CN103328548A

CN103328548A - Resin composition sheet, resin composition sheet with metal foil attached, metal base wiring board material, metal base wiring board, and LED light source member

Info

Publication number: CN103328548A
Application number: CN2012800062967A
Authority: CN
Inventors: 西村正人; 宫崎靖夫; 天沼真司; 田仲裕之; 原直树
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co ltd
Priority date: 2011-01-25
Filing date: 2012-01-20
Publication date: 2013-09-25
Anticipated expiration: 2032-01-20
Also published as: CN103328548B; KR20140005923A; JPWO2012102212A1; JP5904126B2; WO2012102212A1; TW201245295A; TWI455969B; KR101929067B1

Abstract

A resin composition sheet of the present invention is formed from a resin composition comprising a thermosetting resin, phenolic resin, and insulating inorganic filler. The occupancy percentage of recesses having a maximum depth of 0.5 [mu]m or more in the surface of the resin composition sheet is 4% or less by area percentage.

Description

Resin combination sheet material, the resin combination sheet material with tinsel, metal matrix wiring board material, metal matrix wiring board and led light source member

Technical field

The present invention relates to resin combination sheet material, the resin combination sheet material with tinsel, metal matrix wiring board material, metal matrix wiring board and led light source member.

Background technology

Along with the densification of electronics, the development of densification, have in the first-class local pyrexia amount of circuit to increase tendency, for the circuit substrate that is equipped with the electronic unit such as semiconductor element, demanding heat dispersion.On the other hand, necessarily require as before high electric insulation.

Therefore, the resin combination that has high heat conductance and a high electric insulation is as heat conductivity sealing material, thermal conductive adhesive and practical gradually.

About above-mentioned, in TOHKEMY 2008-13759 communique, disclose and comprised the Resins, epoxy that shows liquid crystal liquid crystal property and the composition epoxy resin of insulativity mineral filler, this composition epoxy resin has high heat conductance and excellent processibility.

Summary of the invention

The problem that invention will solve

Yet, in the composition epoxy resin that patent documentation 1 is put down in writing, the situation that can not obtain sufficient electrical insulating property is arranged.

Problem of the present invention is: provide the resin combination sheet material of the resin cured matter that can form thermal conductivity and electrical insulating property excellence, with the resin combination sheet material of tinsel and use them and the metal matrix wiring board material, metal matrix wiring board and the led light source member that form.

The method of dealing with problems

The present invention relates to following content.

＜1〉a kind of resin combination sheet material, it comprises thermosetting resin, resol and insulativity mineral filler,

In the resin combination sheet surface, the occupation rate of the recess that full depth 0.5 μ m is above is counted below 4% with area occupation ratio.

＜2〉above-mentioned＜1〉described resin combination sheet material, the lowest melt viscosity under 20 ℃～200 ℃ is 10Pas～1000Pas.

＜3〉the described resin combination sheet material in above-mentioned＜1〉or＜2 〉, it contains the following above-mentioned insulativity mineral filler of the above 82vol% of 40vol%.

＜4〉at least a filler of selecting in the group that wantonly 1 described resin combination sheet material in above-mentioned＜1 〉～＜3 〉, above-mentioned insulativity mineral filler are comprised of aluminum oxide, magnesium oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide and aluminum fluoride.

＜5〉wantonly 1 described resin combination sheet material in above-mentioned＜1 〉～＜4 〉, above-mentioned resol has the represented structural unit of following general formula (I).

[changing 1]

In general formula (I), R ¹Expression alkyl, aryl or aralkyl, R ²And R ³Represent independently of one another hydrogen atom, alkyl, aryl or aralkyl, m represents 0～2 integer, and n represents 1～10 integer.

＜6〉wantonly 1 described resin combination sheet material in above-mentioned＜1 〉～＜5 〉, it is formed by the resin combination that comprises above-mentioned thermosetting resin, above-mentioned resol and above-mentioned insulativity mineral filler,

The viscosity of above-mentioned resin combination is below the above 10000mPas of 1000mPas,

Above-mentioned resin combination sheet material forms by above-mentioned resin combination is coated on the support base material.

＜7〉a kind of resin combination sheet material, its lowest melt viscosity under 20 ℃～200 ℃ is 10Pas～1000Pas,

In its surface, the occupation rate of the recess that full depth 0.5 μ m is above is counted below 4% with area occupation ratio.

＜8〉wantonly 1 described resin combination sheet material in above-mentioned＜1 〉～＜7 〉, its mean thickness are below the above 500 μ m of 20 μ m.

＜9〉a kind of resin combination sheet material with tinsel, it has wantonly 1 described resin combination sheet material and tinsel in above-mentioned＜1 〉～＜8 〉.

＜10〉a kind of metal matrix wiring board material, it has tinsel, metal substrate and the heat conductivity insulation layer between above-mentioned tinsel and said metal substrates,

Above-mentioned heat conductivity insulation layer is the cured article of wantonly 1 described resin combination sheet material in above-mentioned＜1 〉～＜8 〉.

＜11〉a kind of metal matrix wiring board, it has wiring layer, metal substrate and the heat conductivity insulation layer between above-mentioned wiring layer and said metal substrates,

＜12〉a kind of led light source member, wantonly 1 in the metal matrix wiring board of wantonly 1 described resin combination sheet material in above-mentioned by using＜1 〉～＜8 〉, above-mentioned＜9〉described resin combination sheet material with tinsel, above-mentioned＜10〉described metal matrix wiring board material or above-mentioned＜11〉forms.

The effect of invention

According to the present invention, can provide the resin combination sheet material of the resin cured matter that can form thermal conductivity and electrical insulating property excellence, with the resin combination sheet material of tinsel and use them and the metal matrix wiring board material, metal matrix wiring board and the led light source member that form.

Description of drawings

Fig. 1 represents the cross-section structure of an example of metal matrix wiring board material of the present invention.

Fig. 2 represents the cross-section structure of an example of metal matrix wiring board of the present invention.

Fig. 3 represents the cross-section structure of an example of led light source member of the present invention.

Embodiment

In the present invention, independently operation be not only in " operation " word, even in the situation that can not clearly distinguish with other operation, if can realize the effect of this operation expectation, then is also contained in this term.

In addition, in this manual, the numerical value that uses "～" represented numerical range to represent to comprise to put down in writing before and after "～" is respectively as minimum value and peaked scope.

＜resin combination sheet material 〉

The first resin combination sheet material of the present invention is to comprise thermosetting resin, resol and insulativity mineral filler, in the surface of resin combination sheet material, the occupation rate of the recess that full depth 0.5 μ m is above is counted resin combination sheet material below 4% with area occupation ratio.

The second resin combination sheet material of the present invention is that the lowest melt viscosity under 20 ℃～200 ℃ is 10～1000Pas, and in its surface, the occupation rate of the recess that full depth 0.5 μ m is above is counted resin combination sheet material below 4% with area occupation ratio.

Above-mentioned recess of the present invention refers to be present in the recess of the resin combination sheet surface of B scalariform attitude.More particularly, recess of the present invention refers to: in the recess of the resin combination sheet surface that is present in B scalariform attitude, full depth is apart from more than the resin combination sheet surface 0.5 μ m and less than the recess of resin combination sheet thickness.

Resin combination sheet material of the present invention is fitted on tinsel, wiring layer or the metal substrate etc., forms resin combination sheet material with tinsel, wiring board material, wiring board etc.Therefore, form bubble at the recess of resin combination sheet surface and the interface of the applyings such as tinsel, wiring layer or metal substrate.Below, sometimes this bubble is called in " interface bubble ".When using the resin combination sheet material to form wiring board material, wiring board, the interface bubble that is included in wherein becomes the starting point of insulation breakdown, thereby reduces the insulation breakdown voltage of wiring board material, wiring board.

Yet in the less situation of the containing ratio of above-mentioned interface bubble, the pressurized, heated during by making wiring board material (the so-called curing heating etc. that is used to form the C rank) makes the resin combination sheet material flow the interface bubble collapse.Therefore, in the former resin combination sheet material, the pressurized, heated during by formation C rank makes the interface bubble collapse, manages to make the interface bubble not exist after forming the C rank.The method of the flowability of the resin combination sheet material during pressurized, heated when specifically, improve making the wiring board material is studied.

Yet, in the mobile too high situation of the resin combination sheet material when pressurized, heated, pressurized, heated during by making wiring board material, the resin combination sheet material flows out sheet material from the end of wiring board material, and the situation that thickness changes, thickness produces deviation at the resin combination sheet material of end is arranged.This thickness deviation can cause the aberrations in property in the face of metal matrix wiring board material.In addition, because the resin combination sheet material flows out sheet material from the end, so operability reduces.

Particularly known, if improve the filling ratio of insulativity mineral filler in order to improve thermal conductivity, then the surface of resin combination sheet material produces more recess and the interface bubble is increased.In the situation that the interface bubble exists is many, the situation that in method before this, has the interface bubble not exclusively to disappear.

Therefore in the present invention, under the B scalariform attitude before fitting with tinsel, wiring layer or metal substrate etc., the occupation rate of the recess in the resin combination sheet surface is suppressed at below the specific scope, thus the reduction of the interface bubble when reducing applying and then inhibition insulation breakdown voltage.Particularly the recess occupation rate in the if tree oil/fat composition sheet surface is counted below 4% with area occupation ratio, then is of value to the reduction that suppresses insulation breakdown voltage.In addition, known in the recess of resin combination sheet surface the recess of specific size can produce considerable influence to the reduction of insulation breakdown voltage, therefore being that recess more than the 0.5 μ m is specific with full depth in the recess on surface is recess.

In addition, because the method the flowability of the resin combination sheet material of the present invention by except pressurized, heated the time suppresses the generation of interface bubble, therefore, during pressurized, heated when making the wiring board material, also can solve the resin combination sheet material and flow out the such problem of sheet material from the end of wiring board material.

That is to say, in the former resin sheet, no matter how many occupation rates of recess is, by improving the mobile of resin and filling recess and improved insulation breakdown voltage, but then, caused that thickness deviation in the face of metal matrix wiring material, the operability that is caused by the outflow of resin combination reduce.

Relative therewith, in resin combination sheet material of the present invention, count below 4% with area occupation ratio by the occupation rate that makes the recess more than the full depth 0.5 μ m in its surface, even do not improve the flowability of resin, also can fill fully recess, improve insulation breakdown voltage.And then, also can solve thickness deviation in the face of metal matrix wiring board material, because the problem that the operability that the outflow of resin combination causes reduces.

The method of " occupation rate of the recess in the surface more than the full depth 0.5 μ m is counted below 4% with area occupation ratio " of the present invention as making resin combination sheet material, for example can enumerate: (1) adjusts the kind of insulativity mineral filler and the method for use level; The method of the viscosity of the resin combination that uses when (2) adjusting manufacturing resin combination sheet material; When (3) making the resin combination sheet material, by making 2 resin combination sheet materials and fitting these 2 and reduce the method for surperficial recess occupation rate; (4) through with the method for the operation of the surface smoothing of resin combination sheet material etc.

Here, the recess occupation rate among the present invention is defined as: the ratio of the total area of the scope that the area of being calculated by the summation of the recess area of observing is observed with respect to the recess that carries out the resin combination sheet surface.More particularly represent with following formula.

Recess occupation rate (%)=(area of being calculated by the summation of the recess area of observing)/(carrying out the total area of the scope that recess observes) * 100.

Recess of the present invention is observed, and can be undertaken by scanning electron microscope (SEM), opticmicroscope, laser microscope, light interference type microscope.

In the resin combination sheet material with tinsel behind applying tinsel, wiring layer or metal substrate etc., metal matrix wiring board material or the metal matrix wiring board etc., occupation rate for the recess of measuring the resin combination sheet surface, in the situation that tinsel, wiring layer or metal substrate etc. can be peeled off, the recess of the resin combination sheet surface after observation is peeled off is obtained by above-mentioned formula.In the situation that tinsel, wiring layer or metal substrate etc. can not be peeled off, can estimate by the observation of section the occupation rate of recess.In this case, with the summation of the length on the limit of the interface bubble observed with respect to 2 powers of the ratio of the overall length of carrying out the scope that section observes as recess occupation rate (%).

In the present invention, above-mentioned recess occupation rate, consider from the viewpoint that improves insulation breakdown voltage, be below 4%, be preferably below 3% in order more positively to improve insulation breakdown voltage, for respect to surfaceness large more positively improved insulation breakdown voltage more preferably below 2% by convered structure.

Specifically, as the method for the occupation rate of adjusting the recess in the resin combination sheet surface, for example can enumerate: (1) adjusts the kind of insulativity mineral filler and the method for use level; The method of the viscosity of the resin combination that uses when (2) adjusting manufacturing resin combination sheet material; When (3) making the resin combination sheet material, by making 2 resin combination sheet materials and fitting these 2 and reduce the method for surperficial recess occupation rate; (4) through with the method for the operation of the surface smoothing of resin combination sheet material etc.

More particularly, in (1), can enumerate for the insulativity mineral filler with different-grain diameter for example large footpath particle, central diameter particle, path mix particles the method that further according to its ratio of mixture the oil absorbency etc. of JIS-K-5101-13-2 etc. is cooperated for minimum mode.Thus, even improve the filling ratio of insulativity mineral filler in order to improve heat conductivity, also can be between filler potting resin, can reduce the area occupation ratio of the recess of resin combination sheet material.

In (2), for the reduced viscosity of resin combination extremely being fit to the viscosity of coating, preferably add solvent etc.When situation about amount of solvent being made as below the appropriate amount, can suppress the recess that the performance owing to solvent etc. causes and produce.

In (3), can use the resin combination sheet material of the known method applying such as laminating machine, pressing machine more than 2.Because the resin combination sheet material is good knitting each other, therefore can engage the resin combination sheet material each other, can form single resin sheet.Therefore, for example in the one side of resin combination sheet material, in the high situation of the area occupation ratio of recess or formed in the concavo-convex situation, by this face is bonded to each other, can make recess, concavo-convex disappearance.Therefore, can reduce the recess occupation rate of resin combination sheet surface.

In (4), in 1 of resin combination sheet material, perhaps when fitting 2 resin combination sheet materials of (3), also can use the method for pressurized, heated.Thus, can reduce at the resin combination sheet material back side recess that namely produces on the interface of resin combination sheet material and base material.Further, when pressurized, heated, the substrate that is connected with the resin combination sheet material uses level and smooth and concavo-convex few base material, thereby easily reduces the recess that produces at the interface of resin combination sheet material and base material.

But, the invention is not restricted to these methods.

Below, the employed material of resin combination sheet material and physical property are described.

The first resin combination sheet material of the present invention is formed by the resin combination that comprises thermosetting resin, resol and insulativity mineral filler.Resin combination sheet material of the present invention further can comprise other composition as required.

In addition, the second resin combination sheet material of the present invention is as long as lowest melt viscosity in above-mentioned scope, just is not particularly limited about its composition, but preferred and the first resin combination sheet material are similarly, comprise thermosetting resin, resol and insulativity mineral filler and consist of.About the measuring method of lowest melt viscosity as described later.

(thermosetting resin)

Resin combination sheet material of the present invention comprises at least a kind of thermosetting resin.As above-mentioned thermosetting resin, just be not particularly limited so long as have heat cured resin, can use normally used thermosetting resin.As thermosetting resin, particularly such as enumerating: epoxy is that resin, polyimide are that resin, polyamidoimide are that resin, triazine resin, phenolic aldehyde are that resin, melamine series resin, polyester based resin, cyanate are modification system of resin and these resins etc.These resins can be used alone or two or more kinds may be used.

Thermosetting resin among the present invention considers that from the thermotolerance viewpoint being preferably from epoxy is the resin of selecting resin and the triazine resin, and more preferably epoxy is resin.In addition, also can comprise solidifying agent, curing catalyst as required.Epoxy is that resin can be used alone or two or more kinds may be used.

Be resin (following sometimes only be called " Resins, epoxy ") as above-mentioned epoxy, can enumerate the polyglycidyl ether that the polyvalent alcohols such as polyphenol such as making dihydroxyphenyl propane, Bisphenol F, xenol, phenolic varnish type resol, ortho-cresol phenolic varnish type resol, tris-phenol phenolic varnish type resol and BDO and epichlorohydrin reaction obtain; The poly glycidyl ester that the polyprotonic acids such as phthalic acid, hexahydrophthalic acid and epichlorohydrin reaction are obtained; Amine, acid amides or have the N-Racemic glycidol radical derivative of the compound of hetero ring type nitrogen base; With alicyclic epoxy resin etc.

Above-mentioned epoxy is in the resin, considers from the aspect that itself thermal conductivity of resin improves, melt viscosity during heating reduces, and preferably has epoxy monomer or its polymkeric substance of the mesomorphic skeleton take biphenyl structural etc. as representative.

Mesomorphic skeleton representation of the present invention has the functional group of the possibility of performance liquid crystal liquid crystal property.Specifically, can enumerate biphenyl, phenol benzoate, nitrogen benzide, stilbene etc., its derivative, the material that has 6 Yuans ring structures more than 3 in biphenyl or the molecule can be enumerated, the following general formula (A) that " liquid crystal handbook (liquid crystal Bian list) " (the kind liquid crystal handbook of ball returns federal communications commission and compiles publication in 2000) put down in writing can be enumerated.

[changing 2]

Perhaps

…（A）

In the general formula (A), as ring 1, ring 2 and encircle 3 represented ring structures independently of one another from

[changing 3]

Middle selection, in conjunction with basic X1 and X2 be independently of one another singly-bound,

[changing 4]

Or with the concatenating group of the combination more than two in them, Y1, Y2 and Y3 represent independently of one another-R ,-OR(R represents the aliphatic alkyl of carbonatoms 1～8) ,-F ,-Cl ,-Br ,-I ,-CN ,-NO ₂, or-CO-CH ₃, n, m and l represent 0～4 integer independently of one another.

As the epoxy monomer with mesomorphic skeleton, preferred biphenyl type epoxy resin, connection xylol type Resins, epoxy, 1-(3-methyl-4-Oxyranyle p-methoxy-phenyl)-4-(4-Oxyranyle p-methoxy-phenyl)-1-tetrahydrobenzene or 1-(3-methyl-4-Oxyranyle p-methoxy-phenyl)-4-(4-Oxyranyle p-methoxy-phenyl)-benzene etc., consider from the viewpoint of the thermal conductivity of fusing point and cured article, more preferably 1-(3-methyl-4-Oxyranyle p-methoxy-phenyl)-4-(4-Oxyranyle p-methoxy-phenyl)-the 1-tetrahydrobenzene.Such epoxy compounds for example can be made by the method that above-mentioned patent documentation 1 is put down in writing.

In above-mentioned epoxy monomer or its polymkeric substance with mesomorphic skeleton, preferably containing at least a kind of 2 official with biphenyl backbone can Resins, epoxy.Above-mentioned 2 officials with biphenyl backbone can Resins, epoxy so long as comprise at least 1 biphenyl backbone, compound with 2 epoxy group(ing) just is not particularly limited.For example can enumerate particularly biphenyl type epoxy resin, inferior biphenyl type epoxy resin.

As above-mentioned biphenyl type epoxy resin, preferably use the represented Resins, epoxy of following general formula (III) etc.

[changing 5]

R in general formula (III) ¹～R ⁸Represent independently of one another replacement or the unsubstituted alkyl of hydrogen atom or carbonatoms 1～10, n represents 0～3 integer.

As replacement or the unsubstituted alkyl of carbonatoms 1～10, such as enumerating: methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-etc.Wherein, R ¹～R ⁸Independently of one another preferred hydrogen atom or methyl.

As the biphenyl type epoxy resin shown in the above-mentioned general formula (III), for example can enumerate: with 4,4 '-two (2,3-epoxy group(ing) propoxy-) biphenyl or 4,4 '-two (2,3-epoxy group(ing) propoxy-)-3,3 ', 5,5 '-tetramethyl biphenyl is the Resins, epoxy of main component, make epoxy chloropropane and 4,4 '-xenol or 4,4 '-(3,3 ', 5,5 '-tetramethyl-) Resins, epoxy that obtains of xenol reaction etc.Wherein preferably with 4,4 '-two (2,3-epoxy group(ing) propoxy-)-3,3 ', 5,5 '-tetramethyl biphenyl is the Resins, epoxy of main component.As such compound, can obtain YX-4000(japan epoxy resin Co., Ltd. system), YL-6121(japan epoxy resin Co., Ltd. system), YSLV-80XY(Toto Kasei KK system) etc. as commercially available product.

In addition, as above-mentioned inferior biphenyl type epoxy resin, can enumerate the represented Resins, epoxy of following general formula (IV) etc.

[changing 6]

In general formula (IV), R ¹～R ⁹Represent independently of one another the alkyl of hydrogen atom, carbonatoms 1～10, the alkoxyl group of carbonatoms 1～10, the aryl of carbonatoms 6～10 or the aralkyl of carbonatoms 7～10, n represents 0～10 integer.

As the alkyl of above-mentioned carbonatoms 1～10, such as enumerating: methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-etc.As the alkoxyl group of carbonatoms 1～10, such as enumerating methoxyl group, oxyethyl group, propoxy-, butoxy etc.As the aryl of carbonatoms 6～10, such as enumerating phenyl, tolyl, xylyl etc.In addition, as the aralkyl of carbonatoms 7～10, such as enumerating benzyl, styroyl etc.Wherein, R ¹～R ⁹Independently of one another preferred hydrogen atom or methyl.

As the represented biphenyl type epoxy resin of above-mentioned general formula (IV), for example can obtain NC-3000(Nippon Kayaku K. K trade(brand)name processed) as commercially available product.

As the 2 officials energy Resins, epoxy that has biphenyl backbone among the present invention, consider from the flexual viewpoint of thermal conductivity, electrical insulating property and aftermentioned B rank sheet material, preferably comprise at least a kind of above-mentioned general formula (III) or the represented compound of general formula (IV), more preferably comprise the represented compound of at least a kind of general formula (III).

Containing ratio as above-mentioned thermosetting resin in all solids composition of resin combination sheet material of the present invention, be not particularly limited, but consider from the flexual viewpoint of thermal conductivity, electrical insulating property and B rank sheet material, be preferably 1 quality %～15 quality %, more preferably 2 quality %～12 quality %, more preferably 3 quality %～10 quality %.

Resin combination sheet material of the present invention, may be used above-mentioned 2 officials with biphenyl backbone can Resins, epoxy and other Resins, epoxy.As other Resins, epoxy, so long as do not have the material of biphenyl backbone, known Resins, epoxy before just can using with being not particularly limited.

As other Resins, epoxy, particularly such as enumerating: carry out epoxidised Resins, epoxy take phenol novolak type epoxy resin, o-cresol phenolic epoxy varnish, Resins, epoxy with triphenyl methane skeleton as compound that the aphthols such as the phenols such as phenol, cresols, xylenol, Resorcinol, pyrocatechol, dihydroxyphenyl propane, Bisphenol F and/or naphthyl alcohol, 2-Naphthol, dihydroxy naphthlene and formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, salicylic aldehyde etc. have the aldehyde radical novolac resin of condensation or cocondensation gained under an acidic catalyst that will make of representative.

In addition, can enumerate dihydroxyphenyl propane, Bisphenol F, bisphenol S, stilbene type Resins, epoxy; Resorcinol type Resins, epoxy; Glycidyl ester type epoxy resin by the polyprotonic acids such as phthalic acid, dimeracid and epichlorohydrin reaction gained; Glycidyl amine type epoxy resin by the polyamines such as diaminodiphenyl-methane, isocyanuric acid and epichlorohydrin reaction gained; The epoxide of the cocondensation resin of Dicyclopentadiene (DCPD) and phenols; Resins, epoxy with naphthalene nucleus; Phenol-aralkyl resin, contain the epoxide of the phenol of inferior biphenyl backbone-aralkyl resin, naphthols-aralkyl-type phenol resin such as aralkyl resin; Trimethylolpropane type Resins, epoxy; The terpene modified epoxy; The wire aliphatic epoxy resin that utilizes the peracid such as peracetic acid that the oxidation of alkene key is obtained; Cycloaliphatic epoxy resin; The Resins, epoxy of sulfur atom-containing etc., they can use separately, and also two or more kinds may be used.

Resin combination sheet material of the present invention is considered from the flexual viewpoint of B rank sheet material, preferably comprises at least a kind that selects from the Resins, epoxy with naphthalene nucleus.

Resin combination sheet material of the present invention is in the situation that comprise other Resins, epoxy, its containing ratio is not particularly limited, but for example, with respect to above-mentioned 2 officials energy Resins, epoxy with biphenyl backbone, be preferably 1 quality %～30 quality %, more preferably 2 quality %～20 quality %, more preferably 3 quality %～15 quality %.By being such containing ratio, the pliability of thermal conductivity, electrical insulating property and B rank sheet material more effectively improves.

(resol)

Resin combination sheet material of the present invention contains at least a kind of resol.As above-mentioned resol, preferably comprise and contain at least a kind of resol with compound of the represented structural unit of following general formula (I) (below be sometimes referred to as " novolac resin ").Above-mentioned resol for example works as the solidifying agent of Resins, epoxy.

By comprising the resol with ad hoc structure, thermal conductivity can improve effectively, further can fully prolong the usable time under the state before curing.

[changing 7]

In above-mentioned general formula (I), R ¹Expression alkyl, aryl or aralkyl, R ¹Represented alkyl, aryl or aralkyl can further have substituting group if possible, as this substituting group, can enumerate alkyl, aryl, halogen atom and hydroxyl etc.

M represents 0～2 integer, in the situation that m is 2,2 R ¹Can be the same or different.In the present invention, m is preferably 0 or 1, and more preferably 0.N represents 1～10 integer, is preferably 1～8, more preferably 1～7.

R in the general formula (I) ²And R ³Represent independently of one another hydrogen atom, alkyl, aryl, phenyl or aralkyl.R ²And R ³Represented alkyl, phenyl, aryl or aralkyl can further have substituting group if possible, as this substituting group, can enumerate alkyl, aryl, halogen atom and hydroxyl etc.

As R of the present invention ²And R ³, consider from the viewpoint of storage stability and thermal conductivity, be preferably hydrogen atom, alkyl, phenyl or aryl, more preferably aryl, the phenyl of the alkyl of hydrogen atom, carbonatoms 1 to 4 or carbonatoms 3 to 6, more preferably hydrogen atom.

Further consider R from the thermotolerance viewpoint ²And R ³At least one party also be preferably aryl.

Resol of the present invention can comprise separately a kind, also can comprise the compound with the represented structural unit of above-mentioned general formula (I) more than 2 kinds.

The represented resol of above-mentioned general formula (I) comprises from the part-structure as the Resorcinol of phenoloid, also can further comprise at least a kind from the part-structure of the phenoloid except Resorcinol.As the phenoloid except Resorcinol, such as enumerating phenol, cresols, pyrocatechol, Resorcinol etc.Above-mentioned resol can comprise independent a kind or comprise part-structure from them with the combination more than 2 kinds.

Here, so-called part-structure from phenoloid refers to: partly remove 1 or 2 hydrogen atoms and 1 valency or the divalent group that consist of from the phenyl ring of phenoloid.In addition, the position of removing hydrogen atom is not particularly limited.

Among the present invention, as the part-structure from the phenoloid except Resorcinol, consider from the viewpoint of thermal conductivity, cementability, storage stability, be preferably since phenol, cresols, pyrocatechol, Resorcinol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene and 1,3, at least a kind the part-structure of selecting in the 5-trihydroxybenzene, at least a kind the part-structure of more preferably in pyrocatechol and Resorcinol, selecting.

In addition, be not particularly limited about the ratio that contains from the part-structure of Resorcinol in the above-mentioned resol, but consider from the viewpoint of thermal conductivity and storage stability, total mass with respect to resol, the ratio that contains from the part-structure of Resorcinol is preferably more than the 30 quality %, more preferably more than the 55 quality %, more preferably more than the 80 quality %.

As resol of the present invention, specifically, be preferably comprise have below shown in general formula (Ia)～general formula (If) in the resol of compound of any represented part-structure.

[changing 8]

The compound that resol among the present invention also preferably has a represented structural unit of above-mentioned general formula (I) is at least a kind of the represented compound of following general formula (II).

[changing 9]

In the general formula (II), R ¹¹Expression hydrogen atom or from 1 valency group of the represented phenoloid of following general formula (IIp), R ¹²Expression is from 1 valency group of phenoloid.In addition, R ¹, R ², R ³, the R in m and n and the general formula (I) ¹, R ², R ³, m and n synonym respectively.

R ¹¹And R ¹²Represented 1 valency group from phenoloid is partly to remove 1 hydrogen atom and the 1 valency group that consists of from the phenyl ring of phenoloid, and the position of removing hydrogen atom is not particularly limited.

[changing 10]

In the general formula (IIp), p represents 1～3 integer.In addition, R ¹, R ²And R ³With the R in the general formula (I) ¹, R ²And R ³The difference synonym, m represents 0～2 integer.

R ¹¹And R ¹²Phenoloid so long as have the compound of phenolic hydroxyl group, just be not particularly limited.Particularly such as enumerating: phenol, cresols, pyrocatechol, Resorcinol, Resorcinol etc.Wherein, consider from the viewpoint of thermal conductivity and storage stability, be preferably at least a kind that from cresols, pyrocatechol, Resorcinol, selects.

In resin combination sheet material of the present invention, comprise the resol of the compound with the represented structural unit of above-mentioned general formula (I), can comprise the monomer as the phenoloid that consists of resol.The ratio (below be sometimes referred to as " monomer contains ratio ") that contains as the monomer of the phenoloid that consists of resol is not particularly limited, but is preferably 5～80 quality %, more preferably 15～60 quality %, more preferably 20～50 quality %.

Be more than the 5 quality % by making monomer contain ratio, thereby suppress the viscosity rise of resol, the adaptation of inorganic filler further improves.In addition, by being below the 80 quality %, the crosslinking reaction during by curing can form more highdensity higher order structure, realize excellent thermal conductivity and thermotolerance.

In addition, as the monomer of the phenoloid that consists of resol, can enumerate Resorcinol, pyrocatechol, Resorcinol, preferably comprise at least Resorcinol as monomer.

In addition, the ratio that contains as the above-mentioned resol in the resin combination sheet material of the present invention is not particularly limited, but considers from the pliability of thermal conductivity, electrical insulating property, B rank sheet material and the viewpoint of usable time, be preferably 1 quality %～15 quality %, more preferably 2 quality %～10 quality %.

In addition, as containing than (thermosetting resin/resol) of above-mentioned thermosetting resin in resin combination sheet material of the present invention and above-mentioned resol, for example in the equivalence ratio benchmark, can be 0.6～1.5, consider from the pliability of thermal conductivity, B rank sheet material and the viewpoint of usable time, be preferably 0.8～1.2.

Resin combination sheet material of the present invention except above-mentioned resol, can also comprise other solidifying agent except resol as required.As other solidifying agent, known solidifying agent before can using with being not particularly limited.Particularly such as using: amine is that solidifying agent, mercaptan are potentiality solidifying agent such as polyaddition type solidifying agent, imidazoles such as solidifying agent etc.

(insulativity mineral filler)

The insulativity mineral filler that resin combination sheet material of the present invention is contained is so long as the insulativity mineral filler just is not particularly limited.The material that preferably has the above thermal conductivity of 1W/mK specifically, can be selected from silicon-dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide, aluminum fluoride or Calcium Fluoride (Fluorspan).In these, can use a kind of or mix more than two kinds and to use.

The inorganic ceramic that further preferably has the above thermal conductivity of 10W/mK specifically, can be selected from aluminum oxide, magnesium oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide or aluminum fluoride.

Wherein, more preferably have 10 ¹⁶The aluminum oxide (Alumina) of the volume specific resistance that Ω cm is above.

They can be used alone, or mix more than two kinds and use.

Particle diameter, the blending ratio of insulativity mineral filler are not particularly limited.Particle diameter about the insulativity mineral filler, blending ratio, when for example enumerating applicable situation with 3 kinds of inorganic filling material groups that different grain size distributes and being example, comprising particle diameter D50 is the following inorganic filling material groups (A) of the above 100 μ m of 5 μ m, D50 be inorganic filling material group (A) below 1/2 and be the following inorganic filling material groups (B) of the above 10 μ m of 1 μ m, with D50 be inorganic filling material group (B) below 1/2 and be that the following inorganic filling material group (C) of the above 5 μ m of 0.1 μ m consists of, the accumulation 50% that described particle diameter D50 begins corresponding to the small particle size side from the weight build-up size-grade distribution, total amount with respect to inorganic filling material, inorganic filling material group (A), (B) and ratio (C) respectively preferably with below the 90 quality % more than the 40 quality %, below the above 40 quality % of 5 quality %, following (wherein, the inorganic filling material group (A) of the above 30 quality % of 1 quality %, (B) and total mass % (C) be 100 quality %) ratio fill.

In addition, when using the wide inorganic filling material of size-grade distribution, the situation that is difficult to separate clearly mixed size-grade distribution is arranged.In this case, preferably after determining maximum particle diameter, when describing the weight build-up size-grade distribution large particle diameter side is designed size-grade distribution according to the mode that meets the knowledge in the past such as Fuller curve at the thickness of considering design.

In addition, median size and the maximum of above-mentioned inorganic filling material group (A), the thickness that is used as target in the situation of the tinsel of sheet material or resin limits.In the situation that there is not other special restriction, to consider from the viewpoint of thermal conducting rate, the median size of above-mentioned inorganic filling material group (A) is the bigger the better, and considers from the viewpoint of hot resistance, makes as far as possible insulativity in the scope of allowing and is preferably thin thickness.In addition, consider from the viewpoint of insulativity, maximum particle diameter is at least below 7/8 of thickness, is preferably below 2/3, more preferably below 1/2.Therefore, the median size of above-mentioned inorganic filling material group (A) be thickness below 1/2 and be preferably below the above 100 μ m of 5 μ m, consider from the viewpoint of fillibility and hot resistance, heat conductivity, more preferably below the above 75 μ m of 10 μ m, more preferably below the above 45 μ m of 10 μ m.

Among the present invention, the particle diameter D50 of insulativity mineral filler uses laser diffractometry to measure, in the situation that begin to describe the weight build-up size distribution curve from the small particle size side, is 50% particle diameter corresponding to weight build-up.

The particle size distribution of use laser diffractometry can use the laser diffraction and scattering particle size distribution device, and (for example, Beckman-Coulter Corporation's system LS230) carries out.

In addition, in the situation that above-mentioned inorganic filling material group (A) and inorganic filling material group (B) they are alumina packing, the alumina packing that is more preferably consisted of by the monocrystal particle of Alpha-alumina.

On the other hand, above-mentioned inorganic filling material group (C) is in the situation of alumina packing, be preferably Alpha-alumina, gama-alumina, δ-aluminum oxide or θ-aluminum oxide, Alpha-alumina more preferably, the alumina packing that is more preferably consisted of by the monocrystal particle of Alpha-alumina.

The containing ratio of the insulativity mineral filler that resin combination sheet material of the present invention is contained is not particularly limited, but in the solids component that consists of the resin combination sheet material, can be 40vol%～82vol%, consider from the flexual viewpoint of thermal conductivity, electrical insulating property and sheet material, more preferably 50vol%～79vol%, more preferably 55vol%～76vol%.In the very few situation of the cumulative volume of insulativity mineral filler, thermal conductivity reduces, in the situation that too much, be difficult to form flap.

In addition, the solids component in the so-called resin combination sheet material refers to remove the residual component of volatile component from the composition that consists of the resin combination sheet material.

As above-mentioned inorganic filling material group (A)～(C), can from commercially available material, suitably select.In addition, for example also can be the material of making by transitional alumina or the alumina packing that becomes transitional alumina by thermal treatment are burnt till (for example, with reference to Japanese kokai publication hei 6-191833 communique, Japanese kokai publication hei 6-191836 communique etc.) in containing the atmosphere gas of hydrogenchloride.

Resin combination sheet material of the present invention except above-mentioned inorganic filling material group (A)～(C), can also comprise take aluminum oxide as main component, its number average Fibre diameter is the inorganic fibre of 1 μ m～50 μ m." inorganic fibre take aluminum oxide as main component " refers to comprise the inorganic fibre of the above aluminum oxide of 41vol% among the present invention.Wherein, be preferably the inorganic fibre that comprises the above aluminum oxide of 58vol%, more preferably comprise the inorganic fibre of the above aluminum oxide of 74vol%.The number average Fibre diameter of such inorganic fibre is 1 μ m～50 μ m, is preferably 1 μ m～30 μ m, more preferably 1 μ m～20 μ m.In addition, the fiber length of such inorganic fibre is generally 0.1mm～100mm.

As such inorganic fibre, usually use commercially available material, specifically, can enumerate ALTEX(Sumitomo Chemical Co system), DENKA ALCEN(Deuki Kagaku Kogyo Co., Ltd system), MAFTEC bulk fibre (Mitsubishi Chemical property Co., Ltd's system) etc.

In the situation of using such inorganic fibre, its usage quantity is generally 4vol%～58vol% with respect to the quality of above-mentioned inorganic filling material group (A)～(C), be preferably 4vol%～41vol%, the total quality of insulativity mineral filler and inorganic fibre, in the solids component of resin combination sheet material, usually use the amount of 30～95 quality %.

Resin combination sheet material of the present invention can further comprise the inorganic filling material except the insulativity mineral filler as required except above-mentioned insulativity mineral filler.As inorganic filling material, for example, can enumerate magnesium oxide, aluminium nitride, boron nitride, silicon nitride, silicon oxide, aluminium hydroxide, barium sulfate etc. as non-conductive material.In addition, as conductive material, can enumerate gold and silver, nickel, copper etc.These inorganic filling materials can use separately a kind, or two or more kinds may be used.

(other composition)

Resin combination sheet material of the present invention also can comprise other composition as required except above-mentioned essential component.As other composition, such as enumerating solvent, silane coupling agent, dispersion agent, anti-sedimentation agent etc.

As above-mentioned solvent, as long as do not hinder the curing reaction of resin combination sheet material just to be not particularly limited, can suitably select normally used organic solvent and use.

In resin combination sheet material of the present invention, preferably comprise silane coupling agent.By comprising silane coupling agent, thereby performance is in the surface of insulativity mineral filler and the effect (being equivalent to tackiness agent) of surrounding formation covalent linkage between its organic resin on every side, more effectively transmit thus heat, further by hindering the invasion of moisture, also help the raising of insulating reliability.

As silane coupling agent, usually can use commercially available material, but consider with the intermiscibility of Resins, epoxy, resol and when reducing heat conduction losses on resin layer and the insulativity mineral filler interface, preferably use has the silane coupling agent of epoxy group(ing), amino, sulfydryl, urea groups, hydroxyl endways.

For example can enumerate particularly: the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, APTES, the 3-(2-amino-ethyl) TSL 8330, the 3-(2-amino-ethyl) TSL 8330, the 3-TSL 8330,3-phenyl amino propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl triethoxyl silane, 3-urea groups propyl-triethoxysilicanes etc. also can be enumerated the silane coupling agent oligopolymer (Hitachi changes into Coated Sand Co., Ltd. system) of SC-6000KS2 representative etc. in addition.These silane coupling agents also can be separately or and with more than 2 kinds.

In resin combination sheet material of the present invention, can add dispersion agent, as dispersion agent, can usually use the effective commercial dispersants of the dispersion of insulativity mineral filler.The AJISPER processed of aginomoto fine chemistry Co., Ltd. is serial such as enumerating, nanmu originally changes into Co., Ltd.'s HIPLAAD series processed, Co., Ltd. spends king's HOMOGENOL series processed etc.These dispersion agents may be used more than two kinds.

(resin combination)

In the present invention, can use resin combination to form the resin combination sheet material.Resin combination comprises above-mentioned thermosetting resin, above-mentioned resol and above-mentioned insulativity mineral filler.Because this resin combination is filled with the insulativity mineral filler, therefore the performance of insulativity mineral filler can affect above-mentioned recess occupation rate when base material supplies to give resin combination.

The viscosity of if tree oil/fat composition is excessively low, then compares with the evaporation of the contained organic solvent of resin combination, and the insulativity mineral filler is faster in the sedimentation of coated substrate side, forms insulativity mineral filler wall.Consequently, compare at the contained volatile matter such as solvent of the resin combination of coated substrate side with insulativity mineral filler wall, bottled up owing to insulativity mineral filler wall, condense, become bubble.Consequently produce the interface bubble in the coated substrate side.Therefore, for the recess occupation rate of the resin combination sheet material that reduces invention, very important for the viscosity controller of giving the resin combination on the base material.Particularly in the situation that coating resin composition and form the resin combination sheet material in tinsel on the tinsel, because usually the surfaceness of tinsel is compared more coarsely with metal substrate as described later, therefore obviously the viscosity adjustment of resin combination is very important.

Viscosity under the viscosity of resin combination is measured 25 ℃ by Brookfield viscometer (axle No4, revolution 30rpm).In order effectively to suppress the generation of interface bubble, be preferably 1000～10000mPas, more preferably 1200～8000mPas, more preferably 1500～6000mPas.If viscosity is excessively low, then the sedimentation of insulativity mineral filler is fast, easily produces the interface bubble.On the other hand, if viscosity is too high, then be difficult to control the thickness of filming.Particularly the resin combination that viscosity is low is coated on the tinsel and makes in the situation with the resin combination sheet material of tinsel, be that 1000mPa is when above in viscosity, the sedimentation that can suppress the insulativity mineral filler is too fast, can be suppressed between the concavo-convex of roughened tinsel and the insulativity mineral filler and produce the gap.

The resin combination that contains the insulativity mineral filler, the viscosity of the more resin combinations of insulativity inorganic filler content is higher, is difficult to be coated with homogeneous film thickness.Yet if reduce viscosity by the addition that increases solvent etc., the sedimentation of insulativity mineral filler is too fast as mentioned above, and the recess occupation rate increases.Therefore, wish resin combination is adjusted to suitable viscosity.

(making method of resin combination sheet material (B rank))

Resin combination sheet material of the present invention is the flap on semi-cured state (B rank).The resin combination sheet material of this semi-cured state (B rank) is used for wiring board material, wiring board, if formally solidify then form the heat conductivity insulation layer.

The resin combination sheet material can be by being coated with thing with above-mentioned resin combination for giving in the upper sheet that form of support base material (coated substrate), is heated to semi-cured state (B rank) and makes.

The confession method of giving of above-mentioned resin combination is not particularly limited, but in the situation that big area forms preferably coating.Coating can be implemented by known method.As coating process, can enumerate particularly that comma coating, mould are coated with, the methods such as die lip is coated with, intaglio plate coating.As the coating process of the resin layer that is used to form specific thickness, can use comma coating method that applied thing is passed through between the gap, adjusted the mould Tu Fa etc. of the resinous varnish of flow by the nozzle coating.Can enumerate in addition die lip coating, intaglio plate coating etc.

When coating, in order to adjust viscosity, can in above-mentioned resin combination, add solvent.As the contained solvent of resin combination, be not particularly limited, can use methyl ethyl ketone, acetone, methyl iso-butyl ketone (MIBK), pimelinketone, hexalin, N,N-DIMETHYLACETAMIDE, Virahol, methyl alcohol, ethanol etc.

Coated substrate is not particularly limited, but owing to when making metal matrix wiring board material, can be removed, so preferred cheap plastic basis material.As the resin that in plastic basis material, uses, can enumerate the thermoplastic polyesters such as polystyrene resin, acrylic resin, plexiglass, polycarbonate resin, polyvinyl chloride (PVC) RESINS, polyvinylidene chloride resin, polyvinyl resin, acrylic resin, polyamide resin, polyamide-imide resin, polyetherimide resin, polyether-ether-ketone resin, polyarylate resin, polyacetal resin, polybutylene terephthalate resin, polyethylene terephthalate resin; Thermoplastic resin, the thermosetting resins such as cellulose acetate resin, fluoro-resin, polysulfone resin, polyethersulfone resin, polymethylpentene resin, urethane resin, diallyl phthalate resin.The thickness of plastic basis material considers to be preferably 0.01mm～5mm from the operability viewpoint.In order to improve the separability of resin combination sheet material, can form release layer on the plastic basis material surface.

The above-mentioned coating thing that obtains can be used for carrying out drying before the heating of semicure.Drying temperature and time of drying are preferably suitably adjusted according to the kind of the contained organic solvent of coating thing.By adjusting drying temperature, time of drying, the velocity of evaporation by organic solvent and insulativity mineral filler are in the adjustment of the settling velocity of coated substrate side, and the recess occupation rate that also can make the resin combination sheet surface that obtains is below 4%.

Specifically, drying temperature is preferably 30 ℃～90 ℃, and more preferably 40 ℃～100 ℃, more preferably 50 ℃～110 ℃.In addition, be preferably 0.2～60 minute time of drying, more preferably 0.5～40 minute, more preferably 1～30 minute.

The coating thing that obtains is heated to semi-cured state (B rank).Here, so-called " semi-cured state (B rank) " refer to as lowest melt viscosity, are 10 at normal temperatures ³～10 ⁶Pas, with it relative reduced viscosity to 10～10 in 80 ℃～200 ℃ scope ³The state of Pas.In addition, for the C rank sheet material (heat conductivity insulation layer) after the formal curing, can the melting owing to heating.

So-called above-mentioned lowest melt viscosity, the viscosity rise that the reduced viscosity that the melt viscosity of terminal-modified imide oligopolymer causes owing to temperature rises and curing reaction cause is got minimum value, just refers to this minimum value.The measuring method of the lowest melt viscosity of resin combination sheet material as described later.

The Heating temperature and the heat-up time that are used for semicure are preferably suitably adjusted according to kind, the amount of the contained organic solvent of above-mentioned coating thing.Specifically, the Heating temperature that is used for semicure is preferably 70 ℃～160 ℃, and more preferably 80 ℃～150 ℃, more preferably 90 ℃～140 ℃.In addition, be preferably 0.2～60 minute heat-up time that is used for semicure, and more preferably 0.5～40 minute, more preferably 1～30 minute.

The content of organic solvent in the resin combination sheet material (B rank sheet material), the viewpoint of the space after suppressing formal curing the heat conductivity insulation layer of (C rank sheet material), the generation of bubble is considered, preferably is reduced at base material for below 40% of content in the resin combination before giving.

In addition, the resin combination sheet material that obtains can be individual layer, also can be the material that 2 resin combination sheet materials is bonded to each other or with the stacked material of resin combination sheet material more than 3 in addition.The applying of 2 above resin combination sheet materials can use the known methods such as laminating machine, pressing machine to implement, at this moment can be by adding thermosetting semi-cured state (B rank).

By the resin combination sheet material of such applying more than 2, the resin combination sheet material is good knitting each other, therefore can engage the resin combination sheet material each other, can form single resin sheet.Therefore, for example in the high situation of the area occupation ratio of the recess of the one side of resin combination sheet material or formed in the concavo-convex situation, by this face is bonded to each other, can make recess, concavo-convex disappearance.Therefore, can reduce the recess occupation rate of resin combination sheet surface.

The applying of resin combination sheet material preferably 70 ℃～160 ℃, more preferably 80 ℃～150 ℃, further preferably carry out 90 ℃～140 ℃ lower heating.

In addition, the pressure of applying is preferably 0.05MPa～1MPa, more preferably 0.1MPa～0.6MPa, 0.2MPa～0.4MPa more preferably.

Further, the resin combination sheet material that obtains also can carry out smoothing and reduce the recess occupation rate on surface by effects on surface.As the method for smoothing, such as enumerating the known methods such as laminating machine, pressing machine etc.By smoothing, owing to pressurization makes the resin combination sheet material mobile a little, the recess of sheet surface is disappeared.Hope is when smoothing, and the member that contacts with the resin combination sheet material is level and smooth.This is because the smoothness of this member can affect the smoothness of resin combination sheet material.For example, the plastics sheet of surface smoothing is contacted with the resin combination sheet material, can prevent that the resin combination sheet attaching is on laminating machine, pressing machine simultaneously.In addition, in the time of also can pressurizeing the resin combination sheet material is heated, thus the flowability of raising resin combination.In the operation of this smoothing, can be by adding thermosetting semi-cured state (B rank).

In the situation of the smoothing of carrying out the resin combination sheet surface by vacuum laminator, vacuum tightness is preferably 0.01kPa～20kPa, more preferably 0.03kPa～10kPa, more preferably 0.1kPa～5kPa.

The Heating temperature of vacuum laminator is preferably 70 ℃～170 ℃, and more preferably 80 ℃～160 ℃, more preferably 90 ℃～150 ℃.

The pressure of vacuum laminator is preferably 0.1MPa～3MPa, more preferably 0.3MPa～2MPa, 0.6MPa～1.5MPa more preferably.

(physical property of resin combination sheet material (B rank))

The lowest melt viscosity of resin combination sheet material can affect the flowability that makes the resin combination its pressurized, heated operation from the B rank to the C rank.Therefore, from operability, suppress the viewpoint that the resin combination sheet material flows out from the end and consider, preferably adjust the lowest melt viscosity under 20 ℃～200 ℃ of the temperature ranges that apply in the pressurized, heated operation.

The lowest melt viscosity of resin combination sheet material is, when measuring the temperature dependency of shear viscoelasticity, and the minimum value that the viscosity increase that the reduced viscosity that causes and curing reaction cause because temperature rises shows.

As the example of the condition of measuring shear viscoelasticity, can enumerate the heat-up rate of 5 ℃/min(of heat-up rate pressing machine), frequency 1～10Hz, clamp the mensuration anchor clamps of sheet material and can enumerate circular dull and stereotyped.Sample can use the material that the resin combination sheet material is laminated as required.

The lowest melt viscosity of resin combination sheet material under 20 ℃～200 ℃ is preferably 10Pas～1000Pas, more preferably 20Pas～800Pas, more preferably 30Pas～600Pas.If lowest melt viscosity is excessively low, then the thickness of heat conductivity insulation layer produces deviation, if lowest melt viscosity is too high, then heat conductivity insulation layer and Copper Foil, metal substrate etc. by not fully driving fit of convered structure, produce the reduction of bonding force, the reduction of insulation breakdown voltage.Therefore, if the lowest melt viscosity under 20 ℃～200 ℃ in above-mentioned scope, shows excellent flowability when then heating, even for having also can being followed by convered structure of concaveconvex structure, therefore, show high bonding force behind formal the curing.

The thickness of resin combination sheet material of the present invention (B rank sheet material) can suitably be selected according to purpose, for example mean thickness is preferably 20 μ m～500 μ m, more preferably 25 μ m～400 μ m consider from the flexual viewpoint of thermal conductivity, electrical insulating property and sheet material, are preferably 30 μ m～300 μ m.In the situation that the above electrical insulating property of 20 μ m is excellent, in the situation that can suppress the increase of hot resistance below the 500 μ m.

＜with the resin combination sheet material (B rank sheet material) of tinsel 〉

Resin combination sheet material with tinsel is the material that is pasted with tinsel at above-mentioned resin combination sheet material.More particularly, can use laminating machine, pressing machine etc. by known method in the resin combination sheet material tinsel of fitting, thereby make resin combination sheet material with tinsel.In addition, can be by tinsel be formed the coating thing as base material for giving resin combination with the resin combination sheet material of tinsel, be heated to semi-cured state (B rank) and make.

Usually, in order to improve the bonding force with the resin combination sheet material, tinsel is by roughened.By the resin combination sheet attaching being made on the tinsel in the situation with the resin combination sheet material of tinsel, if there is the recess of above-mentioned specific size on the surface of resin combination sheet material, then in the pressurization on C rank and heating process, can not follow tinsel fully and carry out surface shape after roughened, thereby may easily produce the interface bubble.

In order to suppress the generation of such interface bubble, find that it is effective using resin combination sheet material of the present invention, resin combination sheet material of the present invention namely is the first resin combination sheet material or the second resin combination sheet material, the first resin combination sheet material comprises thermosetting resin, resol and insulativity mineral filler, and in its surface, the occupation rate of the recess that full depth 0.5 μ m is above is counted below 4% with area occupation ratio, the lowest melt viscosity of the second resin combination sheet material under 20 ℃～200 ℃ is 10～1000Pas, and in its surface, the occupation rate of the recess that full depth 0.5 μ m is above is counted below 4% with area occupation ratio.In addition, resin combination sheet material of the present invention is certainly in the situation that lay the generation that metal substrate also can suppress the interface bubble effectively.

As tinsel, can use by copper, aluminium, nickel, tin or comprise the tinsel that arbitrary material of the alloy of these metals consists of.In addition, the layer structure of tinsel is not limited to 1 layer, also can use 2～3 layers composite foil.In the situation that expectation is low-cost and electric conductivity is high, preferably use Copper Foil.

The thickness of tinsel is preferably 3 μ m～110 μ m, more preferably 5 μ m～90 μ m, more preferably 9 μ m～70 μ m.In the situation that more than the 3 μ m, operation is excellent, can prevent from fractureing under small power.In addition, in the situation that below the 110 μ m, can suppress the usage quantity of the tinsel of high price.

In order to improve the operability of tinsel, can process tinsel being pasted with under the state of carrier film.As such carrier film, can use the adhesive film of little adhesive adhesive film, self-adsorptivity, the adhesive film of UV solidified nature.Utilize the bonding process that the resin combination sheet material carries out or be used for obtaining painting process with the resin combination sheet material of tinsel in metal substrate and tinsel, by being the state that is pasted with carrier film in tinsel, can suppress fractureing of tinsel etc.

Other manufacture method, create conditions, that the preferable range of the thickness of resin combination sheet material, the preferable range of resin combination viscosity etc. and above-mentioned resin combination sheet material are related is same.

＜heat conductivity insulation layer (C rank) 〉

The heat conductivity insulation layer refers to make the adhesive linkage that insulate between metal substrate and wiring layer or the tinsel in metal matrix wiring board described later, metal matrix wiring board material.Above-mentioned resin combination sheet material (B rank) is formally solidified (C rank) and forms heat conductivity insulation layer (C rank).

Specifically, by between metal substrate and tinsel, clamping above-mentioned resin combination sheet material, carry out pressurized, heated with pressing machine etc., thus bonded metal substrate and tinsel.Above-mentioned resin combination sheet material for semi-cured state (B rank), the again melting by the pressurized, heated operation, the driving fit of resin combination sheet material is on metal substrate and tinsel, afterwards, the resin combination sheet material is formally solidified (C rank) and form heat conductivity insulation layer (C rank), make metal substrate and tinsel bonding.Heat conductivity insulation layer behind formal the curing can the melting because of heating.

The insulativity mineral filler that heat conductivity insulation layer of the present invention is heat conductivity and the matrix material of thermosetting resin.As the insulativity mineral filler of heat conductivity, preferably use thermal conductivity high and be the inorganic ceramic of insulativity.In addition, if the resin that uses heat conductivity then can improve thermal conductivity as thermosetting resin under filler content still less.In the present invention, as the resin of heat conductivity, the preferred Resins, epoxy that uses the 2 officials energy with biphenyl backbone.

Have biphenyl backbone 2 officials can Resins, epoxy in biphenyl backbone owing to having anisotropic structure for mesomorphic gene.When the heat conductivity resin layer has anisotropic structure in inside, the performance high heat conductance.Usually, the thermal conduction of isolator is mainly undertaken by phonon, because the static scattering of phonon under the discontinuities (defect) in materials, the phonon that is caused by the non-harmonious property of molecular vibration, lattice vibration collides caused dynamic scattering each other, causes thermal conductivity to reduce.

Yet, high molecular main chain direction with compare with the rectangular direction of main chain (direction between molecular chain), thermal conductivity is large.This is because high molecular main chain direction has been carried out combination by strong conjugated link(age), so the harmonious property of the vibration of main chain direction (phonon) is high, in addition, causes that the defective etc. of static scattering of phonon is also much smaller than direction between molecular chain.Therefore, can anisotropically improve thermal conductivity by high molecular main chain is orientated.The known methods such as the orientation of high polymer main chain can apply by extension, electric field, friction are implemented.If make high polymer main chain to vertical direction (thickness direction) orientation of face, then can improve the thermal conductivity at thickness direction.

On the other hand, if make high polymer main chain to the horizontal direction orientation of face, then can increase the thermal conductivity in the face.On the other hand, usually the thermal conductivity of high molecular vertical direction as direction between molecular chain is compared reduction with non-oriented high molecular situation.Therefore, usually make high polymer main chain in the resin combination sheet material of the horizontal direction of face orientation, reducing in the thermal conductivity of thickness direction.

Yet, if the order of material increases, the harmonious property increase of vibration, defective also reduces, and therefore also can increase the thermal conductivity of direction between molecular chain (thickness direction).Here, what the order of material was the highest is perfect cystal, but in fact the perfect cystal of polymer isolator can not be suitable for as the insulativity adhesives.Relative therewith, mesomorphic state also may be realized after crystal and have high order.Have the 2 officials energy Resins, epoxy of biphenyl backbone owing to having mesomorphic base, therefore, not only in the main chain direction, defective is also few on direction between molecular chain, and the non-harmonious property of vibration is also little.Therefore, can not fettered by specific differently-oriented directivity, thereby show large heat conductivity.

＜metal matrix wiring board material 〉

Metal matrix wiring board material has tinsel 30 and metal substrate 20, has the heat conductivity insulation layer 10 as the cured article of above-mentioned resin combination sheet material between tinsel 30 and metal substrate 20.By the configuration of heat conductivity insulation layer 10, make metal substrate 20 and tinsel 30 insulation.

The metallic substance that metal substrate 20 is high by thermal conductivity, thermal capacity is large consists of, but illustration copper, aluminium, iron, alloy of in lead frame, using etc.The intensity of metal substrate 20 thicker then metal matrix wiring boards is higher, but the metal matrix wiring board that is equipped with electronic unit carries out in the integrated situation with metal-made base etc. by screw, cementitious material etc., because intensity improves, so metal substrate 20 there is no need thick especially.Metal substrate 20 in the situation that preferential intensity is iron, can be selected material according to purpose in the situation that preferential lightweight, processibility be aluminium like this.

After the metal matrix wiring board made with large size, in order to boost productivity, preferably be cut into the size of after electronic unit is installed, using.Therefore, expectation metal substrate 20 is high for the processibility of cutting.

Metal substrate 20 as aluminium, can select aluminium or the alloy take aluminium as main component as material, can obtain the material of a plurality of kinds according to its chemical constitution and heat-treat condition, but the preferred kind of selecting to be very easy to the high and excellent strength of the processibility such as cutting.

Metal substrate wiring board material can be by clamping above-mentioned resin combination sheet material with metal substrate 20 and tinsel 30, with method of the pressurized, heated such as pressing machine etc. and make.Perhaps, the making such as method by pressurized, heated are with resin combination sheet material and the metal substrate 20 of tinsel.The heating of above-mentioned resin combination sheet material curing, the condition of pressure treatment are suitably selected according to the formation of resin combination sheet material.For example, preferred Heating temperature is that 80～250 ℃, pressure are 0.5～8.0MPa, and more preferably Heating temperature is that 130～230 ℃, pressure are 1.5～5.0MPa.

＜metal matrix wiring board 〉

The metal matrix wiring board has metal substrate 20 and wiring layer 40, has the heat conductivity insulation layer 10 as the cured article of above-mentioned resin combination sheet material between metal substrate 20 and wiring layer 40.By the configuration of heat conductivity insulation layer 10, make metal substrate 20 and wiring layer 40 insulation.

Wiring layer 40 obtains by the tinsel 30 of metal matrix wiring board material being carried out distribution processing.As the distribution working method of tinsel 30, preferred etching in industry.

The metal matrix wiring board is preferably removed for the welding disk that carries electronic unit at surface formation soldering-resistance layer.Metal matrix wiring board material preferably is cut into the size of the such electro part carrying member of led light source member after circuit fabrication and soldering-resistance layer formation.For example, at the electrical connection materials such as welding disk coating scolder of metal matrix wiring board, behind the configuration electronic unit, by the solder reflow operation, thus mounting electronic parts.

＜led light source member 〉

The cross-section structure of the led light source member when Fig. 3 represents to encapsulate LED as electronic unit.In led light source member shown in Figure 3, between metal substrate 20 and wiring layer 40, have heat conductivity insulation layer 10, carry electronic unit 50 at wiring layer 40.Use this led light source equipment, can make LED-backlit unit etc., perhaps can make LED electric light, LED electricbulb etc.

The heat that in the LED encapsulation, produces, according to the welding disk that is consisted of by the electrical connection materials such as scolder, tinsel 30, heat conductivity insulation layer 10, the order conduction of metal substrate 20, heat radiation.By using the heat conductivity insulation layer 10 as the cured article of resin combination sheet material of the present invention, the thermal diffusivity from the welding disk to the metal substrate improves, and the temperature that can suppress the LED encapsulation rises.

Embodiment

Specifically describe the present invention below by embodiment, but the invention is not restricted to these embodiment.In addition, unless otherwise specified, then " part " and " % " is quality criteria.

[embodiment 1]

＜resin synthesis example 1 〉

Separate adding 594g Resorcinol, 66g pyrocatechol, 316.2g37% formalin, 15g oxalic acid, 100g water in the flask at the 3L with stirrer, water cooler, thermometer, be warming up to 100 ℃ while in oil bath, heat.Successive reaction is 4 hours under reflux temperature.

Afterwards, Yi Bian dephlegmate, Yi Bian the temperature in the flask is warming up to 170 ℃.While keeping 170 ℃ of successive reactions 8 hours.Under reduced pressure carry out afterwards 20 minutes concentrated and remove intrasystem water etc., take out the resol with the structural unit shown in the general formula (I).The number-average molecular weight of the resol that obtains is 530, and weight-average molecular weight is 930.In addition, the phenol equivalent of resol is 65g/eq..

＜varnish shape resin combination 〉

In the 1L of polypropylene system lidded container, weighing 56.80g(63%(is with respect to insulativity mineral filler total mass)) particle diameter D50 is insulativity mineral filler (Sumitomo Chemical Co's system of 18 μ m, Sumicorundum AA18), 20.29g(22.5%(is with respect to insulativity mineral filler total mass)) particle diameter D50 is insulativity mineral filler (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3) and 13.07g(14.5%(with respect to insulativity mineral filler total mass)) particle diameter D50 is insulativity mineral filler (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), add 0.099g silane coupling agent (Shin-Etsu Chemial Co., Ltd's system, KBM403), 11.18g the 2-butanone (with the pure medicine of light Co., Ltd. system) as solvent, 0.180g (nanmu originally changes into Co., Ltd.'s system to dispersion agent, ED-113), 5.96g the resol that obtains by above-mentioned resin synthesis example 1 stirs.2 officials energy Resins, epoxy (Mitsubishi chemical Co., Ltd's system, YL6121H), 0.657g naphthalene that further interpolation 5.914g has biphenyl backbone are Resins, epoxy (Dainippon Ink Chemicals's system, HP4032D), 0.012g imidazolium compounds (Shikoku Chem's system, 2PHZ).Further, drop into the zirconium white ball processed of 500g diameter 5mm, after 48 hours, removing by filter zirconium white ball processed with the 100rpm stirring on the ball mill pedestal, obtain varnish shape resin combination 1.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

＜viscosity 〉

Measure the viscosity of resin combination 1 under 25 ℃ of varnish shape by Brookfield viscometer (axle No4, revolution 30rpm).Measurement result is shown in Table 1.

＜resin combination sheet material 〉

Use rod to be coated with machine, resin combination 1 obtained above is coated on the PET film (film company of Supreme Being people Du Pont system, A53), under 100 ℃, carry out 20 minutes dryings.Dried thickness is 50 μ m.2 dried resin combination sheet materials are placed in face-to-face mode, used the roll laminating machine, stacked under 110 ℃, 0.3MPa, travelling speed 0.3m/min, obtain the resin combination sheet material (B rank sheet material) of mean thickness 100 μ m.The resin combination sheet material pliability that obtains is excellent.

＜containing ratio of insulativity mineral filler 〉

In addition, whole shared ratios of insulativity mineral filler in the evaluating resin composition sheet material in such a way.At first, measure the weight of resin combination sheet material, this resin combination sheet material was burnt till 2 hours at 400 ℃, then burnt till 3 hours at 700 ℃, make the resinous principle evaporation, measure the quality of remaining insulativity mineral filler, thereby estimate the weight ratio of insulativity mineral filler in the resin combination sheet material.Then, with this insulativity mineral filler submerged, measured the volume of insulativity mineral filler by the variation of water level.Thus, estimate the proportion of insulativity mineral filler.Then, the use the same method proportion of evaluating resin composition sheet material.Then, use the weight ratio of insulativity mineral filler in the resin sheet divided by the proportion of insulativity mineral filler, and then multiply by the proportion of resin sheet, the value of gained is estimated as the volumetric ratio of insulativity mineral filler.Evaluation result is shown in Table 1.

＜lowest melt viscosity of resin combination sheet material 〉

By dynamic viscoelastic device (Rheometric Scientific, Inc. ARES processed), measure the temperature dependency of the complex elastic-modulus of resin combination sheet material, thereby and obtain complex viscosity divided by radian frequency.

The sheet material of 8 resin combination sheet materials of having peeled off the PET film and bed thickness 0.8mm is arranged as working sample with overlapping.With the discoideus mensuration clamp clamps working sample of 25mm Φ, under 80 ℃, carry out 10 second shearing manipulation.Afterwards, measure 5 ℃/min of heat-up rate, frequency 10Hz, from the complex viscosity of 20 ℃ to 200 ℃ scopes.The Schwellenwert of the complex viscosity under 20 ℃～200 ℃ is estimated as lowest melt viscosity.

＜the recess occupation rate of resin combination sheet material 〉

Measure the surface shape of resin combination sheet material by three-dimensional noncontact surface shape measuring system (water chestnutization system house system, MM3200).The mensuration of carrying out within sweep of the eye surface shape at 250 μ m * 190 μ m.For measuring view data, carry out polynomial approximation is made as 2 times face revisal, and the approximate face of mensuration view data deduction before the face revisal, obtain the view data after the revisal.Thus, the slope of the surface elevation of resin combination sheet material carried out revisal.Then, by resolving as the location of binaryzation threshold value (threshold value) than the value of the low 0.5 μ m of center line average (par), the area occupation ratio of the part that contrast threshold value (threshold value) is high is estimated.Thus, estimate the area occupation ratio of par.Then, will estimate as the recess area occupation ratio from the value of the above-mentioned area occupation ratio gained of 100% deduction.Should measure and operate test portion is repeated 10 times randomly, the area occupation ratio shared to recess averages, as the recess occupation rate of this test portion.The results are shown in the table 1.

＜metal matrix wiring board material 〉

The resin combination sheet material of having peeled off 500mm * 600mm of PET is clipped between the aluminium base (A5052,1mmt) of the alligatoring face side of Copper Foil (Japanese electrolysis company system, 35 μ m thick) of 550mm * 650mm and 500mm * 600mm, use the vacuum pressed pressing machine, under the vacuum of 3kPa, add at 2MPa and to depress, 140 ℃ of lower pressurized, heated 2 hours, 190 ℃ of lower pressurized, heated 2 hours, obtain metal matrix wiring board material.

＜thickness deviation of heat conductivity insulation layer 〉

Estimate the thickness deviation of heat conductivity insulation layer by concavo-convex the having or not of copper-clad surface.In addition, if the metal matrix wiring board material of assess sample is increased to 500mm * 600mm, then the thickness deviation of heat conductivity insulation layer embodies as the concavo-convex of copper-clad surface.

＜mensuration of stripping strength 〉

According to JIS-C6481(1996 year version), the aluminium base substrate of use is made 90o stripping test sheet.Metal substrate is cut into 25mm * 100mm, for with the residual Copper Foil of center 10mm width (35 μ m), use universal tensile testing machine (TM-100 processed of Orientex company) to peel off to the 90o direction with the speed of 50mm/min at normal temperatures, measure stripping strength by the mean load in a plurality of moment.

＜electrical insulating property 〉

Circular pattern with the residual 20mm Φ of Copper Foil of the metal matrix wiring board material that obtains carries out etching by ammonium persulfate aqueous solution.By proof voltage determinator (Tokyo TOA Electronics Co., Ltd., Japan's system, Puncture Tester PT-1011), measure the insulation breakdown voltage of the circular pattern more than 50.Minimum insulation breakdown voltage is shown in Table 1.

＜thermal conductivity 〉

Copper Foil and aluminium base to the metal matrix wiring board material that obtains carry out etching, the heat conductivity insulation layer after formally being solidified.In the etching of Copper Foil, use ammonium persulfate aqueous solution.In the etching of aluminium base, use hydrochloric acid.Obtain in the following manner the thermal conductivity of the heat conductivity insulation layer that obtains.

At first, use temperature ripple apparatus for thermal analysis (ai-Phase company system, ai-Phase Mobile1u), the frequency interdependence of the phase differential of mensuration temperature wave.Then, in frequency 200～400Hz scope, obtain phase differential with respect to the subduplicate slope of frequency.The slope of this phase differential and-d(π/α) ^0.5Equate, so obtain thermal diffusivity (α) by the thickness (d) of heat conductivity insulation layer and the slope of phase differential.

Then, measure specific heat by differential scanning calorimeter (DSC, Perkin Elmer company system, Ryris1), measure density by electronic hydrometer (Alfamirage company system, SD-200L).Then, obtain thermal conductivity [W/mK] by following formula.The thermal conductivity that obtains is shown in Table 1.

Thermal conductivity [W/mK]=thermal diffusivity (thermal diffusivity (α)) [mm ²/ s] * specific heat [J/kgK] * density [g/cm ³]

[embodiment 2]

＜resin combination 〉

In embodiment 1, use 62.66g(69.5%(with respect to the alumina packing total mass)) particle diameter D50 is alumina packing (Showa Denko K. K's system of 20 μ m, AS-20), 16.77g(18.6%(is with respect to the alumina packing total mass)) particle diameter D50 is alumina packing (the Sumitomo Chemical system of 3 μ m, Sumicorundum AA3) and 10.73g(11.9%(with respect to the alumina packing total mass)) particle diameter D50 is alumina packing (the Sumitomo Chemical system of 0.4 μ m, Sumicorundum AA04) as alumina packing, and 13.5g2-butanone (with the pure medicine of light Co., Ltd. system) is as solvent, in addition, modulate similarly to Example 1 varnish shape resin combination 2, estimate viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

＜with the resin combination sheet material of tinsel 〉

Use rod to be coated with machine resin combination 2 obtained above is coated on the alligatoring face of Copper Foil (Japanese electrolysis company system, 35 μ m), under 100 ℃, carry out 20 minutes dryings.Dried thickness is 100 μ m.Place PET film (film company of Supreme Being people Du Pont system, A53) at dried resin layer, then, use vacuum laminator (name mechanism is made company of institute system), under the vacuum below the 3kPa, 130 ℃, 1MPa add and depress, carry out 15 second vacuum pressed, obtain the resin combination sheet material (B rank sheet material) with tinsel.Mean thickness with the resin combination sheet material in the resin combination sheet material of tinsel is 100 μ m.

The resin combination sheet material with tinsel that obtains uses method similarly to Example 1 to carry out the evaluation of recess occupation rate.

In addition, similarly to Example 1 operation, but, to the resin combination sheet material being clipped between Copper Foil and the aluminium base according to the mode that contacts with aluminium base with the resin combination sheet material side in the resin combination sheet material of tinsel obtained above is changed, make metal matrix wiring board material.

The metal matrix wiring board materials'use method similarly to Example 1 that obtains is carried out the evaluation of thickness deviation, stripping strength, electrical insulating property and the thermal conductivity of heat conductivity insulation layer.Evaluation result is shown in Table 1.

Further, above-mentioned resin combination 2 is coated on similarly to Example 1 on the PET film and makes resin combination sheet material (B rank sheet material).The resin combination sheet material pliability that obtains is excellent.The lowest melt viscosity of the resin combination sheet material that evaluation obtains.Evaluation result is shown in Table 1.

[embodiment 3]

In embodiment 1, interpolation 9.3g is stirred by the resol that above-mentioned resin synthesis example 1 obtains as 2-butanone (with the pure medicine of light Co., Ltd. system) and the 5.32g of solvent.The 2 officials energy Resins, epoxy (Mitsubishi chemical Co., Ltd's system, YL6121H), the 0.706g naphthalene that further use 6.35g to have biphenyl backbone are Resins, epoxy (Dainippon Ink Chemicals's system, HP4032D), in addition, modulate similarly to Example 1 varnish shape resin combination 3, estimate viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

＜resin combination sheet material 〉

Change to resin combination 3 obtained above, in addition, similarly to Example 1 operation obtains overlapping with 2 and resin combination sheet material (B rank sheet material) that make.The resin combination sheet material pliability that obtains is excellent.About the resin combination sheet material that obtains, use method similarly to Example 1 to carry out the evaluation of lowest melt viscosity and recess occupation rate.

＜metal matrix wiring board material 〉

In addition, similarly to Example 1 operation, but the resin combination sheet material is changed to resin combination sheet material obtained above, make metal matrix wiring board material.For the metal matrix wiring board material that obtains, by method similarly to Example 1, carry out the evaluation of thickness deviation, stripping strength, electrical insulating property and the thermal conductivity of heat conductivity insulation layer.Evaluation result is shown in Table 1.

[embodiment 4]

In embodiment 1, except adding the 2-butanone (with light pure medicine Co., Ltd. system) of 13.7g as solvent, modulate similarly to Example 1 varnish shape resin combination 4, estimate viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

Then, similarly to Example 1 operation, but resin combination 1 is changed to resin combination 4, make the resin combination sheet material.The resin combination sheet material pliability that obtains is excellent.About the resin combination sheet material that obtains, carry out similarly to Example 1 the evaluation of lowest melt viscosity and recess occupation rate.

Further, similarly operate with embodiment, change to resin combination sheet material obtained above, make metal matrix wiring board material, carry out the evaluation of thickness deviation, stripping strength, electrical insulating property and the thermal conductivity of heat conductivity insulation layer.Evaluation result is shown in Table 1.

[embodiment 5]

In embodiment 1, interpolation 9.3g is stirred by the resol that above-mentioned resin synthesis example 1 obtains as 2-butanone (with the pure medicine of light Co., Ltd. system), the 5.32g of solvent.The 2 officials energy Resins, epoxy (Mitsubishi chemical Co., Ltd's system, YL6121H), the 0.706g naphthalene that further use 6.35g to have biphenyl backbone are Resins, epoxy (Dainippon Ink Chemicals's system, HP4032D), in addition, modulate similarly to Example 1 varnish shape resin combination 5, estimate viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

＜resin combination sheet material 〉

Use rod to be coated with machine resin combination 5 obtained above is coated on the PET film (film company of Supreme Being people Du Pont system, A53), under 100 ℃, carry out 20 minutes dryings.Dried thickness is 38 μ m.2 dried resin combination sheet materials are placed in aspectant mode, used the roll laminating machine, stacked under 110 ℃, 0.3MPa, travelling speed 0.3m/min, obtain the resin combination sheet material (B rank sheet material) of mean thickness 75 μ m.The resin combination sheet material pliability that obtains is excellent.

＜metal matrix wiring board material 〉

[embodiment 6]

In embodiment 1, interpolation 9.3g is stirred by the resol that above-mentioned resin synthesis example 1 obtains as 2-butanone (with the pure medicine of light Co., Ltd. system), the 5.32g of solvent.The 2 officials energy Resins, epoxy (Mitsubishi chemical Co., Ltd's system, YL6121H), the 0.706g naphthalene that further use 6.35g to have biphenyl backbone are Resins, epoxy (Dainippon Ink Chemicals's system, HP4032D), in addition, modulate similarly to Example 1 varnish shape resin combination 6, estimate viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

＜resin combination sheet material 〉

Use rod to be coated with machine resin combination 6 obtained above is coated on the PET film (film company of Supreme Being people Du Pont system, A53), under 100 ℃, carry out 20 minutes dryings.Dried thickness is 63 μ m.2 dried resin combination sheet materials are placed in aspectant mode, used the roll laminating machine, stacked under 110 ℃, 0.3MPa, travelling speed 0.3m/min, obtain the resin combination sheet material (B rank sheet material) of mean thickness 125 μ m.The resin combination sheet material pliability that obtains is excellent.

＜metal matrix wiring board material 〉

[embodiment 7]

Be the aluminum oxide (AL35-63 of 31 μ m with 63 parts of particle diameter D50, Micron company system, density 3.80g/ml), 18 parts of particle diameter D50 are the aluminum oxide (AX3-32 of 5 μ m, Micron company system, density 3.77g/ml), 17 parts of particle diameter D50 are the aluminum oxide (LS-235 of 0.5 μ m, Nippon Light Metal Co., Ltd's system, density 3.94g/ml) with 2 parts of accurate spherical alumina (AO802 that particle diameter D50 is 0.7 μ m, the Admatechs of Co., Ltd. system, density 3.7g/ml) mixes and obtain the inorganic filling material mixture.

In the 100mL of polypropylene system lidded container, the above-mentioned inorganic filling material mixture of weighing 90.16g adds 0.099g silane coupling agent (Shin-Etsu Chemial Co., Ltd's system, KBM403), 14.33g as 2-butanone (with the pure medicine of light Co., Ltd. system), 0.36g dispersion agent (nanmu originally changes into Co., Ltd.'s system, ED-113), the 2.62g(solids component of solvent) resol that obtained by above-mentioned resin synthesis example 1 stirs.2 officials energy Resins, epoxy (Mitsubishi chemical Co., Ltd's system, YL6121H), 0.69g naphthalene that further interpolation 6.24g has biphenyl backbone are Resins, epoxy (Dainippon Ink Chemicals's system, HP4032D), 0.100g imidazolium compounds (Shikoku Chem's system, 2PZ-CN).Further drop into the oxidation aluminum ball of 120g diameter 5mm, after 12 hours, removing by filter oxidation aluminum ball with the 100rpm stirring on the ball mill pedestal, obtain varnish shape resin combination 7.

Estimate similarly to Example 1 viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

Then, similarly to Example 1 operation, but resin combination 1 is changed to resin combination 7, make the resin combination sheet material.The resin combination sheet material pliability that obtains is excellent.About the resin combination sheet material that obtains, carry out similarly to Example 1 the evaluation of lowest melt viscosity and recess occupation rate.

[embodiment 8]

With 100 mass parts 1-(3-methyl-4-Oxyranyle p-methoxy-phenyl)-4-(4-Oxyranyle p-methoxy-phenyl)-resol (Hitachi changes into the Industry trial-production product), 1.3 mass parts triphenylphosphines, 1.3 chemical industrial company of mass parts KBM-573(SHIN-ETSU HANTOTAI systems that 1-tetrahydrobenzene, 32 mass parts are obtained by above-mentioned resin synthesis example 1), 1483 mass parts alumina powders (Sumitomo Chemical Co's alpha-alumina powder processed; 979 mass parts median sizes are that the aluminum oxide of 18 μ m, aluminum oxide and the 148 mass parts median sizes that 356 mass parts median sizes are 3 μ m are the mixture of the aluminum oxide of 0.4 μ m) and the mixing of 300 mass parts pimelinketone, interpolation converts in solids component and is equivalent to Nano particles of silicon dioxide (Admatechs company system, trade(brand)name: Admanano, median size: 15nm, the NV:23 quality %) slurry that vinyl silanes has carried out hydrophobic treatment that passes through of 15.7 mass parts, modulation varnish shape resin combination 8 is estimated viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

＜resin combination sheet material 〉

About resin combination, use spreader according to drying after thickness be after the mode of 200 μ m is coated on polyethylene terephthalate (PET) film, at room temperature to place drying 30 minutes.After 100 ℃ of temperature are descended further dry 30 minutes, in vacuum press, carry out heat pressurization (120 ℃ of pressed temperatures, vacuum tightness 1kPa, moulding pressure 1MPa, 1 minute treatment time), obtain the resin combination sheet material (B rank sheet material) of mean thickness 200 μ m.Resin combination sheet material about obtaining carries out the evaluation of lowest melt viscosity and recess occupation rate by method similarly to Example 1.

＜metal matrix wiring board material 〉

The resin combination sheet material of having peeled off 500mm * 600mm of PET is clipped between the aluminium base (A5052,1mmt) of the alligatoring face side of Copper Foil (Japanese electrolysis company system, 35 μ m thick) of 550mm * 650mm and 500mm * 600mm, use the vacuum pressed pressing machine, under the vacuum of 3kPa, add at 4MPa and to depress, 150 ℃ of lower pressurized, heated 5 minutes.Then, under atmospheric pressure, 140 ℃ of lower heating 2 hours, 190 ℃ of lower heating 2 hours, obtain metal matrix wiring board material.

For the metal matrix wiring board material that obtains, by method similarly to Example 1, carry out the evaluation of thickness deviation, stripping strength, electrical insulating property and the thermal conductivity of heat conductivity insulation layer.Evaluation result is shown in Table 1.

[comparative example 1]

In embodiment 1, except adding the 2-butanone (with light pure medicine Co., Ltd. system) of 18.2g as solvent, modulate similarly to Example 1 varnish shape resin combination 9, estimate viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

Then, similarly to Example 1 operation, but resin combination 1 is changed to resin combination 9, make the resin combination sheet material.The resin combination sheet material pliability that obtains is excellent.About the resin combination sheet material that obtains, carry out similarly to Example 1 the evaluation of lowest melt viscosity and recess occupation rate.

[comparative example 2]

In embodiment 2, except adding the 2-butanone (with light pure medicine Co., Ltd. system) of 19.3g as solvent, modulate similarly to Example 2 varnish shape resin combination 10, estimate viscosity.Be shown in Table 1 with the particle diameter D50 of each insulativity mineral filler of cooperating with respect to the weight ratio of insulativity mineral filler total mass.

Then, similarly to Example 1 operation, but resin combination 1 is changed to resin combination 10, make the resin combination sheet material.The resin combination sheet material pliability that obtains is excellent.About the resin combination sheet material that obtains, carry out similarly to Example 1 the evaluation of lowest melt viscosity and recess occupation rate.

[table 1]

As known from Table 1, the cured article 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.

In addition, resin combination sheet material of the present invention, even the resin of use except the resin that uses in the above-described embodiments is as thermosetting resin, so long as the occupation rate of the recess more than the full depth 0.5 μ m is counted resin combination sheet material below 4% with area occupation ratio in its surface, then also can obtain same effect.

Claims

1. resin combination sheet material, it comprises thermosetting resin, resol and insulativity mineral filler,

In the surface of described resin combination sheet material, the occupation rate of the recess that full depth 0.5 μ m is above is counted below 4% with area occupation ratio.

2. resin combination sheet material according to claim 1, the lowest melt viscosity under 20 ℃～200 ℃ is 10～1000Pas.

3. according to claim 1 or resin combination sheet material claimed in claim 2, contain the following described insulativity mineral filler of the above 82vol% of 40vol%.

4. according to claim 1～claim 5 in wantonly 1 described resin combination sheet material, at least a filler of selecting in the group that described insulativity mineral filler is comprised of the filler of aluminum oxide, magnesium oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide and aluminum fluoride.

5. according to claim 1～claim 6 in wantonly 1 described resin combination sheet material, described resol has the represented structural unit of following general formula (I),

6. according to claim 1～claim 95 in wantonly 1 described resin combination sheet material, it is formed by the resin combination that comprises described thermosetting resin, described resol and described insulativity mineral filler,

The viscosity of described resin combination is below the above 10000mPas of 1000mPas,

Described resin combination sheet material forms by described resin combination is coated on the support base material.

7. resin combination sheet material, its lowest melt viscosity under 20 ℃～200 ℃ is 10Pas～1000Pas,

8. according to claim 1～claim 87 in wantonly 1 described resin combination sheet material, its mean thickness is below the above 500 μ m of 20 μ m.

9. resin combination sheet material with tinsel, it has wantonly 1 described resin combination sheet material and tinsel in claim 1～claim 8.

10. metal matrix wiring board material, it has tinsel, metal substrate and the heat conductivity insulation layer between described tinsel and described metal substrate,

Described heat conductivity insulation layer is the cured article of wantonly 1 described resin combination sheet material in claim 1～claim 8.

11. a metal matrix wiring board, it has wiring layer, metal substrate and the heat conductivity insulation layer between described wiring layer and described metal substrate,

12. a led light source member, right to use require wantonly 1 and form in the metal matrix wiring board of wantonly 1 described resin combination sheet material, the resin combination sheet material with tinsel claimed in claim 9, metal matrix wiring board material claimed in claim 10 or claim 11 in the 1～claim 8.