminol Fast Violet F6R(C.I.Acid Violet102) Acid Pure Blue VX(C.I.Acid Blue1) Acid Brilliant Blue AF-N(C.I.Acid Blue7) Chugacid Light Blue A(C.I.Acid Blue25) Kayanol Blue N2G(C.I.Acid Blue40) Nylosan Blue E-GL p 250(C.I.Acid Blue72) Chuganol Blue 6B 333%(C.I.Acid Blue83) Chuganol Blue G 333%(C.I.Acid Blue90) Kayanol Navy Blue R(C.I.Acid Blue92)

Suminol Milling Brilliant Sky Blue SE (N)(C.I.Acid Blue112) Suminol Milling Cyanine 5R (N)(C.I.Acid Blue113) Kayanol Milling Blue GW(C.I.Acid Blue127) Lanyl Brilliant Blue G ex cc(C.I.Acid Blue127：1) Kayanol Blue NR(C.I.Acid Blue129) Kayanol Milling Blue BW(C.I.Acid Blue138) Kayanol Milling Blue 2RW(C.I.Acid Blue140) Lanyl Blue 3G ex conc(C.I.Acid Blue171) Nylosan Blue N-GL 150(C.I.Acid Blue230) Tectilon Blue 6G 200%(C.I.Acid Blue258) Telon Blue AFN(C.I.Acid Blue264) Tectilon Blue 4R-01 200%(C.I.Acid Blue277：1) Nylosan B Blue N-FL SGR180(C.I.Acid Blue278) Nylosan Blue N-5GL SGR 200(C.I.Acid Blue280) Kayalax Navy R(C.I.Acid Blue300) Nylosan Blue N-BLN(C.I.Acid Blue350) Lanacron Blue N-3GL Acid Green V(C.I.Acid Green16) Chuganol Cyanine Green G(C.I.Acid Green25)

The content of the visible light absorber (B) in the resin composition layer is appropriately adjusted according to its type in order to adjust the above-mentioned transmittance, so its content is not limited. However, for example, considering the viewpoints of insulation reliability, film durability, etc., It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.05 to 2 parts by mass relative to 100 parts by mass of the total amount of the thermosetting resin (A).

[Inorganic filler (C)] In order to improve the flame resistance, improve the thermal conductivity, and reduce the thermal expansion rate, the resin composition layer preferably contains an inorganic filler (C). By using the inorganic filler (C), the flame resistance and thermal conductivity of the underfill material can be improved, and the thermal expansion rate can be reduced.

The average particle size of the inorganic filler (C) is not particularly limited, but consideration should be given to suppressing the decrease in storage stability of the varnish due to sedimentation when using an inorganic filler with a large particle size, and to improving the melt viscosity and transparency of the resin composition layer. , and from the viewpoint of narrowing the pitch of the electrodes arranged on the wafer and narrowing the gap between the electrodes, it is preferably 400 nm or less, more preferably 300 nm or less, and 1 to 100 nm is particularly preferred. In addition, in this embodiment, the "average particle diameter" of the inorganic filler (C) means the median particle diameter of the inorganic filler (C). The median particle diameter here means that when the particle size distribution of the powder is divided into two groups based on a certain particle diameter, the volume of the particles on the larger particle diameter side and the volume of the particles on the smaller particle diameter side respectively account for the entire 50% of the particle size of the powder. The average particle diameter (median particle diameter) of the inorganic filler (C) is measured by a wet laser diffraction-scattering method.

The inorganic filler (C) is not particularly limited, and examples thereof include silica such as natural silica, fused silica, amorphous silica, and hollow silica; boehmite, aluminum hydroxide, Aluminum compounds such as aluminum oxide and aluminum nitride; magnesium compounds such as magnesium oxide and magnesium hydroxide; calcium compounds such as calcium carbonate and calcium sulfate; molybdenum compounds such as molybdenum oxide and zinc molybdate; boron nitride; barium sulfate; Talc (talc) such as natural talc and calcined talc; mica; glass such as short fiber glass, spherical glass, and fine powder glass (such as E glass, T glass, D glass). In addition, when it is desired to impart conductivity or anisotropic conductivity to the resin composition layer, metal particles such as gold, silver, nickel, copper, tin alloy, and palladium may be used as the inorganic filler (C).

Among them, from the viewpoint of improving the flame resistance of the resin composition layer and reducing the thermal expansion rate, the inorganic filler (C) preferably contains silica, aluminum hydroxide, alumina, boehmite, and boron nitride. , at least one selected from the group consisting of aluminum nitride, magnesium oxide, magnesium hydroxide, and combinations thereof, preferably at least one selected from the group consisting of silicon dioxide, aluminum oxide, and boron nitride, Among them, silicon dioxide is more preferred. Examples of silicon dioxide include: SFP-120MC (trade name) and SFP-130MC (trade name) manufactured by Denka Co., Ltd.; 0.3 μm SX-CM1 (trade name) and 0.3 μm SX-EM1 (trade name) manufactured by Admatechs Co., Ltd. Trade name), 0.3μmSV-EM1 (trade name), SC1050-MLQ (trade name), SC2050-MNU (trade name), SC2050-MTX (trade name), 2.2μm SC6103-SQ (trade name), SE2053-SQ ( Trade name), Y50SZ-AM1 (trade name), YA050C-MJE (trade name), YA050C-MJM (trade name), YA050C-MJF (trade name), and YA050C-MJA (trade name).

These inorganic fillers (C) can be used individually by 1 type or by mixing 2 or more types appropriately.

The inorganic filler (C) may be surface-treated with a silane coupling agent. The silane coupling agent used for the surface treatment of the inorganic filler (C) is not particularly limited as long as it is a silane coupling agent commonly used for the surface treatment of inorganic substances. Examples include: vinylsilane-based silane coupling agents such as vinyltrimethoxysilane and γ-(meth)acryloxypropyltrimethoxysilane; N-phenyl-3-aminopropyltrimethyl phenylaminesilane-based silane coupling agents such as oxysilane; phenylsilane-based silane coupling agents such as trimethoxyphenylsilane; imidazolesilane-based silane coupling agents. These silane coupling agents can be used individually by 1 type or by mixing 2 or more types appropriately.

The content of the inorganic filler (C) in the resin composition layer is not particularly limited. From the viewpoint of insulation reliability and ensuring sufficient flux activity during installation, it is 100 parts by mass relative to the total amount of the thermosetting resin (A). , preferably 10 to 500 parts by mass, more preferably 25 to 400 parts by mass, and even more preferably 30 to 300 parts by mass. The upper limit of the content of the inorganic filler (C) may be 250 parts by mass.

[Flux Activator (D)] In order to exhibit flux activity in flip-chip mounting, the resin composition layer should further contain a flux activator (D). The flux activator (D) is not particularly limited as long as it is an organic compound having one or more acidic sites in the molecule. Acidic sites are preferably, for example, phosphate groups, phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups. It is considered that in semiconductor devices using a resin composition layer as an underfill material, it can more effectively prevent metals such as solder and copper that form the joint. From the perspective of migration and corrosion, phenolic hydroxyl or carboxyl groups are better. The flux activator (D) can be used individually by 1 type or by mixing 2 or more types appropriately.

The flux activator (D) is not particularly limited. From the perspective of fully removing the oxide film at the joint, the acid dissociation constant pKa is preferably 3.8 or more and 15.0 or less, taking into consideration both the storage stability of the varnish and the underfill material and the auxiliary properties. From the viewpoint of flux activity, it is more preferable that it is 4.0 or more and 14.0 or less.

In the resin composition layer, the molecular weight of the flux activator (D) is not particularly limited. Consider preventing the flux activity from volatilizing before it is displayed in flip-chip mounting, that is, before removing the oxide film from the joint. From the viewpoint that the active agent (D) has volatilized, the molecular weight is preferably above 200, and more preferably above 250. From the viewpoint of having mobility as a flux activator and obtaining sufficient flux activity, the molecular weight of the flux activator (D) is preferably 8,000 or less, more preferably 1,000 or less, and still more preferably 600 or less.

The flux activator (D) is not particularly limited and examples thereof include: rosinic acid, neoabietic acid, dehydroabietic acid, pimaric acid, and pimaric acid. ), longleaf rosin acid (palustric acid), bisphenolic acid, dihydroabietic acid (dihydroabietic acid), tetrahydrorosinic acid, hydrogenated rosin ester, and rosin-modified maleic acid resin and other rosin resins; N, N' -Diamine series such as bis(saloylene)-1,2-propanediamine, and N,N'-bis(saloylene)-1,3-propanediamine; 2-[bis(4-hydroxybenzene Methyl]benzoic acid. These flux activators (D) are ideal from the viewpoint of excellent solubility in solvents and excellent storage stability of varnish and underfill materials.

Among them, the flux activator (D) is selected from the group consisting of dehydrorosinic acid, bisphenolic acid, dihydrorosinic acid, tetrahydrorosinic acid, and the like, from the viewpoint of preventing deactivation of the thermosetting resin (A). Hydrogenated rosin ester, rosin-modified maleic acid resin, N,N'-bis(salosinyl)-1,2-propanediamine, and N,N'-bis(salvinyl)-1,3-propane It is more preferable that it is at least one type from the group consisting of diamines, and it is particularly preferable that it contains a rosin-based resin. Since these flux activators have low reactivity, they are more preferable from the viewpoint of causing little reaction with the thermosetting resin (A) and maintaining sufficient flux activity necessary for removing the oxide film. Furthermore, from the viewpoint of obtaining further excellent flux activity, it is more preferable that the flux activator (D) is hydrogenated rosin ester.

As the flux activator (D), a commercially available product can be used. Examples of rosin-based resins include: KR-85 (trade name, the same below), KR-612, KR-614, KE-100, KE-311, PE-590, KE-359, KE-604, KR-120, KR-140, KR-614, D-6011, and KR-50M; MALKYD No32 (the above are manufactured by Arakawa Chemical Industry Co., Ltd.), etc.

The content of the flux activator (D) in the resin composition layer is not particularly limited. From the viewpoint of insulation reliability and ensuring sufficient flux activity during installation, it is 100% of the total amount of the thermosetting resin (A). Parts by mass are preferably 3 to 70 parts by mass, preferably 5 to 50 parts by mass, and even more preferably 8 to 40 parts by mass.

[Hardening Catalyst (E)] The resin composition layer may further contain a curing catalyst (E). By containing the curing catalyst (E) in the resin composition layer, the polymerization rate of the thermosetting resin (A) can be more ideally controlled, and a resin composition with appropriate formability tends to be obtained. The curing catalyst is not particularly limited as long as it is a compound that can accelerate the polymerization of the thermosetting resin (A). The hardening catalyst (E) can be used individually by 1 type or in mixture of 2 or more types.

The curing catalyst (E) is not particularly limited, and examples thereof include organic peroxides, imidazole compounds, azo compounds, and tertiary amines such as triethylamine and tributylamine. Among them, from the viewpoint of obtaining a good polymerization speed and a good hardening speed, it is preferable to include at least one selected from the group consisting of organic peroxides, imidazole compounds, and combinations thereof, including organic peroxides. Both oxides and imidazole compounds are more preferred.

The content of the curing catalyst (E) in the resin composition layer is not particularly limited. From the viewpoint of obtaining a good curing speed, it is preferably 0.02 to 10 parts by mass based on 100 parts by mass of the total amount of the thermosetting resin (A). Parts by mass, preferably 0.05 to 8 parts by mass.

(organic peroxide) The organic peroxide of this embodiment is not particularly limited as long as it is a compound that releases an active material (radical) capable of polymerizing the thermosetting resin (A) due to heat, and a known organic peroxide can be used. The organic peroxide can be used individually by 1 type or in mixture of 2 or more types.

In this embodiment, the 10-hour half-life temperature of the organic peroxide is not particularly limited, but it is preferably 100°C or higher, and from the viewpoint of manufacturability, it is more preferably 110°C or higher. In order to achieve high temperatures in the solvent removal step during production, the organic peroxide should preferably have a half-life temperature of 10 hours within the aforementioned range.

Examples of organic peroxides include dicumyl peroxide, bis(2-tertiary butylisopropylperoxy)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2, 5-dimethyl-2,5-bis(tertiary butyl peroxide) hexyne-3, benzyl peroxide, di(tertiary butyl) peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide Ketone peroxides such as oxides; 1,1-di(tertiary butyl peroxide) cyclohexane, and 2,2-bis(4,4-di(tertiary butyl peroxide) cyclohexyl) propane, etc. Peroxide ketals; hydrogen peroxides such as tertiary butyl hydroperoxide, menthane hydroperoxide, dicumyl hydroperoxide, cumene hydroperoxide, and tertiary butyl hydroperoxide ; Bis(2-tertiary butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tertiary butylperoxide)hexane, tertiary butylcumyl peroxide , di(tertiary hexyl) peroxide, 2,5-dimethyl-2,5-di(tertiary butyl peroxide) hexyne-3, α,α'-di(tertiary butyl peroxide) ) Diisopropylbenzene, and di(tertiary butyl) peroxide and other dialkyl peroxides; Diperoxide benzyl peroxide, and di(4-methylbenzyl) peroxide and other dihydrogens peroxide; peroxydicarbonates such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate; 2,5-dimethyl-2,5-bis(peroxybenzoyl) ) Hexane, tertiary hexyl peroxybenzoate, tertiary butyl peroxybenzoate, and tertiary butyl peroxy-2-ethylhexanoate and other peroxy esters. From the viewpoint of obtaining better reaction speed and hardening speed, it is appropriate to select dicumyl peroxide, di(2-tertiary butylperoxyisopropyl)benzene, 1,1,3,3-tetrakis Methyl butyl hydroperoxide, 2,5-dimethyl-2,5-bis(tertiary butyl peroxide)hexyne-3, α,α'-bis(tertiary butyl peroxy)diiso At least one of the group consisting of propylbenzene and tertiary butyl hydroperoxide.

The content of the organic peroxide in the resin composition layer is not particularly limited. From the viewpoint of obtaining further good polymerization speed and hardening speed, it is preferably: 0.02~10 parts by mass, more preferably 0.05~8 parts by mass.

(imidazole compound) The imidazole compound is not particularly limited as long as it can accelerate the polymerization of the thermosetting resin (A), and known imidazole compounds can be used. One type of imidazole compound may be used, or two or more types may be mixed and used.

Examples of imidazole compounds include: 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-triphenylimidazole, Tertiary amines such as triethylamine and tributylamine, and their derivatives. Among them, 2-ethyl-4-methylimidazole is preferable from the viewpoint of easier adjustment of reaction speed and hardening speed.

The content of the imidazole compound in the resin composition layer is not particularly limited. From the viewpoint of easier adjustment of the polymerization speed and curing speed, it is preferably 0.02 to 10 parts by mass based on 100 parts by mass of the total amount of the thermosetting resin (A). Parts by mass, preferably 0.05 to 8 parts by mass.

(Azo compound) The azo compound is not particularly limited as long as it can accelerate the polymerization of the thermosetting resin (A), and known azo compounds can be used. The azo compound can be used individually by 1 type or in mixture of 2 or more types. Examples of azo compounds include 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4- Methoxy-2,4-dimethylvaleronitrile), etc.

The content of the azo compound in the resin composition layer is not particularly limited. From the viewpoint of easier adjustment of the polymerization rate and curing rate, it is preferably 0.02 to 0.02 parts by mass based on 100 parts by mass of the total amount of the thermosetting resin (A). 10 parts by mass, preferably 0.05~8 parts by mass.

[Hardening agent (F)] The resin composition layer may further contain a hardener (F). The curing agent (F) is used to improve the curing properties of the thermosetting resin (A) and to adjust the curing speed of the thermosetting resin (A). The hardening agent (F) can be appropriately selected from a known one according to the type of the thermosetting resin (A) used, and examples thereof include phenolic resins, amines, mercaptans, and the like.

In this embodiment, the content of the curing agent (F) is not particularly limited. From the viewpoint of easier adjustment of the curing properties and curing speed of the thermosetting resin (A), the content of the curing agent (A) and the curing agent is The total 100 parts by mass of (F) is preferably 3 to 80 parts by mass, more preferably 5 to 70 parts by mass, and particularly preferably 15 to 50 parts by mass.

(Amino tri-phenolic varnish resin) In addition, it is not particularly limited, but as the hardening agent (F), for example, amino trisulfonate novolac resin can be used. For example, when an amino tris-novolak resin is used as the hardener (F) for a resin composition containing a maleimine compound or a citrucon-imine compound as a main component, the amino tris-novolak resin has three 𠯤 skeleton, so it can react well with maleimide and/or citraconimine groups. Therefore, for example, the thermosetting resin can be hardened using an amino tris-novolac resin while ideally controlling the speed of the radical polymerization reaction. In addition, the amine-based novolak resin has a novolak resin skeleton bonded to the triskeleton, so it can still contain a large amount of hydroxyl groups and amine groups even after hardening. Therefore, even after hardening, good chemical bonding will still occur between these groups and the silicone groups of the chip, so the chip adhesion of the resin composition layer can be improved.

The resin composition layer may contain an amine-based novolac resin from the viewpoint of improving low voids and chip adhesion. As long as the amino tris-novolac resin is a phenol-formaldehyde resin (phenol-formaldehyde resin) having a tris-novolac ring in the molecule, a known resin can be used. Such an amino tri-novolak resin can be prepared by a known method, for example, it can be obtained by modifying a phenolic resin with a nitrogen compound such as melamine. Amino tri-novolak resin can be used alone or by appropriately mixing two or more types.

In the resin composition layer, the content of the amino tris-novolak resin is preferably 5 to 70 parts by mass relative to 100 parts by mass of the total of the amino tris-novolak resin and the thermosetting resin (A), considering that it can be obtained From the viewpoint of better low void properties and chip adhesion, 15 to 50 parts by mass is more preferred, and 20 to 40 parts by mass is particularly preferred.

From the perspective of obtaining further excellent low voids and chip adhesion, the weight average molecular weight of the amino tri-novolak resin is preferably 300 to 9,500, and more preferably 500 to 5,000. In addition, in this embodiment, the weight average molecular weight is a standard polystyrene-converted value obtained by GPC (gel permeation chromatography) method.

From the viewpoint of obtaining further excellent low voids and wafer adhesion, the nitrogen content of amino tris-novolak resin is preferably 10 to 25 mass % in 100 mass % of amino tris-novolac resin. From the viewpoint of obtaining further excellent low void properties and at the same time obtaining further excellent wafer adhesion, 15 to 20 mass % is more preferable.

From the perspective of obtaining further excellent low voids and chip adhesion, the hydroxyl equivalent weight of the amine-based tri-novolak resin is preferably 80~200g/eq., and more preferably 100~180g/eq. In addition, in this embodiment, the hydroxyl equivalent represents the number of mg of potassium hydroxide required to acetylate the hydroxyl group contained in 1 g of the amino tris-novolak resin. Specifically, the measurement is performed in accordance with JIS K 0070.

From the viewpoint of obtaining further excellent low void properties and chip adhesion, the amino tris-novolac resin preferably contains a group selected from the group consisting of the compound represented by the following formula (1) and the compound represented by the following formula (2) More than 1 species in the group.

[Chemical 16]

In formula (1), R ₁ each independently represents a hydrogen atom, a methyl group, or an ethyl group. From the viewpoint of obtaining further excellent low void properties and wafer adhesion, R ₁ is preferably each independently a hydrogen atom or a methyl group. l, m, and n each independently represent an integer from 0 to 10. From the viewpoint of obtaining further excellent low void properties and wafer adhesion, l, m, and n are preferably each independently an integer from 1 to 6. (l+m+n) represents an integer from 1 to 20. From the viewpoint of obtaining further excellent low void properties and chip adhesion, (l+m+n) is preferably an integer from 3 to 18. In addition, the compound represented by the formula (1) may also be, for example: a compound containing the functional group of R ₁ in the formula (1) or a compound with a different numerical value; a compound with a different numerical value for l, m, and n; (l+m+ n) A mixture of compounds with different numerical values.

[Chemical 17]

In formula (2), R ₂ each independently represents a hydrogen atom, a methyl group, or an ethyl group. From the viewpoint of obtaining further excellent low void properties and wafer adhesion, R ₂ is preferably each independently a hydrogen atom or a methyl group. o, p, q, r, and s each independently represent an integer from 0 to 10. From the viewpoint of obtaining further excellent low void properties and wafer adhesion, it is preferable that o, p, q, r, and s are each independently an integer between 1 and 4. (o+p+q+r+s) represents an integer from 1 to 20. From the viewpoint of obtaining further excellent low void properties and chip adhesion, (o+p+q+r+s) is preferably an integer between 5 and 20. In addition, the compound represented by formula (2) may also be, for example: a compound containing the functional group of R ₂ in formula (2) or a compound with different numerical values; a compound with different numerical values for o, p, q, r, and s; ( A mixture of compounds with different values of o+p+q+r+s).

From the viewpoint of obtaining further excellent low voids and wafer adhesion, it is more preferable that the amino tris-novolac resin be a mixture of the compound represented by formula (1) and the compound represented by formula (2). From the viewpoint that such a mixture can obtain further excellent low voids and wafer adhesion, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) (compound represented by formula (1) (mass parts ): The compound represented by formula (2) (parts by mass) is preferably 50:50~90:10, more preferably 60:40~85:15.

Commercially available amino tri-novolak resins can also be used. Examples include: LA-1356 (trade name), LA-3018-50P (trade name), LA-7052 (trade name) manufactured by DIC Co., Ltd. LA-7054 (trade name), LA-7751 (trade name).

[Other ingredients] The resin composition layer contains a thermosetting resin (A), a visible light absorber (B), etc., and may also contain one or more other components. Other components are not particularly limited, and examples thereof include flexibility-imparting components. The flexibility-imparting component is not particularly limited as long as it can impart flexibility to the layer containing the resin composition. Examples of such components include thermosetting resin (A), visible light absorber (B), inorganic filler (C), flux activator (D), curing catalyst (E), and hardener (F). Exceptions: polyamide, polyamide, polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), Thermoplastic polymer compounds such as (meth)acrylonitrile butadiene rubber (NBR), polyurethane, polypropylene, (meth)acrylic acid oligomer, (meth)acrylic acid polymer, and polysiloxane resin . These flexibility imparting components can be used individually by 1 type or by mixing 2 or more types appropriately.

In addition, the resin composition layer may contain a silane coupling agent as another component in order to further improve the adhesion and moisture absorption and heat resistance of the interface between the resin component and the inorganic filler (C). Examples of the silane coupling agent include vinylsilane-based silane coupling agents such as vinyltrimethoxysilane and γ-(meth)acryloxypropyltrimethoxysilane; N-phenyl-3-amine Phenylamine silane-based silane coupling agents such as propyltrimethoxysilane; phenylsilane-based silane coupling agents such as trimethoxyphenylsilane; imidazole silane-based silane coupling agents. These silane coupling agents can be used individually by 1 type or by mixing 2 or more types appropriately. When using a silane coupling agent, its content is not particularly limited. From the viewpoint of further improving moisture absorption and heat resistance and further reducing the amount of volatilization during flip-chip mounting, relative to 100 parts by mass of the total amount of thermosetting resin (A), It is suitable to be 0.02~20 parts by mass.

In addition, the resin composition layer may also contain a moist dispersing agent as another component in order to further improve the manufacturability of the film-like underfill material and further improve the dispersibility of the filler material. The wetting and dispersing agent is not particularly limited as long as it is a wetting and dispersing agent commonly used in paints and the like. Examples include DISPERBYK (registered trademark)-110 (trade name), DISPERBYK-111 (trade name), DISPERBYK-180 (trade name), DISPERBYK-161 (trade name), BYK-W996 (trade name) manufactured by BYK Co., Ltd. (trade name), BYK-W9010 (trade name), and BYK-W903 (trade name). These moistening dispersants can be used alone or in an appropriate mixture of two or more kinds. When a wet dispersant is used, its content is not particularly limited. From the viewpoint of further improving the manufacturability of the film-like underfill material, it is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the inorganic filler (C). 0.5~3 parts by mass is better. In addition, when two or more kinds of wetting and dispersing agents are used in combination, their total amount should comply with the above-mentioned ratio.

The resin composition layer may contain various additives as other components for various purposes within a range that does not impair desired characteristics. Examples of additives include: tackifiers, lubricants, defoaming agents, leveling agents, brighteners, flame retardants, and ion trapping agents. These additives can be used individually by 1 type or by mixing 2 or more types appropriately. The content of other additives in the resin composition layer is not particularly limited, but is usually 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of thermosetting resin (A).

[Preparation method of resin composition for film-like underfill material] As described above, the resin composition for film-like underfill materials of this embodiment contains a thermosetting resin (A), a visible light absorber (B), etc., and the preparation method is not particularly limited as long as it has the above composition. The resin composition can be cured, for example, by combining a thermosetting resin (A) and a visible light absorber (B), as well as an inorganic filler (C), a flux activator (D), a curing catalyst (E), and an optional inorganic filler (C) if necessary. Agent (F) and other ingredients are mixed appropriately to prepare. If necessary, these components may be dissolved or dispersed in an organic solvent to form a varnish. Varnishes are ideal for producing film-like underfill materials. For the specific manufacturing method of the film-like underfill material, please refer to the above-mentioned manufacturing method of the laminate and the examples described below. In addition, the resin composition for film-like underfill materials of this embodiment can be ideally used to produce the resin composition layer of the film-like underfill material of this embodiment. However, this embodiment is not limited thereto. Film-like underfill materials other than film-like underfill materials are also applicable.

The organic solvent is not particularly limited as long as it can dissolve or disperse the aforementioned components ideally and does not impair the effects of the present invention. Examples of organic solvents include: alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone (hereinafter sometimes abbreviated as "MEK"), and methyl isobutyl ketone; dimethyl acetamide, and Amines such as dimethylformamide; aromatic hydrocarbons such as toluene and xylene. These organic solvents can be used individually by 1 type or by mixing 2 or more types appropriately.

[Semiconductor chip provided with a resin composition layer and semiconductor chip mounting substrate provided with a resin composition layer] The film-like underfill material of this embodiment can be ideally used as an underfill material for semiconductor wafers and semiconductor wafer mounting substrates.

For example, a semiconductor wafer provided with a resin composition layer includes a semiconductor wafer and a layer including a resin composition layer laminated on the semiconductor wafer. Furthermore, a semiconductor wafer mounting substrate provided with a resin composition layer includes a semiconductor wafer mounting substrate and a layer containing a resin composition layer laminated on the semiconductor wafer mounting substrate.

In the method of manufacturing a semiconductor wafer provided with a resin composition layer of this embodiment, the film-like underfill material of this embodiment described above can be used to manufacture a semiconductor wafer provided with a resin composition layer. The method of producing a semiconductor wafer provided with a resin composition layer is not particularly limited. For example, the surface of the semiconductor wafer on which electrodes are formed, that is, the surface bonded to the substrate, faces the resin of the film-like underfill material of this embodiment. The semiconductor wafer provided with the resin composition layer can be obtained by laminating the wafer in the form of a composition layer, peeling off the base film of the film-like underfill material, and then singulating it using a dicing saw or the like. Furthermore, in the method of manufacturing a semiconductor wafer mounting substrate provided with a resin composition layer of this embodiment, the film-like underfill material of this embodiment can be used to manufacture a semiconductor wafer mounting substrate provided with a resin composition layer. The method of producing the semiconductor wafer mounting substrate provided with the resin composition layer is not particularly limited. For example, the resin composition of the film-like underfill material of the present embodiment may be applied to the surface of the semiconductor wafer mounting substrate facing the wafer mounting side. It is obtained by laminating the film-like underfill material in layers, and then peeling off the base film of the film-like underfill material.

The method of laminating the film-like underfill material of this embodiment to a semiconductor wafer or a semiconductor wafer mounting substrate is not particularly limited, and a vacuum pressure laminator can be ideally used. At this time, it is preferable to use a method of pressing and bonding the film-like underfill material of this embodiment with an elastic body such as rubber. Lamination conditions are not particularly limited if they are conditions commonly used by those with ordinary knowledge in the technical field to which the invention belongs, such as a temperature of 50 to 140°C, a contact pressure in the range of 1 to 11 kgf/cm ² , and an environment below 20 hPa. Implemented under reduced pressure. After the lamination step, the laminated film-like underfill material can also be smoothed by hot pressing with a metal plate. The lamination step and the smoothing step can be performed continuously using a commercially available vacuum pressure laminator. The film-like underfill material attached to the semiconductor wafer or the semiconductor wafer mounting substrate will be removed from the base film before flip-chip mounting of the chip in either case.

[Semiconductor device] A semiconductor device can be constructed using the semiconductor wafer provided with the resin composition layer and/or the semiconductor wafer mounting substrate provided with the resin composition layer. In other words, in the method of manufacturing a semiconductor device of this embodiment, the semiconductor device can be manufactured using the film-like underfill material of this embodiment. Specifically, the semiconductor device includes a semiconductor wafer provided with a resin composition layer and/or a semiconductor wafer mounting substrate provided with a resin composition layer. The method of manufacturing a semiconductor device is not particularly limited, and an example thereof is a method of mounting a semiconductor wafer provided with a resin composition layer on a semiconductor wafer mounting substrate. Furthermore, the semiconductor wafer may be mounted on a semiconductor wafer mounting substrate provided with a resin composition layer. The method of mounting a semiconductor wafer provided with a resin composition layer on a semiconductor wafer mounting substrate and the method of mounting a semiconductor wafer on a semiconductor wafer mounting substrate provided with a resin composition layer can be ideally used for thermocompression bonding. Construction method of flip chip bonder. In addition, in this embodiment, the case where the semiconductor wafer is flip-chip mounted on the semiconductor wafer mounting substrate is simply explained. However, the semiconductor wafer may be flip-chip mounted and the resin composition layer may be used as the semiconductor wafer mounting substrate. outside. For example, the resin composition layer can be used in a joint between semiconductor wafers when the semiconductor wafer is mounted on the semiconductor wafer, or in a wafer stack in which semiconductor wafers are connected via TSV (Through Silicon Via) or the like. The effects of this embodiment can be obtained in any case at the joint between the semiconductor wafers in the layer. [Example]

Hereinafter, this embodiment will be described more specifically using Examples and Comparative Examples. This embodiment is not limited at all by the following examples.

[Example 1] (Preparation of resin composition (varnish)) A bismaleimide compound (long-chain maleimide; MIZ-001 (trade name), Japan) as the thermosetting resin (A) Chemical medicine (stock), containing maleimide compound represented by formula (9), and is a mixture of a in formula (9) 1 to 6 (integer)) 70 parts by mass, bis-(3-ethyl) -5-Methyl-4-maleimidophenyl)methane (phenylene-type maleimide; BMI-70 (trade name), K･I Chemical Co., Ltd.) 10 parts by mass; as 0.1 part by mass of black dye (Kayaset Black AN (trade name, Nippon Kayaku Co., Ltd.)) as the visible light absorber (B); slurry silica (YA050C-MJM (trade name) as the inorganic filler (C) , Admatechs (Co., Ltd.), phenylaminosilane-treated silica, solid content 50% by mass, dispersion medium: MEK, average particle size: 50nm) 180 parts by mass (converted to 90 parts by mass based on non-volatile content); as an assistant The flux activator (D) is hydrogenated rosin ester (PINECRYSTAL (registered trademark); KR-140 (trade name), Arakawa Chemical Industry Co., Ltd.) 25 parts by mass; the hardening catalyst (E) is an organic peroxide 0.05 parts by mass of α,α'-bis(peroxytertiary butyl)diisopropylbenzene (PERBUTYL (registered trademark) P, Nippon Oils & Fats Co., Ltd., 10-hour half-life temperature: 119.20°C), and is an imidazole compound 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Chemical Industry Co., Ltd.); As the hardener (F), amino tris-phenolic varnish resin (PHENOLITE (registered trademark); LA-1356 (Trade name, DIC Co., Ltd.) 33.3 parts by mass (20 parts by mass in terms of non-volatile content) were mixed and stirred using a high-speed stirrer in a hot water bath at 60° C. for 40 minutes. MEK was also added to obtain a solid content. A varnish (resin composition) with a concentration of 60% by mass. In addition, LA-1356 (trade name, DIC Co., Ltd.), which is an amino tris-novolac varnish resin, is a compound represented by the above formula (1) (formula (1) ) represents a mixture of compounds, and the mixture contains R ¹ each independently a hydrogen atom or a methyl group, l, m, n each independently an integer from 1 to 6, (l+m+n) from 3 to 18 (an integer compound group), and the compound represented by formula (2) (which is a mixture of compounds represented by formula (2), and the mixture contains R ² each independently a hydrogen atom or a methyl group, o, p, q, A mixture of compounds in which r, and s are each independently an integer from 1 to 4, and (o+p+q+r+s) is an integer from 5 to 20), and in the mixture, the compound represented by formula (1) ( The mass ratio (formula (1): formula (2)) to the compound (mixture) represented by formula (2) is 65 (parts by mass): 35 (parts by mass).

(Production of film-like underfill material) The obtained varnish (resin composition) was coated on a 38 μm-thick polyethylene terephthalate film (base film; release agent thickness: 0.1 μm, TR1-38 (commercial product) with a release agent on the surface. Named UNITIKA (Co., Ltd.)), heated and dried at 100°C for 5 minutes under 1 atmosphere to obtain a film-like underfill material with a resin composition layer with a thickness of 16.5 μm formed on the base film. In addition, regarding the thickness of the resin composition layer, the thickness of the film-like underfill material was measured using a micrometer (MDH-25M, manufactured by Mitutoyo Corporation), and the base material was deducted from the thickness of the film-like underfill material. The thickness of the film is obtained.

[Example 2] In "Preparation of Film-like Underfill Material", except that the thickness of the resin composition layer was set to 43 μm, the same procedure as in Example 1 was performed to obtain a film-like underfill material.

[Example 3] In "Preparation of resin composition (varnish)", the usage amount of the black dye was changed to 0.3 parts by mass, and in "Preparation of film-like underfill material", the thickness of the resin composition layer was set to 16.0 μm. Except for this, the same procedure as in Example 1 was carried out to obtain a film-like underfill material.

[Example 4] In "Preparation of Film-like Underfill Material", except that the thickness of the resin composition layer was set to 35 μm, the same procedure as in Example 3 was performed to obtain a film-like underfill material.

[Example 5] In "Preparation of resin composition (varnish)", the usage amount of the black dye was changed to 0.5 parts by mass, and in the preparation of the film-like underfill material, the thickness of the resin composition layer was set to 17.0 μm. Except for this, the same procedure as in Example 1 was carried out to obtain a film-like underfill material.

[Example 6] In "Preparation of Film-like Underfill Material", except that the thickness of the resin composition layer was set to 30 μm, the same procedure as in Example 5 was performed to obtain a film-like underfill material.

[Example 7] In "Preparation of resin composition (varnish)", the usage amount of the black dye was changed to 0.7 parts by mass, and in "Preparation of film-like underfill material", the thickness of the resin composition layer was set to 17.0 μm. Except for this, the same procedure as in Example 1 was carried out to obtain a film-like underfill material.

[Example 8] In "Preparation of Film-like Underfill Material", except that the thickness of the resin composition layer was set to 33 μm, the same procedure as in Example 7 was performed to obtain a film-like underfill material.

[Example 9] In "Preparation of resin composition (varnish)", the usage amount of the black dye was changed to 1.0 parts by mass, and in "Preparation of film-like underfill material", the thickness of the resin composition layer was set to 17.0 μm. Except for this, the same procedure as in Example 1 was carried out to obtain a film-like underfill material.

[Example 10] In "Preparation of Film-like Underfill Material", except that the thickness of the resin composition layer was set to 33 μm, the same procedure as in Example 9 was performed to obtain a film-like underfill material.

[Example 11] In "Preparation of resin composition (varnish)", the usage amount of the black dye was changed to 2.0 parts by mass, and in the preparation of the film-like underfill material, the thickness of the resin composition layer was set to 18.0 μm. Except for this, the same procedure as in Example 1 was carried out to obtain a film-like underfill material.

[Comparative example 1] In "Preparation of Film-like Underfill Material", except that the thickness of the resin composition layer was set to 41 μm, the same procedure as in Example 11 was performed to obtain a film-like underfill material.

[Comparative example 2] In "Preparation of resin composition (varnish)", no black dye is used, and in "Preparation of film-like underfill material", the thickness of the resin composition layer is set to 13.0 μm. In addition, the following procedures are carried out: The same procedure as in Example 1 was performed to obtain a film-like underfill material.

[Comparative example 3] In "Preparation of resin composition (varnish)", black dye is not used, and slurry silica (YA050C-MJM) as the inorganic filler (C) is replaced with slurry silica (methacrylic acid). Surface-treated silica; 5SM-CM2 (trade name), manufactured by Admatechs Co., Ltd., solid content 70% by mass, dispersion medium: MEK, average particle size: 500nm) 128.6 parts by mass (converted to 90 parts by mass based on non-volatile content) ), and in "Preparation of Film-like Underfill Material", except that the thickness of the resin composition layer was set to 38 μm, the same procedure as in Example 1 was performed to obtain a film-like underfill material.

[Comparative example 4] In "Preparation of resin composition (varnish)", no black dye is used, and the usage amount of slurry silica (YA050C-MJM) as the inorganic filler (C) is changed to 90 parts by mass (in terms of non-volatile Components converted to 45 parts by mass), then 64.3 parts by mass of slurry silica (methacrylic acid surface-treated silica; 5SM-CM2) (converted to 45 parts by mass as non-volatile components), and placed on the "film-like bottom" In "Preparation of Filling Material", except that the thickness of the resin composition layer was set to 35 μm, the same procedure as in Example 1 was performed to obtain a film-like underfill material.

<Evaluation> (1) Transmittance (Measurement of light transmittance at 600 nm) The film-like underfill material obtained in each Example and Comparative Example was cut into pieces with a width of 5 cm and a length of 5 cm to prepare a sample A. Use a spectrophotometer (SD6000 (trade name), manufactured by JASCO Co., Ltd.) to measure the light transmittance of sample A at 600 nm at room temperature, and determine the "light transmittance of the film-like underfill material at a wavelength of 600 nm" is T ⁰ . Similarly, the base film using each of the Examples and Comparative Examples was cut out with a width of 5 cm and a length of 5 cm to prepare a sample B. Use a spectrophotometer (SD6000 (trade name), manufactured by JASCO Corporation) to measure the light transmittance of sample B at 600 nm at room temperature, and let the "light transmittance of the base film at a wavelength of 600 nm" be T ¹ .

(The difference between the light transmittance of the underfill material and the light transmittance of the base film) Using each example and the comparative example, calculate the light transmittance [T ¹ ] of the base film at a wavelength of 600 nm and the light transmittance of the underfill material at a wavelength of 600 nm. The difference in light transmittance [T ⁰ ], and |T ¹ -T ⁰ |. In addition, values that do not reach 0 are still marked with a negative sign in the table, but these values are judged based on their absolute values.

(Calibration mark legibility) The film-like underfill material obtained in each Example and Comparative Example was attached to a semiconductor wafer mounting substrate (manufactured by WALTS Co., Ltd., WALTS-KIT CC80(W)-0105JY (trade name)) with calibration marks, and was removed from The resin composition layer peels off the base film, and uses a camera mounted on a flip-chip bonder (LFB-2301 (trade name), Shinkawa Co., Ltd.) to observe the calibration marks on the substrate from the resin composition layer side according to the following standards. The legibility of the calibration marks is evaluated. 〈Benchmark〉 A: Calibration marks are identifiable. C: Calibration marks cannot be recognized.

(NCF identifiability) The film-like underfill materials obtained in each of the Examples and Comparative Examples were visually observed to confirm whether the front or back side of the film-like underfill material was the resin composition layer (NCF), and the NCF visibility was evaluated based on the following criteria. 〈Benchmark〉 A: The resin composition layer (NCF) surface can be easily identified (less than 3 seconds). B: It takes more than 3 seconds to identify the resin composition layer (NCF) surface. C: It is difficult to identify the resin composition layer (NCF) surface.

(2) Storage stability of varnish The varnish (resin composition) obtained in each Example and Comparative Example was placed in a sealed container at 25° C. for 1 week, and then it was visually confirmed whether there was sedimentation at the bottom of the container. When sedimentation is observed, only the sedimentation is extracted and the mass of the sedimentation is measured. The sedimentation rate of the inorganic filler after one week is calculated using the following formula. The storage stability of the varnish is evaluated according to the following standards. Inorganic filler sedimentation rate = mass of sedimentation/inorganic filler non-volatile component blending amount × 100 〈Benchmark〉 A: When observed visually, sedimentation cannot be observed. B: The sedimentation can be confirmed visually, but the sedimentation rate of the inorganic filler material does not reach 5%. C: The sedimentation rate of inorganic filler is more than 5%.

[Table 1] [Industrial applicability]

Since the film-like underfill material of this embodiment has excellent workability and can be easily and accurately placed on an object such as a wafer, it can be ideally used as a semiconductor wafer provided with a resin composition layer or a semiconductor wafer provided with a resin composition layer. Materials for semiconductor wafer mounting substrates, semiconductor devices, and their manufacturing methods.

The disclosure content of Japanese Patent Application No. 2021-169233 filed on October 15, 2021 and the disclosure content of Japanese Patent Application No. 2022-26833 filed on February 24, 2022 are cited in their entirety. used as a reference in this manual. Furthermore, all documents, patent applications, and technical standards described in the specification are incorporated into this specification to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually described by reference. Reference.

Claims (23)

A film-like underfill material containing: A resin composition layer including a thermosetting resin (A) and a visible light absorber (B), and base film; The film-like underfill material has a light transmittance of 20~90% at a wavelength of 600nm, and The difference between the light transmittance of the base film at a wavelength of 600 nm and the light transmittance of the film-like underfill material at a wavelength of 600 nm is 2 to 80%. The film-like underfill material of claim 1, wherein the thickness of the resin composition layer is in the range of 5 to 500 μm. The film-like underfill material of claim 1 or 2, wherein the visible light absorber (B) is at least one selected from the group consisting of organic dyes, organic pigments, and combinations thereof. The film-like underfill material of claim 1 or 2, wherein the visible light absorber (B) includes a quinone series, an amino ketone series, a cationic series, a cyanine series, a phthalocyanine series, a quinacridone series, and a quinacridone series. Aryl/triarylmethane series, fulgide, azo series, squarylium series, oxonol series, benzylidene series, nitro series, nitroso series, thiazole At least one compound from the group consisting of indigoid series, indigo series, and combinations thereof. The film-like underfill material of claim 1 or 2, wherein the visible light absorber (B) contains at least one compound selected from the group consisting of quinones, aminoketones, and combinations thereof. The film-like underfill material of claim 1 or 2, wherein the thermosetting resin (A) contains at least one selected from the group consisting of maleimide compounds, citraconide imine compounds, and combinations thereof. 1 species. The film-like underfill material of claim 6, wherein the maleimide compound includes 2,2'-bis{4-(4-maleiminophenoxy)phenyl}propane, 1,2-bis(maleimino)ethane, 1,4-bis(maleimino)butane, 1,6-bis(maleimino)hexane, N, N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-phenyl maleimide, the following formula (3 ), a maleimide compound represented by the following formula (4), a bismaleimine compound containing a maleimide group at both ends, and a maleimide compound represented by the following formula (5) At least one of the group consisting of an imine compound, a maleimine compound represented by the following formula (6), a maleimine compound represented by the following formula (7), and a combination thereof; In formula (3), n3 represents an integer from 1 to 30; In the formula (4), R ¹¹ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkylene group having 2 to 16 carbon atoms; R ¹² represents a carbon number 1 ~16 linear or branched alkylene groups, or linear or branched alkenyl groups with 2 to 16 carbon atoms; R ¹³ each independently represents a hydrogen atom, or a linear or branched alkylene group with 1 to 16 carbon atoms Or a branched alkyl group, or a linear or branched alkenyl group with 2 to 16 carbon atoms; n ⁵ represents an integer from 1 to 10; In formula (5), R ₈ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ₉ each independently represents a hydrogen atom or a methyl group; In formula (6), R ¹⁰ each independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group; n4 represents an integer from 1 to 10; In formula (7), R ¹⁰ each independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more. The film-like underfill material of claim 7, wherein the maleimide compound includes 2,2'-bis{4-(4-maleiminophenoxy)phenyl}propane, The maleimide compound represented by the formula (3), a bismaleimine compound containing the structural unit represented by the formula (4) and maleimide groups at both ends, and the bismaleimine compound represented by the formula (5) At least one of the group consisting of a maleimine compound, a maleimine compound represented by the formula (6), a maleimine compound represented by the formula (7), and a combination thereof. For example, the film-like underfill material of claim 1 or 2 further contains an inorganic filler material (C). The film-like underfill material of claim 9, wherein the average particle size of the inorganic filler (C) is 400 nm or less. The film-like underfill material of claim 9, wherein the inorganic filler material (C) includes silicon dioxide, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, oxide, etc. At least one kind from the group consisting of magnesium, magnesium hydroxide, and combinations thereof. The film-like underfill material of claim 9, wherein the content of the inorganic filler (C) is 10 to 500 parts by mass relative to 100 parts by mass of the total amount of the thermosetting resin (A). The film-like underfill material of claim 9, wherein the average particle size of the inorganic filler (C) is 400 nm or less, The inorganic filler (C) includes at least one selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, magnesium hydroxide, and combinations thereof. 1 species, The content of the inorganic filler (C) is 10 to 500 parts by mass relative to 100 parts by mass of the total amount of the thermosetting resin (A). For example, the film-like underfill material of claim 1 or 2 further contains a flux activator (D). The film-like underfill material of Claim 14, wherein the flux activator (D) contains a rosin-based resin. For example, the film-like underfill material of claim 1 or 2 further contains a hardening catalyst (E). The film-like underfill material of claim 16, wherein the hardening catalyst (E) includes at least one selected from the group consisting of organic peroxides, imidazole compounds, and combinations thereof. For example, the film-like underfill material of claim 1 or 2 further contains a hardener (F). The film-like underfill material of claim 18, wherein the hardener (F) includes an amino tri-novolak resin. A resin composition for film-like underfill materials, containing: thermosetting resin (A), and Visible light absorber (B). A method of manufacturing a semiconductor wafer provided with a resin composition layer using the film-like underfill material according to any one of claims 1 to 19. A method of manufacturing a substrate for mounting a semiconductor chip provided with a resin composition layer, using the film-like underfill material according to any one of claims 1 to 19. A method of manufacturing a semiconductor device using the film-like underfill material according to any one of claims 1 to 19.