JP2009202567A - Manufacturing method of composite comprising resin-made member and metallic member, substrate for mounting led and reflector for mounting led - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a composite which can effectively manufacture a resin-molded part showing high adhesion to a metallic member, can prevent deformation or breakage of the resin-molded part, separation between the resin-molded part and the metallic member and the like when the composite is accompanied by heat history, and can show excellence in thermal resistance and heat radiation, and to provide a substrate for mounting an LED and a reflector for mounting the LED. <P>SOLUTION: The resin-molded part of the composite is made by arranging the metallic member 11 surface-treated with a triazine-based compound in a mold 3, and injection-molding a resin composition containing 15 to 80 mass% of a thermoplastic resin containing at least one kind of a thioether bond, an amide bond, an ester bond and an ether bond and 20 to 85 mass% of boron nitride. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a method for producing a composite made of a resin member and a metal member, an LED mounting substrate on which an LED element is mounted, and an LED reflector. More specifically, the resin molded portion is made of metal with high adhesiveness. A composite manufacturing method capable of efficiently manufacturing a composite formed on the surface of a member and excellent in heat resistance, heat dissipation, and light reflection characteristics, and obtained using this method The present invention relates to an LED mounting substrate and a reflector for LED.

In recent years, LED elements with high brightness have been manufactured at a relatively low cost as light sources to replace fluorescent lamps and incandescent bulbs, and lighting devices and the like including these LED elements have been studied. In a lighting device or the like, in order to obtain a large illuminance, a plurality of LED elements are mounted on a surface-mounted LED package, that is, a base substrate (LED mounting board) made of metal such as aluminum, for example. Therefore, a system is often used in which a reflector that reflects light in a predetermined direction is disposed around it. However, since the LED element generates heat during light emission, in such a type of lighting device, a temperature increase during light emission of the LED element leads to a decrease in luminance, a shortened life of the LED element, and the like. In view of this, there has been proposed an illumination device having a structure in which a bare chip of an LED element is mounted on a base substrate made of a metal having high heat dissipation property, and heat generated during light emission is diffused into the base substrate. (For example, refer to Patent Documents 1 and 2).
Patent Document 3 discloses a lead frame, a resin cup portion made of nylon resin, liquid crystal polymer resin, thermosetting resin or silicone resin, and an inner surface of the resin cup portion away from the lead frame. An LED device having a stainless steel pyramid-shaped metal member disposed therein is disclosed. In this LED device, the cone-shaped metal member is subjected to surface processing such as shot blasting and etching in advance, and then insert-molded to integrate the resin cup portion, the lead frame, and the cone-shaped metal member. It has become.
Patent Document 4 discloses a polyamide resin comprising a dicarboxylic acid unit containing a terephthalic acid unit and a diamine unit containing a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. , Titanium oxide, magnesium hydroxide, and a polyamide resin composition for forming a reflector for LED, containing a reinforcing agent comprising a fibrous filler and / or an acicular filler, is disclosed. There is a description that can be combined with a molded body made of metal or the like.

JP-A-62-149180 JP 2002-344031 A JP 2007-300018 A JP 2006-257314 A

According to the technique disclosed in Patent Document 3, there is a case where a minute gap is formed at the interface between the resin cup portion, the lead frame, and the conical metal member. When the gap is formed, the gap becomes a heat insulating layer, heat generated when the LED element emits light tends to stay, heat radiation is not sufficient, separation (peeling) of members, resin cup portion May lead to deformation or destruction.
The same applies to the technique disclosed in Patent Document 4, and as the use of the LED device is repeated, the LED reflector made of the polyamide resin composition and the metal member bonded to the reflector are separated (peeled). Or the LED reflector may be deformed or destroyed.
The present invention can efficiently form a resin molded part having high adhesion to a metal member, and when accompanied by a thermal history, deformation and destruction of the resin molded part, resin molded part and metal Separation of members and the like are suppressed, and a composite manufacturing method capable of efficiently manufacturing a composite excellent in heat resistance and heat dissipation, and a member such as an LED mounting substrate and an LED reflector, and the member are provided. In the case of an article, etc., it is excellent in heat resistance and heat dissipation by suppressing deformation and destruction of the resin molded part, separation of the resin molded part and the metal member, etc., and an article provided with a light emitter such as an LED element. In this case, in the resin molded part, a composite manufacturing method capable of efficiently manufacturing a composite excellent in light reflection characteristics, and an LED mounting substrate and an LED reflector obtained by using this method are provided. It aims to provide.

  The present inventors arrange a metal member surface-treated with a triazine compound inside a mold, and a thermoplastic containing a specific thermoplastic resin and boron nitride on the surface of the metal member. By injecting the resin composition in a molten state into the cavity space inside the mold, it is possible to efficiently form a resin molded part (resin member) having high adhesion to a metal member, and heat history In this case, deformation and destruction of the resin molded part, separation of the resin molded part and the metal member, etc. were suppressed, and a composite excellent in heat resistance and heat dissipation was manufactured, and a heat history was accompanied. Suppresses deformation and destruction of the resin molded part, separation of the resin molded part and the metal member, etc. when the LED element is mounted on a member such as an LED mounting substrate, an LED reflector, or an article including the member. LED element When an article having a light emitter etc., the resin molding part, found that was excellent in reflection characteristic for light, and have completed the present invention.

That is, the present invention is as follows.
1. A metal member treated with a triazine compound is placed inside the mold, and at least part of the surface of the metal member is selected from [A] a thioether bond, an amide bond, an ester bond and an ether bond. 15 to 80% by mass of a thermoplastic resin containing at least one bond and [B] boron nitride 20 to 85% by mass (provided that [A] + [B] = 100% by mass) A method for producing a composite, comprising forming a resin molded part made of the composition by an injection molding method.
2. 2. The method for producing a composite according to 1 above, wherein the thermoplastic resin [A] is polyphenylene sulfide.
3. 2. The method for producing a composite according to 1 above, wherein the thermoplastic resin [A] is a polyamide resin having a melting point in the range of 250 ° C. to 400 ° C.
4). When the thermoplastic resin [A] is composed of polyphenylene sulfide and a polyamide resin having a melting point in the range of 250 ° C. to 400 ° C., and the content ratio of these is 100% by mass, respectively, 2. The method for producing a composite according to 1 above, which is 40 to 90% by mass and 60 to 10% by mass.
5. 5. The method for producing a composite according to 3 or 4 above, wherein the polyamide resin contains an aromatic polyamide resin.
6). 6. The method for producing a composite according to 5 above, wherein the aromatic polyamide resin contains hexamethylene terephthalamide units.
7). The boron nitride [B], the particle diameter _{D 10} and _{D 90} when the cumulative volume obtained by the measurement of the particle size distribution is 10% and 90%, respectively, and the 4~6μm and 35～50Myuemu, and The method for producing a composite according to any one of 1 to 6 above, wherein the ratio D ₉₀ / D _{10 of} D ₁₀ and D ₉₀ is 7 to 11.
8). 8. The method for producing a composite according to any one of 1 to 7 above, wherein the boron nitride [B] has a volume average particle diameter of 12 to 20 μm.
9. 9. The composite according to any one of 1 to 8, which is a plate-shaped LED mounting substrate including the metal member and the resin molded portion formed on at least one surface of the metal member. A method for producing the composite.
10. In the composite, as the metal member, one metal member is a heat-dissipating metal plate, the other metal member is a lead frame electrically connected to the LED element, and the heat-dissipating metal A plate comprising the plate and the resin molded portion formed on at least one surface of the heat radiating metal plate, and the lead frame is disposed on the surface and / or inside the resin molded portion. 9. A method for producing a composite according to any one of 1 to 8, which is a shaped LED mounting substrate.
11. 11. The method for producing a composite according to 9 or 10 above, wherein in the LED mounting substrate, the resin molded part includes a reflector part having a concave cross-sectional shape for disposing the LED element.
12 The composite is a reflector for LED in which the metal member is disposed on the surface and / or inside of the resin molded part,
The metal member is a lead frame electrically connected to the LED element, and the resin molded portion has a concave cross-sectional shape for disposing the LED element. The manufacturing method of the composite_body | complex described.
13. The composite is a reflector for LED in which the metal member is disposed on the surface and / or inside of the resin molded part,
9. The method for producing a composite according to any one of 1 to 8, wherein the metal member is a heat radiating member, and the resin molded portion has a concave cross-sectional shape for disposing the LED element.
14 An LED mounting substrate obtained by the method for producing a composite according to any one of 9 to 11 above.
15. An LED reflector obtained by the method for producing a composite according to 12 or 13 above.

According to the method for producing a composite of the present invention, a metal and a resin are chemically bonded via a triazine compound, and a resin molded portion having high adhesion (adhesion) is efficiently formed on a metal member. can do. Further, in the present invention, when accompanied by a thermal history, deformation and destruction of the resin molded part, separation of the resin molded part and the metal member, etc. are suppressed, heat resistance and heat dissipation (heat radiation from the metal member, A composite excellent in heat radiation from the resin molded part and heat release to the low temperature part side of the metal member or resin molded part by heat conduction can be efficiently produced. Regardless of which part of the resin molded part and metal member in the composite is subjected to heat load, heat conduction to the other part is good and heat is efficiently transferred to the outside without causing deformation of the composite. It can radiate | emit and can obtain the outstanding heat dissipation. In particular, heat can be efficiently transferred from a metal member to which heat is applied to the resin molded portion, and the resin molded portion can be radiated to the outside. In addition, when the composite is a member such as an LED mounting substrate or an LED reflector with a thermal history, such as an article provided with the member, deformation and destruction of the resin molded portion, resin molded portion and metal In the case where an article including a light emitting body such as an LED element is suppressed, separation of the manufactured member can be efficiently produced in the resin molded portion.
When the thermoplastic resin [A] is polyphenylene sulfide, it is excellent in the adhesiveness of the resin molded part and the metal member in the obtained composite, the dimensional stability as the resin molded part, and as the composite Excellent heat resistance, heat dissipation, and light reflection characteristics. In addition, since the water absorption rate in the resin molded part is less than 0.05% and water absorption can be suppressed, blisters (swells) can be produced when surface mount parts and the like are manufactured in a reflow furnace using this composite. Etc. can be suppressed. Furthermore, when the composite is used as a light reflecting member such as an LED reflector, the light reflection characteristics are also excellent.
When the thermoplastic resin [A] is a polyamide resin having a melting point in the range of 250 ° C. to 400 ° C., it is excellent in the adhesiveness of the resin molded part and the metal member in the resulting composite, It is excellent in impact resistance, heat resistance as a composite, heat dissipation, and light reflection characteristics.
When the thermoplastic resin [A] is composed of polyphenylene sulfide and a polyamide resin having a melting point in the range of 250 ° C. to 400 ° C., and the content ratio of these is 100% by mass, respectively, When the content is 40 to 90% by mass and 60 to 10% by mass, the resulting composite has excellent adhesion to the resin-molded part and the metal member, and the composite has heat resistance, impact resistance, heat dissipation, and resistance to heat. Excellent balance of blister properties and light reflection characteristics.
When the polyamide resin contains an aromatic polyamide resin, it is excellent in the adhesiveness of the resin molded part and the metal member in the resulting composite, heat resistance, impact resistance, heat dissipation, blister resistance as a composite, And it is excellent in the balance of the reflection characteristic with respect to light.
When the aromatic polyamide resin contains a hexamethylene terephthalamide unit, it is excellent in the adhesiveness of the resin molded part and the metal member in the resulting composite, heat resistance, impact resistance, heat dissipation as a composite, It is particularly excellent in the balance of blister resistance and light reflection characteristics.

Above in boron nitride (B), the particle diameter _{D 10} and _{D 90} when the cumulative volume obtained by the measurement of the particle size distribution is 10% and 90%, respectively, and the 4~6μm and 35～50Myuemu, and , when the ratio _D 90 _{/ D 10} of _{D 10} and _{D 90} of 7 to 11 is that the excellent adhesiveness of the resin molded portion and the metal member to obtain a better composite by heat radiation and heat resistance Can do.
Further, when the volume average particle diameter of the boron nitride [B] is 12 to 20 μm, it has further excellent heat dissipation and heat resistance compared to boron nitride having a particle diameter smaller than 12 μm, and a resin molded part And the composite_body | complex excellent in the adhesiveness of metal members can be obtained. In addition, it is possible to obtain a composite having excellent impact resistance and fluidity as compared with boron nitride having a particle diameter larger than 20 μm and excellent adhesion between the resin molded portion and the metal member.

When the composite is an LED mounting substrate including the metal member and the plate-shaped resin molded portion formed on at least one surface of the metal member, the adhesiveness between the members Excellent heat resistance, heat dissipation, and light reflection characteristics. Further, when an LED element or the like is provided on the obtained LED mounting substrate, a product having excellent dimensional stability can be provided without causing blistering or deformation.
The composite is the metal member, wherein one metal member is a heat dissipation metal plate, the other metal member is a lead frame electrically connected to the LED element, and the heat dissipation metal A plate and the plate-shaped resin molded portion formed on at least one surface of the heat radiating metal plate, and the lead frame is disposed on the surface and / or inside the resin molded portion. In the case of the LED mounting substrate, the heat dissipation metal plate and the lead frame are excellent in adhesiveness between the resin molded portion, heat resistance as a composite, heat dissipation, and light reflection characteristics. Further, when an LED element or the like is provided on the obtained LED mounting substrate, a product having excellent dimensional stability can be provided without causing blistering or deformation.
In the LED mounting substrate, when the resin molding portion includes a reflector portion having a concave cross-sectional shape for disposing the LED element, the heat resistance, heat dissipation, and light reflection characteristics are excellent. In addition, even when an LED element or the like is provided on the LED mounting substrate, a product having excellent dimensional stability can be provided without causing blistering or deformation.

The composite is an LED reflector. In the LED reflector, the metal member is disposed on the surface and / or inside of the resin molded portion, and the metal member is electrically connected to the LED element. If the resin molded part has a concave cross-sectional shape in order to dispose the LED elements, the resin frame is excellent in heat resistance and light reflection characteristics. When the part (reflector part) absorbs heat associated with light emission of the LED element, the heat dissipation to the outside is also excellent.
The composite is an LED reflector, and in the LED reflector, the metal member is disposed on the surface and / or inside of the resin molded portion, and the metal member is a heat dissipation member. In addition, when the cross-sectional shape of the resin molding part is concave to dispose the LED element, the resin molding part (reflector part) is excellent in heat resistance and light reflection characteristics. When absorbing heat generated by the light emission of the element, heat dissipation to the outside is also excellent.

  As described above, when the composite is an article related to a light-emitting device including an LED element, it has excellent heat dissipation, thereby suppressing a decrease in luminous efficiency and a decrease in luminance in the LED element. And the article can be used for a long time.

  In the method for producing a composite of the present invention, a metal member treated with a triazine compound is disposed inside a mold, and [A] a thioether bond is formed on at least a part of the surface of the metal member. 15-80% by mass of a thermoplastic resin (hereinafter referred to as “component [A]”) containing at least one bond selected from an amide bond, an ester bond and an ether bond, and [B] boron nitride (hereinafter referred to as “ Component [B] ”) 20-85% by mass (however, [A] + [B] = 100% by mass) forming a resin molded part made of a thermoplastic resin composition by an injection molding method. Features.

  First, the thermoplastic resin composition which comprises the said resin molding part is demonstrated. This thermoplastic resin composition contains components [A] and [B].

The component [A] includes at least one bond selected from a thioether bond, an amide bond, an ester bond, and an ether bond, and is preferably a resin in which the bond is included in the main chain.
As said component [A], it can be set as the thermoplastic resin containing a thioether bond, the thermoplastic resin containing an amide bond, the thermoplastic resin containing an ester bond, the thermoplastic resin containing an ether bond, etc. These thermoplastic resins can be used singly or in combination of two or more.

  Examples of the thermoplastic resin containing a thioether bond include polyarylene sulfide and polyalkylene sulfide. These can be used alone or in combination of two or more. Of these, polyarylene sulfide is preferred because of its excellent heat resistance, strength, and rigidity.

尚、上記式（１）及び（２）において、芳香環を構成する炭素原子に結合する水素原子は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、フェニル基、カルボキシル基及びその金属塩、ニトロ基、並びに、フッ素原子、塩素原子、臭素原子等のハロゲン原子、から選ばれた基等と置換されていてもよい。複数の水素原子が置換されている場合は、互いに同一であってよいし、異なってもよい。 The polyarylene sulfide is a polymer containing a bond represented by -Ar-S- (wherein -Ar- is an arylene group). The bonding form of Ar and S is not particularly limited, but for example, shown in the following (1) and (2).

In the above formulas (1) and (2), the hydrogen atom bonded to the carbon atom constituting the aromatic ring is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a carboxyl group. And a metal salt thereof, a nitro group, and a group selected from a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom. When a plurality of hydrogen atoms are substituted, they may be the same as or different from each other.

（式中、Ｒ^１及びＲ^２は、互いに、同一又は異なって、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、フェニル基、カルボキシル基及びその金属塩、ニトロ基、並びに、フッ素原子、塩素原子、臭素原子等のハロゲン原子、から選ばれる。但し、Ｒ^１及びＲ^２が、ともに水素原子である場合を除く。）

Therefore, as said polyarylene sulfide, the polymer containing the unit shown below can be used, for example.

(In the formula, R ¹ and R ² are the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a carboxyl group, and a metal salt thereof, nitro A group, and a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, except that R ¹ and R ² are both hydrogen atoms.)

As said polyarylene sulfide, the polymer containing the unit of said Formula (1) is preferable. A more preferable polymer is a linear type containing 70 mol% or more, preferably 90 mol% or more (upper limit is 100 mol%) of the above formula (1) when the total of each unit is 100 mol%. Polyarylene sulfide, and a particularly preferred polymer is polyphenylene sulfide in which the unit of the above formula (1) is 100 mol%. When this polyphenylene sulfide is used, it is excellent in moldability and heat resistance.
In addition, when the polyarylene sulfide contains other units in an amount of less than 30 mol%, a polymer containing at least one unit selected from the above formulas (4) to (9) is used. Can do.

  The melt viscosity of the polyarylene sulfide is not particularly limited, but is preferably 300 to 800 poise (temperature: 310 ° C., shear rate: 1,000 / second).

  The thermoplastic resin containing an amide bond is not particularly limited as long as it is a resin having an amide bond [—NH—C (═O) —] in the repeating unit of the polymer main chain, but a polyamide resin is preferable. As the polyamide resin, a resin obtained by polycondensation of diamine and dicarboxylic acid, ring-opening polymerization of a lactam compound, polycondensation of aminocarboxylic acid, or the like can be used. These resins may be either homopolyamide or copolyamide, or may be used in combination.

Examples of the diamine for polycondensation of diamine and dicarboxylic acid include aliphatic diamine, alicyclic diamine, and aromatic diamine. Specific examples include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 1,9-nonane diamine, 2-methyl-1,8-octane diamine, 2,2,4- Trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine , M-xylylenediamine, p-xylylenediamine and the like. These diamines may be used alone or in combination of two or more.
Examples of the dicarboxylic acid include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and aromatic dicarboxylic acid. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer An acid etc. are mentioned. These dicarboxylic acids may be used alone or in combination of two or more.

Examples of the lactam compound used in the ring-opening polymerization include ε-caprolactam, enantolactam, and ω-laurolactam. These lactam compounds may be used alone or in combination of two or more.
Examples of the aminocarboxylic acid for polycondensation of aminocarboxylic acids include ε-aminocaproic acid, aminoenanoic acid, aminocaprylic acid, aminobergonic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11 -Aminoundecanoic acid, 12-aminododecanoic acid, 13-aminotridecanoic acid and the like. These aminocarboxylic acids may be used alone or in combination of two or more.

  The method for producing the polyamide resin is not particularly limited, and any of melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and a combination thereof may be used. Of these, melt polymerization is preferred.

The polyamide resin may be either an aliphatic polyamide resin or an aromatic polyamide resin, or a combination thereof. As the polyamide resin, polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, polyamide 6 / 6,12, polyamide MXD (m-xylylenediamine), 6, polyamide 6, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I, polyamide 6,6 / 6, T, polyamide 6,6 / 6 , I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T, polyamide 6, 6/12/6, T, polyamide 6 / 12/6, I, polyamide 6, 6/12/6, I, polyamide 9, T and the like.
Among these, it is excellent in the adhesiveness of the resin molded part and the metal member in the obtained composite, in the impact resistance as the resin molded part, and in the heat resistance, heat dissipation, and light reflection characteristics as the composite. A polyamide resin having a melting point of 250 ° C. to 400 ° C. is preferable because it is excellent. If a polyamide resin having a low melting point is used, the resulting resin molded part and the composite may not have sufficient heat resistance, whereas if the melting point is too high, the moldability of the resin molded part may not be sufficient.
As said aliphatic polyamide resin, the polyamide containing the tetramethylene adipamide unit obtained by polycondensing the dicarboxylic acid containing 20 mass% or more of adipic acid and the diamine compound containing 20 mass% or more of tetramethylenediamine 4,6 (nylon 4,6) and modified products thereof are preferred.

The polyamide resin is preferably an aromatic polyamide resin because it is particularly excellent in impact resistance, heat dissipation, and light reflection characteristics in the resin molded part to be obtained. The aromatic polyamide resin is preferably polyamide 6, T, polyamide 9, T, or a modified product thereof, and particularly preferably polyamide 6, T or a modified product thereof. The preferred configuration of polyamide 6, T and its modified product is such that the content of hexamethylene terephthalamide units is preferably 20-100 mol%, more preferably 30-95, relative to 100 mol% of this polyamide 6, T. The mol%, more preferably 40 to 80 mol%, particularly preferably 50 to 70 mol%. Examples of the other structural units in the case of the modified product include hexamethylene isophthalamide units, 2-methylpentamethylene terephthalamide units, hexamethylene adipamide units, and caproamide units.
When the polyamide resin contains an aromatic polyamide resin, the content of the aromatic polyamide resin is preferably 40 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 70% with respect to the polyamide resin. ˜100 mass%. When the content of the aromatic polyamide resin is within this range, the resulting molded resin part is particularly excellent in impact resistance, heat dissipation and light reflection characteristics.

In addition, the terminal of the said polyamide resin may be sealed with carboxylic acid, amine, etc. Examples of carboxylic acids include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine.
The said polyamide resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of the thermoplastic resin containing an ester bond include polyester resins such as aliphatic polyester, alicyclic polyester, and aromatic polyester. As this polyester resin, a resin obtained by reaction of an acid component containing dicarboxylic acid and / or an ester-forming derivative of dicarboxylic acid with a diol component and / or a diol component containing an ester-forming derivative of a diol compound is used. Can do. This resin may be a homopolyester or a copolyester.

Among the acid components, dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4 ′. -Aromatic dicarboxylic acids such as diphenylmethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, and 4,4′-diphenylisopropylidenedicarboxylic acid. These substitution products (alkyl group substitution products such as methyl isophthalic acid) and derivatives (alkyl ester compounds such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used.
Furthermore, oxyacids and their ester-forming derivatives such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid can also be used.
The said acid component can be used individually by 1 type or in combination of 2 or more types.

Examples of the diol component include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and neopentyl glycol; and alicyclic glycols such as 1,4-cyclohexanedimethanol. In addition, these substitution bodies and derivatives can also be used. A cyclic ester compound such as ε-caprolactone can also be used.
Furthermore, long-chain diol compounds (polyethylene glycol, polytetramethylene glycol, etc.), alkylene oxide addition polymers of bisphenols, etc. (ethylene oxide addition polymers of bisphenol A, etc.), etc. can be used as necessary. .
The said diol component can be used individually by 1 type or in combination of 2 or more types.

  When the polyester resin is a homopolyester, polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, polyneopentyl terephthalate, polyethylene isophthalate Polyethylene naphthalate, polybutylene naphthalate, polyhexamethylene naphthalate and the like can be used. These can be used alone or in combination of two or more.

In addition, when the polyester resin is a copolyester, general dicarboxylic acid components used for the formation thereof include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; adipic acid, pimelic acid, suberic acid, azelaic acid And aliphatic dicarboxylic acids such as sebacic acid. The dihydroxy component includes aliphatic alkylene glycols such as linear alkylene glycols such as ethylene glycol, propylene glycol, and 1,4-butanediol; and poly (oxy-alkylene) units such as diethylene glycol and polytetramethylene glycol. And polyoxyalkylene glycol having an oxyalkylene unit having a repeating number of about 2 to 4.
Furthermore, in addition to the above compounds, hydroxycarboxylic acids such as glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, etc., if necessary And monofunctional components such as stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, tert-butylbenzoic acid, and benzoylbenzoic acid or ester derivatives thereof; tricarballylic acid, trimellitic acid, trimesic acid, pyro Polyvalent carboxylic acids such as merit acid; polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol; one or two or more multifunctional components such as gallic acid or ester derivatives thereof The above components for polycondensation It may be used in.

  In the present invention, preferred copolyesters include dicarboxylic acid components mainly containing terephthalic acid and / or derivatives thereof (lower alkyl esters such as dimethyl ester, acid anhydrides, acid halides such as acid chloride, etc.), and 1,4-butane. A polymer obtained by polycondensation with a dihydroxy component containing a diol, etc., having a glass transition temperature of preferably 0 ° C. to 75 ° C .; copolymer polybutylene terephthalate; terephthalic acid and / or a derivative thereof ( A copolyethylene terephthalate obtained by polycondensation of a dicarboxylic acid component mainly containing a lower alkyl ester such as dimethyl ester, an acid anhydride such as acid anhydride or acid chloride) and a dihydroxy component containing ethylene glycol, etc. . Of these, copolymerized polybutylene terephthalate is particularly preferred. The copolymerized polybutylene terephthalate is known to be substantially flexible as compared with the above-mentioned polybutylene terephthalate (PBT), and is also called “soft PBT”. A copolymer of dimethyl terephthalate, 1,4-butanediol and polytetramethylene glycol is known as a modified PBT imparted with flexibility.

  The dicarboxylic acid component used in the production of the copolymerized polyethylene terephthalate is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more of terephthalic acid and / or its total amount. Including derivatives. Other dicarboxylic acid components other than terephthalic acid and its derivatives are as described above for isophthalic acid and the like. Other dicarboxylic acid components can be used singly or in combination of two or more.

  The dihydroxy component used in the production of the copolymerized polyethylene terephthalate is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more of 1,4-butanediol, based on the total amount. Including. Other dihydroxy components other than 1,4-butanediol include linear or branched aliphatic alkylene glycol such as alkylene glycol having about 2 to 12 carbon atoms such as ethylene glycol; aromatic diol; polyoxy Alkylene glycol and the like are as described above. Other dihydroxy components can be used singly or in combination of two or more.

In the present invention, particularly preferred copolymer polybutylene terephthalate is exemplified as follows, but includes a dicarboxylic acid component containing 50% by mass or more of terephthalic acid and / or a derivative thereof, 1,4-butanediol and other dihydroxy components. And a polymer obtained by polycondensation with a dihydroxy component containing 1,4-butanediol, preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and the other dihydroxy component The polyoxyalkylene glycol having a poly (oxy-alkylene) unit such as diethylene glycol and polytetramethylene glycol and having an oxyalkylene unit having a number of repetitions of about 2 to 4 is preferred.
(1) A dicarboxylic acid component composed of terephthalic acid and / or a derivative thereof, 1,4-butanediol and other dihydroxy components, and 1,4-butanediol is preferably 50 to 90% by mass, more preferably Is a polymer obtained by polycondensation with a dihydroxy component containing 60 to 90% by mass.
(2) Preferably from 50% by weight or more, more preferably 70% by weight or more of terephthalic acid and / or a derivative thereof, and preferably 50% by weight or less, more preferably 30% by weight or less of isophthalic acid and / or a derivative thereof. And a dihydroxy component containing 1,4-butanediol and other dihydroxy components, and preferably containing 1,4-butanediol in an amount of 50 to 90% by mass, more preferably 60 to 90% by mass. A polymer obtained by polycondensation.

  The glass transition temperature of the copolymerized polybutylene terephthalate is preferably 0 ° C to 75 ° C. The lower limit temperature is more preferably 0 ° C. Further, the upper limit temperature is preferably less than 70 ° C, more preferably less than 65 ° C, still more preferably less than 60 ° C, and particularly preferably less than 50 ° C. When this glass transition temperature is in the above range, the resin molded part is excellent in mechanical strength and heat resistance. The glass transition temperature can be obtained by a dynamic viscoelasticity measurement method.

As a method for producing the copolymerized polybutylene terephthalate, raw material components such as a dicarboxylic acid component containing terephthalic acid and / or a derivative thereof, and a dihydroxy component containing 1,4-butanediol are used in one or more esterification reaction vessels. In the presence of an esterification reaction catalyst comprising a titanium compound, a tin compound, a magnesium compound, a calcium compound, a zirconium compound, etc., usually, a temperature of 150 ° C. to 280 ° C., preferably 180 ° C. to 265 ° C., and usually, An esterification reaction is carried out for 2 to 5 hours with stirring under conditions of 50 to 1,000 Torr (6,666 to 133,322 Pa), preferably 70 to 760 Torr (9,333 to 101,325 Pa). Esterification reaction product (oligomer) is transferred to a polycondensation reaction tank In a plurality of polycondensation reaction tanks, usually in the presence of a polycondensation reaction catalyst, a temperature of 210 ° C. to 280 ° C., preferably 220 ° C. to 265 ° C., and usually 200 Torr (26,664 Pa) or less, preferably The polycondensation reaction can be performed for 2 to 5 hours with stirring under conditions of 150 Torr (19,998 Pa) or less. The reaction format may be any of continuous type, semi-continuous type or batch type.
In addition, the resin obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die and extracted into a strand shape, cooled with water, or after being cooled with water and cut with a cutter to give pellets. And a granular material such as a chip.

  Examples of the thermoplastic resin containing an ether bond include polyacetal and polyether ether ketone.

  As described above, the component [A] is composed of two or more of a thermoplastic resin containing a thioether bond, a thermoplastic resin containing an amide bond, a thermoplastic resin containing an ester bond, a thermoplastic resin containing an ether bond, and the like. It may be. In that case, in order to improve the compatibility between the resins, pretreatment may be performed, or a compatibilizing agent may be used.

As said component [A], the following resin is preferable.
(I) a thermoplastic resin containing a thioether bond (ii) a thermoplastic resin containing a thioether bond and a resin obtained by combining a thermoplastic resin containing an amide bond (iii) a thermoplastic resin containing an ester bond

When the component [A] is the embodiment (ii), the content ratio of the thermoplastic resin containing a thioether bond and the thermoplastic resin containing an amide bond is 100% by mass, respectively. Preferably they are 40-90 mass% and 60-10 mass%, More preferably, they are 60-90 mass% and 40-10 mass%, More preferably, they are 70-90 mass% and 30-10 mass%. When the content ratio of each resin is in the above range, the resin molded part obtained has an excellent balance among heat resistance, impact resistance, heat dissipation, blister resistance, and light reflection characteristics.
The thermoplastic resin containing a thioether bond is preferably polyphenylene sulfide, and the thermoplastic resin containing an amide bond is preferably polytetramethylene adipamide (nylon 4, 6).

Next, component [B] contained in the thermoplastic resin composition, that is, boron nitride has hexagonal structure (h-BN), zinc blende structure (c-BN), wurtzite structure (w-BN). ) Or a rhombohedral crystal structure (r-BN) or the like, so long as it has a plurality of stable structures. In the present invention, any boron nitride can be used, but hexagonal boron nitride is preferred. The resin molded part containing hexagonal structure boron nitride is excellent in heat dissipation, thermal conductivity, heat resistance and insulation. Therefore, for example, when the LED mounting substrate including the resin molded portion is used and when the LED reflector is used, the above-described effect becomes remarkable. Further, it is possible to reduce the wear of the mold used when obtaining the resin molded part.
The purity of the component [B] is preferably 98% or more, more preferably 99% or more.

  The volume average particle diameter of the component [B] is preferably 2 to 100 μm, more preferably 3 to 50 μm, still more preferably 5 to 30 μm, particularly preferably from the viewpoints of heat dissipation, thermal conductivity, heat resistance and insulation. Is 12-20 μm. In particular, when boron nitride having a volume average particle diameter in the range of 12 to 20 μm is used, further excellent heat dissipation, thermal conductivity, and heat resistance can be obtained as compared with boron nitride having a particle diameter smaller than 12 μm. In addition, it is possible to obtain a composite having excellent impact resistance and fluidity as compared with boron nitride having a particle diameter larger than 20 μm and excellent adhesion between the resin molded portion and the metal member. The volume average particle diameter can be measured by a laser diffraction method, a liquid phase precipitation method (light transmission method) or the like.

Further, heat radiation, from the viewpoints of heat resistance, thermal conductivity and insulating properties, particle diameter D ₁₀ of the cumulative volume obtained by measuring the particle size distribution of the component [B] is 10%, preferably 3-8 μm, more preferably 4-8 μm, still more preferably 4-7 μm, particularly preferably 4-6 μm, and the particle diameter D ₉₀ when the cumulative volume is 90% is preferably 10 μm or more, more preferably Is 20 to 60 μm, more preferably 30 to 55 μm, and particularly preferably 35 to 50 μm. _The ratio _D 90 _{/ D 10} of _{D 10} and _{D 90} is preferably 3 to 15, more preferably 6 to 12, more preferably from 7 to 11. Thereby, the further outstanding heat dissipation, heat conductivity, heat resistance, and insulation can be obtained.

The specific surface area of the component [B], heat dissipation, thermal conductivity, in view of heat resistance and insulation properties, preferably not more than ^8m 2 / g, more preferably 1 to 4 m ² / g, more preferably 1.5 ˜3 m ² / g.
The aspect ratio of the component [B] is preferably 3 or more, more preferably 4 or more, and still more preferably 5 to 10.
The tap density of the component [B] is preferably 0.5 g / cm ³ or more, more preferably 0.7 g / cm ³ or more.
Furthermore, the L value of the component [B] is preferably 93 or more, more preferably 95 or more.
About the property of the said component [B], the resin molding part excellent in heat dissipation, heat conductivity, and the reflection characteristic with respect to light can be obtained by setting it as said each range. Note that different types of boron nitride may be used in combination as long as they constitute each of the above ranges.
In the present invention, the component [B] is more preferably dispersed than the aggregated type in which primary particles are aggregated.

  The content ratio of the components [A] and [B] contained in the thermoplastic resin composition is 15 to 80% by mass and 20 to 85% by mass, preferably 100% by mass. Is 15 to 70 mass% and 30 to 85 mass%, more preferably 30 to 70 mass% and 30 to 70 mass%. When the content ratio of the components [A] and [B] is in the above range, the obtained resin molded part is excellent in heat dissipation, thermal conductivity, insulation and heat resistance.

  The said thermoplastic resin composition may contain the additive according to the use etc. of the composite_body | complex obtained. These additives include fillers, colorants, light stabilizers, heat stabilizers, antioxidants, UV absorbers, anti-aging agents, antistatic agents, plasticizers, lubricants, flame retardants, mold release agents, antibacterial agents , Crystal nucleating agents, flow modifiers, impact modifiers, transesterification inhibitors and the like, and any known compounds can be used. In addition, when using the said thermoplastic resin composition for formation of white-type resin molding parts, such as a board | substrate for LED mounting, and a reflector for LED, an additive so that this composition can maintain a white-type color. Is preferably selected.

In general, the above-mentioned filler has different effects depending on the type, shape, and the like, and therefore is appropriately selected depending on the purpose, application, and the like. For example, a fibrous filler can be used to maintain the rigidity of the resin molded part included in the composite at high temperatures (for example, 250 ° C. to 280 ° C.) for several seconds (for example, 3 to 6 seconds). .
Examples of the fibrous filler include inorganic fibers such as glass fibers and ceramic whiskers, and organic fibers such as carbon fibers and aramid fibers.

  When the composite, for example, an LED mounting substrate, an LED reflector, or the like is manufactured in a reflow furnace held at a temperature in the range of 250 ° C. to 280 ° C. for 3 to 6 seconds, it is included in the composite. In order to maintain the rigidity of the resin molded part under the above conditions, the fibrous filler is preferably an inorganic fiber. If the rigidity is maintained, it is preferable that deformation of the resin molded portion hardly occurs. In particular, in the above applications, glass fibers are particularly preferred as the fibrous filler when used in resin molded parts that require whiteness.

Although the composition of the glass which comprises the said glass fiber is not specifically limited, For example, silicate glass, borosilicate glass, phosphate glass etc. are mentioned. Moreover, as a kind of glass, E glass, C glass, A glass, S glass, M glass, AR glass, L glass, etc. are mentioned, Among these, E glass and C glass are preferable. The glass fiber may be formed using a sizing agent such as a surface treatment agent, a film forming agent, a lubricant, a surfactant, or an antistatic agent.
Examples of the surface treatment agent include amine-based, silane-based, and epoxy-based coupling agents.

The glass fiber may be a long fiber type using roving or a chopped strand.
When the said glass fiber is mix | blended with the thermoplastic resin composition which forms a resin molding part, the average length of the glass fiber used for preparation of this composition becomes like this. Preferably it is 1-10 mm, More preferably, it is 2-6 mm. is there. Moreover, an average diameter becomes like this. Preferably it is 5-25 micrometers, More preferably, it is 8-20 micrometers. And the residual average fiber length of the glass fiber contained in the resin molding part obtained using this thermoplastic resin composition becomes like this. Preferably it is 150-1,000 micrometers, More preferably, it is 200-800 micrometers, More preferably, it is 250-700 micrometers. It is. When the residual average fiber length is in the above range, a composite having much higher rigidity at a temperature in the above range can be obtained.
The residual average fiber length is measured, for example, by cutting out a part of the resin molded portion, heating it to 800 ° C. to decompose the resin component, and then analyzing the image of the fiber length of the remaining glass fiber. The

  Further, when glass fiber is used as the filler, the glass fiber content in the thermoplastic resin composition is preferably when the total amount of the components [A] and [B] is 100 parts by mass. 5-30 mass parts, More preferably, it is 5-25 mass parts, More preferably, it is 8-20 mass parts. When the content of the glass fiber is in the above range, it is excellent in maintaining the rigidity of the resin molded portion at a high temperature (for example, 250 ° C. to 280 ° C.) and also excellent in impact resistance.

As the colorant, any of inorganic pigments such as titanium oxide, organic pigments, and dyes may be used. Moreover, you may use combining these. In addition, zinc oxide, aluminum oxide, magnesium oxide, aluminum nitride, silicon nitride, calcium titanate, and the like, which are usually white compounds used as fillers, may be used.
When the thermoplastic resin composition contains a colorant, the content is preferably 5 to 20 parts by mass when the total amount of the components [A] and [B] is 100 parts by mass. Preferably it is 5-15 mass parts, More preferably, it is 7-15 mass parts.

  Examples of the light stabilizer include hindered amine compounds and semicarbazone compounds. These can be used alone or in combination of two or more.

  Examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy}- 2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2,4-dione 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetrasuccinate Tilpiperidine polycondensate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino}, 2- (3,5-di-tert-butyl-4-hydroxybenzyl)- 2-n-butyl-bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 A condensate of 4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, 2,2, 6,6-tetramethyl Condensation product of 4-piperidinol and tridecyl alcohol, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, β, β, β ′ , Β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] undecane) diethanol, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] Undecane) condensate with diethanol, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, bis (1-octyloxy-2, 2,6,6-tetra Til-4-piperidyl) sebacate, 2- (3,5-di-tert-butyl-4-hydroxyphenyl) -2-n-butyl-bis (2,2,6,6-tetramethyl-4-piperidyl) Malonate, 2- (3,5-di-tert-butyl-4-hydroxyphenyl) -2-n-butyl-bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, 2- ( 3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butyl-bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, tetrakis (1,2,2,6 , 6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2-bis (3-oxo-2,2,6,6-tetramethyl-4-piperidyl) ethane, 1- (3,5 -Di-tert-butyl-4-hydroxyphenyl) -1,1-bis (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) pentane, poly [1-oxyethylene (2,2,6 , 6-tetramethyl-1,4-piperidyl) oxysuccinyl], poly [2- (1,1,4-trimethylbutylimino) -4,6-triazinediyl- (2,2,6,6-tetramethyl) -4-piperidyl) iminohexamethylene- (2,2,6,6-tetramethyl-4-piperidyl) imino], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N— And butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.

  Examples of semicarbazone compounds include 1,6-hexamethylenebis- (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylenedi-p-phenylene). Examples include disemicarbazide.

  When the thermoplastic resin composition contains a light stabilizer, the content is preferably 0.3 to 5 parts by mass, more preferably 0 when the amount of the thermoplastic resin is 100 parts by mass. 0.5-4 parts by mass, more preferably 0.5-2 parts by mass. When the light stabilizer is used in this range, a resin molded part that can maintain a high light reflectance over a long period of time can be obtained.

  Examples of the heat stabilizer include phosphite compounds, hindered phenol compounds, thioether compounds, and the like. These can be used alone or in combination of two or more.

  Examples of the phosphite compound include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis [2,4-bis ( 1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite Bis (nonylphenyl) pentaerythritol diphosphite, bisstearyl pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis ( 4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexylo) B) Phosphorus, tetra (tridecyl) -4,4′-butylidene-bis (2-tert-butyl-5-methylphenyl) diphosphite, hexatridecyl-1,1,3-tris (3-tert-butyl-6) -Methyl-4-oxyphenyl) -3-methylpropane triphosphite, mono (dinonylphenyl) mono-p-nonylphenyl phosphite, tris (monononylphenyl) phosphite, diphenylisodecyl phosphite, trisdecyl phosphite And triphenyl phosphite.

  Examples of hindered phenol compounds include 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3 -Tert-butyl-5-methyl-4-hydroxyphenyl) propionate], glycerol tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-diion -Tert-butyl-4-hydroxyphenyl) propionate], N, N -Hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [ [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, calcium diethylbis [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] Phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris 3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4- tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane.

  When the thermoplastic resin composition contains a thermal stabilizer, the content is preferably 0.3 to 5 parts by mass, more preferably 0 when the amount of the thermoplastic resin is 100 parts by mass. 0.5-4 parts by mass, more preferably 0.5-2 parts by mass. When the heat stabilizer is used in this range, a resin molded part that hardly undergoes discoloration, deterioration, etc. can be obtained even during processing and long-term use.

The transesterification inhibitor can be contained when a polyester resin is used as the thermoplastic resin. The transesterification inhibitor is not particularly limited, but a phosphoric acid compound having a PO bond is preferably used. Specific examples thereof include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid and pyrophosphoric acid, derivatives thereof, silyl phosphate, and the like.
When the thermoplastic resin composition contains a transesterification inhibitor, the content is preferably 0.01 to 5 parts by mass, more preferably when the amount of the thermoplastic resin is 100 parts by mass. It is 0.02-3 mass parts, More preferably, it is 0.03-1 mass part. When the transesterification inhibitor is used within this range, deterioration due to heat during molding processing is suppressed, and a resin molded part having excellent impact resistance, whiteness, and glossiness can be obtained.

  The thermoplastic resin composition is obtained by charging the above components [A], [B], additives, etc. into various extruders, Banbury mixers, kneaders, continuous kneaders, rolls, etc., and melt-kneading under heating. It is done.

  In the present invention, a metal member treated with a triazine-based compound is disposed inside a mold, and a thermoplastic resin composition in a molten state is injected into the cavity space, so that the surface of the metal member is A resin molded part is formed at least partially.

The metal member is obtained by treating the surface of a predetermined shape made of a metal or an alloy (hereinafter collectively referred to as “metal”) with a triazine compound. This metal includes copper (oxygen-free copper, etc.) and alloys containing it (brass, bronze, aluminum brass, etc.), aluminum and alloys containing it (aluminum alloy), nickel, chromium, titanium, iron, cobalt, tin, Zinc, palladium, silver, stainless steel, magnesium, manganese and the like can be mentioned. Among these, copper, a copper alloy, and aluminum are preferable from the viewpoint of welding strength. When these are used, the adhesive strength between the metal member and the resin molded portion is further improved.
The shape of the metal member may be a flat plate shape, a curved plate shape, a rod shape, a cylindrical shape, a lump shape, or the like, and may be a structure formed by a combination thereof. Moreover, you may have a through-hole, a bending part, etc. Furthermore, the surface shape of the metal member on which the resin molded portion is formed is not particularly limited, and examples thereof include a flat surface, a curved surface, an uneven surface, a corner portion, and a pointed portion. As described above, the resin molded portion may be formed on a part of the surface of the metal member or on the entire surface.

これらのうち、上記式（１０）〜（１７）で表されるトリアジンチオール系化合物が好ましい。 Examples of the triazine compound include compounds represented by the following formulas (10) to (20). These can be used alone or in combination of two or more.

Of these, triazine thiol compounds represented by the above formulas (10) to (17) are preferable.

A specific pretreatment method for the metal member is a solution of the triazine compound in an organic solvent such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, ethyl cellosolve, dimethylformamide, and tetrahydrofuran. This is an electrochemical surface treatment in which a metal member is used as an anode and a plate made of platinum, titanium, or carbon or the like is used as a cathode, thereby forming a film of the triazine compound. By adjusting the voltage and current, a metal member having a thickness of 10 to 1,000 mm is preferable.
The pretreatment using the triazine compound may be performed at least on the surface of the metal member that will form the resin molded portion.

In this invention, the composite body shown by FIGS. 1-23 can be manufactured, for example using said thermoplastic resin composition and metal members.
FIG. 1 is a schematic cross-sectional view showing a plate-shaped composite body 1, and is an aspect including a flat metal member 11 and a resin molded portion 12 formed on one surface side of the metal member 11. On the upper side of the resin molded portion 12 in this drawing, a convex portion, a concave portion, or the like may be formed.
FIG. 2 is a schematic cross-sectional view showing the plate-like composite 1, and a resin molding formed so as to cover the flat metal member 11, one surface side of the metal member 11, and the entire end surface. It is an aspect provided with the part 12. FIG. On the upper side of the resin molded portion 12 in this drawing, a convex portion, a concave portion, or the like may be formed.
FIG. 3 is a schematic cross-sectional view showing the plate-shaped composite body 1, two flat metal members 11, and a resin molded portion 12 formed so as to cover all end surfaces of the metal members 11. It is an aspect provided with. 3 is a disk or the like in which the metal member 11 has a through hole, and the resin molded portion 12 is formed on the portion embedded in the through hole and on the outer peripheral surface of the metal member 11. It can also be set as the aspect which consists of the made part.

FIG. 4 shows a flat metal member 11a, a resin molded part 12a having a recess 125 formed on one surface side of the metal member 11a, and the resin molded part 12a disposed on the upper surface in the drawing. It is a schematic sectional drawing which shows the composite_body | complex 1 provided with two made metal members 11b.
FIG. 5 shows a horizontal shape of a flat metal member 11a, a resin molded portion 12a having a concave portion 125 formed on one surface side of the metal member 11a, and a side wall in the concave portion 125 of the resin molded portion 12a. It is a schematic sectional drawing which shows the composite body 1 provided with the two metal members 11b arrange | positioned by penetrating in.
FIG. 6 shows a metal member 11c having a through hole in the vertical direction, a resin molded portion 12b embedded in the through hole, and a metal member 11b disposed through the resin molded portion 12b in the vertical direction. It is a schematic sectional drawing which shows the composite_body | complex 1 provided.
FIG. 7 shows a metal member 11c having a through hole in the vertical direction, a resin molded portion 12c embedded in the through hole and disposed on the upper surface in the drawing to form a continuous phase, and the embedded resin molded portion 12c. It is a schematic sectional drawing which shows the composite body 1 provided with the metal member 11c arrange | positioned by penetrating the part to the vertical direction.

FIG. 8 is a schematic cross-sectional view showing the composite body 1 including a flat metal member 11 and a resin molded portion 12 having a concave portion 125 formed on one surface side of the metal member 11.
FIG. 9 shows a plate-shaped metal member 11 and a concave portion 125 on the upper side formed so as to cover one surface side of the metal member 11, that is, the upper surface side of the metal member 11 and all the end surfaces. 2 is a schematic cross-sectional view showing the composite 1 in which the metal member 11 is disposed on the bottom surface of the recess 125 and all the inner wall surfaces of the resin molded portion 12.
FIG. 10 shows two flat metal members 11 and an upper side formed so as to cover one surface side of these metal members 11, that is, the upper surface side of the metal member 11 and all end surfaces. FIG. 2 is a schematic cross-sectional view showing the composite 1 in which the metal member 11 is provided on the lower side of the inner wall surface of the recess 125 in the resin molded portion 12. 10 is a ring-shaped body or the like in which the metal member 11 has a through-hole, and the metal member 11 is disposed below the inner wall surface of the recess 125 in the resin molded portion 12. It can also be set as an aspect.
FIG. 11 shows a flat metal member 11 and a concave portion 125 on the upper side formed so as to cover one surface side of the metal member 11, that is, the upper surface side of the metal member 11 and the entire end surface. FIG. 2 is a schematic cross-sectional view showing the composite body 1 in which the metal member 11 is disposed on the lower side of the bottom surface of the recess 125 in the resin molded portion 12.
FIG. 12 includes a flat metal member 11 and a resin molded portion 12 having a concave portion 125 formed on the upper side so as to embed the metal member 11, and the metal member 11 is formed by resin molding. FIG. 6 is a schematic cross-sectional view showing the composite 1 disposed on the bottom side of the recess 125 and the lower side of the inner wall surface in the portion 12. At least a part of the surface of the metal member 11 is exposed on the front side and / or the back side of the drawing.
FIG. 13 includes two flat metal members 11 and a resin molded portion 12 having a concave portion 125 formed on the upper side so as to embed these metal members 11. FIG. 3 is a schematic cross-sectional view showing the composite 1 disposed on the lower side of the inner wall surface of the recess 125 in the resin molded portion 12. 13 is a ring-shaped body or the like in which the metal member 11 has a through-hole, and the metal member 11 is buried below the inner wall surface of the recess 125 in the resin molded portion 12. It can also be. At least a part of the surface of the metal member 11 is exposed on the front side and / or the back side of the drawing.
FIG. 14 includes a flat metal member 11 and a resin molded portion 12 having a concave portion 125 formed on the upper side so as to embed the metal member 11, and the metal member 11 is formed by resin molding. FIG. 6 is a schematic cross-sectional view showing the composite body 1 embedded under the bottom surface of the recess 125 in the portion 12. At least a part of the surface of the metal member 11 is exposed on the front side and / or the back side of the drawing.
8 to 14, the shape of the recess 125 is shown as a step shape, but is not limited thereto, and may be a straight line or a curved line. The same applies to other drawings.

The composite body 1 in FIG. 15 further includes an aspect in which two metal members 11b are provided penetrating in the lateral direction through the side wall in the recess 125 of the resin molded portion 12 with respect to the aspect in FIG. It is a schematic sectional drawing shown.
The composite body 1 in FIG. 16 further includes an aspect in which two metal members 11b are provided penetrating in the lateral direction through the side wall in the concave portion 125 of the resin molded portion 12a with respect to the aspect in FIG. It is a schematic sectional drawing shown.
The composite body 1 in FIG. 17 further includes an aspect in which two metal members 11b are provided penetrating in the lateral direction through the side wall in the recess 125 of the resin molded portion 12a with respect to the aspect in FIG. It is a schematic sectional drawing shown.
The composite body 1 in FIG. 18 further includes an aspect in which two metal members 11b are provided penetrating in the lateral direction through the side wall in the recess 125 of the resin molded portion 12a with respect to the aspect in FIG. It is a schematic sectional drawing shown.

FIG. 19 has a concave portion 126, a circular or square flat plate-shaped resin molded portion 12d, and two metal members 11b disposed laterally penetrating the side wall in the concave portion 126 of the resin molded portion 12d. It is a schematic sectional drawing which shows an aspect provided with.
FIG. 20 shows a circular or square dish-shaped resin molded portion 12d having two concave portions 126, and two metal members 11b disposed penetrating laterally in the side walls of the concave portions 126 of the resin molded portion 12d. It is a schematic sectional drawing which shows an aspect provided with.
FIG. 21 is an example of a top view of the composite body 1 of FIGS. 19 and 20 in which the resin molding portion 12d is circular. As described above, the resin molded portion 12d may be rectangular.
FIG. 22 shows a mode in which a circular or square resin molded portion 12d having a concave portion 126 and two metal members 11b disposed vertically through a side wall in the concave portion 126 of the resin molded portion 12d are provided. It is a schematic sectional drawing shown.
FIG. 23 shows a planar or curved metal member 11e having a concave portion 126 and arranged so as to expose a circular or square flat plate-shaped resin molded portion 12d and the outer peripheral side of the resin molded portion 12d. It is a schematic sectional drawing which shows the aspect provided. 23, the metal member 11 is a cylinder or the like, and the metal member 11 is embedded in the resin molded portion 12d so as to be coaxial with the center of the recess 126 in the resin molded portion 12d. You can also

As a mold used for manufacturing the composite, a mold used for normal injection molding can be applied. Therefore, the structure of the mold and its constituent materials are not particularly limited.
The mold reciprocates for opening and closing for the purpose of, for example, taking out a molded product (composite) and a fixed mold provided with an inlet for injecting a molten thermoplastic resin composition and components therefor. A movable mold (see FIGS. 24 and 25). The fixed mold may be a combination of a plurality of molds as long as it achieves a predetermined purpose. In addition, the movable mold has a surface-treated metal member fixed inside, and when injecting the thermoplastic resin composition, the movable mold is closed at a pressure that can withstand the injection pressure (mold closing). Open to take out the molded product (composite) (open the mold). Further, the fixed mold and the movable mold may include a heating device, a cooling device, and the like.
The mold may be any of a two-plate mold, a sleep rate mold, and the like. Moreover, the constituent material of the mold is usually stainless steel, nickel, nickel alloy, aluminum, aluminum alloy, copper, copper alloy or the like.

An example of a mold used for manufacturing the composite is shown below.
The composite shown in FIG. 19 can be manufactured using the mold shown in FIG. The mold 3 in FIG. 24 has two concave portions (cavities) that are symmetrical to each other, and is usually a movable core type 31 and an inlet for introducing a molten thermoplastic resin composition. A cavity mold 32, which is normally a fixed mold, is formed by integrating a fixed mold 32a with a resin introduction port and a fixed mold 32b with a cavity having a cavity that forms a common space with the recess of the core mold 31. It is a schematic sectional drawing provided. In manufacturing the composite, in the mold 3, the molds are closed in a state where the end portions of the two metal members 11 are fitted in the recesses provided in the longitudinal direction in the core mold 31. The molten thermoplastic resin composition is injected (injected) into the cavity space 3.

  The resin temperature of the thermoplastic resin composition introduced into the mold is not particularly limited as long as it is in a molten state. It is selected according to the type of thermoplastic resin and is usually 230 ° C to 330 ° C. Moreover, the temperature of a metal mold | die is also not specifically limited, Preferably it is 40 to 150 degreeC. Further, the metal member may be heated in advance, but in the present invention, the thermoplastic resin composition can be injected without preheating.

A predetermined pressure can be applied for a certain period of time immediately after the thermoplastic resin composition is filled in the cavity space until the injected resin composition is solidified. The pressure (holding pressure, resin pressure) is preferably 50 to 150 MPa, more preferably 70 to 100 MPa.
After the resin molded portion corresponding to the shape of the cavity space is formed, the mold is cooled and opened in order, a metal member, and a resin molded portion formed on at least a part of the surface of the metal member, Can be obtained.
Since this composite has a structure in which both are chemically bonded via a triazine compound at the joint (joint surface) of the metal member and the resin molded part, high adhesion (adhesion) between the two. Is obtained. Further, in the above composite, when a thermal history is given, deformation and destruction of the resin molded part, separation of the resin molded part and the metal member, etc. are suppressed, heat resistance and heat dissipation (from the metal member) It is excellent in heat radiation, heat radiation from the resin molded part, and heat release to the low temperature part side of the metal member or resin molded part). Regardless of which part of the resin molded part or metal member is subjected to heat load, heat conduction to the other part is good, and heat is efficiently transferred to the outside without incurring defects such as deformation of the composite. Can escape.

It is preferable that this invention is a manufacturing method of the composite_body | complex of the following aspect.
(A) A plate-shaped LED mounting substrate comprising a metal member and a resin molded portion formed on at least one surface of the metal member.
As this aspect, it is illustrated by the composite 1 of FIGS. 1 to 3, when the LED element is disposed on the metal member 11 side, heat can be radiated not only from the metal member 11 but also from the resin molded portion 12 when the LED element emits light. When the LED element is disposed on the resin molded portion 12 side, heat can be radiated not only from the resin molded portion 12 but also from the metal member 11 when the LED element emits light.
In the LED mounting substrate of this aspect (a), the resin molded portion 12 may include a reflector portion having a concave cross-sectional shape in order to dispose the LED element on the inner bottom surface (with a reflector portion). LED mounting substrate (see FIGS. 8 to 14). By the inner wall surface of this reflector part, the light of the emitted LED element can be reflected and high brightness can be obtained. 8 to 11, when the LED element is disposed on the bottom surface of the recess 125 in the resin molding portion 12, not only the other parts of the resin molding portion 12 but also the metal when the LED element emits light. Heat can be released from the member 11. 12 to 14, when the LED element is disposed on the bottom surface of the recess 125 in the resin molded part 12, the LED element can be radiated mainly from the resin molded part 12 during light emission.

(B) As the metal member, one metal member is a heat radiating metal plate, the other metal member is a lead frame electrically connected to the LED element, and the heat radiating metal plate, A plate-like LED comprising the resin molded part formed on at least one surface of the heat radiating metal plate, and the lead frame being disposed on the surface and / or inside of the resin molded part Mounting board.
As this aspect, it is illustrated by the composite 1 of FIGS. The lead frame is indicated by a metal member 11b in the drawing. Although the LED elements are not shown in FIGS. 4 to 7, the LED elements are disposed on the bottom surface of the recess 125 in FIGS. 4 and 5. Moreover, in FIG.6 and FIG.7, an LED element is normally arrange | positioned between the two metal members 11b. In FIG. 7, the LED element may be disposed on the upper surface side (the surface of the resin member 12c) in the drawing, or may be disposed on the lower surface side (the surface of the metal member 11c).
4 and 5, when the LED element is disposed on the bottom surface of the recess 125, when the LED element emits light, the resin molded part 12 having excellent thermal conductivity is thermally conducted to the metal member 11a without thermal resistance. The metal member 11a can sufficiently dissipate heat. Heat can also be radiated by the metal member 11b which is a lead frame.
In FIG. 6, when the LED element is disposed, the metal member 11c can dissipate heat when the LED element emits light. Heat can also be radiated by the metal member 11b which is a lead frame.
In FIG. 7, when the LED element is disposed on the surface of the resin molded portion 12c, the resin molded portion 12c having excellent thermal conductivity is thermally conducted to the metal member 11c without thermal resistance when the LED element emits light. Heat can be radiated from the surface of the metal member 11c (the lower surface side of the metal member 11c in FIG. 7). Heat can also be radiated by the metal member 11b which is a lead frame.
Further, in FIG. 7, when the LED element is disposed on the surface of the metal member 11c (the lower surface side of the metal member 11c in FIG. 7), there is no thermal resistance from the metal member 11c when the LED element emits light. It is possible to conduct heat to the resin molding portion 12c and to dissipate heat by the resin molding portion 12c. Heat can also be radiated by the metal member 11b which is a lead frame.
In the LED mounting substrate of this aspect (b), the resin molded portion may include a reflector portion having a concave cross-sectional shape in order to dispose the LED element on the inner bottom surface (LED mounting with reflector portion). (See FIGS. 15 to 18). Since the resin molding part 12c is excellent also in the reflection characteristic with respect to light, the light of the emitted LED element can be reflected by the inner wall surface of this reflector part, and high brightness can be obtained. In the LED mounting substrate of FIGS. 15 to 18, when the LED element is disposed on the bottom surface of the recess 125 in the resin molding portion 12, not only the other parts of the resin molding portion 12 but also the metal when the LED element emits light. Heat can be dissipated from the member 11. Further, heat can be radiated by the metal member 11b which is a lead frame.

  In the above aspects (a) and (b), the LED mounting substrate may be provided with a concave portion, a convex portion, a through-hole, and the like according to the purpose and application.

(C) A metal member is disposed on the surface and / or inside of the resin molded portion, the metal member is a lead frame electrically connected to the LED element, and the LED element is A reflector for LED in which the cross-sectional shape of the resin molded portion is concave for placement.
As this aspect, it is illustrated by the composite 1 of FIGS. The lead frame is indicated by a metal member 11b in the drawing. Although the LED elements are not shown in FIGS. 19 to 22, the LED elements are disposed on the bottom surface of the recess 126.
19 to 22, when the LED element is disposed, the heat generated by the light emission of the LED element can be dissipated by the metal member 11b which is a lead frame. Moreover, since the resin molding part 12d is excellent also in the reflective characteristic with respect to light, the light of the emitted LED element can be reflected by the inner wall surface of this reflector, and high brightness can be obtained.

(D) The metal member is disposed on the surface and / or the inside of the resin molded portion, the metal member is a heat radiating member, and the resin molding is performed to dispose the LED element. Reflector for LED whose section shape is concave.
This embodiment is exemplified by the complex 1 in FIG. In FIG. 23, the lead frame is not used as a metal member, but is formed from above the drawing. Although LED elements are not shown, the LED elements are disposed on the bottom surface of the recess 126.
In FIG. 23, when the LED element is disposed, heat generated by light emission of the LED element can be dissipated by the metal member 11e. Moreover, since the resin molding part 12d is excellent also in the reflective characteristic with respect to light, the light of the emitted LED element can be reflected by the inner wall surface of this reflector, and high brightness can be obtained.

In addition, as an LED reflector having another structure, an embodiment including a metal member (lead frame) 11b and a substantially cylindrical resin molded portion 12e constituting the light emitting device 6 shown in FIG. 28, FIG. The aspect provided with the metal members (lead frame) 11b and the substantially cylindrical resin molding part 12f which comprise the light-emitting device 6 shown by these are mentioned.
The LED reflector in FIG. 28 may be obtained by combining the resin molded portion 12e and the metal substrate 11f.
Further, in the LED reflector in FIG. 29, the inner surface of the resin molded portion 12f is expanded upward in a taper shape in order to enhance the directivity of light from the LED element 51.

In the above aspects (c) and (d) and the other aspects described above, the LED reflector may include a concave portion, a convex portion, a through-hole, and the like depending on the purpose, application, and the like.
Further, in the LED reflectors of the above aspects (c) and (d), and the LED reflectors having the other structures described above, in particular, the whiteness of the inner surface of the recess 126 in the resin molded portion 12d corresponding to the main body is high. However, in order to obtain higher reflection characteristics, a light reflection layer may be formed on the inner wall surface. The thickness of the light reflecting layer is preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less, from the viewpoint of reducing thermal resistance.

1 to 18 are used as LED mounting substrates, or the composites shown in FIGS. 19 to 23 are used as LED reflectors. A light-emitting device having a structure can be formed. Schematic diagrams of the light emitting device are illustrated in FIGS.
The light emitting device 6 of FIG. 26 is obtained using the composite body (LED mounting substrate with a reflector portion) 1 shown in FIG. 15, and further connects the LED element 51, the LED element 51, and the lead frame 11b. A bonding wire 53 and a lens 55 are provided. In addition, the mounting method of LED element 51 is not specifically limited, Moreover, the part represented with the code | symbol 57 may be a transparent sealing part as mentioned later, and may be a space | gap part as needed. . The same applies to the following.
The light emitting device 6 of FIG. 27 is obtained using the composite body (LED mounting substrate with a reflector portion) 1 shown in FIG.
The light emitting device 6 of FIG. 28 includes a metal member (lead frame) 11b, another metal substrate 11f, a composite body (LED reflector) composed of a substantially cylindrical resin molded portion 12e, and a metal substrate 11f. An insulating pedestal 54 disposed on the surface, an LED element 51 disposed on the surface of the insulating pedestal 54, a bonding wire 53, and a lens 55 are provided.
In addition, the light emitting device 6 of FIG. 29 includes a resin substrate 4 having a recess, a metal member (lead frame) 11b disposed on the surface of the resin substrate 4, and a substantially cylindrical resin molded portion 12f. A composite body (LED reflector), an LED element 51 disposed on the concave surface of the resin substrate 4, a bonding wire 53, and a lens 55.

The LED element 51 emits radiated light (generally UV or blue light in a white light LED), for example, an active layer made of AlGaAs, AlGaInP, GaP, or GaN sandwiched between n-type and p-type cladding layers. A semiconductor chip (light emitter) having a double heterostructure, for example, has a hexahedral shape with a side length of about 0.5 mm.
Each of the light-emitting devices shown in FIGS. 26 to 29 is an example by wire bonding mounting, but the light-emitting device is not limited thereto. For example, the bonding wire 53 is not used, and the chip can be flip-chip mounted on a wiring pattern disposed near the LED element 51 via a bump.

In FIGS. 26 to 29, the part denoted by reference numeral 57 is a transparent sealing part or a gap part. This portion is usually a transparent sealing portion filled with a material that provides translucency and insulation, and in wire bonding mounting, a force applied by directly contacting the bonding wire 53 and indirectly applied. Prevents electrical problems caused by the bonding wire 53 being disconnected, cut, or short-circuited from the connection with the LED element 51 and / or the connection with the lead frame 11b due to vibration, impact, or the like. can do. At the same time, the LED element 51 can be protected from moisture, dust, etc., and the reliability can be maintained over a long period of time.
In addition, the said transparent sealing part 57 may also contain the inorganic type and / or organic type fluorescent substance which converts the wavelength of the light emitted from the LED element 51 into a predetermined wavelength as needed.

The material (transparent encapsulant composition) that imparts translucency and insulation usually contains silicone, epoxy silicone, epoxy resin, acrylic resin, polyimide resin, polycarbonate resin, and the like. Among these, silicone is particularly preferable from the viewpoints of heat resistance, weather resistance, low shrinkage, and discoloration resistance. Moreover, these components can be used individually by 1 type or in combination of 2 or more types. The transparent sealant composition is preferably a composition in which a curable component among the above components, a curing agent that cures the component, and a curing catalyst, if necessary, are blended.
The transparent sealant composition may contain a fluorescent substance, a reaction inhibitor, an antioxidant, a light stabilizer, a discoloration inhibitor, and the like.

The transparent sealant composition containing silicone will be described. Silicone may be either rubber or resin. The composition may be any of an addition reaction curable type, a condensation reaction curable type, a UV curable type, and the like, but an addition reaction curable composition is preferred in that it can be quickly cured. Of these, room temperature curable or heat curable compositions are preferred.
The addition reaction curable composition is preferably a composition in which silicone, a curing agent that cures the silicone, and a curing catalyst, if necessary, are blended. This composition is usually a composition comprising silicone having a functional group such as a vinyl group, a polymer having a Si-H bond in the molecule, and a curing catalyst (platinum catalyst, palladium catalyst, etc.). .

  Moreover, this invention can also be made into the manufacturing method of the composite_body | complex which is a screw, a pin, a nail | claw, a rib, a boss | hub, etc. In the case of such a composite body, structural parts, exterior parts (such as industrial control equipment, household appliances, mobile phones, portable electronic information terminal communication equipment, medical equipment, vehicle electronic equipment, etc.) It is suitable as a housing or the like.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the examples, parts and% are based on mass unless otherwise specified.

1. Raw material components of thermoplastic resin composition The raw material components used for the preparation of the composition are shown below.
1-1. Thermoplastic resin polyphenylene sulfide (A1)
“Fortron 0220A9” (trade name) manufactured by Polyplastics was used. Linear type structure.
(2) Polyamide 4, 6 (A2)
“Stanyl TS300” (trade name) manufactured by DSM Japan was used. The melting point is 295 ° C.
(3) Copolymerized polybutylene terephthalate (A3)
“NOVADURAN 5505S” (trade name) manufactured by Mitsubishi Engineering Plastics was used. This resin is a modified PBT resin that is a copolymer of dimethyl terephthalate, 1,4-butanediol and polytetramethylene glycol, and is known as a modified PBT imparted with flexibility. The glass transition temperature is 27 ° C.
(4) Polybutylene terephthalate (A4)
“NOVADURAN 5020” (trade name) manufactured by Mitsubishi Engineering Plastics was used. The glass transition temperature is 27 ° C.
(5) ABS resin (A5)
“TECHNO ABS 330” (trade name) manufactured by Techno Polymer Co., Ltd. was used.
(6) Modified polyamide 6, T (A6)
“Aren AE4200” (trade name) manufactured by Mitsui Chemicals, Inc. was used. The melting point is 320 ° C.

1-2. Boron nitride (1) B1
“Denkaboron nitride powder SGP” (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd. was used. It has a hexagonal structure, a specific surface area of 2 m ² / g, a tap density of 0.8 g / cm ³ , and a volume average particle size by liquid phase precipitation of 16.6 μm. The particle diameters D ₁₀ and D ₉₀ when the cumulative volume obtained by measuring the particle size distribution is 10% and 90% are 5.4 μm and 41.6 μm, respectively (D ₉₀ / D ₁₀ = 7 7).
(2) B2
“Denkaboron nitride powder GP” (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd. was used. It has a hexagonal structure, a specific surface area of 8 m ² / g, a tap density of 0.5 g / cm ³ , and a volume average particle size by liquid phase precipitation method of 6.2 μm. The particle diameters D ₁₀ and D ₉₀ are 3.2 μm and 17.1 μm, respectively (D ₉₀ / D ₁₀ = 5.3).
(3) B3
“PT120” (trade name) manufactured by GE Advanced Material was used. It has a hexagonal structure, a specific surface area of 3.47 m ² / g, a tap density of 0.370 g / cm ³ , and a volume average particle size by liquid phase precipitation method of 8 μm. The particle diameters D ₁₀ and D ₉₀ are 6.7 μm and 24.4 μm, respectively (D ₉₀ / D ₁₀ = 3.6).

1-3. Magnesium oxide “A-10” (trade name) manufactured by Kamishima Chemical Co., Ltd. was used.
1-4. Colorant Titanium oxide “Taipaque PF691” (trade name) manufactured by Ishihara Sangyo Co., Ltd. was used.
1-5. Filler A chopped strand glass fiber “Microglass RES03-TP89Z” (trade name) manufactured by Nippon Sheet Glass Co., Ltd. was used.

1-6. Light stabilizer 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] undecane) A condensate with diethanol (trade name “Adekastab LA-63P”, manufactured by ADEKA) was used.
1-7. Thermal stabilizer 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10- Tetraoxaspiro [5,5] undecane (trade name “ADEKA STAB AO-80”, manufactured by ADEKA) was used.

2. Preparation and Evaluation of Thermoplastic Resin Composition The thermoplastic resin composition used in the production of the composite is prepared by mixing the above raw material components with a Henschel mixer based on the blending ratios shown in Tables 1 to 4. It was melt-kneaded using a shaft extruder to obtain pellets. The cylinder temperature in the twin-screw extruder was 280 ° C. to 330 ° C. in Examples 1-1 to 1-11, 240 ° C. to 265 ° C. in Examples 1-12 and 1-13, and Examples 1-14 to 1 -18 to 300 ° C to 340 ° C, Comparative Example 1-1 to 200 ° C to 230 ° C, Comparative Examples 1-2 to 1-5 to 280 ° C to 330 ° C, Comparative Example 1-6 to 240 ° C to 265 ° C, Comparison It is 240 degreeC-265 degreeC in Example 1-7.

Each composition was evaluated as follows. The results are shown in Tables 1 to 4.
2-1. Thermal emissivity Using pellets made of a thermoplastic resin composition, a test piece having a size of 150 × 150 × 3 mm was prepared by injection molding, and a thermo spot sensor “TSS-5X” (model name) manufactured by Japan Sensors was used. The measurement was performed at an ambient temperature of 25 ° C. by a reflection energy measurement method using infrared detection. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 1-1 to 1-11, 40 to 80 degreeC in Examples 1-12 and 1-13, and Example 1-14. 120 to 170 ° C. in Comparative Example 1-1, 40 ° C. to 60 ° C. in Comparative Example 1-1, 90 ° C. to 150 ° C. in Comparative Examples 1-2 to 1-5, and 40 ° C. to 80 ° C. in Comparative Example 1-6 In Comparative Example 1-7, the temperature is 90 ° C to 150 ° C.
2-2. Thermal conductivity Using pellets made of a thermoplastic resin composition, the melt is injected from below a mold having a cavity space with a diameter of 10 mm and a length of 50 mm to produce a cylinder having a diameter of 10 mm and a length of 50 mm. did. The temperature of the mold is 90 ° C. to 150 ° C. in Examples 1-1 to 1-11, 40 ° C. to 80 ° C. in Examples 1-12 and 1-13, and Examples 1-14 to 1-18. 120 ° C. to 170 ° C., Comparative Example 1-1 at 40 ° C. to 60 ° C., Comparative Examples 1-2 to 1-5 at 90 ° C. to 150 ° C., Comparative Example 1-6 at 40 ° C. to 80 ° C., Comparative Example 1 It is 90 degreeC-150 degreeC in -7.
Then, it cut out so that it might become a disk with a thickness of 1.5 mm in the substantially central part, and this was made into the test piece (diameter 10mm and thickness 1.5mm). In order to measure the thermal conductivity with respect to the flow direction of the thermoplastic resin composition, a probe is applied to each of the upper surface and the lower surface of the test piece, and a laser flash method thermal constant measuring device “TR-” manufactured by ULVAC-RIKO Inc. 7000R "(model name) and measured at 25 ° C.
2-3. Thermal deformation temperature Measured under conditions of a load of 1.80 MPa according to ISO75.
2-4. Blister resistance A test piece having a size of 127 × 12.7 × 0.8 mm was prepared by injection molding, immersed in water at a temperature of 23 ° C. for 24 hours, and the test piece after immersion was made into glass having a thickness of 1.6 mm. Fixed to an epoxy substrate. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 1-1 to 1-11, 40 to 80 degreeC in Examples 1-12 and 1-13, and Example 1-14. 120 to 170 ° C. in Comparative Example 1-1, 40 ° C. to 60 ° C. in Comparative Example 1-1, 90 ° C. to 150 ° C. in Comparative Examples 1-2 to 1-5, and 40 ° C. to 80 ° C. in Comparative Example 1-6 In Comparative Example 1-7, the temperature is 90 ° C to 150 ° C.
Thereafter, this integrated product was subjected to conditions such that the temperature of the preheating portion was 150 ° C. ± 3 ° C., the passage time was 120 seconds, the maximum temperature of the reflow portion was 230 ° C. ± 3 ° C., and the passage time was 60 seconds. Was passed through a desktop far-infrared reflow furnace set to 1. And the surface of the test piece was visually observed, and the blister resistance was determined according to the following criteria.
○: No change was observed on the surface of the test piece.
X: Swelled and discolored on the surface of the test piece.
Further, as the passage conditions in the reflow furnace, the blister resistance when the maximum temperature was 260 ° C. ± 3 ° C. and the passage time was 10 seconds was also evaluated in the same manner as described above.
2-5. Charpy impact strength Charpy impact strength (Edgewise Impact, with notch) at room temperature was measured according to ISO179. The measurement conditions are as follows.
Specimen type: Type 1
Notch type: Type A
Load: 2J
2-6. Surface specific resistance Using a pellet made of a thermoplastic resin composition, a circular test piece having a diameter of 200 mm and a thickness of 2 mm was prepared by injection molding, and a high resistance meter “4339B” (model name) manufactured by Agilent Technologies was used. And measured. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 1-1 to 1-11, 40 to 80 degreeC in Examples 1-12 and 1-13, and Example 1-14. 120 to 170 ° C. in Comparative Example 1-1, 40 ° C. to 60 ° C. in Comparative Example 1-1, 90 ° C. to 150 ° C. in Comparative Examples 1-2 to 1-5, and 40 ° C. to 80 ° C. in Comparative Example 1-6 In Comparative Example 1-7, the temperature is 90 ° C to 150 ° C.
2-7. Light reflectance With respect to the test piece used for the measurement of the thermal conductivity, the reflectance with respect to ultraviolet rays (wavelength 460 nm) was incident on an ultraviolet-visible near-infrared spectrophotometer “V-670” (model name) manufactured by JASCO Corporation. Measurements were made at an angle of 60 degrees.
In addition, using a UV long life fade meter “FAL-5H • B” (model name) manufactured by Suga Test Instruments Co., Ltd., the test piece used for the measurement of the thermal conductivity was 135 V, 16 A, temperature 83 ° C., rain Exposure (light irradiation) was performed for 400 hours under the condition of no. The light reflectance of this exposed test piece was also measured in the same manner as described above.
2-8. Water absorption rate Using a pellet made of a thermoplastic resin composition, a circular test piece having a diameter of 50 mm and a thickness of 3.2 mm was prepared by injection molding, and immersed in water at a temperature of 23 ° C. for 24 hours in an absolutely dry state. The amount of weight change before and after immersion was calculated, and the increased amount was defined as the water absorption rate. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 1-1 to 1-11, 40 to 80 degreeC in Examples 1-12 and 1-13, and Example 1-14. 120 to 170 ° C. in Comparative Example 1-1, 40 ° C. to 60 ° C. in Comparative Example 1-1, 90 ° C. to 150 ° C. in Comparative Examples 1-2 to 1-5, and 40 ° C. to 80 ° C. in Comparative Example 1-6 In Comparative Example 1-7, the temperature is 90 ° C to 150 ° C.
2-9. Dielectric breakdown characteristics A test piece of size 100 × 100 × 1 mm produced by injection molding is left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and a relative humidity of 62% for 48 hours, and then conforms to ASTM D149. The dielectric breakdown characteristics were measured. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 1-1 to 1-11, 40 to 80 degreeC in Examples 1-12 and 1-13, and Example 1-14. 120 to 170 ° C. in Comparative Example 1-1, 40 ° C. to 60 ° C. in Comparative Example 1-1, 90 ° C. to 150 ° C. in Comparative Examples 1-2 to 1-5, and 40 ° C. to 80 ° C. in Comparative Example 1-6 In Comparative Example 1-7, the temperature is 90 ° C to 150 ° C.

3. Manufacture and evaluation of composites As metallic members used in the manufacture of composites, a copper plate having a width of 1.2 cm, a length of 5.0 cm and a thickness of 0.1 cm was previously described in JP-A-2-298284. What gave the surface treatment (triazine treatment) by the method was used.

Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-7
As shown in FIG. 25, the copper plate is placed inside a mold placed on an injection molding machine “EC40N” (model name) manufactured by Toshiba Machine Co., Ltd., and based on the blending ratios shown in Tables 1 to 4. The melt of each pellet (thermoplastic resin composition) obtained in this manner was injected at a holding pressure (resin pressure) of 70 MPa into the cavity space of the mold to produce a test specimen (composite) for evaluation shown in FIG. did. The resin molded portion has a width of 1.2 cm, a length of 5.0 cm, and a thickness of 0.3 cm, and an adhesion area of 1.2 cm in width and 1.2 cm in length. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 1-1 to 1-11, 40 to 80 degreeC in Examples 1-12 and 1-13, and Example 1-14. 120 to 170 ° C. in Comparative Example 1-1, 40 ° C. to 60 ° C. in Comparative Example 1-1, 90 ° C. to 150 ° C. in Comparative Examples 1-2 to 1-5, and 40 ° C. to 80 ° C. in Comparative Example 1-6 In Comparative Example 1-7, the temperature is 90 ° C to 150 ° C.

The following evaluation was performed about the obtained test piece for evaluation (composite). The results are shown in Tables 1 to 4.
(1) Adhesion stability test between metal member and resin molded part Using a precision universal testing machine “Autograph AG5000E” (trade name) manufactured by Shimadzu Corporation, about 5 test pieces at a tensile speed of 50 cm / min. The adhesive strength was measured. At that time, the fracture mode was visually observed, and the adhesion stability was evaluated according to the following criteria. “Material destruction” means that the resin molded part is destroyed in a state where the metal member and the resin molded part are bonded, and “interface failure” means that the interface between the metal member and the resin molded part is bonded. It is to peel off.
○: The failure mode of all 5 is material failure, and there is no variation in the adhesive strength.
X: Two or more of the five, and the fracture mode is interface fracture on the bonded surface.

(2) Thermal conductivity test For the above evaluation using a support stand and a resin clamp at the center of a room (25 ° C) made of an acrylic resin transparent plate with a height, width and height of 1 m. A test piece (composite) was placed (FIGS. 31 and 32), and a voltage was applied using the silicone rubber heater 7 to measure the temperature distribution. Specifically, the end of the copper plate 111 in the test piece was covered with a silicone rubber heater 7 (13 × 50 × 1.7 mm), and a voltage of 15 V (12 W) was applied. Then, after leaving for 15 minutes and the temperature reaches equilibrium, the central portion of the surface of the silicone rubber heater 7 that is in contact with the copper plate 111, and a resin plate (resin molding portion) 121 that is 70 mm away from the central portion, Each temperature was measured by thermography from the front side of FIG. 31 (measurement points are indicated as T1 and T2 in FIG. 32, respectively).

From Tables 1 to 4, the following is clear.
Comparative Example 1-1 is an example in which an ABS resin that is outside the scope of the present invention is used as a thermoplastic resin, and although excellent in impact resistance, the heat resistance and dielectric breakdown characteristics are not sufficient, Inferior in adhesion to copper plate. Comparative Example 1-2 is an example that does not contain boron nitride, and is excellent in impact resistance but has insufficient heat dissipation, thermal conductivity, and dielectric breakdown characteristics. In the thermal conductivity test of the composite, the temperature at T1 is 79 ° C., the temperature at T2 is 27 ° C., the difference is as large as 52 ° C., and it is difficult for heat to be transferred from the copper plate to the resin molded portion. It is inferior in heat dissipation from the part. Comparative example 1-3 is the example which produced the composite_body | complex using the copper plate which did not perform the surface treatment by a triazine type compound using polyphenylene sulfide as a thermoplastic resin, and did not adhere | attach with a resin molding part and a copper plate. . Therefore, in the thermal conductivity test of the composite, the copper plate and the resin plate are fixed with a rubber band for evaluation, and heat is not sufficiently dissipated in the resin molded portion. Since the difference is as large as 53 ° C. and heat is not easily transmitted from the copper plate to the resin molded portion, the heat dissipation from the resin molded portion is inferior. Comparative Example 1-4 is an example in which the content ratio of boron nitride relative to the thermoplastic resin is small and is outside the scope of the present invention, the thermal conductivity is not sufficient, and the temperature at T1 in the thermal conductivity test of the composite is 75 ° C., the temperature at T2 is 27 ° C., the difference is as large as 47 ° C., and it is difficult for heat to be transferred from the copper plate to the resin molded portion, so the heat dissipation from the resin molded portion is inferior. Comparative Example 1-5 is an example in which the content of boron nitride relative to the thermoplastic resin is large and is outside the scope of the present invention, and the impact resistance is poor. Comparative example 1-6 is the example which produced the composite_body | complex using the copper plate which has not surface-treated with a triazine type compound using polytetramethylene adipamide as a thermoplastic resin, a resin molding part, a copper plate, It did not adhere. Therefore, in the thermal conductivity test of the composite, the copper plate and the resin plate are evaluated by fixing with rubber bands, and heat is not sufficiently dissipated in the resin molded portion, the temperature at T1 is 81 ° C., and the temperature at T2 is 26 ° C. Since the difference is as large as 55 ° C. and heat is not easily transmitted from the copper plate to the resin molded part, the heat dissipation from the resin molded part is inferior. In addition, Comparative Example 1-7 was an example using magnesium oxide instead of boron nitride, and the thermal emissivity, thermal conductivity, and impact resistance were not sufficient. In the thermal conductivity test of the composite, heat is not sufficiently dissipated in the resin molded portion, the temperature at T1 is 75 ° C., the temperature at T2 is 27 ° C., and the difference is as large as 48 ° C. Since heat is not easily transmitted to the molded part, heat dissipation from the resin molded part is inferior.
On the other hand, Examples 1-1 to 1-13 are excellent in heat dissipation, thermal conductivity, heat resistance, blister resistance, impact resistance, and light reflection characteristics. In addition, as a composite, the fracture mode is material destruction, and since the resin molded part and the copper plate have excellent adhesion stability, thermal conduction from the copper plate to the resin molded part is sufficient even in the thermal conductivity test. The temperature at T1 is 65 ° C to 73 ° C, the temperature at T2 is 28 ° C to 45 ° C, the temperature difference between T1 and T2 is small, and excellent thermal conductivity from the copper plate to the resin molded part, Excellent heat dissipation as a composite. In particular, Examples 1-4 to 1-7, in which polyphenylene sulfide and polytetramethylene adipamide were used as the thermoplastic resin, had a balance of heat resistance, impact resistance, heat dissipation, and light reflection characteristics. Excellent, in particular, Examples 1-5 to 1-7 are particularly excellent in blister resistance.
Examples 1-14 to 1-18 are examples using a resin composition containing polyamide 6, T, which is an aromatic polyamide resin, and are not only more excellent in the balance between thermal conductivity and Charpy impact strength. The light reflectance after the light resistance test was also excellent.

4). Production of LED Reflector Example 2-1
Two long copper plates (corresponding to a lead frame) were prepared, and surface treatment (triazine treatment) was performed in advance in the same manner as described above by the method described in JP-A-2-298284.
The mold which has the cavity space of the metal mold | die (refer FIG. 24) which melt | dissolved the pellet which consists of a thermoplastic resin composition of Example 1-1 at 310 degreeC, and has arrange | positioned the said elongate copper plate inside. (Mold temperature: 90 ° C. to 150 ° C.) to obtain a reflector for LED as shown in FIG.

Examples 2-2 to 2-18
Each pellet made of the thermoplastic resin composition of Examples 1-2 to 1-18 was melted at a temperature based on the “melting temperature of the resin composition at the time of producing the composite” described in Tables 1 to 3, and gold An LED reflector as shown in FIG. 19 was obtained in the same manner as in Example 2-1, except that the mold temperature was as follows. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 2-2 to 2-11, 40 to 80 degreeC in Examples 2-12 and 2-13, and Example 2-14. It is 120 degreeC-170 degreeC in ~ 2-18.

Comparative Examples 2-1 to 2-7
Each pellet made of the thermoplastic resin composition of Comparative Examples 1-1 to 1-7 was melted at a temperature based on the “melting temperature of the resin composition at the time of producing the composite” described in Table 4, and the mold temperature was Except for the following, an LED reflector as shown in FIG. 19 was obtained in the same manner as in Example 2-1. The temperature of the mold used for injection molding was 40 ° C. to 60 ° C. in Comparative Example 2-1, 90 ° C. to 150 ° C. in Comparative Examples 2-2 to 2-5, and 40 ° C. in Comparative Example 2-6. 80 ° C. and 90 ° C. to 150 ° C. in Comparative Example 2-7.

5. Production of LED mounting substrate Example 3-1
A flat copper plate (7 × 7 × 1 mm) was prepared, and surface treatment (triazine treatment) was performed in advance in the same manner as described above by the method described in JP-A-2-298284.
The mold which has the cavity space of the metal mold | die (not shown) which melt | dissolved the pellet which consists of a thermoplastic resin composition of Example 1-1 at 310 degreeC, and has arrange | positioned the said elongate copper plate inside. (Die temperature: 90 ° C. to 150 ° C.) to obtain an LED mounting substrate on which an LED element as shown in FIG. 18 can be mounted.

Examples 3-2 to 3-18
Each pellet made of the thermoplastic resin composition of Examples 1-2 to 1-18 was melted at a temperature based on the “melting temperature of the resin composition at the time of producing the composite” described in Tables 1 to 3, and gold An LED mounting substrate as shown in FIG. 18 was obtained in the same manner as in Example 3-1, except that the mold temperature was as follows. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 3-2 to 3-11, 40 to 80 degreeC in Examples 3-12 and 3-13, Example 3-14. It is 120 degreeC-170 degreeC in ~ 3-18.

Comparative Examples 3-1 to 3-7
Each pellet made of the thermoplastic resin composition of Comparative Examples 1-1 to 1-7 was melted at a temperature based on the “melting temperature of the resin composition at the time of producing the composite” described in Table 4, and the mold temperature was Except as described below, an LED mounting substrate as shown in FIG. 18 was obtained in the same manner as in Example 3-1. The temperature of the mold used for injection molding was 40 ° C. to 60 ° C. in Comparative Example 3-1, 90 ° C. to 150 ° C. in Comparative Examples 3-2 to 3-5, and 40 ° C. in Comparative Example 3-6. 80 ° C. and 90 ° C. to 150 ° C. in Comparative Example 3-7.

  The method for producing a composite according to the present invention is suitable as a method for obtaining a composite in which a metal member and a resin member are integrated with excellent adhesiveness. Formation of a light-emitting device including an LED element, and the like , Industrial control equipment, household appliances, mobile phones, portable electronic information terminals and other communication equipment, medical equipment, automotive electronic equipment, etc., structural parts, exterior parts, etc. It is suitable for the manufacture of products, parts, etc. that have resin molded parts such as screws, pins, claws, ribs, and bosses on the surface or inner surface.

It is a schematic sectional drawing which shows an example of the composite_body | complex (LED mounting board | substrate) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (substrate for LED mounting with a reflector part) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (LED reflector) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (LED reflector) manufactured by this invention. It is a top view of the composite_body | complex (LED reflector) represented by FIG.19 and FIG.20. It is a schematic sectional drawing which shows the other example of the composite_body | complex (LED reflector) manufactured by this invention. It is a schematic sectional drawing which shows the other example of the composite_body | complex (LED reflector) manufactured by this invention. It is a schematic sectional drawing which shows the metal mold | die used in order to manufacture the composite_body | complex represented by FIG. It is a schematic sectional drawing which shows the metal mold | die used for manufacture of the test piece for evaluation (composite) in an Example. It is a schematic sectional drawing which shows an example of a light-emitting device. It is a schematic sectional drawing which shows the other example of a light-emitting device. It is a schematic sectional drawing which shows the other example of a light-emitting device. It is a schematic sectional drawing which shows the other example of a light-emitting device. It is a perspective view which shows the test piece for evaluation (composite body) manufactured in the Example. It is a schematic perspective view which shows the thermal conductivity evaluation apparatus in an Example. It is a schematic explanatory drawing which shows the test body used for thermal conductivity evaluation in an Example.

Explanation of symbols

1: Composite 11: Metal member (substrate or heat sink)
11a: Metal member (substrate or heat sink)
11b: Metal member (lead frame)
11c: Metal member (substrate or heat sink)
11e: Metal member (reinforcing material or heat sink)
11f: Metal member (substrate or heat sink)
111: Copper plate 12: Resin molding part (insulating part)
12a: Resin molding part (insulating part)
12b: Resin molded part (insulating part)
12c: Resin molded part (insulating part)
12d: Resin molding part (reflector part)
12e: Resin molding part (reflector part)
12f: Resin molded part (reflector part)
121: Resin plate 125: Recessed portion 126: Recessed portion 3: Mold 31: Core die 32: Cavity die 32a: Fixed die with resin inlet 32b: Fixed die with cavity 4: Resin substrate 51: LED element 53: Wire bonding 54 : Insulating base 55: Lens 57: Transparent sealing part (or gap part)
6: Light emitting device 7: Silicone rubber heater

Claims (15)

  A metal member surface-treated with a triazine compound is placed inside the mold, and [A] a thioether bond, an amide bond, an ester bond and an ether bond are formed on at least a part of the surface of the metal member. Thermoplastic containing 15-80% by mass of thermoplastic resin containing at least one selected bond and 20-85% by mass of [B] boron nitride (where [A] + [B] = 100% by mass) A method for producing a composite, comprising forming a resin molded part made of a resin composition by an injection molding method.   The method for producing a composite according to claim 1, wherein the thermoplastic resin [A] is polyphenylene sulfide.   The method for producing a composite according to claim 1, wherein the thermoplastic resin [A] is a polyamide resin having a melting point in the range of 250C to 400C.   When the thermoplastic resin [A] is composed of polyphenylene sulfide and a polyamide resin having a melting point in the range of 250 ° C. to 400 ° C., and the content ratio of these is 100% by mass, respectively, It is 40-90 mass% and 60-10 mass%, The manufacturing method of the composite_body | complex of Claim 1.   The manufacturing method of the composite_body | complex of Claim 3 or 4 in which the said polyamide resin contains an aromatic polyamide resin.   The manufacturing method of the composite_body | complex of Claim 5 in which the said aromatic polyamide resin contains a hexamethylene terephthalamide unit. The boron nitride [B], the particle diameter _{D 10} and _{D 90} when the cumulative volume obtained by the measurement of the particle size distribution is 10% and 90%, respectively, and the 4~6μm and 35～50Myuemu, and the method of producing a composite body according to any one of claims 1 to 6 ratio _D 90 _{/ D 10} of _{D 10} and _{D 90} of 7 to 11.   The method for producing a composite according to any one of claims 1 to 7, wherein the boron nitride [B] has a volume average particle diameter of 12 to 20 µm.   The said composite body is a plate-shaped LED mounting substrate provided with the said metal member and the said resin molding part formed in the at least one surface of this metal member. The manufacturing method of the composite_body | complex described.   In the composite, as the metal member, one metal member is a heat-dissipating metal plate, the other metal member is a lead frame electrically connected to the LED element, and the heat-dissipating metal A plate comprising the plate and the resin molded portion formed on at least one surface of the heat radiating metal plate, and the lead frame is disposed on the surface and / or inside the resin molded portion. A method for producing a composite according to any one of claims 1 to 8, wherein the composite substrate is an LED mounting substrate.   11. The method for manufacturing a composite according to claim 9, wherein in the LED mounting substrate, the resin molded portion includes a reflector portion having a concave cross-sectional shape for disposing the LED element. The composite is a reflector for LED in which the metal member is disposed on the surface and / or inside of the resin molded part,
The said metal member is a lead frame electrically connected to an LED element, and the cross-sectional shape of the said resin molding part is concave shape in order to arrange | position the said LED element. A method for producing the composite according to 1. The composite is a reflector for LED in which the metal member is disposed on the surface and / or inside of the resin molded part,
The method for producing a composite according to any one of claims 1 to 8, wherein the metal member is a heat radiating member, and the cross-sectional shape of the resin molded portion is concave in order to dispose the LED element. .   An LED mounting substrate obtained by the method for producing a composite according to claim 9.   An LED reflector obtained by the method for producing a composite according to claim 12.

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