JPH0691694A - Molded product and production thereof - Google Patents

Abstract

PURPOSE:To obtain an integrated molded product excellent in the sealability of a material of a different kind using a thermoplastic resin excellent in moldability. CONSTITUTION:A crosslinkable compsn. (1) such as a thermosetting compsn., a photo-setting compsn. or an electron beam curable compsn. is applied to the contact scheduled part of a thermoplastic resin and crosslinked by the method corresponding to the compsn. to be cured or a soln. of a rubbery polymer (2) such as saturated polyolefinic rubber, alpha-olefin/diene rubber, a polystyrenic thermoplastic elastomer or a polyolefinic thermoplastic elastomer is applied to the contact scheduled surface to volatilize a solvent or the rubbery polymer is melted to be applied to the contact scheduled surface to be cooled to produce a material of a different kind having an intermediate layer formed thereto, for example, an electronics element such as a light emitting diode. This material is fixed to a mold and a thermoplastic resin such as polycarbonate, polymethyl methacrylate or a thermoplastic norbornene resin is subjected to injection molding and solidified to obtain an integrated molded product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin molded product containing different materials such as metals and ceramics and a method for producing the same.

[0002]

2. Description of the Related Art Electronic devices such as IC devices and light emitting diodes are made of metal or ceramics.
Therefore, by contact with oxygen and moisture in the air,
It may be deteriorated by being oxidized. for that reason,
Generally, an electronic element is used by being sealed so as not to come into direct contact with air or the like.

In the manufacture of such a sealed electronic device, the device is generally sealed with an epoxy resin. However, since the epoxy resin is a thermosetting resin, there is a problem in that it takes time to cure due to cross-linking and the manufacturing time becomes long. To improve manufacturing efficiency,
It has been desired to reduce the time required for sealing.

Recently, research has been conducted using a thermoplastic resin as an encapsulating material instead of a thermosetting resin. For example, a method of encapsulating an electronic element using an addition type copolymer resin of norbornenes and olefins. Has been proposed (JP-A-2-31451). The method of using a thermoplastic resin as the encapsulant is excellent in that the time required for molding is short, but the encapsulation of different materials is insufficient, and the expansion of different materials and encapsulant due to temperature change. -There is a problem that interfacial peeling easily occurs due to the difference in the size of shrinkage. For this reason, air or moisture may enter between the sealing material and the dissimilar material, contact the dissimilar material, and cause the dissimilar material to be oxidized.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have made diligent efforts toward the development of integral molding using a thermoplastic resin, which is excellent in sealing property of different materials. It was found that the above object was achieved by forming an intermediate layer on the surface, and the present invention was completed.

[0006]

Thus, according to the present invention, there is provided an integrally molded article composed of a thermoplastic resin portion and a dissimilar material portion, wherein the molten thermoplastic resin in the mold and the surface embedded in it. Provided are a molded article obtained by cooling a heterogeneous material having an intermediate layer formed thereon to solidify a thermoplastic resin, and a method for producing the same.

(Thermoplastic Resin) The thermoplastic resin used in the present invention is not particularly limited, and examples thereof include polycarbonate, polymethyl methacrylate, polyethyl terephthalate,
Polybutyl terephthalate, polyimide, polyamide,
Examples thereof include diallyl phthalate, chlorinated polyether, polyamino bismaleimide, polysulfone, silicone resin and thermoplastic norbornene-based resin.

It is preferable that the thermoplastic resin of the present invention has heat resistance and moisture resistance depending on the purpose of use and the glass transition temperature is not particularly limited. A glass transition temperature that facilitates injection molding is preferred. In the case of an electronic device, a metal portion protruding from a thermoplastic resin portion may be soldered, and heat conduction from the metal portion may heat a portion sealed in the thermoplastic resin. In such a case, the glass transition temperature of polyimide is 26
It is preferably about 0 ° C. or higher. However, when the foreign material sealed in the thermoplastic resin is apt to be eroded in the presence of water, the thermoplastic norbornene-based resin is preferable because it hardly permeates water and hardly absorbs moisture.

(Thermoplastic Norbornene Resin) The thermoplastic norbornene resin of the present invention is disclosed in JP-A-3-14882.
No. 3,122,137, and 4-63807.
Known resins such as ring-opening polymers of norbornene-based monomers, hydrogenated products thereof, addition-type polymers of norbornene-based monomers, addition of norbornene-based monomers and olefins. Type polymers and the like.

The norbornene-based monomer is also a monomer known in the above publications, JP-A-2-227424 and JP-A-2-276842, and examples thereof include norbornene, its alkyl, alkylidene, and aromatic substituted derivatives. And halogens, hydroxyl groups of these substituted or unsubstituted olefins,
Polar group substituents such as ester group, alkoxy group, cyano group, amide group, imide group and silyl group, for example, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5- Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-
2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl- 2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene, etc .; a monomer in which one or more cyclopentadiene is added to norbornene, or a derivative similar to the above. Substitutes, such as 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-methyl-1,4: 5 ，
8-Dimethano-1,4,4a, 5,6,7,8,8a-
Octahydronaphthalene, 1,4: 5,10: 6,9-
Trimethano-1,2,3,4,4a, 5,5a, 6
9,9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc .; a polycyclic monomer which is a multimer of cyclopentadiene, a derivative or substituent similar to the above, for example, dicyclo Pentadiene, 2,3
-Dihydrodicyclopentadiene and the like; addition products of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1,
4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a,
5,8,8a-octahydro-2,3-cyclopentadienonaphthalene and the like; and the like.

In the present invention, when a norbornene-based monomer is polymerized, other copolymerizable cycloolefins and the like can be used in combination within a range that does not substantially impair the effects of the present invention. Can be Specific examples of the copolymerizable cycloolefin in the case of ring-opening polymerization include, for example, cyclopentene, cyclooctene, 5,6.
Examples thereof include compounds having one or more reactive double bonds such as dihydrodicyclopentadiene.

The norbornene-based monomer may be polymerized by a known method, and if necessary, may be hydrogenated by a known method to be used as a thermoplastic norbornene-based hydrogenated resin.

The Tg of the thermoplastic norbornene-based resin used in the present invention is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. Number average molecular weight is GPC with toluene solvent
The polystyrene conversion value measured by the (gel permeation chromatography) method is 10,000 to 200,
000, preferably 20,000 to 100,000, more preferably 25,000 to 50,000. If the number average molecular weight is too small, the mechanical strength will be poor, and if it is too large, the moldability will be poor.

When the thermoplastic norbornene-based resin is hydrogenated, the hydrogenation rate is 90% or more, preferably 95% or more, and more preferably 99% or more from the viewpoint of heat deterioration resistance and light deterioration resistance. To do.

Further, the hydrogenated norbornene ring-opening polymer may contain, if necessary, an antiaging agent, a light stabilizer, an ultraviolet absorber, a flexibility-imparting agent, a plasticizer, a tackifier, a colorant, Lubricants, fillers, carbon black, white carbon (silicate compounds), inorganic fillers such as calcium carbonate, talc and clay, and other additives may be added.

(Dissimilar material) The dissimilar material used in the present invention may be any material that does not melt or deform at the molding temperature of the thermoplastic resin used in the present invention, and particularly gold, silver,
Metals such as copper, platinum, aluminum and their alloys;
Ceramics such as silicon oxide, aluminum oxide and silicon; and combinations thereof are preferable, and among them, those used for semiconductor chips of electronic parts such as light emitting diodes, diodes, transistors and integrated circuits are preferable.

These are molded in advance into the shape of the molded article of the present invention. The method for molding the different materials is not particularly limited, and may be molded according to each purpose. In the case of an electronic element, it may be formed by a method used for an electronic element such as vapor deposition on a metal frame.

The intermediate layer used in the present invention comprises a crosslinkable polymer or a rubbery polymer. The intermediate layer may be a multilayer. The thickness of the intermediate layer is preferably 10 mm or less as a whole, more preferably about 0.001 to 5 mm. In the case of a minute molded product such as an electronic element sealing body, it is preferably about 0.001 to 1 mm.

(Crosslinkable Polymer) The crosslinkable polymer used in the present invention means a thermosetting composition obtained by crosslinking and curing a crosslinkable composition such as a thermosetting composition, a photocurable composition and an electron beam curable composition. Among resins, photocurable resins, electron beam curable resins, etc., those having excellent heat resistance, which do not melt or deform at the molding temperature of the thermoplastic resin used in the present invention, may be used.
It is preferable that the heat distortion temperature is 100 ° C. or higher under a load of 18.6 kg / cm ² , particularly 150 ° C. or higher, more preferably 200 ° C. or higher.

As the thermosetting resin, phenol resin,
Xylene resin, diallyl phthalate resin, unsaturated polyester resin, epoxy resin, acrylic resin, furan resin, aniline resin, polyurethane resin, polybutadiene resin, melamine phenol resin, silicone resin, etc.
Examples of electron beam curable resins include acrylic resins and epoxy resins, polystyrene resins and polyolefin resins, and photocurable resins include acrylic resins. In particular, the photocurable resin is preferable in that the curing rate due to crosslinking is high and the process can be made efficient.

Further, it is preferable that the crosslinkable polymer has a good sealing property between different materials. If a layer of such a crosslinkable polymer is formed on the surface of a different material, interfacial peeling does not occur due to the difference in the magnitude of expansion and contraction of both, unless a considerable temperature change occurs, and the surface of the different material is It does not deteriorate due to air or moisture entering the peeled interface. When the dissimilar material is a metal or ceramics, an epoxy resin or an acrylic resin is preferable because these heterogeneous materials have good sealing properties.

Further, among the acrylic photo-curable resins which are excellent in two points, that is, the simplification of the process and the sealing property with different materials such as metal, especially as the UV-curable resin, a monofunctional acrylate monomer is used. A UV-curable composition comprising a di- or tri-functional acrylate monomer, a tetra- or higher functional acrylate monomer, and a photopolymerization initiator is preferably crosslinked.

In the present invention, among the photopolymerizable monomers, those having an acrylate group are referred to as a monofunctional acrylate monomer, a bifunctional acrylate monomer, a trifunctional acrylate monomer, etc., depending on the number of acrylate groups. Further, in the present invention, the acrylate group includes a methacrylate group, an ethacrylate group and the like in addition to the acrylate group in a narrow sense.

Examples of monofunctional acrylate monomers include n-butyl acrylate, isoamyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate, phenoxypropyl acrylate and other higher alkyl acrylates. And so on. Among them, those not having a methacrylate group and having only an acrylate group in a narrow sense are preferred so that the curing reaction is not inhibited by radical oxygen. Further, in order to reduce the curing shrinkage of the UV hard resin, the number of carbon atoms is 4 to 4 Those having about 6 side chains are preferable.

Examples of the bifunctional or trifunctional acrylate monomer include ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, hexanediol, tremethylolpropane, tetramethylolpropane, pentaerythritol and dipentaerythritol. It is a polyol obtained by esterifying 2 or 3 acrylic acids.

Examples of tetrafunctional or higher-functional acrylate monomers include polyols such as tetramethylolpropane, pentaerythritol, and dipentaerythritol.
It is an esterified product of 4 or more, preferably 4 to 8 acrylic acid. Particularly, an easily available 4- to 6-functional acrylate monomer is particularly preferable.

As the photopolymerization initiator, acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone and chlorinated acetophenone; benzophenones; benzyl, methylorthobenzoylbenzoate, benzoin alkyl ether And the like; azo compounds such as α, α′-azobisisobutyronitrile, 2,2′-azobispropane and hydrazone; organic peroxides such as benzoyl peroxide and ditertiary butyl peroxide;
Diphenyl disulfides such as diphenyl disulfide, dibenzyl disulfide, dibenzoyl disulfide; and the like.

The mixing ratio of these is usually 25 to 60% by weight, preferably 30 to 40% by weight, of the monofunctional acrylate monomer, or the difunctional or trifunctional acrylate, based on the total weight of the acrylate monomer and the photopolymerization initiator. Monomer is 10 to 40% by weight, preferably 15 to 30% by weight, tetrafunctional or higher functional acrylate monomer is 20 to 50% by weight, preferably 25 to 40% by weight, and photopolymerization initiator is 1 to
It is 10% by weight, preferably 2 to 6% by weight. When the amount of the tetrafunctional or higher functional acrylate monomer is too large, the curing shrinkage increases, and when the amount is too small, the hardness of the crosslinkable polymer after curing is lowered and the curing speed is lowered. When the amount of the monofunctional acrylate monomer is small, the viscosity becomes high and the workability becomes poor. Further, when the amount of the monofunctional acrylate monomer is large, the curing shrinkage is reduced, and the amount of the bifunctional or trifunctional acrylate monomer is small, so that the flexibility of the crosslinkable polymer after curing is reduced, which causes cracks. Further, in order to improve the sealing property, it is preferable that the amount of the bifunctional or trifunctional acrylate monomer is large.

Further, appropriate additives may be added to the crosslinkable composition as long as the sealing property and hardness of the crosslinkable polymer layer are satisfied. For example, by adding a suitable surfactant, for example, a nonionic surfactant having good compatibility with an ultraviolet curing agent, particularly an amine surfactant or other antistatic agent, the surface chargeability can be improved. Alternatively, by adding a fluorine-based nonionic surfactant, wetting with the substrate and the surface smoothness after the effect can be improved. Further, by adding an appropriate thermoplastic resin, the viscosity can be adjusted and the sealing property can be improved. As the thermoplastic resin for improving the sealing property, a thermoplastic saturated norbornene-based resin or a resin having a structure similar to that of the thermoplastic resin, for example, a ring-opening polymer of norbornene-based monomer, dicyclopentadiene-based, diene-based, or aliphatic And petroleum resins such as water white type and hydrogenated products thereof.

These mixtures can be used as they are as a crosslinkable composition, but depending on the operability, aromatic hydrocarbon solvents such as toluene, xylene, chlorobenzene, etc .; cyclohexane, methylcyclohexane Alicyclic hydrocarbon solvents such as; ketone-based solvents such as methyl isobutyl ketone, methyl ethyl ketone, and acetone; ether-based solvents such as n-butyl ether, diethyl ether; etc., ester-based solvents, cellosolve-based solvents, chlor-based solvents Etc. may be used after being dissolved at a concentration of 80% by weight or more.

When the linear expansion coefficient of the different material used in the present invention and that of the thermoplastic resin are greatly different, depending on the use environment of the molded article of the present invention, the interface may be peeled off due to the difference in expansion between the two materials. And in such cases,
It is preferable to use a crosslinkable composition having flexibility after crosslinking.

The crosslinkable composition also contains a polymerization initiation aid, an antifoaming agent, a filler, a pigment, an ultraviolet stabilizer, an ultraviolet absorber, an antiaging agent, a heat stabilizer, a tackifier, and a flexibility imparting agent. You may add and use an agent.

The method of applying the crosslinkable composition to the surface of the dissimilar material to be contacted with the thermoplastic resin portion is not particularly limited.
Examples include dipping, spraying, brush coating, spin coating, and the like. It may be selected according to the simplification of the process and the required accuracy. When the coating composition contains an organic solvent in the crosslinkable composition, it must be sufficiently removed before crosslinking so as not to cause cracking or corrosion of different materials after molding. Without using an organic solvent
It is preferable to adjust the viscosity by a method such as adjusting the amount of the monomer.

To a different material coated with this crosslinkable composition,
Each of the crosslinkable compositions is subjected to a treatment suitable for crosslinking, and crosslinked to form a crosslinkable polymer layer.

(Rubber Polymer) The rubber polymer used in the present invention has a glass transition temperature of 40 ° C. or less. The block copolymerized rubbery polymer or the like may have two or more glass transition temperatures. In that case, if the lowest glass transition temperature is 40 ° C. or lower, the glass transition temperature of the present invention is 40 ° C. or lower. It can be used as a rubbery polymer. When an intermediate layer composed of such a rubbery polymer is formed on the surface of a different material, the rubbery polymer may melt due to contact with the molten thermoplastic resin, but even if it is in a molten state, it is freed from the surface of the different material. However, since the rubber-like polymer is solidified as the thermoplastic resin is solidified by cooling and the intermediate layer is re-formed, there is no problem.

Examples of the rubbery polymer of the present invention include ethylene / propylene copolymers, ethylene / α-olefin copolymers, propylene / α-olefin copolymers, saturated polyolefins such as chlorinated polyethylene and chlorosulfonated polyethylene. -Based rubber; ethylene-propylene-diene copolymer, α-olefin-diene copolymer, ethylene-diene copolymer, propylene-diene copolymer, α-olefin-diene such as halides and hydrogenated products thereof Copolymer type rubber; Diene polymer type rubber such as isoprene rubber, butadiene rubber, their halides and hydrogenated compounds; Silicone type rubber such as methyl silicone rubber, vinyl / methyl silicone rubber, finyl / methyl silicone rubber; Fluorosilicone Rubber, vinylidene fluoride rubber, four layers Fluorinated rubbers such as chlorinated ethylene / propylene rubber and tetrafluoroethylene / perfluoromethyl vinyl ether rubber; Styrene / diene copolymer rubbers such as styrene / butadiene copolymers and styrene / isoprene copolymers; Butyl rubber and its halides Butyl rubbers such as hydrogenated compounds; chloroprene rubbers such as chloroprene, its halides and hydrogenated compounds; epichlorohydrin rubbers such as epichlorohydrin rubber, epichlorohydrin / ethylene oxide rubbers; urethane type rubbers such as polyether urethane rubber and polyester urethane rubber Rubber; Acrylonitrile
Acrylonitrile-butadiene rubber such as butadiene rubber and its halides and hydrogenated compounds; carboxylated nitrile rubber such as carboxylated nitrile rubber, its halides and hydrogenated compounds; norbornene-based monomer / ethylene copolymer rubber, Norbornene-based monomer / α
-Olefin copolymer rubber, norbornene-based monomer / ethylene / α-olefin copolymer rubber, norbornene-based monomer ring-opening polymer rubber, norbornene-based rubbers such as halobenates and hydrogenated products thereof; acrylic rubber , Acrylic rubber such as ethylene / acrylic rubber; styrene / butadiene / styrene / block copolymer, styrene / isoprene / styrene / block copolymer, styrene / ethylene / butadiene / styrene / block copolymer, styrene / isoprene Polystyrene-based thermoplastic elastomers such as butadiene / styrene / block copolymers, styrene / ethylene / propylene / styrene / block copolymers, their halides and hydrogenated compounds;
Polyolefin-based thermoplastic elastomers such as blends of olefin resins and olefin rubbers, blends of olefin resins and olefin / diene copolymers, halides and hydrogenates thereof; polyurethane-based thermoplastic elastomers; polyester-based thermoplastic elastomers; Polyamide-based thermoplastic elastomer; and the like.

As the rubbery polymer used in the present invention, saturated polyolefin rubber, α
-Olefin / diene copolymer rubber, polystyrene-based thermoplastic elastomer, and polyolefin-based thermoplastic elastomer are preferred, polystyrene-based thermoplastic elastomer is more preferred, and polystyrene-based thermoplastic elastomer that is a hydrogenated product is particularly preferred.

If necessary, additives such as an antioxidant, a light resistance stabilizer, a flame retardant, a defoaming agent, and an inorganic filler such as glass fiber or glass beads may be added to the rubbery polymer. .

In the present invention, a rubbery polymer solution is applied to the surface of a different material to volatilize the solvent, or the rubbery polymer is melted and applied and cooled to form a rubbery polymer layer. When the solution is applied, the solvent is not particularly limited as long as it does not react with or corrode different materials and dissolves the rubbery polymer. For example, in the case of a polystyrene-based thermoplastic elastomer, toluene, cycloolefin, etc. are used. The concentration is not particularly limited.
Depending on the type of rubbery polymer to be used and the coating method, the rubbery polymer layer may have an appropriate workability concentration in order to have an appropriate thickness. The coating method is not particularly limited, and spraying, brush coating, dipping, spin coating and the like can be used. The drying method is also not particularly limited, and heat drying, reduced pressure drying, heating reduced pressure drying and the like can be used. In order to shorten the process time, which is one of the effects of the present invention, heating under reduced pressure is preferable. 5 to prevent foaming after application
It is preferable to provide a gradual drying time of about 10 minutes. When the molten rubbery polymer is applied, the molten rubbery polymer is applied at a temperature that does not change the quality of different materials.

(Molding Method) The molded article of the present invention is an integrally molded article composed of a thermoplastic resin portion and a dissimilar material portion,
The molten thermoplastic resin in the mold and the dissimilar material having an intermediate layer formed on the surface embedded therein are cooled, and the thermoplastic resin is solidified and molded. Generally, a different material with an intermediate layer formed on the surface is fixed in a mold, and an injection molding machine is used.
Insert molding is performed in which a molten thermoplastic resin is injected into a mold for molding. The thermoplastic resin may be deformed during the solidification process or may be embedded with a different material, or may be polished, cut, or bonded to another molded product after solidification.

When the purpose is to seal a different material portion with a thermoplastic resin, it is usually molded so that the different material is embedded in the thermoplastic resin. For example, when encapsulating a semiconductor or the like, the entire semiconductor, which is a different material portion, is covered with the intermediate layer and molded so as to be embedded in the thermoplastic resin. The lead wire connected to the semiconductor or the like is usually a substance that is not easily deteriorated by oxygen or moisture, and in that case, the lead wire itself does not need to be covered with the intermediate layer. Rather,
In the case of encapsulating a semiconductor or the like, it is not preferable to completely cover the end of the lead wire in the portion not encased with the thermoplastic resin with the intermediate layer because electric current cannot be applied. For the sealed part,
Although it is preferable that the lead wire in the portion close to the semiconductor is covered with the intermediate layer, the entire lead wire to be sealed need not be covered with the intermediate layer. Similarly, as for the lead wire of the unsealed portion, there is a portion which is not covered with the intermediate layer for energization. The portion covered with the norbornene-based ring-opening polymer hydrogenated product is preferably 0.01 mm or more, more preferably 0.05 mm or more, and particularly preferably 0.08 mm, except for the portion where the lead wire projects to the outside.
The thickness should be at least mm.

(Use) As a molded article of the present invention, an LSI
Electronic element encapsulant encapsulating electronic elements such as elements, IC elements, LED elements and CCD elements; Electronic component encapsulation encapsulating electronic components such as capacitors, resistors, coils, microswitches, dip switches and connectors In addition to the stopper, etc., examples include a magneto-optical disk hub, a taper type flow meter with a connector inserted, and the like.

[0043]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. The sealability test and heat cycle test were performed as follows.

(Sealing test) The sealing light emitting diode was made into 20% of red ink (INK RED, manufactured by Pilot Inc.)
It was immersed in the aqueous solution, boiled for 1 hour, then taken out, the red ink aqueous solution on the surface was wiped off, and visually observed.

(Heat cycle test) -30 ° C., 30
The temperature change was applied to the sealed light emitting diode with one cycle of 100 minutes and 100 ° C. for 30 minutes.

Example 1 Acrylic resin so that a light emitting diode chip (rated current 20 mA) composed of a metal lead frame (EME2003-2, manufactured by Enomoto Co., Ltd.), a semiconductor PN junction, and a gold wire is completely sealed. Composition (10 parts by weight of n-butyl acrylate, 28 parts by weight of isoamyl acrylate, 30 parts by weight of trimethylolpropane triacrylate, 42 parts by weight of dipentaerythritol hexaacrylate, photopolymerization initiator (manufactured by Ciba Geigy, Irgacure 651) 5
(Parts by weight) was applied, left at room temperature for 10 minutes, and thoroughly dried. The average thickness of the acrylic composition after drying is 0.
It was 1 mm. Ultraviolet irradiation by 80 mW high-pressure mercury lamp (peak irradiation intensity on substrate surface: 150 mW / c
m ² , cumulative light amount 150 mJ / cm ² , irradiation time 10 seconds) was performed to crosslink the acrylic composition.

The portion sealed with the crosslinked polymer was fixed in a mold so as to be further sealed, and the norbornene-based ring-opening polymer hydrogenated product (Zeonex 280, Tg1) was placed in the mold.
40 ° C, number average molecular weight of about 28,000, manufactured by Nippon Zeon Co., Ltd. injection molding machine (upper mold fixed, lower mold movable mold, vertical injection molding machine, Yamashiro Seiki Seisakusho Co., Ltd., SAV-30 / 3)
0) resin temperature 300 ℃, mold temperature 100 ℃,
Injection molding was performed at an injection pressure of 25 kgG / cm ² and an injection molding speed of 2 g / sec to obtain 100 sealed light emitting diodes. The thickness of the norbornene-based ring-opening polymer hydrogenated material was 0.20 mm in the thinnest part except the sealed part and the unsealed part of the metal lead frame.

In all the encapsulated light emitting diodes, the cured surface resin layer was encapsulated in a thermoplastic norbornene resin. When energized, all the sealed light emitting diodes emitted light normally.

As a result of the sealing property test, no penetration of red ink into the inside of the sealed body was observed in all the sealed light emitting diodes.

After the heat cycle test of 50 cycles, all the sealed light emitting diodes normally emitted light when energized.

When the sealed light emitting diode after the heat cycle test of 50 cycles was again subjected to the sealing property test,
In the two sealed light emitting diodes, the penetration of the red ink into the inside of the encapsulant from the metal lead frame was observed, but the invasion into the crosslinkable polymer layer was not observed.

Further, the metal lead frame in the part which was doubly sealed with the thermoplastic norbornene resin and the crosslinkable polymer was examined, but no particular corrosion was observed.

Example 2 As a crosslinkable polymer, 90 parts by weight of 2-methylhexahydrophthalic anhydride was added to 100 parts by weight of a bisphenol F type epoxy resin (XPY-306, manufactured by Ciba Geigy) instead of an acrylic composition. The same treatment as in Example 1 was performed, except that the curing treatment was performed by leaving it at 120 ° C. for 15 hours instead of irradiating it with ultraviolet rays.

The thickness of the crosslinked epoxy resin layer is 0.18 mm on average, and the norbornene ring-opening polymer hydrogenated material layer is the thinnest part except the sealed and unsealed parts of the metal lead frame. It was 0.10 mm.

When energized, all the sealed light emitting diodes emitted light normally.

As a result of the sealing property test, no penetration of the red ink into the inside of the sealed body was observed in all the sealed light emitting diodes.

After the heat cycle test of 50 cycles, all the sealed light emitting diodes normally emitted light when energized.

When the sealed light emitting diode after the heat cycle test of 50 cycles was subjected to the sealing property test again,
In the five sealed light emitting diodes, the penetration of the red ink into the inside of the encapsulant from the metal lead frame was observed, but the invasion into the crosslinkable polymer layer was not observed.

Further, the metal lead frame in the portion which was doubly sealed with the thermoplastic norbornene resin and the crosslinkable polymer was examined, but no particular corrosion was observed.

Example 3 The same light emitting diode chip as in Example 1 was used as a rubbery polymer solution and styrene / ethylene / butadiene / styrene /
Block copolymer hydrogenated product (Asahi Kasei, Tuftec M
1911) 10 wt% toluene solution was applied using a spray, allowed to stand at room temperature for 10 minutes, and then dried at 40 ° C. and 0.5 atm for 50 minutes to form a rubbery polymer layer on the surface of the light emitting diode chip. . The thickness of the rubbery polymer layer was 5 μm on average.

This rubbery polymer layer-formed portion was fixed in a mold so as to be sealed, and a norbornene-based ring-opening polymer hydrogenated product (Zeonex 280) was used in Example 1 as a mold.
Injection molding was performed under the same conditions as above to obtain 300 sealed light emitting diodes. The thickness of the norbornene-based ring-opening polymer hydrogenated material was 0.20 mm in the thinnest part except for the vicinity of the boundary between the sealed part and the unsealed part of the metal lead frame.

In all of the sealed light emitting diodes, the rubber polymer layer was sealed in the thermoplastic norbornene resin. When energized, all the sealed light emitting diodes emitted light normally.

As a result of the sealing property test, no penetration of red ink into the inside of the sealed body was observed in all the sealed light emitting diodes.

Each of 100 sealed light emitting diodes was subjected to a heat cycle test of 50 cycles, 100 cycles and 200 cycles, and when energized, all the sealed light emitting diodes normally emitted light.

The sealed light emitting diode after the heat cycle test was again subjected to the sealing property test. As a result, a metal lead was obtained with three sealed light emitting diodes, one after 100 cycles and two after 200 cycles. The red ink penetrated from the frame portion into the sealed body, but not into the rubbery polymer layer.

Further, the metal lead frame in the portion which was doubly sealed with the thermoplastic norbornene resin and the rubbery polymer was examined, but no particular corrosion was observed.

Example 4 The same as Example 3 except that a 5 wt% toluene solution of a styrene / ethylene / propylene / styrene / block copolymer hydrogenated product (SEPTON 2043 manufactured by Asahi Kasei) was used as the rubbery polymer solution. A rubbery polymer layer was formed on the surface of the light emitting diode chip. The thickness of the rubbery polymer layer was 13 μm on average.

This rubbery polymer layer-formed portion was fixed in a mold so as to be sealed, and a norbornene-based ring-opening polymer hydrogenated product (Zeonex 280) was used in Example 1 as a mold.
Injection molding was performed under the same conditions as above to obtain 300 sealed light emitting diodes. The norbornene-based ring-opening polymer hydrogenated material layer had a thickness of 0.10 mm in the thinnest part except for the vicinity of the boundary between the sealed part and the unsealed part of the metal lead frame.

In all of the sealed light emitting diodes, the rubbery polymer layer was sealed in the thermoplastic norbornene resin. When energized, all the sealed light emitting diodes emitted light normally.

As a result of the sealing property test, no penetration of red ink into the inside of the sealed body was observed in all the sealed light emitting diodes.

Each of 100 sealed light emitting diodes was subjected to a heat cycle test of 50 cycles, 100 cycles and 200 cycles, and when energized, all the sealed light emitting diodes normally emitted light.

When the sealed light emitting diode after the heat cycle test was again subjected to the sealing property test, it was confirmed that the red ink penetrated from the metal lead frame portion into the inside of the sealed body in three after 200 cycles. However, no invasion into the rubbery polymer layer was observed.

Further, the metal lead frame in the part which was doubly sealed with the thermoplastic norbornene resin and the rubber polymer was examined, but no particular corrosion was observed.

Comparative Example 1 300 sealed light emitting diodes were obtained in the same manner as in Example 1 except that the acrylic composition was not applied and cured. When a current was applied, all the sealed light emitting diodes emitted light normally.

As a result of the sealing property test, no penetration of red ink into the inside of the sealed body was observed in any of the sealed light emitting diodes.

After the heat cycle test, even if a current was applied, three sealed LEDs after 50 cycles, eight after 100 cycles, and 21 after 200 cycles did not emit light.

The sealed light emitting diode after the heat cycle test was again subjected to the sealing property test. As a result, 6 after 50 cycles, 20 after 100 cycles, 20 after 20 cycles.
After the 0th cycle, 45 pieces of the sealed light-emitting diodes were found to allow the red ink to enter the inside of the sealed body from the metal lead frame part. Of these, 3 pieces after the 50th cycle,
Intrusion into the interior of the crosslinkable polymer layer was observed in 8 after 100 cycles and 19 after 200 cycles. It should be noted that, except for the two after 200 cycles, those in which the entry into the crosslinkable polymer layer was observed were all sealed light emitting diodes that stopped emitting light after the heat cycle test.

Further, when the metal lead frame of the portion which is doubly sealed with the thermoplastic norbornene resin and the crosslinkable polymer is examined, four after 50 cycles,
Corrosion was observed in 8 pieces after 100 cycles and 17 pieces after 200 cycles. Among them, 3 after 50 cycles, 7 after 100 cycles, and 13 after 200 cycles were sealed light emitting diodes that did not emit light after the heat cycle test, and the remaining corrosion was observed. Except for one after 50 cycles, after the heat cycle test, penetration of the red ink into the inside of the sealed body was recognized from the portion of the metal lead frame, and no light was emitted.

[0079]

EFFECTS OF THE INVENTION Since the molded product of the present invention uses a thermoplastic resin having excellent moldability, it is easy to mold, the time required for molding is short, the sealing property of different materials is excellent, and it is embedded. It is difficult for the dissimilar material portion to undergo changes such as oxidation.
Further, since the intermediate layer is formed on the surface of the different material portion, interfacial peeling is unlikely to occur due to the difference in expansion / contraction magnitude due to temperature change.

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Claims (9)

[Claims] 1. An integrally molded article comprising a thermoplastic resin portion and a dissimilar material portion, wherein a molten thermoplastic resin in a mold and a dissimilar material having an intermediate layer formed on a surface embedded therein are cooled. A molded product made by solidifying a thermoplastic resin. 2. The molded article according to claim 1, wherein the different material portion is made of metal or ceramics. 3. The molded article according to claim 1, wherein the intermediate layer is a crosslinkable polymer layer. 4. The molded article according to claim 1, wherein the intermediate layer is a rubbery polymer layer. 5. The intermediate layer is made of a thermosetting resin, an electron beam curable resin, or a photocurable resin.
The molded article according to 2 or 3. 6. The intermediate layer is a saturated polyolefin rubber, α
The molded article according to claim 1, 2 or 4, which comprises an olefin / diene copolymer rubber, a thermoplastic polystyrene elastomer, or a thermoplastic polyolefin elastomer. 7. The molded article according to claim 1, wherein the different material portion is an electronic element. 8. A dissimilar material portion having a crosslinkable polymer layer formed on the surface to be contacted with the thermoplastic resin portion is fixed to a mold,
The method for producing a molded article according to claim 1, 2, 3, 5, or 7, wherein a thermoplastic resin is injection-molded. 9. A thermoplastic resin is injection-molded by fixing a dissimilar material portion having a rubbery polymer layer formed on a surface to be contacted with the thermoplastic resin portion to a mold and injecting the thermoplastic resin. Or the method for producing a molded article according to 7.