TW201341513A - Sealant for semiconductor light emitting element, cured film and semiconductor light emitting device using the same, and method for manufacturing semiconductor light emitting device - Google Patents

Abstract

A sealant for a semiconductor light emitting element is provided, which is a thermal curing sealant for forming a cured film that covers at least a portion of the semiconductor light emitting element. The sealant includes acrylate monomers having an average molecular weight of 1, 000 or less as curable compounds. A viscosity η 25 of the sealant before being cured at 25 DEG C is 1, 000 mPa.sec or more and 1, 000, 000 mPa.sec or less, and a ratio of the viscosity η 25 to a viscosity η 50 at 50 DEG C is 10 or more.

Description

Encapsulant for semiconductor light-emitting device, cured film using the same, and semi-conductive Body illuminating device

The present invention relates to a sealing agent for a semiconductor light-emitting element (Semiconductor Light Emitting Element), a cured film using the same, and a semiconductor light-emitting device.

The semiconductor light-emitting device is expected to be a next-generation light source in place of an incandescent lamp or a fluorescent lamp, and is actively developing technology for improving power and the like at home and abroad. The application range of the semiconductor light-emitting device also covers various aspects, and is widely used not only as indoor lighting but also as a backlight of a liquid crystal display device. In particular, in recent years, the awareness of energy saving has increased, and semiconductor light-emitting devices that consume low power have attracted attention, and various companies or research institutions are accelerating the development of technology for light-emitting diode (LED) lighting.

The type of the semiconductor light-emitting device can be, for example, a projectile type, a surface mounted device (SMD), a chip on board (COB), or the like. Fig. 1 is a view showing an example of a surface mount type. In this example, The LED wafer 1 is mounted on a reflector package substrate 2 molded of ceramic or resin. The cavity (concave space) W is sealed by a resin cured film (sealing material) 3 such as epoxy or silicone which is obtained by dispersing the phosphor 7 . Further, in the semiconductor light-emitting device 10, the element 1 is fixed by the conductive adhesive 8, and conduction with the electrode 4 is obtained via a bonding wire 6. The surface on the inner side of the cavity is given a function of a reflector, and is a structure in which a large amount of light is taken out.

According to the above configuration, it is also known that a semiconductor light-emitting device requires a structure and a member different from those of a conventional incandescent light bulb or a fluorescent lamp, and its development is not sufficient. In the case of the above-mentioned sealing material, epoxy resin or anthrone-based resin is currently in the mainstream, but development research and material exploration for further improving performance have been sought. On the other hand, a phosphor is dispersedly disposed in the sealing material, thereby adjusting the color of light emitted from the optical semiconductor light-emitting element. In order to optimize the dispersion state of the phosphor, heating conditions such as curing of the sealing resin are adjusted (see Patent Document 1).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-9905

Although the above-mentioned Patent Document 1 proposes adjustment setting of the temperature increase rate when the sealing resin is cured, there is no disclosure relating to the specific resin component used in the sealant, and it is actually difficult to manufacture a product. According to the confirmation by the inventors of the present invention, it is difficult to obtain a dispersed state of the target phosphor in the curable composition using the fluorenone resin disclosed in the above-mentioned known document (see a comparative example described later).

Accordingly, it is an object of the present invention to provide a sealing agent for a semiconductor light-emitting device having a viscosity and a temperature characteristic required for use in a semiconductor light-emitting device, and a semiconductor light-emitting device using the same, wherein the viscosity and temperature characteristics thereof can be The dispersion state required for the phosphor in the cured film and good manufacturing suitability are achieved.

The above problems are solved by the following means.

[1] A sealant for a semiconductor light-emitting device, which is a thermosetting sealant that forms a cured film covering at least a part of a semiconductor light-emitting device, and the sealant contains an acrylate monomer having an average molecular weight of 1,000 or less as a curable compound. The above sealant has a viscosity η ₂₅ at 25 ° C of 1,000 mPa. Above sec, 1,000,000 mPa. Below sec, the ratio η ₂₅ /η ₅₀ of the viscosity η ₂₅ to the viscosity η ₅₀ at 50 ° C is 10 or more.

[2] The sealant for a semiconductor light-emitting device according to [1], wherein the acrylate monomer is a monomer having an isocyanurate skeleton, and a monomer having a norbornane skeleton. A monomer having an adamantane skeleton, a phosphate group-containing monomer, or a monomer having a bisphenylene group.

[3] The encapsulant for a semiconductor light-emitting device according to [1], wherein the acrylate monomer contains a hydroxyl group-containing (OH)-containing compound.

[4] The sealing agent for a semiconductor light-emitting device according to any one of the above [1], wherein the acrylate monomer comprises a compound represented by the following formula (1): [Chemical Formula 1]

(wherein R ¹ , R ² and R ³ each independently represent a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and a carbon number; An aryl group of 6 to 24, an acryloxy group represented by the following formula (I), or a mercaptooxy group represented by the following formula (II); and ^a represents a single bond or a alkylene having 1 to 4 carbon atoms; Wherein at least one of R ¹ , R ² and R ³ is the above propylene decyloxy group)

(wherein R ^a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; * represents a bonding hand)

(wherein R ^b represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms; * means a bonding bond).

The sealant for a semiconductor light-emitting device according to any one of the above-mentioned [1], wherein the acrylate monomer comprises a compound represented by the following formula (21):

(wherein R ²¹ and R ²² represent a substituent; Ac represents an acryloxy group; L ^e represents a single bond or a linking group; and L ^f represents a linking group; and n21 and n22 represent an integer of 0 to 4).

[6] The sealing agent for a semiconductor light-emitting device according to any one of [1] to [5], which comprises two or more kinds of the acrylate monomers.

[7] The sealing agent for a semiconductor light-emitting device according to any one of [1] to [6] further comprising a phosphor.

[8] The sealant for a semiconductor light-emitting device according to the above aspect, wherein the phosphor has an average particle diameter of from 1 μm to 100 μm.

[9] The sealing agent for a semiconductor light-emitting device according to [7], wherein the phosphor has a specific gravity of 2 to 10.

[10] [1] to the semiconductor light emitting element [9] according to any sealing agent, wherein the viscosity at 25 deg.] C [eta] of the sealant _25, and said viscosity [eta] viscosity at ₂₅ and 50 ℃ η ratio of ₅₀ η ₂₅ / η ₅₀ satisfies the following relation equation (F1) and the equation _{(F2): η 25 / η} 50> a. Log ₁₀ (η ₂₅ )+b...F1

η ₂₅ /η ₅₀ <c. Log ₁₀ (η ₂₅ )+d...F2

a=34

b=-200

c=34

d=50.

[11] A sealant for a semiconductor light-emitting device, which is a thermosetting sealant that forms a cured film covering at least a part of the semiconductor light-emitting device, and the sealant for a semiconductor light-emitting device is used by containing a phosphor, and the seal is used. The agent comprises an acrylate monomer having an average molecular weight of 1,000 or less as a curable compound, and the above-mentioned sealant has a viscosity η ₂₅ at 25 ° C of 1,000 mPa. Above sec, 1,000,000 mPa. Below sec, the ratio η ₂₅ /η ₅₀ of the viscosity η ₂₅ to the viscosity η ₅₀ at 50 ° C is 10 or more.

[12] A cured film obtained by hardening the sealant according to any one of [1] to [11].

[13] A semiconductor light-emitting device comprising: the cured film according to [12], and a semiconductor light-emitting element sealed by the cured film.

[14] A method of manufacturing a semiconductor light-emitting device, comprising: a step of hardening a sealant for a semiconductor light-emitting device in a cavity of a reflector package to form a cured film, and the method of manufacturing the semiconductor light-emitting device includes: preparing The step of sealing a semiconductor light-emitting device according to any one of [1] to [11], wherein the sealing agent is filled in a cavity of the reflector package; and the filled sealant is at 25 ° C a step of heating and soaking in a range of ~90 ° C; and a step of heating and hardening the above-mentioned soaked filler in a range of from 100 ° C to 200 ° C.

The sealing agent for a semiconductor light-emitting device of the present invention can set the phosphor in a desired dispersed state at the time of curing, and achieves good manufacturing suitability. In particular, when the sealant is filled, the dispersion of the manufacturing lot is suppressed by stably dispersing the phosphor at a high viscosity, which is a difference in the amount of the phosphor which is easily generated due to the change over time. cause. On the other hand, in the case of heat hardening, the sedimentation of the phosphor can be promoted by lowering the viscosity more greatly. By the sedimentation effect, the semiconductor light-emitting device produced by using the above-described sealant can realize good light-emitting characteristics without color unevenness due to the emission angle.

The above as well as other features and advantages of the present invention will be apparent from the description and appended claims.

1‧‧‧Semiconductor light-emitting elements

2‧‧‧Reflector package substrate

3‧‧‧Sealing material/hardened film

4‧‧‧Electrode

6‧‧‧bonding leads

7‧‧‧Fertior

8‧‧‧ Conductive adhesive

9a‧‧‧Glossy

9b‧‧‧ bottom

10‧‧‧Semiconductor light-emitting device

21A, 21B‧‧‧ polarizing plate

22‧‧‧Color filter substrate

23‧‧‧Liquid layer

24‧‧‧Array substrate

25‧‧‧Light guide plate

26‧‧‧LED backlight

D1, d2‧‧‧ bottom diameter

Length of D‧‧‧ side

Ls‧‧‧ Short side length

W‧‧‧ concave space/cavity

FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor light-emitting device.

Fig. 2 is a plan view schematically showing a bottom surface of the semiconductor light emitting device shown in Fig. 1.

3 is a developed perspective view schematically showing a configuration of a liquid crystal display device of a semiconductor light-emitting device according to a preferred embodiment of the present invention.

4 is a graph in which the temperature characteristics of the respective sealant samples adjusted in the examples and the comparative examples were plotted.

The sealant of the present invention contains an acrylate monomer of a specific molecular weight, Specific viscosity and its temperature characteristics. Thereby, it exhibits sufficient viscosity at normal temperature and exhibits good manufacturing adaptability, exhibits low fluidity by heating, exhibits remarkable fluidity, and promotes sedimentation of the phosphor to achieve desired dispersion configuration. . Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.

[Acrylate monomer]

The sealant of the present invention preferably contains an acrylate monomer and substantially contains only the acrylate monomer as its organic hardening component. Here, the acrylate monomer means a polymerizable compound having an acryloyl group which may have a substituent at the α-position, and preferably has an acryloyl group (unsubstituted) or a methacryl fluorenyl group (via a methyl group). Replace). The specific acrylate monomer can be applied to a user as a curable composition, preferably a monomer having an isomeric cyanate skeleton, an acrylate monomer having a biphenyl group, and a decane skeleton. An acrylate monomer, a monomer having an adamantane skeleton, or an acrylate monomer containing phosphoric acid. Further, the term "skeleton" as used herein refers to a residue having a main portion of the molecule. Further, the propylene fluorenyl group is broadly defined to mean an unsubstituted propylene group having a substituent and, in a narrow sense, an unsubstituted acryl fluorenyl group. Unless otherwise stated, it is used in a broad sense. This is also the case when it is called an acrylate or the like.

(Acrylate monomer having an isomeric cyanate skeleton)

In the present invention, a compound having an isomeric cyanate skeleton represented by the following formula (1) is preferably used as the acrylate monomer.

[Chemical 5]

. R ¹ , R ² , R ³

R ¹ , R ² and R ³ in the formula each independently represent a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and a carbon number of 6 An aryl group of ~24, an acryloxy group represented by the following formula (I), or a mercaptooxy group represented by the following formula (II). L ^a represents a single bond or an alkylene group having 1 to 4 carbon atoms. Wherein at least one of R ¹ , R ² and R ³ is the above acryloxy group.

In the formula, R ^a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; and * represents a bond.

In the formula, R ^b represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms; * represents a bonding bond.

Among R ¹ , R ² , R ³ and R ^b , the alkyl group having 1 to 10 carbon atoms may, for example, be a linear alkyl group, a branched alkyl group or a cyclic alkyl group. Among them, a linear chain having a carbon number of 3 to 10 is preferred. An alkyl group, a branched alkyl group having 6 to 10 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms.

When R ¹ , R ² , R ³ and R ^b are an aryl group, the aryl group may have a single ring or a polycyclic ring. The aryl group is preferably a phenyl group therein.

In the present specification, the alkyl group and the aryl group may be further accompanied by a substituent, and examples thereof include the substituent T described later.

L ^a is a single bond or an alkylene group having 1 to 4 carbon atoms, and preferably a ethyl or isopropylene group (N-CH ₂ -CH(CH ₃ )-R has a tendency: R is R ¹ , R ² or R ³ ), more preferably an ethyl group.

In the sealant of the present invention, it is preferred that the specific acrylate monomer has a hydroxyl group. Therefore, in the acrylate monomer represented by the formula (1), at least one of R ¹ , R ² and R ³ is preferably a hydroxyl group or a group having a hydroxyl group. Thereby, a bonding structure formed by hydrolysis and dehydration condensation can be formed with the alkoxy group of the above specific alkoxyalkylene group compound, whereby a stronger and more stable cured product can be formed.

(Acrylate monomer with extended biphenyl)

The acrylate monomer is preferably a monomer represented by the following formula (21).

. R ²¹ , R ²²

R ²¹ and R ²² represent a substituent, and preferred examples of the group include a substituent T to be described later.

. Ac

Ac represents an acryloxy group, and a preferable example thereof is a group represented by the above formula (I).

. L ^e

L ^e represents a single bond or a linking group. The preferred range thereof is a cyclic or chain (branched or linear) alkylene group, an aryl group, a heteroaryl group, an oxy group (-O-), a carbonyl group, or an amine group (-NR-: R is a hydrogen atom or an organic group), or a combination thereof. Preferably, it is an alkylene group having 1 to 10 carbon atoms or an alkylene group having an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms bonded to the benzene ring in the formula by an oxygen atom. An alkyl group having an oxy group.

As described above, the acrylate monomer preferably has a hydroxyl group, and it is preferred that the above-mentioned linking group L ^e has a hydroxyl group.

. L ^f

L ^f represents a linking group. Examples thereof include: -O-, -CH ₂ -, -C(CH ₃ )H-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(Ph)-, -C(CF ₃ ) ₂ -, -C(CH ₃ )(C ₂ H ₅ )-, -C(Ph) ₂ -, -C(=CCl ₂ )-, -SO ₂ -, and the like. Further, L ^f may also be a group represented by the following formula.

Where * represents a bond key. R ³¹ and R ³² represent an alkylene group having 1 to 5 carbon atoms, preferably a methylene group, an exoethyl group, a propyl group, and more preferably a 2,2-propanediyl group. . R ³³ represents a substituent, and examples thereof include an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group, and a halogen atom. N3 represents an integer of 0 to 4, preferably 0.

. N21 and n22 represent integers of 0 to 4.

(Acrylate monomer having an alicyclic hydrocarbon skeleton)

The acrylate monomer having an alicyclic hydrocarbon skeleton which is suitably used in the invention may, for example, be an acrylate monomer having a norbornane skeleton or an acrylate monomer having an adamantane skeleton. Specifically, a monomer represented by the following formula (11) or formula (12) can be mentioned.

. R ¹¹ , R ¹²

R ¹¹ and R ¹² represent a substituent. A plurality of R ¹¹ and R ¹² may be bonded to each other to form a ring. The preferred range of the substituent is exemplified by the substituent T described later. The substituent containing Ac may be substituted for R ¹¹ and R ¹² or may be substituted for the ring formed above.

. L ^d

L ^d represents a single bond or a linking group. Which L ^a preferred range above the same.

. Ac

Ac represents an acryloxy group which may have a substituent. Preferred groups of Ac have the same meanings as in the above formula (I).

N11 represents an integer from 0 to 6. N12 represents an integer from 0 to 9. Na represents an integer from 1 to 4.

(Acrylate monomer having a phosphate group)

The acrylate monomer is also preferably a monomer represented by the following formula (31) or formula (32).

. Ac

Ac represents an acryloxy group, and a preferred example thereof is a group represented by the above formula (I).

. L ^g

L ^g represents a linking group, and its preferred range is the same as that of the above L ^e .

[Regulations relating to molecular weight and viscosity]

The sealant of the present invention has a specific molecular weight and specific viscosity characteristics. This point will be described in detail below.

(molecular weight)

In the present invention, the molecular weight of the acrylate monomer is 1,000 or less, preferably 700 or less. There is no particular lower limit, and it is preferably 100 or more, more preferably 200 or more. By setting the molecular weight to the above lower limit value or more, it is possible to prevent the monomer from volatilizing in the resin curing step, which is preferable. By setting it as the above upper limit or less, it can make a viscosity at a high temperature. It is easy to reduce, which is one of the features of the present invention. Further, unless otherwise specified, the molecular weight was measured by the method described in the following examples.

(viscosity characteristics)

. Low temperature viscosity (η ₂₅ )

The viscosity of the sealant of the present invention at 25 ° C before curing is η ₂₅ of 1,000 mPa. Above sec, 1,000,000 mPa. Sec below. The lower limit is preferably 2,000 mPa. Above sec, especially 3,000 mPa. Sec or above. The upper limit is preferably 100,000 mPa. Below sec, especially 10,000 mPa. Sec below. By setting the value to be equal to or higher than the above lower limit value, the phosphor can be stably dispersed for a long period of time, which is preferable. On the other hand, it is preferable to set it as the said upper limit or less, and it is easy to operate or convey.

. High temperature viscosity (η ₅₀ )

In the sealant of the present invention, the viscosity η ₅₀ at 50 ° C before curing is not particularly limited, and is preferably 1 mPa. Above sec, 10,000 mPa. Below sec, more preferably 1 mPa. Above sec, 5,000 mPa. Sec below. The lower limit is preferably 5 mPa. Above sec, especially good for 10 mPa. Sec or above. The upper limit is preferably 3,000 mPa. Below sec, especially good for 1,000 mPa. Sec below. By setting the value to be equal to or higher than the above lower limit value, it is possible to suppress liquid from overflowing or unintended infiltration into a gap, which is preferable. On the other hand, it is preferable to set the phosphor to be settled by setting it as the upper limit or less.

. Viscosity reduction rate by heating (η ₂₅ /η ₅₀ )

The viscosity of the sealant of the present invention, the viscosity at 25 deg.] C to ₂₅ [eta] and [eta] ratio of ₅₀ to 50 deg.] C η ₂₅ / η ₅₀ of 10 or more. The ratio η ₂₅ /η _{50 is more} preferably 20 or more, and particularly preferably 30 or more. The upper limit is not particularly limited, and is actually 1,000 or less. One of the features of the present invention is that the reduction rate is equal to or higher than the above lower limit value. Specifically, by this, the above-mentioned sealant does not excessively flow at a low temperature, and achieves good manufacturing suitability. On the other hand, the fluidity of the sealant is rapidly increased by heating, and the sedimentation of the phosphor contained in the sealant is appropriately promoted, so that the sealant is biased to exist around the semiconductor light-emitting device as shown in FIG. form. Then, by directly raising the heating temperature, the monomer in the sealant can be polymerized and cured, and a product having a cured cured film (sealing material) can be obtained.

The sealant of the present invention is preferably, its viscosity in the uncured viscosity [eta] at 25 deg.] C and 50 deg.] C _{25 50} [eta] ratio η ₂₅ / η ₅₀ satisfies the following relation equation (F1) and the equation (F2 ).

η ₂₅ /η ₅₀ >a. Log ₁₀ (η ₂₅ )+b...F1

η ₂₅ /η ₅₀ <c. Log ₁₀ (η ₂₅ )+d...F2

a=34

b=-200

c=34

d=50

The above relationship is also based on the viewpoint of the production suitability of the sealant of the present invention or the sedimentation property of the phosphor. However, in consideration of the availability of the material, the scope of the invention defined by the above η ₂₅ and η ₅₀ is further specified. The meaning of the actual value. From the same viewpoint, it is more preferable that c=-150 and d=0.

[component composition]

In the sealant of the present invention, the concentration of the acrylate monomer is preferably more than 70% by mass, more preferably 80% by mass or more, and particularly preferably 85% by mass or more, based on the total amount of the organic hardening component of the composition. Good is 90% by mass or more. There is no particular upper limit, and it is particularly preferably about 100% by mass. Here, in the case where the residual solvent is substantially mixed in a ratio of about 0% by mass to 10% by mass, the presence of the unavoidable mixed matter is allowed to be within a range that does not impair the effects of the present invention. Alternatively, a necessary amount of an additive or a solvent may be imparted when it is necessary to lower the viscosity of the sealant. In addition, the sealing agent of the present invention may contain an optional component such as a polymerization initiator or a polymerization inhibitor to be described later, in addition to an essential component, and is preferably used in a solvent-free state. In this case, since it has no solvent, it has sufficient fluidity and suitable viscosity, and therefore the sealant of the semiconductor light-emitting device is excellent in moldability. In particular, it is possible to effectively cope with the formation by potting, and contributes to a large improvement in manufacturing efficiency as compared with mold forming and the like. In addition, the organic hardening component of the sealant refers to a hardened component (a component which contributes to direct hardening by polymerization or the like) containing a compound containing a carbon atom, and contains no phosphor or polymerization even if it contains a carbon atom. The meaning of the initiator and organic solvent. In addition, in the case where it is necessary to strictly perform the comparison, the organic hardening component of the above-mentioned sealant is not limited to a trace component such as water or an inorganic salt.

(iso-isocyanate compound [A])

The specific isocyanurate compound represented by the above formula (1) is preferably a compound represented by the following formula (1-1), formula (1-2) or formula (1-3). In the present specification, the compounds represented by the formula (1-1), the formula (1-2), or the formula (1-3) are collectively referred to as different Cyanurate compound [A].

. R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴

In the formula, R ⁷¹ , R ⁷² and R ⁷³ are each independently hydrogen or methyl. R ⁷⁴ is any one or more selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and a mercaptooxy group represented by the formula (II).

In the present invention, R ^{74 is} preferably a substituent containing a hydroxyl group, more preferably a hydroxyl group. The reason for this is preferably the same as that of the monomer containing any one of R ¹ , R ² and R ³ of the formula (1) which is a hydroxyl group.

. L ^a

L ^a has the same meaning as formula (1), and the preferred range is also the same.

The above isomeric cyanurate compound [A] is preferably contained in a specific ratio with respect to the compound of the above formula. When the above-mentioned isocyanurate compound [A] is 100% by mass, the compound represented by the formula (1-1) is preferably 0% by mass or more and 35% by mass or less, more preferably 0% by mass or more. 25% by mass or less, particularly preferably 0% by mass or more and 10% by mass or less.

The compound represented by the formula (1-2) is preferably 65 mass% or more and 100 mass%. In the following, it is more preferably 70% by mass or more and 100% by mass or less, and particularly preferably 80% by mass or more and 100% by mass or less.

The compound represented by the formula (1-3) is preferably 0% by mass or more and 25% by mass or less, more preferably 0% by mass or more and 15% by mass or less, particularly preferably 0% by mass or more and 10% by mass or less.

By containing the isocyanurate compound [A] in the above ratio, transparency, heat-resistant colorability, thermal shock resistance, and gas barrier properties can be satisfied at a higher level.

(isomeric cyanurate compound [B])

In the present invention, the specific isocyanurate compound is preferably a compound represented by the following formula (1-4), which is contained in an amount of 1% by mass or more and less than 50% by mass. In the present specification, the compound represented by the formula (1-4) is referred to as an isocyanurate compound [B].

. R ⁷¹ , R ⁷² and R ^b have the same meanings as in the formula (1-1) and the formula (II). L ^a has the same meaning as formula (1).

The amount of the isocyanurate compound [B] to be added is not particularly limited, and is preferably 1% by mass or more and less than 50% by mass in the organic hardening component of the composition. More preferably, it is 3% by mass or more and 40% by mass or less, and particularly preferably 5% by mass or more and 30% by mass or less. By applying the isomeric cyanurate compound [B] within the above range, the water absorption rate can be lowered without deteriorating the thermal shock resistance (crack resistance) of the cured product and the heat-resistant coloring property. It is possible to reduce a failure caused by water absorption (for example, moisture reflow soldering cracking which occurs when reflow processing is performed in a state where water is sucked), and as a result, a highly reliable semiconductor light-emitting element can be provided.

The acid value of the sealant of the present invention is preferably 0.10 mgKOH/g or less, more preferably 0.05 mgKOH/g or less, and particularly preferably 0.02 mgKOH/g or less. It is preferable to have an advantage that the heat-resistant coloring property is further improved by setting it as the upper limit or less. The lower limit is not particularly limited, and is actually 0.001 mgKOH/g or more. The method for adjusting the acid value of the sealant is not particularly limited, and an adsorbent such as activated carbon or silica may be mixed with the isocyanurate compound of the present invention, and after standing, filtered. The adsorbent is removed, thereby lowering the acid value of the isomeric cyanurate compound.

In addition, in this specification, the term "compound" is referred to as the end, or when it is represented by a specific name or chemical formula, and the meaning of the salt and the ion thereof is included in addition to the compound itself. Further, the meaning of the derivative modified in a predetermined form is included in the range in which the desired effect is exerted. Further, the substituent or the linking group which is substituted or unsubstituted is not clearly described in the present specification, and is a meaning which may have any substituent in the group. The same meaning is also used for a compound which is not clearly described as substituted or unsubstituted. Preferred substituents include the following substituents T.

The substituent T can be exemplified by the following groups.

The alkyl group (preferably an alkyl group having 1 to 20 carbon atoms) such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a pentyl group, a heptyl group, a 1-ethylpentyl group or a benzyl group is exemplified. , 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl (preferably an alkenyl group having 2 to 20 carbon atoms, such as a vinyl group, an allyl group, an oleyl group, etc.), an alkynyl group (compared Preferably, the alkynyl group having 2 to 20 carbon atoms, such as an ethynyl group, a butadiynyl group or a phenylethynyl group, or a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, for example) Cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), aryl (preferably an aryl group having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxy) Phenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazole a base, a 2-benzimidazolyl group, a 2-thiazolyl group, a 2-oxazolyl group, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, or a different group) a propoxy group, a benzyloxy group or the like), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, such as a phenoxy group, a 1-naphthyloxy group, a 3-methylphenoxy group, 4-methoxyphenoxy group or the like), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as an ethoxycarbonyl group, a 2-ethylhexyloxycarbonyl group, etc.), an amine group (preferably an amine group having 0 to 20 carbon atoms, such as an amine group, an N,N-dimethylamino group, an N,N-diethylamino group, an N-ethylamino group, an anilino group, etc.), a sulfonylamino group (preferably a sulfonylamino group having 0 to 20 carbon atoms, such as N,N-dimethylsulfonamide, N-phenylsulfonamide, etc.) or a mercaptooxy group (preferably a mercaptooxy group having 1 to 20 carbon atoms, for example, an ethoxymethyloxy group, a benzhydryloxy group or the like, an amine methyl sulfonyl group (preferably an aminocarbenyl group having 1 to 20 carbon atoms, for example, N) , N-dimethylaminecarbamyl, N-phenylaminecarbamyl, etc.), mercaptoamine group (preferably having 1 to 20 carbon atoms) a mercaptoamine group, for example, an ethylamino group, a benzhydrylamino group, a cyano group, a hydroxyl group, or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), more preferably an alkyl group. , alkenyl, aryl, heterocyclic, alkoxy, aryloxy, alkoxycarbonyl, amine, decylamino, cyano or halogen atom, particularly preferably alkyl, alkenyl, heterocyclic Alkyl, alkoxy, alkoxycarbonyl, amine, decylamino or cyano.

The specific isocyanurate compound may be synthesized by a usual method, and the synthesis method is not particularly limited. For example, Japanese Patent Laid-Open Publication No. 2003-213159 can be referred to for the information of the commercial product.

[Polymerization initiator]

The sealant of the present invention preferably contains a polymerization initiator.

Among them, a blending radical polymerization initiator can be mentioned.

Examples of the thermal radical polymerization initiator which generates a starting radical by thermal cracking include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetyl ketone peroxide, and cyclohexane. Ketone peroxides and ketone peroxides such as methylcyclohexanone peroxide; 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and Hydroperoxides such as tributyl hydroperoxide; diisobutyl hydrazino peroxide, bis-3,5,5-trimethylhexanol peroxide, lauryl peroxide, benzamidine Di-n-based peroxides such as oxides and m-tolylbenzimidyl peroxide; dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy) Hexane, 1,3-bis(t-butylperoxyisopropyl)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl- Dialkyl peroxides such as 2,5-di(t-butylperoxy)hexene; 1,1-di(t-butylperoxy-3,5,5-trimethyl Peroxyketal such as cyclohexane, 1,1-di-t-butylperoxycyclohexane and 2,2-di(t-butylperoxy)butane; new peroxidation 1,1,3,3-tetramethylbutyl dicarbonate, α-cumyl peroxydicarbonate, tert-butyl peroxydicarbonate, trihexyl peroxydiacetate, peroxidation Tert-butyl methyl acetate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, third amyl peroxy-2-ethylhexanoate, peroxy-2- Tert-butyl ethylhexanoate, tert-butyl peroxyisobutyrate, di-t-butyl peroxydihydroterephthalate, peroxy-3,5,5-trimethylhexanoic acid 1, 1,3,3-tetramethylbutyl ester, third amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, Alkyl peroxyesters such as tert-butyl acetate acetate, tert-butyl peroxybenzoate and dibutyl trimethyl adipate; di-3-methoxybutyl peroxydicarbonate, Di-2-ethylhexyl peroxydicarbonate, bis(1,1-butylcyclohexyloxydicarbonate), diisopropoxydicarbonate, isopropyl peroxycarbonate Peroxycarbonate such as ester, tert-butyl isopropyl peroxycarbonate, tert-butyl peroxy-2-ethylhexyl carbonate, and 1,6-bis(t-butylperoxycarboxy)hexane; 1,1-bis(trihexylperoxy)cyclohexane and (4-t-butylcyclohexyl)peroxydicarbonate.

Specific examples of the azo compound used as a polymerization initiator for azo-based (azobisisobutyronitrile (AIBN)) include 2,2'-azobisisobutyronitrile and 2,2'. - azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis-l-cyclohexanecarbonitrile, Dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis-(2-methylamidinopropane) diphosphate An acid salt or the like (refer to Japanese Patent Laid-Open Publication No. 2010-189471, etc.).

In addition to the above thermal radical polymerization initiator, a radical polymerization initiator may be used as a radical polymerization initiator which generates a radical by light, electron beam or radiation.

Such a radical polymerization initiator may, for example, be benzoin ether, 2,2-dimethoxy-1,2-diphenylethane-1-one [IRGACURE 651, Ciba Specialty Chemicals ( (manufacturing, trademark), 1-hydroxy-cyclohexyl-phenyl-ketone [IRGACURE 184, manufactured by Ciba Specialty Chemicals, trademark], 2-hydroxy-2-methyl-1-phenyl-propane- 1-ketone [DAROCUR 1173, manufactured by Ciba Specialty Chemicals, trade name], 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane- 1-ketone [IRGACURE 2959, manufactured by Ciba Specialty Chemicals, trade name], 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]benzene 2-methyl-propan-1-one [IRGACURE 127, manufactured by Ciba Specialty Chemicals, trade name], 2-methyl-1-(4-methylthiophenyl)-2-morpholine Propane-1-one [IRGACURE 907, manufactured by Ciba Specialty Chemicals, trade name], 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone- 1[IRGACURE 369, Ciba Specialty Chemicals, Trademark], 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Morpholinyl)phenyl]-1-butanone [IRGACURE 379, manufactured by Ciba Specialty Chemicals, trade name], 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide [DA] ROCUR TPO, Ciba Specialty Chemicals, Trademark], bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide [IRGACURE 819, Ciba Specialty Chemicals, Trademarks, Trademarks ], bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium [IRGACURE 784, Ciba Specialty Chemicals Co., Ltd., Trademark], 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzhydrylhydrazine)][IRGACURE OXE 01, Ciba Specialty Chemicals, Trademark], Ethyl Ketone, 1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-( O-acetyl group 肟) [IRGACURE OXE 02, Ciba Specialty Chemicals Co., Ltd., trademark], etc.

These radical polymerization initiators may be used alone or in combination of two or more.

Among them, a peroxide compound is preferable, and Perbutyl O (t-butyl peroxy-2-ethylhexanoate, manufactured by Nippon Oil Co., Ltd.) or the like can be used.

The amount of the polymerization initiator is not particularly limited, and is preferably 0.1% by mass or more and 5 parts by mass or less, more preferably 0.5% by mass or more and 2 parts by mass or less based on 100 parts by mass of the organic hardening component. By setting it as the said lower limit or more, a polymerization reaction can be started favorably. On the other hand, by setting it as the said upper limit or less, the outstanding effect of the sealing agent by the application of the above-mentioned specific isocyanate compound can be fully guided, and it is preferable.

Further, in the present invention, the sealant (curable composition) may be polymerized by heating alone or may be configured without using a polymerization initiator.

[Polymerization inhibitor]

A polymerization inhibitor may also be added to the sealant of the present invention. As the polymerization inhibitor, for example, phenols such as hydroquinone, tributyl hydroquinone, catechol, hydroquinone monomethyl ether, and the like; benzoquinone, Anthraquinones such as diphenylphenylhydrazine; phenothiazines; coppers, and the like.

The content of the polymerization inhibitor is not particularly limited, but is preferably 0 ppm to 20,000 ppm (parts by mass), preferably 100 ppm to 10,000 ppm, and particularly preferably 300 ppm to 8000 ppm, based on 1 part of the organic hardening component. Come add. If the polymerization inhibitor When the amount of addition is too small, the polymerization is performed while the seal is hardened, and the adhesion to the reflector package base material is lowered. When the thermal shock is applied, the sealant/substrate interface is likely to be peeled off. On the other hand, when the amount of the polymerization inhibitor added is too large, when the curable composition is cured in the air, the curing rate is remarkably lowered to cause surface hardening failure.

[fluorescent body]

In the present invention, it is preferred to prepare the phosphor in an amount of from 1 part by mass to 40 parts by mass, more preferably from 2 parts by mass to 30 parts by mass, even more preferably from 5 parts by mass, based on 100 parts by mass of the organic hardening component of the sealant. Above 20 parts by mass or less. The phosphor may be converted into a wavelength by absorbing fluorescence by absorbing light from the semiconductor light-emitting device, and is preferably at least one selected from the group consisting of the following phosphors: mainly Eu, Ce An alkali-based halogen apatite fluorescent lamp activated by a lanthanide-based phosphor or an oxynitride-based phosphor activated by a lanthanoid element, mainly composed of a lanthanoid element such as Eu or a transition metal element such as Mn. Body, alkaline earth metal boric acid halogen phosphor, alkaline earth metal aluminate phosphor, alkaline earth silicate phosphor, alkaline earth sulfide phosphor, alkaline earth thiogallate phosphor, alkaline earth A lanthanum nitride-based phosphor, a phthalate phosphor, a rare earth aluminate phosphor mainly activated by a lanthanide such as Ce, a rare earth silicate phosphor, or a lanthanide mainly composed of Eu Elements to activate organic as well as organic complexes and the like. More preferably used: (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Ca, Sr, Ba) ₂ SiO ₄ : Eu, (Ca, Sr) ₂ Si ₅ N ₈ : Eu, CaAlSiN ₃ :Eu et al.

The average particle diameter of the phosphor is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm. By setting it to the above lower limit value, it can be low viscosity It is preferred that the resin is easily precipitated. By setting it as the said upper limit or less, it can suppress sedimentation at room temperature, and it is preferable.

The specific gravity of the phosphor is not particularly limited in the range of the phosphor to be used in such a use, but it is preferably 2 g/cm ³ to 10 from the viewpoint that the effect of the present invention is remarkable. g/cm ³ , particularly preferably 4 g/cm ³ to 6 g/cm ³ .

[Antioxidants]

The sealant of the present invention preferably contains an antioxidant as needed. Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a thioether antioxidant, a vitamin-based antioxidant, a lactone-based antioxidant, and an amine-based antioxidant.

Examples of the phenolic antioxidant include Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1076 (manufactured by Ciba Specialty Chemicals Co., Ltd., trademark), and Irganox 1330 (manufactured by Ciba Specialty Chemicals Co., Ltd., Trademarks) ), Irganox 3114 (made by Ciba Specialty Chemicals Co., Ltd.), Irganox 3125 (made by Ciba Specialty Chemicals Co., Ltd., trademark), Adekastab AO-20 (ADEK Co., Ltd., trademark), Adekastab AO-50 (Adico Co., Ltd., trademark), Adekastab AO-60 (Adico Co., Ltd., trademark), Adekastab AO-80 (Adico Co., Ltd., trademark), Adekastab AO-30 ( Aidike Co., Ltd., Trademark), Adekastab AO-40 (Adico Co., Ltd., trademark), BHT (manufactured by Takeda Pharmaceutical Co., Ltd., trademark), Cyanox 1790 (manufactured by Cyanamid), trademark ), Sumilizer GP (Sumitomo Chemical Co., Ltd., trademark), Sumilizer GM (Sumitomo Chemical Co., Ltd., trademark), Sumilizer GS (Sumitomo Chemical Co., Ltd., trademark), and Commercial products such as Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd., trademark).

Examples of the phosphorus-based compound include: IRAGAFOS 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS 12 (manufactured by Ciba Specialty Chemicals Co., Ltd., and IRGAGOS 38 (manufactured by Ciba Specialty Chemicals, Trademark) , IRAGAFOSP-EPQ (Ciba Specialty Chemicals, Trademark), IRAGAFOS 126 (Ciba Specialty Chemicals, Trademark), ADKSTAB 329K (Adico Co., Ltd., Trademark), ADKSTAB PEP-36 ( Aidike Co., Ltd., trademark), ADKSTAB PEP-8 (Adico Co., Ltd., trademark), ADKSTAB HP-10 (Adico Co., Ltd., trademark), ADKSTAB 2112 (Adico Co., Ltd., Trademark), ADKSTAB 260 (Adico Co., Ltd., trademark), ADKSTAB 522A (Adico Co., Ltd., trademark), Weston 618 (manufactured by GE, trademark), Weston 619G (manufactured by GE, trademark), and Commercial products such as Weston 624 (manufactured by GE Corporation, trademark).

Examples of the sulfur-based antioxidants include DSTP (Yoshitomi) [made by Kyrgyzstan Co., Ltd., trademark], DLTP (Yoshitomi) [made by Kyrgyzstan Co., Ltd., trademark], DLTOIB [made by Kyrgyzstan Co., Ltd., trademark], DMTP (Yoshitomi) [Jifu (share) manufacturing, trademark], Seenox 412S [Shipro Kasei (share) manufacturing, trademark], Cyanox 1212 (manufactured by cyanamide company, trademark) and TP-D, TPS, TPM, TPL- R [Commodity of Sumitomo Chemical Co., Ltd., trademark]. Examples of vitamin antioxidants: tocopherol (made by Eisai), trademark] and Irganox E201 [made by Ciba Specialty Chemicals, trademark, compound name: 2, 5, 7, 8 - Commercial products such as tetramethyl-2(4',8',12'-trimethyltridecyl)benzofuran-6-ol].

The thioether-based antioxidant may, for example, be a commercial product such as Adekastab AO-412S (manufactured by Aidike Co., Ltd., trademark) or Adekastab AO-503 (manufactured by Aidike Co., Ltd., trademark). As the lactone-based antioxidant, the antioxidant described in JP-A-H07-233160 and JP-A-H07-247278 can be used. Further, HP-136 [Ciba Specialty Chemicals Co., Ltd., trade name, compound name: 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzene can be cited. Commercial products such as furan-2-one].

Examples of the amine-based antioxidants include Irgastab FS042 [Manufactured by Ciba Specialty Chemicals, Trademark] and GENOX EP [Manufactured by Crompton Corporation, Trademark, Compound Name: Dialkyl-N-Methylamine Oxide ] and other commercial products. These antioxidants may be used alone or in combination of two or more.

The content of the antioxidant is usually 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the organic hardening component, from the viewpoint of reducing the transparency of the curable composition which is a sealant (resin material), that is, from the viewpoint of yellowing. It is preferably from 0.01 part by mass to 5 parts by mass, more preferably from 0.02 part by mass to 2 parts by mass.

[light stabilizers, etc.]

In the sealing agent of the present invention, in addition to the above-mentioned antioxidant, a lubricant, a light stabilizer, an ultraviolet absorber, a plasticizer, an antistatic agent, an inorganic filler, a colorant, a mold release agent, a flame retardant may be formulated as needed. A component for the purpose of improving the adhesion to an inorganic compound such as titanium oxide or cerium oxide. As the lubricant, a higher dicarboxylic acid metal salt, a higher carboxylic acid ester or the like can be used.

A known light stabilizer can be used, and a hindered amine light stabilizer is preferred. Subject to Specific examples of the hindered amine light stabilizers include: ADKSTAB LA-77, ADKSTAB LA-57, ADKSTAB LA-52, ADKSTAB LA-62, ADKSTAB LA-67, ADKSTAB LA-68, ADKSTAB LA-63, ADKSTAB LA- 94, ADKSTAB LA-94, ADKSTAB LA-82, and ADKSTAB LA-87 [above manufactured by AIDCO Co., Ltd.], Tinuvin 123, Tinuvin 144, Tinuvin 440, and Tinuvin 662, Chimassorb 2020, Chimassorb 119, Chimassorb 944 [above] Manufactured by CSC Corporation], Hostavin N30 (manufactured by Hoechst), Cyasorb UV-3346, Cyasorb UV-3526 (above manufactured by Cytec), Uval 299 (GLC) and Sanduvor PR-31 (Clariant) and so on. These light stabilizers may be used alone or in combination of two or more.

The amount of the light stabilizer to be used is usually 0.005 parts by mass to 5 parts by mass, preferably 0.02 parts by mass to 2 parts by mass, per 100 parts by mass of the organic hardening component.

The component for the purpose of improving the adhesion to an inorganic compound such as titanium oxide or cerium oxide may, for example, be a decane coupling agent containing a methacryloxy group or an acryloxy group as a decane compound. It may be contained in the above-mentioned sealant to carry out polymerization and molding.

[Semiconductor Light Emitting Device

(sealing method)

The sealing agent for a semiconductor light-emitting device of the present invention is preferably applied to a production method including a step of curing the sealant in a cavity of a reflector package to form a cured film. Further, specifically, a method of manufacturing a semiconductor light-emitting device comprising the steps of: preparing the sealing agent for a semiconductor light-emitting device; and filling the sealing agent in a cavity of the reflector package; filling a step of heating and homogenizing the sealant in a predetermined range; and a step of heating and curing the above-mentioned soaked sealant in a predetermined range.

The heating temperature in the soaking step is not particularly limited, but is preferably heated in the range of 25 ° C to 90 ° C, and is softened without hardening the sealant. From this point of view, it is more preferable to set the heating temperature to 35 to 80 ° C, and more preferably to 45 to 70 ° C. If it is considered that the phosphor is sufficiently settled in this step, the heating time is preferably from 1 hour to 5 hours.

The heating temperature in the hardening step is not particularly limited, but it is preferably heated in a range of from 100 ° C to 200 ° C to cure the sealant. From the viewpoint of sufficiently curing the film, the heating temperature is preferably 110 ° C to 180 ° C, and particularly preferably 130 ° C to 160 ° C. When it is considered that a good cured film which is sufficiently hardened by this step is formed, the heating time is preferably from 1 hour to 5 hours.

The sealing method of the sealant can be either a method generally used for sealing of a semiconductor light-emitting element or a method of forming a general thermosetting resin. For example, perfusion (dispense), printing, coating, injection molding, compression molding, transfer molding, and insert molding can be cited. The "filling" means an operation of ejecting the inside of the cavity (concave space) in which the curable composition (sealant) is ejected to the inside of the package. In addition, the printing means an operation of arranging a sealant at a target portion using a mask, and a so-called vacuum printing method in which the surrounding pressure is reduced in accordance with the purpose. Various coating methods may be employed for coating, for example, a bank which is prepared in advance as a retained sealant called a dam material, and a sealant coated on the inner side thereof may be used. method. Further, various mold forming methods include a method in which a sealant is filled inside the mold to directly perform thermal curing. Further, the hardening after sealing may be performed by heat hardening, ultraviolet (UV) hardening, or the like, or a combination thereof.

A semiconductor light-emitting device according to a preferred embodiment of the present invention is formed by including a sealing material produced by curing the curable composition (sealant). As the hardening method, the same method as the molding of a usual thermosetting resin can be used. For example, a method of polymerizing or molding the above-mentioned sealant or a preliminary polymer by injection molding, compression molding, transfer molding, insert molding, or the like of the liquid resin may be mentioned. Further, the formed body can also be obtained by a potting process or a coating process. Further, the molded body can be obtained by the same method as the molding of a photocurable resin such as UV hardening.

The sealant (curable composition) of the present invention has moderate fluidity or viscosity as described above, and thus is preferably used for perfusion.

The perfusion is described here. The "filling" means an operation of discharging the sealing liquid to the inside of the cavity (concave space) W (FIG. 1) of the reflector package base material to fill the inside. The curing process is a reflector package in which a sealing liquid is filled after being filled (including a semiconductor light-emitting element, a component fixing adhesive member, a bonding wire, and an electrode package, except for a reflector package substrate) It is put into a general heating device such as an oven to be hardened, so that the system can be completed only by a very simple configuration of a dispenser and a heating device. In addition, since a mold or a mask is not required, it can be quickly and inexpensively handled when the shape of the apparatus is changed, and it can be said that it is a highly versatile sealing method. Furthermore, In the mold forming method such as compression mold forming or transfer mold forming, the mold release property is poor, the sealing liquid disposal rate is high, and the viscosity is limited. However, these problems do not exist in the filling method.

Examples of the discharge method of the sealing liquid include a mechanical distribution method such as a screw type, an air pulse type distribution, and a non-contact injection type distribution. As the dispenser of the infusion device, for example, a device manufactured by Musashi Engineering Co., Ltd., San-Ei Tech Co., Ltd., or the like can be specifically used.

The sealing liquid that can be used in the infusion must be liquid at normal temperature, preferably using a viscosity of about 1 mPa. s~1000 Pa. s solution.

(semiconductor light emitting element)

As the semiconductor light-emitting element, a blue-emitting light-emitting diode (LED) wafer including a gallium nitride (GaN)-based semiconductor, an ultraviolet light-emitting LED chip, a laser diode, or the like can be used. In addition, for example, a light-emitting element in which a nitride semiconductor such as InN, AlN, InGaN, AlGaN, or InGaAlN is formed as a light-emitting layer on a substrate by a metal organic vapor deposition (MOCVD) method or the like can be used. . Any of a semiconductor light emitting element mounted on a face up or a semiconductor light emitting element mounted on a flip chip may be used. A typical example of the semiconductor light-emitting device is a semiconductor light-emitting device having an n-side electrode and a p-side electrode on the light-emitting surface side. However, a semiconductor light-emitting device having an n-side electrode on one side and a p-side electrode on the opposite side may be used.

(package)

As the package, an electrode may be used as an integrated mold, and an electrode may be provided as a circuit wiring by plating or the like after molding the package. The shape of the package may be any shape such as a cylinder, an elliptical cylinder, a cube, a rectangular parallelepiped, a shape between a rectangular parallelepiped and an elliptical cylinder, or a combination thereof. The shape of the inner wall portion may be selected from an arbitrary angle with respect to the bottom portion, and a box shape having a right angle with respect to the bottom surface or a mortar shape having an obtuse angle. The bottom shape of the concave portion may be any shape such as a flat shape or a concave shape. Further, as the mounting method, a package corresponding to any mounting method such as a top view or a side view can be used.

As the material constituting the package, an electrically insulating material having excellent light resistance and heat resistance can be suitably used. For example, a thermoplastic resin such as polyphthalamide or a thermosetting resin such as an epoxy resin or an anthrone resin can be used. Epoxy, ceramic, etc. Further, in order to efficiently reflect the light from the semiconductor light-emitting element, a white pigment such as titanium oxide or the like may be mixed with the resins. As the molding method of the package, insert molding, injection molding, extrusion molding, transfer molding, or the like which is performed by previously setting the electrode in a mold can be used.

(electrode)

The electrode is electrically connected to the semiconductor light emitting element, and may be, for example, a plate electrode embedded in the package or a conductive pattern formed on a substrate such as glass epoxy or ceramic. The material of the electrode may be a material in which silver or a silver-containing alloy is plated on a part of an electrode containing copper or iron as a main component in addition to silver or an alloy containing silver.

(side view package)

A package of a semiconductor light-emitting element used in a backlight unit or the like of a liquid crystal display is required to be thin. In the case of forming a thinner backlight unit, a so-called side view package in which light is taken out in parallel with the mounting substrate of the semiconductor element is often used. The aspect ratio in the side view package (the depth seen from the light extraction surface (or the depth of the cavity) is increased with respect to the ratio of the specific length of the surface on which the LED is mounted (the bottom surface 9b [refer to FIG. 1]), the sealing material The ratio of the area in contact with the reflector package is increased, so there is a problem that the interface is likely to be peeled off.

Here, the aspect ratio described above will be described in further detail based on the drawings. In the example shown in FIG. 1, d1/d2 corresponds to the aspect ratio. Since the depth is usually the same in the apparatus, a special calculation method is not required, but the bottom diameter (width) d1 is different. Therefore, a typical example will be confirmed below. If the bottom surface is a rectangle ((a) in FIG. 2), the short side (Ls) refers to a line segment that passes through the center of the bottom surface of the reflector package and has the shortest length in the straight line passing through the outer end of the package. If the bottom surface is a square, the length (D) of one side may be used ((b) in Fig. 2). When the bottom surface has a circular shape, the diameter D may be measured as d1. In the case of an elliptical bottom surface, the length Ls of the short side is measured, and this is taken as d1.

Further, it will be specifically described based on the attached FIG. 3. 3 is an exploded perspective view showing a configuration of a constituent member (part of) of a liquid crystal display device using an example of a backlight of a semiconductor light-emitting device using a side view package. 21A and 21B are polarizing plates, 22 is a color filter substrate, 23 is a liquid crystal layer, 24 is an array substrate, and 25 is a light guide plate. Moreover, 26 is a semiconductor light emitting device 10 including a side view package. The LED backlight is continuously provided with a plurality of semiconductor light-emitting devices 10 in such a manner that light is irradiated from the light guide plate 25. Further, in detail, the semiconductor light-emitting device of the embodiment shown in FIG. 1 has a plurality of openings 9a facing the light guide plate 25 and continuously provided inside the backlight case.

According to this configuration, it is also known that the semiconductor light-emitting device to which the application is applied must emit light of sufficient brightness in a small space, and thus high performance and miniaturization are required. In addition, components that are frequently exchangeable are not required, and high durability reliability is required. According to the present invention, such a demand can be suitably handled.

(evaluation method)

The semiconductor light-emitting device can be evaluated in an existing test method. For example, electrical characteristics, optical characteristics, temperature characteristics, thermal characteristics, life, reliability, safety, and the like can be cited. As a method, for example, a method or a reference described in Chapter 2, page 71 to page 84 of the book "LED Lighting Manual LED Lighting Promotion Agreement" is issued by Ohmsha.

(use)

Semiconductor light-emitting devices can be used for various applications requiring maintenance of brightness, such as backlights for liquid crystal displays, mobile phones or information terminals, LED displays, flash lights, and indoor and outdoor lighting. Further, the acrylic sealing material used in the present invention is used not only for a light-emitting element such as an LED or a laser diode but also for a light-receiving element, a large scale integration (LSI) or an integrated body. Sealing of a semiconductor light-emitting element other than a semiconductor light-emitting element such as an integrated circuit (IC).

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, which are not to be construed as limited.

(Example 1, Comparative Example 1)

[Preparation of sealing liquid]

M215 (trade name: a mixture of the following compound 1-1 to compound 1-3 manufactured by Toagosei Co., Ltd.) was used to prepare a column-purified product of a bifunctional monomer (the following compound 1-2) (hereinafter referred to as "IC")).

- Determination of molecular weight -

Regarding the commercially available compound, the molecular weight calculated from the chemical structure described in the catalog is applied. When the chemical structure is unknown, the following method is applied: after column separation by liquid chromatography mass spectrometry (LC-MS), mass spectrometry is used to determine the molecular weight. Further, when the molecular weight is large and the analysis by mass spectrometry is difficult, the weight average molecular weight in terms of polystyrene is measured by gel permeation chromatography (GPC). The GPC apparatus HLC-8220 (manufactured by Tosoh Corporation) was used, and the eluent was tetrahydrofuran (THF) (manufactured by Shonan Wako Pure Chemical Co., Ltd.). The column was detected by RI using G3000HXL+G2000HXL at 23 ° C and a flow rate of 1 mL/min.

- Determination of viscosity -

The viscosity was measured using a RheoStress RS6000 (HAAKE). The sensor was measured using a cone-plate system (C35/1) at a shear rate of 10 sec ^-1 and a heating rate of 1 ° C/min.

[化15]

(Comparative Example 2)

The sealant sample c61 for comparison was prepared in the following formulation. In addition, this formulation is set with reference to Example 1 described in the specification of JP-A-2003-261770.

<c61>

In the sample c61, η ₂₅ , η ₅₀ , and η ₂₅ /η ₅₀ were measured in the same manner as described above, but the ratio of the above-mentioned cerium oxide was in a state in which it was not sufficiently dispersed (almost no resin). Only the powder of cerium oxide is used as the volume). Therefore, the viscosity measurement was abandoned.

(Reference example)

In comparison with the invention described in Japanese Laid-Open Patent Publication No. 2003-261770, the evaluation used, that is, the measurement of the gap penetration time, was carried out. Specifically, the aluminum foil spacer was sandwiched between two glass plates, and as shown in Fig. 2 of the above publication, a gap of 50 μm in length of 1.8 cm was formed with a width of 15 mm. Immediately after standing on the hot plate and adjusting to the set temperature, the time from when the sealant flowed down from one side of the gap to when the infiltrated sealant reached a distance of 1 cm from the side was measured. The test samples were the sealant samples used in Test 101 and Test 107 of Example 1. The results are shown below.

Regarding the gap penetration time shown in Example 1 and Example 2 of Japanese Laid-Open Patent Publication No. 2003-261770, the ratio (T ₁₅ /T ₆₀ ) at 15 ° C to 60 ° C is 9.5 (c71), 5.3, respectively. (c72). On the other hand, the ratio (T ₁₅ /T ₆₀ ) of the sealant of the above-described embodiment of the present invention was 33.2 in the sample 101 and 28.9 in the sample 105, which was considerably larger than the ratio of the examples of the above publication. From this, it is understood that the range of η ₂₅ /η ₅₀ prescribed by the present invention is highly likely to be different from the range of physical properties of the sample disclosed in the above publication.

As is apparent from the above examples and comparative examples, it is understood that the sealant according to the present invention exhibits an appropriate viscosity and temperature characteristics, suppresses manufacturing batch unevenness when the sealant is filled, and promotes the phosphor during heat hardening. Appropriate sedimentation.

The present invention has been described in connection with its embodiments, but we believe that as long as it is not specifically specified, it will not be sent to us in any of the details of the description. The invention is defined broadly and can be construed broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

The present application claims priority based on Japanese Patent Application No. 2012-081642, filed on Jan. 30, 2012, and Japanese Patent Application No. 2012-114330, filed on Jan. The content of the disclosure is incorporated herein by reference in its entirety for all of its entireties.

1‧‧‧Semiconductor light-emitting elements

2‧‧‧Reflector package substrate

3‧‧‧Sealing material/hardened film

4‧‧‧Electrode

6‧‧‧bonding leads

7‧‧‧Fertior

8‧‧‧ Conductive adhesive

9a‧‧‧Glossy

9b‧‧‧ bottom

10‧‧‧Semiconductor light-emitting device

D1, d2‧‧‧ bottom diameter

W‧‧‧ concave space/cavity

Claims (14)

A sealant for a semiconductor light-emitting device, which is a thermosetting sealant that forms a cured film covering at least a part of a semiconductor light-emitting device, and the sealant contains an acrylate monomer having an average molecular weight of 1,000 or less as a curable compound, and the above sealant The viscosity η ₂₅ at 25 ° C is 1,000 mPa. Above sec, 1,000,000 mPa. Below sec, the ratio η ₂₅ /η ₅₀ of the viscosity η ₂₅ to the viscosity η ₅₀ at 50 ° C is 10 or more. The sealing agent for a semiconductor light-emitting device according to claim 1, wherein the acrylate monomer is a monomer having an isomeric cyanate skeleton, a monomer having a norbornane skeleton, and an adamantane skeleton. Monomer, a phosphate group-containing monomer, or a monomer having a biphenyl group. The sealant for a semiconductor light-emitting device according to claim 1, wherein the acrylate monomer contains a hydroxyl group-containing (OH)-containing compound. The sealant for a semiconductor light-emitting device according to the first aspect of the invention, wherein the acrylate monomer comprises a compound represented by the following formula (1): (wherein R ¹ , R ² and R ³ each independently represent a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and a carbon number; An aryl group of 6 to 24, an acryloxy group represented by the following formula (I), or a mercaptooxy group represented by the following formula (II); and ^a represents a single bond or a alkylene having 1 to 4 carbon atoms; Wherein at least one of R ¹ , R ² and R ³ is the above propylene decyloxy group) (wherein R ^a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; * represents a bond) (wherein R ^b represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms; * means a bonding bond). The sealing agent for a semiconductor light-emitting device according to the first aspect of the invention, wherein the acrylate monomer comprises a compound represented by the following formula (21): (wherein R ²¹ and R ²² represent a substituent; Ac represents an acryloxy group; L ^e represents a single bond or a linking group; and L ^f represents a linking group; and n21 and n22 represent an integer of 0 to 4). The sealing agent for a semiconductor light-emitting device according to claim 1, which comprises two or more kinds of the above acrylate monomers. The sealing agent for a semiconductor light-emitting device according to claim 1, further comprising a phosphor. The sealing agent for a semiconductor light-emitting device according to claim 7, wherein the phosphor has an average particle diameter of from 1 μm to 100 μm. The sealing agent for a semiconductor light-emitting device according to claim 7, wherein the phosphor has a specific gravity of 2 to 10. The semiconductor light emitting element ratio as defined in claim 1 with a range of item sealant, wherein the viscosity of the viscosity of the sealant ₂₅ ℃ η 25 and 50 deg.] C at ₅₀ [eta] η ₂₅ / η satisfies the following mathematical relationship ₅₀ Formula (F1) and Mathematical Formula (F2): η ₂₅ /η ₅₀ >a. Log ₁₀ (η ₂₅ )+b...F1 η ₂₅ /η ₅₀ <c. Log ₁₀ (η ₂₅ )+d...F2 a=34 b=-200 c=34 d=50. A sealant for a semiconductor light-emitting device, which is a thermosetting sealant that forms a cured film covering at least a part of a semiconductor light-emitting device, and the sealant for a semiconductor light-emitting device is used by containing a phosphor, and the sealant includes an average An acrylate monomer having a molecular weight of 1,000 or less is used as a curable compound, and the above-mentioned sealant has a viscosity η ₂₅ at 25 ° C of 1,000 mPa. Above sec, 1,000,000 mPa. Below sec, the ratio η ₂₅ /η ₅₀ of the viscosity η ₂₅ to the viscosity η ₅₀ at 50 ° C is 10 or more. A cured film obtained by curing the sealing agent for a semiconductor light-emitting device according to any one of the first to eleventh aspects of the invention. A semiconductor light-emitting device comprising: the cured film according to claim 12; and a semiconductor light-emitting device sealed by the cured film. A method of manufacturing a semiconductor light-emitting device, comprising the steps of: curing a sealing agent for a semiconductor light-emitting device in a cavity of a reflector package to form a cured film, and manufacturing the semiconductor light-emitting device includes: preparing a patent application The step of sealing the semiconductor light-emitting device according to any one of the items 1 to 11, wherein the sealing agent is filled in a cavity of the reflector package; and the filled sealant is at 25 ° C a step of heating and soaking in a range of ~90 ° C; and a step of heating and hardening the above-mentioned soaked filler in a range of 100 ° C to 200 ° C.