JP2018002948A - Resin composition, cured product, semiconductor device and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that makes it possible to obtain a cured product that can prevent light reflection while preventing light transmission.SOLUTION: A resin composition contains (a) a (meth) acrylic polymer, (b) a compound having a (meth) acryloyl group, (c) a polymerization initiator, and (d) a black colorant.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a cured product thereof, a semiconductor device using the resin composition, and a manufacturing method thereof.

  In recent years, with the spread of digital still cameras and camera-equipped mobile phones, solid-state imaging devices (solid-state imaging devices) have been reduced in power consumption and miniaturization. Conventional CCD (Charge Coupled Device) image sensors In addition, a CMOS (Complementary Metal Oxide Semiconductor, complementary metal oxide semiconductor) image sensor is used. These image sensors include a sensor unit (imaging pixel unit) in which a plurality of pixels are two-dimensionally arranged on one semiconductor chip, and a peripheral circuit unit arranged outside the sensor unit.

  As a structure of a CMOS image sensor, a “front surface irradiation type” structure and a “back surface irradiation type” structure are known (see, for example, Patent Document 1 below). In a front-illuminated CMOS image sensor, light incident from the outside passes through a glass substrate and a cavity (cavity), enters each microlens, is collected by the microlens, and then passes through a color filter layer and a wiring layer. Then, it enters the photodiode. Then, light incident on the photodiode is photoelectrically converted to generate a signal charge, and an electric signal is generated from the signal charge, whereby image data is acquired.

  On the other hand, in the back-illuminated CMOS image sensor, a photodiode is formed on one surface of a semiconductor substrate, and a color filter layer and a microlens are disposed on the one surface. A glass substrate is disposed above the microlens via an adhesive layer and a cavity. On the other hand, a wiring layer is disposed on the other surface of the semiconductor substrate. According to this back-illuminated structure, the light incident on the microlens is received by the light receiving unit without passing through the wiring layer, so that attenuation of light by the wiring layer is avoided and the light receiving sensitivity is increased.

  In addition, as a structure of the back-illuminated CMOS image sensor, an adhesive layer disposed on the outer peripheral side so as not to cover the microlens is surrounded by the adhesive layer on a silicon substrate including the microlens. A structure in which a glass substrate is arranged through a low refractive index layer filled in a cavity is known (for example, see Patent Document 1 below).

International Publication No. 2015/115537

  By the way, in a solid-state image sensor, when light reflection, light leakage, light omission, etc. occur around the sensor unit, the sensor unit detects unnecessary light, and problems such as image quality degradation and malfunction may occur. Such a problem is likely to occur as the solid-state imaging device becomes smaller or thinner. For this reason, it is required to suppress the sensor unit from detecting unnecessary light for a constituent material of a semiconductor device having a sensor unit such as a solid-state imaging device.

  This invention is made | formed in view of the said situation, and it aims at providing the resin composition which can obtain the hardened | cured material which can suppress light reflection, suppressing light transmission. Moreover, an object of this invention is to provide the hardened | cured material which can suppress light transmission and light reflection. Furthermore, an object of this invention is to provide the semiconductor device using the said resin composition, and its manufacturing method.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by a resin composition containing a specific component, and have completed the present invention.

  That is, the present invention contains (a) a (meth) acrylic polymer, (b) a compound having a (meth) acryloyl group, (c) a polymerization initiator, and (d) a black colorant. A resin composition is provided.

  According to the resin composition of the present invention, a cured product that can suppress light reflection while suppressing light transmission can be obtained. In this case, occurrence of problems due to light reflection, light leakage, light leakage, and the like can be suppressed, and the characteristics of the semiconductor device can be improved.

  Moreover, the resin composition which concerns on this invention can adjust a viscosity low, without containing an organic solvent. Therefore, the resin composition according to the present invention can be easily supplied (filled or the like) to a wide variety of places such as narrow gaps without using an organic solvent. Or even if it is a case where the application location of a resin composition narrows with thickness reduction, it can use suitably.

  The component (b) may contain a compound having at least two (meth) acryloyl groups in one molecule.

  The component (d) may contain at least one selected from the group consisting of black dyes and black pigments.

  Moreover, this invention provides the hardened | cured material of the resin composition mentioned above.

  Furthermore, this invention provides a semiconductor device provided with the resin part containing the resin composition mentioned above or its hardened | cured material.

  Furthermore, this invention provides the manufacturing method of a semiconductor device provided with the process of forming the resin composition part containing the resin composition mentioned above, and the process of hardening | curing the said resin composition part.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the hardened | cured material which can suppress light reflection, suppressing light transmission can be provided. Moreover, according to this invention, the hardened | cured material which can suppress light transmission and light reflection can be provided. For example, according to the present invention, light reflection can be suppressed while suppressing light transmission with respect to visible light having a wavelength of at least 400 nm (for example, a wavelength of 350 to 750 nm). Furthermore, according to this invention, the semiconductor device using the said resin composition and its manufacturing method can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, use of the resin composition for a semiconductor device or its manufacture can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the resin composition for an optical component or its manufacture can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the resin composition for a solid-state image sensor or its manufacture can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the hardened | cured material of the resin composition to a semiconductor device can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the hardened | cured material of the resin composition for an optical component can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the hardened | cured material of the resin composition for a solid-state image sensor can be provided.

  Hereinafter, although embodiment of this invention is described, this invention is not limited to these embodiment at all.

  In the present specification, “(meth) acryloyl group” means at least one of “acryloyl group” and “methacryloyl group” corresponding thereto. The same applies to other similar expressions such as “(meth) acrylate”.

  In this specification, the numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. The terms “layer” and “film” include not only a structure formed on the entire surface but also a structure formed on a part when observed as a plan view. The term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. “A or B” only needs to include either A or B, and may include both. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.

<Resin composition and cured product>
The resin composition according to the present embodiment includes (a) (meth) acrylic polymer (hereinafter sometimes referred to as “(a) component”) and (b) a compound having a (meth) acryloyl group (hereinafter, depending on circumstances). "(B) component"), (c) polymerization initiator (hereinafter sometimes referred to as "(c) component"), and (d) black colorant (hereinafter sometimes referred to as "(d) component"). And containing. The resin composition which concerns on this embodiment can exhibit black by containing (d) component. The cured product according to the present embodiment is a cured product of the resin composition according to the present embodiment.

  The resin composition according to this embodiment may be liquid (varnish-like) or film-like. The resin composition according to the present embodiment is a curable resin composition (for example, a thermosetting resin composition and a photocurable resin composition). The resin composition according to the present embodiment can be used as an adhesive composition, and for example, can be used as an adhesive composition for a semiconductor device.

((A) (meth) acrylic polymer)
The “(meth) acrylic polymer” is a polymer having a structural unit derived from a monomer having a (meth) acryloyl group ((meth) acrylic monomer), for example, one (meth) acryloyl group. A polymer (homopolymer) having a structure obtained by polymerizing a (meth) acrylic monomer having one kind, and a structure obtained by copolymerizing two or more kinds of the (meth) acrylic monomers in combination And a polymer (copolymer) having a structure obtained by copolymerizing the (meth) acrylic monomer and another monomer. The monomer copolymerizable with the (meth) acrylic monomer includes a compound having at least two (meth) acryloyl groups in one molecule; one polymerizable unsaturated bond, and (meth ) A polymerizable compound having no acryloyl group (for example, (meth) acrylonitrile, styrene, vinyl acetate and alkene (ethylene, propylene, etc.)); having at least two polymerizable unsaturated bonds in one molecule; and And polymerizable compounds having no (meth) acryloyl group (such as divinylbenzene).

  The component (a) preferably has a functional group, for example, preferably has a structural unit having a functional group. In these cases, excellent stress relaxation, reflow peel resistance, crack resistance, adhesion and heat resistance associated with a low elastic modulus can be easily expressed. As the functional group, at least one selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an amide group, a phosphoric acid group, a cyano group, a maleimide group, and an epoxy group can be used. As the functional group, an epoxy group is preferable. When the component (a) has an epoxy group, adhesion to an inorganic material member such as metal or glass can be improved.

  The method for introducing the functional group into the (meth) acrylic polymer is not particularly limited. Random polymerization of functional group-containing monomers having functional groups by existing methods such as suspension polymerization (also called bead polymerization, granular polymerization, pearl polymerization, etc.), solution polymerization, bulk polymerization, precipitation polymerization, emulsion polymerization, etc. Thus, a functional group can be introduced into the (meth) acrylic polymer.

  The functional group-containing monomer is at least one selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an amide group, a phosphoric acid group, a cyano group, a maleimide group, and an epoxy group in one molecule. It is preferable to have at least one polymerizable carbon-carbon double bond.

  The functional group is an amino group, an amide group, a phosphate group, a cyano group, from the viewpoint of easily avoiding problems such as gelation in a varnish state, nozzles during use, that is, pinhole generation during spin coating, and the like. It is preferably at least one selected from the group consisting of a maleimide group and an epoxy group. The functional group is preferably at least one selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, a phosphoric acid group, and an epoxy group from the viewpoint of preventing coloring of the resin portion to a higher degree. . Furthermore, from both these viewpoints, the functional group is preferably at least one selected from the group consisting of a phosphate group and an epoxy group, and more preferably an epoxy group. The resin part is, for example, a resin composition in a state before mixing a black colorant or a resin existing position in a cured product thereof, or a resin composition after mixing a black pigment or a cured product thereof in black. It refers to the location of the resin where no pigment is present.

  As functional group-containing monomers, carboxyl group-containing monomers such as (meth) acrylic acid and itaconic acid; acid anhydride group-containing monomers such as maleic anhydride; (meth) acrylic acid-2-hydroxymethyl Hydroxyl group-containing simple substances such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene Monomers; amino group-containing monomers such as diethylaminoethyl (meth) acrylate; phosphate group-containing monomers such as 2- (meth) acryloyloxyethyl acid phosphate; vinyl cyanide compounds such as (meth) acrylonitrile N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Ni-propylmale N-substituted maleimides such as amide, N-butylmaleimide, Ni-butylmaleimide, Nt-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide; ) Glycidyl acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) Acrylic acid-6,7-epoxyheptyl, (meth) acrylic acid-3-methyl-3,4-epoxybutyl, (meth) acrylic acid-4-methyl-4,5-epoxypentyl, (meth) acrylic acid- 5-methyl-5,6-epoxyhexyl, (meth) acrylic acid-β-methylglycidyl, α-ethyl acetate Epoxy group-containing monomers such as crylic acid-β-methylglycidyl can be used. A functional group containing monomer can be used individually by 1 type or in combination of 2 or more types.

  Among these, it is particularly preferable to use an epoxy group-containing monomer such as glycidyl (meth) acrylate. Furthermore, the (meth) acrylic polymer (for example, glycidyl group-containing (meth) acrylic polymer) obtained by using such a monomer is compatible with the (meth) acrylic monomer or oligomer. Is preferred. The glycidyl group-containing (meth) acrylic polymer may be synthesized by a conventional method, or a commercially available product may be obtained. As a commercial item, HTR-860P-3 (Nagase ChemteX Corporation, a brand name) etc. are mentioned. Such a (meth) acrylic polymer is preferable from the viewpoint of further exhibiting excellent crack resistance, adhesion, and heat resistance, and from the viewpoint of easily ensuring excellent storage stability.

Examples of monomers other than the functional group-containing monomer that can be used when the component (a) is synthesized include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, I-propyl (meth) acrylate, butyl (meth) acrylate (n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate), pentyl (meth) acrylate N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, butoxyethyl (meth) acrylate, (Meth) acrylic such as isostearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, etc. Acid esters; methylstyrene (eg, α-methylstyrene), ethylstyrene (eg, α-ethylstyrene), fluorostyrene (eg, α-fluorostyrene), chlorostyrene (eg, α-chlorostyrene), bromostyrene (eg, α- Aromatic vinyl compounds such as bromostyrene), methoxystyrene, styrene; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, trimethylhexyl (meth) acrylate, (meth) acrylic acid Norbornyl, norbornyl methyl (meth) acrylate, phenyl norbornyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, (Meta Adamantyl acrylate, (meth) acrylic acid tricyclo [5.2.1.0 ^{2, 6]} dec-8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ^{2, 6]} deca-4 Examples thereof include alicyclic monomers such as methyl and cyclodecyl (meth) acrylate. Monomers other than the functional group-containing monomer can be used singly or in combination of two or more.

  Among these, (meth) acrylic acid esters are preferable from the viewpoint of easily synthesizing a (meth) acrylic polymer (for example, a (meth) acrylic polymer having a weight average molecular weight of 100,000 or more) without gelation. Among (meth) acrylic acid esters, from the viewpoint of excellent copolymerizability with a functional group-containing monomer, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate More preferred is at least one selected from the group consisting of

  The component (a) preferably has at least one selected from the group consisting of an alicyclic structure and a heterocyclic structure, and more preferably has an alicyclic structure. For example, the component (a) preferably has a structural unit having at least one selected from the group consisting of an alicyclic structure and a heterocyclic structure, and more preferably has a structural unit having an alicyclic structure. . When the component (a) has an alicyclic structure, the amorphous component in the (meth) acrylic polymer increases, so when compared with an aliphatic structure having the same carbon number (such as an aliphatic structural unit), The glass transition temperature (Tg) tends to improve and the heat resistance tends to increase. Examples of the monomer having an alicyclic structure or a heterocyclic structure used in producing a (meth) acrylic polymer having a structural unit having an alicyclic structure or a heterocyclic structure include, for example, the following general The compound represented by Formula (1) is mentioned.

［式（１）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は脂環基又は複素環基を示し、Ｘは炭素数１〜６のアルキレン基を示し、ｎは０〜１０の整数を示す。ｎが２以上の整数であるとき、複数存在するＸは互いに同一であっても異なっていてもよい。ここで「脂環基」とは、炭素原子が環状に結合した構造を有する基であり、「複素環基」とは、炭素原子及び１以上のヘテロ原子が環状に結合した構造を有する基である。］

[In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alicyclic group or a heterocyclic group, X represents an alkylene group having 1 to 6 carbon atoms, and n represents 0 to 10 Indicates an integer. When n is an integer of 2 or more, a plurality of Xs may be the same or different from each other. Here, the “alicyclic group” is a group having a structure in which carbon atoms are bonded cyclically, and the “heterocyclic group” is a group having a structure in which a carbon atom and one or more heteroatoms are bonded cyclically. is there. ]

［式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０はそれぞれ独立に、水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^１１は水素原子、炭素数１〜４のアルキル基、又は、ＯＲ^１１ａで示される構造を示し、Ｒ^１１ａは水素原子又は炭素数１〜８のアルキル基を示す。］ Examples of R ² include groups represented by the following formulas (2a) to (2h).

[Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹¹ represents hydrogen. atom, an alkyl group having 1 to 4 carbon atoms, or ^represents a structure represented by ^{oR 11a, R 11a} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

Examples of the compound represented by the formula (1) include cyclohexyl (meth) acrylate (also known as cyclohexyl (meth) acrylate), isobornyl (meth) acrylate (also known as isobornyl (meth) acrylate), and (meth) ) Acrylic acid tricyclo [5.2.1.0 ^2,6 ] dec-8-yl (also known as: tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate).

  The component (a) is composed of a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (II), and a structural unit represented by the following general formula (III). You may have at least 1 sort chosen.

［式（Ｉ）中、Ｒ^１ａは、水素原子又はメチル基を示し、Ｘ^ａは、エポキシ基を含む基を示す。］

[In Formula (I), R ^1a represents a hydrogen atom or a methyl group, and X ^a represents a group containing an epoxy group. ]

［式（ＩＩ）中、Ｒ^２ａは、水素原子又はメチル基を示し、Ｙ^ａは、置換基を有していてもよい炭素数５〜２２の脂環基（式（Ｉ）のＸに該当する基を除く）を示す。］

[In Formula (II), R ^2a represents a hydrogen atom or a methyl group, and Y ^a represents an alicyclic group having 5 to 22 carbon atoms which may have a substituent (corresponding to X in Formula (I) The group to be excluded). ]

［式（ＩＩＩ）中、Ｒ^３ａは、水素原子又はメチル基を示し、Ｚ^ａは、置換基を有していてもよい炭素数１〜１０の直鎖又は分岐アルキル基（式（Ｉ）のＸに該当する基を除く）を示す。］

Wherein ^{(III), R 3a} represents a hydrogen atom or a methyl group, ^{Z a} represents a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent (Formula (I) The group corresponding to X is excluded). ]

  (A) A component can be used individually by 1 type or in combination of 2 or more types.

  The weight average molecular weight of the component (a) is appropriate for strength, flexibility and tackiness in the case of a film, and from the viewpoint of easily obtaining a suitable viscosity when used as a gap filling material, A range is preferred. The weight average molecular weight of the component (a) is preferably 50,000 or more, more preferably 80,000 or more, further preferably 100,000 or more, particularly preferably 150,000 or more, and extremely preferably 180,000 or more. The weight average molecular weight of the component (a) is preferably 450,000 or less, more preferably 400,000 or less, still more preferably 350,000 or less, and particularly preferably 300,000 or less.

The weight average molecular weight can be obtained by conversion from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve can be obtained by approximating with a cubic equation using a standard polystyrene kit PStQuick series C (Tosoh Corporation, trade name). The GPC conditions are, for example, as follows.
Pump: L6000 Pump (Hitachi, Ltd.)
Detector: L3300 RI Monitor (Hitachi, Ltd.)
Column: Gelpack GL-S300MDT-5 (two in total) (Hitachi Chemical Co., Ltd., trade name)
Column size: Diameter 8mm x 300mm
Eluent: DMF / THF (mass ratio 1/1) + LiBr · H ₂ O 0.03 mol / L + H ₃ PO ₄ 0.06 mol / L
Sample concentration: 0.1% by mass
Flow rate: 1 mL / min
Measurement temperature: 40 ° C

  The content of the component (a) shows a good storage elastic modulus, can ensure flowability during molding, and can be sufficiently obtained at high temperatures, so that the total amount of the component (b) is 100 mass. The following ranges are preferred for parts. 10 mass parts or more are preferable and, as for content of (a) component, 15 mass parts or more are more preferable. Moreover, since it becomes a suitable viscosity range when using as a space | gap filling material, 20 mass parts or more are more preferable, and 25 mass parts or more are especially preferable. 400 mass parts or less are preferable and, as for content of (a) component, 350 mass parts or less are more preferable. Moreover, since it becomes a suitable viscosity range when using as a space | gap filling material, 300 mass parts or less are further more preferable, 200 mass parts or less are especially preferable, 150 mass parts or less are very preferable, and 100 mass parts or less are very preferable. 50 parts by mass or less is even more preferable. From these viewpoints, the content of the component (a) is preferably 10 to 400 parts by mass, more preferably 15 to 350 parts by mass, still more preferably 20 to 300 parts by mass, and particularly preferably 25 to 200 parts by mass. -150 mass parts is very preferable, 25-100 mass parts is very preferable, and 25-50 mass parts is still more preferable.

((B) Compound having (meth) acryloyl group)
Examples of the compound having a (meth) acryloyl group include (meth) acrylic monomers and oligomers thereof (excluding compounds corresponding to the component (a)). Examples of the compound having a (meth) acryloyl group include a compound having one (meth) acryloyl group, a compound having at least two (meth) acryloyl groups in one molecule, and the like. The molecular weight of the component (b) may be, for example, 1000 or less, 800 or less, or 400 or less.

  By using a (meth) acrylic polymer and a compound having at least two (meth) acryloyl groups in one molecule, it is possible to sufficiently suppress a decrease in heat resistance. This is considered to be because heat resistance can be improved by forming a three-dimensional cross-linking with a compound having at least two (meth) acryloyl groups in one molecule.

  In the resin composition according to the present embodiment, since the compatibility between the (meth) acrylic polymer and the compound having at least two (meth) acryloyl groups in one molecule is high, it is compatible in a varnish state or a semi-cured state. Separation is unlikely to occur and storage stability is excellent. Further, even when the phase separation occurs due to the heat of curing after the radical curing, only the micro phase separation is achieved, and variations in the cured product characteristics such as the adhesive strength can be suppressed.

  Examples of the compound having one (meth) acryloyl group include monofunctional (meth) acrylic monomers (monomers having one (meth) acryloyl group). Examples of the compound having at least two (meth) acryloyl groups in one molecule include polyfunctional (meth) acrylic monomers (monomers having at least two (meth) acryloyl groups in one molecule). It is done. “Polyfunctional” refers to a (meth) acryloyl group and means that the compound has at least two (meth) acryloyl groups.

  Examples of the monofunctional (meth) acrylic monomer include the (meth) acrylic monomer exemplified by the component (a) (such as glycidyl (meth) acrylate).

  As a polyfunctional (meth) acrylic monomer, (meth) acrylic monomer having two (meth) acryloyl groups in one molecule, and having three or more (meth) acryloyl groups in one molecule (meta ) Acrylic monomer and the like.

  The polyfunctional (meth) acrylic monomer includes a polyfunctional (meth) acrylic monomer having an alicyclic structure, a polyfunctional (meth) acrylic monomer having an aliphatic structure, and a polyfunctional having a dioxane glycol structure. Examples thereof include (meth) acrylic monomers and polyfunctional (meth) acrylic monomers having functional groups (excluding (meth) acryloyl groups). As the polyfunctional (meth) acrylic monomer having a functional group, a polyfunctional (meth) acrylic monomer having an alicyclic structure, an aliphatic structure or a dioxane glycol structure is excluded.

  Examples of the (meth) acrylic monomer having two (meth) acryloyl groups in one molecule include cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, and tricyclode Candimethylol di (meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-684, tricyclodecane dimethylol diacrylate), tricyclodecane dimethanol di (meth) acrylate (for example, Shin-Nakamura Chemical Co., Ltd., A-DCP, tricyclodecane dimethanol diacrylate), dioxane glycol di (meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-604, dioxane glycol diacrylate; Shin-Nakamura Chemical Co., Ltd., A-DOG, Dioqui Sun glycol diacrylate), nonanediol di (meth) acrylate (for example, Hitachi Chemical Co., Ltd., FA-129AS), neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, ethylene oxide modified 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (poly) ethylene oxide modified neopentyl glycol di (meth) acrylate, hydroxypivalate neo Pentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate Preferably polyethylene oxide modified bisphenol A type di (meth) acrylate, more preferably 5 to 15 mol ethylene oxide modified bisphenol A type di (meth) acrylate), (poly) ethylene oxide modified phosphoric acid di (meth) acrylate, etc. be able to.

  Among the above, from the viewpoint of further improving the transparency of the resin part in the resin composition or cured product, from dioxane glycol di (meth) acrylate, nonanediol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate. At least one selected from the group consisting of dioxane glycol diacrylate, nonanediol diacrylate and tricyclodecane dimethanol diacrylate is more preferable.

  Examples of other polyfunctional (meth) acrylic monomers include three (meth) acryloyl groups in one molecule, such as pentaerythritol tri (meth) acrylate and ethylene oxide-modified isocyanuric acid tri (meth) acrylate. The (meth) acryl monomer which it has can be mentioned.

  The component (b) is a polyfunctional (meth) acrylic monomer having an alicyclic structure and a polyfunctional having a dioxane glycol structure from the viewpoint of further improving the transparency of the resin part in the resin composition or cured product. At least one selected from the group consisting of (meth) acrylic monomers is preferred. The component (b) is preferably a polyfunctional (meth) acrylic monomer having an aliphatic structure from the viewpoint of easily preventing cracks in the cured product and peeling from the substrate. The base material refers to a member to which the resin composition according to the present embodiment can be applied, such as a semiconductor element.

  (B) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (b) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 70 parts by mass or more, with respect to 100 parts by mass of the total amount of the components (a) and (b). 80 parts by mass or more is particularly preferable. The content of the component (b) is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 85 parts by mass or less, with respect to 100 parts by mass of the total amount of the components (a) and (b). 83 parts by mass or less is particularly preferable. The content of the component (b) is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, and 70 to 85 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferred is 80 to 83 parts by mass. When the content of the component (b) is within the above ranges, three-dimensional crosslinking is easily performed, and thus heat resistance tends to be further improved. Even if phase separation occurs after curing, the phase separation range can be kept on a microscale. Therefore, variations in cured product characteristics such as adhesive strength can be easily suppressed, and warpage or cracks in the manufacturing process of a semiconductor or electronic component can be easily suppressed.

((C) polymerization initiator)
Examples of the (c) polymerization initiator include (c1) a thermal polymerization initiator (hereinafter, sometimes referred to as “(c1) component”) and / or (c2) a photopolymerization initiator (hereinafter, sometimes referred to as “(c2)”. Component)).

  As the component (c1), t-hexyl peroxypivalate (for example, perhexyl PV, trade name: 1 hour half-life temperature 71.3 ° C., 10 hour half-life temperature 53.2 ° C.), dilauroyl peroxide (for example, , Perhexyl L, trade name: 1 hour half-life temperature 79.3 ° C., 10 hour half-life temperature 61.6 ° C.), di (3,5,5-trimethylhexanoyl), peroxide (eg, paroyl 355, product) Name: 1 hour half-life temperature 76.8 ° C., 10 hour half-life temperature 59.4 ° C., 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (for example, Perocta O, commercial product) Name: 1 hour half-life temperature 84.4 ° C., 10 hour half-life temperature 65.3 ° C., t-butyl peroxy-2-ethylhexanoate (eg, perbutyl O, trade name: 1 hour) Half-life temperature 92.1 ° C, 10-hour half-life temperature 72.1 ° C), benzoyl peroxide (for example, Nyper BW, trade name: 1-hour half-life temperature 92.0 ° C, 10-hour half-life temperature 73.6 ° C) ), 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane (for example, Perhexa TMH, trade name: 1 hour half-life temperature 106.4 ° C., 10 hour half-life temperature 86.7) ° C), 1,1-di (t-hexylperoxy) cyclohexane (for example, perhexa HC, trade name: 1 hour half-life temperature 107.3 ° C, 10 hour half-life temperature 87.1 ° C), t-hexylper Oxyisopropyl monocarbonate (for example, perhexyl I, trade name: 1 hour half-life temperature 114.6 ° C., 10 hour half-life temperature 95.0 ° C.), t-butyl peroxyisopropyl Monocarbonate (for example, perbutyl I, trade name: 1 hour half-life temperature 118.4 ° C., 10 hour half-life temperature 98.7 ° C.), dicumyl peroxide (eg, park mill D, trade name: 1 hour half-life) Temperature 135.7 ° C., 10 hour half-life temperature 116.4 ° C.), n-butyl 4,4-bis (t-butylperoxy) valerate (eg, Perhexa V, trade name: 1 hour half-life temperature 126.5) , 10 hour half-life temperature 104.5 ° C.), etc .; 2,2′-azobisisobutyronitrile, 1,1 ′-(cyclohexane-1,1-carbonitrile) -2,2 Examples include azo compounds such as' -azobis (2-cyclopropylpropionitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile). The exemplified commercial products can be obtained from NOF Corporation.

  (C1) A component can be used individually by 1 type or in combination of 2 or more types.

  Among the components (c1), an organic peroxide is preferable from the viewpoint of the effect of improving the cured product characteristics, and a good balance between the handleability (shelf life, pot life, etc.) of the resin composition and curability is maintained. From the viewpoint, an organic peroxide having a 10-hour half-life temperature of 90 to 150 ° C. is more preferable.

  The half-life temperature of the organic peroxide is measured as follows.

An organic peroxide solution adjusted to 0.1 mol / L using benzene as a solvent is sealed in a glass tube subjected to nitrogen substitution. This is immersed in a thermostat set at a predetermined temperature and thermally decomposed. In general, the decomposition of an organic peroxide in a dilute solution can be treated approximately as a first order reaction. Therefore, the decomposition amount of the organic peroxide is x (mol / L), and the decomposition rate constant is k (1 / h). ) And t (h), and the initial concentration of organic peroxide is a (mol / L), the following formulas (A) and (B) are established.
dx / dt = k (ax) (A)
ln {a / (ax)} = kt (B)

Since the half-life is the time until the concentration of the organic peroxide is reduced to half of the initial value due to decomposition, if the half-life is represented by t _1/2 and a / 2 is substituted for x in the formula (B), The following formula (C) is obtained. Therefore, the temperature is decomposed at a certain temperature, the relationship between time t and ln {a / (ax)} is plotted, and k is obtained from the slope of the obtained straight line. The half-life (t _1/2 ) can be determined.
kt _1/2 = ln2 (C)

On the other hand, regarding the decomposition rate constant k, the frequency factor is A (1 / h), the activation energy is E (J / mol), the gas constant is R (8.314 J / mol · K), and the absolute temperature is T (K ), The following equation (D) is established.
lnk = lnA−ΔE / RT (D)

When k is eliminated from the equations (C) and (D), the following equation (E) is obtained. Therefore, t _1/2 is obtained for several temperatures, the relationship between ln (t _1/2 ) and 1 / T is plotted, and the temperature at t _1/2 = 1 h (1 hour half-life) is obtained from the obtained straight line. Temperature). The 10-hour half-life temperature can also be obtained by determining the temperature when t _1/2 = 10 h.
ln (t _1/2 ) = ΔE / RT−ln (A / 2) (E)

  Among the components (c1) mentioned above, as the organic peroxide, dicumyl peroxide (for example, park mill D) and n-butyl 4,4- are used from the viewpoint of excellent storage stability and thermosetting. At least one selected from the group consisting of bis (t-butylperoxy) valerate (for example, perhexa V) is preferable.

  The component (c1) improves the reliability of the semiconductor device (optical component etc.) by exhibiting further excellent heat resistance, peeling resistance and stress relaxation in combination with the component (a) and the component (b). Can do.

  The content of the component (c1) is preferably in the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (b) from the viewpoint of easily suppressing the generation of outgas. The content of the component (c1) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more. The content of the component (c1) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less, and extremely preferably 3 parts by mass or less. The content of the component (c1) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, still more preferably 0.5 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. 1 to 3 parts by mass is preferable.

  As component (c2), acylphosphine oxide, oxime esters, aromatic ketones, quinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives, coumarin compounds, N-phenylglycine, N-phenylglycine derivatives and the like can be mentioned. (C2) A component may be synthesize | combined by a conventional method and a commercially available thing may be obtained.

  Among these, at least one selected from the group consisting of acylphosphine oxides and oxime esters is preferable from the viewpoint of improving photocurability and increasing sensitivity.

  (C2) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (c2) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). 75-5 mass parts is still more preferable. When the content of the component (c2) is within these ranges, foaming, turbidity, and cracks of the cured product can be further prevented.

((D) Black colorant)
The black colorant is a colorant that exhibits a black color when dissolved or dispersed in the resin composition. The black colorant can include at least one selected from the group consisting of black dyes and black pigments.

  Examples of the black dye include ionic compounds such as metal complex dyes.

  Examples of black pigments include colored resins and carbon materials. Examples of the colored resin include an acrylic resin. As the black pigment, colored resin beads, carbon filler, and the like can be used. Examples of the colored resin beads include acrylic beads. Examples of the shape of the black pigment include a spherical shape and a flake shape.

  The particle diameter of the black pigment is good in dispersibility of the black pigment in the resin composition, from the viewpoint of easily reducing the light transmittance, and from the viewpoint of easily obtaining a suitable viscosity when used as a void filling material, 1 μm or more is preferable, 2 μm or more is more preferable, and 3 μm or more is even more preferable. From the same viewpoint, the particle diameter of the black pigment is preferably 15 μm or less, more preferably 13 μm or less, still more preferably 10 μm or less, and particularly preferably 8 μm or less.

  The particle diameter of the black pigment can be measured, for example, as follows. First, the resin composition is diluted (or dissolved) 1000 times (volume ratio) with a solvent (such as methyl ethyl ketone). Then, using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter, Inc.), the particles dispersed in the resin composition with a refractive index of 1.38 are measured according to the international standard ISO 13321. The particle diameter is obtained at an integrated value of 50% (volume basis) in the particle size distribution.

  The content of the component (d) is preferably 1 part by mass or more from the viewpoint of easily obtaining a suitable viscosity when used as a gap filling material with respect to 100 parts by mass of the total amount of the components (a) and (b). 3 parts by mass or more is more preferable, 5 parts by mass or more is more preferable, and 10 parts by mass or more is particularly preferable, and 15 parts by mass or more is preferable from the viewpoint of easily reducing the light transmittance because the resin composition is easily blackened. It is very preferable, and 20 parts by mass or more is very preferable. The content of the component (d) is 70 parts by mass from the viewpoint of easily reducing the light transmittance due to the resin composition being easily blackened with respect to the total amount of the component (a) and the component (b) being 100 parts by mass. The following is preferable, 60 parts by mass or less is more preferable, 50 parts by mass or less is further preferable, 40 parts by mass or less is particularly preferable, and 35 parts by mass or less is preferable from the viewpoint of easily obtaining a suitable viscosity when used as a gap filling material. Extremely preferred, 30 parts by weight or less is very preferred. From these viewpoints, the content of the component (d) is preferably 1 to 70 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b).

(Antioxidant)
The resin composition according to the present embodiment can contain an antioxidant as necessary. Examples of the antioxidant include phenolic antioxidants, thioether antioxidants, and thiol antioxidants. Antioxidant can be used individually by 1 type or in combination of 2 or more types.

  Examples of phenolic antioxidants include hindered phenolic compounds. Examples of hindered phenol compounds include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoate] (for example, “IRGANOX1010” (BASF)), bis (3-tert- Butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylenebis (oxyethylene) (for example, “IRGANOX245” (BASF)), 4-[[4,6-bis (octylthio) -1,3,5- Triazin-2-yl] amino] -2,6-di-tert-butylphenol (eg, “IRGANOX565” (BASF)), 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid Octadecyl (for example, “IRGANOX1076” (BASF)), N N ′-(1,6-hexanediyl) bis [3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanamide] (for example, “IRGANOX1098” (BASF)), tris (4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid (for example, “CYANOX1790” (American Cyanamide)), 6-tert-butyl-4- [3-[(2,4,8,10 -Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl) oxy] propyl] -2-methylphenol (for example, “Sumilyzer GP” (Sumitomo Chemical Co., Ltd.) )), 3,9-bis [1,1-di-methyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propiyl Onyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (for example, “Adekastab AO-80” (ADEKA)), 2,2′-methylenebis- (4-ethyl- 6-t-butylphenol) (for example, “Yoshinox 425” (API Corporation)) and the like.

  Examples of the thioether-based antioxidant include ditridecyl 3,3-thiobispropionate (for example, “ADEKA STAB AO-503” (ADEKA)). Examples of the thiol-based antioxidant include compounds having a thiol group. Examples of the compound having a thiol group include 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (for example, “Karenz MT-NR1” (Kyoeisha Chemical Co., Ltd.)) and the like.

  The content of the antioxidant is preferably in the following range with respect to 100 parts by mass of the total amount of the component (a), the component (b), and the component (c) from the viewpoint of hardly adversely affecting the radical polymerization reactivity. The content of the antioxidant is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more. 10 mass parts or less are preferable, as for content of antioxidant, 8 mass parts or less are more preferable, 5 mass parts or less are still more preferable, and 4 mass parts or less are especially preferable. From these viewpoints, the content of the antioxidant is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, still more preferably 1 to 5 parts by mass, and particularly preferably 3 to 4 parts by mass. preferable.

(Coupling agent)
The resin composition according to the present embodiment can contain a coupling agent. The coupling agent is not particularly limited, and various coupling agents such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, and a zircoaluminate coupling agent are used. be able to. A coupling agent can be used individually by 1 type or in combination of 2 or more types.

  Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl-tris (2-methoxyethoxy) ) Silane, γ-methacryloxypropyltrimethoxysilane (also known as: 3- (trimethoxysilyl) propyl methacrylate), γ-methacryloxypropylmethyldimethoxysilane, methyltri (methacryloxyethoxy) silane, γ-acryloxypropyltrimethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ Aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxy Silane, 3- (4,5-dihydroimidazolyl) propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldi Ethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, methyltriglycidoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysila , Trimethylsilyl isocyanate, dimethylsilyl isocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, methyl triisocyanate, vinylsilyl triisocyanate, and ethoxysilane triisocyanate and the like.

  Titanate coupling agents include isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, Isopropyldimethacrylisostearoyl titanate, isopropyl (dioctyl phosphate) titanate DOO, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxy aluminum diisopropionate.

  Examples of the zirconate coupling agent include tetrapropyl zirconate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate acetylacetone zirconium butyrate, and zirconium stearate butyrate.

  Among these coupling agents, a silane coupling agent is preferable from the viewpoint of high effect of improving the bonding or wettability at the interface between materials.

  The content of the coupling agent is preferably in the following range with respect to 100 parts by mass of the total amount of the components (a), (b) and (c). The content of the coupling agent is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more from the viewpoint that the effect of improving the adhesive strength tends to be obtained. preferable. The content of the coupling agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and more preferably 10 parts by mass from the viewpoint that the volatile content is small and generation of voids in the cured product tends to be easily suppressed. The following is more preferable, 5 parts by mass or less is particularly preferable, 3 parts by mass or less is extremely preferable, and 1 part by mass or less is very preferable. From these viewpoints, the content of the coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, still more preferably 0.8 to 10 parts by mass, and 0.8 to 5 parts. Part by mass is particularly preferred, 0.8 to 3 parts by mass is very particularly preferred, and 0.8 to 1 part by mass is very particularly preferred.

(Other ingredients)
The resin composition according to the present embodiment includes, if necessary, a filler (excluding a filler corresponding to a black colorant); a leveling agent; an epoxy curing agent; an epoxy curing accelerator; Surfactants, wetting improvers such as higher fatty acids; antifoaming agents such as silicone oils; ion trapping agents such as inorganic ion exchangers; refractive index adjusting agents or light absorbers (UV absorbers, IR absorbers, etc.) Can be contained. These can be used alone or in combination of two or more.

Although the resin composition which concerns on this embodiment can contain an organic solvent as needed, it does not need to contain the organic solvent substantially. Here, “substantially does not contain an organic solvent” means that an organic solvent is not intentionally added, so long as it does not significantly reduce the properties after curing of the resin composition according to the present embodiment, A trace amount of organic solvent may be present. Specifically, the content of the organic solvent in the resin composition is preferably 1.0 × 10 ³ ppm or less, more preferably 5.0 × 10 ² ppm or less, based on the total amount of the resin composition. 0.0 × 10 ² ppm or less is more preferable, and it is particularly preferable that no organic solvent is contained. The organic solvent in the present embodiment refers to a component that does not have a reactive structural unit and volatilizes from the resin composition by heating.

(viscosity)
The viscosity at 25 ° C. of the resin composition according to the present embodiment is 15000 cP or less from the viewpoint of easily supplying a resin composition colored with a black colorant (black dye, black pigment, etc.) in a narrow portion. Preferably, it is 10000 cP or less, more preferably 5000 cP or less, and particularly preferably 3000 cP or less. The viscosity at 25 ° C. of the resin composition according to the present embodiment is preferably 100 cP or more, more preferably 300 cP or more, and even more preferably 500 cP or more from the viewpoint of favorably dispersing the black pigment when using a black pigment as a black colorant. Preferably, 800 cP or more is particularly preferable. The viscosity can be measured using, for example, a cone plate viscometer (BROOKFIELD, trade name: HB DV-III).

<Semiconductor device and manufacturing method thereof>
The semiconductor device according to the present embodiment includes a resin portion including the resin composition according to the present embodiment or a cured product thereof. Examples of the semiconductor device include an optical component. Examples of the optical component include an optical device such as a solid-state image sensor. Examples of the solid-state imaging device include a CCD image sensor and a CMOS image sensor.

  The method for manufacturing a semiconductor device according to the present embodiment includes a resin supply step of forming a resin composition part (resin part) including the resin composition according to the present embodiment, and curing the resin composition part. A curing step for obtaining a cured resin part (resin part) may be further provided. The resin part may be a resin composition part or a resin cured product part. The resin portion may be supplied (filled or the like) to a space sandwiched between the constituent members of the semiconductor device, or may be formed in a layered manner on the semiconductor substrate.

  In the resin supply step, the resin composition part can be obtained by supplying the resin composition to the application site. Examples of a method for supplying the resin composition include a dispensing method (syringe dispensing method and the like), a spin coating method, a die coating method, and a knife coating method.

  In the curing step, the cured resin part (resin part) can be obtained by thermosetting or photocuring the resin composition part. The thermosetting temperature is, for example, 100 to 200 ° C.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

<Preparation of resin composition>
The components of Tables 1 to 4 were mixed to obtain resin compositions of Examples and Comparative Examples. The unit of the blending amount in the table is “part by mass”. Each component in the table is shown below.

((Meth) acrylic polymer)
Acrylic rubber (trade name: CT-865Y2SS)

((Meth) acrylic monomer)
[Bifunctional]
Dioxane glycol diacrylate (Shin Nakamura Chemical Co., Ltd., trade name: A-DOG)
Nonanediol diacrylate (Hitachi Chemical Co., Ltd., trade name: FA-129AS)
[Monofunctional]
Isostearyl acrylate (Hitachi Chemical Co., Ltd., trade name: FA-117A)
Acrylic acid tricyclo [5.2.1.0 ^2,6 ] dec-8-yl (Hitachi Chemical Co., Ltd., trade name: FA-513AS)

(Polymerization initiator)
Dicumyl peroxide (thermal polymerization initiator, NOF Corporation, trade name: Park Mill D, 1 hour half-life temperature: 135.7 ° C., 10 hour half-life temperature: 116.4 ° C.)

(Black colorant)
Acrylic beads (pigment, Negami Industrial Co., Ltd., trade name: Art Pearl GR-004BK, particle size: 3.8 μm)
Spherical carbon filler (pigment, natural graphite, particle size: 8μm)
Flaky carbon filler (pigment, natural graphite, particle size: 5μm)
Organic black dye 1 (Oriento Chemical Co., Ltd., trade name: VALIFAST-BLACK 3820)
Organic black dye 2 (Orient Chemical Co., Ltd., trade name: SOC-L-170)

(Antioxidant)
Bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diyl) bis ( 2,2-Dimethyl-2,1-ethanediyl (hindered phenol antioxidant, ADEKA Corporation, trade name: ADK STAB AO-80)
Ditridecyl 3,3-thiobispropionate (thioether antioxidant, ADEKA Corporation, trade name: ADK STAB AO-503)
1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Kyoeisha Chemical Co., Ltd., trade name: Karenz MT) -NR1)

(Other)
Coupling agent (adhesion aid): 3- (trimethoxysilyl) propyl methacrylate (silane coupling agent, Shin-Etsu Chemical Co., Ltd., trade name: KBM-503)
Leveling agent: AGC Seimi Chemical Co., Ltd. (trade name: S-420)
Filler: Nanosilica filler (amorphous silica, Nippon Aerosil Co., Ltd., trade name: R972, average particle size: 16 nm)

<Evaluation>
The following evaluation was performed using the resin compositions of Examples and Comparative Examples. The results are shown in Tables 1-4. “-” In the column of the evaluation result in the table means a case where measurement is impossible or a case where measurement is not performed. For example, in Comparative Examples 1 to 7, the reflectance could not be measured due to the poor surface condition of the cured product.

(Transmittance and reflectance)
A resin film having a film thickness of 120 μm was prepared by applying the resin compositions of Examples and Comparative Examples on a soda glass plate using an applicator and then drying. Next, the resin film was cured at 150 ° C. for 1 hour in a nitrogen atmosphere, and then cured at 180 ° C. for 1 hour to obtain a glass plate with a cured film.

  The transmittance and reflectance of the glass plate with a cured film were measured. Specifically, using a spectrophotometer (Hitachi, Ltd., trade name: U4100, start wavelength: 800 nm, end wavelength: 300 nm, scan speed: 600 nm / min, sampling interval: 1.0 nm), a wavelength of 800 to The transmittance and reflectance were measured in the range of 300 nm, and the transmittance and reflectance at a wavelength of 400 nm were obtained. Baseline was soda glass. The transmittance was measured with the cured film facing the incident light side. In the measurement of the reflectance, both the case where the cured film was directed to the incident light side and the case where the glass plate was directed to the incident light side were measured.

(Appearance evaluation)
The external appearance of the cured film in the glass plate with a cured film similar to the measurement of transmittance and reflectance was visually confirmed. The symbols A to I shown in the table indicate the following results.
A: Black, with gloss B: Black, without gloss C: Black (slightly whitish)
D: Black (slightly brown)
E: Black, surface roughness F: Cloudiness (pure white)
G: Slightly transparent H: Transparent I: Cloudiness, white ball-like roughness

(Viscosity at 25 ° C.)
Using a viscoelasticity measuring device (rheometer, manufactured by Anton Paar, trade name: modular compact rheometer Physica MCR301), the resin compositions of Examples and Comparative Examples were heated from 25 ° C. to 150 ° C. in 30 minutes, and 5 rpm The viscosity when rotating at (rpm, 1/60 sec ⁻¹ ) was measured. The viscosity when the temperature was 25 ° C. was confirmed.

  The number of times per minute varies depending on the viscosity of the liquid to be measured. Specifically, the viscosity of the liquid to be measured is roughly estimated in advance, and every minute is determined according to the estimated value. In this specification, when the estimated value of the viscosity of the liquid to be measured is 6000 to 60000 mPa · s, the rate is 30 rpm, and when the estimated value of the viscosity is 1000 to 10,000 mPa · s, the rate is 50 rpm. When the estimated value of the viscosity is 200 to 2000 mPa · s, the number of times is set to 100 rpm.

(Achieving temperature of viscosity 1100 cP)
Using a viscoelasticity measuring device (rheometer, Anton Paar, product name: modular compact rheometer Physica MCR301), the resin compositions of Examples and Comparative Examples were heated from 25 ° C. to 150 ° C. in 30 minutes, and 5 rpm ( The viscosity when rotating at rpm, 1/60 sec ⁻¹ ) was measured. The temperature when the viscosity reached 1100 cP was confirmed. In Example 9, the viscosity did not decrease to 1100 cP. In Example 23, the measurement was not performed because the viscosity was below 1100 cP at 25 ° C.

(Weight reduction rate)
1 mL of the resin compositions of Examples and Comparative Examples were taken on a glass plate, and the weight of the resin composition was measured. Next, after heating at 110 ° C. for 1 hour, the temperature was raised to 200 ° C. at 10 ° C./min, and further heated at 200 ° C. for 1 hour to obtain a cured product. The weight of the cured product was measured, and the weight reduction rate was calculated based on the following formula.
Weight reduction rate (%) = 100 − {(weight of cured product after heating at 200 ° C. for 1 hour) / (weight of resin composition before curing) × 100}

  As shown in the evaluation results, in the examples, it was confirmed that a cured product having low light transmittance and light reflectance can be obtained. On the other hand, in the comparative example, it was confirmed that a low light transmittance could not be obtained.

Claims (6)

  A resin composition comprising (a) a (meth) acrylic polymer, (b) a compound having a (meth) acryloyl group, (c) a polymerization initiator, and (d) a black colorant.   The resin composition according to claim 1, wherein the component (b) includes a compound having at least two (meth) acryloyl groups in one molecule.   The resin composition according to claim 1 or 2, wherein the component (d) contains at least one selected from the group consisting of a black dye and a black pigment.   Hardened | cured material of the resin composition as described in any one of Claims 1-3.   A semiconductor device provided with the resin part containing the resin composition as described in any one of Claims 1-3, or its hardened | cured material. Forming a resin composition part comprising the resin composition according to any one of claims 1 to 3,
And a step of curing the resin composition part.