JP3004059B2 - Light emitting diodes and electronic components - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting diode in which a semiconductor chip is sealed with a thermoplastic resin, a semiconductor chip in which a semiconductor chip is sealed with a thermoplastic resin, and external leads made of glass fiber reinforced poly-4-methyl-1. The present invention relates to an electronic component sealed with a pentene composition, and more particularly to a light emitting diode and an electronic component in which the thermoplastic resin contains a specific cyclic olefin-based random copolymer and a rubber-like elastic material.

[0002]

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Light-emitting diodes (infrared light-emitting diodes, light-emitting diodes for optical communication),
In electronic components other than light-emitting diodes, such as diodes, transistors, and integrated circuits (ICs), semiconductor chips are generally sealed with a thermosetting resin.

On the other hand, the present applicant has proposed a light emitting diode and an electronic component having a semiconductor chip sealed with a thermoplastic resin containing an olefin polymer having an alicyclic structure (Japanese Patent Application Laid-Open No. 2-31450). Gazette, JP-A-2-31451). By using a thermoplastic resin containing an olefin polymer having an alicyclic structure as described above, the heat resistance and infrared transmittance of a light-emitting diode or an electronic component are excellent. Due to the difference in the coefficient of linear expansion between the thermoplastic resin and the lead frame, sufficient heat cycle characteristics cannot be obtained, and the long-term reliability of light-emitting diodes or electronic components is reduced, or the thermoplastic resin that seals semiconductor chips It has been found that the adhesion strength with the lead frame may be reduced.

[0004]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide heat resistance, heat cycle characteristics, infrared and near-infrared transmittance, long-term reliability and sealing resin. It is an object of the present invention to provide a light emitting diode and an electronic component having excellent adhesion between the light emitting diode and a lead frame.

[0005]

SUMMARY OF THE INVENTION A light emitting diode according to the present invention comprises a semiconductor chip mounted on a metal lead frame sealed with a thermoplastic resin, wherein the thermoplastic resin is composed of ethylene and the following formula [I] or [II]. ]

[0006]

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Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring; And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. May be).

[0008]

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During [0009] (Formula [II], r is 0 or an integer of 1 or more, s and t is 0, 1 or 2, R ¹ ~
R ¹⁵ each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R ⁵ (or R ⁶ ) and R ⁹ ( Or, R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. A) a copolymer with at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the formula:
Intrinsic viscosity [η] measured in decalin at a temperature of 0.05 to 10 dl
/ g, a cyclic olefin random copolymer [A] having a softening temperature (TMA) of 70 ° C. or higher, ethylene, and an unsaturated monomer represented by the above formula [I] or [II]. A copolymer with at least one type of cyclic olefin selected from the group consisting of: a copolymer having an intrinsic viscosity [η] of 0.05 to 5 dl / g measured in decalin at 135 ° C., and a softening temperature (TMA) ) Is less than 70 ° C. and the cyclic olefin-based random copolymer [B] is [A] / [B] (weight ratio) by 10%.
0 / 0.1 to 100/10, and further contains a rubber-like elastic body [C] in a total amount of 10% of the above components [A] and [B].
It is characterized by being a thermoplastic resin contained in a proportion of 0.01 to 100 parts by weight with respect to 0 parts by weight.

An electronic component according to the present invention comprises: a semiconductor chip sealed with a thermoplastic resin;
It comprises an external lead sealed with a methyl-1-pentene composition, and the thermoplastic resin is the above-mentioned thermoplastic resin.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a light emitting diode and an electronic component according to the present invention will be specifically described.

The thermoplastic resin used for sealing a semiconductor chip in the present invention comprises a cyclic olefin-based random copolymer [A] having a softening temperature (TMA) of 70 ° C. or more;
A resin containing a cyclic olefin random copolymer [B] having a softening temperature (TMA) of less than 70 ° C. and a rubber-like elastic body [C].

The cyclic olefin random copolymer [A] used in the present invention is a random copolymer of ethylene and a specific cyclic olefin, and has a softening temperature (TMA) of 70 ° C. or more; The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.05 to 10 dl / g. The softening temperature (TMA) was measured by Thermo from DuPont.
It was measured by a thermal deformation behavior of a sheet having a thickness of 1 mm using a mechanical analyzer. That is, a quartz needle is placed on the sheet, a load of 49 g is applied, and the temperature is raised at 5 ° C./min.
The temperature at which 0.635 mm penetrated was defined as TMA.

The cyclic olefin random copolymer [B] used in the present invention is a random copolymer of ethylene and a specific cyclic olefin, and has a softening temperature (T
MA) is less than 70 ° C. and the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.05 to 5 dl / g.

The cyclic olefin-based random copolymer [A] and the cyclic olefin-based random copolymer [B] as described above are composed of a repeating unit derived from ethylene and the following formulas [I] and [II] And a repeating unit derived from a cyclic olefin represented by any one of the above formulas. Here, two or more cyclic olefins can be used in combination.

[0016]

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(Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring; And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. May be).

[0018]

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During [0019] (Formula [II], r is 0 or an integer of 1 or more, s and t is 0, 1 or 2, R ¹ ~
R ¹⁵ each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R ⁵ (or R ⁶ ) and R ⁹ ( Or, R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. However, in the above formula [I], n is 0 or 1, and preferably 0
It is. M is 0 or a positive integer, preferably 0 to 3. And q is 0 or 1.

In the above formula [II], r is 0 or an integer of 1 or more, preferably 0 to 3.
R ^{1 to} R ¹⁸ and R ^a and R ^b (Formula [I]) or R ^{1 to} R ¹⁵ (Formula [II]) each independently represent a group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Represents an atom or group selected from Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the hydrocarbon group include, independently of each other, usually an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the alkyl group include: Methyl group, ethyl group, isopropyl group,
Examples thereof include an isobutyl group and an amyl group, and specific examples of the cycloalkyl group include a cyclohexyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group.

In the above formula [II], R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms. They may be directly bonded without a group.

In the above formula [I], when q is 0, the ring represented by q forms a 5-membered ring. Further, in the above formula [I], R ^{15 to} R ¹⁸ may combine with each other (jointly) to form a monocyclic or polycyclic ring,
Further, the monocyclic or polycyclic ring may have a double bond.
As such a monocyclic or polycyclic ring, the following monocyclic or polycyclic rings can be exemplified. Further, these rings may have a substituent such as a methyl group.

[0023]

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In the above formula, carbon atoms denoted by 1 and 2 represent carbon atoms of an alicyclic structure to which the groups represented by R ^{15 to} R ¹⁸ in formula [I] are bonded. . Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Examples of such an alkylidene group include an alkylidene group having usually 2 to 4 carbon atoms, and specific examples thereof include an ethylidene group,
And propylidene, isopropylidene and isopropylidene.

The cyclic olefin represented by the above formula [I] or [II] can be easily produced by condensing cyclopentadiene with the corresponding olefin or cyclic olefin by a Diels-Alder reaction. it can.

Specific examples of the cyclic olefin represented by the above formula [I] or [II] include bicyclo [2.2.1] hept-2-ene derivative, tetracyclo [4.4.0.
1 ^2,5 .1 ^7,10 ] -3-dodecene derivative, hexacyclo [6.6.
1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7. 1 11,18} 1 13,16 .0 ^3,8 .0
^12,17 ] -5-docosene derivative, pentacyclo [6.6.1.1 ^3,6 .
0 ^2,7 .0 ^9,14] -4-hexadecene derivative, heptacyclo-5
Eicosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4.3.0.1 ^2,5] -3- decene derivatives, tricyclo [4.4.0.1 ^2,5] -3- undecene derivatives, pentacyclo [6.5.1.1 ^{3, 6} .0 ^2,7 .0 ^9,13] -4-pentadecene derivatives,
Penta cyclopentadiene decadiene derivative, pentacyclo ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3- pentadecene derivatives, heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1 ^12,15 .0 ^2,7 .0 ^11,16 ]
4-eicosene derivatives, Nonashikuro [10.9.1.1 ^{4, 7} .1
^13,20 .1 ^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21. 0 ^14,19] -5-pentacosene derivatives, pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3
- hexadecene derivative, heptacyclo [8.8.0.1 ^4,7 .1
^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives,
Nonashikuro ^{[10.10.1.1 5,8 .1 14,21 .1 16,19 .0} 2,11 .0 4,9 .0
^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives, 5-phenyl - bicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenyl - bicyclo [2.2.1] hept-2-ene , 5-benzyl-bicyclo [2.
2.1] Hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-
2-ene, 5- (ethylphenyl) -bicyclo [2.2.1] hept
2-ene, 5- (isopropylphenyl) -bicyclo [2.2.
1] Hept-2-ene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene, cyclopentadiene- Acenaphthylene adduct, 5- (α-naphthyl) -bicyclo [2.2.1] hept-2-
Ene, 5- (anthracenyl) -bicyclo [2.2.1] hept-2
-You can say en.

The following are more specific examples of such compounds.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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The cyclic olefin-based random copolymer [A] and the cyclic olefin-based random copolymer [B] used in the present invention can be prepared by combining the above-mentioned specific cyclic olefins alone or in combination with ethylene. It can be prepared by copolymerization.

Cycloolefin random copolymer [A]
And the cyclic olefin random copolymer [B] are obtained, for example, by polymerizing ethylene and the cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. It can be manufactured by doing.
Such a polymerization method itself is already known, and is disclosed in
No. 0-168708, for example.

The above-mentioned cyclic olefin random copolymer [A] and cyclic olefin random copolymer [B] contain ethylene and the above-mentioned cyclic olefin as essential components. In addition to the above, other copolymerizable unsaturated monomer components may be contained, if necessary, as long as the object of the present invention is not impaired. As the unsaturated monomer which may be optionally copolymerized, specifically, for example, propylene, 1-butene, 4-
Methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
Octacene, 1-eicosene, etc. with 3-20 carbon atoms
Α-olefin and the like.

Further, in the present invention, the physical properties of the obtained polymer and the like are not impaired when producing the cyclic olefin random copolymer [A] and the cyclic olefin random copolymer [B] as described above. Within the range, a cyclic olefin other than the cyclic olefin represented by the formula [I] or [II] can be polymerized. Such cyclic olefins include, for example, cyclobutene,
Cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, 2,3,3a, 7a-tetrahydro-4,7-
And methano-1H-indene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene. Such other cyclic olefins can be used alone or in combination, and are usually used in an amount of 0 to 50 mol%.

In the above cyclic olefin random copolymer [A], the repeating unit derived from ethylene is present in the range of 40 to 85 mol%, preferably 50 to 75 mol%. The repeating unit derived from the cyclic olefin is 15 to 60 mol%, preferably 25 to 5 mol%.
It is present in the range of 0 mol%, and the repeating units derived from ethylene and the repeating units derived from the cyclic olefin are randomly and substantially linearly arranged. In addition,
¹³ C-NMR for ethylene composition and cyclic olefin composition
Was measured by The fact that the cyclic olefin-based random copolymer [A] is substantially linear and does not have a gel-like cross-linked structure can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

The intrinsic viscosity [η] of such a cyclic olefin random copolymer [A] measured in decalin at 135 ° C. is 0.05 to 10 dl / g, preferably 0.08 to 8 dl / g.
g, particularly preferably in the range of 0.1 to 5 dl / g.

The softening temperature (TMA) of the cycloolefin random copolymer [A] measured by a thermal mechanical analyzer is 70 ° C. or higher, preferably 90 to 90 ° C.
It is in the range of 250 ° C, more preferably 100-200 ° C. Further, the glass transition temperature (Tg) of the cyclic olefin-based random copolymer [A] is usually in the range of 50 to 230 ° C, preferably 70 to 210 ° C.

The crystallinity of the cyclic olefin-based random copolymer [A] measured by the X-ray diffraction method is as follows:
0 to 10%, preferably 0 to 7%, particularly preferably 0 to
The range is 5%.

Such a cyclic olefin random copolymer [A] is disclosed in JP-A-60-168708 and JP-A-61-1208.
No. 16, JP-A-61-115912, JP-A-61-115916, JP-A-62-252406, JP-A-62-252407, JP-A-61-271308, It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in Japanese Patent Laid-Open No. 61-272216.

In the above cyclic olefin random copolymer [B], the repeating unit derived from ethylene accounts for 40 to 98 mol%, preferably 50 to 90 mol%.
And the repeating unit derived from the cyclic olefin is 2 to 50 mol%, preferably 5 to 40 mol%.
The repeating unit derived from ethylene and the repeating unit derived from the cyclic olefin are randomly and substantially linearly arranged. The ethylene composition and the cyclic olefin composition were measured by ¹³ C-NMR. The fact that the cyclic olefin-based random copolymer [B] is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

The intrinsic viscosity [η] of such a cyclic olefin-based random copolymer [B] measured in decalin at 135 ° C. is 0.05 to 5 dl / g, preferably 0.08 to 8 dl / g.
g, particularly preferably in the range of 0.1 to 7 dl / g.

The softening temperature (TMA) of the cyclic olefin random copolymer [B] measured by a thermal mechanical analyzer is less than 70 ° C., preferably 20 to
It is in the range of 60 ° C, more preferably 30-50 ° C. The glass transition temperature (Tg) of the cyclic olefin random copolymer [B] is usually 30 ° C. or lower, preferably 20 ° C. or lower.
It is desirably in the range of not more than ° C.

The crystallinity of this cyclic olefin-based random copolymer [B] measured by an X-ray diffraction method is as follows:
0 to 10%, preferably 0 to 7%, particularly preferably 0 to
The range is 5%.

Such a cyclic olefin-based random copolymer [B] can be produced by appropriately selecting conditions according to the method described in the above publication. In the thermoplastic resin used in the present invention, the cyclic olefin-based random copolymer [A] and the cyclic olefin-based random copolymer [B] are 100/0 in [A] / [B] (weight ratio).
The compounding ratio is 1 to 100/10, preferably 100/1 to 100/9, particularly preferably 100/2 to 100/8.

In such cyclic olefin random copolymers [A] and [B], the structural unit derived from the cyclic olefin represented by the above formula [I] or [II] has the following formula [III] or It is considered that a repeating unit having the structure represented by [IV] was formed.

[0061]

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(In the formula [III], m, n, q and R ¹ to
R ¹⁸ and R ^a and R ^b are the same as defined in the above formula [I]. )

[0063]

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(In the formula [IV], r, s, t and R ^{1 to} R
¹⁵ is the same as defined in the above formula [II]. In the present invention, in addition to the above-mentioned cyclic olefin random copolymers [A] and [B], a cyclic olefin ring-opening polymer obtained by ring-opening the same or different cyclic olefin monomer, A ring copolymer or a hydrogenated product thereof can also be used. Such a cyclic olefin ring-opening polymer, a ring-opening copolymer and a hydrogenated product thereof will be described with reference to the cyclic olefin represented by the formula [I] as an example. Ring opening (co)
It is believed that they constitute polymers and their hydrogenated products.

[0065]

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Examples of such polymers include ring-opening copolymers of tetracyclododecene with norbornene and derivatives thereof, and hydrogenated products thereof. In the present invention, the ring-opened polymer as described above,
Ring-opening copolymers, hydrogenated products thereof, and cyclic olefin-based random copolymers [A] and [B] (hereinafter, these are collectively referred to as cyclic olefin-based resins) are partially substituted with maleic anhydride or the like. It may be modified with an unsaturated carboxylic acid or the like. Such a modified product can be produced by reacting the cyclic olefin resin as described above with an unsaturated carboxylic acid, an anhydride thereof, or a derivative such as an alkyl ester of an unsaturated carboxylic acid. In addition,
In this case, the content of the structural unit derived from the modifying agent in the modified product of the cyclic olefin-based resin is usually 50 to 10 mol% or less. Such a modified cyclic olefin-based resin can be produced by blending a modifier with a cyclic olefin-based resin and graft-polymerizing the modified olefin-based resin so as to have a desired modification rate, or preparing a modified product having a high modification rate in advance. Then, it can also be produced by mixing this modified product with an unmodified cyclic olefin resin.

In the present invention, the above-mentioned ring-opened polymer, ring-opened copolymer, hydrogenated product thereof, cyclic olefin random copolymer and modified product thereof may be used alone or in combination. Can be.

The thermoplastic resin used in the present invention contains a rubber-like elastic material [C] in addition to the cyclic olefin-based random copolymers [A] and [B]. The glass transition temperature (Tg) of the rubber-like elastic body [C] used in the present invention is usually in the range of -10 to -60C, preferably in the range of -20 to -55C. Further, the intrinsic viscosity [η] of the rubber-like elastic body [C] measured in decalin at 135 ° C. is desirably 0.2 to 10 dl / g, preferably 1 to 5 dl / g. The tensile modulus of the rubber-like elastic material [C] is usually ^{0.1kg / cm 2 ~20000kg / cm 2} , preferably in the range of ^{10kg / cm 2 ~15000kg / cm 2} . Its density is 0.82 to 0.96 g / cm ³ , preferably 0.84 to 0.96 g / cm ³ .
Desirably, it is 0.92 g / cm ³ . Further, the degree of crystallinity of the rubber-like elastic body [C] measured by an X-ray diffraction method is usually 90% or less, preferably 25% or less, and the rubber-like elastic body [C] has a low crystallinity. Preferably, it is crystalline or amorphous.

Specific examples of the rubber-like elastic material [C] used in the present invention include ethylene / α-olefin copolymer rubber and propylene / α-olefin copolymer rubber. The above-mentioned ethylene / α-olefin copolymer rubber and propylene / α-olefin copolymer rubber can be used alone or in combination.

The α-olefin constituting the ethylene / α-olefin copolymer rubber is usually an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1
-Octene, 1-decene and mixtures thereof. Of these, propylene and / or 1-
Butene is preferred.

The α-olefin constituting the propylene / α-olefin copolymer rubber is usually an α-olefin having 4 to 20 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl -1-pentene, 1-octene, 1
-Decene and mixtures thereof.
Of these, 1-butene is particularly preferred.

The α-olefin copolymer used in the present invention is prepared from an α-olefin such as a component unit derived from a diene compound within a range that does not impair the properties of the α-olefin copolymer. A component unit other than the derived component unit may be included.

For example, the component units that can be contained in the α-olefin copolymer used in the present invention include 1,4-hexadiene, 1,6-octadiene, and 2-methyl-
Linear non-conjugated dienes such as 1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, Cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; 2,3- Component units derived from diene compounds such as diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene can be mentioned. The content of such a diene component is usually 10 mol% or less, preferably 5 mol% or less.
Mol% or less.

In the ethylene / α-olefin copolymer used in the present invention, the molar ratio of ethylene to α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but is generally 1%. / 99-99 / 1,
Preferably it is 50/50 to 95/5. The above molar ratio is α-
When the olefin is propylene, 50/50 to 90 /
It is preferably 10. When the α-olefin is an α-olefin having 4 or more carbon atoms, the ratio is preferably 80/20 to 95/5.

The propylene / α- used in the present invention
In the olefin copolymer, the molar ratio of propylene to α-olefin (propylene / α-olefin) is
Although it depends on the type of α-olefin, generally 50/5
It is preferably from 0 to 95/5. The above molar ratio is preferably 50/50 to 90/10 when the α-olefin is 1-butene, and is 80/20 to 95/95 when the α-olefin has 5 or more carbon atoms. It is preferably 5.

In the present invention, among the above α-olefin copolymers, an ethylene / propylene random copolymer or an ethylene / α-olefin having an ethylene content of 35 to 50 mol% and a crystallinity of 10% or less is used. It is particularly preferred to use a random copolymer.

Further, as the rubber-like elastic material [C] used in the present invention, a graft-modified α-olefin copolymer obtained by graft-modifying the above-mentioned α-olefin copolymer with an unsaturated carboxylic acid or a derivative thereof is used. Can also be used. A graft-modified α-olefin copolymer is preferred because it is excellent in improving mechanical properties such as impact strength.

As the graft monomer used for producing the above graft-modified α-olefin copolymer, it is preferable to use an unsaturated carboxylic acid or a derivative thereof. Examples of such unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,
Examples thereof include isocrotonic acid and nadic acid ^TM (endosis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid). Further, examples of the derivative of the unsaturated carboxylic acid include unsaturated carboxylic anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides and ester compounds of unsaturated carboxylic acids. . Specific examples of such derivatives include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

These graft monomers can be used alone or in combination. Among the above graft monomers, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferable.

The graft-modified α-olefin copolymer used in the present invention is obtained, for example, by modifying the above-mentioned graft monomer and α-olefin copolymer by various conventionally known methods. Can be manufactured. For example, there is a method in which the α-olefin copolymer is melted and a graft monomer is added for graft polymerization, or a method in which the α-olefin copolymer is dissolved in a solvent and the graft monomer is added for graft copolymerization. Further, as a method for producing a graft-modified α-olefin copolymer,
A method in which an unmodified α-olefin copolymer is modified by blending a graft monomer so as to have a desired graft modification rate, a graft-modified α-olefin copolymer having a high graft modification rate is prepared in advance, and the high modification rate Is diluted with an unmodified α-olefin copolymer to produce a graft-modified α-olefin copolymer having a desired modification ratio. In the present invention, a graft-modified olefin copolymer produced by any method can be used. Then, the graft-modified α-olefin copolymer used in the present invention is a copolymer having a modification ratio in the range of usually 0.01 to 5% by weight, preferably 0.1 to 4% by weight.

For such a reaction, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The usage ratio of the radical initiator is usually in the range of 0.001 to 5 parts by weight based on 100 parts by weight of the unmodified α-olefin elastic copolymer.

As radical initiators, organic peroxides and organic peresters are preferably used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert- Butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-
3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5- Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, t
ert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate,
Mention may be made of tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate. Further, in the present invention, an azo compound may be used as a radical initiator, and specific examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate.

Of these, benzoyl peroxide, dicumyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (t
ert-butylperoxy) hexyne-3,2,5-dimethyl-2,5
-Di (tert-butylperoxy) hexane, 1,4-bis (te
Dialkyl peroxides such as (rt-butylperoxyisopropyl) benzene are preferably used.

The graft-modified α-olefin copolymer used in the present invention is usually used alone or in combination with the above-mentioned graft-modified ethylene / α-olefin copolymer and graft-modified propylene / α-olefin copolymer. The above graft-modified elastic copolymer contains another polymer or another copolymer or another graft copolymer within a range that does not impair the properties of the graft-modified α-olefin elastic copolymer. Is also good.

In the present invention, examples of such another polymer or copolymer include an aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof. Specifically, such an aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof includes styrene / butadiene copolymer rubber, styrene / butadiene / styrene copolymer rubber, and styrene / isoprene block copolymer. Polymer rubber, styrene / isoprene / styrene block copolymer rubber, hydrogenated styrene / butadiene / styrene block copolymer rubber and hydrogenated styrene /
Examples include isoprene / styrene block copolymer rubber.

In the present invention, the rubber-like elastic material [C] as described above is added in an amount of 0.1 to 100 parts by weight of the total weight of the cyclic olefin-based random copolymers [A] and [B].
It is used in an amount of from 01 to 100 parts by weight, preferably from 1 to 95 parts by weight. By blending the three components [A], [B], and [C] at such a ratio, a resin excellent in impact resistance, long-term stability, and adhesion strength to a lead frame can be obtained.

The thermoplastic resin used in the present invention may have a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, an anti-fogging agent for the purpose of improving impact strength, heat resistance, weather resistance and the like. , A lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, etc., and the mixing ratio is an appropriate amount. For example, as a stabilizer blended as an optional component, specifically, tetrakis [methylene-3 (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate]
Methane, β- (3,5-di-t-butyl-4-hydroxyphenyl)
Propionic acid alkyl ester, 2,2'-oxamidobis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)]
Phenolic antioxidants such as propionate, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol Examples thereof include fatty acid esters of polyhydric alcohols such as distearate and pentaerythritol tristearate. These may be used alone or in combination. For example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate may be used. Examples thereof include a combination with glycerin monostearate.

In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol, wherein the fatty acid ester of the polyhydric alcohol is one of alcoholic hydroxyl groups of a trihydric or higher polyhydric alcohol. It is preferable that the polyhydric alcohol fatty acid ester is partly esterified.

Examples of the fatty acid esters of such polyhydric alcohols include glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin dilaurate and the like. Fatty acid esters of pentaerythritol such as fatty acid esters, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate are used.

Such a phenolic antioxidant is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, more preferably 0 to 5 parts by weight, based on 100 parts by weight of the total of [A], [B] and [C]. The polyhydric alcohol fatty acid ester is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the total of [A], [B] and [C].
Used in parts by weight.

In the present invention, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, and the like may be used as long as the object of the present invention is not impaired. Basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, Molybdenum sulfide, boron fiber, silicon carbide fiber,
Fillers such as polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

As the method for producing the thermoplastic resin used in the present invention, known methods can be applied, and the above-mentioned components [A], [B] and [C] and other components to be added as required are extruded, kneaded. Mechanical blending with each other, or each component is a suitable good solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene,
Examples thereof include a method of simultaneously dissolving in a hydrocarbon solvent such as xylene or a method of separately dissolving and then mixing and removing the solvent, and a method of combining these two methods.

Glass fiber reinforced poly-4-methyl-1 used to seal external leads in the electronic component of the present invention
-Pentene composition (hereinafter abbreviated as FR-PMP) is a composition comprising poly-4-methyl-1-pentene and glass fibers.

The poly-4-methyl-1-pentene is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and another α-olefin such as ethylene, propylene, 1-butene, -Hexene, 1-octene, 1-decene, 1-
Copolymers with α-olefins having 2 to 20 carbon atoms, such as tetradecene and 1-octadecene, which are polymers mainly composed of 4-methyl-1-pentene which usually contains 85% by mole or more of 4-methyl-1-pentene , Its melt flow rate (MFR; load:
5 kg, temperature: 260 ° C.) is usually 0.5 to 200 g / 1.
0 minutes, preferably in the range of 10 to 200 g / 10 minutes.

Such poly-4-methyl-1-pentene,
Close contact with semiconductor chips, metal lead frames, leads, etc.
Poly 4-methyl-1-pentene to increase adhesion and adhesion
Part or all of the unsaturated carboxylic acid or its derivative
It may be graft-modified with the body. Unsaturated carboxylic acid
The amount of grafting is usually the total amount of poly 4-methyl-1-pentene.
It is in the range of 0.01 to 10% by weight based on the body. Take
As the unsaturated carboxylic acid or its derivative, acrylic
Acid, maleic acid, fumaric acid, tetrahydrophthalic acid,
Itaconic acid, citraconic acid, crotonic acid, isocrotone
Acid, nadic acid ^TM(Endocis-bicyclo [2,2,1] hep
Unsaturated carboxylic acids such as -5-ene-2,3-dicarboxylic acid)
Acids or derivatives thereof, such as acid halides, amides,
Examples include imides, anhydrides, and esters.
Is maleenyl chloride, maleimide, maleic anhydride,
Citraconic acid, monomethyl maleate, maleic acid
Chill and glycidyl maleate are exemplified. these
Of these, unsaturated dicarboxylic acids or their anhydrides are preferred.
Suitable, especially maleic acid, nadic acid^TMOr these
Acid anhydrides are preferred.

The glass fiber used in the present invention is used as a reinforcing material for a thermoplastic resin and usually has a fiber diameter of 1 to 20 μm.
m, preferably 6 to 12 μm, and a glass fiber having a fiber length of 1 to 10 mm, preferably 3 to 6 mm.

The glass fibers constituting the FR-PMP may not necessarily be subjected to a surface treatment, but using a surface-treated glass fiber further improves the heat distortion temperature and mechanical properties. As surface treated glass fiber,
What has been surface-treated with a silane compound having an amino group is generally used. Examples of the silane-based compound having an amino group include γ-aminopropyltrimethoxysilane and γ-aminopropyl, which are easily reacted with an unsaturated carboxylic acid or an acid anhydride thereof.
Examples include aminopropyltriethoxysilane and N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane.

In the present invention, the above glass fiber is usually used in an amount of 1 to 100 parts by weight of poly-4-methyl-1-pentene.
It is used in an amount of up to 300 parts by weight, preferably 10 to 100 parts by weight. By using glass fiber in the above range, heat resistance to the heat of the soldering iron or the heat transmitted from the external leads when soldering the lead frame connected to the sealed semiconductor chip to other electronic components. The performance is improved.

The glass fiber reinforced poly-4-methyl-1-pentene composition used in the present invention contains a heat stabilizer, a weather stabilizer,
A lubricant, a nucleating agent, a pigment, a dye, a release agent, and the like may be added as long as the object of the present invention is not impaired.

The FR-PMP used in the present invention includes a heat stabilizer, a weather stabilizer, a lubricant, a nucleating agent, a flame retardant, a flame retardant aid, an inorganic filler, a potassium titanate fiber, a release agent, and a carbon fiber. May be added to the extent that the object of the present invention is not impaired.

The MFR of FR-PMP is usually 0.1
２００200 g / 10 min, preferably 1-100 g / 10 min. The light-emitting diode according to the present invention includes, for example, a thermoplastic resin containing a cyclic olefin-based random copolymer as described above in an injection molding die into which a semiconductor chip (such as an LED) mounted on a metal lead frame is inserted. It is manufactured by injection molding and sealing a semiconductor chip.

Examples of the semiconductor chip used in the electronic component of the present invention include a light emitting diode (LED) element and an IC chip. Further, the external lead used in the electronic component of the present invention refers to a single wire or a stranded wire that serves to connect the electronic component to another electronic component, and has a function of electrical connection and mechanical fixing. As an external lead,
Specifically, a copper wire, a steel wire, an aluminum wire, a gold wire, a copper alloy, a Fe-Ni alloy, or the like is used.

[0103]

The light emitting diode according to the present invention is sealed with a thermoplastic resin containing a specific cyclic olefin-based random copolymer and a rubber-like elastic material, so that it has heat resistance, heat cycle characteristics, and near-infrared transmission. It has excellent properties, long-term reliability and adhesion between the sealing resin and the lead frame. Further, the electronic component according to the present invention includes a semiconductor chip sealed with a thermoplastic resin containing a specific cyclic olefin-based random copolymer and a rubber-like elastic material, and glass fiber reinforced poly 4-methyl.
-1-Because it is composed of an external lead sealed with a pentene composition, it has excellent heat resistance, heat cycle characteristics, near-infrared transmittance, long-term reliability, and adhesion between the sealing resin and the lead frame. In particular, heat resistance is almost equal to that of current electronic components using epoxy resin as a sealing resin.

[0104]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0105]

Example 1 Cyclic olefin random copolymer [A]
(Intrinsic viscosity [η] 0.6 dl / g, Tg 122 ° C, MFR
(260 ° C.) 15 g / 10 min and softening temperature TMA138
At ° C., ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3
-Random copolymer with dodecene: ethylene content 66m
ol%) and a cyclic olefin-based random copolymer [B] (intrinsic viscosity [η] 0.47 dl / g, Tg 15 ° C, M
FR (260 ° C.) 35 g / 10 min and softening temperature TMA2
At 8 ° C., ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
Random copolymer with 3-dodecene: ethylene content 7
6 mol%) in a weight ratio of [A] / [B] of 10%.
A cyclic olefin random copolymer [I] and a rubbery elastic body [C] (ethylene / propylene random copolymer: ethylene content: 80 mol%, Tg mixed at a ratio of 0/5)
Is -54 ° C, MFR (230 ° C) is 0.7 g / 10 minutes,
[Η] of 2.2 dl / g) were blended in the ratio shown in Table 1.

These blended pellets were melt-blended at a cylinder temperature of 250 ° C. by a twin-screw extruder (PCM45 manufactured by Ikegai Iron and Steel Co., Ltd.) and pelletized by a pelletizer.

Using the obtained pellet, a light emitting diode chip mounted on a metal lead frame is set in an injection mold, and the light emitting diode chip is sealed with an injection molding machine (model IS-55PEN: Toshiba Corporation). Stopped.

The molding conditions are 300 ° C., injection pressure 5-7 kg.
/ Cm ² G, injection speed 0.5 g / sec, mold temperature 85-9
It was 0 ° C. A metal lead frame with the light emitting diode chips sealed as described above is placed in an injection mold, then the MFR is 26 g / 10 min and the 1-decene content is 3.0% by weight. 100 parts by weight of 4-methyl-1-pentene / 1-decene copolymer and glass fiber (trade name: G
RS-3A, diameter 13 μm: Asahi Fiber Glass Co., Ltd.
30 parts by weight) and a grafted amount of maleic anhydride of 4.0 parts by weight.
% By weight, [η] is 0.95 dl / g, and the melting point is 2
A composition obtained by mixing 5 parts by weight of a modified poly 4-methyl-1-pentene having a crystallinity of 18% at 10 ° C. with a Henschel mixer and melt-kneading with a 40 mmφ extruder (setting 260 ° C.). (MFR: 100 g / 10 min) using an injection molding machine (model M-100, manufactured by Meiki Seisakusho).
External leads were sealed. Injection molding conditions are: resin temperature 29
0 ° C, injection molding pressure 35 kg / cm ² G, injection speed 3 g / sec
The mold temperature was 80 ° C.

The obtained light-emitting diode (I) did not cut the thin gold wire and sufficiently exhibited the operation function of the target device. In addition, evaluation of adhesion, heat resistance, long-term reliability, and the like between the obtained light-emitting diode (I) and the lead frame were performed by the following methods.

[0110]

[Adhesion test] Sealed light emitting diode at -30 ° C, 1
After leaving for 30 minutes each in an environment of 00 ° C. and repeating up to 10 cycles, the resin sealing portion was fixed, and the lead frame was pulled to evaluate the adhesion between the sealing portion and the lead frame.

[0111]

[Evaluation method] Δ: Breakage of lead frame △: Breakage of sealing part ×: Interface peeling between lead frame and sealing part

[0112]

[Heat Resistance Test- (I)] The package was immersed in a solder bath at a solder temperature of 260 ° C. for 10 seconds to a position 2 mm from the base of the main body of the sealed light emitting diode, and after taking out, the appearance was visually evaluated. (Refer to JIS C7021 A-1 standard)

[0113]

[Evaluation method]: No change in appearance of immersed part. Δ: The immersed part slightly melts.

×: The immersed portion is melted, and the lead frame moves or foams.

[0115]

[Heat resistance test- (II)] 0.8m / m for a solder bath (50cm long, 1.2m wide) with a solder temperature of 260 ° C
at a line speed of in, immersed up to the position of 4 mm at the root of the sealed diode mounted on the printed circuit board.
The reliability was evaluated by passing a current of 0 mA.

[0116]

[Evaluation method] 〇: No defective products occurred. Δ: Defective product was found.

[0117]

[Long-term reliability test] Encapsulated light emitting diode at -30
Each was left for 15 minutes in an environment of 100 ° C. and 100 ° C., and was repeated up to 200 cycles. Thereafter, a current having a rated current of 30 mA was passed to evaluate the reliability.

[0118]

[Evaluation method] 〇: No defective products occurred. ×: Defective products occurred.

Table 1 shows the results.

[0120]

Examples 2 to 4 The amount of the component [C] used in Example 1 was changed, and the pellet MF after blending with the components [A] / [B] was melted.
Evaluation was performed in the same manner as in Example 1 except that R was changed.

Table 1 shows the results.

[0122]

Comparative Example 1 4-methyl-1-pentene-1 having an MFR of 100 g / 10 min and a 1-decene content of 3.0% by weight
-The semiconductor chip of the light emitting diode, the gold wire, and the entire external lead were sealed in the injection mold with a decene copolymer. Injection molding conditions are: resin temperature 300 ° C, injection pressure 1
The same injection molding machine as in Example 1 was used. The injection molding machine was 5 kg / cm ² G, the injection speed was 3 g / sec, and the mold temperature was 80 ° C.

The sealed light emitting diode had a good appearance without breaking the gold wire. . Table 1 shows the results.

[0124]

Comparative Example 2 A polycarbonate having an MFR of 35 g / 10 minutes was molded using the same injection molding machine as in Comparative Example 1 at a molding temperature of 310 ° C., an injection pressure of 20 kg / cm ² G, and an injection speed of 3 g / s.
A sealed light emitting diode was obtained under the molding conditions of ec and a mold temperature of 90 ° C.

Table 1 shows the results.

[0126]

Comparative Example 3 4-methyl-1-pentene / 1 having an MFR of 180 g / 10 min and a 1-decene content of 3.0% by weight
The semiconductor chip of the light emitting diode and the gold wire were sealed with a decene copolymer, and then the entire external lead was injection-molded and sealed with a glass fiber reinforced poly-4-methyl-1-pentene composition.

The injection molding conditions were as follows: resin temperature 310 ° C., injection pressure 8 kg / cm ² G, injection speed 1 g / sec, mold temperature 80
C. and the same injection molding machine as in Example 1 was used to obtain a sealed light emitting diode.

Table 1 shows the results.

[0129]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI // (C08L 23/08 23:16) (C08L 45/00 23:16)

Claims (2)

(57) [Claims] 1. A light emitting diode in which a semiconductor chip mounted on a metal lead frame is sealed with a thermoplastic resin, wherein the thermoplastic resin is composed of ethylene and the following formula [I] or [II]. Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a ,
R ^b each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring; And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R
¹⁷ and R ¹⁸ may form an alkylidene group). Embedded image (In the formula [II], r is 0 or an integer of 1 or more, s and t are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon. Group,
An atom or group selected from the group consisting of an aromatic hydrocarbon group and an alkoxy group, wherein R ⁵ (or R ⁶ ) and R 5
⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. A) a copolymer with at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the formula:
Intrinsic viscosity [η] measured in decalin at a temperature of 0.05 to 10 dl
/ g, a cyclic olefin random copolymer [A] having a softening temperature (TMA) of 70 ° C. or higher, ethylene, and an unsaturated monomer represented by the above formula [I] or [II]. A copolymer with at least one type of cyclic olefin selected from the group consisting of: a copolymer having an intrinsic viscosity [η] of 0.05 to 5 dl / g measured in decalin at 135 ° C., and a softening temperature (TMA) ) Is less than 70 ° C. and a cyclic olefin random copolymer [B] with [A] / [B] (weight ratio)
100 / 0.1 to 100/10, and a rubber-like elastic body [C] in total of the above-mentioned [A] component and [B] component.
A light emitting diode comprising a thermoplastic resin containing 0.01 to 100 parts by weight with respect to 100 parts by weight. 2. An electronic component comprising a semiconductor chip sealed with a thermoplastic resin and external leads sealed with a glass fiber reinforced poly-4-methyl-1-pentene composition. An electronic component, comprising: the thermoplastic resin according to claim 1.