JPS5999782A - Resin-sealed light emitting device and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain the titled device with high resistance to heat and moisture, by sealing a light emitting element using a cured epoxy resin composition comprising an epoxy resin, an aluminum compound and an organosilicon compound having a non-substituted or substituted o-nitrobenzyloxy group directly bonded to a silicon atom. CONSTITUTION:A light emitting element is sealed by using a resin composition comprising a mixture of an alicyclic epoxy of an epoxy equivalent of 145, a bisphenol type epoxy of an epoxy equivalent of 900-1,000, tris(ethyl acetoacetonato) aluminum and diphenyldi(o-nitrobenzyloxy)silane. The mixture is heated, stirred and mixed for about 10min at 150 deg.C. In the resin composition thus obtained is immersed and light emitting element and, after picked up, light is radiated from a metal halide lamp for one min to photo-cure the composition. As a result, the composition is cured in a short time and the titled light emitting device with excellent characteristics is obtained.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a resin-sealed light emitting device and a method for manufacturing the same.
More specifically, the present invention relates to a resin-sealed light emitting device with excellent properties such as moisture resistance and heat resistance, and a method for manufacturing the same.

[Technical background of the invention and its problems]

Conventionally, light-emitting devices such as light-emitting diomids, which have been put into practical use for various displays, have been manufactured by sealing 50 light-emitting elements with resin. In this case, as the sealing resin, a resin-based composition having excellent electrical properties, moisture resistance, and heat resistance is preferably used.

However, since thermosetting epoxy resin compositions have conventionally been used, curing time of about 10 hours or more is required. For this reason, the cough suppressant method using a cough composition has a drawback in terms of productivity.

In recent years, photocurable epoxy resin compositions have been developed for the purpose of shortening the heating time, saving heat resources, and improving productivity. Such resin compositions are broadly classified into the following two types. , .

One of them is to modify it with a vinyl group-containing compound such as epoxy resin gold or photopolymerizable acrylic acid main ester, and photopolymerize via this vinyl group. but,
Is this epoxy resin modified product? It has poorer heat resistance than the resin itself.

The other method is to cure the epoxy resin itself using a photodegradable catalyst. The catalyst used at this time has the following formula: ・Yo... ・: Ar -X■-Ar (wherein A- represents an aromatic group such as -11 group□);
X represents an iodine atom, a sulfur atom, a soazo group, etc.;
Y is BF4 + PFa z AsF5 r 5bF
), which represents s, etc.

The following complexes can be mentioned. Macromolecules, Chapter 1.0, 1. :307 pages, 197.7 (
Macromolecules, jl 0, 13-
．． 07 (1977): Journal Op.
Curing, 5, 2 (1978);ノ□ --Chemist ga I (Edition, Vol. 17).

2877 pages, 1979 (Journal of, P
polymerScience Polymer Che
Mistry Edition, I 7.

2877 (1979); Ibid., Vol. 17, p. 1047, 197.9 (Ibid., 17.1o47 (1979))
: Soyarnal Off 1 Poly 2 = Fist Science lI Polymer Folding Tarzu Edition f i ], Volume 7 j
, 759 pages, 1979 (Jo*rnalof Po
'll:yrner,5cie'ncePolyme
r Letters Edit'i6n,"l 7
”, 759 ”' (1979)): Japanese Patent Application Publication m''''?
s 5' = 652''19 specification; U.S. Patent '40
See the specification of British Patent No. 69054; the specification of British Patent No. 151651'1; the specification of British Patent No. 1518141, etc.
, .

However, when the poxy resin is cured with these catalyst components, the resulting cured product has good mechanical properties and heat resistance, but on the other hand, the catalyst components become ionic impurities. When the cured product is used in electrical equipment, there is a risk of deterioration of electrical insulation and corrosion phenomenon.
``As described above, when a resin-suppressed light emitting device is manufactured using a photocurable epoxy resin composition, there is a risk that the characteristics of the resulting light emitting device itself may deteriorate.
・ ′ □ [Object of the Invention] The object of the present invention is to provide a resin-sealed light emitting device that is excellent in various properties such as heat resistance and moisture resistance.

Another purpose is 5. It is an object of the present invention to provide a complete method for manufacturing a resin-sealed light emitting device that allows resin to be cured in a short time. , [Summary of the invention].

The present inventors have conducted extensive research in response to the above points, and have found that an aluminum compound having an organic group in an epoxy resin and an unsubstituted or substituted aluminum compound directly bonded to a silicon atom,
It has been discovered that the objects of the present invention can be achieved by using an organosilicon compound having an O-nitrobenoloxy group as a photocuring catalyst and irradiating it with light, particularly UV light, thereby achieving the object of the present invention. I was able to complete it.

That is, in the device of the present invention, the inhibiting resin is an epoxy resin comprising (a) a synthetic resin, (b) an aluminum compound, and (C) an organosilicon compound having an unsubstituted or substituted 0-nitrobenzyloxy group directly bonded to a silicon atom. It is characterized by being a cured product of a resin-based composition.

Further, the manufacturing method of the present invention is characterized in that the above-mentioned epoxy resin composition is cured to prevent light emitting elements;
Ru. , ・Hereinafter, Himi 8A will be explained in more detail.

The light emitting element used in the present invention is not particularly limited as long as it is commonly used in light emitting devices. A specific example thereof is, for example, a light emitting diode.

The polyoxy resin used in the present invention may include all commonly used compounds, such as -functional epoxy compounds and polyfunctional epoxy compounds. −
Examples of the functional epoxy compounds include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, phenyldalicidyl ether, butylglycidyl ether, and the like. Polyfunctional epoxy compounds include, but are not particularly limited to, bisphenol A type epoxy resins; bisphenol Fi-2 resins; phenol novolak type epoxy resins; alicyclic epoxy resins; Heterocyclic-containing epoxy resins such as in-epoxy; hydrogenated bisphenol A type epoxy resins; aliphatic epoxy resins such as zolobylene glycol-soglycisol ether, pentaerythritol-polyglycyl ether; aromatic, aliphatic or alicyclic An epoxy resin obtained by the reaction of a carboxylic acid with epichlorohydrin; a spiro ring-containing epoxy resin; a glycidyl ether type epoxy resin which is a reaction product of an 0-allyl-phenol novolak compound and epichlorohydrin; Examples include glycidyl ether type epoxy ml fat, which is a reaction product of a soaryl bis-enol compound having an allyl group at the -position and epichlorohydrin, and two or more of these are optionally used. It can be used for.

The aluminum and mitium compounds used in the present invention may be inorganic aluminum compounds, but are preferably organic aluminum compounds that do not form ionic impurities. As the organoaluminum compound, all compounds commonly used in 1,000 poxy resin compositions can be used. Specifically, methoxy group, ethoxy group,
Alkoxy groups having 1 to 10 carbon atoms such as isopropoxy groups; aryloxy groups such as phenoxy groups and p-methylphenoxy groups; acetoxy groups, propionyloxy groups, isopropionyl, and oxy groups5. Acyloxy groups such as butyryloxy, stear, and loyl groups; alkyl groups;
Examples include those in which an aryl group; a haloalkyl group; an acyl group, etc. are bonded; and complexes having acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, ethylacetoacetate, salicylaldehyde, soethylmalonate, etc. as a ligand.

These organoaluminum compounds can be used alone or in an appropriate mixture of two or more.

The amount added to the epoxy resin is usually 0.
It is in the range of 001 to 5 weight buns.

,! , In addition, the organic silicate compound having an 0-nitropentyloxy group used in the present invention has the following formula: (in the formula, p
+(1, r is 0≦p+(ltr≦3゜l≦p+q+, r
Represents an integer that satisfies the condition ≦3. ) can be found.

Above R1. R2 and R3 may be the same or different, and each is a hydrogen atom; a halogen atom; a vinyl group;
Allyl group: 1-10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, t-butyl group, chloromethyl group, chloroethyl group, fluoromethyl group, cyanomethyl group, etc.
unsubstituted or substituted alkyl group; alkoxy group having 1 to 10 carbon atoms such as methoxy group = ethoxy group; phenyl group,
p-methoxyphenyl s, p-chlorophenyl g,
p-,)'l) Represents an unsubstituted or substituted aryl group such as a fluoromethylphenyl group; an aryloxy group such as a phenoxy group; a siloxy group, etc.

In addition, R4 is a hydrogen atom; an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a cyanmethyl group, a chloromethyl group, a fluoroethyl group; a phenyl group; p-methoxyphenyl group, p-chlorophenyl group5. Represents a substituted phenyl group such as Ω-nitrophenyl group.

R-R may be the same or different, and each represents a hydrogen atom; a nitro group; a cyano group; a hydroxy group; a merkaft group; a halo atom; an acetyl group; an allyl group; a methyl group, an ethyl group, a pentyl group, 1 to 5 carbon atoms such as chloromethyl group
unsubstituted or substituted alkyl group; alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; phenyl group, p
It represents an unsubstituted or substituted aryl group such as -methoxyphenyl group; or -ruoxy group such as phenoxy group.

In addition, the V-organic silicon compound has an 0-nitropentyloxysilyl group as a terminal group, and the main chain has the following formula: (wherein, n represents an integer of 0 or 1 or more; R1 and R2 have the same meanings as above. has: X and Y may be the same or different,
Each represents an acid atom, an alkylene group, an aryl group, etc. ) may be a compound consisting of a group represented by

A specific example of an organosilicon compound having an unsubstituted or substituted 0-nitropentyloxy group directly bonded to a silicon atom used in the present invention is ld:, trimethyl(0-nitropentyloxy)silanezmethylphenyl(0-nitropentyloxy) silane) silanesophenylmethyl (0-nitropentsuroxy) silane triphenyl (o-nitropentsuroxy) silane vinylmethylphenyl (0-nitropennoroxysilane t-butylmethylphenyl (
0-Nitrobenzyloxy) silane Triethyl (0-nitropentyloxy) silane) (2-#roloethyl) o-nitrobenzyloxysilane) IJ (p-trifluoromethylphenyl) o-nitrobenzyloxysilane') ) thyl[α-(0-nitrophenyl)◇-nitropentyloxy]silanedimethylphenyl[α-(0-nitrophenyl)o-nitropensoloxy]silanemethylphenylso[α-(0-nitrophenyl]so・−
Nitropentyloxycosilane triphenyl(α-ethyl-〇-nitrobenzyloxy)silanetrimethyl(3-methyl-2-nitropentyloxy)silantho)l Tylphenyl(3,4,5-)
Liftoxy-2-nitropentyloxy)silane) Lift! Nyl(4,5,6-tri)toxy-2-nitrobenzyloxy)silanesophenylmethyl(5-methyl-4-methoxy-2-nitrobenzyloxy)silanetriphenyl(4,5-tmethyl-2-nitropene) silane triphenyl (2,6-sonitrobenzoloxy) silanthophenylmethyl (2,4-dunitrobenzoloxy) silane triphenyl (2,6-sonitrobenzoloxy)silane Phenyl(3-methoxy-2-nitropenoloxy)silanevinylmethylphenyl(3,4-'#)xy-2-nitrobenzyloxy)silanethomethylso(0-nitrobenzyloxy)silanetstylphenylso(0-nitrobenzyloxy) 2-Chloroethylphenylso(o-nitropentyloxy)silane
(sophenylso(0-nitropenzyloxy)silanthophenylso(3-methoxy-2-nitropentyloxy)silanthophenylso(3,4-dimethoxy-2
-nitropentyloxy)silanesophenylso(2,6-sonitropendyloxy)silanethophenyldi(2,4-sonitropenzoloxy)silanemethyltri(0-benzyloxy)silanephenyltri(o-nitro benzyloxy)silane rubis(0-nitropenzyloxytsumethylsilyl)benzene], , 1,3,3-tetraphenyl-1,3
-di(0-nitrobenzyloxy)siloxane 1.1,3,3,5.5-hexaphenyl-1,5-ㅅ(o-nitrobenzyloxy)siloxane and a 5iCt-containing silicone resin. -Silicon produced by reaction with nitropentyl alcohol, including arsenic compounds.

The above organosilicon compounds can be used alone or in an appropriate mixture of two or more.

The amount added to the epoxy resin is usually), 0
01-10 weight ip, g, preferably in the range of 0.1 to 5 weight t.

In the present invention, in addition to the above-mentioned essential components, other components commonly used in epoxy resin introduction products may be added. Other components include, for example, acid anhydrides used to make epoxy resins transparent. Specifically, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nanotsunic anhydride, methyl nanotsunic anhydride, chlorendic anhydride, dodecynyl anhydride. Examples include succinic acid, methylsuccinic anhydride, benzophenonetetracarboxylic anhydride, pyromellitic anhydride, and maleic anhydride. The amount of acid anhydride added is usually 0.2 to 1.5 to the epoxy resin.
The amount of a is preferably within the range of 0.5 to 1.2 equivalents.

Additionally, additives such as colorants and fillers may be added as necessary.

The method for manufacturing the resin-sealed light emitting device of the present invention is as follows. That is, after the light-emitting element is encapsulated by a known method such as potting, casting, dipping, or dropping using the photocurable epoxy resin composition,
, p-curing with light, especially UV light. In addition, it is also possible to cure by using both light irradiation and heating means.

During photocuring, the original wavelength of irradiation varies depending on the resin composition and light emitting element, but is usually 180 to 7 Q Onm.
Among these, UV light is preferred. As a light source, a high-pressure mercury lamp, a carton arc lamp, a xenon lamp lamp, an argon glow discharge tube, a metalnoparide lamp, etc. can be used. The irradiation time varies depending on the resin composition, stopping method, light source, etc., but is usually 10 seconds to 30 minutes.

As described above, the light emitting device of the present invention can be obtained.

[Effect of home town]

The resin-blocking light emitting device of the present invention is free from coloring caused by the photocuring agent, and the photocuring agent does not contain ionic impurities, so even if the sealing resin part is discolored, it will not be connected. There is no risk of corrosion of aluminum electrodes, etc. Furthermore, it has excellent electrical insulation, moisture resistance, heat resistance, and solder resistance.

In addition, according to the manufacturing method of the present invention, the light emitting device can be manufactured in a short time, which improves productivity.Furthermore, the resin can be cured by light irradiation alone or in combination with a heating means, so it is possible to save energy. Can be done.

[Embodiments of the invention]

Example 14 (Preparation of resin) -ERL-4221 (trade name, UCC40 (manufactured by 1 company, alicyclic epoxy, engineering equivalent: 145) ΦEbiko) 1004 (trade name, CIE 1002# Chemistry (a) M, Bisphenol type Epokin, epoxy equivalent: 900-1000, molecular weight: approximately 1400) - Trisethyl acetoacetate 1 sodium aluminum lv
-Sophenyldi(0-nitropentyl□oxy)silane 5f The composition in the above ratio was heated and stirred at 150°C for 10 minutes to obtain a sealing resin composition.

(Sealing of Light-Emitting Element) The light-emitting element was immersed in the resin composition thus formed, pulled up, and irradiated with light for 1 minute. Light source, output 80 W/lyn Metalno Ride Drumf''
The distance to the light source was 10 cm.

Regarding the resin-sealed light emitting device obtained in this way,
Its properties are shown in Table 1.

Table 1 Example 2 (Preparation of resin) - Epicote 828 (trade name, Shell 2502 Chemical)
Co., Ltd., bisphenol type epoxy, epoxy equivalent: 190-210゜molecular weight: 380) ・ERL4221 250 ri・Trissalicylaldehyde toaluminum 0.52nium++) Riphenyl (0-nitrobenzyl 1(1)
Composition f of oxy)silane in the above ratio: The mixture was heated and stirred at 60° C. for 10 minutes to obtain a sealing resin composition.

(Sealing of Light-Emitting Element) The resin composition thus obtained was poured into a transparent container, the light-emitting element was buried to a specified point, and then light was irradiated for 3 minutes. The characteristics of the resin-sealed light emitting device thus obtained are shown in Table 2.

Table 2 Example 3 (Preparation of resin) ・ERL4221 200Si'・
Anhydrous hexahydrophthal rR16oy/trisethylacetoacetonate 1.02aluminum/diphenyldi(o-nitropendzyloxy)silane The above materials were heated and stirred at 60°C for 30 minutes to prepare a sealing resin.

(Sealing of Light-emitting Element) The sealing resin prepared above was injected into a mold, the light-emitting element was placed therein, and light was irradiated for 1 minute.

The light source used was a metal halide lamp 2 of 80 W/cm.
In the book, the distance was 10 crn. After 1 minute of irradiation, the curing reaction had progressed to the extent that it could be removed from the mold. After taking it out from the mold, it was further irradiated with light for 1 minute to completely cure it. Table 3 shows the characteristics of the resin-sealed light emitting device obtained.

Table 3 Examples 4 to 14 A resin-suppressed light-emitting device R was manufactured in the same manner as in Example 1 using the resin compositions shown in Table 4 consisting of an epoxy resin, an aluminum compound, and an organosilicon compound. If other additives were used, they were also listed. In the table, the time of light irradiation until the resin was cured was also listed.

Claims (1)

[Claims] (1) In a resin-sealed light emitting device in which a light emitting element is sealed with a resin, the resin is (a) an epoxy resin (b) an aluminum compound (c) an unsubstituted compound directly bonded to a silicon atom. Alternatively, a resin-sealed light emitting device is a cured product of an epoxy resin composition comprising an organosilicon compound having a substituted o-nitrobenzyloxy group. (2J (a) Di-coconut compounds having one or more epoxy groups in the molecule (b) Aluminum compounds □ (C) Organic compounds that are directly bonded to the silicon atom and have a substituted or substituted 0-nitrobenzyloxy group 1. A method for manufacturing a resin-sealed light emitting device, comprising photocuring an epoxy resin composition containing a silicon compound □-' □ and sealing a light emitting element.