JP2018016757A - Resin composition, method for producing semiconductor device and solid state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that is cured to have sufficiently high transparency and adhesiveness and sufficiently low elastic moduli, and a method for producing a semiconductor device using the same, and a solid state image sensor.SOLUTION: The present invention provides a resin composition or the like containing (A) an acrylic polymer, (B) a compound having at least two (meth) acryloyl groups, (C) alkyl (meth) acrylate with a C8-30 alkyl group, and (D) a polymerization initiator.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a resin composition, a method for manufacturing a semiconductor device using the resin composition, and a solid-state imaging device.

  In recent years, with the spread of digital still cameras and camera-equipped mobile phones, solid-state imaging devices have also been reduced in power consumption and miniaturization. In addition to conventional CCD (Charge Coupled Device) image sensors, CMOS (Complementary Metal Oxide Semiconductor, Complementary Metal Oxide Semiconductor) Image sensors are used. These image sensors are formed by 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 Documents 1 and 2). In the front-illuminated CMOS image sensor of Patent Document 1, light incident from the outside passes through the glass substrate and the cavity (cavity), enters each microlens, and is collected by the microlens, and then the color filter layer. And passes through the wiring layer and enters the photodiode. The 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 of Patent Document 2, 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 provided on the other surface of the semiconductor substrate. According to this back-illuminated structure, 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 a backside illumination type CMOS image sensor, an acrylic material (resin) is used to reduce light loss due to a difference in refractive index between air in the cavity portion and the glass plate and microlens. A method of bonding with a composition) or the like has been proposed (see Patent Documents 3 and 4).

JP 2007-281375 A JP 2005-142221 A International Publication No. 2015/115553 International Publication No. 2015/115537

  By the way, when the glass plate and the microlens are bonded, that is, when cured, the resin composition used for the above-mentioned application is transparent to reduce light loss, and the glass plate and the microlens are more firmly fixed. Therefore, properties such as high adhesiveness for suppressing the substrate and low elasticity for suppressing warpage of the substrate are required.

  Therefore, the present disclosure provides a resin composition having sufficiently high transparency and adhesiveness when cured and a sufficiently low elastic modulus, and a method of manufacturing a semiconductor device using the resin composition and a solid-state imaging device. Objective.

  The present disclosure includes (A) an acrylic polymer, (B) a compound having at least two (meth) acryloyl groups, (C) a (meth) acrylic acid alkyl ester having 8 to 30 carbon atoms in the alkyl group, and ( D) A resin composition containing a polymerization initiator is provided. In the present specification, these components may be simply referred to as (A) component, (B) component, (C) component, (D) component and the like.

  According to the resin composition of the present disclosure, when cured, the transparency and adhesiveness are sufficiently high, and the elastic modulus is sufficiently low.

  The resin composition preferably further contains (E) an adhesion assistant. Thereby, the adhesive strength can be further improved.

  The resin composition preferably further contains (F) an antioxidant. Thereby, the coloring by the deterioration at the time of the heat | fever of a resin composition can be suppressed, and the transparency at the time of a heat | fever can be improved.

  The resin composition preferably further contains (G) a compound having one (meth) acryloyl group and a heterocyclic ring. Thereby, the adhesive strength at the time of curing can be further improved and the elastic modulus can be further reduced.

  Moreover, this indication provides the resin composition mentioned above for optical components. The above-described resin composition is highly transparent even after curing, has excellent adhesion when used as an adhesive, and can suppress warping of the substrate, and thus can be suitably used for optical components. In that case, particularly excellent effects are exhibited.

  Furthermore, the present disclosure provides a step of forming an adhesive layer containing the above-described resin composition on a semiconductor substrate, sandwiching the adhesive layer between the semiconductor substrate and the transparent substrate, and crimping the semiconductor substrate and the transparent substrate. There is provided a method for manufacturing a semiconductor device, comprising a step and a step of curing an adhesive layer. Since the resin composition described above has an excellent function as an adhesive and is highly transparent even after curing, it exhibits a particularly excellent effect by using the resin composition in the manufacturing process of a semiconductor device, The characteristics of the obtained semiconductor device are also improved.

  Furthermore, the present disclosure includes a semiconductor substrate having a light receiving portion on the upper surface, an adhesive layer provided on the semiconductor substrate so as to cover the light receiving portion, a transparent substrate bonded to the semiconductor substrate by the adhesive layer, A solid-state imaging device comprising: the adhesive layer containing the resin composition described above. Since the solid-state imaging device having such a configuration uses the above-described resin composition, the solid-state imaging device has an adhesive layer provided on the outer peripheral side so as not to cover the microlens. In addition to a configuration in which the resin composition is filled in the enclosed cavity (cavity), a configuration in which an adhesive layer containing the resin composition is formed on the entire surface of the substrate can be employed.

  According to the present disclosure, it is possible to provide a resin composition having sufficiently high transparency and adhesiveness when cured and a sufficiently low elastic modulus, and a method for manufacturing a semiconductor device using the resin composition and a solid-state imaging device. Can do.

It is a top view which shows an example of the solid-state image sensor concerning this embodiment. It is sectional drawing by the A-A 'line | wire shown in FIG. It is sectional drawing which shows the other example of the solid-state image sensor which concerns on this embodiment.

Hereinafter, preferred embodiments of the present disclosure will be described, but the present disclosure is not limited to these embodiments. In the present specification, “(meth) acryloyl group” means “acryloyl group” or a “methacryloyl group” corresponding thereto. The same applies to other similar expressions such as (meth) acrylate.
Further, in the present specification, “transparency” means that interaction between the resin composition and visible light hardly occurs, and electromagnetic wave absorption and scattering hardly occur. As an index of “transparency”, a transmittance in which the intensity ratio between incident light and transmitted light is expressed as a percentage is used, but it can also be determined by visual observation of turbidity. Although the transmittance varies depending on the wavelength of light of interest, in this specification, visible light is targeted. The electromagnetic wave corresponding to visible light has a lower limit of approximately 400 nm and an upper limit of approximately 760 nm according to the definition of JIS Z8120.

  In addition, in this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when viewed in plan.

  In addition, in this specification, the term “process” is not only an independent process, but even if it cannot be clearly distinguished from other processes, if the intended purpose of the process is achieved, Included in the term.

  In the present specification, numerical ranges indicated using “to” indicate ranges including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In addition, 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. Further, in the numerical ranges 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.

  In the present specification, the “substituent” means, for example, a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an ether group, an ester group, or a carboxy group. Represents a cyano group or the like.

<Resin composition>
The resin composition according to this embodiment includes (A) an acrylic polymer, (B) a compound having at least two (meth) acryloyl groups, and (C) an alkyl group having 8 to 30 carbon atoms (meth) acrylic. An acid alkyl ester and (D) a polymerization initiator are contained.

<(A) Acrylic polymer>
The (A) acrylic polymer according to this embodiment refers to a polymer obtained by polymerizing one acrylic monomer having one (meth) acryloyl group in the molecule, or a copolymer obtained by combining two or more. As long as the effect of the present invention is not impaired, a compound having two or more (meth) acryloyl groups in the molecule, or a polymerizable compound having no (meth) acryloyl group (acrylonitrile, styrene, vinyl acetate) , A compound having one polymerizable unsaturated bond in the molecule such as ethylene and propylene, and a compound having two or more polymerizable unsaturated bonds in the molecule such as divinylbenzene) copolymerized with an acrylic monomer. There may be. From such a viewpoint, the acrylic polymer preferably has 30 to 100% by mass of an acrylic monomer having one (meth) acryloyl group in the molecule based on the total amount of the acrylic polymer. It is more preferable to have the mass%.

［式（Ｉ）中、Ａは置換基を有していてもよい炭素数５〜２２の脂環基を示し、Ｒは水素原子又はメチル基を示す。］

［式（ＩＩ）中、Ｙ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を示し、Ｒは水素原子又はメチル基を示す。］ The component (A) preferably includes a structural unit having an alicyclic group or a linear or branched alkyl group structure, and is represented by a structural unit represented by the following general formula (I) or the following general formula (II). More preferably, the structural unit is included. Thereby, since light absorption of the short wavelength (especially wavelength 400nm) in a resin composition is suppressed, it exists in the tendency for higher transparency to be acquired.

[In formula (I), A shows the C5-C22 alicyclic group which may have a substituent, and R shows a hydrogen atom or a methyl group. ]

[In Formula (II), Y represents a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and R represents a hydrogen atom or a methyl group. ]

  Moreover, it is preferable that (A) component contains the structural unit which has an alicyclic group, and it is more preferable that the structural unit represented by the said general formula (I) is included. This tends to further improve the heat resistance.

［式（ＩＩＩ）中、Ｚはカルボキシル基、ヒドロキシル基、酸無水物基、アミノ基、アミド基、エポキシ基及びニトリル基からなる群より選ばれる少なくとも１種の官能基を含む基を示す。Ｒは水素原子又はメチル基を示す。］ The component (A) preferably includes a structural unit having a functional group, and more preferably includes a structural unit represented by the following general formula (III). Thereby, the outstanding stress relaxation property by low elasticity modulus, crack resistance, adhesiveness, and heat resistance can be expressed.

[In the formula (III), Z represents a group containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, an amide group, an epoxy group and a nitrile group. R represents a hydrogen atom or a methyl group. ]

  In the structural unit represented by the general formula (III), Z may be a glycidyl group. When Z is a glycidyl group, the adhesiveness at the time of reflow is improved, and peeling at the time of reflow can be further suppressed.

  The content of the structural unit represented by the general formula (III) in which Z is a glycidyl group is preferably 30% by mass or less, and 2 to 25% by mass based on the total amount of the component (A). More preferably, the content is 4 to 20% by mass. When the content is 30% by mass or less, the transparency is improved and the warpage of the wafer due to the stress in the manufacturing process can be further suppressed.

  The method for introducing the functional group into the acrylic polymer is not particularly limited, but the functional group-containing monomer having a functional group is not limited to suspension polymerization, which is also called bead polymerization, granular polymerization, pearl polymerization, or the like, but is also solution polymerization or bulk polymerization. The functional group can be introduced into the acrylic polymer by random copolymerization by an existing method such as precipitation polymerization or emulsion polymerization. Among these, it is preferable to apply the suspension polymerization method from the viewpoint of high molecular weight at low cost.

  Suspension polymerization is performed by adding a suspending agent in an aqueous solvent. Examples of the suspending agent include water-soluble polymers such as polyvinyl alcohol, methylcellulose, and polyacrylamide, and poorly soluble inorganic substances such as calcium phosphate and magnesium pyrophosphate. Among them, nonionic water-soluble polymers such as polyvinyl alcohol are preferable. When a nonionic water-soluble polymer is used, it is preferable in that the possibility that ionic impurities remain in the obtained acrylic copolymer is low. The water-soluble polymer is preferably used in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of monomers.

  Moreover, in a polymerization reaction, you may use the polymerization initiator generally used, a chain transfer agent, etc. As a polymerization initiator, the thing similar to the polymerization initiator (D) mentioned later is mentioned. Examples of the chain transfer agent include thiols such as n-octyl mercaptan.

The functional group-containing monomer is at least one group 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 the molecule. And at least one polymerizable carbon-carbon double bond.
The functional group is an amino group, an amide group, a phosphate group, a cyano group, a maleimide from the viewpoint of avoiding problems such as gelation in a varnish state, nozzles during use, that is, pinhole generation during spin coating, etc. It is preferably at least one selected from the group consisting of a group and an epoxy group. Moreover, it is preferable that the said functional group is at least 1 sort (s) chosen from the group which consists of a carboxyl group, an acid anhydride group, a hydroxyl group, a phosphoric acid group, and an epoxy group from a viewpoint which prevents coloring more highly. Furthermore, from both these viewpoints, the functional group is more preferably a phosphoric acid group or an epoxy group, and even more preferably an epoxy group. When the functional group contains an epoxy group, the adhesion of an inorganic material such as metal or glass to the substrate can be further improved.

  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-containing single monomers such as (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, N-methylyl (meth) acrylamide, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene Body, 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-propylmaleimide N-substituted maleimides such as N-butylmaleimide, Ni-butylmaleimide, Nt-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, (meth) 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-ethylacrylic Epoxy group-containing monomers such as phosphoric acid-β-methylglycidyl can be used. These can be used alone or in combination of two or more.

  Among these, it is particularly preferable to use a glycidyl group-containing monomer such as glycidyl (meth) acrylate. Furthermore, for example, the glycidyl group-containing (meth) acrylic polymer obtained by using such a monomer is preferably compatible with the acrylic monomer or oligomer. 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 an acrylic polymer is preferable in that it exhibits more excellent crack resistance, adhesion, and heat resistance, and is preferable in terms of ensuring storage stability.

  The amount of the structural unit having the functional group is preferably 0.5 to 6.0% by mass, more preferably 0.5 to 5.0% by mass based on the total amount of the acrylic polymer. It is especially preferable that it is 0.8-5.0 mass%. When the amount of the structural unit having a functional group is within this range, the adhesiveness can be improved and gelation can be suppressed.

  In the acrylic polymer according to this embodiment, the structural unit having a nitrogen atom-containing group is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less of the entire acrylic polymer. More preferably, it is particularly preferable that no structural unit having a nitrogen atom-containing group is contained. Examples of the nitrogen atom-containing group include an amino group, an amide group, a cyano group, and a maleimide group. Examples of the structural unit having a nitrogen atom-containing group include structural units derived from monomers containing a nitrogen atom among the functional group-containing monomers listed above, and vinyl cyanide such as (meth) acrylonitrile. Compounds.

Examples of monomers other than the functional group-containing monomer used when synthesizing the acrylic polymer according to the present embodiment include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate n-. Propyl, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic acid n-hexyl, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, butoxyethyl (meth) acrylate, phenyl (meth) acrylate , (Meth) acrylic acid esters such as benzyl (meth) acrylate and naphthyl (meth) acrylate, α-methylstyrene, α-ethyls Tylene, α-fluorostyrene, α-chlorostyrene, α-bromostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, methoxystyrene, styrene and other aromatic vinyl compounds, (meth) acrylic acid cyclopentyl, (meth) Cyclohexyl acrylate, methyl cyclohexyl (meth) acrylate, trimethylhexyl (meth) acrylate, norbornyl (meth) acrylate, norbornyl methyl (meth) acrylate, phenyl norbornyl (meth) acrylate, (meth) Isobornyl acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fentil (meth) acrylate, adamantyl (meth) acrylate, tricyclo (meth) acrylate [5.2.1.0 ^2,6 ] Dec-8-yl Cyclopentanyl acrylate les - g), and the like (meth) acrylic acid tricyclo [5.2.1.0 ^{2, 6]} deca-4-methyl, (meth) alicyclic monomers such cyclodecyl acrylate . These can be used alone or in combination of two or more.

  The content of monomers other than these functional group-containing monomers is not particularly limited, but is preferably adjusted so that the Tg of component (A) is in the range of -50 to 50 ° C. , By using 2.5% by mass of glycidyl methacrylate, 43.5% by mass of methyl methacrylate, 18.5% by mass of ethyl acrylate and 35.5% by mass of butyl acrylate as monomers, Can synthesize | combine (A) component which is a glycidyl group containing acrylic polymer at 12 degreeC.

  Among the monomers other than the functional group-containing monomer, (meth) acrylic acid esters are preferably used because they easily synthesize the component (A) without gelation. Among (meth) acrylic acid esters, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are excellent in copolymerizability with a functional group-containing monomer. Further preferred.

［式（１）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は脂環式基又は複素環式基を示し、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。ここで脂環式基とは、炭素原子が環状に結合した構造を有する基であり、複素環式基とは、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。］ The component (A) preferably contains a structural unit having an alicyclic or heterocyclic structure. As an alicyclic or heterocyclic structure containing monomer used when manufacturing the acrylic polymer containing these structural units, what is represented by following General formula (1) is mentioned, for example.

[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 0. An integer of 10 is shown. When n is an integer of 2 or more, a plurality of Xs may be the same or different from each other. Here, an alicyclic group is a group having a structure in which carbon atoms are bonded in a ring, and a heterocyclic group is a group having a structure in which a carbon atom and one or more heteroatoms are bonded in a ring. ]

［式（２）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^１２で示される構造を示し、Ｒ^１２は水素原子又は炭素数１〜８のアルキル基を示す。］ The R ^2, for example, those represented by the following formula (2).

[In the formula (2), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a structure represented by OR ¹² , and R ¹² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

Examples of the compound represented by the general formula (1) include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate.

  The content of these alicyclic or heterocyclic structure-containing monomers is not particularly limited. For example, dicyclopentanyl acrylate (FA-513A, manufactured by Hitachi Chemical Co., Ltd., trade name) is 25.8. Weight% molecular weight by using 20% by mass, 20% by mass of butyl acrylate, 31.1% by mass of butyl methacrylate, 18.6% by mass of 2-ethylhexyl methacrylate, and 4.5% by mass of glycidyl methacrylate. Can synthesize an acrylic polymer containing an alicyclic skeleton and a glycidyl group.

  The mixing ratio when the functional group-containing monomers are used in combination is determined in consideration of the Tg of the acrylic polymer, and the Tg is preferably −50 ° C. or higher. This is because when the Tg is −50 ° C. or higher, the tackiness of the resin composition in the B-stage state is appropriate, and problems in handling are unlikely to occur.

  When an acrylic polymer containing a structural unit having a functional group is produced by polymerizing the above monomers, the polymerization method is not particularly limited, and methods such as pearl polymerization, solution polymerization, and suspension polymerization are used. be able to.

  The weight average molecular weight of the acrylic polymer according to this embodiment is preferably 100,000 to 3,000,000, and more preferably 120,000 to 2,000,000. When the weight average molecular weight is within this range, the strength, flexibility, and tackiness when sheet-like or film-like are appropriate, and the circuit filling property of the wiring can be ensured because the flow property is appropriate. In this embodiment, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve as described in the examples.

  As for content of (A) component in a resin composition, 10-400 mass parts is preferable with respect to 100 mass parts of total amounts of the following (B) component and (C) component. When it is in this range, a better storage elastic modulus is exhibited, flowability during molding can be suppressed, and handling properties at high temperatures can be improved. From such a viewpoint, the content is more preferably 15 to 350 parts by mass, and particularly preferably 20 to 300 parts by mass.

<(B) Compound having at least two (meth) acryloyl groups>
(B) The compound having at least two (meth) acryloyl groups according to this embodiment is not particularly limited, and is a polyfunctional (meth) acryl monomer having an alicyclic skeleton, a polyfunctional having an aliphatic skeleton. Examples include (meth) acrylic monomers, polyfunctional (meth) acrylic monomers having a dioxane glycol skeleton, and polyfunctional (meth) acrylic monomers having a functional group. Here, “polyfunctional” refers to a (meth) acryloyl group, and means that the compound has at least two (meth) acryloyl groups.

  From the viewpoint of improving the transparency of the cured product, a polyfunctional (meth) acrylic monomer having an alicyclic skeleton and a polyfunctional (meth) acrylic monomer having a dioxane glycol skeleton are preferable. On the other hand, it is preferable to use a polyfunctional (meth) acrylic monomer having an aliphatic skeleton from the viewpoint of further suppressing cracking of the cured product and peeling from the substrate.

  As a polyfunctional (meth) acryl monomer, the following (meth) acryl monomer which has two (meth) acryloyl groups can be mentioned.

  Examples of the (meth) acrylic monomer having two (meth) acryloyl groups include cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, tricyclodecane dimethylol di ( (Meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-684, tricyclodecane dimethylol diacrylate, etc.), tricyclodecane dimethanol di (meth) acrylate (for example, Shin-Nakamura Chemical Co., Ltd., A-DCP) , Tricyclodecane dimethanol diacrylate, etc.), dioxane glycol di (meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-604, dioxane glycol diacrylate, Shin-Nakamura Chemical Co., Ltd., A-DOG, dioxane glycol) Coal diacrylate, etc.), neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexanediol 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 neopentyl 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 preferred Ethylene oxide from 5 to 15 mol-modified bisphenol A Kataji (meth) acrylate), and (poly) ethylene oxide-modified phosphoric acid di (meth) acrylate.

  Among the above, dioxane glycol diacrylate or tricyclodecane dimethanol diacrylate is more preferable from the viewpoint of improving the transparency of the cured product.

  The polyfunctional (meth) acrylic monomer has three or more (meth) acryloyl groups such as pentaerythritol tri (meth) acrylate, ethylene oxide-modified isocyanuric acid tri (meth) acrylate, and dipentaerythritol hexaacrylate. Mention may also be made of (meth) acrylic monomers.

  These (B) component can be used individually by 1 type or in combination of 2 or more types, (meth) acrylic monomer and two (meth) acryloyl groups which have two (meth) acryloyl groups are used. It is preferable to use in combination with one or more (meth) acrylic monomers.

<(C) (meth) acrylic acid alkyl ester whose alkyl group has 8 to 30 carbon atoms>
The (C) alkyl group having 8 to 30 carbon atoms in the (C) alkyl group according to this embodiment is not particularly limited, and the alkyl group may be linear, branched, or cyclic. May be.

(C) Component includes 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate (isostearyl acrylate) ), Trimethylhexyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fentil (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid Tricyclo [5.2.1.0 ^2,6 ] dec-8-yl, tricyclo [5.2.1.0 ^2,6 ] dec-4-methyl (meth) acrylate, cyclodecyl (meth) acrylate, etc. Can be mentioned.

  The number of carbon atoms of the alkyl group is preferably 8 to 25, and more preferably 10 to 20. The alkyl group is preferably branched or cyclic.

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

<(D) Polymerization initiator>
As the (D) polymerization initiator according to this embodiment, for example, (D1) a thermal polymerization initiator, (D2) a photopolymerization initiator, or both can be used. From the viewpoint of more uniformly proceeding the curing reaction of the resin composition according to this embodiment and further improving the adhesive strength, it is more preferable to contain (D1) a thermal polymerization initiator.

  (D1) As the thermal polymerization initiator, t-hexyl peroxypivalate (perhexyl PV, trade name: 1 hour half-life temperature 71.3 ° C., 10 hour half-life temperature 53.2 ° C.), dilauroyl peroxide ( 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 (Perroyl 355, trade name; 1 hour) Half-life temperature 76.8 ° C, 10-hour half-life temperature 59.4 ° C, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, trade name; 1-hour half-life Temperature 84.4 ° C., 10-hour half-life temperature 65.3 ° C., t-butyl peroxy-2-ethylhexanoate (Perbutyl O, trade name; 1-hour half-life temperature 92.1 ° C., 10 and a half hours Benzoyl peroxide + water (Nyper BW, trade name; 1 hour half-life temperature 92.0 ° C., 10 hour half-life temperature 73.6 ° C.), 1,1-di (t-hexyl) Peroxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, trade name; 1 hour half-life temperature 106.4 ° C., 10 hour half-life temperature 86.7 ° C.), 1,1-di (t-hexyl par Oxy) cyclohexane (Perhexa HC, trade name; 1-hour half-life temperature 107.3 ° C., 10-hour half-life temperature 87.1 ° C.), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, trade name; half-hour 1 hour) Period temperature 114.6 ° C., 10 hour half-life temperature 95.0 ° C., t-butyl peroxyisopropyl monocarbonate (Perbutyl I, trade name; 1 hour half-life temperature 11) 4 ° C., 10-hour half-life temperature 98.7 ° C.), dicumyl peroxide (Park Mill D, trade name; 1-hour half-life temperature 135.7 ° C., 10-hour half-life temperature 116.4 ° C.), n-butyl Organic peroxides such as 4,4-bis (t-butylperoxy) valerate (Perhexa V, trade name; 1 hour half-life temperature 126.5 ° C., 10 hour half-life temperature 104.5 ° C.), 2,2 '-Azobisisobutyronitrile, 1,1'-(cyclohexane-1,1-carbonitrile) -2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2, And azo compounds such as 4-dimethylvaleronitrile).

  These thermal polymerization initiators can be used singly or in combination of two or more.

  Among these thermal polymerization initiators, an organic peroxide is preferable from the viewpoint that the effect of improving the physical properties of the cured product is greater, and the handleability and curability of the shelf life, pot life, etc. of the resin composition are preferable. From the viewpoint of maintaining a better balance, an organic peroxide having a 10-hour half-life temperature of 90 to 150 ° C. is more preferable.

  The blending amount of the component (D1) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). More preferably, it is 0.5 to 10 parts by mass.

  In addition, the half-life temperature of an 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 primary reaction, so the amount of decomposed organic peroxide is x (mol / L), the decomposition rate constant is k (1 / h), When time is t (h) and the initial concentration of organic peroxide is a (mol / L), the following formulas (1) and (2) are established.
dx / dt = k (ax) (1)
ln {a / (ax)} = kt (2)
Since the half-life is the time until the organic peroxide concentration is reduced to half of the initial value due to decomposition, if the half-life is represented by t1 / 2 and a / 2 is substituted for x in the formula (2), the following formula (3 )become that way.
kt1 / 2 = ln2 (3)
Therefore, thermal decomposition is performed 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 at temperature (t1 / 2) can be determined.

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 formula (4) is established.
lnk = lnA−ΔE / RT (4)
When k is eliminated from the equations (3) and (4),
ln (t1 / 2) = ΔE / RT−ln (A / 2) (5)
The temperature at t1 / 2 = 1h from the straight line obtained by plotting the relationship between ln (t1 / 2) and 1 / T (1 hour half-life temperature) ) Is required. The 10-hour half-life temperature can also be obtained by obtaining the temperature when t1 / 2 = 10 h.

  Among the above-mentioned thermal polymerization initiators, suitable organic peroxides include dicumyl peroxide (Parkmill D) and n-butyl 4,4-bis (t-butylperoxy) valerate (Perhexa V). It is done.

  The thermal polymerization initiator exhibits excellent heat resistance, peel resistance and stress relaxation in combination with the components (A), (B) and (C), and further improves the reliability of the optical component. Can do.

  (D2) As photopolymerization initiators, acyl phosphine oxide, oxime esters, aromatic ketones, quinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives, coumarins Compounds, N-phenylglycine derivatives, and the like. In addition, a photoinitiator (D2) may be synthesize | combined by a conventional method and a commercially available thing may be obtained.

  Among these, acylphosphine oxide and oxime esters are preferable from the viewpoint of improving photocurability, increasing sensitivity, and further improving transparency of the cured film.

  In addition, a photoinitiator (D2) can be used individually by 1 type or in combination of 2 or more types.

  Examples of the acylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE-819, BASF, trade name), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (LUCIRIN). TPO, BASF, trade name) and the like.

  Examples of oxime esters include 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime)] (IRGACURE-OXE01, BASF Corporation, trade name), 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (IRGACURE-OXE02, trade name of BASF), 1-phenyl-1,2-propanedione -2- [o- (ethoxycarbonyl) oxime] (Quantacure-PDO, Nippon Kayaku Co., Ltd., trade name) and the like.

  Aromatic ketones include benzophenone, N, N, N ′, N′-tetramethyl-4,4′-phenone (Michler ketone), N, N, N ′, N′-tetraethyl-4,4′-diaminobenzophenone 4-methoxy-4′-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE-651, BASF, trade name), 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one (IRGACURE-369, BASF, trade name), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (IRGACURE-907, BASF Corporation, trade name), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propiyl) Onyl) -benzyl] phenyl} -2-methyl-propan-1-one (IRGACURE-127, BASF Corporation, trade name) and the like.

  As quinones, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, Examples include 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether.

  Examples of the benzyl derivative include benzyl dimethyl ketal in addition to benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin.

  As 2,4,5-triarylimidazole dimer, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like. As 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazole -2-yl] -4,5-diphenylimidazole and the like.

  Examples of the acridine derivative include 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane and the like.

  Examples of coumarin compounds include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, and 7-ethylamino-4. -Methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6 -Diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-diethyl- 7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydro-1H, 5 -Cyclopenta [3,4] [1] benzopyrano- [6,7,8-ij] quinolizine 12 (9H) -one, 7-diethylamino-5 ', 7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3′-carbonylbis [7- (diethylamino) coumarin], 7-diethylamino-3-thienoxysilkine and the like can be mentioned.

  N-phenylglycine derivatives include N-phenylglycine, N-phenylglycine butyl ester, Np-methylphenylglycine, Np-methylphenylglycine methyl ester, N- (2,4-dimethylphenyl) glycine, N-methoxyphenylglycine etc. are mentioned.

  (D2) The blending amount of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 100 parts by mass with respect to the total amount of the components (A), (B) and (C). It is 10 mass parts, More preferably, it is 0.75-5 mass parts. By making a compounding quantity into the said range, foaming, turbidity, coloring, and a crack of hardened | cured material can be prevented more highly.

<(E) Adhesive aid>
(E) An adhesion assistant (coupling agent) can be added to the resin composition according to the present embodiment. There is no restriction | limiting in particular as a coupling agent, Various things, such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, a zircoaluminate coupling agent, are used.

  Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl-tris (2-methoxyethoxy) ) Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, methyltri (methacryloxyethoxy) silane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (N-bi Rubenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, 3- (4,5-dihydroimidazolyl) propyl Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiisopropeno Xysilane, methyltriglycidoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate Sulfonate, phenyl 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.

［式（６）中、Ｒ’はカルボキシル基又はアミノ基を示す。］ As a zirco aluminate coupling agent, the compound represented by following General formula (6) is mentioned, for example.

[In the formula (6), R ′ represents a carboxyl group or an amino group. ]

  Examples of the compound in which R ′ is a carboxyl group include Manschem CPG-carboxyzircoaluminate, and examples of the compound in which R ′ is an amino group include Mansheim APO-X-aminozircoaluminate solution. Available from Rhône Poulenc.

  These (E) components can be used individually by 1 type or in combination of 2 or more types.

  (E) As for the compounding quantity of a component, 0.1-20 mass parts is preferable with respect to 100 mass parts of total amounts of (A), (B), and (C) component, and 1-15 mass parts is especially preferable. If the blending ratio is 0.1 parts by mass or more, the adhesive strength tends to be further improved, and if it is 20 parts by mass or less, the volatile content is less and voids tend not to occur in the cured product. .

  Among these coupling agents, a silane coupling agent having a high effect in terms of improving the bonding or wettability of the interface between materials is preferable, and a silane coupling agent having a (meth) acryloyl group is more preferable, It is more preferable to use a silane coupling agent having an acryloyl group in combination with another silane coupling agent.

<(F) Antioxidant>
(F) Antioxidant can be added to the resin composition which concerns on this embodiment. (F) The antioxidant may be selected according to the composition of the resin composition. (F) The antioxidant is preferably one or more antioxidants selected from the group consisting of phenolic antioxidants, phosphite antioxidants, and sulfur antioxidants.

  The phenolic antioxidant is preferably a compound having a substituent having a large steric hindrance such as a t-butyl group (tert-butyl group) or a trimethylsilyl group at the ortho position of the phenolic hydroxyl group. The phenolic antioxidant is also referred to as a hindered phenolic antioxidant.

  This phenolic antioxidant includes 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-4-ethylphenol, 2,2′- Methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t) -Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane and 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) is preferably one or more compounds selected from the group consisting of bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2,4,8, More preferably, it is 10-tetraoxaspiro [5.5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl).

  Phosphite antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite, Click neopentanetetrayl bis (nonylphenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetrayl tris ( Dinonylphenyl) phosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diisodecylpentaerythritol diphosphite and tris (2 It is preferably one or more compounds selected from the group consisting of 4-di-t-butylphenyl) phosphite and 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene. More preferably, it is -10-oxide.

Examples of sulfur-based antioxidants include thioether compounds and thiol compounds. Examples of the thioether compound include dilauryl thiodiisopropionate (S (CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ ), ditridecyl thiodipropionate (S (CH ₂ CH ₂ COOC ₁₃ H ₂₇ ) ₂ ). , Dimyristyl thiodipropionate (S (CH ₂ CH ₂ COOC ₁₄ H ₂₉ ) ₂ ), lauryl stearyl thiodipropionate ((H ₂₅ C ₁₂ O (O) CCH ₂ CH ₂ ) S (CH ₂ CH ₂ COOC) ₁₈ H ₃₇ )) and distearyl thiodipropionate (S (CH ₂ CH ₂ COOC ₁₈ H ₃₇ ) ₂ ). Examples of thiol compounds include 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and pentaerythritol. Tetrakis (3-mercaptobutyrate) is mentioned.

  These (F) components can be used individually by 1 type or in combination of 2 or more types, It is preferable to use combining a phenolic antioxidant and sulfur type antioxidant, and a phenolic antioxidant More preferably, the agent, the thioether compound and the thiol compound are used in combination.

  The content of the component (F) in the resin composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B), (C) and (D).

<(G) Compound having one (meth) acryloyl group and heterocyclic ring>
(G) The compound which has one (meth) acryloyl group and a heterocyclic ring can be added to the resin composition which concerns on this embodiment.

  As the component (G), glycidyl (meth) 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- Epoxy group-containing monomers such as epoxypentyl, (meth) acrylic acid-5-methyl-5,6-epoxyhexyl, (meth) acrylic acid-β-methylglycidyl, α-ethylacrylic acid-β-methylglycidyl, (Meth) acryloylmorpholine and the like are mentioned, and (meth) acryloylmorpholine is preferred.

  In addition, the resin composition which concerns on this embodiment may contain a monofunctional (meth) acryl monomer separately from (G) component. As a monofunctional (meth) acryl monomer, the acrylic monomer which has one (meth) acryloyl group illustrated by the said (a) component in a molecule | numerator is mentioned.

<Filler>
You may add a filler further to the resin composition which concerns on this embodiment as needed. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are preferable from the viewpoint of improving heat resistance or thermal conductivity, or adjusting melt viscosity or imparting thixotropic properties.

  The inorganic filler is not particularly limited, and includes aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, titanium oxide, zirconium oxide, Examples thereof include cerium oxide, zinc oxide, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica, and antimony oxide. These can be used alone or in combination of two or more.

  In order to improve thermal conductivity, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferable. For adjusting melt viscosity or imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline silica, amorphous Silica etc. are preferable.

  From the viewpoint of further improving the transparency and workability, the blending amount of the filler is preferably 3% by mass or less of the entire resin composition excluding the organic solvent.

  In the production of the varnish when the filler is added to the resin composition according to the present embodiment, in consideration of dispersibility, a physical shearing force is applied by a reiki machine, a three roll, a ball mill, a bead mill, etc. It is preferable to use after sufficiently dispersing so that there is no next aggregated particle. The above dispersion methods can be used in combination.

  Further, the mixing time can be shortened by mixing the filler and the low molecular weight material in advance and then blending the high molecular weight material.

  There is no particular limitation on the method of stirring and mixing each component uniformly, but rotation and revolution of a dissolver, static mixer, homogenizer, ultrasonic homogenizer, paint shaker, ball mill, planetary mixer, mix rotor, universal agitator, etc. In addition to the type stirrer, a method using a laika machine, a kneading apparatus such as a three-roller, and the like can be mentioned, and these can be used in combination as appropriate. After the varnish is formed, it is preferable to remove bubbles in the varnish. In this sense, the rotation and revolution type stirrer is preferably used because it can simultaneously perform mixing and dissolution and removal of bubbles.

  The resin composition according to the present embodiment may further include a moisture absorbent such as calcium oxide and magnesium oxide, a fluorosurfactant, a nonionic surfactant, a wetting improver such as a higher fatty acid, silicone oil, and the like as necessary. An anti-foaming agent, an ion trapping agent such as an inorganic ion exchanger, or the like can be added as appropriate, alone or in combination.

  In the entire resin composition excluding the organic solvent according to this embodiment, the nitrogen content is preferably 8% by mass or less, and more preferably 5% by mass or less. By setting the nitrogen content in this range, it is preferable because coloring derived from nitrogen oxides can be further suppressed.

<Organic solvent>
In the resin composition according to this embodiment, the above components can be dissolved or dispersed in an organic solvent to form a varnish. Thereby, the applicability | paintability to a base material can be improved and workability | operativity can be made favorable.

  There is no restriction | limiting as an organic solvent used in order to make it into a varnish form, if a component used as a resin composition can be stirred and mixed, melt | dissolved, knead | mixed, or disperse | distributed uniformly, a conventionally well-known thing can be used. The organic solvent to be used is not particularly limited, and examples thereof include alcohols, ethers, ketones, amides, aromatic hydrocarbons, esters, and nitriles. Specific examples include low boiling point solvents such as diethyl ether, acetone, methanol, tetrahydrofuran, hexane, ethyl acetate, ethanol, methyl ethyl ketone, and 2-propanol in consideration of volatility at low temperatures. In addition, for the purpose of improving coating film stability, toluene, methyl isobutyl ketone, 1-butanol, 2-methoxyethanol, 2-ethoxyethanol, xylene, N, N-dimethylacetamide, N, N-dimethylformamide, Examples include high-boiling solvents such as cyclohexanone, dimethylacetamide, butyl cellosolve, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, and γ-butyrolactone. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  Among these, it is preferable to use propylene glycol monomethyl ether acetate, methyl ethyl ketone, cyclohexanone, etc. because of its excellent solubility and fast drying speed.

  The amount of the organic solvent is determined by the viscosity when it is in a varnish state and is not particularly limited, but is generally preferably 5 to 95% by mass, more preferably 10 to 10% with respect to the entire resin composition. It is used in the range of 90% by mass.

<Method for Manufacturing Semiconductor Device>
The method for manufacturing a semiconductor device according to the present embodiment includes a step of forming an adhesive layer containing the resin composition according to the present embodiment (hereinafter also referred to as “adhesive resin layer”) on a semiconductor substrate (adhesive layer formation). Step), a step of sandwiching the adhesive layer between the semiconductor substrate and the transparent substrate, crimping the semiconductor substrate and the transparent substrate (crimping step), and a step of curing the adhesive layer (curing step).

(Adhesive layer forming process)
As the adhesive layer forming step, a method of applying the resin composition according to this embodiment on a semiconductor substrate or a method of attaching a film-like resin composition to a semiconductor substrate can be employed. The semiconductor substrate may be either a semiconductor wafer or a semiconductor element (semiconductor chip).
Examples of the method for applying the resin composition include a dispensing method, a spin coating method, a die coating method, a knife coating method, and the like, and a spin coating method particularly suitable for applying a composition containing a high molecular weight compound. Or the die-coating method is preferable.
When the method of sticking the film-like resin composition is adopted, it is preferable to laminate in the range of 0 to 90 ° C. in order to ensure sufficient wetting and spreading. Moreover, in order to affix uniformly, roll lamination is preferable.
The manufacturing method of a film-form resin composition is demonstrated below. By applying the resin composition according to the present embodiment uniformly on a support film and heating the solvent used sufficiently at a temperature of 60 to 200 ° C. for 0.1 to 30 minutes, for example, a film is obtained. The resin composition is formed. At this time, the solvent amount of the resin composition, the viscosity, and the initial coating thickness (when using a coater such as a die coater or a comma coater, the coater and the support film so that the film-like resin composition has a desired thickness. Adjusting the gap), adjusting the drying temperature, air volume, etc.
The support film preferably has flatness. For example, since a support film such as a PET film has high adhesion due to static electricity, a smoothing agent may be used to improve workability. Depending on the type and temperature of the smoothing agent, fine unevenness may be transferred to the adhesive to lower the flatness. Therefore, it is preferable to use a support film that does not use a smoothing agent or a support film that contains few smoothing agents. In addition, a support film such as a polyethylene film is preferable in terms of excellent flexibility, but it is preferable to appropriately select the thickness and density of the support film so that roll marks and the like are not transferred to the adhesive layer surface during lamination.

(Crimping process)
Subsequently, the adhesive layer formed on the semiconductor substrate is dried by heating as desired. The temperature for drying is not particularly limited, but when dissolved or dispersed in a solvent to form a varnish, it is 20-60 ° C. lower than the boiling point of the solvent used, and bubbles are generated due to foaming of the solvent during drying. It is preferable in the sense that does not make. For these reasons, it is more preferable to lower the boiling point of the solvent used by 25 to 55 ° C., and it is even more preferable to lower the boiling point of the solvent used by 30 to 50 ° C.

  Further, when it is dissolved or dispersed in a solvent to form a varnish, it is particularly preferable to reduce the residual amount of the solvent as much as possible in terms of not forming bubbles due to foaming of the solvent after curing.

  The time for performing the above-mentioned heat drying is not particularly limited as long as the solvent used is sufficiently volatilized and (D) the polymerization initiator does not substantially generate radicals, but usually at 40 to 100 ° C., Heat for 0.1 to 90 minutes. Note that “substantially no radicals” means that radicals are not generated at all or very little if any, and even if the polymerization reaction does not proceed or proceeds temporarily, It means that it does not affect the physical properties of the agent layer. Further, drying under reduced pressure is preferable because the residual amount of the solvent can be reduced while suppressing generation of radicals from the (D) polymerization initiator by heating.

  From the viewpoint of suppressing peeling of the adhesive layer at the time of solder reflow due to foaming when the adhesive layer is heat-cured, for example, residual solvent, low molecular weight impurities, reaction generation existing in or on the surface of the adhesive layer Volatile components such as products, decomposition products, water derived from materials, surface adsorbed water and the like are preferably sufficiently reduced.

After heat drying, the transparent substrate is pressure-bonded onto the adhesive layer.
In addition, the said heat drying can be abbreviate | omitted when the method of affixing a film-form resin composition in an adhesive bond layer formation process is employ | adopted.

(Curing process)
After the semiconductor substrate and the transparent substrate are pressure-bonded via the adhesive layer, the adhesive layer is cured. Examples of the curing method include a method of curing by heat or light or heat and light, and it is particularly preferable to cure by heat.

  In the curing step of forming the cured product of the adhesive layer, it is preferable to perform the thermosetting (curing) for 1 to 2 hours while selecting the temperature and gradually increasing the temperature. It is preferable to perform thermosetting at 100-200 degreeC.

  Note that the crimping step and the curing step are not necessarily independent steps, and curing may be performed simultaneously while performing the crimping.

<Physical properties of the cured adhesive layer>
The Tg of the cured product of the adhesive layer according to this embodiment having the above composition is preferably −10 ° C. or higher, more preferably 0 ° C. or higher.

  The elastic modulus at 25 ° C. of the cured product of the adhesive layer according to this embodiment is preferably 1.0 GPa or less. The lower limit value of the elastic modulus at 25 ° C. is not particularly limited, but is 0.1 GPa or more from a practical viewpoint.

<Optical parts>
The optical component according to the present embodiment has a non-cavity structure using the above-described resin composition. Hereinafter, as an example of the optical component according to the present embodiment, a back-illuminated structure of a solid-state imaging device will be described with reference to the drawings as the case may be.

  FIG. 1 is a plan view showing an example of a solid-state imaging device according to this embodiment. As shown in FIG. 1, the CMOS image sensor 1 according to the present embodiment includes a sensor unit (also referred to as “light receiving unit”) 3 in which a plurality of microlenses 12 are arranged in a central region. Further, there is a peripheral circuit unit 4 in which a circuit is formed around the sensor unit 3. A glass substrate 5 is provided so as to cover at least the sensor unit 3.

  2 is a cross-sectional view taken along line A-A ′ shown in FIG. 1. As shown in FIG. 2, a plurality of photodiodes 10 are formed on one surface of the silicon substrate 2. A color filter 11 is provided on the upper surface of the photodiode 10 so as to cover at least the photodiode 10, and a microlens 12 is formed on the upper surface of the color filter 11. The color filter 11 is provided for each photodiode 10, and each microlens 12 is provided at a position corresponding to each color filter 11. Moreover, the adhesive layer 6 containing the resin composition according to the present embodiment is formed on the entire surface of the silicon substrate 2 on which the microlenses 12 are provided, and glass is formed on the surface of the adhesive layer 6. A substrate 5 is provided. By having such a structure, the structure has no cavity portion (non-cavity structure). On the other hand, a wiring layer 8 is disposed on the other surface of the silicon substrate 2, and solder balls 9 are provided on the lower surface of the wiring layer 8.

  The CMOS image sensor according to the present embodiment is built in, for example, an in-vehicle, medical, surveillance camera, mobile phone, or the like. In this case, the CMOS image sensor is mounted on a mother board such as an in-vehicle, medical, surveillance camera, or mobile phone via a solder ball, and an optical lens is disposed above the sensor, that is, on the glass substrate side.

  Although the embodiments have been described above, the present invention is not limited to the embodiments. For example, regarding the above-described embodiments, those in which a person skilled in the art appropriately added, deleted, or changed a design, or added a process, omitted, or changed conditions do not contradict the spirit of the present invention. As long as it is within the scope of the present invention.

  For example, when manufacturing an optical member using the resin composition according to the present embodiment in a liquid state, a method of injecting the liquid resin composition between a wafer or a chip and a glass substrate may be used.

  Further, for example, in the above-described embodiment, an example in which a glass substrate is used has been described. However, the present invention is not limited to this, and another transparent substrate having necessary strength, rigidity, and light transmittance is used as the glass substrate. It can be used instead.

  In addition, as described above, the resin composition according to the present embodiment has high transparency, airtightness, and high refractive index even after thermosetting. For example, the solid-state imaging device according to the present embodiment is illustrated in FIG. Thus, it is not necessary to seal using a transparent substrate such as a glass substrate.

  Hereinafter, the objects and advantages of the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples. That is, the specific materials listed in these examples, their amounts, and other conditions and details should not be construed to unduly limit this disclosure.

((A) component)
The weight average molecular weight of the component (A) was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using a standard polystyrene kit PStQuick series C (Tosoh Corporation, trade name). The GPC conditions are shown below.
Pump: L6000 Pump (Hitachi, Ltd., trade name)
Detector: L3300 RI Monitor (Hitachi, Ltd., trade name)
Column: Gelpack GL-S300MDT-5 (two in total) (Hitachi High-Technologies Corporation, 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

<Synthesis of acrylic polymer (component (A))>
(A-1)
300 g of dicyclopentanyl acrylate (FA-513A, Hitachi Chemical Co., Ltd., trade name), 350 g of butyl acrylate (BA), 300 g of butyl methacrylate (BMA), 50 g of glycidyl methacrylate (GMA) and 2-ethylhexyl methacrylate ( 2EHMA) was mixed to obtain a monomer mixture. To the obtained monomer mixture, 5 g of dilauroyl peroxide and 0.45 g of n-octyl mercaptan as a chain transfer agent were further dissolved to obtain a mixed solution.
As a suspending agent, 0.44 g of polyvinyl alcohol and 2000 g of ion-exchanged water were added to a 5 L autoclave equipped with a stirrer and a condenser. Further the mixture was added with stirring, stirring rotational speed 250min ^-1, 5 hours at 60 ° C. under nitrogen atmosphere and then polymerized for 2 hours at 90 ° C., to obtain a resin particle (polymerization ratio, in mass method 99 %Met.). The resin particles were washed with water, dehydrated and dried to obtain an acrylic polymer (A-1). The weight average molecular weight of the obtained (A-1) was Mw = 480,000.

(A-2)
By the same method as (A-1) except that the amount of glycidyl methacrylate (GMA) was 4.4 times the amount (220 g) and the amounts of other monomers were reduced by 16% in terms of weight. An acrylic polymer (A-2) was obtained. The weight average molecular weight of the obtained (A-2) was Mw = 490,000.

(Examples 1-7 and Comparative Examples 1-4)
The obtained acrylic polymers (A-1) and (A-2) and the following components were blended in the blending ratio (parts by mass) shown in Table 1 to obtain a resin composition. In Table 1, the number of each component excluding the organic solvent indicates the mass part of the solid content. Moreover, solid content as used in this specification points out the non volatile matter except the volatile substances, such as water and an organic solvent, of the resin composition. That is, it refers to components other than the solvent that remains without being volatilized in the drying step, and includes liquid, water tank-like and wax-like substances at room temperature around 25 ° C.

<(B) component>
NK ester A-DOG (Shin Nakamura Chemical Co., Ltd., trade name: dioxane glycol diacrylate)
・ KAYARAD DPHA (Nippon Kayaku Co., Ltd., trade name: dipentaerythritol hexaacrylate)
<(C) component>
・ Fancryl FA-117A (Hitachi Chemical Co., Ltd., trade name: isostearyl acrylate)
・ Fancryl FA-513AS (Hitachi Chemical Co., Ltd., trade name: dicyclopentanyl acrylate)
<(D) component>
・ Park Mill D (NOF Corporation, trade name: Dicumyl peroxide, 1 hour half-life temperature 135.7 ° C., 10 hour half-life temperature 116.4 ° C.)
<(E) component>
KBM-503 (Shin-Etsu Chemical Co., Ltd., trade name; silane coupling agent, 3- (trimethoxysilyl) propyl methacrylate)
AY-43031 (Toray Dow Corning Co., Ltd., trade name: γ-ureidopropyltriethoxysilane)
<(F) component>
Adeka Stab AO-80 (ADEKA Corporation, trade name; 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))
Adeka Stub AO-503 (ADEKA Corporation, trade name: ditridecyl 3,3-thiobispropionate)
Karenz MT PE-1 (Showa Denko Co., Ltd., trade name: pentaerythritol tetrakis (3-mercaptobutyrate))
<(G) component>
・ ACMO (KJ Chemicals, trade name: acryloylmorpholine)

  The following evaluations were performed using the resin composition solutions obtained in the examples and comparative examples. The evaluation results are shown in Table 2.

(Die shear strength at 260 ° C (adhesion strength))
A half cut of 3 mm × 3 mm was performed at a depth of 300 μm on the surface opposite to the mirror surface of the silicon substrate of a 400-inch thick 6-inch wafer. A dicing sheet was attached as a support to the half-cut surface side. The solution of the resin composition of an Example and a comparative example was uniformly apply | coated using the spin coater on the mirror surface of the said half-cut silicon substrate. Thereafter, it was dried on a hot plate at 100 ° C. for 5 minutes to form an adhesive layer having a thickness of 20 μm, and a test substrate was produced. About the test board | substrate which formed this adhesive bond layer, the silicon substrate was divided along the cut line of a half cut, and the silicon chip with an adhesive bond layer of 3 mm x 3 mm was obtained. On the other hand, a glass plate (MATUNAMI MICRO COVER GLASS 100 mm × 100 mm TICHKNESS No. 5; Matsunami Glass Industry Co., Ltd., trade name, thickness 0.45 to 0.60 mm) was diced to a size of 10 mm × 10 mm to obtain a glass chip. . On the obtained glass chip, the silicon chip was affixed at 70 ° C. for 2 seconds at a pressure of 1 N, and cured by heating at 180 ° C. for 2 hours to obtain a test chip. The test chip was allowed to stand on a hot plate at 260 ° C. for 20 seconds or longer and within 1 minute, and then the die shear strength was measured using Dage-4000 (Dage Corporation, trade name). Ten test chips were prepared, and the average value of the ten chips was defined as the die shear strength at 260 ° C. The die shear strength is good when it is 4 MPa or more, and particularly good when it is 6 MPa or more.

(Elastic modulus of cured product at 25 ° C. (room temperature))
The resin composition solutions of Examples and Comparative Examples were uniformly applied onto a release-treated PET film using a knife coater, dried in an oven at 115 ° C. for 15 minutes, and a dried film thickness of 25 μm was adhered. An agent layer was formed. The four adhesive layers were laminated to a thickness of 100 μm and cured in an oven at 180 ° C. for 2 hours. The elastic modulus at 25 ° C. of the cured product was measured with a viscoelasticity tester (RSA-III; TA Instruments, trade name). The measurement was performed under the conditions of test mode: tensile test, test temperature: −50 ° C. to 300 ° C., heating rate: 5 ° C./min, frequency: 1 Hz, and distance between chucks: 20 mm. The elastic modulus is evaluated to be good when it is 1 GPa or less.

(Curing film transmittance @ 400nm)
The resin compositions obtained in the Examples and Comparative Examples were 4.0 cm × 5.0 cm × 120-170 μm (actual measurement 140-160 μm) glass substrate (MATSUNAMI MICRO COVER GLASS 40 mm × 50 mm TICHKNESS No. 1; Matsunami Glass Industry (Co., Ltd., trade name) was uniformly applied using a spin coater and dried on a hot plate at 100 ° C. for 10 minutes to form an adhesive layer having a thickness of 50 μm after drying. To this adhesive layer, using a roll laminator at 90 ° C., a 4.0 cm × 5.0 cm × 120 to 170 μm (actual measurement 140 to 160 μm) glass substrate (MATSANAMI MICRO COVER GLASS 40 mm × 50 mm TICHKNESS No. 1; Matsunami Glass Kogyo Co., Ltd., trade name) was attached to obtain a test substrate having a three-layer structure of glass substrate / adhesive layer / glass substrate. The obtained adhesive layer of the test substrate was cured at 200 ° C. for 2 hours to obtain a test specimen for measurement.
The transmittance of the test piece for measurement was measured at a wavelength of 400 nm using a spectrophotometer U4100 (Hitachi, Ltd., trade name: start 800 nm, end 300 nm, scan speed 600 nm / min, sampling interval 1.0 nm). In addition, the transmittance | permeability numerical value of glass simple substance (for 2 sheets) was used for the baseline. Moreover, it is evaluated that the transmittance is 99% or more.

  DESCRIPTION OF SYMBOLS 1 ... CMOS image sensor, 2 ... Silicon substrate, 3 ... Sensor part, light-receiving part, 4 ... Peripheral circuit part, 5 ... Glass substrate, 6 ... Adhesive layer, 8 ... Wiring layer, 9 ... Solder ball, 10 ... Photodiode , 11 ... color filters, 12 ... microlenses.

Claims (7)

Acrylic polymer,
A compound having at least two (meth) acryloyl groups,
The resin composition containing the (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 8-30, and a polymerization initiator.   The resin composition according to claim 1, further comprising an adhesion assistant.   The resin composition according to claim 1 or 2, further comprising an antioxidant.   The resin composition according to any one of claims 1 to 3, further comprising a compound having one (meth) acryloyl group and a heterocyclic ring.   The resin composition according to any one of claims 1 to 4, which is used for an optical component. Forming an adhesive layer containing the resin composition according to any one of claims 1 to 5 on a semiconductor substrate;
Sandwiching the adhesive layer between the semiconductor substrate and the transparent substrate, and crimping the semiconductor substrate and the transparent substrate;
Curing the adhesive layer;
A method for manufacturing a semiconductor device. A semiconductor substrate provided with a light receiving portion on the upper surface;
An adhesive layer provided on the semiconductor substrate so as to cover the light receiving portion;
A transparent substrate bonded to the semiconductor substrate by the adhesive layer;
A solid-state imaging device comprising:
The said adhesive bond layer is a solid-state image sensor containing the resin composition as described in any one of Claims 1-5.

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