JP2016092299A - Method for manufacturing electronic component, film-like curable resin composition for sealing optical semiconductor device, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for manufacturing an electronic component, which is superior in the production efficiency of electronic components; and a film-like curable resin composition for sealing an optical semiconductor device, which can be used therefor, and which can be cured in a short time.SOLUTION: A method for manufacturing an electronic component comprises the steps of: sticking a film-like curable resin composition to a face of a device member having a substrate and an optical semiconductor device provided on the substrate on the side of the optical semiconductor device so that the optical semiconductor device is located inward from an outer edge of the film-like curable resin composition; and curing the film-like curable resin composition thus stuck, thereby forming a cured product of the film-like curable resin composition as an encapsulation member for encapsulating the optical semiconductor device. The film-like curable resin composition includes (A) an acrylic polymer, (B) an acrylic monomer and (C) a polymerization initiator.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing an electronic component, a film-like curable resin composition for sealing an optical semiconductor element, and an electronic component.

  In general, in a white LED, the phosphor is dispersed in the vicinity of the chip by a method such as coating the LED chip with a silicone resin or an epoxy resin in which the phosphor is dispersed, and blue light is converted into pseudo white light. Among them, silicone resins are attracting attention as materials for sealing and protecting LED chips because they are excellent in light resistance.

  As a material for sealing the LED chip, a thermosetting liquid silicone resin composition has been studied (see, for example, Patent Document 1). Further, as a material for protecting the LED chip, a thermosetting sheet-like silicone resin composition has been studied (for example, see Patent Document 2).

JP 2004-339482 A JP 2009-235368 A

  FIG. 2 is a process diagram illustrating a method for manufacturing an LED package using a conventional liquid transparent sealing material. When an LED package is manufactured using a liquid transparent sealing material, a dam material 28 is applied around the optical semiconductor element 24 provided on the substrate 20 via the adhesive 22 and connected to the substrate 20 by the gold wire 26. A step (FIG. 2A), a step of curing the applied dam material to form a dam 28 for blocking the liquid transparent sealing material (FIG. 2B), and a liquid transparent sealing A step of pouring the potting material in which the phosphor 30 is dispersed in the material into the inside of the dam 28 (FIG. 2C), and a step of curing the poured potting material with heat to form the sealing member 32 (FIG. 2 ( d)) is necessary and there is a problem that the number of steps is large.

  Moreover, in the thermosetting type silicone resin composition, since a hydrosilylation reaction is used for curing, a platinum-based catalyst is often added in advance. When a platinum-based catalyst is added, the reaction proceeds immediately after the addition. Therefore, it is necessary to add a reaction control agent to the silicone resin composition in order to ensure pot life. However, when a reaction control agent is blended, there is a problem that the curing rate of the silicone resin composition becomes slow and two-stage curing is required, which requires a long time for curing.

  The present invention has been made in view of the above circumstances, and a method for producing an electronic component that is excellent in the production efficiency of an electronic component, and a film shape for optical semiconductor element sealing that can be used in this and can be cured in a short time A curable resin composition is provided.

  The present invention relates to a film-like curable resin composition in which an optical semiconductor element is a film-like curable resin composition with respect to a surface on an optical semiconductor element side of an element member having a substrate and an optical semiconductor element provided on the substrate. A step of pasting so as to be positioned inside the outer edge of the object, and curing the pasted film-like curable resin composition to seal the optical semiconductor element with the cured product of the film-like curable resin composition And a step of forming as a stop member, wherein the film-like curable resin composition contains (A) an acrylic polymer, (B) an acrylic monomer, and (C) a polymerization initiator. .

  The method of manufacturing an electronic component according to the present invention eliminates the need for a dam material for blocking the resin when sealing an optical semiconductor element by using a film-like curable resin composition, thereby reducing the number of steps. it can. Moreover, since the film-like curable resin composition contains (A) an acrylic polymer, (B) an acrylic monomer, and (C) a polymerization initiator, curing in a short time by radical polymerization is possible. The production time of electronic parts can be shortened.

  The weight average molecular weight of the (A) acrylic polymer may be 100,000 to 800,000. Thereby, while the film formability of the said film-form curable resin composition improves, the brittleness as a film is reduced more and it can handle more easily.

  The present invention also provides a film-like curable resin composition for sealing an optical semiconductor element, comprising (A) an acrylic polymer, (B) an acrylic monomer, and (C) a polymerization initiator. The film-like curable resin composition for sealing an optical semiconductor element of the present invention can be cured in a short time by radical polymerization.

  The weight average molecular weight of the (A) acrylic polymer may be 100,000 to 800,000.

  The present invention is also an electronic component comprising a substrate, an element member having an optical semiconductor element provided on the substrate, and a sealing member for sealing the optical semiconductor element on the optical semiconductor element side of the element member. The sealing member has an outer edge that surrounds the optical semiconductor element on the substrate and at least a part thereof is exposed to the outside, and (A) an acrylic polymer, (B) an acrylic monomer, and (C ) An electronic component that is a cured product of a film-like curable resin composition containing a polymerization initiator is provided.

  The weight average molecular weight of the (A) acrylic polymer may be 100,000 to 800,000.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the electronic component which is excellent in the production efficiency of an electronic component, and the film-form curable resin composition for optical semiconductor element sealing which can be used for this and can be hardened in a short time are provided. be able to. Moreover, the electronic component excellent in transparency, heat resistance, and gas-barrier property can be manufactured by using the film-form curable resin composition concerning this invention.

It is process drawing which shows one Embodiment of the manufacturing method of the LED package using a film-form curable resin composition. It is process drawing which shows the manufacturing method of the LED package using the conventional liquid transparent sealing material.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  In the present specification, “transparency” means that visible light has good transparency. Further, “heat resistance” means that the resin composition after curing has good visible light transmittance. In addition, “gas barrier property” means that a member such as silver used as a conductive line or a light reflecting material of an LED light-emitting element is hardly corroded by suppressing permeation of gas, particularly sulfur-containing gas. means.

<Method for manufacturing electronic parts>
A method for manufacturing an electronic component according to this embodiment will be described. FIG. 1 is a process diagram showing one embodiment of a manufacturing process of an LED package using the film-like curable resin composition according to this embodiment. The method shown in FIG. 1 mainly includes (a) a step of affixing a film-like curable resin composition to an element member 18 produced through application of an adhesive, die bonding, and wire bonding, and (b). It comprises a step of curing the film-like curable resin composition, and (c) a step of peeling off the support.

  As shown in FIG. 1A, first, a laminated film 6 having a support 2 and a film-like curable resin composition 4 formed on the support 2 is prepared. A phosphor 8 is dispersed in the film-like curable resin composition 4. The laminated film 6 may further include a protective film that covers the surface of the film-like curable resin composition 4 opposite to the support 2 and protects the surface of the film-like curable resin composition 4.

  As the support 2, for example, an organic film such as a polyethylene terephthalate film can be used. As a protective film, organic films, such as a polyethylene terephthalate film, a polyethylene film, a polypropylene film, can be used, for example. If the film-like curable resin composition 4 has self-supporting property, the support 2 of the laminated film 6 is peeled off from the film-like curable resin composition 4, and the film-like curable resin composition 4 is used alone. It is also possible to use it.

  The film-like curable resin composition 4 can be formed, for example, by applying the curable resin composition to the support 2. Moreover, the film-like curable resin composition 4 prepares a coating liquid by dissolving or dispersing the resin composition in a solvent, if necessary, and forms the coating film by applying the coating liquid to the support 2. Then, it may be formed by removing the solvent from the coating film. As a method for forming the film-like curable resin composition 4 using the coating liquid, for example, a coating liquid containing a resin composition and a solvent is applied to the support 2 to form a coating film, and then a hot plate is used. Or the method of forming the film-form curable resin composition 4 on the support body 2 by heating at 60-150 degreeC, for example for 1 minute-1 hour, and drying a coating film using oven etc. is mentioned. .

  The film curable resin composition 4 is preferably formed by a method in which the film thickness becomes uniform. The thickness of the film-shaped curable resin composition 4, the support body 2, and the protective film which comprises the laminated | multilayer film 6 can set suitably suitable thickness by a use. For example, the thickness of the film-like curable resin composition 4 is preferably 1 to 500 μm. The thickness of the support 2 is preferably 10 to 3000 μm. The thickness of the protective film is preferably 10 to 200 μm.

  When the film-like curable resin composition 4 is used for sealing an optical semiconductor element having irregularities such as a dam part or a reflector part, the thickness of the film-like curable resin composition 4 is flat with the irregularity embedding property. From a viewpoint of surface formation, Preferably it is 10-500 micrometers, More preferably, it is 20-450 micrometers, More preferably, it is 30-400 micrometers.

  Subsequently, as shown in FIG. 1A, the film-like curable resin composition 4 is applied onto the substrate 10 via the substrate 10, the adhesive 12 applied on the substrate 10, and the adhesive 12. The optical semiconductor element 14 has a film-like curability with respect to the surface 18 a on the optical semiconductor element 14 side of the element member 18 having the provided optical semiconductor element 14 and the gold wire 16 connecting the substrate 10 and the optical semiconductor element 14. It affixes so that it may be located inside the outer edge 4a of the resin composition 4. FIG. The film-like curable resin composition 4 does not necessarily need to be adhered and adhered to the entire surface 18a of the element member 18 (including the surface of the optical semiconductor element 14 and the surface of the substrate 10). You may affix the film-form curable resin composition 4 so that it may be embedded.

  In the step of applying the film-like curable resin composition 4, specifically, the film-like curable resin composition 4 is to be covered, for example, the size of the surface of the optical semiconductor element 14 or the entire surface of the element member 18 or the like. It is used in a state of being fragmented according to. For example, when the laminated film 6 has a protective film, the laminated film 6 is cut into a desired size together with the protective film. The protective film of the laminated film 6 that has been cut into pieces is peeled off, placed so as to be in contact with the surface to be coated, and the laminated film 6 is pressure-bonded, heat-molded, or the like as necessary to form a film-like curable resin composition. 4 is applied to the surface to be coated.

  When the laminated film 6 is pressure-bonded to the element member 18 or heated while being pressure-bonded, an apparatus such as a film bonder is used, and usually room temperature (20 to 25 ° C.) to 300 ° C. or less and 10 MPa or less (usually 0.00. 01 to 10 MPa). The pressure bonding is preferably performed by pressurization of 5 MPa or less (for example, 0.1 to 5 MPa), more preferably 0.5 to 5 MPa. A suitable pressure bonding temperature is 60 to 150 ° C.

  Subsequently, as shown in FIG. 1B, the film-like curable resin composition 4 attached to the element member 18 is irradiated with light (active light) from the support 2 side to form a film. The curable resin composition 4 is cured to form a sealing member 4 that is a cured product of the film-like curable resin composition 4 and seals the optical semiconductor element 14. This light irradiation reduces the tack force on the surface of the film-like curable resin composition 4 and increases the hardness, thereby protecting the optical semiconductor element 14 from external factors such as heat, light, dust, moisture, etc. A gas barrier property against moisture in the air, sulfur-containing gas, and the like can be increased due to an increase in the crosslinking density.

The type of light to be irradiated is not particularly limited. Light irradiation can be performed using, for example, a light source that is usually used in the field. The actinic ray is, for example, at least one selected from the group consisting of ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays or visible rays are particularly preferable. Exposure, for example 1~10000mJ / cm ^2, preferably 1000~8000mJ / cm ^2, more preferably in the range of 1000~4000mJ / cm ^2. The exposure amount can be appropriately adjusted in consideration of a suitable balance of tack force, hardness and gas barrier properties on the surface of the film-like curable resin composition.

  Curing of the film-like curable resin composition 4 may be performed by heat curing in addition to the above-described photocuring, or may be performed by combining photocuring and heat curing.

  After the film-like curable resin composition 4 is cured and the optical semiconductor element 14 is sealed, the support 2 is peeled from the sealing member 4 as shown in FIG. The support 2 may be peeled before the film-like curable resin composition 4 is cured. Since the film-like curable resin composition 4 according to this embodiment contains an acrylic monomer as will be described later, in order to prevent polymerization inhibition due to oxygen, the support is obtained after the film-like curable resin composition 4 is cured. 2 is preferably peeled off.

  The film-like curable resin composition 4 according to the present embodiment is easy to handle because it is in a solid or semi-solid state at room temperature in an uncured state. By using the film-like curable resin composition 4 according to the present embodiment, a dam material for blocking the resin at the time of producing the LED module becomes unnecessary, and the process can be simplified. In addition, large-area collective sealing that seals a plurality of optical semiconductor elements such as a light emitting element or a light receiving element at a time can be performed.

  As shown in FIG. 1C, the electronic component 100 according to this embodiment is provided on the substrate 10, the adhesive 12 applied on the substrate 10, and the adhesive 12. An element member 18 having the optical semiconductor element 14 and a sealing member 4 for sealing the optical semiconductor element 14 on the optical semiconductor element 14 side of the element member 18 are provided. The sealing member 4 has an outer edge 4 c formed so as to surround the optical semiconductor element 14 on the substrate 10. Usually, the outer edge 4c of the sealing member 4 has the same shape (rectangular etc.) as the outer edge 4a of the film-like curable resin composition 4, and the optical semiconductor element 14 is arranged inside thereof. Here, the “outer edge of the sealing member” is a portion of the outer surface of the sealing member that surrounds the semiconductor element outside the optical semiconductor element when viewed from a direction perpendicular to the main surface of the substrate, When the sealing member is viewed from a direction parallel to the main surface of the substrate, it means the entire portion that can fall within the field of view. In the case of the present embodiment, the entire outer edge 4c is exposed to the outside, but a part of the outer edge 4c may be covered with another member. In the embodiment of FIG. 1, the sealing member 4 has a main surface 4 b that faces the substrate 10 at a position farther from the substrate 10 than the optical semiconductor element 14 on the optical semiconductor element 14 side of the element member 18. The outer edge 4c is a wall surface formed between the main surface 4b and the surface of the substrate 10 on the optical semiconductor element 14 side. The sealing member 4 is a cured product of a film-like curable resin composition containing (A) an acrylic polymer, (B) an acrylic monomer, and (C) a polymerization initiator. In other words, the sealing member 4 is entirely composed of a single cured product, and the inside thereof is not divided by the interface.

  Since the electronic component according to the present embodiment uses the film-like curable resin composition 4, the electronic component is superior in transparency, heat resistance, and gas barrier properties than the electronic components that have been developed so far.

  Hereinafter, the film-like curable resin composition according to the present embodiment will be described.

<Film curable resin composition>
The film-like curable resin composition of this embodiment contains (A) an acrylic polymer, (B) an acrylic monomer, and (C) a polymerization initiator.

  By adopting the above configuration, since the film-like curable resin composition can be cured in a short time by radical polymerization, the curing time can be shortened and the production efficiency of electronic parts can be improved. Moreover, it is excellent in the transparency, heat resistance, and gas barrier property after hardening, maintaining the fluidity | liquidity of the film before hardening of a film-form curable resin composition.

((A) component: acrylic polymer)
The acrylic polymer used in the present 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. Within the scope of the present invention, a compound having two or more (meth) acryloyl groups in the molecule, or a polymerizable compound having no (meth) acryloyl group ((meth) acrylonitrile, styrene, acetic acid) Vinyl, ethylene, propylene, etc.) and a monomer having one polymerizable unsaturated bond in the molecule, and a compound having two or more polymerizable unsaturated bonds in the molecule such as divinylbenzene) are copolymerized with an acrylic monomer. It may be made. From such a viewpoint, the acrylic polymer used in this embodiment has 1 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. Preferably 50 to 100% by mass or more.

  From the viewpoint of preventing coloring due to bonding with moisture in the air, styrene, vinyl acetate, ethylene, propylene, or the like can be used as the polymerizable compound having no (meth) acryloyl group.

（式（Ｉ）中、Ｘは置換基を有していてもよい炭素数５〜２２の脂環基を示す。Ｒ_１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す。Ｒ_２は水素原子又はメチル基を示す。）

（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種の官能基を含む置換基を示す。Ｒ_３は水素原子又はメチル基を示す。） The acrylic polymer preferably has at least one selected from the following general formulas (I), (II) and (III) as a structural unit. Thereby, the film-like curable resin composition which has the higher transmittance | permeability after hardening, higher heat resistance, and higher gas barrier property can be obtained.

(In formula (I), X represents an alicyclic group having 5 to 22 carbon atoms which may have a substituent. R ₁ represents 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. R ₂ represents a hydrogen atom or a methyl group.)

(In formula (III), Z represents a substituent 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 ₃ represents a hydrogen atom or a methyl group.)

  From the viewpoint of improving heat resistance, an acrylic polymer having the structural unit of the general formula (I) is preferable. From the viewpoint of reducing the elastic modulus of the cured product in order to relieve the stress accompanying curing, an acrylic polymer having the structural unit of the general formula (II) is preferable. From the viewpoint of improving the gas barrier property to the adherend of the cured product, an acrylic polymer having the structural unit of the general formula (III) is preferable.

  In the structural unit of the general formula (I), X is preferably a cyclohexyl group, a bicyclopentanyl group, an isobornyl group, a norbornyl group, a tricyclodecanyl group, or an adamantyl group from the viewpoint of heat resistance.

（式（ＩＶ）中、Ｒ_４は、水素原子又はメチル基を示す。Ｒ_５及びＲ_６はそれぞれ独立に、直鎖アルキル基を示す。） In the structural unit of the general formula (II), Y is preferably a linear or branched alkyl group from the viewpoint of low elasticity. Among these, a branched alkyl group is more preferable from the viewpoint of elastic modulus. The structural unit represented by the general formula (II) is particularly preferably a structural unit represented by the following formula (IV).

(In formula (IV), R ₄ represents a hydrogen atom or a methyl group. R ₅ and R ₆ each independently represents a linear alkyl group.)

  The structural unit of the general formula (III) is 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 in the ester moiety from the viewpoint of gas barrier properties. It is preferably a substituent containing at least one kind of functional group. Among these, Z is more preferably a substituent containing an epoxy group from the viewpoint of improving gas barrier properties, heat resistance and reducing odor of the cured product. Thereby, the high gas barrier property accompanying ring-opening polymerization of an epoxide is obtained.

  The acrylic polymer is preferably synthesized by free radical polymerization. Thereby, unlike living polymerization, an acrylic copolymer can be synthesized without using a catalyst such as halogen or heavy metal, and coloring derived from the catalyst that occurs during a lighting test of an LED can be prevented.

  As the acrylic polymer according to the present embodiment, for example, one synthesized by the following method can be used, but is not limited thereto.

300 g of tricyclo [5.2.1.0 ^2,6 ] dec-8-yl acrylate (product name: “FA-513A” (manufactured by Hitachi Chemical Co., Ltd.)), 350 g of butyl acrylate (BA), butyl methacrylate (BMA) 300 g, glycidyl methacrylate (GMA) 50 g and 2-ethylhexyl methacrylate (2EHMA) 50 g were mixed, and the resulting monomer mixture was further mixed with 5 g of lauroyl peroxide and n-octyl mercaptan as a chain transfer agent. Dissolve 45 g to make a mixed solution. To a 5 L autoclave equipped with a stirrer and a condenser, 0.04 g of polyvinyl alcohol and 2000 g of ion-exchanged water are added as a suspending agent, and the above mixture is added with stirring. The mixture is stirred at 250 rpm and 60 ° C. in a nitrogen atmosphere. For 5 hours and then at 90 ° C. for 2 hours to obtain resin particles. An acrylic polymer can be obtained by washing, dehydrating and drying the resin particles.

  In the acrylic polymer, the proportion of each structural unit is 5 to 94.5 parts by mass of the structural unit of the general formula (I), 5 to 90 parts by mass of the structural unit of the general formula (II), and the general formula. The structural unit of (III) is 0.5 to 30 parts by mass and the other structural units of 0 to 90 parts by mass, and the total mass of the structural units (that is, the total mass of the acrylic polymer) is 100 parts by mass. The mixed ratio is preferable.

  The proportion of the structural unit of the general formula (I) in the acrylic polymer is preferably 5 to 94.5 parts by mass, and more preferably 10 to 80 parts by mass from the viewpoint of hygroscopicity. If the ratio is 5 parts by mass or more, the hygroscopicity is satisfactory, and if it is 94.5 parts by mass or less, the mechanical strength is sufficient.

  The proportion of the structural unit of the general formula (II) in the acrylic polymer is preferably 5 to 90 parts by mass, and more preferably 15 to 80 parts by mass from the viewpoint of electric corrosion resistance and low elastic modulus. When the ratio is 5 parts by mass or more, the effect of improving the electric corrosion resistance is sufficient, and when it is 80 parts by mass or less, an appropriate Tg (glass transition temperature) of the acrylic polymer is easily obtained.

  The proportion of the structural unit of the general formula (III) in the acrylic polymer is preferably 0.5 to 30 parts by mass, and more preferably 1 to 20 parts by mass. When this ratio is 0.5 parts by mass or more, the adhesiveness and strength are sufficient, and when it is 30 parts by mass or less, there is no cross-linking reaction when copolymerizing, and the storage stability is good. .

  In this embodiment, (A) acrylic polymer is 60 mass parts or more from the viewpoint of moldability as a film product with respect to 100 mass parts of the total amount of (A) acrylic polymer and (B) acrylic monomer. It is preferable that it is 80 parts by mass or more from the viewpoint of heat resistance. When the acrylic polymer is 60 parts by mass or more, the tack force on the film surface before curing can be reduced, and the handleability of the film can be improved.

  The weight average molecular weight (Mw) of the acrylic polymer according to this embodiment is preferably 100,000 to 800,000 from the viewpoints of transparency and fluidity, and 150,000 to 750,000 from the viewpoint of reducing the brittleness of the film. More preferably, from the viewpoint of forming a thick film, it is more preferably 200000-700000. When a weight average molecular weight (Mw) is larger than 100,000, it becomes easy to make a film shape, and it can be set as the film which can reduce the brittleness of a film and can handle it easily. Furthermore, an optical semiconductor element such as a light emitting element or a light receiving element provided on the substrate can be easily sealed. The weight average molecular weight (Mw) is measured as follows.

It is measured by GPC method using tetrahydrofuran (THF) as an eluent and is calculated in terms of standard polystyrene. The details of the GPC method are as follows.
-Device name: HLC-8220GPC (product name, manufactured by Tosoh Corporation)
Column: Gelpack R-420, R-430, R-440 (product name, manufactured by Hitachi Chemical Co., Ltd.)
-Detector: RI detector-Column temperature: 40 ° C
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1 ml / min ・ Standard: Polystyrene

  (A) As a commercial item of an acrylic polymer, HTR-860P-3 (Mw = 700000-900000, Nagase ChemteX Corporation make) etc. are mentioned, for example.

((B) component: acrylic monomer)
Examples of the (B) acrylic monomer according to this embodiment include (B1) a (meth) acrylic monomer having a linear or branched alkyl group, and (B2) a (meth) acrylic single monomer having an alicyclic group. Body, (B3) polyfunctional (meth) acrylic monomer, and (B4) (meth) acrylic monomer having a functional group.

  As (B) acrylic monomer, (B1) a (meth) acrylic monomer having a linear or branched alkyl group or (B2) a (meth) acrylic monomer having an alicyclic group is used to form a film. High transparency can be maintained while ensuring the fluidity of the curable resin composition. The following can be considered as reasons why the above-mentioned effects can be achieved. As (B) acrylic monomer, (B1) a (meth) acrylic monomer having a linear or branched alkyl group or (B2) a (meth) acrylic monomer having an alicyclic group, (A) Since an acrylic polymer similar to the molecular skeleton of the acrylic polymer is formed, compatibility is improved, and high transparency can be maintained after curing, particularly when photocuring and thermal curing are used in combination. In addition, the transparency, heat resistance, and gas barrier properties of the (B) acrylic monomer can also be an element for improving the properties of the cured product.

((B1) (Meth) acrylic monomer having linear or branched alkyl group)
The (meth) acrylic monomer having a linear or branched alkyl group is preferably a (meth) acrylic acid ester having a linear or branched group in the ester portion and having one (meth) acryloyl group. . The straight or branched alkyl group of the ester moiety may be directly bonded to the oxygen atom of the ester group. As a linear or branched alkyl group of an ester part, a C1-C20 linear or branched alkyl group is mentioned, for example. From the viewpoint of the volatility of the acrylic monomer during film coating, the carbon number is more preferably 8 or more, and further preferably 12 or more. The structure of the alkyl group may be either a straight chain or a branched chain, but from the viewpoint that mass loss due to thermal decomposition hardly occurs at a low temperature and heat resistance is improved, a branched chain having no straight chain or tertiary carbon. Alkyl groups are preferred. From the above viewpoint, a (meth) acrylic acid ester having a branched alkyl group having 8 or more carbon atoms and no linear or tertiary carbon in the ester portion is more preferable.

  Examples of the (meth) acrylic acid ester having an alkyl group having 1 to 20 carbon atoms in the ester moiety include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) I-propyl acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, n-hexyl (meth) acrylate, Examples include n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and isostearyl (meth) acrylate.

  Among these, from the viewpoint of the volatility of the acrylic monomer during film coating, dodecyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate Etc. are particularly preferred. These can be used alone or in combination of two or more.

((B2) (Meth) acrylic monomer having alicyclic group)
The (meth) acrylic monomer having an alicyclic group is preferably a (meth) acrylic acid ester having an alicyclic group in the ester portion. Here, the alicyclic group of the ester part may be directly bonded to the oxygen atom of the ester part. Examples of the alicyclic group include cycloalkane, bicycloalkane, novolak type and isobornyl type. Among these, from the viewpoint of improving transparency, it is preferable to use a bicycloalkane or a novolac type.

Examples of the (meth) acrylic acid ester having an alicyclic group in the ester portion include, for example, cyclopentyl acrylate, cyclopentanyl acrylate, cyclohexyl acrylate, methyl cyclohexyl acrylate, trimethyl cyclohexyl acrylate, norbornyl acrylate, nor acrylate Bornylmethyl, phenylnorbornyl acrylate, cyanonorbornyl acrylate, isobornyl acrylate, bornyl acrylate, menthyl acrylate, fentil acrylate, adamantyl acrylate, dimethyladamantyl acrylate, tricycloacrylate [5.2 .1.0 ^2,6] dec-8-yl, acrylic acid tricyclo [5.2.1.0 ^2,6] deca-4-methyl, cyclodecyl acrylate, cyclopentyl methacrylate, Sansi Chlohexyl, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, norbornyl methacrylate, norbornyl methyl methacrylate, cyano norbornyl methacrylate, phenyl norbornyl methacrylate, isobornyl methacrylate, bornyl methacrylate, menthyl methacrylate, methacrylic acid Fentyl acid, adamantyl methacrylate, dimethyladamantyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decamethacrylate 4-methyl, cyclodecyl methacrylate, etc. are mentioned.

Among these, from the viewpoint of heat resistance, cyclopentanyl acrylate, cyclohexyl acrylate, isobornyl acrylate, norbornyl acrylate, norbornyl methyl acrylate, tricycloacrylate [5.2.1.0 ^2,6 ] Dec-8-yl, tricyclo [5.2.1.0 ^2,6 ] deca-4-methyl acrylate, adamantyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, methacryl Norbornyl acid, norbornyl methyl methacrylate, isobornyl methacrylate, bornyl methacrylate, menthyl methacrylate, fentil methacrylate, adamantyl methacrylate, dimethyl adamantyl methacrylate, methacrylic acid Tricyclo [5.2.1.0 ^2,6 ] dec-8-yl, tricyclo [5.2.1.0 ^2,6 ] dec-4-methyl methacrylate, cyclodecyl methacrylate, phenyl norbornyl methacrylate Etc. are preferred.

Further, from the viewpoint of improving heat resistance, cyclopentanyl acrylate, cyclohexyl acrylate, isobornyl acrylate, norbornyl acrylate, norbornyl methyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decyl acrylate 8-yl, tricyclo [5.2.1.0 ^2,6 ] dec-4-methyl acrylate, adamantyl acrylate, and the like are more preferable.

  The (meth) acrylic monomer having an alicyclic group may contain a polyfunctional (meth) acrylic monomer. Examples of the polyfunctional (meth) acrylic monomer having an alicyclic group include cyclohexane 1,4-dimethanol di (meth) acrylate, cyclohexane 1,3-dimethanol di (meth) acrylate, and tricyclodecane dimethylol di (meth). Acrylate (eg, Nippon Kayaku Co., Ltd., KAYARAD R-684, tricyclodecane dimethylol diacrylate, etc.), tricyclodecane dimethanol di (meth) acrylate (eg, Shin-Nakamura Chemical Co., Ltd., A-DCP, And tricyclodecane dimethanol diacrylate). From the viewpoint of preventing cracks in the cured product and peeling from the LED package, it is preferable to use a polyfunctional (meth) acrylic monomer having an alicyclic group.

((B3) polyfunctional (meth) acrylic monomer)
The polyfunctional (meth) acrylic monomer has two or more (meth) acryloyl groups and is not limited as long as it is other than (B1) and (B2). Examples of such a polyfunctional (meth) acrylic monomer include a polyfunctional (meth) acrylic monomer having a dioxane glycol skeleton, a polyfunctional (meth) acrylic monomer having a functional group, and the like.

  From the viewpoint of improving the transparency of the cured product, it is preferable to use a polyfunctional (meth) acrylic monomer having a dioxane glycol skeleton.

  As the polyfunctional (meth) acrylic monomer, a (meth) acrylic monomer having two (meth) acryloyl groups, for example, dioxane glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclo Pentanyl 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, hydroxypivalic acid 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 preferably ethylene oxide 5-15 mol-modified bisphenol A-type di (meth) acrylate), (poly) ethylene oxide Examples thereof include modified phosphoric acid di (meth) acrylate. Among the above, from the viewpoint of improving the transmittance of the cured product, dioxane glycol di (meth) acrylate (eg, Nippon Kayaku Co., Ltd., KAYARAD R-604, dioxane glycol diacrylate, etc.), 1,6-hexanediol Di (meth) acrylate and the like are preferable.

（式（Ｖ）中、Ｒ_９は水素原子又はメチル基を示す。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、アミド基及びエポキシ基からなる群より選ばれる少なくとも１種の官能基を有する置換基を示す。） ((B4) (meth) acrylic monomer having functional group)
The (meth) acrylic monomer having a functional group is a group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, an amide group, and an epoxy group in the molecule as shown in the following general formula (V). A (meth) acrylic monomer having at least one functional group selected from the above is preferable.

(In formula (V), R ₉ represents a hydrogen atom or a methyl group. Z represents 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, and an epoxy group. A substituent having a group is shown.)

  Examples of the (meth) acrylic monomer having a functional group include 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2 -(Meth) acryloyloxypropyl hexahydrophthalic acid-containing (meth) acrylic monomers (compounds wherein Z is a substituent containing a carboxyl group in the above formula (V)), (meth) acrylic acid, etc. Unsaturated carboxylic acid (compound in which Z is a hydroxyl group in the above formula (V)), hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (Meth) acrylate, N-methylol (meth) acrylamide, etc. Acid anhydride group-containing (meth) acrylic monomers such as droxyl group-containing (meth) acrylic monomer, trimellitic anhydride (meth) acryloyloxyethyl ester, cyclohexanetricarboxylic acid anhydride (meth) acryloyloxyethyl ester ( A compound in which Z is a substituent containing an acid anhydride group in the above formula (V)), diethylaminoethyl (meth) acrylate, -2,2,6,6-tetramethylpiperidinyl (meth) acrylate, An amino group-containing (meth) acrylic monomer such as (meth) acrylic acid-1,2,2,6,6-pentamethylpiperidinyl (in the above formula (V), Z is a substituent containing an amino group) Certain compounds), amide group-containing (meth) acrylic monomers such as (meth) acrylamide and N- (meth) acryloylglycinamide (in the above formula (V)) A compound in which Z is a substituent containing an amide group), glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 2- (2,3-epoxypropoxy) ethyl (meth) acrylate, 3- (2,3-epoxypropoxy) propyl (meth) acrylate, 4- (2,3-epoxypropoxy) butyl (meth) acrylate, 5- (2,3-epoxypropoxy) pentyl (meth) acrylate, 6- (2,3 epoxypropoxy) hexyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4, 5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethyl (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 Epoxy group-containing (meth) acrylic monomers such as -5,6-epoxyhexyl, (meth) acrylic acid-β-methylglycidyl, α-ethyl (meth) acrylic acid-β-methylglycidyl (formula (V) above) In which Z is a substituent containing an epoxy group).

  Among these, from the viewpoint of improving gas barrier properties, an epoxy group-containing (meth) acrylic monomer is preferable, and glycidyl methacrylate is more preferable.

  In the present embodiment, the (B) acrylic monomer is not particularly limited as long as it does not impair the transparency, heat resistance and gas barrier properties of the cured product, and the following monomers may be blended.

<Acrylic acid ester>
Examples of the acrylate ester include butoxyethyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, and tetrahydrofurfuryl acrylate.

<Methacrylic acid ester>
Examples of the methacrylic acid ester include butoxyethyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and tetrahydrofurfuryl methacrylate.

<Aromatic vinyl compound>
Examples of the aromatic vinyl compound include 4-vinylpyridine, 2-vinylpyridine, α-methylstyrene, α-ethylstyrene, α-fluorostyrene, α-chlorostyrene, α-bromostyrene, fluorostyrene, chlorostyrene, Examples thereof include bromostyrene, methylstyrene, methoxystyrene, (o-, m-, p-) hydroxystyrene, and styrene.

<Unsaturated dicarboxylic acid anhydrides>
Examples of the unsaturated dicarboxylic acid anhydrides include maleic anhydride.

<N-substituted maleimides>
Examples of N-substituted maleimides include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Ni-propylmaleimide, N-butylmaleimide, Ni-butylmaleimide, and Nt-butylmaleimide. N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide and the like.

  The blending amount of the (B) acrylic monomer is preferably 1 to 90 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the total amount of the (A) acrylic polymer and the (B) acrylic monomer. Part, more preferably 15 to 40 parts by weight. By setting the blending amount within the above range, the film is easy to handle, the fluidity of the uncured film-like curable resin composition is excellent, and the optical semiconductor such as a light emitting element or a light receiving element provided on the substrate. The element can be easily sealed. Moreover, foaming, turbidity, coloring and cracking of the cured product can be prevented.

((C) component: polymerization initiator)
As the (C) polymerization initiator according to this embodiment, (C1) a thermal polymerization initiator or (C2) a photopolymerization initiator can be used. These may be used in combination. As a result, it is possible to design not only a thermosetting system but also a photocuring system. For example, by using an exposure process, a conventional silicone material takes about 30 minutes for primary curing and 4 for secondary curing. While the time and curing time are long, it is possible to shorten the curing time. However, when short-time curing is desired, it is preferable to use only the (C2) photopolymerization initiator.

  (C1) Examples of the thermal polymerization initiator include dilauroyl peroxide (commercial product: “Perroyl L” (manufactured by NOF Corporation)), 1,1,3,3-trimethylbutylperoxy-2-ethylhexanate ( Commercial products: “Perocta O” (manufactured by NOF Corporation)), benzoyl peroxide (commercial products: “NIPER BW” (manufactured by NOF Corporation)), 1,1-di (t-hexylperoxy) cyclohexane (commercially available product) : “Perhexa HC” (manufactured by NOF Corporation)), t-butylcumyl peroxide (commercially available product: “Perbutyl C (manufactured by NOF Corporation)”), n-butyl 4,4-di- (t-butyl) Peroxy) valerate (commercial product: “Perhexa V” (manufactured by Nippon Oil & Fats Co., Ltd.)), dicumyl peroxide (commercial product: “Park Mill D” (Nippon Oils and Fats Co., Ltd.) )) Peroxide such like.

  In addition, (C1) thermal polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  (C1) The blending amount of the thermal polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the total amount of (A) acrylic polymer and (B) acrylic monomer. It is 2-5 mass parts, More preferably, it is 0.5-3 mass parts.

  Examples of (C2) photopolymerization initiators include acylphosphine oxides, 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. In addition, a photoinitiator may be synthesize | combined by a conventional method and a commercially available thing may be obtained.

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

  In addition, a photoinitiator (C2) can be used individually by 1 type or in combination of 2 or more types.

<Acylphosphine oxide>
Examples of the acylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercial product: “IRGACURE-819” (manufactured by BASF)), 2,4,6-trimethylbenzoyl- And diphenyl-phosphine oxide (commercially available product: “LUCIRIN TPO” (manufactured by BASF)).

<Oxime esters>
Examples of oxime esters include 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime) (commercial product: “IRGACURE-OXE01” (manufactured by BASF)), 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (commercial product: “IRGACURE-OXE02” (manufactured by BASF)), 1 -Phenyl-1,2-propanedione-2- [o- (ethoxycarbonyl) oxime] (commercially available product: “Quantacure-PDO” (manufactured by Nippon Kayaku Co., Ltd.)) and the like.

<Aromatic ketone>
Examples of the aromatic ketone include benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N′-tetraethyl-4,4 ′. -Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (commercial product: "IRGACURE-651" (manufactured by BASF)), 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (commercial product: “IRGACURE-369” (manufactured by BASF)), 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one (commercial product: “IRGACURE-907” (manufactured by BASF)), 2-hydroxy-1- {4- [4 -(2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (commercially available product: “IRGACURE-127” (manufactured by BASF)) and the like.

<Quinones>
Examples of quinones include 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenyl. Anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone and the like can be mentioned.

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

<Benzyl derivative>
Examples of benzyl derivatives include benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, as well as benzyldimethyl ketal.

<2,4,5-triarylimidazole dimer>
Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxy). Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- And methoxyphenyl) -4,5-diphenylimidazole dimer. Specific examples of 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer include 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1, 3-diazol-2-yl] -4,5-diphenylimidazole and the like.

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

<Coumarin-based compounds>
Examples of the coumarin compound 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- H, 5H-cyclopenta [3,4] [1] benzopyrano- [6,7,8-ij] quinolizine 12 (9H) -one, 7-diethylamino-5 ′, 7′-dimethoxy-3,3′-carbonyl Biscumarin, 3,3′-carbonylbis [7- (diethylamino) coumarin], 7-diethylamino-3-thienoxysilkine and the like can be mentioned.

<N-phenylglycine derivative>
Examples of N-phenylglycine derivatives include N-phenylglycine, N-phenylglycine butyl ester, Np-methylphenylglycine, Np-methylphenylglycine methyl ester, and N- (2,4-dimethylphenyl). Examples include glycine and N-methoxyphenylglycine.

  (C2) The compounding quantity of a photoinitiator becomes like this. Preferably it is 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A) acrylic polymer and (B) acrylic monomer, More preferably, it is 0.00. It is 5-5 mass parts, More preferably, it is 0.75-3 mass parts. By making the said compounding quantity into the said range, foaming, turbidity, coloring, and a crack of hardened | cured material can be prevented.

((D) component: antioxidant)
The film-like curable resin composition according to the present embodiment may further contain (D) an antioxidant. Thereby, it is possible to prevent oxidation of the polymerization terminal of (C) polymerization initiator and (A) acrylic polymer and (B) acrylic monomer remaining in the cured product after the curing reaction. As a result, the cured product is prevented from being colored, and an excellent visible light transmittance is obtained.

  (D) Although there is no restriction | limiting in particular as antioxidant, It is preferable to mix | blend the compound (henceforth a "hindered phenol type compound") which has a hindered phenol type structure.

（式（ＶＩ）中、Ｒ_７及びＲ_８はそれぞれ独立に、水素原子、直鎖状アルキル基又は分枝鎖状アルキル基を表す。なお、直鎖状アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。分枝鎖状アルキル基としては、例えば、イソプロピル基、イソブチル基、ｔ−ブチル基等が挙げられる。１分子中に上記式（ＶＩ）で表わされる基が複数あるとき、Ｒ_７及びＲ_８は、複数の基において、同一であっても異なっていてもよい。また、上記式（ＶＩ）中の芳香族環において、フェノール基、Ｒ_７及びＲ_８以外に、低級アルキル基等の基を有していてもよい。） In addition, as a hindered phenol type compound, the compound which has at least 1 group (hindered phenol group) represented by the following general formula (VI) in 1 molecule is mentioned.

(In formula (VI), R ₇ and R ₈ each independently represents a hydrogen atom, a linear alkyl group or a branched alkyl group. Examples of the linear alkyl group include a methyl group, Examples thereof include an ethyl group, a propyl group, a butyl group, etc. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a t-butyl group, etc. The molecule is represented by the above formula (VI) in one molecule. When there are a plurality of groups, R ₇ and R ₈ may be the same or different in the plurality of groups, and in the aromatic ring in the above formula (VI), a phenol group, R ₇ and (In addition to R ₈ , it may have a group such as a lower alkyl group.)

The hindered phenol compound is preferably a compound in which R ₇ and / or R ₈ in the above formula (VI) is a branched alkyl group, and at least one of R ₇ and R ₈ is a t-butyl group. A compound is more preferable, and a compound in which R ₇ and R ₈ are both t-butyl groups is more preferable.

  Such a hindered phenol compound may be synthesized by a conventional method, or a commercially available product may be obtained.

  Examples of the hindered phenol compound include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoate] (commercial product: “IRGANOX1010” (manufactured by BASF)), bis ( 3-tert-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylenebis (oxyethylene) (commercially available product: “IRGANOX245” (manufactured by BASF)), 4-[[4,6-bis (octylthio)- 1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol (commercial product: “IRGANOX565” (manufactured by BASF)), 3- (3,5-di-tert-butyl -4-Hydroxyphenyl) octadecyl propanoate (commercial product: “IRGANOX1076” (BA F)), N, N ′-(1,6-hexanediyl) bis [3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanamide] (commercial product: “IRGANOX1098” ( BASF)), tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid (commercial product: “CYANOX 1790” (manufactured by American Cyanamide)), 6-tert-butyl-4- [3-[(2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] propyl] -2-methylphenol (Commercially available product: “Sumilyzer GP” (manufactured by Sumitomo Chemical Co., Ltd.)), 3,9-bis [1,1-di-methyl-2- {β- (3-tert-butyl-4-hydroxy-5-methyl) Phenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (commercially available product: “ADEKA STAB AO80” (manufactured by ADEKA)), 2,2′-methylenebis- (4- Ethyl-6-t-butylphenol) (commercially available product: “Yoshinox 425” (manufactured by API Corporation)) and the like.

  Among these, from the viewpoints of molecular weight and solubility, 3,9-bis [1,1-di-methyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy } Ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (commercial product: “ADK STAB AO80” (manufactured by ADEKA)) is preferable.

  In addition, these antioxidants can be used individually by 1 type or in combination of 2 or more types.

  (D) The compounding quantity of antioxidant becomes like this. Preferably it is 0.1-20 mass parts with respect to 100 mass parts of total amounts of (A) acrylic polymer and (B) acrylic monomer, More preferably, it is 0.5. -15 parts by mass, more preferably 0.75-10 parts by mass. By making the said compounding quantity into the said range, resin coloring at high temperature can be suppressed.

  The film-like curable resin composition according to the present embodiment further contains a phosphor 8. The phosphor to be blended is not particularly limited, and examples thereof include Yttrium Aluminium oxide (manufactured by Sigma Aldrich). The phosphor is not necessarily contained in the resin composition.

  The film-like curable resin composition includes, for example, the above (A) acrylic polymer, (B) acrylic monomer and (C) polymerization initiator, and (D) an antioxidant and other components as necessary. It can form by apply | coating the curable resin composition which mixed etc. to the support body etc. From the viewpoint of workability when applied to a substrate, a support or the like, a solvent or a dispersion of the resin composition may be prepared as a coating liquid by adding a solvent to the resin composition. The solvent to be used is not particularly limited, but includes, for example, polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, propylene glycol monomethyl ether acetate, and γ-butyrolactone. It may be at least one selected from the group. The concentration of the resin composition in the coating liquid is preferably 20 to 85 mass%, more preferably 30 to 80 mass%, based on the mass of the coating liquid.

  The light transmittance at a wavelength of 450 nm of the film-like curable resin composition having a film thickness of 500 μm is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. In addition, the value of the light transmittance of a wavelength means the value measured by the method as described in an Example.

  The film-like curable resin composition according to the present invention has excellent visible light transmittance even in a thick film, and has excellent heat resistance with little resin coloring even after a long heat history at a high temperature. Therefore, the film-like curable resin composition according to the present invention is required to be downsized and densely packed, and is suitable as a sealing member for an optical semiconductor element such as a light emitting element or a light receiving element that is used for a long time in a high temperature environment. It is. That is, an electronic component manufactured by sealing an optical semiconductor element such as a light-emitting element or a light-receiving element using the film-like curable resin composition according to the present invention is an illumination for a camera used for a mobile phone or the like. And can be applied as an LED display component.

  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.

  (A) Acrylic polymer as component, (B) Acrylic monomer as component, (C) Polymerization initiator, (D) Antioxidant as component, and other components as solvent In N, N-dimethylacetamide, mixing was carried out at the blending ratios (parts by mass, solid content ratio) shown in Table 1 to obtain solutions of the resin compositions of Examples 1 to 5 and Comparative Example 1. The numbers in Table 1 indicate parts by mass of the solid content of each component. The detail of each component in a table | surface is shown below.

((A) component: acrylic polymer)
Acrylic polymer synthesized by the following method was used.
300 g of tricyclo [5.2.1.0 ^2,6 ] dec-8-yl acrylate (commercially available product: “FA-513A” (manufactured by Hitachi Chemical Co., Ltd.)), 350 g of butyl acrylate (BA), butyl methacrylate (BMA) 300 g, glycidyl methacrylate (GMA) 50 g and 2-ethylhexyl methacrylate (2EHMA) 50 g were mixed, and the resulting monomer mixture was further mixed with 5 g of lauroyl peroxide and n-octyl mercaptan as a chain transfer agent. 45 g was dissolved to prepare a mixed solution.

  To a 5 L autoclave equipped with a stirrer and a condenser, 0.04 g of polyvinyl alcohol and 2000 g of ion-exchanged water are added as a suspending agent, and the above mixture is added with stirring. The mixture is stirred at 250 rpm and 5 ° C. in a nitrogen atmosphere at 60 ° C. Polymerization was conducted for 2 hours at 90 ° C. for 2 hours to obtain resin particles. The polymerization rate was 99% by mass method. The resin particles were washed with water, dehydrated and dried to obtain an acrylic polymer. The weight average molecular weight of the obtained acrylic polymer was Mw = 650000.

The weight average molecular weight (Mw) is determined by GPC method using tetrahydrofuran (THF) as an eluent. Details of the GPC method are as follows.
-Device name: HLC-8220GPC (product name, manufactured by Tosoh Corporation)
Column: Gelpack R-420, R-430, R-440 (product name, manufactured by Hitachi Chemical Co., Ltd.)
-Detector: RI detector-Column temperature: 40 ° C
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1 ml / min ・ Standard: Polystyrene

((B) component: acrylic monomer)
・ Tricyclodecane dimethanol diacrylate (commercially available product: “A-DCP” (manufactured by Shin-Nakamura Chemical Co., Ltd.))
・ Glycidyl methacrylate (commercial product: “GMA” (Wako Chemical Co., Ltd.))
・ Hexanediol diacrylate (commercially available product: “FA-126AS” (manufactured by Hitachi Chemical Co., Ltd.))
・ Lauryl acrylate (commercially available product: “Light Ester L” (manufactured by Kyoeisha Chemical Co., Ltd.))
2-ethylhexyl methacrylate (commercially available product: “Light Ester EH” (manufactured by Kyoeisha Chemical Co., Ltd.))
Isostearyl acrylate (commercial product: “NK ester S-1800A” (manufactured by Shin-Nakamura Chemical Co., Ltd.))

((C) component: polymerization initiator)
2,2-dimethoxy-1,2-diphenylethane-1-one (commercially available product: “I-651” (manufactured by Ciba Specialty Chemicals))

((D) component: antioxidant)
3,9-bis [1,1-di-methyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10- Tetraoxaspiro [5,5] undecane (commercially available product: “ADEKA STAB AO80” (manufactured by ADEKA))

(Other ingredients)
3-Glycidoxypropyltrimethoxysilane (commercially available product: “KBM-403” (manufactured by Shin-Etsu Chemical Co., Ltd.))
・ Phenoxy resin (commercial product: "YP-50" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.))

<Preparation of laminated film>
The solution of the resin composition of an Example and a comparative example was uniformly apply | coated using the applicator on the polyethylene terephthalate as a support body. The applied solution is heated for 10 minutes with a dryer at 120 ° C. to remove the solvent, thereby forming a film-like curable resin composition, and the film-like curable resin formed on the support. A two-layer laminated film having the composition was obtained. Then, the protective film was affixed with respect to the film-form curable resin composition, and it was set as 3 layer structure. The thickness of the film-like curable resin composition in the obtained laminated film was 50 μm. By further laminating the film curable resin composition using a laminator, the thickness of the film curable resin composition was set to a predetermined film thickness.

<Measurement of haze and total light transmittance>
The protective film of the laminated film whose thickness of the film-like curable resin composition was 200 μm was peeled off, and laminated on the glass substrate in such a direction that the support was located on the opposite side of the glass substrate. Lamination was performed using a laminator. The laminated film laminated on the glass substrate was irradiated with light at an exposure amount of 2000 mJ / cm ² using a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd.). This glass with resin is allowed to stand in an oven at 200 ° C. for 3 hours, and then a color / turbidity simultaneous measuring device (product name: “COH 300A” (Nippon Denshoku) is used with reference to the haze value and total light transmittance of the glass alone. Haze value and total light transmittance were measured using Kogyo Co., Ltd.). This was defined as the initial total light transmittance. Next, the glass with resin was left in an oven at 200 ° C. for 48 hours, and the total light transmittance was measured. The results are shown in Table 2. When the haze value was 1 or less, it was defined as a non-turbid state. Regarding Comparative Example 1, measurement was performed at a film thickness of 50 μm.

<Measurement of gas barrier properties>
The protective film of the laminated film with a film-like curable resin composition having a thickness of 600 μm is peeled off and pasted on the LED package using a pressure type vacuum laminator (product name: “V130” (manufactured by Nichigo Morton Co., Ltd.)). I attached. The application conditions were a temperature of 80 ° C., a pressure of 0.5 MPa, a vacuum drawing time of 18 seconds, and a pressurization time of 60 seconds. Thereafter, the laminated film laminated on the LED package was irradiated with light at an exposure amount of 8000 mJ / cm ² using a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd.). The prepared sample was heated at 100 ° C. for 2 hours under a sulfur atmosphere of 5 g / L. This was soldered to a substrate, connected to a constant current power supply device by connecting wires, and the luminance was measured using an instantaneous multi-photometry system. In addition, the presence or absence of sulfuration of the lead frame and the silver-plated reflector was visually confirmed. The results are shown in Table 2.
A: Luminance retention before and after exposure to sulfurized gas is 90% or more B: Luminance retention before and after exposure to sulfurized gas is less than 90%

<Observation of coloring after lighting test>
The protective film of the laminated film with a film-like curable resin composition having a thickness of 600 μm is peeled off and pasted on the LED package using a pressure type vacuum laminator (product name: “V130” (manufactured by Nichigo Morton Co., Ltd.)). I attached. The application conditions were a temperature of 80 ° C., a pressure of 0.5 MPa, a vacuum drawing time of 18 seconds, and a pressurization time of 60 seconds. Thereafter, the laminated film laminated on the LED package was irradiated with light at an exposure amount of 8000 mJ / cm ² using a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd.). The LED package soldered to the board is put into a constant temperature and humidity chamber (product name: “ESPEC HUMIDITY CABINET LHL-112” (manufactured by Espec Engineering Co., Ltd.)), connected to the wiring, and a constant current power supply device (product name: "PMC-A series PMC70-1A" (manufactured by Kikusui Electronics Co., Ltd.)). The environment in the constant temperature and humidity chamber was set to a temperature of 85 ° C. and a humidity of 85%, and a constant current power supply device was used for continuous lighting at 120 mA for 168 hours. After lighting was completed, the presence or absence of coloring on the lead frame was confirmed. The results are shown in Table 2.
A: Without coloring B: With coloring

  The film-like curable resin composition containing the acrylic monomer in Examples 1 to 5 can be cured for a short time because the curing reaction proceeds by radical polymerization by light irradiation. While the conventionally used silicone material has a long curing time of about 30 minutes for primary curing and 4 hours for secondary curing, the time required for photocuring in Examples 1 to 5 is about 5 minutes. I was able to save time.

  Further, as shown in FIG. 2, when manufacturing an LED package using a liquid transparent sealing material, the light provided on the substrate 20 via the adhesive 22 and connected to the substrate 20 by the gold wire 26. A step of applying the dam material 28 around the semiconductor element 24 (FIG. 2A), and a step of curing the applied dam material to form the dam 28 for blocking the liquid transparent sealing material ( 2 (b)), a step of pouring the potting material in which the phosphor 30 is dispersed in the liquid transparent sealing material into the inside of the dam 28 (FIG. 2 (c)), and the poured potting material is cured by heat. The step of forming the sealing member 32 (FIG. 2D) was necessary. On the other hand, in Examples 1-5 using a film-like curable resin composition, since a dam is unnecessary, a process of attaching the film-like curable resin composition to the optical semiconductor element on the substrate, and a film The LED package can be manufactured only by the process of curing the curable resin composition, and the number of processes can be reduced.

  Furthermore, as shown in Table 2, the film-like curable resin composition containing the acrylic monomer in Examples 1 to 5 can be cured in a short time by light irradiation, and was cured by light irradiation. The film-like curable resin composition had a low haze value and was not turbid. Therefore, the initial transmittance was high and excellent transparency was exhibited. Further, even after 200 ° C. for 48 hours, the transmittance was equal to the initial transmittance, and excellent heat resistance was exhibited. Furthermore, in the LED package sealed using the film-like curable resin compositions of Examples 1 to 5, sulfuration of the lead frame and the silver plating reflective material was not observed, and the gas barrier property was good. In addition, since an acrylic copolymer synthesized by free radical polymerization was used, the appearance after the lighting test was good without coloration.

  On the other hand, as in Comparative Example 1, when a phenoxy resin that was not an acrylic monomer was used, the flexibility of the film alone was poor, and it was not possible to laminate the glass substrate satisfactorily. Further, it was confirmed that the transmittance after 48 hours at 200 ° C. was significantly lower than the initial transmittance, and there was no heat resistance at 200 ° C.

  The film-like curable resin composition of the present invention can be cured in a short time by radical polymerization, and the cured product is excellent in transparency, heat resistance and gas barrier properties. Therefore, it is suitable as a sealing member for an optical semiconductor element such as a light-emitting element or a light-receiving element that is used for a long time in a miniaturized and high-density environment and in a high-temperature environment.

  DESCRIPTION OF SYMBOLS 2 ... Support body, 4 ... Film-like curable resin composition (sealing member), 4a ... Outer edge of film-like curable resin composition, 4b ... Main surface facing substrate, 4c ... Outer edge of sealing member (wall surface) ), 6 ... laminated film, 8, 30 ... phosphor, 10, 20 ... substrate, 12, 22 ... adhesive, 14, 24 ... optical semiconductor element, 16, 26 ... gold wire, 18 ... element member, 18a ... element The surface of the member on the side of the optical semiconductor element, 28 ... Dam material (dam), 32 ... Sealing member, 100 ... Electronic component.

Claims (6)

The optical semiconductor element is a film-like curable resin composition with respect to a surface on the optical semiconductor element side of an element member having an optical semiconductor element provided on the substrate and the optical semiconductor element. A step of attaching to be located inside the outer edge of the
Curing the pasted film curable resin composition, and forming a cured product of the film curable resin composition as a sealing member for sealing the optical semiconductor element,
The method for producing an electronic component, wherein the film-like curable resin composition contains (A) an acrylic polymer, (B) an acrylic monomer, and (C) a polymerization initiator.   The manufacturing method of the electronic component of Claim 1 whose weight average molecular weights of the said (A) acrylic polymer are 100,000-800000.   A film-like curable resin composition for sealing an optical semiconductor element, comprising (A) an acrylic polymer, (B) an acrylic monomer, and (C) a polymerization initiator.   The film-like curable resin composition for optical semiconductor element sealing of Claim 3 whose weight average molecular weights of the said (A) acrylic polymer are 100,000-800000. An electronic component comprising a substrate and an element member having an optical semiconductor element provided on the substrate, and a sealing member for sealing the optical semiconductor element on the optical semiconductor element side of the element member,
The sealing member has an outer edge that surrounds the optical semiconductor element on the substrate and at least a part thereof is exposed to the outside, and (A) an acrylic polymer, (B) an acrylic monomer, and (C ) An electronic component that is a cured product of a film-like curable resin composition containing a polymerization initiator.   The electronic component according to claim 5, wherein the acrylic polymer (A) has a weight average molecular weight of 100,000 to 800,000.

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