WO2012090360A1

WO2012090360A1 - Metal base circuit board, and method for producing metal base circuit board

Info

Publication number: WO2012090360A1
Application number: PCT/JP2011/005510
Authority: WO
Inventors: 洋次白土; 光男武谷; 孝幸馬塲; 飛澤　晃彦
Original assignee: 住友ベークライト株式会社
Priority date: 2010-12-28
Filing date: 2011-09-29
Publication date: 2012-07-05
Also published as: JP5870934B2; KR20130132560A; TW201234940A; JPWO2012090360A1; CN103283313A; TWI527504B

Abstract

A metal base circuit board (10) is laminated with an aluminum substrate (12), an insulating resin layer (14), and a metal layer (16) in said order. The surface of the aluminum substrate (12) is brought into contact with water having a temperature of 50 to 80°C for 0.5 to 3 minutes such that the surface roughness (Rz) of the surface of the aluminum substrate (12) is between 3 and 9 µm and the water contact angle thereof is between 50° and 95°.

Description

Metal base circuit board and method for manufacturing metal base circuit board

The present invention relates to a metal base circuit board and a method for manufacturing the metal base circuit board.

Conventionally, a metal base circuit board in which a metal layer is laminated on an aluminum substrate via an insulating resin layer has been used for the purpose of dissipating heat generated from the mounted components.

When an oxide film is formed on the surface of the metal substrate constituting the metal base circuit board, the adhesion with the insulating resin layer is lowered. Therefore, as described in Patent Document 1 or 2, in order to remove the oxide film on the surface of the aluminum substrate, mechanical polishing for polishing the surface or chemical etching of the surface as described in Patent Documents 3 to 5 is performed. A roughening method is performed.
In recent years, light emitting elements such as LEDs are mounted and used as light sources for liquid crystal display devices (Patent Document 6).

JP 07-197272 A JP-A-10-296908 JP 2002-12653 A Japanese Patent Laid-Open No. 2002-114836 JP 2008-266535 A JP 2007-194155 A

However, along with demands for thinning and miniaturization of electronic devices such as liquid crystal display devices, there is a need to mount in a small space due to restrictions on the area of the mounting position. When mounting in such a small space, there has been a problem that the metal base circuit board is bent and peeled between the aluminum substrate and the insulating resin layer.

According to the mechanical polishing or chemical etching treatment described in the above patent document, irregularities are formed on the surface of the aluminum substrate, and the adhesion with the resin layer is improved by the anchor effect. However, due to the unevenness of the aluminum substrate surface, the resin layer formed on the surface is not flat, and the circuit formed on the resin layer may not be flat. Therefore, the connection with the elements mounted on the circuit becomes insufficient, and the yield of various devices using the metal base circuit board may be lowered. On the other hand, if these treatments are not performed, the adhesion between the aluminum substrate surface and the resin layer is low, and the yield of various devices using a metal base circuit board is greatly reduced. For this reason, surface treatment such as mechanical polishing and chemical etching has become an essential process.

Also, since a large amount of polishing residue is generated in mechanical polishing, an apparatus and a process for accurately removing these are necessary. On the other hand, in the chemical etching process, hydrogen gas or the like is generated during the process, and an apparatus and a process for neutralizing the substrate surface after the process are separately required. As described above, the mechanical polishing and the chemical etching process have to be improved in safety, manufacturing cost, and complexity of the process.

As described above, the present inventors have found a new problem of improving the adhesion between the aluminum substrate and the resin layer and further improving the yield of various apparatuses using the metal base circuit board.

The LED light source unit described in Patent Document 6 has a predetermined shape in which the metal base circuit board is disposed in the housing, but still has the above-described problems when processed into various shapes. It was.

The present inventors have intensively studied in view of the above problems, and even when the surface of the aluminum substrate is smooth, by making the contact angle with water within a predetermined range, the adhesion with the resin layer is improved, and the metal It has been found that all of the improvement in the yield of various devices using the base circuit board can be satisfied, and the present invention has been completed.

In addition, the present inventors have intensively studied in view of the above problems, and by treating the surface of the aluminum substrate with a safe and simple method, the adhesion with the resin layer is improved and the metal base circuit board is obtained. The present inventors have found that it is possible to satisfy any of the improvement in yield of various devices using the present invention.

According to the present invention,
A metal base circuit board in which an aluminum substrate, an insulating resin layer, and a metal layer are sequentially laminated,
The contact angle of the aluminum substrate surface with water is 50 ° or more and 95 ° or less,
A metal base circuit board having a surface roughness (Rz) of 3 μm or more and 9 μm or less is provided.

Furthermore, according to the present invention,
A method of manufacturing the metal base circuit board,
Contacting the aluminum substrate with water at 50 ° C. or more and 80 ° C. or less for 0.5 minutes or more and 3 minutes or less;
Forming the insulating resin layer on the surface of the aluminum substrate after processing, and then forming the metal layer on the insulating resin layer.

Furthermore, according to the present invention,
A method for treating an aluminum substrate used in the metal base circuit board,
There is provided a method for treating an aluminum substrate for a metal base circuit board, wherein the aluminum substrate is contacted with water at 50 ° C. or higher and 80 ° C. or lower for 0.5 minutes or longer and 3 minutes or shorter.

Furthermore, according to the present invention,
A method of manufacturing the metal base circuit board,
Irradiating the aluminum substrate surface with ultraviolet rays;
Forming the insulating resin layer on the surface of the aluminum substrate after irradiation with the ultraviolet light, and then forming the metal layer on the insulating resin layer.

Furthermore, according to the present invention,
A method for treating an aluminum substrate used in the metal base circuit board,
The integrated light quantity of the ultraviolet to be irradiated to the aluminum substrate surface is 0.1 J / cm ² or more 1.0 J / cm ² or less, the processing method of an aluminum substrate metal base circuit board is provided.

The metal base circuit board of the present invention is excellent in the adhesion between the aluminum substrate and the insulating resin layer, solder heat resistance, and bending resistance, and can improve the yield of various devices using the same.

The above-described object and other objects, features, and advantages will be further clarified by a preferred embodiment described below and the following drawings attached thereto.

It is sectional drawing which shows typically an example of the metal base circuit board of this embodiment. It is the schematic which shows the adhesiveness test method in an Example. It is a graph which shows the relationship between the contact angle and adhesion strength in an Example. It is a graph which shows the relationship between the process conditions and adhesion strength in an Example.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, similar constituent elements are denoted by the same reference numerals, and description thereof is omitted appropriately.

<Metal base circuit board>
As shown in FIG. 1, the metal base circuit board 10 according to this embodiment includes an aluminum substrate 12, an insulating resin layer 14, and a metal layer 16 stacked in order. The metal base circuit board 10 is used as a heat spreader.

(Aluminum substrate 12)
The surface of the aluminum substrate 12 in contact with the insulating resin layer 14 has a surface roughness (Rz) in the range of 3 μm to 9 μm, more preferably in the range of 3 μm to 5 μm, and is smooth. The surface of the aluminum substrate 12 has a contact angle with water of 50 ° to 95 °, preferably 55 ° to 90 °.

With such a contact angle, even when the surface of the aluminum substrate 12 is smooth, wettability with the resin composition forming the insulating resin layer 14 is improved, and the aluminum substrate 12 and the insulating resin layer 14 Improved adhesion.
The contact angle with water can be calculated according to JIS R3257, and an average of 5 or more points can be calculated as the contact angle. The surface roughness can be calculated according to JIS B0601, and can be calculated as a ten-point average roughness (Rz).

In this embodiment, since the surface of the aluminum substrate 12 is not subjected to mechanical polishing or chemical etching, it has an oxide layer by natural oxidation. The thickness of the aluminum substrate 12 is not less than 100 μm and not more than 5000 μm. If the thickness is less than 100 μm, the heat dissipation as a heat spreader decreases. When the thickness exceeds 5000 μm, workability such as bending is degraded.

In this embodiment, the aluminum substrate 12 may not be surface-treated with a coupling agent. Even if the aluminum substrate 12 of this embodiment is not surface-treated with a coupling agent, the adhesion to the insulating resin layer 14 is excellent. Therefore, the process of processing the surface of the aluminum substrate 12 with a coupling agent can be omitted.

(Insulating resin layer 14)
The bending elastic modulus of the insulating resin layer 14 is 5 GPa or more and 20 GPa or less. Thereby, even when stress is applied to the metal base circuit board, the insulating resin layer 14 is excellent in flexibility, so that the adhesion between the aluminum substrate 12 and the insulating resin layer 14 is further improved.
The flexural modulus can be measured as follows.
Two copper foils with resin are stacked so that the resin layers face each other and pressed at 220 ° C. for 180 minutes to obtain a resin plate with double-sided copper foil. The entire surface of the resin plate with the double-sided copper foil is etched to produce a test piece of 6 mm × 25 mm × 0.2 mm (thickness). And it heats up at 5 degree-C / min using DMA apparatus (TA Instruments company make dynamic viscoelasticity measuring apparatus DMA983), and measures the bending elastic modulus in 25 degreeC.

The insulating resin layer 14 may be a single layer or a multilayer.

The insulating resin layer 14 contains a thermosetting resin and an inorganic filler as main components.
Examples of the thermosetting resin include an epoxy resin, a phenol resin, a melamine resin, and an unsaturated polyester resin, and it is preferable to use an epoxy resin.

The epoxy resin is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. For example, bisphenol type such as bisphenol A type and bisphenol F type, biphenyl type, novolac type, polyfunctional phenol These include glycidyl ethers such as naphthylene, naphthalene, alicyclic and alcohols, glycidylamines and glycidylesters, and one or a mixture of two or more can be used.
Among epoxy resins, it is preferable to use bisphenol F-type or A-type epoxy resins and those obtained by hydrogenating these resins. In particular, bisphenol F type or A type epoxy resin which is liquid at normal temperature is preferable. By using these resins, the insulating resin layer 14 is excellent in flexibility, and even when the metal base circuit board 10 is bent and used, peeling between the aluminum substrate 12 and the insulating resin layer 14 is suppressed. .

The thermosetting resin can be contained in the insulating resin layer 14 in an amount of 10% by mass to 90% by mass. A resin other than the thermosetting resin can also be blended. Thereby, adhesiveness with the aluminum substrate 12 can be improved more.

Examples of the inorganic filler include, but are not limited to, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride, aluminum borate whisker, boron nitride, and crystallinity. Silica, amorphous silica, silicon carbide and the like can be mentioned.
Among these, alumina, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferable from the viewpoint of high thermal conductivity. More preferred is alumina. When alumina is used, it is preferable in terms of heat resistance and insulation in addition to high thermal conductivity. Further, crystalline silica or amorphous silica is preferable in that it has few ionic impurities. A metal base substrate having excellent insulation reliability can be manufactured.
Crystalline silica or amorphous silica is preferable in that it has high insulation under a water vapor atmosphere such as a pressure cooker test and has little corrosion on metals, aluminum wires, aluminum plates, and the like.
On the other hand, from the viewpoint of flame retardancy, aluminum hydroxide and magnesium hydroxide are preferred.
Furthermore, for the purpose of adjusting melt viscosity and imparting cyclotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, crystalline silica, Amorphous silica is preferred.

The content of the inorganic filler is not particularly limited, but is preferably included in the insulating resin layer 14 in an amount of 10% by mass to 90% by mass. (B) By making content of an inorganic filler into 10 mass% or more, thermal resistance can be reduced and sufficient heat dissipation can be obtained. By making content of an inorganic filler into 90 mass% or less, it can suppress that the fluidity | liquidity at the time of a press deteriorates and a void etc. generate | occur | produce.

(Metal layer 16)
The metal layer 16 is comprised from copper, aluminum, nickel, iron, tin, etc., and may contain 2 or more types. The metal layer 16 has a thickness of about 0.1 to 1500 μm. Other layers such as an adhesive layer may be interposed between the insulating resin layer 14 and the metal layer 16.

In the metal base circuit board 10 having such a configuration, since the surface of the aluminum substrate 12 has a contact angle with water in the range of 50 ° to 95 °, the adhesion between the aluminum substrate 12 and the insulating resin layer 14 is improved. To do. Furthermore, it is excellent in solder heat resistance and bending resistance, and the yield of various devices using the same is improved.

The smaller the contact angle with water on the surface of the aluminum substrate 12, the better the wettability with water. However, when the contact angle with water is less than 50 °, the adhesion between the aluminum substrate 12 and the insulating resin layer 14 decreases. Although the cause of this is not clear, when the contact angle with the water on the surface of the aluminum substrate 12 is within a predetermined range, the wettability with the resin composition forming the insulating resin layer 14 becomes an appropriate range, and the aluminum substrate 12 It is considered that the adhesion with the insulating resin layer 14 is improved even if the surface is smooth.

In the metal base circuit board 10 of the present embodiment, the adhesion strength between the aluminum substrate 12 and the insulating resin layer 14 is 20 kg / cm ² or more and 50 kg / cm ² or less, preferably 30 kg / cm ² or more and 45 kg / cm ² or less. can do.
The adhesion strength can be measured under the following conditions.
・ Test equipment: NXT-250P (manufactured by Toyama Sangyo Co., Ltd.)
A resin varnish for obtaining the insulating resin layer is applied to an aluminum test chip (disc-shaped, bonding surface 2.0 cmφ), and the coated surface is bonded to a fixed aluminum test plate. The resin varnish is cured under conditions of 180 ° C. for 60 minutes, and the aluminum test chip and the aluminum test plate are bonded via a resin layer.
-The aluminum test chip is pulled up in the vertical direction at a speed of 1.5 mm / min, and the time when the aluminum test chip or the aluminum test plate and the resin layer are peeled is measured as the adhesion strength.

The metal base circuit board 10 of the present embodiment can form a circuit by etching the metal layer 16 into a predetermined pattern. The metal base circuit board 10 functions as a heat spreader by mounting various heating elements such as LEDs, semiconductor elements, or laser elements on the circuit.

<Manufacturing method of metal base circuit board>
As a manufacturing method of the metal base circuit board 10 of this embodiment, (1) the aluminum substrate is treated with water, and then an insulating resin layer and a metal layer are formed. (2) the aluminum substrate is treated with ultraviolet rays, and thereafter And a method of forming an insulating resin layer and a metal layer.

<Production Method of Metal Base Circuit Board (1)>
Hereinafter, (1) a method of treating an aluminum substrate with water and then forming an insulating resin layer and a metal layer will be described.
The manufacturing method of the metal base circuit board 10 of this embodiment includes the following steps (a) to (b).
(A) The step of bringing the aluminum substrate 12 into contact with water at 50 ° C. or more and 80 ° C. or less for 0.5 to 3 minutes (b) The insulating resin layer 14 is formed on the surface of the aluminum substrate 12 after the treatment, Step of forming metal layer 16 on 14

(Process (a))
The aluminum substrate 12 is brought into contact with water at 50 ° C. or more and 80 ° C. or less, preferably 50 ° C. or more and 70 ° C. or less for 0.5 minutes or more and 3 minutes or less, preferably 0.5 minutes or more and 2 minutes or less. As water used for the treatment, pure water can be used. In addition, alcohols such as isopropyl alcohol, ethanol, and tert-butyl alcohol, and various ions such as Ca ²⁺ , Mg ²⁺ , Na ⁺ , K ⁺ , and Cl ⁻ are included as long as the surface tension of the aluminum substrate 12 is not affected. You may go out.

As the treatment method, it is sufficient if water can be brought into contact with the surface of the aluminum substrate 12 under the above conditions, and examples include immersion treatment, running water treatment, and spray treatment. After the contact treatment, moisture is removed by a predetermined method. The surface roughness (Rz) of the aluminum substrate 12 hardly changes before and after the treatment and is 3 to 9 μm and is smooth. The surface roughness can be calculated according to JIS B0601, and can be calculated as a ten-point average roughness (Rz).
By such contact treatment, the contact angle of the aluminum substrate 12 with water can be adjusted to 50 ° to 95 °, preferably 55 ° to 85 °.

The aluminum substrate 12 of this embodiment has excellent adhesion to the insulating resin layer 14 even if it is not surface-treated with a coupling agent. Therefore, since the process of processing the surface of the aluminum substrate 12 with a coupling agent can be omitted, the process can be simplified.

(Process (b))
Next, an insulating resin layer 14 is formed on the surface of the treated aluminum substrate 12, and then a metal layer 16 is formed on the insulating resin layer 14.
Specifically, taking into account the thickness after curing, the resin composition is applied to the surface of the aluminum substrate 12 and preliminarily cured to obtain a B-staged state. And metal foil is bonded together, post-curing is performed, and the metal base circuit board 10 by which the insulating resin layer 14 and the metal layer 16 were laminated | stacked on the aluminum substrate 12 surface is manufactured.

Alternatively, the resin composition can be applied to the surface of the aluminum substrate 12 and cured to form the insulating resin layer 14, and then the metal layer 16 can be formed on the insulating resin layer 14 by metal vapor deposition.
Further, after the step (a), an insulating resin layer may be formed on the surface of the metal foil and bonded to the processed aluminum substrate 12. Specifically, in consideration of the thickness after curing, the resin composition is applied to the surface of the metal foil and pre-cured to obtain a B-stage state. Then, the metal base circuit board 10 in which the insulating resin layer 14 and the metal layer 16 are laminated on the surface of the aluminum substrate 12 is manufactured by bonding with the aluminum substrate 12 and post-curing.

The metal foil is not particularly limited. For example, copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys Metal foils, such as an alloy, iron, and an iron-type alloy, are mentioned. Among these, copper foil is preferable in that the metal foil can be used as a conductor circuit by etching. From the viewpoint of low thermal expansion, an iron-nickel alloy is preferable.

Note that the method for producing the metal foil may be either an electrolytic method or a rolling method. The metal foil may be plated with metal such as Ni plating, Ni—Au plating, solder plating, etc., but from the point of adhesiveness to the insulating resin layer 14, the insulating resin layer 14 of the conductor circuit is formed. It is more preferable that the surface on the side in contact with the surface is previously roughened by etching, plating, or the like.

The thickness of the metal foil is not particularly limited, but is preferably 0.5 μm or more and 105 μm or less, more preferably 1 μm or more and 70 μm or less, and particularly preferably 9 μm or more and 35 μm or less. By controlling the thickness of the metal foil to the lower limit or less, the occurrence of pinholes is suppressed, and when the metal foil is etched and used as a conductor circuit, plating variations during circuit pattern formation, circuit disconnection, etching solution and desmear solution It is possible to avoid the possibility of infiltration of a chemical solution such as the above. Moreover, the thickness variation of metal foil can be made small by making the thickness of metal foil below an upper limit, and the surface roughness variation of a metal foil roughening surface can be suppressed.
Further, as the metal foil, an ultrathin metal foil with a carrier foil can be used. The ultrathin metal foil with a carrier foil is a metal foil obtained by laminating a peelable carrier foil and an ultrathin metal foil. Since an ultrathin metal foil layer can be formed on both sides of an insulating layer by using an ultrathin metal foil with a carrier foil, for example, when forming a circuit by a semi-additive method, an ultrathin metal without performing electroless plating By electroplating the foil as a direct power supply layer, the ultrathin copper foil can be flash etched after the circuit is formed. By using an ultra-thin metal foil with a carrier foil, even with an ultra-thin metal foil having a thickness of 10 μm or less, for example, a reduction in handling properties of the ultra-thin metal foil in a pressing process, and cracking or cutting of the ultra-thin copper foil are prevented. Can do.

Hereinafter, a method for forming the insulating resin layer 14 will be specifically described.
First, the resin composition is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, anisole, etc. Dissolve, mix, and stir in various organic solvents using various mixing machines such as the ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation and revolution dispersion method. To prepare a resin varnish.

The content of the resin composition in the resin varnish is not particularly limited, but is preferably 45% by mass or more and 85% by mass or less, and particularly preferably 55% by mass or more and 75% by mass or less.

Next, a resin varnish is applied to the surface of the aluminum substrate 12 using various coating apparatuses, and dried. Alternatively, the resin varnish is spray-coated on the surface of the aluminum substrate 12 by a spray device and then dried.
The coating apparatus is not particularly limited, and for example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, or the like can be used. Among these, a method using a die coater, a knife coater, and a comma coater is preferable. Thereby, the insulating resin layer 14 which has no void and has a uniform thickness can be efficiently manufactured.

The thickness of the insulating resin layer 14 is preferably in the range of 20 μm to 250 μm. By setting the thickness of the insulating resin layer 14 to 20 μm or more, the generation of thermal stress due to the difference in thermal expansion coefficient between the aluminum substrate 12 and the insulating resin layer 14 can be sufficiently mitigated by the insulating resin layer 14. Moreover, the insulation of the metal base circuit board 10 is improved.
When a semiconductor element, a resistance component, or the like is surface-mounted on such a metal base circuit board 10, it is possible to suppress an increase in distortion between members and obtain sufficient thermal shock reliability. In addition, by setting the thickness of the insulating resin layer 14 to 250 μm or less, the amount of strain at the surface mounting portion of the metal base circuit board 10 is reduced, and good thermal shock reliability can be obtained, and the thermal resistance is reduced. And sufficient heat dissipation can be obtained. Therefore, if the thickness of the insulating resin layer 14 is within the above range, the balance of these characteristics is excellent.

The manufacturing method of the metal base circuit board 10 according to the present embodiment includes a step of bringing the surface of the aluminum substrate into contact with water under a predetermined condition. It is possible to obtain a metal base circuit board that is excellent in adhesion, solder heat resistance, and bending resistance and that can improve the yield of various devices using the same.

In addition to the above thermosetting resin and inorganic filler, the resin composition for preparing the insulating resin layer 14 includes a curing agent, a curing accelerator, a coupling agent, a flexibility-imparting component, an antioxidant, and a leveling agent. Etc. can be included.

Curing agents include diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA), isophoronediamine (IPD), 1,3-bisaminomethylcyclohexane (1,3BAC), diaminodiphenylmethane (DDM) , Mphenylenediamine (MPDA), diaminodiphenyl sulfone (DDS), dicyandiamide (DICY), organic acid hydrazide, dodecenyl succinic anhydride (DDSA), polyazeline anhydride (PAPA), hexahydrophthalic anhydride (HHPA), methyl Tetrahydrophthalic anhydride (MTHPA), methyl nadic anhydride (MNA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenonetetracarboxylic acid (BTDA), tetrabromoanhydride Examples thereof include phthalic acid (TBPA) and heptic anhydride (HET).

Curing accelerators include various imidazoles such as 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole, and various phosphorus compounds such as triphenylphosphine and triphenylphosphite. And various tertiary amines such as triethylamine, benzyldimethylamine, pyridine, DBU (diazabicycloundecene), and quaternary ammonium salts.

Coupling agents include 2- (3,4-epoxycyclohexyl), 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanate Examples include various silane coupling agents such as propyltriethoxysilane.

The content of the coupling agent preferably satisfies the following formula (1).
5 × 10 ⁻² <c− (b × 1/100) <11 (1)
Here, c (mass%) shows content of a coupling agent with respect to 100 mass% of total amounts of a resin composition. b (mass%) shows content of the inorganic filler with respect to 100 mass% of total amounts of a resin composition.
In the above formula (1), [c- (b × 1/100)] is a coupling agent present in the resin composition without adhering to the surface of the inorganic filler (that is, free in the resin composition) Content of the coupling agent).

Hereinafter, this point will be described.
First, the coupling agent has a functional group bonded to an organic material and an inorganic material in the molecule. An inorganic material and an organic material are combined through this coupling agent.
In this technical field, the coupling agent is used for adhesion between the inorganic filler and the resin composition, and is treated on the surface of the inorganic filler. For this reason, the processing amount (content of a coupling agent with respect to the whole resin composition) of a coupling agent is determined according to content of an inorganic filler.
Usually, it is known that the treatment amount of the coupling agent is about 0.5 to 1% by mass with respect to 100% by mass of the total amount of inorganic filler.
Therefore, (b × 1/100) in the above formula (1) indicates a general processing amount of the coupling agent with respect to the inorganic filler. Then, by subtracting the coupling agent treatment amount (b × 1/100) from the total amount c of the coupling agent, the content of the free coupling agent in the resin composition [c− (B × 1/100)] can be estimated.

Such a free coupling agent in the resin composition is present in the resin composition without adhering to the surface of the inorganic filler. Such a coupling agent acts on the aluminum substrate 12 which is an inorganic material, and can improve the adhesion between the insulating resin layer 14 and the aluminum substrate 12.
In this embodiment, by setting the content of the free coupling agent in the resin composition within a specific range, the adhesion between the insulating resin layer 14 and the aluminum substrate 12 and the balance of heat cycle characteristics are realized. can do. That is, the lower limit of the content of the free coupling agent in the resin composition is preferably 5 × 10 ⁻² mass% or more, more preferably 1 × 10 ⁻¹ mass% or more, and further preferably 5 ×. 10 is a ^-1% by weight or more, the upper limit amount is not particularly limited, for example, preferably not more than 11 wt%, more preferably 10 wt% or less, more preferably not more than 9 mass%.

By making the content of the free coupling agent in the resin composition equal to or higher than the lower limit value, the effect obtained from the inorganic filler is sufficiently brought out and the adhesion between the insulating resin layer 14 and the aluminum substrate 12 is enhanced. It becomes possible to improve the insulating properties of the metal base circuit board 10.
Moreover, by making content of the coupling agent which is free in a resin composition below into an upper limit, it is suppressed that a coupling agent is hydrolyzed and solder heat resistance falls.

Conventionally, for example, [c- (b × 1/100)] is 0 or less when the processing amount of the coupling agent is about 1% by mass with respect to 100% by mass of the total amount of the inorganic filler. In other words, it can be said that this is a case where a general processing amount of the coupling agent is used. The metal base circuit board using this type of resin composition has considerable room for improving the adhesion between the metal plate and the resin layer.
On the other hand, in this embodiment, [c− (b × 1/100)]> 0.05. As a result, the adhesion between the insulating resin layer 14 and the aluminum substrate 12 can be improved, and the insulating properties of the metal base circuit board 10 can be improved.

Examples of the flexibility-imparting component include a phenoxy resin and a rubber component. By including the flexibility imparting component in the insulating resin layer 14, not only the adhesion between the insulating resin layer 14 and the aluminum substrate 12 is improved, but also the fluidity is improved at the time of pressing and molding without voids is possible. It becomes possible.

Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a naphthalene skeleton, a phenoxy resin having an anthracene skeleton, and a phenoxy resin having a biphenyl skeleton. A phenoxy resin having a structure having a plurality of these skeletons can also be used.

Among these, it is preferable to use bisphenol A type or bisphenol F type phenoxy resin. Thereby, the adhesiveness to the laminated board of a wiring layer can further be improved at the time of manufacture of a circuit board.

The weight average molecular weight of the phenoxy resin is not particularly limited, but is preferably 4.0 × 10 ⁴ or more and 8.0 × 10 ⁴ or less.
When the molecular weight is 4.0 × 10 ⁴ or more and 8.0 × 10 ⁴ or less, the following effects can be obtained. First, the elastic modulus can be reduced, and when used for the metal base circuit board 10, the stress relaxation property is also excellent. For example, when a semiconductor device on which electronic components are mounted is manufactured, the semiconductor device cracks at or near the solder joint that joins the electronic component and the metal base substrate even under rapid heating / cooling environments. The occurrence of defects such as these is suppressed.

Further, by setting the weight average molecular weight of the phenoxy resin to 4.0 × 10 ⁴ or more, it is possible to sufficiently reduce the elastic modulus, and when used in a semiconductor device, solder bonding is performed under rapid heating / cooling. Cracks at or near the portion are less likely to occur. Thus, the heat cycle characteristics of the metal base substrate can be improved. In addition, by setting the weight average molecular weight of the phenoxy resin to 4.9 × 10 ⁴ or less, the fluidity at the time of pressing deteriorates due to an increase in viscosity, and generation of voids and the like is suppressed. It becomes possible to improve the insulation reliability. Thus, the insulation characteristic of the metal base circuit board 10 can be improved. In addition, the weight average molecular weight of a phenoxy resin is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the phenoxy resin is preferably 10% by mass or more and 40% by mass or less of the entire resin composition. By making the content of the phenoxy resin 10% by mass or more, the effect of lowering the elastic modulus can be sufficiently obtained, excellent in stress relaxation when used in the metal base circuit board 10, and subjected to rapid heating / cooling. Also, it is possible to suppress the occurrence of cracks in the solder or in the vicinity thereof. By setting the content of the phenoxy resin to 40% by mass or less, fluidity at the time of pressing is deteriorated, generation of voids and the like is suppressed, and the insulation reliability of the metal base circuit board 10 can be improved.
In addition, in the case of the varnish using a solvent etc., for example, the whole resin composition means solid except a solvent, and liquid components, such as a liquid epoxy and a coupling agent, are contained in a resin composition.

As the rubber component, for example, rubber particles can be used. Preferable examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and silicone particles.

The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, the outer shell layer is composed of a glassy polymer, and the inner core layer is composed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is composed of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate. The rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (trade names, manufactured by Ganz Kasei Co., Ltd.), and Metabrene KW-4426 (trade names, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR).

Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter 0.5 μm, manufactured by JSR). Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like.

The silicone particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane. For example, fine particles made of silicone rubber (organopolysiloxane cross-linked elastomer) itself, and a core part made of silicone mainly composed of two-dimensional cross-links. Examples thereof include core-shell structured particles coated with silicone mainly composed of a three-dimensional crosslinking type. As silicone rubber fine particles, commercially available products such as KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical), Trefil E-500, Trefil E-600 (manufactured by Toray Dow Corning), etc. Can be used.

The content of the rubber particles is not particularly limited, but is preferably 20% by mass or more and 80% by mass or less, and particularly preferably 30% by mass or more and 75% by mass or less of the entire resin composition together with the inorganic filler. When the content is within the range, particularly low water absorption can be achieved.

<Method of manufacturing metal base circuit board (2)>
Next, (2) a method of treating an aluminum substrate with ultraviolet rays and then forming an insulating resin layer and a metal layer will be described.
The manufacturing method of the metal base circuit board 10 of this embodiment includes the following steps (c) and (d).
(C) Step of irradiating the surface of the aluminum substrate 12 with ultraviolet rays (d) Step of forming the insulating resin layer 14 on the surface of the aluminum substrate 12 after processing, and then forming the metal layer 16 on the insulating resin layer 14 Since d) is the same process as the process (b) described above, the description thereof is omitted.

(Process (c))
The surface of the aluminum substrate 12 is irradiated with ultraviolet rays. As the ultraviolet rays used for the treatment, those having a wavelength of 185 nm or 254 nm can be used.

Integrated light quantity of ultraviolet light irradiating the aluminum surface of the substrate 12 is preferably not 0.1 J / cm ² or more 1.0 J / cm ² or less, more preferably 0.2 J / cm ² or more 0.8 J / cm ² or less is there. Since this integrated light quantity is the product of the ultraviolet radiation intensity (mW / cm ² ) and the irradiation time (seconds), the integrated light quantity can be adjusted by the intensity of ultraviolet light used and the irradiation time.
Moreover, the radiation intensity of the ultraviolet rays applied to the surface of the aluminum substrate 12 is not particularly limited, but is preferably 1.0 mW / cm ² or more and 100 mW / cm ² or less.
By such ultraviolet treatment, the contact angle of the surface of the aluminum substrate 12 with water can be adjusted to 50 ° to 95 °, preferably 55 ° to 90 °. Further, the surface roughness (Rz) of the aluminum substrate 12 hardly changes before and after the treatment and is 3 to 9 μm, which is smooth.

Note that the distance from the aluminum substrate 12 is preferably 5 cm or less, more preferably 3 cm or less, and particularly preferably 1 cm or less. If the distance to the aluminum substrate 12 exceeds 5 cm, the irradiation effect may not be sufficiently obtained.

The ultraviolet irradiation device to be used is not particularly limited as long as it can irradiate ultraviolet rays having a wavelength of 185 nm or 254 nm, and examples thereof include an ultraviolet irradiation device using a low-pressure mercury lamp.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.
Example 1
In the following Example 1, the case where the resin varnish a is used is referred to as “Example 1a”, and the case where the resin varnish b is used is referred to as “Example 1b”. The same applies to other examples and comparative examples.

(Preparation of resin varnish a)
Phenoxy resin having bisphenol F skeleton and bisphenol A skeleton (Mitsubishi Chemical Co., Ltd., 4275, weight average molecular weight 6.0 × 10 ⁴ , ratio of bisphenol F skeleton to bisphenol A skeleton = 75: 25) 22.0 parts by mass, bisphenol F epoxy resin (DIC, 830S, epoxy equivalent 170) 10.0 parts by mass, bisphenol A epoxy resin (Mitsubishi Chemical Corporation, 1001, epoxy equivalent 475) 15.0 parts, 2-phenylimidazole (Shikoku Chemicals) 2PZ) 1.0 parts by mass, 2.0 parts by mass of γ-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone) as a silane coupling agent, aluminum hydroxide (manufactured by Showa Denko KK, HP-360) , Particle size 3.0 μm) 50.0 parts by mass dissolved in cyclohexanone and mixed And stirred using a high speed stirrer, a resin composition was obtained 70 wt% of varnish on a solids basis.

(Preparation of resin varnish b)
Phenoxy resin having bisphenol F skeleton and bisphenol A skeleton (Mitsubishi Chemical Co., Ltd., 4275, weight average molecular weight 6.0 × 10 ⁴ , ratio of bisphenol F skeleton to bisphenol A skeleton = 75: 25) 22.0 parts by mass, biphenyl Skeletal epoxy resin (Mitsubishi Chemical Corporation, YX4000, epoxy equivalent 185) 10.0 parts by mass, bisphenol A epoxy resin (Mitsubishi Chemical Corporation, 1001, epoxy equivalent 475) 15.0 parts by mass, 2-phenylimidazole (Shikoku Chemicals) 1.0 parts by mass of 2PZ), 2.0 parts by mass of γ-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone) as a silane coupling agent, aluminum hydroxide (manufactured by Showa Denko KK, HP- 360, particle size 3.0 μm) 50.0 parts by mass dissolved in cyclohexanone Was, and stirred using a high speed stirrer, a resin composition was obtained 70 wt% of varnish on a solids basis.

(Washing treatment of aluminum substrate)
An aluminum plate having a thickness of 1 mm and a length and width of 10 cm was used as a substrate. This substrate was immersed in pure water at a predetermined temperature for a predetermined time in accordance with the processing conditions shown in Table 1, and then washed and dried with acetone to obtain an aluminum test plate.

(Examples 2 to 5 and Comparative Examples 1 to 8)
The aluminum plate was treated according to the treatment conditions shown in Tables 1 to 3, washed with acetone and dried to obtain an aluminum test plate.

(Reference example)
An aluminum plate having a thickness of 1 mm and a length and width of 10 cm was used as a substrate. The surface of this substrate was polished with sandpaper (# 1500), then washed with acetone and dried to obtain an aluminum test plate.

(Examples 6 to 8)
An aluminum plate having a thickness of 1 mm and a length and width of 10 cm was used as a substrate. As the ultraviolet irradiation device, a low-pressure mercury lamp (manufactured by Oak Co., Ltd., wavelength: 185 nm, radiation intensity 5.0 mW / cm ² ) was used. According to the processing conditions shown in Table 4, one side of the substrate was irradiated with ultraviolet rays to obtain an aluminum test plate.

The aluminum test plates obtained in each of the examples, comparative examples, and reference examples were subjected to the following evaluations by the following measurement methods. The evaluation results are shown in Tables 1 to 4. The relationship between the contact angle and the adhesion strength is shown in FIG. Moreover, the relationship between processing conditions and adhesion strength is shown in FIG.

a. Contact angle with water Measured according to JIS R3257, an average of 5 or more points was calculated as the contact angle.
b. Surface roughness (Rz)
It carried out based on JIS B0601 and computed as ten-point average roughness (Rz).
c. Adhesion strength Using an adhesion test device (model: NXT-250P, manufactured by Toyama Sangyo Co., Ltd.), as shown in FIG. 2, the resin varnish a or b was applied to the aluminum test chip (adhesion surface 2.0 cmφ) of the adhesion test device. It was applied, and the coated surface was adhered to a fixed aluminum test plate and cured under a curing condition of 180 ° C. for 60 minutes. Then, as shown in FIG. 2, the aluminum test chip was pulled up at a rate of 1.5 mm / min in the vertical direction, and the time when the aluminum test chip or the aluminum test plate and the resin layer were peeled was measured as the adhesion strength. The evaluation results are shown in Tables 1 to 4.

In Comparative Examples 7a, 7b, 8a, and 8b in Table 3, the adhesion strength was not measured because it was presumed that the adhesion strength was clearly low from the results of separate bending tests.
As described above, even when the surface of the aluminum substrate is smooth (surface roughness (Rz): 3 to 9 μm), the contact angle with water on the surface of the aluminum substrate is 50 ° or more and 95 ° or less. It was estimated that the adhesion strength between the substrate and the insulating resin layer was excellent, and that the solder heat resistance and bending resistance were also excellent. Therefore, it has been clarified that the yield of various devices using this is improved.

This application claims priority based on Japanese Patent Application No. 2010-291893 filed on Dec. 28, 2010 and Japanese Patent Application No. 2010-291895 filed on Dec. 28, 2010. , The entire disclosure of which is incorporated herein.

Claims

A metal base circuit board in which an aluminum substrate, an insulating resin layer, and a metal layer are sequentially laminated,
The contact angle of the aluminum substrate surface with water is 50 ° or more and 95 ° or less,
A metal-based circuit board having a surface roughness (Rz) of 3 μm or more and 9 μm or less.
The metal base circuit board according to claim 1,
A metal base circuit board having an adhesion strength between the aluminum substrate and the insulating resin layer of 20 kg / cm 2 or more and 50 kg / cm 2 or less, measured under the following conditions;
A resin varnish for obtaining the insulating resin layer is applied to an aluminum test chip (disc-shaped, bonding surface 2.0 cmφ), and the coated surface is bonded to a fixed aluminum test plate. The resin varnish is cured under conditions of 180 ° C. for 60 minutes, and the aluminum test chip and the aluminum test plate are bonded via a resin layer.
-The aluminum test chip is pulled up in the vertical direction at a speed of 1.5 mm / min, and the time when the aluminum test chip or the aluminum test plate and the resin layer are peeled is measured as the adhesion strength.
The metal base circuit board according to claim 1 or 2,
The said insulating resin layer is a metal base circuit board containing the hardened | cured material of the bisphenol F type or A type epoxy resin which is liquid at normal temperature.
The metal base circuit board according to any one of claims 1 to 3,
The said insulating resin layer is a metal base circuit board containing 1 or more types of flexibility provision components selected from a phenoxy resin and a rubber component.
The metal base circuit board according to claim 4,
Content of the said flexibility provision component is a metal base circuit board which is 10 to 40 mass% with respect to 100 mass% of said insulating resin layers.
The metal base circuit board according to any one of claims 1 to 5,
The aluminum substrate is a metal-based circuit board that is not surface-treated with a coupling agent.
The metal base circuit board according to any one of claims 1 to 6,
The insulating resin layer includes an inorganic filler and a silane coupling agent,
The content of the silane coupling agent with respect to a total amount of 100% by mass of the insulating resin layer is c% by mass,
When the content of the inorganic filler with respect to 100% by mass of the total amount of the insulating resin layer is b% by mass,
5 × 10 −2 <c− (b × 1/100) <11
Meet the metal base circuit board.
The metal base circuit board according to claim 7,
A metal-based circuit board, wherein the inorganic filler is aluminum hydroxide, magnesium hydroxide or alumina.
A method of manufacturing a metal base circuit board according to any one of claims 1 to 8,
Contacting the aluminum substrate with water at 50 ° C. or more and 80 ° C. or less for 0.5 minutes or more and 3 minutes or less;
Forming the insulating resin layer on the surface of the aluminum substrate after processing, and then forming the metal layer on the insulating resin layer.
In the manufacturing method of the metal base circuit board of Claim 9,
The method of manufacturing a metal base circuit board, wherein the aluminum substrate is not surface-treated with a coupling agent.
A method of manufacturing a metal base circuit board according to any one of claims 1 to 8,
Irradiating the aluminum substrate surface with ultraviolet rays;
Forming the insulating resin layer on the surface of the aluminum substrate after irradiation with the ultraviolet light, and then forming the metal layer on the insulating resin layer.
In the manufacturing method of the metal base circuit board of Claim 11,
A method for producing a metal base circuit board, wherein the wavelength of the ultraviolet light is 185 nm or 254 nm.
In the manufacturing method of the metal base circuit board of Claim 11 or 12,
It said aluminum integral light quantity of the ultraviolet rays irradiated to the substrate surface is 0.1 J / cm 2 or more 1.0 J / cm 2 or less, the production method of the metal base circuit board.
In the manufacturing method of the metal base circuit board as described in any one of Claims 11 thru | or 13,
The method of manufacturing a metal base circuit board, wherein the aluminum substrate is not surface-treated with a coupling agent.
A method for treating an aluminum substrate used in a metal base circuit board according to any one of claims 1 to 8,
A method for treating an aluminum substrate for a metal base circuit board, comprising bringing the aluminum substrate into contact with water at 50 ° C. or more and 80 ° C. or less for 0.5 minutes or more and 3 minutes or less.
A method for treating an aluminum substrate used in a metal base circuit board according to any one of claims 1 to 8,
The integrated quantity of ultraviolet light is 0.1 J / cm 2 or more 1.0 J / cm 2 or less, the processing method of an aluminum substrate metal base circuit board to be irradiated to the aluminum substrate surface.