JP2009185102A - Thermoplastic resin composition used for manufacture of composite consisting of resin- and metal-made members - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition, which, in the method of manufacturing a composite by arranging a metal-made member whose surface is treated with a triazine compound in the inside of a mold and by forming a resin molding part by an injection molding method on at least part of the surface of the metal-made member, can efficiently form the resin molding part having high adhesiveness for the metal-made member, which restrains deformation and failure of the resin molding part and separation of the resin molding part and the metal-made member when heat history is accompanied, and which makes the composite excellent in the balance of heat resistance, heat radiation properties, impact resistance, water resistance, insulation and reflective characteristics to light. <P>SOLUTION: The thermoplastic resin composition contains [A] a thermoplastic resin consisting of 40-90 mass% of a polyarylene sulfide and 10-60 mass% of a polytetramethylene adipamide and [B] boron nitride. The proportion of the component [A] and that of the component [B] are 15-80 mass% and 20-85 mass%, respectively, when the total of both is 100 mass%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition used for producing a composite made of a resin member and a metal member. More specifically, a resin molded part (resin member) can be efficiently formed by injection molding on at least part of the surface of a metal member surface-treated with a triazine compound, and the resulting composite The present invention relates to a thermoplastic resin composition having an excellent balance among heat resistance, heat dissipation, impact resistance, low water absorption, insulation, and light reflection characteristics. The thermoplastic resin composition of the present invention is used for forming light-emitting related members, heat generating related members, etc., such as LED mounting substrates and LED reflectors.

In LED-related articles such as lighting devices including LED elements, composites composed of resin members and metal members are configured in various shapes from the viewpoints of heat dissipation, light reflection characteristics, lightness, and the like.
For example, Patent Document 1 discloses an LED device, which includes a lead frame, a resin cup portion made of a nylon resin, a liquid crystal polymer resin, a thermosetting resin, or a silicone resin, A stainless steel cone-shaped metal member disposed on the inner surface of the resin cup portion away from the lead frame. And this LED device preliminarily performs surface processing such as shot blasting and etching on the cone-shaped metal member, then insert mold processing, and the resin cup portion, the lead frame and the cone-shaped metal member Are integrated.
Patent Document 2 discloses a polyamide resin composition for forming a reflector for LED. This composition comprises 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 reinforcing agent composed of a fibrous filler and / or an acicular filler. This document describes that this composition can be combined with a molded body made of metal or the like.
Furthermore, Patent Document 3 contains polyphenylene sulfide, which is useful for lamp reflectors (reflecting mirrors for lighting devices), and synthetic inorganic fillers that are not surface-treated (carbonates, sulfates, silicates, silicic acids, etc.). A resin composition is disclosed.
Patent Document 4 discloses polyphenylene sulfide, fatty acid ester, polyolefin, and fillers (carbonate, sulfate, silicate) that are useful for light reflection molded articles such as lamp reflectors (reflectors for lighting devices). , Silicic acid and the like) are disclosed.

JP 2007-300018 A JP 2006-257314 A JP 2001-98151 A JP 2004-91685 A

According to the technique disclosed in Patent Document 1, a minute gap may be 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 dissipation is not sufficient, separation (peeling) of members, and the resin cup portion It could lead to deformation or destruction.
The same applies to the technique disclosed in Patent Document 2, and as the use of the LED device is repeated, the reflector for LED 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.
In addition, according to the resin compositions disclosed in Patent Documents 3 and 4, water absorption in the resin molded portion can be suppressed, and the resulting composite is used as an LED mounting substrate, and a surface mounting component or the like is used as a reflow furnace. However, there is a problem that the impact resistance is not sufficient, although the occurrence of blisters (blowing) and the like can be suppressed.
The present invention is suitable for forming light emitting related members, heat generating related members and the like, and can efficiently form a resin-molded portion having high adhesion to a metal member when accompanied by a thermal history. The balance between heat resistance, heat dissipation, impact resistance, low water absorption, insulation, and light reflection properties is suppressed, deformation and destruction of the resin molded part, separation of the resin molded part and metal member, etc. An object of the present invention is to provide a thermoplastic resin composition capable of efficiently producing a composite having excellent resistance.

  The inventors arrange a metal member surface-treated with a triazine-based compound inside the mold, and form a resin molded portion on at least a part of the surface of the metal member by an injection molding method. In the method for producing a composite, a thermoplastic resin composition containing a specific thermoplastic resin and boron nitride is injected into the cavity space in a molten state, thereby having high adhesion to a metal member. The resin molded part (resin member) can be efficiently formed, and when accompanied by a thermal history, deformation and destruction of the resin molded part, separation of the resin molded part and metal member, etc. are suppressed, heat resistance, The present inventors have found that a composite having excellent balance among heat dissipation, impact resistance, low water absorption, insulation, and reflection characteristics with respect to light can be efficiently produced, and the present invention has been completed.

That is, the present invention is as follows.
1. A metal member surface-treated with a triazine compound is placed inside the mold, and a resin molded part is formed on at least a part of the surface of the metal member by injection molding to produce a composite. A thermoplastic resin composition used for forming the resin molded part, comprising [A] polyarylene sulfide and polytetramethylene adipamide, and the polyarylene sulfide and the polytetraethylene. When the total content of methylene adipamide is 100% by mass, the thermoplastic resin is 40 to 90% by mass and 10 to 60% by mass, respectively, and [B] boron nitride. When the total content of the thermoplastic resin [A] and the boron nitride [B] is 100% by mass, 15 to 80% by mass and 20 to 8%, respectively. The thermoplastic resin composition, which is a mass%.
2. 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 thermoplastic resin composition according to 1 above, wherein the ratio D ₉₀ / D _{10 of} D ₁₀ and D ₉₀ is 7 to 11.
3. 3. The thermoplastic resin composition according to 1 or 2 above, wherein the boron nitride [B] has a volume average particle diameter of 12 to 20 μm.
4). 4. The thermoplastic resin composition according to any one of 1 to 3, wherein the polyarylene sulfide is polyphenylene sulfide.
5. 5. The thermoplastic resin composition according to any one of 1 to 4 above, which is used for forming an LED mounting substrate or an LED reflector.

According to the thermoplastic resin composition of the present invention, a resin molded part having high adhesion can be efficiently formed on a metal member, and when accompanied by a thermal history, deformation of the resin molded part and Efficient composite with excellent balance between heat resistance, heat dissipation, impact resistance, low water absorption, insulation, and light reflection properties, with prevention of breakage, separation of resin molded parts and metal parts Can be manufactured well. Even if any part of the resin molded part and the metal member in the composite is subjected to heat load, the heat conduction to the other part is good, excellent in heat resistance without causing deformation of the composite, Excellent heat dissipation. Then, when the obtained composite is a member such as an LED mounting substrate or an LED reflector with thermal history, and an article including the member, the resin molded portion is deformed and destroyed, and the resin molded portion In the case where the article is provided with a light emitter such as an LED element, the resin molded part has heat resistance, heat dissipation, impact resistance, low water absorption, insulation, and light. It is possible to efficiently produce a composite having an excellent balance between the reflection characteristics. Furthermore, since it is excellent in low water absorption, the use of this composite can suppress the occurrence of blisters (swelling) or the like when a surface mount component or the like is disposed in a reflow furnace.
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 , if _{D 10} and the ratio _D 90 _{/ D 10} with _{D 90} of 7 to 11, the heat resistance of the resulting composite, heat dissipation, insulation, and reflection characteristics with respect to light is excellent.
When the volume average particle diameter of the boron nitride [B] is 12 to 20 μm, the resulting composite is excellent in heat resistance, heat dissipation, insulation, and light reflection characteristics.
When the polyarylene sulfide is polyphenylene sulfide, a composite having better impact resistance can be obtained.

  In the thermoplastic resin composition of the present invention, a metal member surface-treated with a triazine compound is placed inside a mold, and a resin is applied to at least a part of the surface of the metal member by an injection molding method. In the method of forming a molded part and producing a composite, a thermoplastic resin composition used for forming the resin molded part, comprising (A) polyarylene sulfide and polytetramethylene adipamide, And when the total content of the polyarylene sulfide and the polytetramethylene adipamide is 100% by mass, thermoplastic resins (40 to 90% by mass and 10 to 60% by mass, respectively) Hereinafter referred to as “component [A]”) and [B] boron nitride (hereinafter referred to as “component [B]”), and the content ratio of component [A] and component [B] is When the sum of person 100 mass%, respectively, characterized in that it is a 15 to 80% by weight and 20 to 85 wt%.

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、カルボキシル基又はその金属塩、ニトロ基、及び、フッ素原子、塩素原子、臭素原子等のハロゲン原子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。 Among the above components [A], 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. Alternatively, the metal salt, a nitro group, and a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom may be substituted. 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、カルボキシル基又はその金属塩、ニトロ基、及び、フッ素原子、塩素原子、臭素原子等のハロゲン原子である。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.

(Wherein 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 or a metal salt thereof, nitro 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 (310 ° C., shear rate 1000 / sec).

  Of the components [A], polytetramethylene adipamide is a resin obtained by condensation polymerization of adipic acid and tetramethylenediamine. The terminal of this resin is a carboxylic acid such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, or hexylamine, octylamine, decylamine, laurylamine, myristyl. It may be sealed with an amine such as amine, palmitylamine, stearylamine, and behenylamine.

  The content ratios of polyarylene sulfide and polytetramethylene adipamide in the component [A] are 40 to 90% by mass and 10 to 60% by mass, respectively, when the total of both is 100% by mass, Preferably they are 60-90 mass% and 10-40 mass%, More preferably, they are 70-90 mass% and 10-30 mass%. When the content ratio of each resin is within the above range, the resulting composite has a balance among heat resistance, heat dissipation, impact resistance, low water absorption, blister resistance, insulation, and light reflection characteristics. Excellent.

Next, the above component [B], that is, boron nitride has hexagonal structure (h-BN), zinc blende structure (c-BN), wurtzite structure (w-BN), rhombohedral structure (r- There is no particular limitation as long as it has a plurality of stable structures such as (BN). In the present invention, any boron nitride can be used, but hexagonal boron nitride is preferred. The resin molded part formed of a composition containing hexagonal structure boron nitride is particularly excellent in heat dissipation, thermal conductivity, heat resistance and insulation.
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 ratios of the components [A] and [B] contained in the thermoplastic resin composition of the present invention are 15 to 80% by mass and 20 to 85% by mass when the total of these components is 100% by mass. , Preferably 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 resulting composite has a heat resistance, heat dissipation, impact resistance, low water absorption, insulation, and reflection characteristics with respect to light. Excellent balance.

  The thermoplastic resin composition of the present invention may contain an additive depending on the use of the resulting composite. The additives include fillers, heat stabilizers, antioxidants, UV absorbers, light stabilizers, anti-aging agents, antistatic agents, plasticizers, lubricants, flame retardants, mold release agents, antibacterial agents, and coloring agents. , Crystal nucleating agents, flow modifiers, impact modifiers and the like, and any known compounds can be used. In addition, when the thermoplastic resin composition of the present invention is used for forming a white resin molded part such as an LED mounting substrate, an LED reflector, etc., so that the composition can maintain a white color, It is preferred to select an additive.

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 of the present invention 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. More preferably, it is 5-15 mass parts, More preferably, it is 7-15 mass parts.

  In the thermoplastic resin composition of the present invention, the above components [A], [B], additives and the like are charged into various extruders, Banbury mixers, kneaders, continuous kneaders, rolls, etc., and melt kneaded under heating. Is obtained.

A molded product (resin molded part) formed from the thermoplastic resin composition of the present invention has excellent heat resistance, thermal conductivity of 2.5 W / mK or more, excellent heat dissipation, and Charpy impact strength. It is 0 kJ / m ² or more, has excellent impact resistance, has a water absorption of 0.35% or less, has excellent low water absorption, and further has excellent insulating properties and light reflection characteristics.

  In the thermoplastic resin composition of the present invention, a metal member surface-treated with a triazine compound is placed inside a mold, and a resin is applied to at least a part of the surface of the metal member by an injection molding method. In the method of forming a molded part and manufacturing a composite, it is used to form the resin molded part.

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 aluminum and alloys containing the same (aluminum alloy), copper (oxygen-free copper, etc.) and alloys containing it (brass, bronze, aluminum brass, etc.), nickel, chromium, titanium, iron, cobalt, tin, Examples include zinc, palladium, silver, stainless steel, magnesium, and manganese. 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.

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.
As shown in FIG. 1 and FIG. 2, the mold includes an inlet for injecting the thermoplastic resin composition of the present invention in a molten state and a fixed mold provided with parts therefor, and a molded product (composite). For example, the metal member 11 is shown in order to show the position of the metal member 11 in FIGS. 1 and 2. . 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 unit, a cooling unit, 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. 21 can be manufactured using the mold shown in FIG. The mold 3 in FIG. 1 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 of the present invention is filled in the cavity space until the introduced 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.

Examples of the composite produced using the thermoplastic resin composition and the metal member of the present invention include a composite having the structure shown in FIGS.
FIG. 3 is a schematic cross-sectional view showing a plate-like or linear composite body 1 and includes a flat metal member 11 and a resin molded portion 12 formed on one surface side of the metal member 11. It is. 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. 4 is a schematic cross-sectional view showing the plate-like or linear composite body 1, and is formed so as to cover the flat plate-like metal member 11, one surface side of the metal member 11, and the entire end surface. And a resin molded part 12. 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. 5 is a schematic cross-sectional view showing a plate-like or linear composite body 1, which is a resin molding formed so as to cover two flat metal members 11 and all end surfaces of the metal members 11. It is an aspect provided with the part 12. FIG. 5 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 made part.
3 to 5 described above all show a flat plate-like composite body, but may have a curved plate shape.

FIG. 6 shows a plate-shaped 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. 7 shows a flat metal member 11a, a resin molded portion 12a having a recess 125 formed on one surface side of the metal member 11a, and a side wall in the recess 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 through by.
FIG. 8 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. 9 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 members 11c arrange | positioned by penetrating a part to the vertical direction.

FIG. 10 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 recess 125 formed on one surface side of the metal member 11.
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. 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. 12 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. 12 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. 13 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 all the end surfaces. 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. 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 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. 15 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 body 1 disposed on the lower side of the inner wall surface of the recess 125 in the resin molded portion 12. 15 is a ring-shaped body or the like in which the metal member 11 has a through-hole, and the metal member 11 is embedded 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. 16 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.
10-16, although the shape of the recessed part 125 is shown stepwise, it is not limited to this, A straight line may be sufficient and a curve may be sufficient. The same applies to other drawings.

The composite body 1 in FIG. 17 further includes an aspect in which two metal members 11b are provided penetrating the side wall in the recess 125 of the resin molded portion 12 in the lateral direction 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.
The composite body 1 of FIG. 19 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. It is a schematic sectional drawing shown.
The composite body 1 in FIG. 20 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. 21 has a concave portion 126, a circular or square flat plate-shaped resin molded portion 12d, and two metal members 11b disposed laterally penetrating through 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. 22 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. 23 is an example of a top view of the composite 1 in FIGS. 21 and 22 in which the resin molding portion 12d is circular. As described above, the resin molded portion 12d may be rectangular.
FIG. 24 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. 25 shows a flat 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. 25, 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

  In the composites shown in FIGS. 3 to 25, when these are light emission related members, heat generation related members, etc., deformation and destruction of the resin molded portion, separation of the resin molded portion and the metal member are suppressed. Excellent balance among heat resistance, heat dissipation, impact resistance, low water absorption, insulation, and light reflection characteristics.

The thermoplastic resin composition of the present invention is preferably a composition used for forming an LED mounting substrate or an LED reflector as a composite. Specific examples are shown below.
(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, the composite 1 of FIGS. 3 to 5 can be applied. 3 to 5, 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 composite 1 of FIGS. 3 and 4, the metal member 11 can act as a heat sink.
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. 10 to 16). 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. In the LED mounting substrate of FIGS. 10 to 13, when the LED element is disposed on the bottom surface of the recess 125 in the resin molded part 12, not only the other parts of the resin molded part 12 but also the metal when the LED element emits light. Heat can be released from the member 11. 14 to 16, when the LED element is disposed on the bottom surface of the recess 125 in the resin molded portion 12, heat can be radiated mainly from the resin molded portion 12 when the LED element emits light. In addition, in the composite 1 of FIGS. 10-16, the metal members 11 can be made to act as a heat sink.

(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 embodiment, the composite 1 of FIGS. 6 to 9 can be applied. The lead frame is indicated by a metal member 11b in the drawing. Although the LED elements are not shown in FIGS. 6 to 9, the LED elements are disposed on the bottom surface of the recess 125 in FIGS. 6 and 7. Moreover, in FIG.8 and FIG.9, the LED element is normally arrange | positioned between the two metal members 11b. In FIG. 9, 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).
6 and 7, 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. Moreover, in the composite 1 of FIG.6 and FIG.7, the metal members 11 can be made to act as a heat sink.
In FIG. 8, 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. 9, when the LED element is disposed on the surface of the resin molded portion 12 c, when the LED element emits light, the resin molded portion 12 c having excellent thermal conductivity is thermally conducted to the metal member 11 c without thermal resistance. Heat can be radiated from the surface of the metal member 11c (the lower surface side of the metal member 11c in FIG. 9). Heat can also be radiated by the metal member 11b which is a lead frame.
Further, in FIG. 9, 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. 9), 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 part 12c and to dissipate heat by the resin molding part 12c. Heat can also be radiated by the metal member 11b which is a lead frame.
In addition, in the LED mounting substrate of this aspect (b), the resin molded portion may include a reflector portion having a concave cross-sectional shape for disposing the LED element on the inner bottom surface (LED mounting with reflector portion). (See FIGS. 17 to 20). 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. 17-20, when the LED element is disposed on the bottom surface of the recess 125 in the resin molding part 12, not only the other parts of the resin molding part 12 but also the metal when the LED element emits light. Heat can be released 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 embodiment, the composite 1 shown in FIGS. 21 to 24 can be applied. The lead frame is indicated by a metal member 11b in the drawing. Although the LED elements are not shown in FIGS. 21 to 24, the LED elements are disposed on the bottom surface of the recess 126.
21 to 24, 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.
As this aspect, the complex 1 of FIG. 25 can be applied. In FIG. 25, 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. 25, 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.

3 to 20 are used as LED mounting substrates, or the composites shown in FIGS. 21 to 25 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 part) 1 shown in FIG. 17, 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.

  Moreover, the composite which is a screw, a pin, a nail | claw, a rib, a boss | hub etc. can also be manufactured using the thermoplastic resin composition of this invention. 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) Polytetramethylene adipamide (A2)
“Stanyl TS300” (trade name) manufactured by DSM Japan was used. The melting point is 295 ° 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).

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.

2. Production and Evaluation of Thermoplastic Resin Composition Examples 1-4 and Comparative Examples 1-9
The thermoplastic resin composition used for 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 and 2, and then melt-kneading them using a twin screw extruder. A pellet was obtained. In addition, the cylinder temperature in a twin-screw extruder is 280 degreeC-330 degreeC in Examples 1-4, and is 280 degreeC-330 degreeC in Comparative Examples 1-9.

Each composition was evaluated as follows. The results are shown in Tables 1 and 2.
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 1-4, and is 90 to 150 degreeC in Comparative Examples 1-9.
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. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC in Examples 1-4, and is 90 to 150 degreeC in Comparative Examples 1-9.
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 heat-dissipating resin composition, a probe was applied to each of the upper and lower surfaces of the test piece, and a laser flash method thermal constant measuring device “TR- 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 1-4, and is 90 to 150 degreeC in Comparative Examples 1-9.
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 1-4, and is 90 to 150 degreeC in Comparative Examples 1-9.
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.
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 1-4, and is 90 to 150 degreeC in Comparative Examples 1-9.
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 1-4, and is 90 to 150 degreeC in Comparative Examples 1-9.

2-9. 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.

  As shown in FIG. 2, the copper plate is placed inside a mold placed on an injection molding machine “EC40N” (model name) manufactured by Toshiba Machine Co., Ltd. Based on the blending ratios shown in Tables 1 and 2. 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 1-4, and is 90 to 150 degreeC in Comparative Examples 1-9.

The evaluation items of the obtained test specimen for evaluation (composite) are as follows.
(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 and 2, the following is clear.
Comparative Example 1 is an example in which only polyphenylene sulfide is used as the thermoplastic resin, and the impact resistance is not sufficient. Comparative Example 2 is an example in which only polytetramethylene adipamide was used as the thermoplastic resin, and although it was excellent in impact resistance, the water absorption was high and the blister property at 260 ° C. was not sufficient. Comparative Example 3 is an example using polyphenylene sulfide and polytetramethylene adipamide having a content ratio outside the scope of the present invention as a thermoplastic resin, and was excellent in impact resistance but high in water absorption. Comparative Example 4 is an example in which the content of boron nitride relative to the thermoplastic resin is small, which is outside the scope of the present invention, the thermal conductivity is not sufficient, and the temperature at T1 is 75 ° C. in the thermal conductivity test of the composite. The temperature at T2 is 27 ° C., the difference is as large as 48 ° C., and heat is not easily transmitted from the copper plate to the resin molded portion, so the heat dissipation from the resin molded portion is poor. Comparative Example 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 6 is an example in which only polyphenylene sulfide is used as the thermoplastic resin, and boron nitride (B2) different from that in Comparative Example 1 is used. In the thermal conductivity test of the composite, heat is sufficiently dissipated in the resin molded portion. The temperature at T1 is 73 ° C., the temperature at T2 is 28 ° C., the difference is as large as 45 ° C., and heat is not easily transferred from the copper plate to the resin molded portion, so the heat dissipation from the resin molded portion is inferior. . Comparative Example 7 is an example not containing boron nitride, the thermal conductivity is not sufficient, the temperature at T1 is 79 ° C., the temperature at T2 is 27 ° C., and the difference is as large as 52 ° C. Since heat is not easily transmitted to the resin molded part, heat dissipation from the resin molded part is inferior. Comparative Example 8 is an example in which a composite was prepared using a copper plate that was not surface-treated with a triazine compound, and was not bonded to the resin molded portion and the 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 9 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, in Examples 1-4, the content ratios of polyarylene sulfide and polytetramethylene adipamide are 40 to 90% by mass and 10 to 60% by mass, respectively. It has an excellent balance among impact properties, low water absorption, insulating properties, and light reflection properties. In particular, as a composite, the fracture mode is material destruction, and the resin molded part is excellent in adhesion stability between the copper plate, so that heat conduction from the copper plate to the resin molded part is sufficient even in the thermal conductivity test. The temperature at T1 is 67 ° C. to 68 ° C., the temperature at T2 is 41 ° C. to 43 ° C., the temperature difference between T1 and T2 is small, and the heat dissipation is excellent. Moreover, in the test piece for evaluation (composite) after this thermal conductivity test, deformation of the resin molded part, peeling of the copper plate and the resin molded part, etc. were not observed.

4). Production of LED reflector Production example 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.
Pellets made of the thermoplastic resin composition of Example 1 were melted at 310 ° C., and this melt was injected into a mold having a cavity space of a mold (see FIG. 1) in which the long copper plate was placed. (Mold temperature: 90 to 150 ° C.) to obtain a reflector for LED as shown in FIG.

Production Examples 2 to 13
Each pellet made of the thermoplastic resin composition of Examples 2 to 4 and Comparative Examples 1 to 9 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 and 2. Except for the above, an LED reflector as shown in FIG. 21 was obtained in the same manner as in Production Example 1. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC.

5. Manufacture example 14 of LED mounting substrate
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.
Pellets made of the thermoplastic resin composition of Example 1 were melted at 310 ° C., and this melt was injected into a mold having a cavity space of a mold (not shown) in which the long copper plate was placed. (Mold temperature: 90 to 150 ° C.) to obtain an LED mounting substrate on which the LED element as shown in FIG. 20 can be mounted.

Production Examples 15 to 26
Each pellet made of the thermoplastic resin composition of Examples 2 to 4 and Comparative Examples 1 to 9 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 and 2. Except that, an LED mounting substrate as shown in FIG. 20 was obtained in the same manner as in Production Example 11. In addition, the temperature of the metal mold | die used for injection molding is 90 to 150 degreeC.

  The thermoplastic resin composition of the present invention is a production of a composite comprising a metal member surface-treated with a triazine compound and a resin molded portion joined to at least a part of the surface of the metal member. And is suitable for forming the resin molded part. For example, formation of components such as light-emitting devices including LED elements, and further, industrial control devices, household appliances, mobile phones, portable electronic information terminals and other communication devices, medical devices, vehicle electronic devices, etc. It is suitable for the manufacture of products, parts, etc. having resin molded parts such as screws, pins, claws, ribs, bosses on the surface or inner surface of various shapes of metal members such as structural parts and exterior parts.

It is a schematic sectional drawing which shows an example of the metal mold | die used for manufacture of a composite_body | complex. 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 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.21 and FIG.22. 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 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 (5)

A metal member surface-treated with a triazine compound is placed inside the mold, and a resin molded part is formed on at least a part of the surface of the metal member by injection molding to produce a composite. A thermoplastic resin composition used to form the resin molded part, comprising:
[A] It is composed of polyarylene sulfide and polytetramethylene adipamide, and when the content ratio of the polyarylene sulfide and the polytetramethylene adipamide is 100% by mass of the both, Containing -90 mass% and 10-60 mass% thermoplastic resin, and [B] boron nitride,
The content ratio of the thermoplastic resin [A] and the boron nitride [B] is 15 to 80% by mass and 20 to 85% by mass, respectively, when the total of both is 100% by mass. A thermoplastic resin composition. 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 thermoplastic resin composition according to claim 1, wherein a ratio D ₉₀ / D _{10 of} D ₁₀ and D ₉₀ is 7 to 11.   The thermoplastic resin composition according to claim 1 or 2, wherein the boron nitride [B] has a volume average particle diameter of 12 to 20 µm.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyarylene sulfide is polyphenylene sulfide.   The thermoplastic resin composition according to any one of claims 1 to 4, which is used for forming an LED mounting substrate or an LED reflector.

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