CN103328548B - Resin combination sheet material, with the resin combination sheet material of metal forming, Metal Substrate distributing board material, Metal Substrate distributing board and LED light source member - Google Patents

Resin combination sheet material, with the resin combination sheet material of metal forming, Metal Substrate distributing board material, Metal Substrate distributing board and LED light source member Download PDF

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Publication number
CN103328548B
CN103328548B CN201280006296.7A CN201280006296A CN103328548B CN 103328548 B CN103328548 B CN 103328548B CN 201280006296 A CN201280006296 A CN 201280006296A CN 103328548 B CN103328548 B CN 103328548B
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resin combination
sheet material
combination sheet
resin
metal
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CN103328548A (en
Inventor
西村正人
宫崎靖夫
天沼真司
田仲裕之
原直树
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • H05K1/189—Printed circuits structurally associated with non-printed electric components characterised by the use of a flexible or folded printed circuit
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10106—Light emitting diode [LED]

Abstract

The resin combination sheet material of the present invention is formed by the resin combination comprising thermosetting resin, phenolic resin and insulating properties inorganic filler, in the surface of described resin combination sheet material, the occupation rate of the recess that depth capacity is more than 0.5 μm is calculated as less than 4% with area occupation ratio.

Description

Resin combination sheet material, with the resin combination sheet material of metal forming, Metal Substrate distributing board material, Metal Substrate distributing board and LED light source member
Technical field
The present invention relates to resin combination sheet material, with the resin combination sheet material of metal forming, Metal Substrate distributing board material, Metal Substrate distributing board and LED light source member.
Background technology
Along with the development of the densification of electronic equipment, densification, there is increase tendency in the local pyrexia amount that circuit is first-class, for the circuit substrate being equipped with the electronic units such as semiconductor element, it is desirable to high heat dispersion.On the other hand, high electrical insulating properties is necessarily required as before.
Therefore, have the resin combination of high heat conductance and high electrical insulating properties as heat conductivity encapsulant, thermal conductive adhesive and practical gradually.
About above-mentioned, comprising the epoxy resin of display liquid crystal liquid crystal property and the composition epoxy resin of insulating properties inorganic filler disclosed in the Japanese Unexamined Patent Publication 2008-13759 publication, this composition epoxy resin has high heat conductance and excellent processability.
Summary of the invention
The problem that invention to solve
But, in the composition epoxy resin described in patent documentation 1, there is the situation that can not obtain sufficient electrical insulating property.
The problem of the present invention is: provide Metal Substrate distributing board material, Metal Substrate distributing board and the LED light source member that can form the excellent resin combination sheet material of resin cured matter of thermal conductivity and electrical insulating property, the resin combination sheet material with metal forming and use them and formed.
The method of solution problem
The present invention relates to herein below.
< 1 > resin combination sheet material, it comprises thermosetting resin, phenolic resin and insulating properties inorganic filler,
In resin combination sheet material surface, the occupation rate of the recess that depth capacity is more than 0.5 μm is calculated as less than 4% with area occupation ratio.
Resin combination sheet material described in < 2 > above-mentioned < 1 >, the lowest melt viscosity at 20 DEG C～200 DEG C is 10Pa s～1000Pa s.
Resin combination sheet material described in < 3 > above-mentioned < 1 > or < 2 >, it contains the above-mentioned insulating properties inorganic filler of more than 40vol% below 82vol%.
Wantonly 1 described resin combination sheet material in < 4 > above-mentioned < 1 >～< 3 >, at least one filler selected in the group that above-mentioned insulating properties inorganic filler is made up of aluminium oxide, magnesium oxide, boron nitride, aluminium nitride, silicon nitride, carborundum and aluminium fluoride.
Wantonly 1 described resin combination sheet material in < 5 > above-mentioned < 1 >～< 4 >, above-mentioned phenolic resin has the construction unit represented by following formula (I).
[changing 1]
In formula (I), R1Represent alkyl, aryl or aralkyl, R2And R3Representing hydrogen atom, alkyl, aryl or aralkyl independently of one another, m represents the integer of 0～2, and n represents the integer of 1～10.
Wantonly 1 described resin combination sheet material in < 6 > above-mentioned < 1 >～< 5 >, it is formed by the resin combination comprising above-mentioned thermosetting resin, above-mentioned phenolic resin and above-mentioned insulating properties inorganic filler
The viscosity of above-mentioned resin combination is above below the 10000mPa s of 1000mPa s,
Above-mentioned resin combination sheet material is formed on support base material by being coated on by above-mentioned resin combination.
< 7 > resin combination sheet material, its lowest melt viscosity at 20 DEG C～200 DEG C is 10Pa s～1000Pa s,
In its surface, the occupation rate of the recess of depth capacity more than 0.5 μm is calculated as less than 4% with area occupation ratio.
Wantonly 1 described resin combination sheet material in < 8 > above-mentioned < 1 >～< 7 >, its average thickness is more than 20 μm less than 500 μm.
The < 9 > mono-kind resin combination sheet material with metal forming, it has wantonly 1 described resin combination sheet material and metal forming in above-mentioned < 1 >～< 8 >.
< 10 > Metal Substrate distributing board material, it has metal forming, metal basal board and the heat conductivity insulating barrier between above-mentioned metal forming and said metal substrates,
Above-mentioned heat conductivity insulating barrier is the solidfied material of wantonly 1 described resin combination sheet material in above-mentioned < 1 >～< 8 >.
< 11 > Metal Substrate distributing board, it has wiring layer, metal basal board and the heat conductivity insulating barrier between above-mentioned wiring layer and said metal substrates,
Above-mentioned heat conductivity insulating barrier is the solidfied material of wantonly 1 described resin combination sheet material in above-mentioned < 1 >～< 8 >.
< 12 > LED light source member, by using wantonly 1 described resin combination sheet material in above-mentioned < 1 >～< 8 >, the resin combination sheet material with metal forming described in above-mentioned < 9 >, Metal Substrate distributing board material described in above-mentioned < 10 >, or in the Metal Substrate distributing board of above-mentioned < 11 > wantonly 1 and formed.
The effect of invention
According to the present invention it is possible to provide Metal Substrate distributing board material, Metal Substrate distributing board and the LED light source member that can form the excellent resin combination sheet material of resin cured matter of thermal conductivity and electrical insulating property, the resin combination sheet material with metal forming and use them and formed.
Accompanying drawing explanation
Fig. 1 represents the cross-section structure of an example of the Metal Substrate distributing board material of the present invention.
Fig. 2 represents the cross-section structure of an example of the Metal Substrate distributing board of the present invention.
Fig. 3 represents the cross-section structure of an example of the LED light source member of the present invention.
Detailed description of the invention
In the present invention, independent operation be not only in " operation " word, even if when can not clearly distinguish with other operation, if the desired effect of this operation can be realized, is then also contained in this term.
It addition, in this manual, use "～" represented by numerical range represent and comprise "～" before and after described numerical value respectively as the scope of minima and maximum.
< resin combination sheet material >
The first resin combination sheet material of the present invention is to comprise thermosetting resin, phenolic resin and insulating properties inorganic filler, in the surface of resin combination sheet material, the occupation rate of the recess that depth capacity is more than 0.5 μm is calculated as the resin combination sheet material of less than 4% with area occupation ratio.
The second resin combination sheet material of the present invention is the lowest melt viscosity at 20 DEG C～200 DEG C is 10～1000Pa s, and in its surface, the occupation rate of the recess that depth capacity is more than 0.5 μm is calculated as the resin combination sheet material of less than 4% with area occupation ratio.
The above-mentioned recess of the present invention refers to the recess on the resin combination sheet material surface being present in B scalariform state.More specifically, the recess of the present invention refers to: in the recess on resin combination sheet material surface being present in B scalariform state, and depth capacity is from 0.5 μm of the resin combination sheet material surface recess less than resin combination sheet material thickness.
The resin combination sheet material of the present invention is fitted on metal forming, wiring layer or metal basal board etc., is formed with the resin combination sheet material of metal forming, distributing board material, distributing board etc..Therefore, the interface that the recess on resin combination sheet material surface and metal forming, wiring layer or metal basal board etc. are fitted forms bubble.Hereinafter, sometimes this bubble is called " interfacial bubbles ".When using resin combination sheet material to form distributing board material, distributing board, the interfacial bubbles being included in becomes the starting point of insulation breakdown, thus reducing the insulation breakdown voltage of distributing board material, distributing board.
But, in the less situation of containing ratio of above-mentioned interfacial bubbles, the pressurized, heated (the so-called solidification heating etc. for forming C rank) during by making distributing board material, make resin combination sheet material flow, interfacial bubbles disappears.Therefore, in former resin combination sheet material, make interfacial bubbles disappear by pressurized, heated when forming C rank, manage to make interfacial bubbles be absent from after forming C rank.Specifically, the method for the mobility of resin combination sheet material when improving pressurized, heated when making distributing board material is studied.
But, the mobility of the resin combination sheet material when pressurized, heated is too high, by making pressurized, heated during distributing board material, resin combination sheet material flows out sheet material from the end of distributing board material, has the thickness of the resin combination sheet material in end to change, thickness produces the situation of deviation.This thickness deviation can cause the aberrations in property in the face of Metal Substrate distributing board material.Further, since resin combination sheet material flows out sheet material from end, therefore operability reduces.
If particularly it is known that improve the filling rate of insulating properties inorganic filler to improve thermal conductivity, then the surface of resin combination sheet material produces more recess and makes interfacial bubbles increase.Deposit in many cases at interfacial bubbles, method before this has the situation that interfacial bubbles not exclusively disappears.
Therefore in the present invention, by under the B scalariform state before fitting with metal forming, wiring layer or metal basal board etc., the occupation rate of the recess in resin combination sheet material surface is suppressed below specific scope, thus interfacial bubbles when reducing laminating and then suppress the reduction of insulation breakdown voltage.Particularly when the recess occupation rate in resin combination sheet material surface is calculated as less than 4% with area occupation ratio, then it is of value to the reduction suppressing insulation breakdown voltage.Additionally, it is known that the reduction of insulation breakdown voltage can be produced considerable influence by the recess of particular size in the recess on resin combination sheet material surface, therefore by recess that depth capacity in the recess on surface is more than 0.5 μm specifically for recess.
Additionally, owing to the present invention suppresses the generation of interfacial bubbles by the method except the mobility of the resin combination sheet material when the pressurized, heated, therefore, during pressurized, heated when making distributing board material, it is also possible to solve resin combination sheet material and flow out the such problem of sheet material from the end of distributing board material.
That is, in former resin sheet, regardless of the occupation rate of recess is how many, by improving the mobility of resin and filling recess and improve insulation breakdown voltage, but then, the operability cause thickness deviation in the face of Metal Substrate wiring material, being caused by the outflow of resin combination reduces.
On the other hand, in the resin combination sheet material of the present invention, by making the occupation rate of the recess of depth capacity more than 0.5 μm in its surface be calculated as less than 4% with area occupation ratio, even if not improving the mobility of resin, recess can also be fully filled, improve insulation breakdown voltage.And then, it is also possible to solve the problem that the operability that in the face of Metal Substrate distributing board material, thickness deviation, outflow due to resin combination cause reduces.
Method as " in surface, the occupation rate of the recess of depth capacity more than 0.5 μm is calculated as less than 4% with area occupation ratio " the resin combination sheet material making the present invention, for instance can enumerate: (1) adjusts the kind of insulating properties inorganic filler and the method for use level；(2) method adjusting the viscosity of the resin combination used when manufacturing resin combination sheet material；(3) when manufacturing resin combination sheet material, by the method manufacturing 2 resin combination sheet materials these the 2 recess occupation rates reducing surface of fitting；(4) through the method etc. by the surface smoothing operation of resin combination sheet material.
Here, the recess occupation rate in the present invention is defined as: the ratio of the gross area of the scope that the area calculated by the summation of the recess area observed is observed relative to the recess carrying out resin combination sheet material surface.More specifically represent by formula the following.
Recess occupation rate (%)=(area calculated by the summation of the recess area observed)/(carrying out the gross area of the scope of recess observation) × 100.
The recess of the present invention is observed, it is possible to undertaken by scanning electron microscope (SEM), optical microscope, laser microscope, light interference type microscope.
After laminating metal forming, wiring layer or metal basal board etc. with in the resin combination sheet material of metal forming, Metal Substrate distributing board material or Metal Substrate distributing board etc., in order to measure the occupation rate of the recess on resin combination sheet material surface, when metal forming, wiring layer or metal basal board etc. can be peeled off, the recess on the resin combination sheet material surface after observation stripping, is obtained by above-mentioned formula.When metal forming, wiring layer or metal basal board etc. can not be peeled off, it is possible to evaluated the occupation rate of recess by the observation of section.In this case, using the summation of the length on the limit of the interfacial bubbles of observation relative to 2 powers of the ratio of the overall length of the scope carrying out section observation as recess occupation rate (%).
In the present invention, above-mentioned recess occupation rate, from the viewpoint of improve insulation breakdown voltage, it is less than 4%, it is preferably less than 3% to more reliably improve insulation breakdown voltage, more reliably improves insulation breakdown voltage more preferably less than 2% for the adherend big relative to surface roughness.
Specifically, as the method for the occupation rate of the recess adjusted in resin combination sheet material surface, for instance can enumerate: (1) adjusts the kind of insulating properties inorganic filler and the method for use level；(2) method adjusting the viscosity of the resin combination used when manufacturing resin combination sheet material；(3) when manufacturing resin combination sheet material, by the method manufacturing 2 resin combination sheet materials these the 2 recess occupation rates reducing surface of fitting；(4) through the method etc. by the surface smoothing operation of resin combination sheet material.
More specifically, in (1), can enumerate different-grain diameter such as big footpath particle, central diameter particle, path mix particles for insulating properties inorganic filler, make the method that the oil absorbency etc. of JIS-K-5101-13-2 etc. carries out coordinating for minimum mode further according to its mixing ratio.Thus, even if improve the filling rate of insulating properties inorganic filler to improve heat conductivity, it is also possible to potting resin between filler, it is possible to reduce the area occupation ratio of the recess of resin combination sheet material.
In (2), in order to by the decrease in viscosity of resin combination to the viscosity being suitable for coating, it is preferable that add solvent etc..When amount of solvent is set to the situation of below appropriate amount, the recess caused due to the performance of solvent etc. can be suppressed to produce.
In (3), it is possible to use the resin combination sheet material of the known method such as laminating machine, forcing press laminating more than 2.Owing to resin combination sheet material is fusion together well, therefore can engage resin combination sheet material each other, it is possible to form single resin sheet.It is thus possible, for instance in the one side of resin combination sheet material, when the area occupation ratio of recess is high or when defining concavo-convex, by by bonded to each other for this face, it is possible to make recess, concavo-convex disappearance.Therefore, it is possible to reduce the recess occupation rate on resin combination sheet material surface.
In (4), in 1 of resin combination sheet material, or when fitting 2 resin combination sheet materials of (3), it is possible to use the method for pressurized, heated.Thus, it is possible to reduce at the resin combination sheet material back side, i.e. resin combination sheet material and the recess of generation on the interface of base material.Further, when pressurized, heated, the substrate being connected with resin combination sheet material uses smooth and concavo-convex few base material, thus easily reducing the recess produced on the resin combination sheet material interface with base material.
But, the invention is not restricted to these methods.
Below, the material and the physical property that resin combination sheet material are used illustrate.
The first resin combination sheet material of the present invention is formed by the resin combination comprising thermosetting resin, phenolic resin and insulating properties inorganic filler.The resin combination sheet material of the present invention can comprise other composition further as required.
Additionally, the second resin combination sheet material of the present invention, as long as lowest melt viscosity is in above-mentioned scope, is just not particularly limited about its composition, but preferably in the same manner as the first resin combination sheet material, comprise thermosetting resin, phenolic resin and insulating properties inorganic filler and constitute.About lowest melt viscosity assay method as be described hereinafter.
(thermosetting resin)
The resin combination sheet material of the present invention comprises at least one thermosetting resin.As above-mentioned thermosetting resin, just it is not particularly limited as long as have heat cured resin, it is possible to use normally used thermosetting resin.As thermosetting resin, specifically include, for example: the modified system etc. of epoxy system resin, polyimides system resin, polyamidoimide system resin, triazine resin, phenolic aldehyde system resin, melamine series resin, polyester based resin, cyanate ester based resin and these resins.These resins can be used alone or two or more kinds may be used.
Thermosetting resin in the present invention, considers from thermostability viewpoint, it is preferred to the resin selected from epoxy system resin and triazine resin, more preferably epoxy system resin.It addition, firming agent, curing accelerator can also be comprised as required.Epoxy system resin can be used alone or two or more kinds may be used.
As above-mentioned epoxy system resin (being sometimes only called " epoxy resin " below), the polyglycidyl ether that the polyhydric alcohol such as polyhydric phenols and BDO such as making bisphenol-A, Bisphenol F, xenol, novolak phenolics, ortho cresol novolak type phenolic resin, tris-phenol novolak phenolics obtains can be enumerated with epichlorohydrin reaction；Make the poly glycidyl ester that the polyprotic acid such as phthalic acid, hexahydrophthalic acid and epichlorohydrin reaction obtain；Amine, amide or there is the N-glycidyl derivatives of compound of hetero ring type nitrogen base；With alicyclic epoxy resin etc..
In above-mentioned epoxy system resin, improve from the viewpoint of itself thermal conductivity of resin, heating time melt viscosity reduce, it is preferable that have with biphenyl structural etc. be representative the epoxy monomer of mesomorphic skeleton or its polymer.
The mesomorphic skeleton representation of the present invention has the functional group of the probability of performance liquid crystal liquid crystal property.Specifically, biphenyl, phenol benzoate, diphenyl diimide, stilbene etc., its derivant can be enumerated, the material of 6 Yuans ring structures in biphenyl or molecule with more than 3 can be enumerated, the following formula (A) described in " liquid crystal handbook (liquid crystal is just) " (the kind liquid crystal handbook of ball returns federal communications commission and compiles publication in 2000) can be enumerated.
[changing 2]
Or
... (A)
In formula (A), as the ring structure represented by ring 1, ring 2 and ring 3 independently of one another from
[changing 3]
Middle selection, in conjunction with base X1 and X2 be each independently singly-bound,
[changing 4]
Or the concatenating group by two combination of the above in them, Y1, Y2 and Y3 represent that-R ,-OR(R represent the aliphatic alkyl of carbon number 1～8 independently of one another) ,-F ,-Cl ,-Br ,-I ,-CN ,-NO2, or-CO-CH3, n, m and l represent the integer of 0～4 independently of one another.
As the epoxy monomer with mesomorphic skeleton, preferred biphenyl type epoxy resin, connection xylol type epoxy resin, 1-(3-methyl-4-oxiranylmethoxy benzene base)-4-(4-oxiranylmethoxy benzene base)-1-cyclohexene or 1-(3-methyl-4-oxiranylmethoxy benzene base)-4-(4-oxiranylmethoxy benzene base)-benzene etc., from the viewpoint of the thermal conductivity of fusing point and solidfied material, more preferably 1-(3-methyl-4-oxiranylmethoxy benzene base)-4-(4-oxiranylmethoxy benzene base)-1-cyclohexene.Such epoxide such as can be manufactured by the method described in above-mentioned patent documentation 1.
In the above-mentioned epoxy monomer with mesomorphic skeleton or its polymer, it is preferable that there are 2 functional epoxy resins of biphenyl backbone containing at least one.As long as the compound that above-mentioned 2 functional epoxy resins with biphenyl backbone comprise at least 1 biphenyl backbone, have 2 epoxy radicals is just not particularly limited.Specifically include, for example biphenyl type epoxy resin, sub-biphenyl type epoxy resin.
As above-mentioned biphenyl type epoxy resin, it is preferred to use the epoxy resin etc. represented by following formula (III).
[changing 5]
R in formula (III)1～R8Representing the substituted or unsubstituted alkyl of hydrogen atom or carbon number 1～10 independently of one another, n represents the integer of 0～3.
Substituted or unsubstituted alkyl as carbon number 1～10, for instance can enumerate: methyl, ethyl, propyl group, butyl, isopropyl, isobutyl group etc..Wherein, R1～R8Preferred hydrogen atom or methyl independently of one another.
As the biphenyl type epoxy resin shown in above-mentioned formula (III), for instance can enumerate: with 4,4 '-bis-(2,3-epoxy radicals propoxyl group) biphenyl or 4,4 '-bis-(2,3-epoxy radicals propoxyl group)-3,3 ', 5,5 '-tetramethyl biphenyl is the epoxy resin of main component, make epoxychloropropane and 4,4 '-xenol or 4,4 '-(3,3 ', 5,5 '-tetramethyl) epoxy resin etc. that is obtained by reacting of xenol.Wherein preferably with 4,4 '-bis-(2,3-epoxy radicals propoxyl group)-3,3 ', 5,5 '-tetramethyl biphenyl is the epoxy resin of main component.As such compound, it is possible to obtain epoxy resin Co., Ltd. of YX-4000(Japan system), epoxy resin Co., Ltd. of YL-6121(Japan system), YSLV-80XY(Toto Kasei KK system) etc. as commercially available product.
It addition, as above-mentioned sub-biphenyl type epoxy resin, it is possible to enumerate the epoxy resin etc. represented by following formula (IV).
[changing 6]
In formula (IV), R1～R9Representing the aralkyl of hydrogen atom, the alkyl of carbon number 1～10, the alkoxyl of carbon number 1～10, the aryl of carbon number 6～10 or carbon number 7～10 independently of one another, n represents the integer of 0～10.
Alkyl as above-mentioned carbon number 1～10, for instance can enumerate: methyl, ethyl, propyl group, butyl, isopropyl, isobutyl group etc..Alkoxyl as carbon number 1～10, for instance methoxyl group, ethyoxyl, propoxyl group, butoxy etc. can be enumerated.Aryl as carbon number 6～10, for instance phenyl, tolyl, xylyl etc. can be enumerated.It addition, as the aralkyl of carbon number 7～10, for instance benzyl, phenethyl etc. can be enumerated.Wherein, R1～R9Preferred hydrogen atom or methyl independently of one another.
As the biphenyl type epoxy resin represented by above-mentioned formula (IV), for instance NC-3000(Nippon Kayaku K. K trade name can be obtained) as commercially available product.
As 2 functional epoxy resins in the present invention with biphenyl backbone, consider from the flexual viewpoint of thermal conductivity, electrical insulating property and aftermentioned B rank sheet material, preferably comprise the compound represented by the above-mentioned formula of at least one (III) or formula (IV), more preferably comprise the compound represented by least one formula (III).
As the containing ratio of above-mentioned thermosetting resin in all solids composition at the resin combination sheet material of the present invention, it is not particularly limited, but consider from the flexual viewpoint of thermal conductivity, electrical insulating property and B rank sheet material, it is preferably 1 mass %～15 mass %, it is more preferably 2 mass %～12 mass %, more preferably 3 mass %～10 mass %.
The resin combination sheet material of the present invention, it is possible to and with above-mentioned 2 functional epoxy resins with biphenyl backbone and other epoxy resin.As other epoxy resin, as long as do not have the material of biphenyl backbone, it is possible to use previously known epoxy resin without particular limitation.
As other epoxy resin, specifically include, for example: with phenol novolak type epoxy resin, o-cresol phenolic epoxy varnish, have that the epoxy resin of triphenyl methane skeleton is representative the compound novolac resin of condensation or cocondensation gained under acidic catalyst making the aphthols such as the phenols such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol-A, Bisphenol F and/or alpha-Naphthol, betanaphthol, dihydroxy naphthlene and formaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde, salicylide etc. have aldehyde radical is carried out epoxidised epoxy resin.
It addition, bisphenol-A, Bisphenol F, bisphenol S, stilbene type epoxy resin can be enumerated；Hydroquinone type epoxy resin；Glycidyl ester type epoxy resin by the polyprotic acid such as phthalic acid, dimeric dibasic acid Yu epichlorohydrin reaction gained；Glycidyl amine type epoxy resin by the polyamines such as diaminodiphenyl-methane, isocyanuric acid Yu epichlorohydrin reaction gained；The epoxide of the cocondensation resin of bicyclopentadiene and phenols；There is the epoxy resin of naphthalene nucleus；Phenol-aralkyl resin, phenol-aralkyl-type phenol resin such as aralkyl resin, naphtol-aralkyl resins containing sub-biphenyl backbone epoxide；Trimethylolpropane type epoxy resin；Terpene modified epoxy；Utilize the wire aliphatic epoxy resin that the oxidation of alkene key is obtained by the peracid such as peracetic acid；Cycloaliphatic epoxy resin；The epoxy resin etc. of sulfur atom-containing, they can be used alone, it is also possible to and use two or more.
The resin combination sheet material of the present invention, considers from the flexual viewpoint of B rank sheet material, it is preferable that comprise at least one selected from the epoxy resin with naphthalene nucleus.
The resin combination sheet material of the present invention is when comprising other epoxy resin, its containing ratio is not particularly limited, but such as, relative to above-mentioned 2 functional epoxy resins with biphenyl backbone, it is preferably 1 mass %～30 mass %, it is more preferably 2 mass %～20 mass %, more preferably 3 mass %～15 mass %.By being such containing ratio, the pliability of thermal conductivity, electrical insulating property and B rank sheet material more effectively improves.
(phenolic resin)
The resin combination sheet material of the present invention contains at least one phenolic resin.As above-mentioned phenolic resin, it is preferable that comprise the phenolic resin (being sometimes referred to as " novolac resin " below) of the compound containing at least one with construction unit represented by following formula (I).Above-mentioned phenolic resin such as firming agent as epoxy resin works.
By comprising the phenolic resin with ad hoc structure, thermal conductivity can be effectively improved, and can fully extend the pot life under state before curing further.
[changing 7]
In above-mentioned formula (I), R1Represent alkyl, aryl or aralkyl, R1Represented alkyl, aryl or aralkyl can have substituent group if possible further, as this substituent group, it is possible to enumerate alkyl, aryl, halogen atom and hydroxyl etc..
M represents the integer of 0～2, when m is 2, and 2 R1Can be the same or different.In the present invention, m is preferably 0 or 1, more preferably 0.N represents the integer of 1～10, it is preferred to 1～8, more preferably 1～7.
R in formula (I)2And R3Represent hydrogen atom, alkyl, aryl, phenyl or aralkyl independently of one another.R2And R3Represented alkyl, phenyl, aryl or aralkyl can have substituent group if possible further, as this substituent group, it is possible to enumerate alkyl, aryl, halogen atom and hydroxyl etc..
R as the present invention2And R3, from the viewpoint of storage stability and thermal conductivity, it is preferred to hydrogen atom, alkyl, phenyl or aryl, more preferably hydrogen atom, the alkyl of carbon number 1 to 4 or the aryl of carbon number 3 to 6, phenyl, more preferably hydrogen atom.
Consider from thermostability viewpoint further, R2And R3At least one party be preferably also aryl.
The phenolic resin of the present invention, it is possible to individually comprise a kind, the compound of the construction unit having represented by above-mentioned formula (I) of more than two kinds can also be comprised.
Phenolic resin represented by above-mentioned formula (I) comprises the part-structure from the resorcinol as phenoloid, it is also possible to comprise at least one part-structure from the phenoloid except resorcinol further.As the phenoloid except resorcinol, for instance phenol, cresol, catechol, hydroquinone etc. can be enumerated.Above-mentioned phenolic resin, it is possible to comprise independent a kind or comprise the part-structure from them with combination of more than two kinds.
Here, the so-called part-structure from phenoloid refers to: remove 1 or 2 hydrogen atoms from the phenyl ring part of phenoloid and 1 valency that constitutes or divalent group.It addition, the position removing hydrogen atom is not particularly limited.
In the present invention, as the part-structure from the phenoloid except resorcinol, from the viewpoint of thermal conductivity, cementability, storage stability, it is preferred to come since phenol, cresol, catechol, hydroquinone, 1,2,3-trihydroxy benzene, 1,2,4-trihydroxy benzenes and 1,3, the part-structure of at least one selected in 5-trihydroxy benzene, more preferably carry out the part-structure of at least one selected in catechol and hydroquinone.
Additionally, about being not particularly limited containing ratio from the part-structure of resorcinol in above-mentioned phenolic resin, but from the viewpoint of thermal conductivity and storage stability, gross mass relative to phenolic resin, the ratio that contains from the part-structure of resorcinol is preferably more than 30 mass %, it is more preferably more than 55 mass %, more preferably more than 80 mass %.
As the phenolic resin of the present invention, in particular, it is preferred that the phenolic resin of the compound for comprising any one the represented part-structure having in formula (Ia)～formula (If) shown below.
[changing 8]
Phenolic resin in the present invention is it is also preferred that at least one that the compound with the construction unit represented by above-mentioned formula (I) is the compound represented by following formula (II).
[changing 9]
In formula (II), R11Represent hydrogen atom or the 1 valency group from the phenoloid represented by following formula (IIp), R12Represent the 1 valency group from phenoloid.It addition, R1、R2、R3, R in m and n and formula (I)1、R2、R3, m and n respectively synonym.
R11And R12The represented 1 valency group from phenoloid is that the phenyl ring part from phenoloid removes 1 hydrogen atom and the 1 valency group that constitutes, and the position removing hydrogen atom is not particularly limited.
[changing 10]
In formula (IIp), p represents the integer of 1～3.It addition, R1、R2And R3With the R in formula (I)1、R2And R3Synonym respectively, m represents the integer of 0～2.
R11And R12Phenoloid as long as there is the compound of phenolic hydroxyl group, be just not particularly limited.Specifically include, for example: phenol, cresol, catechol, resorcinol, hydroquinone etc..Wherein, from the viewpoint of thermal conductivity and storage stability, it is preferred at least one selected from cresol, catechol, resorcinol.
In the resin combination sheet material of the present invention, comprise the phenolic resin of the compound with the construction unit represented by above-mentioned formula (I), it is possible to comprise the monomer as the phenoloid constituting phenolic resin.The ratio (being sometimes referred to as " monomer contains ratio " below) that contains as the monomer of the phenoloid constituting phenolic resin is not particularly limited, but is preferably 5～80 mass %, more preferably 15～60 mass %, more preferably 20～50 mass %.
Being more than 5 mass % by making monomer contain ratio, thus suppressing the viscosity of phenolic resin to rise, the adaptation of inorganic filler improves further.It addition, by being below 80 mass %, cross-linking reaction during by solidifying, more highdensity higher order structure can be formed, realize excellent thermal conductivity and thermostability.
It addition, as the monomer of the phenoloid constituting phenolic resin, it is possible to enumerate resorcinol, catechol, hydroquinone, it is preferable that including at least resorcinol as monomer.
Additionally, as the above-mentioned phenolic resin in the resin combination sheet material of the present invention containing ratio, it does not have limit especially, but from the viewpoint of the pliability of thermal conductivity, electrical insulating property, B rank sheet material and pot life, it is preferably 1 mass %～15 mass %, more preferably 2 mass %～10 mass %.
Additionally, as thermosetting resin above-mentioned in the resin combination sheet material of the present invention and above-mentioned phenolic resin containing ratio (thermosetting resin/phenolic resin), such as in equivalent proportion benchmark, can be 0.6～1.5, from the viewpoint of the pliability of thermal conductivity, B rank sheet material and pot life, it is preferred to 0.8～1.2.
The resin combination sheet material of the present invention, except above-mentioned phenolic resin, can also comprise other firming agent except phenolic resin as required.As other firming agent, it is possible to use previously known firming agent without particular limitation.Specifically such as can use: the potentiality firming agent etc. such as polyaddition type firming agent, imidazoles such as amine system firming agent, mercaptan system firming agent.
(insulating properties inorganic filler)
The insulating properties inorganic filler contained by resin combination sheet material of the present invention, as long as insulating properties inorganic filler is just not particularly limited.Preferably there is the material of more than 1W/mK thermal conductivity, specifically, can select from silicon dioxide, aluminium oxide, magnesium oxide, beryllium oxide, boron nitride, aluminium nitride, silicon nitride, carborundum, aluminium fluoride or calcium fluoride.In these, it is possible to use one or mixing two kinds are used above.
It is preferred that have the inorganic ceramic of more than 10W/mK thermal conductivity, specifically, can select from aluminium oxide, magnesium oxide, boron nitride, aluminium nitride, silicon nitride, carborundum or aluminium fluoride.
Wherein, more preferably have 1016The aluminium oxide (Alumina) of the specific insulation of more than Ω cm.
They can be used alone one, or mixing two kinds is used above.
The particle diameter of insulating properties inorganic filler, mixed proportion are not particularly limited.Particle diameter about insulating properties inorganic filler, mixed proportion, such as enumerate and be suitable for the situation of 3 kinds of inorganic filling material groups with different grain size distribution when being example, comprise the inorganic filling material group (A) that particle diameter D50 is more than 5 μm less than 100 μm, D50 is less than the 1/2 of inorganic filling material group (A) and is the inorganic filling material group (B) of more than 1 μm less than 10 μm, with D50 is inorganic filling material group (B) less than 1/2 and be more than 0.1 μm less than 5 μm inorganic filling material group (C) constitute, the described particle diameter D50 accumulation 50% corresponding to starting from the little particle diameter side of weight build-up particle size distribution, total amount relative to inorganic filling material, inorganic filling material group (A), (B) distinguish preferably with the ratio of (C) with below more than 40 mass % 90 mass %, below more than 5 mass % 40 mass %, below more than 1 mass % 30 mass % is (wherein, inorganic filling material group (A), (B) and the gross mass % of (C) be 100 mass %) ratio be filled with.
It addition, when the inorganic filling material that use particle size distribution is wide, have the situation being difficult to separate mixed particle size distribution clearly.In such a situation it is preferred to consider the thickness of design and after determining maximum particle diameter, when describing weight build-up particle size distribution by big particle diameter side according to the mode of the knowledge met before Fuller curve etc. to design particle size distribution.
It addition, the mean diameter of above-mentioned inorganic filling material group (A) and maximum, the thickness being taken as target when the metal forming of sheet material or resin is limited.When not having other restriction especially, from the viewpoint of thermal conducting rate, the mean diameter of above-mentioned inorganic filling material group (A) is the bigger the better, from the viewpoint of thermal resistance, makes insulating properties as far as possible in the scope allowed and is preferably thin thickness.It addition, from the viewpoint of insulating properties, maximum particle diameter is at least less than the 7/8 of thickness, is preferably less than 2/3, more preferably less than 1/2.Therefore, above-mentioned inorganic filling material group (A) mean diameter is thickness less than 1/2 and be preferably more than 5 μm less than 100 μm, from the viewpoint of fillibility and thermal resistance, heat conductivity, more preferably more than 10 μm less than 75 μm, more preferably more than 10 μm less than 45 μm.
In the present invention, the particle diameter D50 of insulating properties inorganic filler uses laser diffractometry to measure, and when starting to describe weight build-up size distribution curve from little particle diameter side, is the particle diameter of 50% corresponding to weight build-up.
The particle size distribution using laser diffractometry can use laser diffraction and scattering particle size distribution device (such as, Beckman-Coulter Corporation's system, LS230) to carry out.
It addition, when above-mentioned inorganic filling material group (A) and inorganic filling material group (B) are for alumina packing, it is preferred that for the alumina packing being made up of the monocrystal particle of Alpha-alumina.
On the other hand, when above-mentioned inorganic filling material group (C) is for alumina packing, it is preferably Alpha-alumina, gama-alumina, δ-aluminium oxide or θ-aluminium oxide, more preferably Alpha-alumina, it is preferred that be the alumina packing being made up of the monocrystal particle of Alpha-alumina.
The containing ratio of the insulating properties inorganic filler contained by resin combination sheet material of the present invention is not particularly limited, but in the solid constituent constituting resin combination sheet material, can be 40vol%～82vol%, consider from the flexual viewpoint of thermal conductivity, electrical insulating property and sheet material, it is more preferably 50vol%～79vol%, more preferably 55vol%～76vol%.When the cumulative volume of insulating properties inorganic filler is very few, thermal conductivity reduces, when too much, it is difficult to form tablet.
It addition, the solid constituent in so-called resin combination sheet material, refer to the residual component eliminating volatile ingredient from the composition constituting resin combination sheet material.
As above-mentioned inorganic filling material group (A)～(C), it is possible to suitably select from commercially available material.Additionally, such as can also for by by transitional alumina or become the alumina packing of transitional alumina by heat treatment and burn till (for example, referring to Japanese Unexamined Patent Publication 6-191833 publication, Japanese Unexamined Patent Publication 6-191836 publication etc.) in the atmosphere gas containing hydrogen chloride and the material that manufactures.
The resin combination sheet material of the present invention, except above-mentioned inorganic filling material group (A)～(C), it is also possible to comprise with aluminium oxide be main component, its equal fibre diameters of number be the inorfil of 1 μm～50 μm.In the present invention, " inorfil being main component with aluminium oxide " refers to the inorfil comprising more than 41vol% aluminium oxide.Wherein, it is preferred to comprise the inorfil of more than 58vol% aluminium oxide, more preferably comprise the inorfil of more than 74vol% aluminium oxide.The equal fibre diameter of number of such inorfil is 1 μm～50 μm, it is preferred to 1 μm～30 μm, more preferably 1 μm～20 μm.It addition, the fiber length of such inorfil is generally 0.1mm～100mm.
As such inorfil, generally use commercially available material, specifically, ALTEX(Sumitomo Chemical Co system can be enumerated), DENKAALCEN(Deuki Kagaku Kogyo Co., Ltd system), MAFTEC staple in bulk (Mitsubishi Chemical property Co., Ltd's system) etc..
When using such inorfil, it makes the consumption quality relative to above-mentioned inorganic filling material group (A)～(C) be generally 4vol%～58vol%, it is preferably 4vol%～41vol%, the total quality of insulating properties inorganic filler and inorfil, in the solid constituent of resin combination sheet material, it is common to use the amount of 30～95 mass %.
The resin combination sheet material of the present invention, except above-mentioned insulating properties inorganic filler, can comprise the inorganic filling material except insulating properties inorganic filler as required further.As inorganic filling material, for instance, magnesium oxide, aluminium nitride, boron nitride, silicon nitride, silicon oxide, aluminium hydroxide, barium sulfate etc. can be enumerated as non-conducting material.It addition, as conductive material, gold, silver, nickel, copper etc. can be enumerated.These inorganic filling materials can be used alone a kind, or two or more kinds may be used.
(other composition)
The resin combination sheet material of the present invention, except above-mentioned essential component, can also comprise other composition as required.As other composition, for instance solvent, silane coupler, dispersant, sagging inhibitor etc. can be enumerated.
As above-mentioned solvent, as long as the curing reaction not interfering with resin combination sheet material is just not particularly limited, it is possible to suitably select normally used organic solvent to use.
The resin combination sheet material of the present invention preferably comprises silane coupler.By comprising silane coupler, thus playing on the surface of insulating properties inorganic filler and surrounding the effect (being equivalent to binding agent) forming covalent bond between organic resin about, thus more effectively transmit heat, further by hindering the invasion of moisture, it helps the raising of insulating reliability.
As silane coupler, generally can use commercially available material, but consider with epoxy resin, the intermiscibility of phenolic resin and reduce on resin bed and insulating properties inorganic filler interface heat conduction losses time, it is preferred to use there is the silane coupler of epoxy radicals, amino, sulfydryl, urea groups, hydroxyl at end.
Specifically include, for example: 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, APTES, 3-(2-amino-ethyl) TSL 8330, 3-(2-amino-ethyl) TSL 8330, 3-TSL 8330, 3-phenyl amino propyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane, 3-sulfydryl triethoxysilane, 3-ureidopropyltriethoxysilane etc., additionally also can enumerate the silane coupler oligomer (chemical conversion CoatedSand Co., Ltd. of Hitachi system) etc. representated by SC-6000KS2.These silane couplers can also individually or and use two or more.
The resin combination sheet material of the present invention can add dispersant, as dispersant, can generally use the effective commercial dispersants of dispersion to insulating properties inorganic filler.Include, for example that aginomoto fine chemistry Co., Ltd. AJISPER series, nanmu this chemical conversion Co., Ltd. HIPLAAD be serial, Co., Ltd. spends king HOMOGENOL serial.These dispersants can be used together more than two kinds.
(resin combination)
In the present invention, it is possible to use resin combination forms resin combination sheet material.Resin combination comprises above-mentioned thermosetting resin, above-mentioned phenolic resin and above-mentioned insulating properties inorganic filler.Owing to this resin combination is filled with insulating properties inorganic filler, therefore on base material, above-mentioned recess occupation rate can be affected for the performance of insulating properties inorganic filler when giving resin combination.
The viscosity of if tree oil/fat composition is too low, then, compared with the evaporation of the organic solvent contained by resin combination, insulating properties inorganic filler settles faster in coating substrate side, forms insulating properties inorganic filler wall.As a result of which it is, at volatile material such as the solvents contained by the resin combination of coating substrate side compared with insulating properties inorganic filler wall, bottled up due to insulating properties inorganic filler wall, condense, become bubble.Its result is to produce interfacial bubbles in coating substrate side.Therefore, in order to reduce the recess occupation rate of the resin combination sheet material of invention, the viscosity for the resin combination given on base material controls critically important.Particularly on metal foil coating resin compositions and when forming resin combination sheet material on metal foil, due to as described later generally the surface roughness of metal forming compared with metal basal board more coarse, it is apparent that the viscosity of resin combination adjusts critically important.
The viscosity of resin combination measures the viscosity at 25 DEG C by Brookfield viscometer (axle No4, revolution 30rpm).In order to effectively suppress the generation of interfacial bubbles, it is preferred to 1000～10000mPa s, more preferably 1200～8000mPa s, more preferably 1500～6000mPa s.If viscosity is too low, then the sedimentation of insulating properties inorganic filler is fast, it is easy to produce interfacial bubbles.On the other hand, if viscosity is too high, then it is difficult to control to the thickness of film.When particularly resin combination coating low for viscosity being made the resin combination sheet material with metal forming on metal foil, when viscosity is more than 1000mPa, the sedimentation that can suppress insulating properties inorganic filler is too fast, can suppress generation gap between the concavo-convex of roughened metal forming and insulating properties inorganic filler.
Containing the resin combination of insulating properties inorganic filler, the viscosity of the more many resin combinations of insulating properties inorganic filler content is more high, it is difficult to be coated with homogeneous film thickness.But, if reducing viscosity by increasing the addition of solvent etc., then the sedimentation of insulating properties inorganic filler is too fast as mentioned above, and recess occupation rate increases.Therefore, it is intended that resin combination is adjusted to suitable viscosity.
(manufacture method of resin combination sheet material (B rank))
The resin combination sheet material of the present invention is the tablet on semi-cured state (B rank).The resin combination sheet material of this semi-cured state (B rank) is for, in distributing board material, distributing board, then forming heat conductivity insulating barrier if carried out formal solidification.
Resin combination sheet material by above above-mentioned resin combination is formed lamellar coating material for giving in support base material (coating base material), can be heated to semi-cured state (B rank) and make.
Being not particularly limited for the method for giving of above-mentioned resin combination, but be preferably coated with when large area is formed.Coating can be implemented by known method.As coating process, the methods such as comma coating, die coating, die lip coating, intaglio plate coating specifically can be enumerated.As being used for being formed the coating process of the resin bed of specific thickness, it is possible to application makes the comma rubbing method that applied thing passes through between gap, the die coating method etc. being coated with the resin varnish that have adjusted flow by nozzle.In addition die lip coating, intaglio plate coating etc. can be enumerated.
When coating in order to adjust viscosity, it is possible to add solvent in above-mentioned resin combination.As the solvent contained by resin combination, it does not have limit especially, it is possible to use methyl ethyl ketone, acetone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, Hexalin, dimethyl acetylamide, isopropanol, methanol, ethanol etc..
Coating base material is not particularly limited, but owing to can be removed when making Metal Substrate distributing board material, it is thus preferred to cheap plastic basis material.As the resin used in plastic basis material, the thermoplastic polyesters such as polystyrene resin, acrylic resin, plexiglass, polycarbonate resin, Corvic, polyvinylidene chloride resin, polyvinyl resin, acrylic resin, polyamide, polyamide-imide resin, polyetherimide resin, polyether-ether-ketone resin, polyarylate resin, polyacetal resin, polybutylene terephthalate resin, polyethylene terephthalate resin can be enumerated；Thermoplastic resin, the thermosetting resins such as cellulose acetate resin, fluororesin, polysulfone resin, polyethersulfone resin, polymethylpentene resin, polyurethane resin, diallyl phthalate resin.The thickness of plastic basis material, considers to be preferably 0.01mm～5mm from operability viewpoint.In order to improve the fissility of resin combination sheet material, it is possible to form release layer on plastic basis material surface.
The above-mentioned coating material obtained, it is possible to be dried before for the heating of semi-solid preparation.Baking temperature and drying time, the kind of preferably organic solvent contained by coating material suitably adjusted.By adjusting baking temperature, drying time, by adjustment in the sedimentation velocity of coating substrate side of the evaporation rate of organic solvent and insulating properties inorganic filler, it is also possible to the recess occupation rate making the resin combination sheet material surface obtained is less than 4%.
Specifically, baking temperature is preferably 30 DEG C～90 DEG C, more preferably 40 DEG C～100 DEG C, more preferably 50 DEG C～110 DEG C.It addition, be preferably 0.2～60 minute drying time, more preferably 0.5～40 minute, more preferably 1～30 minute.
The coating material obtained is heated to semi-cured state (B rank).Here, so-called " semi-cured state (B rank) ", refer to as lowest melt viscosity, be 10 at normal temperatures3～106Pa s, in contrast in the scope of 80 DEG C～200 DEG C decrease in viscosity to 10～103The state of Pa s.It addition, for the C rank sheet material (heat conductivity insulating barrier) after formally solidifying, will not melt due to heating.
So-called above-mentioned lowest melt viscosity, the melt viscosity of terminal-modified acid imide oligomer gets minima owing to temperature rises the decrease in viscosity caused and curing reaction causes viscosity rises, it is simply that refer to this minima.The assay method of the lowest melt viscosity of resin combination sheet material is as be described hereinafter.
For the heating-up temperature of semi-solid preparation and heat time heating time, preferably the kind of organic solvent contained by above-mentioned coating material, amount suitably adjust.Specifically, it is preferably 70 DEG C～160 DEG C for the heating-up temperature of semi-solid preparation, more preferably 80 DEG C～150 DEG C, more preferably 90 DEG C～140 DEG C.It addition, the heat time heating time for semi-solid preparation is preferably 0.2～60 minute, more preferably 0.5～40 minute, more preferably 1～30 minute.
The content of organic solvent in resin combination sheet material (B rank sheet material), from the viewpoint of the generation of the space in the heat conductivity insulating barrier of (C rank sheet material), bubble after the formal solidification of suppression, it is preferable that less than the 40% of the content reduced to the resin combination supplied on base material before giving.
It addition, the resin combination sheet material obtained can be monolayer, can also be additionally by material bonded to each other for 2 resin combination sheet materials or by material folded for the resin combination sheet layer of more than 3.The laminating of more than 2 resin combination sheet materials can use the known method such as laminating machine, forcing press to be carried out, and at this moment can pass through to be thermally formed semi-cured state (B rank).
By so fitting the resin combination sheet material of more than 2, resin combination sheet material is fusion together well, therefore can engage resin combination sheet material each other, it is possible to form single resin sheet.It is thus possible, for instance when the area occupation ratio of the recess of the one side of resin combination sheet material is high or when defining concavo-convex, by by bonded to each other for this face, it is possible to make recess, concavo-convex disappearance.Therefore, it is possible to reduce the recess occupation rate on resin combination sheet material surface.
The laminating of resin combination sheet material is preferably in 70 DEG C～160 DEG C, more preferably in 80 DEG C～150 DEG C it is preferred that heat at 90 DEG C～140 DEG C and carry out.
It addition, the pressure of laminating is preferably 0.05MPa～1MPa, is more preferably 0.1MPa～0.6MPa, more preferably 0.2MPa～0.4MPa.
Further, surface can also be smoothed and reduce the recess occupation rate on surface by the resin combination sheet material obtained.Method as smoothing, for instance the known method such as laminating machine, forcing press etc. can be enumerated.By smoothing, resin combination sheet material is made somewhat to flow due to pressurization, it is possible to make the recess of sheet surface disappear.Wish that the component contacted with resin combination sheet material smooths when smoothing.This is because the flatness of this component can affect the flatness of resin combination sheet material.For example, it is possible to the plastic sheet making surface smooth contacts with resin combination sheet material, it is possible to prevent resin combination sheet material to be pasted onto on laminating machine, forcing press simultaneously.Alternatively, it is also possible to resin combination sheet material is heated during pressurization, thus improving the mobility of resin combination.In the operation of this smoothing, it is possible to by being thermally formed semi-cured state (B rank).
When being carried out the smoothing on resin combination sheet material surface by vacuum laminator, vacuum is preferably 0.01kPa～20kPa, more preferably 0.03kPa～10kPa, more preferably 0.1kPa～5kPa.
The heating-up temperature of vacuum laminator is preferably 70 DEG C～170 DEG C, more preferably 80 DEG C～160 DEG C, more preferably 90 DEG C～150 DEG C.
The pressure of vacuum laminator is preferably 0.1MPa～3MPa, is more preferably 0.3MPa～2MPa, more preferably 0.6MPa～1.5MPa.
(physical property of resin combination sheet material (B rank))
The lowest melt viscosity of resin combination sheet material, can affect the mobility of resin combination making it from B rank to the pressurized, heated operation on C rank.Therefore, from the viewpoint of operability, suppression resin combination sheet material flow out from end, it is preferable that adjust the lowest melt viscosity at the temperature range 20 DEG C～200 DEG C applied in pressurized, heated operation.
The lowest melt viscosity of resin combination sheet material is, when measuring the temperature dependency of shear viscoelasticity, and the minima that the viscosity that the decrease in viscosity caused due to temperature rising and curing reaction cause increases and shows.
As the example of condition measuring shear viscoelasticity, the programming rate of programming rate 5 DEG C/min(forcing press can be enumerated), frequency 1～10Hz, the mensuration fixture clamping sheet material can enumerate circular flat board.Sample can use the material folded by resin combination sheet layer as required.
Resin combination sheet material lowest melt viscosity at 20 DEG C～200 DEG C is preferably 10Pa s～1000Pa s, more preferably 20Pa s～800Pa s, more preferably 30Pa s～600Pa s.If lowest melt viscosity is too low, then the thickness of heat conductivity insulating barrier produces deviation, if lowest melt viscosity is too high, then heat conductivity insulating barrier will not be fully closely sealed with the adherend of Copper Foil, metal basal board etc., produces the reduction of the reduction of bonding force, insulation breakdown voltage.Therefore, if the lowest melt viscosity at 20 DEG C～200 DEG C is in above-mentioned scope, then the mobility that during heating, performance is excellent, also can follow even for the adherend with concaveconvex structure, therefore, after formal solidification, show high bonding force.
The thickness of the resin combination sheet material (B rank sheet material) of the present invention suitably can select according to purpose, such as average thickness is preferably 20 μm～500 μm, it is more preferably 25 μm～400 μm, considers from the flexual viewpoint of thermal conductivity, electrical insulating property and sheet material, it is preferred to 30 μm～300 μm.More than 20 μm, electrical insulating property is excellent, can suppress the increase of thermal resistance below 500 μm.
< resin combination sheet material (the B rank sheet material) > with metal forming
Resin combination sheet material with metal forming is the material being pasted with metal forming on above-mentioned resin combination sheet material.More specifically, it is possible to use laminating machine, forcing press etc. are fitted metal forming by known method on resin combination sheet material, thus making the resin combination sheet material with metal forming.It addition, the resin combination sheet material with metal forming by supplying to give resin combination and form coating material as base material using metal forming, can be heated to semi-cured state (B rank) and make.
Generally, in order to improve and the bonding force of resin combination sheet material, metal forming is roughened.When by being pasted onto in metal forming by resin combination sheet material to make the resin combination sheet material with metal forming, if there is the recess of above-mentioned particular size on the surface of resin combination sheet material, then will not follow completely in the pressurization on C rank and heating process metal forming carry out roughened after surface configuration, consequently, it is possible to easily produce interfacial bubbles.
In order to suppress the generation of such interfacial bubbles, find that the resin combination sheet material using the present invention is effective, namely the resin combination sheet material of the present invention is the first resin combination sheet material or the second resin combination sheet material, first resin combination sheet material comprises thermosetting resin, phenolic resin and insulating properties inorganic filler, and in its surface, the occupation rate of the recess that depth capacity is more than 0.5 μm is calculated as less than 4% with area occupation ratio, second resin combination sheet material lowest melt viscosity at 20 DEG C～200 DEG C is 10～1000Pa s, and in its surface, the occupation rate of the recess that depth capacity is more than 0.5 μm is calculated as less than 4% with area occupation ratio.It addition, the resin combination sheet material of the present invention, certainly also can effectively suppress the generation of interfacial bubbles when laying metal basal board.
As metal forming, it is possible to use the metal forming being made up of arbitrary material of copper, aluminum, nickel, stannum or the alloy that comprises these metals.It addition, the Rotating fields of metal forming is not limited to 1 layer, it is possible to use the composite insulating foil of 2～3 layers.When expecting that low cost and conductivity are high, it is preferred to use Copper Foil.
The thickness of metal forming is preferably 3 μm～110 μm, more preferably 5 μm～90 μm, more preferably 9 μm～70 μm.More than 3 μm, operation excellence, it is possible to prevent from fractureing under small power.It addition, below 110 μm, can suppress high price metal forming make consumption.
In order to improve the operability of metal forming, it is possible to process metal forming when being pasted with carrier film.As such carrier film, it is possible to use micro-adhesive adhesive film, oneself the adhesive film of adsorptivity, UV curable adhesive film.Bonding process that resin combination sheet material carries out is utilized or for obtaining with in the painting process of the resin combination sheet material of metal forming at metal basal board and metal forming, by being the state being pasted with carrier film on metal foil, it is possible to suppress fractureing of metal forming.
Other manufacture method, manufacturing condition, the preferable range of thickness of resin combination sheet material, resin combination viscosity preferable range etc. same with involved by above-mentioned resin combination sheet material.
< heat conductivity insulating barrier (C rank) >
Heat conductivity insulating barrier, refers in Metal Substrate distributing board described later, Metal Substrate distributing board material, makes the adhesive linkage of insulation between metal basal board and wiring layer or metal forming.Undertaken above-mentioned resin combination sheet material (B rank) formally solidifying (C rank) and forming heat conductivity insulating barrier (C rank).
Specifically, by clamping above-mentioned resin combination sheet material between metal basal board and metal forming, carry out pressurized, heated with forcing press etc., thus bonded metal substrate and metal forming.Above-mentioned resin combination sheet material for semi-cured state (B rank), remelted by pressurized, heated operation, resin combination sheet material is closely sealed on metal basal board and metal forming, afterwards, undertaken resin combination sheet material formally solidifying (C rank) and forming heat conductivity insulating barrier (C rank), make metal basal board and metal forming bonding.Heat conductivity insulating barrier after formal solidification will not melt because of heating.
The heat conductivity insulating barrier of the present invention is the composite of the insulating properties inorganic filler of heat conductivity and thermosetting resin.Insulating properties inorganic filler as heat conductivity, it is preferred to use thermal conductivity is high and be the inorganic ceramic of insulating properties.If it addition, the resin of use heat conductivity is as thermosetting resin, then thermal conductivity can be improved under less filer content.In the present invention, as the resin of heat conductivity, it is preferred to use have the epoxy resin of 2 officials' energy of biphenyl backbone.
Have biphenyl backbone 2 officials can epoxy resin in biphenyl backbone owing to there is anisotropic structure for mesomorphic gene.Heat conductivity resin bed, when inside has anisotropic structure, shows high heat conductance.Generally, the conduction of heat of insulator carries out mainly through phonon, due to the static scattering of phonon under discontinuities (defect) in materials, the non-harmonious property of molecular vibration, lattice vibration the phonon caused dynamic scattering impinging one another caused, causes that thermal conductivity reduces.
But, high molecular main chain direction and compared with the direction (molecule interchain direction) that main chain is at a right angle, thermal conductivity is big.This is because, high molecular main chain direction has been combined by strong conjugated bonds, and the harmonious property of the therefore vibration (phonon) in main chain direction is high, it addition, cause the defect etc. of the static scattering of phonon also much smaller than direction between strand.Therefore, it can by making high molecular main chain orientation anisotropically improve thermal conductivity.The orientation of high polymer main chain can be passed through the known methods such as extension, electric field applying, friction and implement.If making high polymer main chain vertical direction (thickness direction) orientation to face, then can improve the thermal conductivity at thickness direction.
On the other hand, if making the high polymer main chain horizontal direction orientation to face, then the thermal conductivity in face can be increased.On the other hand, the thermal conductivity of the generally high molecular vertical direction as molecule interchain direction, reduction compared with non-oriented high molecular situation.Therefore, generally making high polymer main chain in the resin combination sheet material of the horizontal direction orientation of face, the thermal conductivity at thickness direction reduces.
But, if the order of material increases, then the harmonious property vibrated increases, and defect also reduces, and therefore can also increase the thermal conductivity in molecule interchain direction (thickness direction).Here, what the order of material was the highest is perfect cystal, but the perfect cystal of polymer insulation body can not be suitable for effectively as insulating properties adhesives.On the other hand, mesomorphic state has high order after crystal, it is also possible to realize.Having 2 functional epoxy resins of biphenyl backbone owing to having mesomorphic base, therefore, not only in main chain direction, on molecule interchain direction, defect is also few, and the non-harmonious property of vibration is also little.Therefore, will not be fettered by specific differently-oriented directivity, thus showing big heat conductivity.
< Metal Substrate distributing board material >
Fig. 1 represents the cross-section structure of an example of the Metal Substrate distributing board material of the present invention.
Metal Substrate distributing board material has metal forming 30 and metal basal board 20, has the heat conductivity insulating barrier 10 of solidfied material as above-mentioned resin combination sheet material between metal forming 30 and metal basal board 20.By the configuration of heat conductivity insulating barrier 10, metal basal board 20 and metal forming 30 is made to insulate.
The metal material that metal basal board 20 is high by thermal conductivity, thermal capacity is big is constituted, and can illustrate copper, aluminum, ferrum, the alloy etc. of use in lead frame.The intensity of metal basal board 20 more thick then Metal Substrate distributing board is more high, but when the Metal Substrate distributing board being equipped with electronic unit carries out integrated by screw, cementitious material etc. with metal base etc., owing to intensity improves, therefore metal basal board 20 there is no need thick especially.Metal basal board 20 is aluminum when preferential lightweight, processability, is ferrum when preferential intensity, it is possible to so according to the selected material of purpose.
After Metal Substrate distributing board is made with large scale, in order to improve productivity ratio, it is preferable that be cut into the size used after electronic unit is installed.Therefore, it is desirable to metal basal board 20 is high for the processability carrying out cutting.
As the metal basal board 20 of aluminum, can select aluminum or using aluminum be main component alloy as material, be obtained in that the material of multiple kind according to its chemical composition and heat treatment condition, but preferably select that the processabilities such as very easy cutting are high and the kind of excellent strength.
Metal basal board distributing board material can pass through to clamp above-mentioned resin combination sheet material by metal basal board 20 and metal forming 30, makes by the method for the pressurized, heated such as forcing press etc..Or, make the resin combination sheet material with metal forming and metal basal board 20 by the method for pressurized, heated etc..The heating, the condition of pressurized treatments that are solidified by above-mentioned resin combination sheet material suitably select according to the composition of resin combination sheet material.For example, it is preferable to heating-up temperature be 80～250 DEG C, pressure be 0.5～8.0MPa, more preferably heating-up temperature be 130～230 DEG C, pressure be 1.5～5.0MPa.
< Metal Substrate distributing board >
Fig. 2 represents the cross-section structure of an example of the Metal Substrate distributing board of the present invention.
Metal Substrate distributing board has metal basal board 20 and wiring layer 40, has the heat conductivity insulating barrier 10 of solidfied material as above-mentioned resin combination sheet material between metal basal board 20 and wiring layer 40.By the configuration of heat conductivity insulating barrier 10, metal basal board 20 and wiring layer 40 is made to insulate.
Wiring layer 40 obtains by the metal forming 30 of Metal Substrate distributing board material is carried out distribution processing.As the distribution processing method of metal forming 30, preferably etch in the industry.
Metal Substrate distributing board preferably removes and forms soldering-resistance layer on surface for carrying the welding disk of electronic unit.Metal Substrate distributing board material is after circuit fabrication and soldering-resistance layer are formed, it is preferable that be cut into the size of the such electro part carrying component of LED light source member.Such as, the welding disk at Metal Substrate distributing board is coated with the electrical connection materials such as solder, after configuration electronic unit, by solder reflow process, thus installing electronic unit.
< LED light source member >
Fig. 3 represents the cross-section structure of LED light source member when LED encapsulation is used as electronic unit.In the LED light source member shown in Fig. 3, there is between metal basal board 20 and wiring layer 40 heat conductivity insulating barrier 10, wiring layer 40 carries electronic unit 50.Use this LED light source equipment, LED backlight unit etc. can be made, or LED electric light, LED light bulb etc. can be made.
The heat produced in LED encapsulates, according to the welding disk being made up of electrical connection material, metal formings 30 such as solders, heat conductivity insulating barrier 10, the order conduction of metal basal board 20, heat radiation.By using the heat conductivity insulating barrier 10 of the solidfied material of the resin combination sheet material as the present invention, the thermal diffusivity from welding disk to metal basal board improves, it is possible to suppress the temperature of LED encapsulation to rise.
Embodiment
Specifically describe the present invention by the examples below, but the invention is not restricted to these embodiments.It addition, unless otherwise specified, then " part " and " % " is quality criteria.
[embodiment 1]
< resins synthesis example 1 >
The 3L separation flask with blender, cooler, thermometer adds 594g resorcinol, 66g catechol, 316.2g37% formalin, 15g oxalic acid, 100g water, heats in oil bath and be warming up to 100 DEG C.Successive reaction 4 hours at a reflux temperature.
Afterwards, water is distilled off, while by the temperature in flask to 170 DEG C.Keep 170 DEG C while successive reaction 8 hours.Under reduced pressure carry out concentration in 20 minutes afterwards and remove intrasystem water etc., take out the phenolic resin with the construction unit shown in formula (I).The number-average molecular weight of the phenolic resin obtained is 530, and weight average molecular weight is 930.It addition, the phenol equivalent of phenolic resin is 65g/eq..
< varnish shape resin combination >
In the 1L lidded container of polypropylene, weigh 56.80g(63%(relative to insulating properties inorganic filler gross mass)) particle diameter D50 is insulating properties inorganic filler (Sumitomo Chemical Co's system of 18 μm, SumicorundumAA18), 20.29g(22.5%(is relative to insulating properties inorganic filler gross mass)) particle diameter D50 is insulating properties inorganic filler (Sumitomo Chemical Co's system of 3 μm, SumicorundumAA3) and 13.07g(14.5%(relative to insulating properties inorganic filler gross mass)) particle diameter D50 is insulating properties inorganic filler (Sumitomo Chemical Co's system of 0.4 μm, SumicorundumAA04), add 0.099g silane coupler (Shin-Etsu Chemial Co., Ltd's system, KBM403), 11.18g the 2-butanone (with Guang Chun medicine Co., Ltd. system) as solvent, 0.180g dispersant (nanmu this chemical conversion Co., Ltd. system, ED-113), the phenolic resin that 5.96g is obtained by above-mentioned resins synthesis example 1 is stirred.Add 5.914g further and there is 2 functional epoxy resins (Mitsubishi chemical Co., Ltd's system, YL6121H) of biphenyl backbone, 0.657g naphthalene system's epoxy resin (Dainippon Ink Chemicals's system, HP4032D), 0.012g imidazolium compounds (Shikoku Chem's system, 2PHZ).Further, put into the zirconium oxide ball of 500g diameter 5mm, after ball mill pedestal stirs 48 hours with 100rpm, be filtered to remove zirconium oxide ball, obtain varnish shape resin combination 1.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
< viscosity >
The resin combination 1 of varnish shape viscosity at 25 DEG C is measured by Brookfield viscometer (axle No4, revolution 30rpm).Measurement result is shown in Table 1.
< resin combination sheet material >
Use bar coater, resin combination 1 obtained above is coated in PET film (Di Ren DuPont Film company system, A53), carries out 20 minutes drying at 100 DEG C.Dried thickness is 50 μm.2 dried resin combination sheet materials are placed in face-to-face mode, uses layer of rolls press, 110 DEG C, stacking under 0.3MPa, travelling speed 0.3m/min, obtain the resin combination sheet material (B rank sheet material) of average thickness 100 μm.The resin combination sheet material pliability obtained is excellent.
The containing ratio > of < insulating properties inorganic filler
It addition, whole ratios shared by insulating properties inorganic filler in evaluating resin compositions sheet material in such a way.First, measure the weight of resin combination sheet material, this resin combination sheet material is burnt till 2 hours at 400 DEG C, then 3 hours are burnt till at 700 DEG C, resinous principle is made to evaporate, measure the quality of the insulating properties inorganic filler of remaining, thus evaluating insulating properties inorganic filler weight ratio in resin combination sheet material.Then, by this insulating properties inorganic filler submerged, the change of water level the volume of insulating properties inorganic filler is measured.Thus, the proportion of insulating properties inorganic filler is evaluated.Then, with the proportion of same method evaluation resin combination sheet material.Then, by the weight ratio of insulating properties inorganic filler in resin sheet divided by the proportion of insulating properties inorganic filler, and then it is multiplied by the proportion of resin sheet, the value of gained is evaluated as the volume ratio of insulating properties inorganic filler.Evaluation result is shown in Table 1.
The lowest melt viscosity > of < resin combination sheet material
By dynamic viscoelastic device (RheometricScientific, Inc. ARES), measure the temperature dependency of the complex elastic-modulus of resin combination sheet material, and divided by angular frequency thus obtaining complex viscosity.
Using the sheet material overlapping with 8 resin combination sheet materials having peeled off PET film and thickness 0.8mm as measuring sample.Clamp mensuration sample with the discoideus mensuration fixture of 25mm Φ, at 80 DEG C, carry out 10 seconds shearing manipulations.Afterwards, 5 DEG C/min of programming rate, frequency 10Hz, complex viscosity from the scopes of 20 DEG C to 200 DEG C are measured.The minimum of the complex viscosity at 20 DEG C～200 DEG C is evaluated as lowest melt viscosity.
The recess occupation rate > of < resin combination sheet material
The surface configuration of resin combination sheet material is measured by three-dimensional non-planar contact surfaces shape measure system (Ling Hua system house system, MM3200).The mensuration carrying out surface configuration within sweep of the eye 250 μ m 190 μm.For measuring view data, carry out being set to polynomial approximation the face correction of 2 times, and be similar to face, the view data after being maked corrections from the mensuration view data deduction before the correction of face.Thus, the slope of the apparent height of resin combination sheet material is maked corrections.Then, by resolving as the location of binaryzation marginal value (threshold value) than the value of low 0.5 μm of average height (par), the area occupation ratio of the part that contrast marginal value (threshold value) is high is evaluated.Thus, the area occupation ratio of par is evaluated.Then, the value deducting above-mentioned area occupation ratio gained from 100% is evaluated as recess area occupation ratio.Test portion is repeated 10 times by this mensuration and operation randomly, the area occupation ratio shared by recess is averaged, as the recess occupation rate of this test portion.The results are shown in table 1.
< Metal Substrate distributing board material >
The resin combination sheet material having peeled off the 500mm × 600mm of PET is clipped between side, alligatoring face and the aluminium base (A5052,1mmt) of 500mm × 600mm of Copper Foil (Japan electrolysis company system, 35 μ m-thick) of 550mm × 650mm, use vacuum pressed forcing press, under the vacuum of 3kPa, pressure is added at 2MPa, at 140 DEG C pressurized, heated 2 hours, at 190 DEG C pressurized, heated 2 hours, obtain Metal Substrate distributing board material.
The thickness deviation > of < heat conductivity insulating barrier
The thickness deviation of heat conductivity insulating barrier is evaluated by the concavo-convex presence or absence of copper-clad surface.If it addition, the Metal Substrate distributing board material evaluating sample is increased to 500mm × 600mm, then the thickness deviation of heat conductivity insulating barrier embodies as the concavo-convex of copper-clad surface.
The mensuration > of < peel strength
According to JIS-C6481(1996 year version), the aluminium base substrate of use makes 90o disbonded test sheet.Metal basal board is cut into 25mm × 100mm, for the Copper Foil (35 μm) remained with center 10mm width, use universal tensile testing machine (Orientex company TM-100) to peel off to 90o direction with the speed of 50mm/min at normal temperatures, the average load in multiple moment measure peel strength.
< electrical insulating property >
The Copper Foil of the Metal Substrate distributing board material obtained is remained the circular pattern of 20mm Φ, is etched by ammonium persulfate aqueous solution.By proof voltage determinator (Tokyo TOA Electronics Co., Ltd., Japan's system, PunctureTesterPT-1011), measure the insulation breakdown voltage of the circular pattern of more than 50.Minimum insulation breakdown voltage is shown in Table 1.
< thermal conductivity >
Copper Foil and aluminium base to the Metal Substrate distributing board material obtained are etched, and obtain the heat conductivity insulating barrier after formally solidifying.The etching of Copper Foil uses ammonium persulfate aqueous solution.The etching of aluminium base uses hydrochloric acid.Obtain the thermal conductivity of the heat conductivity insulating barrier obtained as follows.
First, use temperature wave apparatus for thermal analysis (ai-Phase company system, ai-PhaseMobile1u), measure the frequency dependence of the phase contrast of temperature wave.Then, within the scope of frequency 200～400Hz, obtain the phase contrast subduplicate slope relative to frequency.The slope of this phase contrast and-d(π/α)0.5Equal, so being obtained thermal diffusion coefficient (α) by the thickness (d) of heat conductivity insulating barrier and the slope of phase contrast.
Then, measure specific heat by differential scanning calorimetry (DSC) (DSC, PerkinElmer company system, Ryris1), measure density by electronic hydrometer (Alfamirage company system, SD-200L).Then, following formula thermal conductivity [W/mK] is obtained.The thermal conductivity obtained is shown in Table 1.
Thermal conductivity [W/mK]=thermal diffusivity (thermal diffusion coefficient (α)) [mm2/ s] × specific heat [J/kg K] × density [g/cm3]
[embodiment 2]
< resin combination >
In embodiment 1, use 62.66g(69.5%(relative to alumina packing gross mass)) particle diameter D50 is alumina packing (Showa Denko K. K's system of 20 μm, AS-20), 16.77g(18.6%(is relative to alumina packing gross mass)) particle diameter D50 is alumina packing (the Sumitomo Chemical system of 3 μm, SumicorundumAA3) and 10.73g(11.9%(relative to alumina packing gross mass)) particle diameter D50 is alumina packing (the Sumitomo Chemical system of 0.4 μm, SumicorundumAA04) as alumina packing, and 13.5g2-butanone (with Guang Chun medicine Co., Ltd. system) is as solvent, in addition, modulation varnish shape resin combination 2 similarly to Example 1, evaluate viscosity.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
The < resin combination sheet material > with metal forming
Use bar coater to be coated on by resin combination 2 obtained above on the alligatoring face of Copper Foil (Japan's electrolysis company system, 35 μm), carry out 20 minutes drying at 100 DEG C.Dried thickness is 100 μm.Resin bed after the drying is placed PET film (Di Ren DuPont Film company system, A53), then, use vacuum laminator (Ming Ji manufacturing company system), under the vacuum of below 3kPa, 130 DEG C, 1MPa add pressure, carry out 15 seconds vacuum pressed, obtain the resin combination sheet material (B rank sheet material) with metal forming.Average thickness with the resin combination sheet material in the resin combination sheet material of metal forming is 100 μm.
The resin combination sheet material with metal forming obtained uses method similarly to Example 1 to carry out the evaluation of recess occupation rate.
Additionally, operate similarly to Example 1, but, to being clipped between Copper Foil and aluminium base by resin combination sheet material according to making the mode contacted with aluminium base with the resin combination sheet material side in the resin combination sheet material of metal forming obtained above be modified, make Metal Substrate distributing board material.
The Metal Substrate distributing board materials'use obtained method similarly to Example 1, carries out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
Further, above-mentioned resin combination 2 is coated with similarly to Example 1 makes resin combination sheet material (B rank sheet material) on a pet film.The resin combination sheet material pliability obtained is excellent.Evaluate the lowest melt viscosity of the resin combination sheet material obtained.Evaluation result is shown in Table 1.
[embodiment 3]
In embodiment 1, add 9.3g to be stirred as 2-butanone (with Guang Chun medicine Co., Ltd. system) and the 5.32g of the solvent phenolic resin obtained by above-mentioned resins synthesis example 1.6.35g is used to have 2 functional epoxy resins (Mitsubishi chemical Co., Ltd's system, YL6121H) of biphenyl backbone, 0.706g naphthalene system's epoxy resin (Dainippon Ink Chemicals's system, HP4032D) further, in addition, modulation varnish shape resin combination 3 similarly to Example 1, evaluates viscosity.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
< resin combination sheet material >
It is changed to resin combination 3 obtained above, in addition, operates similarly to Example 1, it is thus achieved that the resin combination sheet material (B rank sheet material) that 2 overlaps are made.The resin combination sheet material pliability obtained is excellent.About the resin combination sheet material obtained, method similarly to Example 1 is used to carry out lowest melt viscosity and the evaluation of recess occupation rate.
< Metal Substrate distributing board material >
It addition, operate similarly to Example 1, but resin combination sheet material is changed to resin combination sheet material obtained above, makes Metal Substrate distributing board material.For the Metal Substrate distributing board material obtained, by method similarly to Example 1, carry out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
[embodiment 4]
In embodiment 1, except add 13.7g as the 2-butanone (with Guang Chun medicine Co., Ltd. system) of solvent except, modulation varnish shape resin combination 4 similarly to Example 1, evaluate viscosity.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
Then, operate similarly to Example 1, but resin combination 1 is changed to resin combination 4, make resin combination sheet material.The resin combination sheet material pliability obtained is excellent.About the resin combination sheet material obtained, carry out the evaluation of lowest melt viscosity and recess occupation rate similarly to Example 1.
Further, operate in the same manner as embodiment, be changed to resin combination sheet material obtained above, make Metal Substrate distributing board material, carry out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
[embodiment 5]
In embodiment 1, add the 9.3g phenolic resin obtained as the 2-butanone (with Guang Chun medicine Co., Ltd. system) of solvent, 5.32g by above-mentioned resins synthesis example 1 to be stirred.6.35g is used to have 2 functional epoxy resins (Mitsubishi chemical Co., Ltd's system, YL6121H) of biphenyl backbone, 0.706g naphthalene system's epoxy resin (Dainippon Ink Chemicals's system, HP4032D) further, in addition, modulation varnish shape resin combination 5 similarly to Example 1, evaluates viscosity.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
< resin combination sheet material >
Use bar coater to be coated on by resin combination 5 obtained above in PET film (Di Ren DuPont Film company system, A53), carry out 20 minutes drying at 100 DEG C.Dried thickness is 38 μm.2 dried resin combination sheet materials are placed in aspectant mode, uses layer of rolls press, 110 DEG C, stacking under 0.3MPa, travelling speed 0.3m/min, obtain the resin combination sheet material (B rank sheet material) of average thickness 75 μm.The resin combination sheet material pliability obtained is excellent.
< Metal Substrate distributing board material >
It addition, operate similarly to Example 1, but resin combination sheet material is changed to resin combination sheet material obtained above, makes Metal Substrate distributing board material.For the Metal Substrate distributing board material obtained, by method similarly to Example 1, carry out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
[embodiment 6]
In embodiment 1, add the 9.3g phenolic resin obtained as the 2-butanone (with Guang Chun medicine Co., Ltd. system) of solvent, 5.32g by above-mentioned resins synthesis example 1 to be stirred.6.35g is used to have 2 functional epoxy resins (Mitsubishi chemical Co., Ltd's system, YL6121H) of biphenyl backbone, 0.706g naphthalene system's epoxy resin (Dainippon Ink Chemicals's system, HP4032D) further, in addition, modulation varnish shape resin combination 6 similarly to Example 1, evaluates viscosity.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
< resin combination sheet material >
Use bar coater to be coated on by resin combination 6 obtained above in PET film (Di Ren DuPont Film company system, A53), carry out 20 minutes drying at 100 DEG C.Dried thickness is 63 μm.2 dried resin combination sheet materials are placed in aspectant mode, uses layer of rolls press, 110 DEG C, stacking under 0.3MPa, travelling speed 0.3m/min, obtain the resin combination sheet material (B rank sheet material) of average thickness 125 μm.The resin combination sheet material pliability obtained is excellent.
< Metal Substrate distributing board material >
It addition, operate similarly to Example 1, but resin combination sheet material is changed to resin combination sheet material obtained above, makes Metal Substrate distributing board material.For the Metal Substrate distributing board material obtained, by method similarly to Example 1, carry out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
[embodiment 7]
By the aluminium oxide (AL35-63 that 63 parts of particle diameter D50 are 31 μm, Micron company system, density 3.80g/ml), 18 parts of particle diameter D50 are the aluminium oxide (AX3-32 of 5 μm, Micron company system, density 3.77g/ml), 17 parts of particle diameter D50 are the aluminium oxide (LS-235 of 0.5 μm, Nippon Light Metal Co., Ltd's system, density 3.94g/ml) with the quasi-spherical alumina (AO802 that 2 parts of particle diameter D50 are 0.7 μm, Co., Ltd.'s Admatechs system, density 3.7g/ml) it is obtained by mixing inorganic filling material mixture.
In the 100mL lidded container of polypropylene, weighing the above-mentioned inorganic filling material mixture of 90.16g, add 0.099g silane coupler (Shin-Etsu Chemial Co., Ltd's system, KBM403), 14.33g as the 2-butanone (with Guang Chun medicine Co., Ltd. system) of solvent, 0.36g dispersant (nanmu this chemical conversion Co., Ltd. system, ED-113), 2.62g(solid constituent) phenolic resin that obtained by above-mentioned resins synthesis example 1 is stirred.Add 6.24g further and there is 2 functional epoxy resins (Mitsubishi chemical Co., Ltd's system, YL6121H) of biphenyl backbone, 0.69g naphthalene system's epoxy resin (Dainippon Ink Chemicals's system, HP4032D), 0.100g imidazolium compounds (Shikoku Chem's system, 2PZ-CN).Put into the oxidation aluminum ball of 120g diameter 5mm further, after ball mill pedestal stirs 12 hours with 100rpm, alumina removed by filtration ball, obtain varnish shape resin combination 7.
Evaluate viscosity similarly to Example 1.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
Then, operate similarly to Example 1, but resin combination 1 is changed to resin combination 7, make resin combination sheet material.The resin combination sheet material pliability obtained is excellent.About the resin combination sheet material obtained, carry out the evaluation of lowest melt viscosity and recess occupation rate similarly to Example 1.
Further, operate in the same manner as embodiment, be changed to resin combination sheet material obtained above, make Metal Substrate distributing board material, carry out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
[embodiment 8]
By 100 mass parts 1-(3-methyl-4-oxiranylmethoxy benzene bases)-4-(4-oxiranylmethoxy benzene base)-1-cyclohexene, 32 mass parts obtained by above-mentioned resins synthesis example 1 phenolic resin (Hitachi's chemical conversion Industry trial-production product), 1.3 parts by mass triphenyl phosphines, 1.3 chemical industrial company of mass parts KBM-573(SHIN-ETSU HANTOTAI systems), 1483 mass parts alumina powder (Sumitomo Chemical Co's alpha-alumina powders；The mixture that aluminium oxide that 979 mass parts mean diameters are 18 μm, 356 mass parts mean diameters are the aluminium oxide of 3 μm and aluminium oxide that 148 mass parts mean diameters are 0.4 μm) and the mixing of 300 mass parts Ketohexamethylene, add Nano particles of silicon dioxide (Admatechs company system, trade name: Admanano, mean diameter: 15nm, NV:23 mass %) slurry having been carried out hydrophobic treatment by vinyl silanes being equivalent to 15.7 mass parts in solid constituent conversion, modulation varnish shape resin combination 8, evaluates viscosity.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
< resin combination sheet material >
About resin combination, after using spreader to be coated on polyethylene terephthalate (PET) film according to the mode that dried thickness is 200 μm, at room temperature place 30 minutes, dry.After being further dried 30 minutes at temperature 100 DEG C, vacuum press carries out heat pressurization (pressed temperature 120 DEG C, vacuum 1kPa, moulding pressure 1MPa, 1 minute time of process), obtains the resin combination sheet material (B rank sheet material) of average thickness 200 μm.About the resin combination sheet material obtained, carried out lowest melt viscosity and the evaluation of recess occupation rate by method similarly to Example 1.
< Metal Substrate distributing board material >
The resin combination sheet material having peeled off the 500mm × 600mm of PET is clipped between side, alligatoring face and the aluminium base (A5052,1mmt) of 500mm × 600mm of Copper Foil (Japan electrolysis company system, 35 μ m-thick) of 550mm × 650mm, use vacuum pressed forcing press, under the vacuum of 3kPa, pressure is added, pressurized, heated 5 minutes at 150 DEG C at 4MPa.Then, under atmospheric conditions, heat at 140 DEG C 2 hours, heat 2 hours at 190 DEG C, obtain Metal Substrate distributing board material.
For the Metal Substrate distributing board material obtained, by method similarly to Example 1, carry out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
[comparative example 1]
In embodiment 1, except add 18.2g as the 2-butanone (with Guang Chun medicine Co., Ltd. system) of solvent except, modulation varnish shape resin combination 9 similarly to Example 1, evaluate viscosity.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
Then, operate similarly to Example 1, but resin combination 1 is changed to resin combination 9, make resin combination sheet material.The resin combination sheet material pliability obtained is excellent.About the resin combination sheet material obtained, carry out the evaluation of lowest melt viscosity and recess occupation rate similarly to Example 1.
Further, operate in the same manner as embodiment, be changed to resin combination sheet material obtained above, make Metal Substrate distributing board material, carry out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
[comparative example 2]
In example 2, except add 19.3g as the 2-butanone (with Guang Chun medicine Co., Ltd. system) of solvent except, modulation varnish shape resin combination 10 similarly to Example 2, evaluate viscosity.By the particle diameter D50 of each insulating properties inorganic filler coordinated be shown in Table 1 relative to the weight ratio of insulating properties inorganic filler gross mass.
Then, operate similarly to Example 1, but resin combination 1 is changed to resin combination 10, make resin combination sheet material.The resin combination sheet material pliability obtained is excellent.About the resin combination sheet material obtained, carry out the evaluation of lowest melt viscosity and recess occupation rate similarly to Example 1.
Further, operate in the same manner as embodiment, be changed to resin combination sheet material obtained above, make Metal Substrate distributing board material, carry out the evaluation of the thickness deviation of heat conductivity insulating barrier, peel strength, electrical insulating property and thermal conductivity.Evaluation result is shown in Table 1.
[table 1]
As known from Table 1, the solidfied material of the resin combination sheet material of embodiment 1～8 is compared with comparative example 1～2, and thermal conductivity and electrical insulating property are excellent.
Additionally, the resin combination sheet material of the present invention, even if using the resin except the resin used in the above-described embodiments as thermosetting resin, as long as the occupation rate of the recess of depth capacity more than 0.5 μm is calculated as the resin combination sheet material of less than 4% with area occupation ratio in its surface, then can also obtain same effect.

Claims (11)

1. a resin combination sheet material, it is formed by the resin combination comprising thermosetting resin, phenolic resin and insulating properties inorganic filler,
In the surface of described resin combination sheet material, the occupation rate of the recess that depth capacity is more than 0.5 μm is calculated as less than 4% with area occupation ratio,
The viscosity of described resin combination is above below the 10000mPa s of 2500mPa s,
Described resin combination sheet material is formed on support base material by being coated on by described resin combination.
2. resin combination sheet material according to claim 1, the lowest melt viscosity at 20 DEG C～200 DEG C is 20～800Pa s.
3. the resin combination sheet material according to claim 1 or claim 2, containing the described insulating properties inorganic filler of more than 40vol% below 82vol%.
4. the resin combination sheet material according to claim 1 or claim 2, at least one filler selected in the group that described insulating properties inorganic filler is made up of the filler of aluminium oxide, magnesium oxide, boron nitride, aluminium nitride, silicon nitride, carborundum and aluminium fluoride.
5. the resin combination sheet material according to claim 1 or claim 2, described phenolic resin has the construction unit represented by following formula (I),
In formula (I), R1Represent alkyl, aryl or aralkyl, R2And R3Representing hydrogen atom, alkyl, aryl or aralkyl independently of one another, m represents the integer of 0～2, and n represents the integer of 1～10.
6. a resin combination sheet material, its lowest melt viscosity at 20 DEG C～200 DEG C is 10Pa s～1000Pa s,
Described resin combination sheet material is formed by the resin combination comprising thermosetting resin, phenolic resin and insulating properties inorganic filler,
In the surface of described resin combination sheet material, the occupation rate of the recess that depth capacity is more than 0.5 μm is calculated as less than 4% with area occupation ratio,
The viscosity of described resin combination is above below the 10000mPa s of 2500mPa s,
Described resin combination sheet material is formed on support base material by being coated on by described resin combination.
7., according to 1 described resin combination sheet material wantonly in claim 1, claim 2 or claim 6, its average thickness is more than 20 μm less than 500 μm.
8. the resin combination sheet material with metal forming, it has wantonly 1 described resin combination sheet material and metal forming in claim 1～claim 7.
9. a Metal Substrate distributing board material, it has metal forming, metal basal board and the heat conductivity insulating barrier between described metal forming and described metal basal board,
Described heat conductivity insulating barrier is the solidfied material of wantonly 1 described resin combination sheet material in claim 1～claim 7.
10. a Metal Substrate distributing board, it has wiring layer, metal basal board and the heat conductivity insulating barrier between described wiring layer and described metal basal board,
Described heat conductivity insulating barrier is the solidfied material of wantonly 1 described resin combination sheet material in claim 1～claim 7.
11. a LED light source member, use in claim 1～claim 7 in the Metal Substrate distributing board with the Metal Substrate distributing board material described in the resin combination sheet material of metal forming, claim 9 or claim 10 described in wantonly 1 described resin combination sheet material, claim 8 wantonly 1 and formed.
CN201280006296.7A 2011-01-25 2012-01-20 Resin combination sheet material, with the resin combination sheet material of metal forming, Metal Substrate distributing board material, Metal Substrate distributing board and LED light source member Expired - Fee Related CN103328548B (en)

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