JP4206899B2 - Surface mount type LED element - Google Patents

Description

  The present invention relates to a surface mount type LED element.

  A surface-mount type LED element is an LED element that is electrically connected to a printed circuit board to be mounted in a state of being in direct contact with solder or the like, and has a wiring pattern on the surface of a resin base material. The LED chip is mounted on the surface of the formed wiring board.

  As a certain type of surface-mount type LED element, as shown in FIG. 4, one surface of a resin substrate 42 made of a plate-like body called a glass-epoxy resin plate or a bismaleimide-triazine resin plate ( A wiring board in which a wiring pattern 43a is formed on the upper surface in FIG. 4 and a terminal 43c electrically connected to the wiring pattern 43a through a through hole 43b is formed on the other surface (lower surface in FIG. 4). 41, an LED chip 45 mounted on the surface of the wiring board 41 (upper surface in FIG. 4), and a power supply wire 46 made of a metal such as gold or aluminum for supplying power to the LED chip 45. The sealing structure 49 is formed of a transparent sealing material provided so as to cover the LED chip 45 and the power supply wire 46. It is intended but made formed (e.g., see Patent Document 1).

  This surface-mount LED element 40 has a wiring 43 formed on the front surface (upper surface in FIG. 4) of the printed circuit board 51 to be mounted with the terminals 43c provided on the rear surface (lower surface in FIG. 4) of the wiring substrate 41. By directly electrically connecting the pattern 52 to the pattern 52 by soldering or the like, the pattern 52 is mounted on the printed circuit board 51 without the need for inserting a lead wire.

  However, in the surface mount type LED element having such a configuration, since the resin base material constituting the wiring board is translucent or opaque, the light emitted from the LED chip in the direction toward the wiring board is resin-based. There is a problem in that a high luminous flux utilization factor cannot be obtained because it enters into the material and is absorbed and is not emitted outward as radiated light of the surface-mounted LED element.

JP 2003-258310 A

  This invention is made | formed based on the above situations, Comprising: The objective is to provide the surface mount type LED element from which a high luminous flux utilization factor is obtained.

In the surface mount type LED element of the present invention, a sealing structure is formed by sealing an LED chip mounted on the surface of a wiring board including a resin base material with a sealing material made of a transparent resin. A surface-mount type LED element,
The resin base material constituting the wiring board, and the sealing material for sealing the LED chip are made of a transparent heat-resistant resin,
The transparent heat-resistant resin comprises a cyclic olefin polymer having a structural unit represented by the following general formula (1) .

[Wherein, A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a halogenated hydrocarbon group, or hydrolysis. Or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _p —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ are each independently carbon atoms having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an axetanyl group, and p is an integer of 0 to 5. ]

In the surface-mount LED element of the present invention, the cyclic olefin polymer has a structure in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1). Including units,
The hydrolyzable silyl group is preferably a group represented by the following general formula (2).

[Wherein Y is an alkoxy group having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 2 to 20 carbon atoms bonded to each other to form a 5- to 7-membered ring, R ⁴ represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ]

  In such a surface-mount type LED element, the cyclic olefin polymer has a content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2), the cyclic olefin polymer. It is preferable that it is 0.2-30 mol% with respect to all the structural units to comprise.

In the surface mount type LED element of the present invention, a sealing structure is formed by sealing an LED chip mounted on the surface of a wiring board including a resin base material with a sealing material made of a transparent resin. A surface-mount type LED element,
The resin base material constituting the wiring board, and the sealing material for sealing the LED chip are made of a transparent heat-resistant resin,
The transparent heat-resistant resin is characterized by comprising the crosslinked product of the cyclic olefin polymer having a structural unit represented by the following general formula (1).

[Wherein, A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a halogenated hydrocarbon group, or hydrolysis. Or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _p —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ are each independently carbon atoms having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an axetanyl group, and p is an integer of 0 to 5. ]

In the surface-mount LED element of the present invention, the cyclic olefin polymer has a structure in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1). Including units,
The hydrolyzable silyl group is preferably a group represented by the following general formula (2).

[Wherein Y is an alkoxy diol having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 2 to 20 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ]

  In such a surface-mount type LED element, the cyclic olefin polymer has a content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2), the cyclic olefin polymer. It is preferable that it is 0.2-30 mol% with respect to all the structural units to comprise.

  In the surface-mounted LED element of the present invention, it is preferable that a reflective film is provided on the back surface of the wiring board.

  According to the surface mount type LED element of the present invention, since the resin base material constituting the wiring board is made of a transparent heat-resistant resin and has transparency, it radiates in the direction from the LED chip toward the wiring board. Since the emitted light passes through the resin base material without being absorbed by the resin base material and is emitted outward as the radiation light of the surface-mount LED element, the light emitted from the LED chip is effectively used. Thereby, a high luminous flux utilization factor can be obtained.

Further, in the surface mount LED element of the present invention, when the resin base material constituting the wiring board is made of a specific cyclic olefin polymer or a specific cross-linked body, the resin base material Has excellent properties derived from these resin materials (for example, transparency, heat resistance, chemical resistance, electrical properties, etc.), so that a high luminous flux utilization factor can be obtained and excellent optical properties can be obtained. , Dimensional stability, and stability over time of light emission performance can be obtained.
Furthermore, in the case where the transparent sealing material constituting the resin base material and the sealing structure is made of a specific cyclic olefin polymer or a specific cross-linked body, the surface mount LED element, Even better optical properties, dimensional stability, and stability over time of light emission performance can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
The surface-mounted LED element of the present invention (hereinafter also referred to as “specific surface-mounted LED element”) is an LED chip mounted on the surface of a wiring board provided with a resin base material. It has a structure in which a sealing structure is formed by sealing with a stopper, and it is electrically connected to a printed circuit board to be mounted in a state of being in direct contact with a method such as soldering. LED element.

FIG. 1 is an explanatory cross-sectional view showing an example of the configuration of the surface-mounted LED element of the present invention.
In this surface-mounted LED element 10, a wiring pattern 13a is formed on one surface (upper surface in FIG. 1) made of a transparent heat-resistant resin having excellent transparency and heat resistance, and the other surface (lower surface in FIG. 1). ), A wiring board 11 on which a terminal 13c electrically connected to the wiring pattern 13a via a through hole 13b is formed, and an LED mounted on the surface (upper surface in FIG. 1) of the wiring board 11 Transparency provided with a chip 15 and a power supply wire 16 made of metal such as gold or aluminum for supplying power to the LED chip 15 so as to cover the LED chip 15 and the power supply wire 16. A sealing structure is formed by a case-like sealing structure 19 made of a sealing material having the following (hereinafter also referred to as “transparent sealing material”). That.
Here, the wiring substrate 11 having a configuration in which the wiring pattern 13a is formed on the resin base material 12 undergoes a process of laminating a resin base material sheet and a wiring material sheet laminated by, for example, roll-to-roll. Can also be formed.

  The surface-mount LED element 10 has a terminal 13c provided on the back surface (the lower surface in FIG. 1) of the wiring board 11 by a wiring pattern formed on the surface of the printed circuit board to be mounted and a technique such as soldering. By directly electrically connecting, it is mounted on the printed circuit board without the need for inserting lead wires or the like (see FIG. 4).

  As the resin base material 12 constituting the wiring substrate 11, a plate-like body and a sheet-like body made of a transparent heat-resistant resin are used.

  As the transparent sealing material constituting the sealing structure 19, a material made of a transparent epoxy resin, a transparent heat resistant resin, or the like is preferably used.

  As the transparent heat-resistant resin used as the resin material of the resin base material 12 and the transparent sealing material (hereinafter also referred to as “specific member”) constituting the specific surface-mounted LED element 10, the general formula (1 ) Or a specific cyclic olefin polymer having a structural unit (hereinafter also referred to as “specific structural unit”) represented by What consists of the crosslinked body (henceforth "specific crosslinked body") of an olefin polymer is preferable.

The specific cyclic olefin polymer has at least one specific structural unit.
The specific cyclic olefin-based polymer preferably has a portion in which at least two or more specific structural units having the same configuration are continuously arranged.

In general formula (1) representing a specific structural unit, A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or cycloalkyl. Group, a halogenated hydrocarbon group, a hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X (hereinafter also referred to as “specific polar group”).
Here, in — (CH ₂ ) _P —X representing the specific polar group, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents the number of carbon atoms. It represents a substituent containing 1 to 10 hydrocarbon groups, halogenated hydrocarbon groups, or oxetanyl groups, and p is an integer of 0 to 5.

A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group, or an arylene group. Further, A ¹ and A ² or A ¹ and A ⁴ may be bonded to each other to form a group derived from an acid anhydride, lactone or imide.
m is 0 or 1.

When the specific cyclic olefin polymer has two or more specific structural units, all the specific monomers constituting the specific cyclic olefin polymer have the same configuration. However, by using a plurality of types of monomers, A ¹ , A ² , A ³ , A ⁴ and m in each specific structural unit may be partially or entirely different. Good.

The specific cyclic olefin-based polymer preferably contains a specific structural unit in which at least one of A ¹ , A ² , A ³ and A ^{4 in} the general formula (1) is a hydrolyzable silyl group.
The specific cyclic olefin polymer has a specific structural unit containing a hydrolyzable silyl group, so that the solubility in hydrocarbon solvents such as toluene and cyclohexane is increased. Preparation of a polymer solution containing the specific cyclic olefin polymer to be used (hereinafter also referred to as “olefin polymer solution”) becomes easy.

The hydrolyzable silyl group is preferably a group represented by the general formula (2) (hereinafter also referred to as “specific hydrolyzable silyl group”).
In the general formula (2), Y is an alkoxy group having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or a fat having 2 to 20 carbon atoms bonded to each other to form a 5- to 7-membered ring. R ⁴ represents a group derived from an aromatic diol, an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
r is an integer of 0 to 5, and s is an integer of 1 to 3.

In the specific cyclic olefin polymer, the content ratio of the specific structural unit containing the specific hydrolyzable silyl group (hereinafter also referred to as “specific silyl group-containing structural unit”) is determined by the specific cyclic olefin polymer. It is preferable that it is 0.2-30 mol% with respect to all the structural units which comprise this, Especially preferably, it is 0.5-20 mol%.
When the content ratio of the specific silyl group-containing structural unit is less than 0.2 mol%, the solubility of the specific cyclic olefin polymer in the organic solvent is lowered, and the specific member is removed by a technique using an olefin polymer solution. There is a possibility that it may be difficult to form, the solvent resistance, chemical resistance and mechanical strength of the specific member to be obtained will be reduced, and further, the other specific member constituting the specific mounting type LED element of the specific member Adhesion may be reduced.
On the other hand, when the content ratio of the specific silyl group-containing structural unit exceeds 30 mol%, the water absorption of the specific member obtained may increase.

  The specific structural unit constituting the specific cyclic olefin polymer is formed by a monomer represented by the following general formula (3) (hereinafter also referred to as “specific monomer”).

[Wherein A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group, or a halogenated hydrocarbon. Group and a hydrolyzable silyl group or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group, an alkenylene group or an arylene group, and A ¹ and A ² are integrated to form an alkylidene group. Furthermore, A ¹ and A ² or A ¹ and A ⁴ may be bonded to each other to form a group derived from an acid anhydride, lactone or imide. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an oxetanyl group, and p is an integer of 0 to 5. ]

As a specific example of such a specific monomer,
Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-propylbicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
5-decylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-ethyl-bicyclo [2.2.1] hept-2-ene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-chlorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,6-dimethylbicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5-cyclohexylbicyclo [2.2.1] hept-2-ene,
5-cyclooctylbicyclo [2.2.1] hept-2-ene,
5-indanylbicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,

Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
3-methyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
4-methyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene,
Tricyclo [8.2.1.0 ^2,9 ] tridec-11-ene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
Tricyclo [6.2.1.0 ^2,7 ] undeca-3,9-diene,
Tricyclo [8.2.1.0 ^2,9 ] trideca-5,11-diene,

5-trimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-triethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldiethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldichlorosilylbicyclo [2.2.1] hept-2-ene,
5-dimethylmethoxysilylbicyclo [2.2.1] hept-2-ene,
5-dimethylethoxysilylbicyclo [2.2.1] hept-2-ene,
5-dimethylchlorosilylbicyclo [2.2.1] hept-2-ene,
4-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
4-methyldimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
4-triethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
5- [1′-methyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1′-ethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 3′-dimethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 3 ′, 4′-trimethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 3 ′, 3 ′, 4 ′, 4′-pentamethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
5- [1′-ethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 3′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] methylbicyclo [2.2.1] hept-2-ene,
5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] ethylbicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
5- [3′-methyl-2 ′, 4′-dioxa-3′-silaspiro [5.5] undecyl] bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-3′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 7′-dioxa-1′-silacycloheptyl] bicyclo [2.2.1] hept-2-ene,
4- [1′-Methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
4- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,

Methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Ethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Methyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Ethyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Trifluoromethyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Trifluoroethyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Dimethyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate,
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate,
2-methylbicyclo [2.2.1] hept-5-en-2-ethyl acetate,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

Bicyclo [2.2.1] hept-5-en-2-yl acrylate,
Bicyclo methacrylate [2.2.1] hept-5-en-2-yl,
Bicyclo [2.2.1] hept-5-en-2-ylmethyl acrylate,
Bicyclo methacrylate [2.2.1] hept-5-en-2-ylmethyl,

2-[(3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene,
2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene,
2-[(3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-5-ene,
2-[(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-5-ene,
4-[(3-Ethyl-3-oxetanyl) methoxymethyl] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl,
And cyclic olefins such as 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl.
These can be used alone or in combination of two or more.

Specific monomers for forming a specific structural unit include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and tricyclo [5. 2.1.0 ^2,6 ] dec-8-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . It is preferable to use one or more cyclic olefins selected from 1 ^7,10 ] dodec-3-ene.
By using such a cyclic olefin as the specific monomer, a cyclic olefin polymer having a sufficiently high glass transition temperature and a low linear expansion coefficient can be obtained.

Specific monomers for forming the specific silyl group-containing structural unit include 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene and 5-triethoxysilylbicyclo [2.2. 1] Hept-2-ene, 5-methyldimethoxysilylbicyclo [2.2.1] hept-2-ene, 5-methyldiethoxysilylbicyclo [2.2.1] hept-2-ene, 4-tri Methoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 5- [1′-methyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene, 5- [ 1′-methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene, 5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6'-dioxa-1'-silacyclohexyl] bicyclo [2.2.1] hept-2-ene is preferably used, and in particular, 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene. 5-triethoxysilylbicyclo [2.2.1] hept-2-ene, 5-methyldimethoxysilylbicyclo [2.2.1] hept-2-ene, 4-trimethoxysilyltetracyclo [6.2 1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hepta-2 It is preferable to use one or more cyclic olefins selected from -enes.

  In the specific cyclic olefin polymer, the glass transition temperature is appropriately selected by appropriately selecting the type of the specific structural unit constituting the specific cyclic olefin polymer and the content ratio of the specific structural unit in all the structural units. In addition, physical properties such as linear expansion coefficient, solubility in organic solvents, and the like can be controlled.

  Specifically, for example, a specific cyclic olefin polymer having a specific structural unit derived from a cyclic olefin having a chain alkyl group such as 5-hexylbicyclo [2.2.1] hept-2-ene, While the solubility with respect to an organic solvent becomes high, the specific member obtained has a softness | flexibility, and also control of the glass transition temperature becomes easy.

In addition, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tricyclo [6.2.1.0 ^2,7 ] undec-9-ene, tricyclo [5.2.1.0 ^{2 , 6} ] The specific cyclic olefin polymer having a plurality of types of specific structural units derived from cyclic olefins such as deca-3,8-diene, the specific member obtained has excellent toughness and flexibility. Become.
Furthermore, the specific cyclic olefin polymer having a specific structural unit containing a specific polar group has excellent adhesion to other members in which the obtained specific member constitutes a specific mounted LED element.

The specific cyclic olefin polymer may contain a structural unit other than the specific structural unit (hereinafter also referred to as “other structural unit”).
Specific examples of other structural units include structural units derived from α-olefins such as ethylene, structural units derived from monocyclic olefins such as cyclohexene, and structural units derived from (meth) acrylic acid esters. .
The content ratio of such other structural units is preferably 20 mol% or less in all the structural units.

The specific cyclic olefin-based polymer has a glass transition temperature in the range of usually 150 to 450 ° C, preferably 300 to 400 ° C.
When the glass transition temperature is lower than 150 ° C., there is a possibility that problems such as thermal deformation of the obtained specific member may occur.
On the other hand, when the glass transition temperature exceeds 450 ° C., the specific cyclic olefin-based polymer becomes rigid, so that the specific member to be obtained is easily cracked and has low toughness.
Here, the glass transition temperature of a specific cyclic olefin polymer is the temperature distribution of Tan δ (ratio E ″ / E ′ of storage elastic modulus E ′ and loss elastic modulus E ″) obtained by dynamic viscoelasticity measurement. It is determined as the peak temperature value.

The specific cyclic olefin polymer has a polystyrene-reduced number average molecular weight (Mn) of 30,000 to 500, as measured by gel permeation chromatography (GPC) at a temperature of 120 ° C. using o-dichlorobenzene as a solvent. The weight average molecular weight (Mw) in terms of polystyrene is preferably 50,000 to 1,000,000, and more preferably the number average molecular weight (Mn) is 50,000 to 200,000 and the weight. The average molecular weight (Mw) is preferably 100,000 to 500,000.
When the number average molecular weight is less than 30,000 and the weight average molecular weight is less than 50,000, the specific cyclic olefin-based polymer is obtained due to its low breaking strength and breaking elongation. There is a possibility that the specific member is easily cracked. On the other hand, when the number average molecular weight exceeds 500,000 and the weight average molecular weight exceeds 1,000,000, it may be difficult to form the specific member by a technique using an olefin polymer solution.

The specific cyclic olefin-based polymer has a linear expansion coefficient in the range of 70 ppm / ° C. or less, and preferably 60 ppm / ° C. or less.
When the linear expansion coefficient exceeds 70 ppm / ° C., there is a possibility that the resulting specific member may be deformed due to a dimensional change in a use environment having a large temperature change.

A known antioxidant can be added to the specific cyclic olefin polymer, whereby the oxidation stability of the specific cyclic olefin polymer can also be improved.
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis- (6-t-butyl-3-methylphenol), 1,1′-bis (4 -Hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, pentaerythrityltetrakis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like phenol compounds or hydroquinone compounds, tris (4-methoxy-3, 5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite Phosphorus compounds such as bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite are used. Of these, compounds having a decomposition temperature (5% weight loss) of 250 ° C. or higher can be preferably used. Such an antioxidant is preferably added at a ratio of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the specific cyclic olefin polymer.

  The specific cyclic olefin polymer as described above can be produced by addition polymerization of a monomer and hydrogenation as necessary.

In the addition polymerization treatment, a monomer, a solvent having a mass ratio of 1 to 20 with respect to the monomer, and a molecular weight regulator as necessary are charged in a reaction vessel in a nitrogen or argon atmosphere. After the system is set to a temperature range of -20 to 100 ° C, a polymerization catalyst is further added to carry out the polymerization reaction of the monomer at a polymerization temperature of -20 to 100 ° C.
The molecular weight of the specific cyclic olefin polymer to be obtained can be adjusted by controlling the amount of polymerization catalyst and molecular weight regulator used for the polymerization reaction, the conversion rate of the monomer to the polymer and the polymerization temperature. it can.

Solvents include cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane and octane, aromatic hydrocarbon solvents such as toluene, benzene, xylene and mesitylene, chloro Halogenated hydrocarbon solvents such as methane, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chloroform, carbon tetrachloride, chlorocyclopentane, chlorocyclohexane, chlorobenzene, dichlorobenzene, ethyl acetate, nitromethane, N -Polar solvents such as methylpyrrolidone, pyridine, dimethylformamide, and acetamide can be used.
These can be used alone or in combination of two or more.

  Examples of molecular weight regulators include α-olefins such as ethylene, 1-hexene and 1-octene, styrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 3,5-dimethylstyrene, 1-vinylnaphthalene, Aromatic vinyl compounds such as divinylbenzene, cyclic non-conjugated polyenes such as cyclooctadiene and cyclododecatriene, diphenyldihydrosilane, hydrogen and the like can be mentioned, and α-olefins or aromatic vinyl compounds are preferably used.

  As the polymerization catalyst, for example, the following catalysts (1) to (3) can be used.

(1) A nickel-based multicomponent catalyst comprising a nickel compound, a compound selected from super strong acids, Lewis acids and ionic boron compounds, and an organoaluminum compound. (2) Sigma bond connecting at least one nickel-carbon. A nickel-based single-component catalyst comprising a nickel complex having a super strong acid anion as a counter anion (3) a palladium compound, a phosphine compound and / or a phosphonium compound, an ionic boron compound, and, if necessary, an organoaluminum compound Alternatively, a palladium-based multicomponent catalyst containing an organolithium compound

  As a polymerization terminator for the polymerization reaction, water, alcohol, organic acid, carbon dioxide gas or the like can be used.

  The polymer contained in the reaction solution obtained by the above addition polymerization treatment is poured into a poor solvent such as methanol, ethanol, isopropanol, acetone after removing the catalyst residue by a known method. As a result, unreacted monomers remaining in the solution can be removed, the polymer can be solidified, and the obtained solidified product can be recovered by drying under reduced pressure. If the reaction solution obtained by the addition polymerization treatment does not impair the performance of the finally obtained specific surface mount LED element, the specific member can be used without removing the catalyst residue or performing the solidification operation. It can be used for the process for forming.

  As a method for removing the catalyst residue, for example, a water / alcohol mixture of an organic acid such as maleic acid, fumaric acid, oxalic acid, malic acid or the like is added to the reaction solution, and this mixed solution is added to the polymer solution phase and the catalyst residue. For example, a method of removing the aqueous phase by separating it into an aqueous phase containing, an adsorption removal method using an adsorbent such as diatomaceous earth, alumina, silica, or a filtration separation method using a filter can be used.

As a specific monomer for obtaining a specific cyclic olefin-based polymer, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene or 5-ethylidenebicyclo [2.2.1] hepta When a specific monomer having an unsaturated bond that does not participate in polymerization, such as 2-ene (hereinafter also referred to as “specific unsaturated bond-containing monomer”), is used. The polymer obtained by subjecting the monomer to an addition polymerization treatment needs to be further subjected to a hydrogenation treatment, whereby a specific structural unit derived from a specific unsaturated bond-containing monomer is formed. .
In addition, when the polymer obtained by the addition polymerization treatment contains an unsaturated bond, the polymer is likely to be oxidized under high temperature conditions and easily deteriorated by heat. It is preferable to perform a hydrogenation treatment so as to hydrogenate 90 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more of the unsaturated bonds in the polymer.

  In particular, when a specific olefin polymer having a specific structural unit having an acryloyl group or a methacryloyl group is to be obtained, a monomer containing a specific unsaturated bond is provided for the addition polymerization treatment. Preferably not.

  As the hydrogenation catalyst, a compound such as nickel, rhodium, palladium, platinum, etc., a heterogeneous catalyst supported on a solid such as silica, diatomaceous earth, alumina, activated carbon, etc., a compound such as titanium, nickel, palladium, cobalt, etc. A homogeneous catalyst obtained by combining an organometallic compound, a catalyst comprising a complex of ruthenium, osmium, rhodium, iridium, or the like can be suitably used.

  As the solvent, aromatic hydrocarbons such as toluene, xylene, ethylbenzene and tetralin, alicyclic hydrocarbons such as cyclohexane, methylpentane, methylcyclohexane and decalin can be used, and if necessary, hexane, Aliphatic hydrocarbons such as heptane, ethers such as tetrahydrofuran, dimethoxyethane, and butyl ether can also be used.

  The hydrogenation treatment is preferably performed at a hydrogen pressure of 0.5 to 15 MPa and a temperature of 20 to 200 ° C.

  The hydrogenated polymer in the state of being contained in the reaction solution obtained by the hydrogenation treatment as described above is a catalyst residue obtained by a known method in the same manner as the polymer obtained directly by the addition polymerization treatment. After removing the catalyst, the hydrogenated polymer is coagulated by pouring the solution from which the catalyst residue is removed into a poor solvent, and the resulting coagulated product is recovered by drying under reduced pressure.

  In addition to the specific cyclic olefin polymer, the transparent heat-resistant resin comprising the specific cyclic olefin polymer includes, for example, a hydrogenated product of a known cyclic olefin ring-opening (co) polymer, a cyclic olefin and ethylene. A polymer or the like may be contained, thereby adjusting the glass transition temperature of the specific cyclic olefin polymer without impairing the toughness derived from the specific cyclic olefin polymer in the specific member to be obtained. be able to.

  As a method for obtaining the resin base material 12 constituting the wiring board 11 with the transparent heat-resistant resin made of the specific cyclic olefin polymer as described above, a specific cyclic olefin polymer is used, for example, a hydrocarbon solvent, a halogen An olefin polymer solution dissolved in a solvent selected from a hydrocarbon solvent or a mixed solvent comprising these is prepared, and the olefin polymer solution is applied to, for example, a glass substrate, such as a spin coater. It can be obtained by applying a method using a coating apparatus or a method applying a printing method such as screen printing and drying the obtained coating film, or by a method such as a solution casting method or a melt extrusion method. Moreover, the transparent sealing material which comprises the sealing structure 19 apply | coats or casts the olefin polymer solution on the LED chip 15 and the electric power supply wire 16 which are sealing objects, and dries the obtained film | membrane. By forming a sealing structure for sealing the object to be sealed, or obtaining a blended composition blended with a specific cyclic olefin polymer and a thermoplastic resin other than the specific olefin polymer, this It can be obtained by forming a sealing structure that seals the object to be sealed by a molded body molded by a melt extrusion method using a melt extruder or the like using the blended composition as a molding material.

The specific cross-linked body is formed by obtaining a cross-linkable composition containing a specific cyclic olefin polymer and cross-linking the cross-linkable composition.
This specific cross-linked product has excellent characteristics of the specific cyclic olefin polymer constituting the cross-linkable composition for forming the specific cross-linked product, and has a cross-linked structure formed. Therefore, the coefficient of linear expansion is further reduced, and the breaking strength and breaking elongation are increased. Therefore, the obtained specific member has more excellent heat resistance, mechanical strength, solvent resistance, Chemical properties will be obtained.

  As a crosslinkable composition for obtaining a cross-linked product, a specific cross-linked product can be obtained in a short time under a relatively mild temperature condition in the range of 10 to 280 ° C. Therefore, radical reaction, hydrolysis / condensation reaction Or the composition which can form a crosslinked body by a cation reaction is used suitably.

  Examples of the crosslinkable composition for obtaining a crosslinked product by radical reaction (hereinafter also referred to as “radical crosslinkable composition”) include the following compositions (1) to (2).

(1) A composition obtained by blending a specific cyclic olefin polymer with a peroxide or an azo compound.
Such a composition is crosslinked by radicals generated by the action of heat, actinic rays, and the like.

(2) A composition obtained by blending a specific cyclic olefin polymer with a peroxide and a reducing metal compound.
Such a composition is crosslinked by radicals generated by a redox reaction.

  The radical crosslinkable composition as described above is used when a cyclic olefin polymer having a specific structural unit having a methacryloyl group or an acryloyl group as a side chain substituent is used as the specific cyclic olefin polymer. Can obtain a crosslinked body more easily.

  A crosslinkable composition for obtaining a crosslinked product by hydrolysis / condensation reaction (hereinafter also referred to as “hydrolyzable crosslinkable composition”), and a crosslinkable composition for obtaining a crosslinked product by cationic reaction (hereinafter, “ As the specific cyclic olefin polymer, the cyclic olefin polymer having a specific silyl group-containing structural unit or the cyclic olefin having a specific unit structure having an oxetanyl group. Examples thereof include the following compositions (1) to (4) using a polymer (hereinafter also referred to as “specific group-containing cyclic olefin polymer”).

(1) Specific group-containing cyclic olefin-based polymer, metal oxide such as tin, aluminum, zinc, titanium, antimony, alkoxide of the metal, phenoxide of the metal, β-diketonate of the metal, alkyl of the metal A composition comprising a metal compound such as a halide, a halide of the metal, or an organic acid salt of the metal.
(2) An aromatic sulfonium salt having a counter anion selected from BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , B (C ₆ F ₅ ) _4, etc., in the specific group-containing cyclic olefin polymer, the counter anion Having an aromatic ammonium salt having the counter anion, an aromatic phosphonium salt having the counter anion, an aromatic iodonium salt having the counter anion, a hydradium salt having the counter anion, and the counter anion A composition comprising a compound that acts as an acid when heated, such as a ferrocenium salt.
(3) To a specific group-containing cyclic olefin polymer, trialkyl phosphite ester, triaryl phosphite ester, dialkyl phosphite ester, monoalkyl phosphite ester, hypophosphite ester, organic carboxylic acid and Esters with secondary or tertiary alcohols, hemiacetal esters of organic carboxylic acids, trialkylsilyl esters of organic carboxylic acids, monocyclic or polycyclic cycloalkyl esters of alkylsulfonic acids, monocyclic or alkylarylsulfonic acids A composition comprising an ester compound that acts as an acid when heated in the presence of water or water vapor, such as a polycyclic cycloalkyl ester.
(4) Bronsted by irradiating a specific group-containing cyclic olefin polymer with light rays such as g- and h-rays in the visible region, i-rays in the ultraviolet region, ultraviolet rays, far ultraviolet rays, X-rays and electron beams. Diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, arsenium salts, oxonium salts and other onium salts that generate acids or Lewis acids, halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogens Halogen-containing organic compounds such as benzophenone compounds, quinonediazide compounds, α, α-bis (sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfonyl compounds, organic acid ester compounds, organic acid amide compounds, organic acids Imide compound Composition obtained by blending a photoacid generator such as.

  Among these hydrolyzable crosslinkable compositions or cationic crosslinkable compositions, the composition (3), specifically, a composition in which an ester compound is blended with a specific cyclic olefin polymer is used as a pot life. Is long and has excellent storage stability, and the specific member made of the crosslinked product is preferably used because it has excellent characteristics such as dimensional stability, solvent resistance and chemical resistance. In addition, the composition (4), specifically a composition containing a photoacid generator, can be crosslinked under relatively mild conditions, and is excellent in the productivity of a crosslinked product. Therefore, it is preferably used.

In the hydrolyzable crosslinkable composition of the above (1) to (4), the content ratio of the specific silyl group-containing structural unit in the specific cyclic olefin-based polymer having the specific silyl group-containing structural unit is the specific cyclic The content is preferably 0.2 to 30 mol%, particularly preferably 0.5 to 20 mol%, based on all structural units constituting the olefin polymer.
When the content ratio of the specific silyl group-containing structural unit is less than 0.2 mol%, the hydrolyzable crosslinkable composition is not sufficiently crosslinked, and the formed crosslinked product has a large linear expansion coefficient. There is a possibility that the water absorption of the specific member to be obtained may increase, the solvent resistance, chemical resistance and mechanical strength of the specific member to be obtained may be reduced, and the specific member may constitute a specific surface-mount LED element. There is a possibility that the adhesion to other members is small. In addition, it may be difficult to form the specific member by a method using a mixed olefin polymer solution described later.
On the other hand, when the content ratio of the specific silyl group-containing structural unit exceeds 30 mol%, the formed crosslinked product has a large linear expansion coefficient, and there is a possibility that the water absorption of the specific member to be obtained increases.

Moreover, in the cationic crosslinkable composition of the above (1) to (4), the content ratio of the specific structural unit having the oxetanyl group in the specific cyclic olefin polymer having the specific structural unit having the oxetanyl group is The content is preferably 0.2 to 30 mol%, particularly preferably 0.5 to 20 mol%, based on all structural units constituting the specific cyclic olefin polymer.
When the content ratio of the specific structural unit having an oxetanyl group is less than 0.2 mol%, the cationic crosslinkable composition is not sufficiently crosslinked, and the formed crosslinked product has a large linear expansion coefficient. Further, the solvent resistance, chemical resistance, and mechanical strength of the obtained specific member may be reduced, and the specific member may have low adhesion to other members constituting the specific surface mount LED element. There is. Further, it may be difficult to form the specific member by a technique using a mixed olefin polymer.
On the other hand, when the content ratio of the specific structural unit having an oxetanyl group exceeds 30 mol%, the formed crosslinked product has a large linear expansion coefficient, and there is a possibility that the water absorption of the specific member to be obtained increases.

  In the crosslinkable composition (radical crosslinkable composition, hydrolyzable crosslinkable composition, and cationic crosslinkable composition) for obtaining a crosslinked product, the content ratio of the composition-forming composition to be blended with the cyclic olefin polymer Is preferably 0.0001 to 5.0 parts by mass with respect to 100 parts by mass of the specific cyclic olefin-based polymer.

  The crosslinkable composition for obtaining a specific crosslinked product includes a alkoxide of a metal selected from titanium, aluminum, and zirconium, or a condensation degree of the metal alkoxide and the alkoxide compound of the metal of 3 to 30. , A silane compound having an alkoxyl group, a silane compound having an allyloxyl group, or a condensate having a condensation degree of 3 to 30 (hereinafter, these are also referred to as “addition compounds”). This makes it possible to make the formed sealing material made of the crosslinked body excellent in dimensional stability, solvent resistance and chemical resistance.

  Specific examples of the additive compound include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, Dicyclohexyldimethoxysilane, cyclopentyltrimethoxysilane, bicyclo [2.2.1] hept-2-yltrimethoxysilane, bicyclo [2.2.1] hept-2-en-5-yltrimethoxysilane, aluminum trimethoxy , Aluminum triethoxide, titanium tetraethoxide, zirconium tetraethoxide, and condensates having a degree of condensation of 3 to 30 thereof.

  The addition ratio of the additive compound in the crosslinkable composition is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the specific cyclic olefin polymer.

  In the crosslinkable composition, oxide particles or colloidal particles such as silica, alumina, zirconia, titania and the like having an average particle size of 100 nm or less (hereinafter also referred to as “added particles”) together with additive compounds. Can be added.

The addition ratio of the additive particles (in terms of solid content in colloidal particles) is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the specific cyclic olefin polymer.
When the addition ratio of the additive particles is less than 1 part by mass, the effect of the additive particles is not sufficiently exerted on the hardness, elastic modulus, and linear expansion coefficient of the formed crosslinked product, while the addition ratio of the additive particles When the amount exceeds 40 parts by mass, the formed specific member made of the crosslinked body may be brittle.

  Moreover, as a crosslinkable composition for obtaining a crosslinked product, a specific cyclic olefin polymer is blended with a silane compound having a radical polymerizable substituent such as a methacryloyl group or an acryloyl group, and a radical generator. Can be used, and such a composition can be crosslinked by the action of light or heat.

As a method for obtaining the resin base material 12 constituting the wiring board 11 with the transparent heat-resistant resin composed of the specific crosslinked body as described above, for example, a composition for forming a composition is blended with a specific cyclic olefin polymer. An olefin polymer solution is prepared by dissolving the crosslinkable composition obtained in a solvent selected from, for example, a hydrocarbon solvent, a halogenated hydrocarbon solvent, or a mixed solvent composed of the solvent, and the olefin polymer. The solution is applied on, for example, a glass substrate by a method using a coating apparatus such as a spin coater or a method using a printing method such as screen printing, and the obtained coating film is dried. For a resin film made of a crosslinkable composition formed by a technique such as a solution casting method or a melt extrusion method. It can be obtained, such as by performing Yichun crosslinking process.
Moreover, the transparent sealing material which comprises the sealing structure 19 apply | coats or casts the olefin polymer solution on the LED chip 15 and the electric power supply wire 16 which are sealing objects, and dries the obtained film | membrane. After that, by further performing an appropriate crosslinking treatment on the film, a sealing structure for sealing the object to be sealed is formed, or the crosslinkable composition and the specific composition constituting the crosslinkable composition are formed. A blended composition blended with a thermoplastic resin other than the cyclic olefin-based polymer is obtained, the blended composition is molded by a melt extrusion method using a melt extruder or the like as a molding material, and the molded body is appropriately crosslinked. It can be obtained by forming a sealing structure that seals the object to be sealed with a cross-linked molded body obtained by performing the treatment.

According to the surface-mounted LED element 10 having such a configuration, since the resin base material 12 constituting the wiring board 11 is made of a transparent heat resistant resin and has transparency, when the LED chip 15 is caused to emit light, The light emitted from the LED chip 15 in the direction toward the sealing structure 19 is transmitted through the sealing structure 19 and emitted outward, and the light emitted in the direction toward the wiring board 11 is also resin. Since the light passes through the resin base material 12 without being absorbed by the base material 12 and is emitted outward from the back surface side of the wiring substrate 11, the light emitted from the LED chip 15 is emitted from the surface-mounted LED element 10. It can be used effectively as radiated light, and thereby a high luminous flux utilization factor can be obtained.
Since the surface-mounted LED element 10 emits light outward from each of the both surface sides of the wiring board 11, a new application development is expected.

Further, the surface-mount type LED element 10 has a resin base material 12 when the resin base material 12 constituting the wiring substrate 11 is made of a specific cyclic olefin polymer or a specific cross-linked body. Has excellent properties derived from these resin materials (for example, transparency, heat resistance, chemical resistance, electrical properties, etc.), so that a high luminous flux utilization factor can be obtained and excellent optical properties can be obtained. , Dimensional stability, and stability over time of light emission performance can be obtained.
Furthermore, when the transparent sealing material which comprises the resin base material 12 and the sealing structure 19 is a thing which consists of a specific cyclic olefin type polymer, or a thing which consists of a specific bridge | crosslinking body, surface mount type LED element 10. Even better optical properties, dimensional stability, and stability over time of light emission performance can be obtained.

The present invention is not limited to the above embodiment, and various modifications can be made.
For example, as shown in FIGS. 2 and 3, a specific surface mount type LED element has a wiring pattern 13 a formed on its surface (upper surface in FIG. 3) and a wiring substrate 21 on which the LED chip 15 is mounted. The reflective film 25 may be provided on the back surface (the lower surface in FIG. 3).

This reflective film 25 is a region on the back surface of the wiring substrate 21 where no adverse effect such as a short circuit occurs due to the formation of the reflective film 25. Specifically, in the example shown in FIG. It can be formed in a region other than the portion where the terminal 13 c is formed on the back surface of the substrate 21 (hereinafter also referred to as “specific back surface region”).
Moreover, it is preferable that the reflective film 25 which comprises the surface mount type LED element 20 has a large area, and specifically, the ratio with respect to the area of a specific back surface area | region has a magnitude | size of 50%. It is preferable.

  The method for forming the reflective film 25 is not particularly limited as long as it is a method capable of forming a reflective film having a desired shape in the specific back region, and specifically, for example, by a silk screen printing method. A method of forming a film with paint (ink), a method of patterning a film formed of a photoresist agent by a photolithography method, a method of forming a film by chemical vapor deposition, and the like can be used.

According to the surface mount LED element 20 having the reflection film 25 as described above, the resin base material 12 constituting the wiring board 21 is made of a transparent heat resistant resin, and the reflection film 25 is formed on the back surface of the wiring board 21. Therefore, the light emitted in the direction from the LED chip 15 toward the wiring substrate 21 is transmitted through the resin base material 12 without being absorbed by the resin base material 12, reflected by the reflective film 25, and again. By transmitting through the resin base material 12, it is transmitted through the sealing structure 19 and emitted outward in the same manner as the light emitted from the LED chip 15 toward the sealing structure 19. Since the light emitted from the LED chip 15 can be used effectively, a high luminous flux utilization factor can be obtained, and the intensity of the light emitted in the direction toward the sealing structure 19 can be increased. .
Since the surface-mounted LED element 20 emits light with a high intensity from the surface side of the wiring board 21 to the outside, new application development is expected.

  Hereinafter, experimental examples performed for confirming the effects of the present invention will be described.

  In the following, molecular weight, glass transition temperature, linear expansion coefficient and total light transmittance were measured by the following methods.

(1) Weight average molecular weight and number average molecular weight In a 150C-type gel permeation chromatography (GPC) apparatus manufactured by WATERS, an H-type column manufactured by Tosoh Corporation was used, and the temperature was determined using o-dichlorobenzene as a solvent. The measurement was performed at 120 ° C. The obtained molecular weight is a standard polystyrene equivalent value.
(2) Total light transmittance This was measured by using a film having a thickness of 150 μm as a sample in accordance with ASTM-D1003.
(3) Tan δ peak temperature (glass transition temperature)
The peak temperature of Tan δ of dynamic viscoelasticity (ratio E ″ / E ′ of storage elastic modulus E ′ and loss elastic modulus E ″) was measured as the glass transition temperature of the polymer.
The measurement of dynamic viscoelasticity uses "DDV-01FP" manufactured by Orientec Co., Ltd., the measurement frequency is 10 Hz, the heating rate is 4 ° C./min, the excitation mode is a single waveform, and the excitation amplitude is 2.5 μm. The temperature dispersion peak temperature of the obtained Tan δ was determined as the peak temperature related to the glass transition temperature.
(4) Linear expansion coefficient:
Using a TMA (Thermal Mechanical Analysis) device “SS6100” manufactured by Seiko Instruments Inc., a sample having a thickness of 100 μm, a width of 3 mm, and a length of 10 cm or more is fixed at a distance between chucks of 10 mm. After raising the temperature from room temperature to about 200 ° C. to remove residual strain, the temperature was raised from room temperature at 3 ° C./min, and the linear expansion coefficient was obtained from the elongation of the distance between chucks.

[Experimental Example 1]
Under a nitrogen atmosphere, a stainless steel reactor having a volume of 2 liters was charged with 700 mmol of bicyclo [2.2.1] hept-2-ene and tricyclo [5.2.1.0 ^2,6 ] deca as specific monomers. 570 mmol of -8-ene (endo isomer / exo isomer = 94/4), 30 mmol of 5-triethoxysilylbicyclo [2.2.1] hept-2-ene, and 5 mmol of 1-hexene as a molecular weight regulator. As a solvent, 400 g of cyclohexane and 100 g of methylene chloride were charged. The system was then charged with 8.0 mmol of methyltriethoxysilane, 0.4 mmol of 1,5-cyclooctadiene, 8.0 mmol of methylalumoxane, and 1.2 mmol of boron trifluoride ethyl etherate. Then, a hexafluoroantimonic acid modified product of nickel octoate was charged in this order, and the polymerization reaction was started.
Here, the hexafluoroantimonic acid modified form of nickel octoate is by-produced by reacting a hexane solution of nickel octoate with hexafluoroantimonic acid at a molar ratio of 1: 1 at a temperature of -10 ° C. The precipitate was obtained by removing the precipitate of bis (hexafluoroantimonate) nickel [Ni (SbF ₆ ) ₂ ] by filtration and diluting with toluene, and the amount added was 0.40 mmol as nickel atoms. Was added as follows.

  And the addition polymerization process was performed over 3 hours on the conditions of the temperature of 30 degreeC, and this addition polymerization process was stopped by adding methanol. The conversion rate of the monomer subjected to the addition polymerization treatment into a polymer was 92%.

The reaction solution obtained by the addition polymerization treatment was diluted by adding 480 g of cyclohexane, 660 ml of water and 48 mmol of lactic acid were added to the diluted solution, and the mixture was sufficiently stirred. The copolymer solution phase containing the coal and the aqueous phase are allowed to stand still to remove the aqueous phase containing residues such as reactants related to the catalyst, and then the copolymer solution is poured into 4 liters of isopropyl alcohol. The copolymer was coagulated with to remove unreacted monomers and residues.
The obtained solidified product was dried to obtain 75 g of a cyclic olefin polymer (hereinafter also referred to as “copolymer (A)”).
The composition of the copolymer (A) was determined by analyzing the unreacted monomer remaining in the obtained copolymer reaction solution by gas chromatography. As a result, bicyclo [2.2 .1] The content ratio of the specific structural unit derived from hept-2-ene is 63 mol%, and the specific structural unit derived from 5-triethoxysilylbicyclo [2.2.1] hept-2-ene Was 2.1 mol%, and the content of the specific structural unit derived from endo-tricyclo [5.2.1.0 ^2,6 ] dec-8-ene was 35 mol%.
The copolymer (A) had a polystyrene-equivalent number average molecular weight of 89,000, a weight average molecular weight of 187,000, and Mw / Mn was 2.1.

Next, 10 g of the copolymer (A) is dissolved in 35.5 g of cyclohexane, and 0.5 part of tributyl phosphite is added to this system as a crosslinking catalyst with respect to 100 parts of the copolymer (A). To obtain a mixed olefin polymer solution (hereinafter, also referred to as “olefin polymer solution (A)”), and a polymer obtained by melt casting using the olefin polymer solution (A). By crosslinking the film, a crosslinked film (hereinafter also referred to as “resin substrate (A)”) was produced.
When the characteristics of the obtained resin substrate (A) were confirmed, the total light transmittance was 90%, the water absorption was 0.02%, and the glass transition of the material constituting the sealing material film (A) The temperature was 375 ° C., and the linear expansion coefficient was 50 ppm / ° C.

A wiring pattern is formed on the surface of the resin base material (A), and a reflective film having a size with a ratio of 50% or more with respect to the total area of the specific back surface region is formed on the back surface of the wiring substrate (hereinafter referred to as “wiring substrate”). (A) ") is obtained, and the LED chip is mounted on the surface of the wiring board (A) on which the wiring pattern is formed by the Philip chip method and the power supply wire is electrically connected. On top of this, by sealing the LED chip and the power supply wire with a case-shaped resin mold obtained by crosslinking the molded body molded using the copolymer (A) as a molding material, a surface-mounted LED element (hereinafter, "LED element (A)" is also produced.
Further, in the LED element (A), a surface mount type LED element (hereinafter referred to as “a”) was prepared by the same method as the method for manufacturing the LED element (A) except that the reflective film was not formed on the back surface of the resin base material (A). An LED element (B) ”was also produced.
Each of the produced LED element (A) and LED element (B) was turned on, and the amount of light emitted outward from the sealing structure side was compared. As a result, in the LED element (A), the LED element (B It was confirmed that an increase in light amount of about 15% was obtained compared to the light amount of

It is sectional drawing for description which shows an example of a structure of the surface mount type LED element of this invention. It is a top view for description which shows an example of other composition of the surface mount type LED element of the present invention. It is AA sectional drawing of the mounting type LED element of FIG. It is sectional drawing for description which shows an example of a structure of the conventional surface mount type LED element.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Surface mount type LED element 11 Wiring board 12 Resin base material 13a Wiring pattern 13b Through hole 13c Terminal 15 LED chip 16 Feeding wire 19 Sealing structure 20 Surface mounting type LED element 21 Wiring board 25 Reflective film 40 Surface mounting type LED element DESCRIPTION OF SYMBOLS 41 Wiring board 42 Resin base material 43a Wiring pattern 43b Through-hole 43c Terminal 45 LED chip 46 Feeding wire 49 Sealing structure 51 Printed circuit board 52 Wiring pattern

Claims (7)

A surface mount type LED element in which a sealing structure is formed by sealing an LED chip mounted on the surface of a wiring board including a resin base material with a sealing material made of a transparent resin,
The resin base material constituting the wiring board, and the sealing material for sealing the LED chip are made of a transparent heat-resistant resin,
A surface-mount type LED element, wherein the transparent heat-resistant resin is composed of a cyclic olefin polymer having a structural unit represented by the following general formula (1) .

[Wherein, A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a halogenated hydrocarbon group, or hydrolysis. Or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _p —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ are each independently carbon atoms having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an axetanyl group, and p is an integer of 0 to 5. ] The cyclic olefin-based polymer includes a structural unit in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1) ,
The surface-mountable LED element according to claim 1, wherein the hydrolyzable silyl group is a group represented by the following general formula (2) .

[Wherein Y is an alkoxy diol having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 2 to 20 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ] In the cyclic olefin polymer, the content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2) is 0.2 relative to the total structural units constituting the cyclic olefin polymer. The surface-mount LED element according to claim 2 , which is ˜30 mol% . A surface mount type LED element in which a sealing structure is formed by sealing an LED chip mounted on the surface of a wiring board including a resin base material with a sealing material made of a transparent resin,
The resin base material constituting the wiring board, and the sealing material for sealing the LED chip are made of a transparent heat-resistant resin,
The surface mount type LED element characterized by the said transparent heat resistant resin consisting of the crosslinked body of the cyclic olefin type polymer which has a structural unit represented by following General formula (1) .

[Wherein, A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a halogenated hydrocarbon group, or hydrolysis. Or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _p —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ are each independently carbon atoms having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an axetanyl group, and p is an integer of 0 to 5. ] The cyclic olefin-based polymer includes a structural unit in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1) ,
The surface-mount type LED element according to claim 4, wherein the hydrolyzable silyl group is a group represented by the following general formula (2) .

[Wherein Y is an alkoxy diol having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 2 to 20 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ] In the cyclic olefin polymer, the content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2) is 0.2 relative to the total structural units constituting the cyclic olefin polymer. The surface-mount type LED element according to claim 5, which is ˜30 mol% . The surface-mount type LED element according to claim 1 , wherein a reflective film is provided on a back surface of the wiring board .

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