CN105308121A

CN105308121A - Resin composition

Info

Publication number: CN105308121A
Application number: CN201480034876.6A
Authority: CN
Inventors: 中村茂雄; 西村嘉生; 本间达也
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2013-06-25
Filing date: 2014-06-12
Publication date: 2016-02-03
Anticipated expiration: 2034-06-12
Also published as: CN105308121B; WO2014208352A1; JPWO2014208352A1; KR102288571B1; TWI699399B; KR20160023679A; TW201518389A; JP6595336B2

Abstract

To provide a resin composition that exhibits adequate thermal diffusion performance and yields a cured product having low surface roughness and high adhesive strength (peel strength) relative to a conductor layer. This resin composition is characterized in containing (A) at least one high-thermal-conductivity inorganic filler selected from the group consisting of aluminum nitride and silicon nitride, (B) an epoxy resin, and (C) a curing agent, component (A) being treated using a silane compound.

Description

Resin combination

Technical field

The present invention relates to resin combination.

Background technology

As the manufacturing technology of multilayer printed circuit board, known utilization is by the manufacture method of insulation layer and alternately stacked stacking (buildup) mode of conductor layer.In the manufacture method utilizing stack manner, usually make resin combination thermofixation and form insulation layer.Such as, Patent Document 1 discloses, make the resin combination thermofixation containing epoxy resin, active ester system solidifying agent, phenol system solidifying agent and silicon-dioxide and form the technology of insulation layer.

In recent years, the miniaturization of electronics and multifunction are in development, and the packing density of the semiconductor element in multilayer printed circuit board has the trend uprised.The multifunction of the semiconductor element that demand is installed also is complemented each other, the technology of heat that produces of diffused semiconductor element effectively.Such as, in patent documentation 2, the technology of the heat produced as diffused semiconductor element discloses following technology: use the film-like adhesive containing high thermal conductivity inorganic filling materials such as aluminium nitride, by semiconductor element mounting on multilayer printed circuit board.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2011-132507 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2012-207222 publication.

Summary of the invention

The technical problem that invention will solve

The present inventor etc. are conceived to will the more effectively thermal diffusivity of heat insulation layer that produces of diffused semiconductor element.So in order to make the thermal diffusivity of insulation layer improve, attempt making the resin combination thermofixation containing demonstrating the high thermal conductivity inorganic filling materials such as the aluminium nitride of more high heat conductance compared with in the past conventional silicon-dioxide form insulation layer.The discoveries such as its result the present inventor, along with the content of high thermal conductivity inorganic filling material in resin combination increases, the thermal diffusivity of gained cured body (insulation layer) improves, if but the content of high thermal conductivity inorganic filling material is increased with the degree presenting sufficient thermal diffusivity, then the surfaceness (surfaceness of the cured body especially after roughened) of gained cured body uprises, when cured body (insulation layer) forms conductor layer with fine wiring pattern on the surface, form obstacle sometimes.The present inventor etc. and then discovery, the cured body of the resin combination thermofixation gained of the high thermal conductivity inorganic filling materials such as aluminium nitride will be contained with high-content, although surfaceness is high, with dhering strength (stripping strength) the significantly deterioration of conductor layer.

Problem of the present invention is to provide the resin combination that can obtain following cured body, described cured body meets the characteristic required by insulation layer of " present sufficient thermal diffusivity, surfaceness is low and good with the dhering strength (stripping strength) of conductor layer simultaneously " such multilayer printed circuit board with high level.

The means of technical solution problem

The present inventor etc. conduct in-depth research for above-mentioned problem, found that, by using the packing material processed by least one high thermal conductivity inorganic filling material silane compound be selected from aluminium nitride and silicon nitride, solving above-mentioned problem, thus completing the present invention.

That is, the present invention includes following content,

[1] resin combination, it contains:

(A) be selected from least one high thermal conductivity inorganic filling material in aluminium nitride and silicon nitride,

(B) epoxy resin and

(C) solidifying agent,

Wherein, (A) composition silane compound is processed;

[2] resin combination described in [1], wherein, silane compound has phenyl;

[3] [1] or the resin combination described in [2], wherein, relative to high thermal conductivity inorganic filling material 100 mass parts, the treatment capacity of silane compound is more than 0.05 mass parts;

[4] resin combination according to any one of [1] ~ [3], wherein, (C) composition comprises the first solidifying agent and second solidifying agent different from this first solidifying agent, and the first solidifying agent is active ester system solidifying agent;

[5] resin combination described in [4], wherein, the second solidifying agent is the solidifying agent containing triazine structure;

[6] [4] or the resin combination described in [5], wherein, the second solidifying agent is the phenol system solidifying agent containing triazine structure or the cyanate system solidifying agent containing triazine structure;

[7] resin combination according to any one of [4] ~ [6], wherein, the first solidifying agent is 0.3 ~ 2 relative to the mass ratio (the first solidifying agent/the second solidifying agent) of the second solidifying agent;

[8] make [1] ~ [7] according to any one of resin combination thermofixation and the cured body obtained;

[9] cured body described in [8], wherein, the arithmetic average roughness (Ra) on surface is below 180nm;

[10] [8] or the cured body described in [9], wherein, thermal conductivity is more than 1W/m K;

[11] cured body according to any one of [8] ~ [10] is carried out roughened and the roughening cured body obtained;

[12] multilayer body, it the possesses roughening cured body described in [11] and the conductor layer be formed on the surface of this roughening cured body;

[13] multilayer body described in [12], wherein, the stripping strength of roughening cured body and conductor layer is more than 0.25kgf/cm;

[14] multilayer printed circuit board, it contains [8] ~ [10] according to any one of cured body or roughening cured body described in [11];

[15] semiconductor device, the multilayer printed circuit board that it contains described in [14].

The effect of invention

According to the present invention, provide the resin combination that can obtain following cured body, described cured body presents sufficient thermal diffusivity, and surfaceness is low and good with the dhering strength (stripping strength) of conductor layer simultaneously.

Embodiment

It is following that according to the preferred embodiment of the present invention, the present invention is described in detail.

[resin combination]

The feature of resin combination of the present invention is, contain: (A) is selected from least one high thermal conductivity inorganic filling material, (B) epoxy resin and (C) solidifying agent in aluminium nitride and silicon nitride, wherein, (A) composition silane compound is processed.

< (A) composition >

(A) of the present invention composition is at least one high thermal conductivity inorganic filling material be selected from aluminium nitride and silicon nitride, it is characterized in that processing with silane compound.

Be selected from the high thermal conductivity inorganic filling material in aluminium nitride and silicon nitride, compared with the silicon-dioxide in the past used usually used as inorganic filling material (thermal conductivity is 1.5W/m K at the most), there is very high thermal conductivity.From the viewpoint of obtaining the cured body with sufficient thermal diffusivity, the thermal conductivity of high thermal conductivity inorganic filling material used in (A) composition is preferably more than 25W/m K, is more preferably more than 50W/m K, more preferably more than 75W/m K, be further preferably more than 100W/m K, be particularly preferably more than 125W/m K, 150W/m more than K, more than 175W/m K, 200W/m more than K or more than 225W/m K.The upper limit of the thermal conductivity of high thermal conductivity inorganic filling material is not particularly limited, and is generally below 400W/m K.The thermal conductivity of high thermal conductivity inorganic filling material such as measures by known methods such as heat flowmeter method and temperature wave analytical methods.

Shape as the high thermal conductivity inorganic filling material of (A) composition use is not particularly limited, preferably spherical.In addition, have sufficient thermal diffusivity and the low cured body of surfaceness from the viewpoint of obtaining, the median size of high thermal conductivity inorganic filling material is preferably less than 5 μm, is more preferably less than 3 μm, more preferably less than 2 μm, is further preferably less than 1.5 μm.The lower limit of the median size of this high thermal conductivity inorganic filling material is not particularly limited, and is generally more than 0.01 μm, is preferably more than 0.05 μm.The median size of high thermal conductivity inorganic filling material is by measuring based on the laser diffraction-scattering method of Michaelis (Mie) scattering theory.Specifically, laser diffraction and scattering formula particle size distribution device can be used with volume reference to be made the size-grade distribution of high thermal conductivity packing material, its median particle diameter is measured as median size.Working sample preferably can use and utilize ultrasonic wave to make high thermal conductivity packing material dispersion sample in a solvent.As laser diffraction and scattering formula particle size distribution device, Horiba Ltd LA-500 etc. can be used.

As the commercially available product of aluminium nitride, (strain) ト Network ヤマ system " シェイパ Le H " (median size 1.1 μm, specific surface area 2.6m can be enumerated such as ²/ g), as the commercially available product of silicon nitride, electrochemically industry (strain) system " SN-9S " (median size 1.1 μm, specific surface area 7m can be enumerated such as ²/ g).

In the present invention, by using the packing material processed by the high thermal conductivity inorganic filling material silane compound be selected from aluminium nitride and silicon nitride, thus realize the resin combination that can obtain following cured body, described cured body presents sufficient thermal diffusivity, and surfaceness is low and good with the dhering strength (stripping strength) of conductor layer simultaneously.Here, aluminium nitride used and silicon nitride in (A) composition, different from the past conventional silicon-dioxide, only there is the functional groups such as the surface hydroxyl that can react with silane compound of minute quantity.Therefore, aluminium nitride and silicon nitride silane compound are carried out process not general matter, moreover when having carried out processing to aluminium nitride and silicon nitride with silane compound, the surfaceness of gained cured body, the characteristic generation noticeable change such with the dhering strength (stripping strength) of conductor layer, the opinion found in such the present invention be from knowledge in the past unpredictablely to obtain.In addition, the confirmations such as the present inventor, from thermal diffusivity, the cured body containing the packing material that aluminium nitride and silicon nitride silane compound are processed, with contain untreated aluminium nitride with same amount and compare with the cured body of silicon nitride, also present higher value.This point, about in the past conventional silicon-dioxide, except silane compound, as surface treatment agent also known aluminium system coupling agent, titanium system coupling agent and zirconium system coupling agent etc., but cannot reach effect of the present invention with other surface treatment agents such as these aluminium system coupling agents, using and can obtaining effect of the present invention specifically when silane compound is that the present inventor waits discovery.

Silane compound used in the process of high thermal conductivity inorganic filling material is in the molecule containing at least one organic group.As this organic group, from the viewpoint of obtaining low and good with the dhering strength (stripping strength) of the conductor layer cured body of surfaceness, the aryl that the alkyl that preferred carbonatoms is 1 ~ 20 (is preferably 1 ~ 10, is more preferably 1 ~ 6, more preferably 1 ~ 4), carbonatoms are 6 ~ 20 (are preferably 6 ~ 14, are more preferably 6 ~ 12, more preferably 6 ~ 10), wherein preferred phenyl.

Silane compound used in process as high thermal conductivity inorganic filling material, as long as the surface above-mentioned organic group can being introduced high thermal conductivity inorganic filling material is then not particularly limited, the reactive group that can react with aftermentioned (B) composition can be had further (such as, amino, epoxy group(ing), sulfydryl etc.), also can not have this reactive group.As the silane compound with reactive group, can enumerate such as: part hydrogen atom i) being bonded to the organic group of Si atom is by reactive group or the silane compound, the ii that replace containing the group of reactive group) reactive group that is bonded to Si atom or the silane compound replaced by organic group containing the part hydrogen atom of the group of reactive group.

The molecular weight of silane compound used in the process of high thermal conductivity inorganic filling material is preferably more than 70, is more preferably more than 90, more preferably more than 110, more than 130, more than 150, more than 170 or more than 190.The upper limit of the molecular weight of silane compound is preferably less than 500, is more preferably less than 400, more preferably less than 350, less than 300, less than 280 or less than 260.

In one embodiment, silane compound used in the process of high thermal conductivity inorganic filling material is the compound shown in following formula (1),

Si(R ¹) _n(R ²) _4-n(1)

[in formula,

R ¹expression-R ¹¹,-R ¹¹'-R ¹², or-R ¹²'-R ¹¹, here, R ¹¹represent alkyl or aryl, R ¹²represent amino, epoxy group(ing) or sulfydryl or the 1 valency group containing amino, epoxy group(ing) or sulfydryl, R ¹¹' represent from R ¹¹the divalent group after 1 hydrogen atom is removed, R in 1 shown valency group ¹²' represent from R ¹²the divalent group after 1 hydrogen atom is removed in 1 shown valency group,

R ²represent hydrogen atom or alkoxyl group,

N represents the integer of 1 ~ 3.R ¹when existing multiple, they can be identical or different, R ²when existing multiple, they can be identical or different.]。

R ¹¹the carbonatoms of shown alkyl is preferably 1 ~ 20, be more preferably 1 ~ 10, more preferably 1 ~ 6, be further preferably 1 ~ 4.R ¹¹the carbonatoms of shown aryl is preferably 6 ~ 20, be more preferably 6 ~ 14, more preferably 6 ~ 12, be further preferably 6 ~ 10.As R ¹¹, preferred aryl groups, particularly preferably phenyl.

As R ¹², preferably amino, sulfydryl, containing 1 valency group of amino, the 1 valency group containing epoxy group(ing).As containing 1 amino valency group, such as N-(amino C can be enumerated _1-10alkyl) amino, amino C _1-10alkoxyl group, amino C _1-10alkyl, preferred N-(2-amino-ethyl) amino, N-(3-aminopropyl) amino, amino ethoxy, amino propoxy-, amino-ethyl, aminopropyl.As the 1 valency group containing epoxy group(ing), can enumerate such as epoxy alkyl, epoxy alkyl oxygen base, their carbonatoms is preferably 3 ~ 10, is more preferably 3 ~ 6.As suitable concrete example, glycidyl, glycidoxypropyl, 3,4-epoxycyclohexyls can be enumerated.

R ¹¹' represent from R ¹¹the divalent group after 1 hydrogen atom, namely, alkylidene group or arylidene is removed in 1 shown valency group.R ¹¹' shown in divalent group suitable carbonatoms can with for R ¹¹the carbonatoms illustrated is identical.As R ¹¹', preferred alkylidene group.

R ¹²' represent from R ¹²remove the divalent group after 1 hydrogen atom in 1 shown valency group, preferably from containing the divalent group after removing 1 hydrogen atom 1 amino valency group, more preferably eliminate and be bonded to amino C _1-10divalent group after 1 hydrogen atom of the nitrogen-atoms of alkyl (being preferably amino-ethyl, aminopropyl).

N represents the integer of 1 ~ 3, is preferably 1 or 2.R ¹when existing multiple, they can be identical or different.From the viewpoint of obtaining low and good with the dhering strength (stripping strength) of the conductor layer cured body of surfaceness, in formula (1), preferably at least one R ¹for-R ¹¹, or-R ¹²'-R ¹¹.

R ²the carbonatoms of shown alkoxyl group is preferably 1 ~ 10, be more preferably 1 ~ 6, more preferably 1 ~ 4, be further preferably 1 or 2.As R ², preferred alkoxyl group.

As the concrete example of silane compound, can enumerate: methyltrimethoxy silane, octadecyl trimethoxysilane, phenyltrimethoxysila,e, the silane compounds such as dimethoxydiphenylsilane, aminopropyl methoxysilane, aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, the amino silane compounds such as N-(2-amino-ethyl) TSL 8330, glycidoxypropyltrimewasxysilane, glycidoxypropyl triethoxyl silane, glycidoxypropyl diethoxy silane, glycidoxypropyl diethylamino phenyl TMOS, glycidyl butyl trimethoxy silane, (3, 4-epoxycyclohexyl) epoxy silane compounds such as ethyl trimethoxy silane, mercaptopropyi Trimethoxy silane, mercaptopropyi phenyidimethoxysilane, the mercaptosilane compound such as Mercaptopropyltriethoxysilane.As the commercially available product of silane compound, can enumerate such as: SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM103 " (phenyltrimethoxysila,e), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 " (N-phenyl-3-TSL 8330), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBE903 " (APTES), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 " (3-glycidoxypropyltrimewasxysilane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM803 " (3-mercaptopropyi Trimethoxy silane) etc.Silane compound can be used alone one, also can combinationally use two or more.

The process of the high thermal conductivity inorganic filling material utilizing silane compound to carry out can be implemented according to any one method of known drying process and damp process.

From the viewpoint of obtaining low and good with the dhering strength (stripping strength) of the conductor layer cured body of surfaceness, relative to high thermal conductivity inorganic filling material 100 mass parts, the treatment capacity of silane compound is preferably more than 0.05 mass parts, is more preferably more than 0.1 mass parts, more preferably more than 0.3 mass parts, be further preferably more than 0.5 mass parts.The upper limit of this treatment capacity is not particularly limited, and is preferably below 5 mass parts.Here, the treatment capacity of above-mentioned silane compound be use in process based on the high thermal conductivity inorganic filling material utilizing silane compound, the quality of silane compound and the quality of high thermal conductivity inorganic filling material and the value calculated.

The degree of the process utilizing silane compound to carry out can be evaluated according to the carbon amounts of the per unit surface-area of high thermal conductivity inorganic filling material.From the viewpoint of obtaining low and good with the dhering strength (stripping strength) of the conductor layer cured body of surfaceness, the carbon amounts of the per unit surface-area of high thermal conductivity inorganic filling material is preferably 0.05mg/m ²above, 0.10mg/m is more preferably ²above, more preferably 0.15mg/m ²above.On the other hand, rise from the viewpoint of the melt viscosity prevented under the melt viscosity of resinous varnish or film morphology, be preferably 1.0mg/m ²below, 0.8mg/m is more preferably ²below, more preferably 0.6mg/m ²below.

High thermal conductivity inorganic filling material solvent (such as, methyl ethyl ketone (MEK)) after silane compound process measures after can be carried out clean by the carbon amounts of the per unit surface-area of high thermal conductivity inorganic filling material.Specifically, the MEK of the q.s as solvent can be joined in the high thermal conductivity inorganic filling material of silane compound process, at 25 DEG C, carry out 5 minutes ultrasonic cleaning.Removing supernatant liquor, after making solids component drying, uses carbon analysis meter to measure the carbon amounts of the per unit surface-area of high thermal conductivity inorganic filling material.As carbon analysis meter, hole field can be used to make made " EMIA-320V " etc.

Should illustrate, high thermal conductivity inorganic filling material used in (A) composition, utilizing before silane compound processes, can also carry out hydrophobization process.As the hydrophobization process of high thermal conductivity inorganic filling material, the heat treated under such as high temperature (such as, more than 200 DEG C, be preferably more than 300 DEG C, be more preferably more than 400 DEG C) can be enumerated.

From the viewpoint of obtaining the cured body with sufficient thermal diffusivity, the content of the high thermal conductivity inorganic filling material in resin combination is preferably more than 50 quality %, is more preferably more than 55 quality %, more preferably more than 60 quality %.

Should illustrate, in the present invention, the content of each composition in resin combination, when illustrating in addition, refers to the value when total amount of the nonvolatile component in resin combination being set to 100 quality %.

In the present invention using the packing material after being processed by the high thermal conductivity inorganic filling material silane compound be selected from aluminium nitride and silicon nitride, the surfaceness of gained cured body can not excessively improve, and can not make to reduce with the dhering strength of conductor layer (stripping strength), the content of high thermal conductivity inorganic filling material can be increased further.Such as, the content of the high thermal conductivity inorganic filling material in resin combination can be increased to more than more than 62 quality %, more than 64 quality %, more than 66 quality %, more than 68 quality %, more than 70 quality %, more than 72 quality %, more than 74 quality %, more than 76 quality %, more than 78 quality % or 80 quality %.

The physical strength of the cured body obtained from the viewpoint of the thermofixation by resin combination, the upper content limit of the high thermal conductivity inorganic filling material in resin combination is preferably below 95 quality %, is more preferably below 90 quality %, more preferably below 85 quality %.

< (B) composition >

(B) composition contained in resin combination of the present invention is epoxy resin.

As epoxy resin, can enumerate such as: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, anthracene type epoxy resin, fluorenes type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, triphenol epoxy resin, phosphorous epoxy resin, alicyclic epoxy resin, linear aliphatic epoxy resins, phenol novolacs (phenolnovolac) type epoxy resin, cresol novolak (cresolnovolac) type epoxy resin, bisphenol A novolac (novolac) type epoxy resin, there is the epoxy resin of butadiene structure, hetero ring type epoxy resin, containing the epoxy resin of volution, cyclohexanedimethanol type epoxy resin, naphthylidene ether type epoxy, trishydroxymethyl type epoxy resin, the diglycidyl ether compound of bisphenols, the diglycidyl ether compound of naphthalene glycol, the glycidyl etherified thing of phenols, with the diglycidyl ether compound of alcohols, and the alkyl of these epoxy resin replaces body, halogenide and hydride etc.These epoxy resin can be used alone one, also can combinationally use two or more.

Epoxy resin preferably is contained in the epoxy resin in 1 molecule with more than 2 epoxy group(ing).When the nonvolatile component of epoxy resin is set to 100 quality %, preferably more than at least 50 quality % are the epoxy resin in 1 molecule with more than 2 epoxy group(ing).Wherein, preferably be contained in 1 molecule and there are more than 2 epoxy group(ing) and for liquid epoxy resin is (hereinafter referred to as " liquid-state epoxy resin " at temperature 20 DEG C.) and there are more than 3 epoxy group(ing) in 1 molecule and for solid-state epoxy resin is (hereinafter referred to as " solid epoxy resin " at temperature 20 DEG C.)。As epoxy resin, by also with liquid-state epoxy resin and solid epoxy resin, can obtain that there is excellent flexible resin combination.In addition, the breaking tenacity of the insulation layer formed by resin composition also improves.

As liquid-state epoxy resin, be preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin or naphthalene type epoxy resin, be more preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin or naphthalene type epoxy resin.As the concrete example of liquid-state epoxy resin, " HP4032 ", " HP4032D ", " EXA4032SS " that DIC (strain) makes can be enumerated, " ZX1059 " (melange of bisphenol A type epoxy resin and bisphenol f type epoxy resin) etc. that " jER828EL " (bisphenol A type epoxy resin) that " HP4032SS " (naphthalene type epoxy resin), Mitsubishi Chemical's (strain) make, " jER807 " (bisphenol f type epoxy resin), " jER152 " (phenol novolak type epoxy resin), Nippon Steel's chemistry (strain) are made.These epoxy resin can be used alone one or and with two or more.

As solid epoxy resin, be preferably 4 officials' energy naphthalene type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol epoxy resin, naphthol novolac varnish (naphtholnovolac) epoxy resin, biphenyl type epoxy resin, di-toluene phenol-type epoxy resin, naphthylidene ether type epoxy or fluorenes type epoxy resin, being more preferably 4 officials can naphthalene type epoxy resin, biphenyl type epoxy resin, di-toluene phenol-type epoxy resin, naphthylidene ether type epoxy or fluorenes type epoxy resin.As the concrete example of solid epoxy resin, can enumerate: " HP-4700 " that DIC (strain) makes, " HP-4710 " (4 officials' energy naphthalene type epoxy resin), " N-690 " (cresol novolak type epoxy resin), " N-695 " (cresol novolak type epoxy resin), " HP-7200 " (dicyclopentadiene-type epoxy resin), " EXA7311 ", " EXA7311-G3 ", " HP6000 " (naphthylidene ether type epoxy), " EPPN-502H " (triphenol epoxy resin) that Japan's chemical drug (strain) makes, " NC7000L " (naphthol novolac novolac epoxy resins), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin), " ESN475 " (naphthol novolac type epoxy resin) that Nippon Steel's chemistry (strain) is made, " ESN485 " (naphthol novolac type epoxy resin), " YX4000H " that Mitsubishi Chemical's (strain) makes, " YL6121 " (biphenyl type epoxy resin), " YX4000HK " (di-toluene phenol-type epoxy resin), " YL7800 " (fluorenes type epoxy resin) etc.

During as epoxy resin and with liquid-state epoxy resin and solid epoxy resin, their amount is preferably the scope of 1:0.1 ~ 1:6 by quality ratio than (liquid-state epoxy resin: solid epoxy resin).By making liquid-state epoxy resin compare in above-mentioned scope with the amount of solid epoxy resin, thus following effect can be obtained: suitable tackiness when i) using with the form of adhesive film, can be obtained; Sufficient flexibility can be obtained when ii) using with the form of adhesive film, operability improves; And iii) insulation layer etc. with sufficient breaking tenacity can be obtained.From the viewpoint of above-mentioned i) ~ iii) effect, the amount of liquid-state epoxy resin and solid epoxy resin is more preferably the scope of scope, the more preferably 1:0.6 ~ 1:4.5 of 1:0.3 ~ 1:5 by quality ratio, is particularly preferably the scope of 1:0.8 ~ 1:4 than (liquid-state epoxy resin: solid epoxy resin).

Epoxy resin content in resin combination is preferably 3 quality % ~ 50 quality %, is more preferably 5 quality % ~ 45 quality %, more preferably 5 quality % ~ 40 quality %, be particularly preferably 7 quality % ~ 35 quality %.

The epoxy equivalent (weight) of epoxy resin is preferably 50 ~ 4500, be more preferably 50 ~ 3000, more preferably 80 ~ 2000, be further preferably 110 ~ 1000.By making the epoxy equivalent (weight) of epoxy resin within the scope of this, thus make the cross-linking density of cured article fully, obtain the low insulation layer of surfaceness.Should illustrate, epoxy equivalent (weight) can measure according to JISK7236, refers to the quality of the resin containing 1 equivalent epoxy group(ing).

The weight-average molecular weight of the polystyrene conversion of epoxy resin be preferably 100 ~ 3000 scope, be more preferably 200 ~ 2500 scope, more preferably 300 ~ 2000 scope.The weight-average molecular weight of the polystyrene conversion of epoxy resin can adopt gel permeation chromatography (GPC) method to measure.Specifically, the weight-average molecular weight of the polystyrene conversion of epoxy resin can use (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as determinator, use Showa electrician's (strain) ShodexK-800P/K-804L/K-804L processed as post, use chloroforms etc. are as moving phase, measure at column temperature 40 DEG C, use the typical curve of polystyrene standard to calculate.

< (C) composition >

(C) composition contained in resin combination of the present invention is solidifying agent.

As solidifying agent, as long as have, the function of (B) epoxy resin cure is then not particularly limited, can enumerates such as: active ester system solidifying agent, phenol (phenol) are solidifying agent, naphthols system solidifying agent, cyanate system solidifying agent, benzoxazine system solidifying agent, acid anhydrides system solidifying agent, their epoxy adduct, microencapsulated material etc.Solidifying agent can be used alone one, also can combinationally use two or more.

As active ester system solidifying agent, have no particular limits, usually preferably use the ester class etc. of phenolic ester class (phenolesters), thiophenol ester (thiophenolesters) class, N-oxyamine ester class, heterocycle hydroxyl compound in 1 molecule, have the compound of the high ester group of more than 2 reactive behavioies.This active ester system solidifying agent is preferably by the condensation reaction of carboxylic acid cpd and/or thiocarboxylic acid compound and oxy-compound and/or mercaptan compound and the active ester system solidifying agent obtained.Wherein, the active ester system solidifying agent preferably obtained by carboxylic acid cpd and oxy-compound.More preferably the active ester system solidifying agent obtained by carboxylic acid cpd and phenol (phenol) compound and/or naphthol compound.

As carboxylic acid cpd, the aromatic carboxylic acid of the aliphatic carboxylic acid of such as carbonatoms 1 ~ 20 (be preferably 2 ~ 10, be more preferably 2 ~ 8), carbonatoms 7 ~ 20 (being preferably 7 ~ 10) can be enumerated.As suitable aliphatic carboxylic acid, such as acetic acid, propanedioic acid, succsinic acid, toxilic acid, methylene-succinic acid etc. can be enumerated.As suitable aromatic carboxylic acid, such as phenylformic acid, phthalic acid, m-phthalic acid, terephthalic acid, pyromellitic acid etc. can be enumerated.

As oxybenzene compound, such as carbonatoms 6 ~ 40 can be enumerated and (be preferably 6 ~ 30, be more preferably 6 ~ 23, more preferably 6 ~ 22) oxybenzene compound, as suitable concrete example, quinhydrones can be enumerated, Resorcinol, dihydroxyphenyl propane, Bisphenol F, bisphenol S, phenolphthalin, methylate dihydroxyphenyl propane, methylate Bisphenol F, methylate bisphenol S, phenol, ortho-cresol, meta-cresol, p-cresol, catechol, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, Phloroglucinol, benzenetriol (benzenetriol), dicyclopentadiene-type xenol etc.Also phenol novolacs can be used as oxybenzene compound.As naphthol compound, the naphthol compound of such as carbonatoms 10 ~ 40 (be preferably 10 ~ 30, be more preferably 10 ~ 20) can be enumerated, as suitable concrete example, naphthyl alcohol, 2-Naphthol, 1 can be enumerated, 5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlenes etc.Also naphthol novolac varnish can be used as naphthol compound.

As the suitable concrete example of active ester system solidifying agent; can enumerate: the active ester compound of the active ester compound of the active ester compound containing dicyclopentadiene-type biphenol structural, the active ester compound containing naphthalene structure, the acetylate containing phenol novolacs, the benzoylate containing phenol novolacs, wherein be more preferably the active ester compound containing naphthalene structure, active ester compound containing dicyclopentadiene-type biphenol structural.Should illustrate, in the present invention, " dicyclopentadiene-type biphenol structural " represents the divalent structural unit comprising phenylene-two ring pentalene (ジシ Network ロペ Application タレ Application)-phenylene.

For the commercially available product of active ester system solidifying agent, as the active ester compound containing dicyclopentadiene-type biphenol structural, " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000-65T " (DIC (strain) system) can be enumerated; As the active ester compound containing naphthalene structure, " EXB9416-70BK " (DIC (strain) system) can be enumerated; As the active ester compound of the acetylate containing phenol novolacs, " DC808 " (Mitsubishi Chemical's (strain) system) can be enumerated; As the active ester compound of the benzoylate containing phenol novolacs, " YLH1026 " (Mitsubishi Chemical's (strain) system) etc. can be enumerated.

As phenol system solidifying agent and naphthols system solidifying agent, from the viewpoint of thermotolerance and water tolerance, the phenol system solidifying agent preferably with novolac structure or the naphthols system solidifying agent with novolac structure.In addition, from the viewpoint of with the combination of (A) composition in obtain the cured body excellent with the dhering strength of conductor layer (stripping strength), more preferably contain the phenol system solidifying agent of triazine structure.Wherein, from the viewpoint of with the combination of (A) composition in highly met the cured body of thermotolerance, water tolerance and the dhering strength (stripping strength) with conductor layer, preferably containing the phenol novolacs solidifying agent of triazine structure.

As the concrete example of phenol system solidifying agent and naphthols system solidifying agent, can enumerate such as bright and change into " MEH-7700 ", " MEH-7810 ", " MEH-7851 " that (strain) make, " NHN ", " CBN ", " GPH " that Japanese chemical drug (strain) is made, Dongdu change into " SN170 ", " SN180 ", " SN190 " that (strain) make, " SN475 ", " SN485 ", " SN495 ", " SN375 ", " SN395 ", DIC (strain) make " TD2090 " etc.As the concrete example of phenol system solidifying agent containing triazine structure, " LA3018 " that such as DIC (strain) makes etc. can be enumerated.As the concrete example of the phenol novolacs solidifying agent containing triazine structure, " LA7052 ", " LA7054 ", " LA1356 " etc. that DIC (strain) makes can be enumerated.

As cyanate system solidifying agent, can enumerate such as: bisphenol A dicyanate, polyphenol cyanate (oligomeric (3-methylene radical-1, 5-phenylenecyanate)), 4, 4'-methylene-bis (2, 6-3,5-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluoro bisphenol-a dicyanate, 2, two (4-cyanate) phenyl-propane of 2-, 1, 1-two (4-cyanate phenylmethane), two (4-cyanate-3, 5-3,5-dimethylphenyl) methane, 1, two (4-cyanate phenyl-1-(methyl the ethylidene)) benzene of 3-, two (4-cyanate phenyl) thioether, can cyanate ester resins with two (4-cyanate phenyl) ether etc. 2 officials, the multifunctional cyanate ester resin derivative by phenol novolacs and cresol novolak etc., the parts of these cyanate ester resins by the prepolymer of triazine (hereinafter also referred to " the cyanate system solidifying agent containing triazine structure ".)。Wherein, from the viewpoint of with the combination of (A) composition in obtain the cured body excellent with the dhering strength of conductor layer (stripping strength), preferably contain the cyanate system solidifying agent of triazine structure.

As the concrete example of cyanate system solidifying agent, " PT30 " and " PT60 " (being phenol novolak type multifunctional cyanate ester resin), " BA230 " (part or all of bisphenol A dicyanate is become the trimerical cyanate system solidifying agent containing triazine structure by triazine) etc. that ロ Application ザジャパ Application (strain) makes can be enumerated.

As the concrete example of benzoxazine system solidifying agent, " HFB2006M " that Showa polymer (strain) makes can be enumerated, four countries change into " P-d ", " F-a " that industry (strain) is made.

As acid anhydrides system solidifying agent, can enumerate such as: Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenating methyl carbic anhydride, trialkyl Tetra Hydro Phthalic Anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furyl (Off ラニ Le))-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic acid anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, bibenzene tetracarboxylic dianhydride, naphthalenetetracarbacidic acidic dianhydride, hydroxyl two O-phthalic acid dianhydride, 3,3'-4,4'-diphenyl sulfone tetraformic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-C] furans-1,3-diketone, ethylene glycol bis (trimellitate acid anhydride) (エチレ Application グリコー Le PVC ス (ア Application ヒ De ロトリメリテート)), vinylbenzene and acid anhydrides etc. that the is maleic acid copolymerized and polymer-type such as styrene-maleic acid resin obtained.

From with the combination of (A) composition, the surfaceness (surfaceness of the cured body particularly after roughened) of gained cured body be suppressed to lower level viewpoint consider, (C) composition preferably comprises active ester system solidifying agent.

In suitable embodiment, (C) composition comprises the first solidifying agent and second solidifying agent different from this first solidifying agent, and the first solidifying agent is active ester system solidifying agent.In this embodiment, the solidifying agent of more than a kind be selected from above-mentioned phenol system solidifying agent, naphthols system solidifying agent, benzoxazine system solidifying agent, cyanate system solidifying agent, acid anhydrides system solidifying agent, their epoxy adduct or microencapsulated material can be used as the second solidifying agent, from the viewpoint of with the combination of (A) composition in obtain the cured body excellent with the dhering strength of conductor layer (stripping strength), in above-mentioned solidifying agent, the solidifying agent of the second solidifying agent preferably containing triazine structure is (hereinafter also referred to " solidifying agent containing triazine structure ".), be more preferably containing the phenol system solidifying agent of triazine structure or containing the cyanate system solidifying agent of triazine structure.As (C) composition, by using the combination of above-mentioned specific solidifying agent, thus the surfaceness of gained cured body (surfaceness of the cured body particularly after roughened) can be suppressed to more low-level, and obtain the cured body excellent with the dhering strength of conductor layer (stripping strength).In addition, by using the combination of above-mentioned specific solidifying agent, thus the content of high thermal conductivity inorganic filling material in resin combination when increasing (such as, more than 70 quality %) also can realize the low and cured body of dhering strength excellence with conductor layer of surfaceness.

When using the combination of above-mentioned first solidifying agent and the second solidifying agent as (C) composition, from the viewpoint of obtaining low and excellent with the dhering strength (stripping strength) of the conductor layer cured body of surfaceness, the first solidifying agent is preferably 0.3 ~ 2 relative to the mass ratio (the first solidifying agent/the second solidifying agent) of the second solidifying agent, is more preferably 0.4 ~ 1.8, more preferably 0.5 ~ 1.6.In addition, from the viewpoint of obtaining low and excellent with the dhering strength (stripping strength) of the conductor layer cured body of surfaceness, [the reactive group number of the first solidifying agent]/[the reactive group number of the second solidifying agent] be preferably 0.1 ~ 2, be more preferably 0.2 ~ 1.8, more preferably 0.3 ~ 1.6, further preferably 0.4 ~ 1.4, be particularly preferably 0.5 ~ 1.2.Here, the reactive group of the first solidifying agent is active ester groups.The reactive group of the second solidifying agent is activity hydroxy etc., different from the kind of solidifying agent.In addition, the reactive group number of the first solidifying agent is the value obtained divided by reactive group equivalent by the solids component quality of active ester system solidifying agent used in (C) composition.The reactive group number of the second solidifying agent is, for all solidifying agent, carries out amounting to and the value obtained divided by the value of reactive group equivalent gained by by the solids component quality of the solidifying agent except active ester system solidifying agent used in (C) composition.

The amount ratio of (B) composition in resin combination and (C) composition, with [sum of the epoxy group(ing) of (B) epoxy resin]: the ratiometer of [sum of the reactive group of (C) solidifying agent], be preferably the scope of 1:0.2 ~ 1:2, be more preferably 1:0.3 ~ 1:1.5, more preferably 1:0.4 ~ 1:1.Here, the sum of the epoxy group(ing) of (B) epoxy resin is, for all epoxy resin, carries out amounting to and the value obtained divided by the value of epoxy equivalent (weight) gained by by the solids component quality of each epoxy resin; (C) sum of the reactive group of solidifying agent is, for all solidifying agent, carries out amounting to and the value obtained divided by the value of reactive group equivalent gained by by the solids component quality of each solidifying agent.

Other composition of < >

Resin combination of the present invention as required can also containing (D) inorganic filling material except aluminium nitride and silicon nitride (hereinafter referred to as " inorganic filling material ".), the additive such as (E) thermoplastic resin, (F) curing catalyst, (G) fire retardant and (H) rubber particles.

(D) inorganic filling material

As inorganic filling material, can enumerate such as: silicon-dioxide, aluminum oxide, glass, trichroite, Si oxide, barium sulfate, barium carbonate, talcum, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, magnesium oxide, boron nitride, nitrogenized manganese, aluminum borate, barium titanate, Strontium carbonate powder, strontium titanate, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, zirconium white, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate and phosphoric acid tungsten wire array etc.Inorganic filling material can be used alone one, also can combinationally use two or more.

The median size of inorganic filling material is preferably less than 3 μm, is more preferably less than 1.5 μm.The median size lower limit of inorganic filling material is not particularly limited, and is generally more than 0.01 μm, is preferably more than 0.05 μm.Same with high thermal conductivity inorganic filling material, the median size of inorganic filling material can utilize the laser diffraction-scattering method based on Michaelis (Mie) scattering theory to measure.

Inorganic filling material can process with surface treatment agents such as amino silane compounds, epoxy silane compounds, mercaptosilane compound, silane compound, organic silazane hydride compounds, aluminium system coupling agent, titanium system coupling agent, zirconium system coupling agents.

When using inorganic filling material, as long as use with the scope making the total content of the high thermal conductivity inorganic filling material in resin combination and this inorganic filling material be preferably 50 quality % ~ 95 quality %, the mode of scope that is more preferably 60 quality % ~ 95 quality %.

(E) thermoplastic resin

As thermoplastic resin, can enumerate such as: phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene, polyimide resin, polyamide-imide resin, polyethersulfone resin, polyphenylene oxide resin and polysulfone resin etc.Thermoplastic resin can be used alone one, also can combinationally use two or more.

The weight-average molecular weight of the polystyrene conversion of thermoplastic resin is preferably 8, the scope of 000 ~ 70,000, is more preferably 10, the scope of 000 ~ 60,000, more preferably 15,000 ~ 60, the scope of 000, be more preferably 20 further, 000 ~ 60, the scope of 000.The weight-average molecular weight of the polystyrene conversion of thermoplastic resin can adopt gel permeation chromatography (GPC) method to measure.Specifically, the weight-average molecular weight of the polystyrene conversion of thermoplastic resin can use (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as determinator, use Showa electrician's (strain) ShodexK-800P/K-804L/K-804L processed as post, use chloroforms etc. are as moving phase, measure at column temperature 40 DEG C, adopt the typical curve of polystyrene standard to calculate.

As phenoxy resin, the phenoxy resin such as with the skeleton of more than a kind be selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol phenyl methyl ketone skeleton, phenolic varnish (ノボラッ Network) skeleton, biphenyl backbone, fluorene skeleton, Dicyclopentadiene (DCPD) skeleton, norbornylene skeleton, naphthalene skeleton, anthracene skeleton, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton can be enumerated.The end of phenoxy resin can be the functional group arbitrarily such as phenolic hydroxyl group, epoxy group(ing).Phenoxy resin can be used alone one, also can combinationally use two or more.As the concrete example of phenoxy resin, " 1256 " and " 4250 " (being the phenoxy resin containing bisphenol A skeleton) that Mitsubishi Chemical's (strain) makes, " YX8100 " (phenoxy resin containing bisphenol S skeleton) and " YX6954 " (phenoxy resin containing bis-phenol phenyl methyl ketone skeleton) can be enumerated, Dongdu changes into " FX280 " and " FX293 " that (strain) make, Mitsubishi Chemical's (strain) makes " YL7553 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc. can be enumerated in addition.

As the concrete example of polyvinyl acetal resin, electrochemical Block チラー Le 4000-2 that electrochemically industry (strain) makes can be enumerated, エスレッ Network BH series that 5000-A, 6000-C, 6000-EP, ponding chemical industry (strain) are made, BX is serial, KS is serial, BL is serial, BM is serial.

As the concrete example of polyimide resin, can enumerate " リカコート SN20 " and " リカコート PN20 " that new Japan Chemical (strain) is made.The modified polyimides such as the linear polyimides (material of Japanese Unexamined Patent Publication 2006-37083 publication record) that the concrete example as polyimide resin also can be enumerated 2 functional hydroxyl groups's end polyhutadiene, diisocyanate cpd and tetraprotic acid anhydride reactant and obtain, the polyimide (material recorded in Japanese Unexamined Patent Publication 2002-12667 publication and Japanese Unexamined Patent Publication 2000-319386 publication etc.) containing silicone matrix.

As the concrete example of polyamide-imide resin, can enumerate " バイロマッ Network ス HR11NN " and " バイロマッ Network ス HR16NN " that Japan's weaving (strain) makes.Concrete example as polyamide-imide resin also can enumerate the modified polyamide imide such as polyamidoimide " KS9100 ", " KS9300 " containing silicone matrix of Hitachi Chemical Industries (Ltd.).

As the concrete example of polyethersulfone resin, can enumerate " PES5003P " that Sumitomo Chemical (strain) is made.

As the concrete example of polysulfone resin, polysulfones " P1700 ", " P3500 " etc. that ソ Le ベイア De バ Application スト Port リマーズ (strain) makes can be enumerated.

Thermoplastic resin level in resin combination is preferably 0.1 quality % ~ 60 quality %, is more preferably 0.1 quality % ~ 50 quality %, more preferably 0.5 quality % ~ 30 quality %, be further preferably 0.5 quality % ~ 10 quality %.By making the content of thermoplastic resin in above-mentioned scope, thus the viscosity of resin combination can be made suitable, forming thickness, the uniform resin combination of entirety (bulk) proterties.

(F) curing catalyst

As curing catalyst, such as phosphorus system curing catalyst, amine system curing catalyst, imidazoles system curing catalyst, guanidine system curing catalyst etc. can be enumerated, be preferably phosphorus system curing catalyst, amine system curing catalyst, imidazoles system curing catalyst, be more preferably amine system curing catalyst, imidazoles system curing catalyst.Curing catalyst can be used alone one, also can combinationally use two or more.

As phosphorus system curing catalyst, can enumerate such as: triphenylphosphine, Peng Suan phosphonium compounds, tetraphenylphosphoniphenolate tetraphenyl borate salts, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4-aminomethyl phenyl) triphenyl phosphonium thiocyanate-, tetraphenylphosphoniphenolate thiocyanate-, Ding base triphenyl phosphonium thiocyanate-etc.

As amine system curing catalyst, can enumerate such as: the trialkylamine such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyl dimethyl amine, 2,4,6 ,-three (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0)-hendecene etc.

As imidazoles system curing catalyst, can enumerate such as: glyoxal ethyline, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-undecyl imidazole, 1-cyano ethyl-2-ethyl-4-methylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-cyano ethyl-2-undecyl imidazole trimellitate, 1-cyano ethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazole base-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine tricarbimide affixture, 2-phenylimidazole tricarbimide affixture, 2-phenyl-4,5-bishydroxymethyl imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo-[1,2-a] benzoglyoxaline, 1-dodecyl-2-methyl-3-benzyl imidazole muriate, glyoxal ethyline quinoline, the imidazolium compoundss such as 2-benzylimidazoline, and the adducts of imidazolium compounds and epoxy resin.

As guanidine system curing catalyst, can enumerate such as: dicyanodiamide, 1-methylguanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-guanidines, 1-(o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylammonium guanidine, tetramethyl guanidine, pentamethyl-guanidine, 1, 5, 7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene, 7-methyl isophthalic acid, 5, 7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene, 1-methyl guanyl guanidine, 1-ethyl guanyl guanidine, 1-normal-butyl guanyl guanidine, 1-Octadecane base guanyl guanidine, 1, 1-dimethyl guanyl guanidine, 1, 1-diethyl guanyl guanidine, 1-cyclohexyl guanyl guanidine, 1-allyl group guanyl guanidine, 1-phenyl guanyl guanidine, 1-(o-tolyl) guanyl guanidine etc.

Curing catalyst content in resin combination is preferably 0.01 quality % ~ 3 quality %, is more preferably 0.01 quality % ~ 2 quality %, more preferably 0.01 quality % ~ 1 quality %.

Metal system curing catalyst also can be used as curing catalyst.As metal system curing catalyst, can enumerate such as: the organometallic complex of the metals such as cobalt, copper, zinc, iron, nickel, manganese, tin or organic metal salt.As the concrete example of organometallic complex, the Organic Manganese complex compounds etc. such as the organic nickel complex compound such as Organic-iron complexes, acetylacetonate nickel (II), manganese acetylacetonate (II) such as the organozinc complex such as organic copper complex, zinc acetylacetonate (II), ferric acetyl acetonade (III) such as the organic cobalt complex compound such as acetylacetone cobalt (II), acetylacetone cobalt (III), acetylacetone copper (II) can be enumerated.As the concrete example of organic metal salt, zinc octoate, stannous octoate, zinc naphthenate, cobalt naphthenate, stearic acid tin, Zinic stearas etc. can be enumerated.

When using metal system curing catalyst, the metal system curing catalyst content in resin combination is set as making the content based on the metal of metal system curing catalyst be preferably the scope of 25ppm ~ 500ppm, be more preferably the scope of 40ppm ~ 200ppm.

(G) fire retardant

As fire retardant, phosphorus compound, nitrogen compound, silicone flame retardant, metal hydroxides etc. that such as organic phosphorus flame retardant, organic system are nitrogenous can be enumerated.Fire retardant can be used alone one, also can combinationally use two or more.Flame retardant agent content in resin composition layer has no particular limits, and is preferably 0.5 quality % ~ 10 quality %, is more preferably 1 quality % ~ 9 quality %, more preferably 1.5 quality % ~ 8 quality %.

(H) rubber particles

As rubber particles, such as can be used in following organic solvent do not dissolve, with the above-mentioned also inconsistent rubber particles such as epoxy resin, solidifying agent and thermoplastic resin.Such rubber particles is generally prepared by making the molecular weight of rubber constituent increase to undissolved level, formation particle shape in organic solvent or resin.

As rubber particles, such as core-sheath-type rubber particles, crosslink propylene nitrile divinyl rubber particle, cross-linked styrene divinyl rubber particle, acrylic rubber particle etc. can be enumerated.Core-sheath-type rubber particles is the rubber particles with sandwich layer and sheaths, 2 Rotating fields that such as, outer field sheaths is made up of glassy polymers, the sandwich layer of internal layer is made up of rubbery polymer; Or the rubber particles etc. of the 3-tier architecture that outer field sheaths is made up of glassy polymers, middle layer is made up of rubbery polymer, sandwich layer is made up of glassy polymers.Glassy polymeric nitride layer is such as made up of methyl methacrylate polymer etc., and rubbery polymeric nitride layer is such as made up of butyl acrylate thing (isoprene-isobutylene rubber) etc.Rubber particles can be used alone one, also can combinationally use two or more.

The median size of rubber particles is preferably the scope of 0.005 μm ~ 1 μm, is more preferably the scope of 0.2 μm ~ 0.6 μm.The median size of rubber particles can use dynamic light scattering method to measure.Such as utilize ultrasonic wave etc. to make rubber particles be evenly dispersed in suitable organic solvent, use dense system particle size analyzer (FPAR-1000; Large mound electronics (strain) system), make the size-grade distribution of rubber particles with quality criteria, using its median diameter as median size, can measure thus.Rubber particles content in resin combination is preferably 1 quality % ~ 10 quality %, is more preferably 2 quality % ~ 5 quality %.

Resin combination of the present invention can also contain other additive as required, as this other additive, can enumerate the resin additives etc. such as such as organic filler, thickening material, defoamer, flow agent, adaptation imparting agent and tinting material.

Resin combination of the present invention, because its cured body presents sufficient thermal diffusivity, therefore can be used for various uses.Such as, resin combination of the present invention can be used for the extensive use that the insulating resin such as adhesive film, prepreg sheet material, circuit substrate (laminated plate purposes, multilayer printed circuit board purposes etc.), solder resist, underfill (underfill) material, die bond (diebonding) material, semiconductor-encapsulating material, filling perforation resin, component landfill resin etc. can enjoy the benefit of thermal diffusivity.Wherein, can be used as suitably: for the formation of the resin combination (resin compositions for insulating layer of metallizing laminated plate) of the insulation layer of metallizing laminated plate, for the formation of the resin combination (resin compositions for insulating layer of multilayer printed circuit board) of the insulation layer of multilayer printed circuit board, can more suitably be used as: in the manufacture of multilayer printed circuit board utilizing stack manner, for the formation of the resin combination (the stacking resin compositions for insulating layer of multilayer printed circuit board) of insulation layer, can be used as suitably further: for the resin combination (utilizing plating to form the stacking resin compositions for insulating layer of the multilayer printed circuit board of conductor layer) utilizing plating to form conductor layer.

Resin combination of the present invention, industrially usually preferably can also to use with the form of the sheet laminated materials such as adhesive film described later, prepreg for various uses with the coating of varnish state.

In one embodiment, the resin composition layer (adhesive linkage) that adhesive film comprises supporter and engages with this supporter, resin composition layer (adhesive linkage) is formed by resin combination of the present invention.

The thickness of resin composition layer is different according to purposes, when the insulation layer as multilayer printed circuit board uses, is preferably less than 100 μm, is more preferably less than 80 μm, more preferably less than 60 μm, is further preferably less than 50 μm.The lower limit of resin combination layer thickness is different according to purposes, when the insulation layer as multilayer printed circuit board uses, is generally more than 10 μm.

As supporter, preferably use the film formed by plastic material.As plastic material, can enumerate such as: polyethylene terephthalate is (below sometimes referred to as " PET ".), PEN is (below sometimes referred to as " PEN ".) etc. polyester, polycarbonate (below sometimes referred to as " PC ".), acrylic acid series, cyclic polyolefin, tri acetyl cellulose (TAC), polyether sulfides (PES), polyetherketone, the polyimide etc. such as polymethylmethacrylate (PMMA).Wherein, be preferably polyethylene terephthalate, PEN, be particularly preferably cheap polyethylene terephthalate.In a suitable embodiment, supporter is polyethylene terephthalate film.

Can to supporter and the surface of resin composition layer engagement side implement delustring process, corona treatment.In addition, as supporter, can be used in the surface of resin composition layer engagement side on there is the supporter of the band release layer of release layer.

The thickness of supporter is not particularly limited, and is preferably the scope of 5 μm ~ 75 μm, is more preferably the scope of 10 μm ~ 60 μm.Should illustrate, when supporter is the supporter of band release layer, the thickness of the supporter entirety of preferably with release layer is above-mentioned scope.

Adhesive film can manufacture as follows: such as, resin combination is dissolved in the resinous varnish of organic solvent by preparation, use die coating machine (ダイコーター) etc., this resinous varnish is coated on supporter, and then forms resin composition layer by dry organic solvents such as heating or blowing hot-airs.

As organic solvent, can enumerate such as: the acid amides series solvents etc. such as Trivalin SF class, toluene and the dimethylbenzene etc. such as the acetate esters such as the ketones such as acetone, methyl ethyl ketone and pimelinketone, ethyl acetate, butylacetate, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, cellosolve and diethylene glycol monobutyl ether are aromatic hydrocarbon based, dimethyl formamide, N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone.Organic solvent can be used alone one, also can combinationally use two or more.

Drying conditions is not particularly limited, and carries out drying in the mode making the organic solvent content in resin composition layer reach below 10 quality %, preferably below 5 quality %.Different according to the boiling point of organic solvent in resinous varnish, such as, when using the resinous varnish containing 30 quality % ~ 60 quality % organic solvents, within 3 ~ 10 minutes, form resin composition layer by dry at 50 DEG C ~ 150 DEG C.

In adhesive film, can in the face face of supporter opposition side (namely with) do not engaged with supporter of resin composition layer further lamination according to the protective membrane of supporter.The thickness of protective membrane is not particularly limited, such as, be 1 μm ~ 40 μm.By lamination protective membrane, resin composition layer surface attachment dust etc. can be prevented or be scratched.Adhesive film can coil into web-like and preserve.When adhesive film has protective membrane, used by peeling protective membrane.

In one embodiment, in sheet-like fiber base material, soak into resin combination of the present invention and form prepreg.

Sheet-like fiber base material used in prepreg is not particularly limited, and can use the base material that woven fiber glass, aramid nonwoven fabric, liquid crystalline polymers non-woven fabrics etc. use usually used as prepreg base material.When the insulation layer for the formation of multilayer printed circuit board, thickness can be used suitably to be the thin type sheet fiber base material of less than 50 μm, particularly preferably thickness is the sheet-like fiber base material of 10 μm ~ 40 μm, more preferably thickness is the sheet-like fiber base material of 10 μm ~ 30 μm, and further preferred thickness is the sheet-like fiber base material of 10 ~ 20 μm.

Prepreg can adopt the known method such as hot melt process, solvent method to manufacture.

The thickness of prepreg can be the scope same with the resin composition layer in above-mentioned adhesive film.

[cured body]

Make resin combination thermofixation of the present invention and obtain cured body of the present invention.

The thermofixation condition of resin combination is not particularly limited, the condition such as, usually adopted when can be used in the insulation layer forming multilayer printed circuit board.

Such as, the thermofixation condition of resin combination is different according to the composition of resin combination etc., the scope (be preferably 10 minutes ~ 75 minutes, be more preferably 15 minutes ~ 60 minutes) that the scope (be preferably the scope of 150 DEG C ~ 210 DEG C, be more preferably the scope of 170 DEG C ~ 190 DEG C) that solidification value can be 120 DEG C ~ 240 DEG C, set time can be 5 minutes ~ 90 minutes.

Before making resin combination thermofixation, at the temperature lower than solidification value, resin combination can be preheated.Such as, can before making resin combination thermofixation, more than 50 DEG C and less than 120 DEG C (be preferably more than 60 DEG C and less than 110 DEG C, be more preferably more than 70 DEG C and less than 100 DEG C) temperature under, preheating of more than 5 minutes (preferably 5 minutes ~ 150 minutes, be more preferably 15 minutes ~ 120 minutes) is carried out to resin combination.

Cured body of the present invention can present sufficient thermal diffusivity.Such as, different according to the high thermal conductivity inorganic filling material content in resin combination used, but cured body of the present invention can present preferably more than 1W/m K, be more preferably more than 1.2W/m K, more preferably more than 1.4W/m K, further be preferably more than 1.5W/m K, be particularly preferably more than 1.6W/m K, more than 1.7W/m K, more than 1.8W/m K, more than 1.9W/m K, more than 2.0W/m K, more than 2.1W/m K, more than 2.2W/m K, more than 2.3W/m K, more than 2.4W/m K, more than 2.5W/m K, more than 2.6W/m K, the thermal conductivity of more than 2.7W/m K or 2.8W/m more than K.The thermal conductivity upper limit of cured body of the present invention is not particularly limited, and is generally below 30W/m K.The thermal conductivity of cured body of the present invention such as can utilize the known method such as heat flowmeter method and temperature wave analytical method to measure.Different according to purposes, but when the thinner thickness of cured body of the present invention (such as, less than 100 μm), can use with the cured body of real use state same thickness to measure thermal conductivity, therefore preferably utilize temperature wave analytical method to measure.As the concrete example of measuring thermal conductivity device utilizing temperature wave analytical method, can enumerate " ai-PhaseMobile1u " of ai-Phase.

The feature of cured body of the present invention is, present thermal diffusivity fully as above, and surfaceness is low.About cured body of the present invention, the arithmetic average roughness (Ra value) on surface is preferably below 300nm, is more preferably below 260nm, more preferably below 220nm, is further preferably below 180nm, is particularly preferably below 160nm, below 150nm, below 140nm, below 130nm, below 120nm, below 110nm, below 100nm, below 90nm or below 80nm.The lower limit of this Ra value is not particularly limited, and usually can be more than 10nm.The arithmetic average roughness (Ra value) on cured body surface can use non-contact type surface roughness meter to measure.As the concrete example of non-contact type surface roughness meter, can enumerate " WYKONT3300 " that Wei Yike precision instrument company limited (PVC ーコイ Application ス Star Le メ Application Star) makes.

The feature of cured body of the present invention is, present sufficient thermal diffusivity, and surfaceness is low.Think that an one reason is, in cured body of the present invention, the high thermal conductivity inorganic filling material be selected from aluminium nitride and silicon nitride disperses very well.

The thickness of cured body of the present invention is different according to purposes, when the insulation layer as multilayer printed circuit board uses, is preferably less than 100 μm, is more preferably less than 80 μm, more preferably less than 60 μm, is further preferably less than 50 μm.The lower limit of cured body thickness is different according to purposes, when the insulation layer as multilayer printed circuit board uses, is generally more than 10 μm.

[roughening cured body]

Roughened is carried out to cured body of the present invention and obtains roughening cured body of the present invention.

Operation, the condition of roughened are not particularly limited, and can adopt normally used known operation, condition when forming the insulation layer of multilayer printed circuit board.Such as can implement to make use of the swelling process of swelling liquid successively, make use of the roughened of oxygenant, make use of the neutralizing treatment of neutralizer, roughened is carried out to cured body surface.As swelling liquid, be not particularly limited, can enumerate alkaline solution, surfactant soln etc., be preferably alkaline solution, this alkaline solution is more preferably sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling liquid, スウェリ Application グディップセキュリガ Application ス P, スウェリ Application グディップセキュリガ Application ス SBU etc. that such as アトテッ Network ジャパ Application (strain) is made can be enumerated.The swelling process that make use of swelling liquid is not particularly limited, such as can by cured body being flooded 1 minute ~ 20 minutes to carry out in the swelling liquid of 30 ~ 90 DEG C.Suppress, for suitable level, in the swelling liquid of 40 ~ 80 DEG C, preferably to make cured body flood 5 seconds ~ 15 minutes from the viewpoint of the swelling of the resin by cured body.Be not particularly limited as oxygenant, the alkaline permanganic acid solution such as having dissolved potassium permanganate, sodium permanganate in the aqueous solution of sodium hydroxide can be enumerated.The roughened that make use of the oxygenants such as alkaline permanganic acid solution is being heated to flood in the oxidizing agent solution of 60 DEG C ~ 80 DEG C carry out for 10 minutes ~ 30 minutes preferably by making cured body.In addition, the concentration of the permanganate in alkaline permanganic acid solution is preferably 5 quality % ~ 10 quality %.As commercially available oxygenant, the alkaline permanganic acid solutions such as the コ Application セ Application トレートコ Application パ Network ト CP, ドージ Application グソリューショ Application セキュリガ Application ス P that such as アトテッ Network ジャパ Application (strain) makes can be enumerated.In addition, as neutralizer, the preferably acid aqueous solution, as commercially available product, can enumerate the リダ Network ショ Application ソリューショ Application セキュリガ Application ト P that such as アトテッ Network ジャパ Application (strain) is made.The process that make use of neutralizer can be carried out by making the treated side utilizing oxidizing agent solution to carry out roughened flood in the neutralizer of 30 ~ 80 DEG C for 5 minutes ~ 30 minutes.From the viewpoint of operability etc., the object of roughened that preferably will oxidizing agent solution utilized to carry out, floods the method for 5 minutes ~ 20 minutes in the neutralizer of 40 ~ 70 DEG C.

About the cured body containing the high thermal conductivity inorganic filling material be selected from aluminium nitride and silicon nitride, the present inventor etc. find sometimes to make its surfaceness sharply increase by roughened.The increase of this surfaceness caused by roughened, at use aluminium nitride as becoming more significant trend during high thermal conductivity inorganic filling material.To this, in the present invention using the packing material processed by high thermal conductivity inorganic filling material silane compound, the increase of the surfaceness caused by roughened can be suppressed, can realize presenting sufficient thermal diffusivity and the low roughening cured body of surfaceness.Known aluminium nitride and silicon nitride are respectively freed from water and alkali and easily decompose.Think in the present invention by with silane compound process aluminium nitride and silicon nitride, surface water, alkali being demonstrated to superior resistance can be formed.

In suitable embodiment, the arithmetic average roughness (Ra value) on roughening cured body surface of the present invention is preferably below 500nm, is more preferably below 400nm, more preferably below 300nm, is further preferably below 280nm, is particularly preferably below 260nm, below 240nm, below 220nm or below 200nm.The lower limit of this Ra value is not particularly limited, and usually can be more than 10nm.In addition, the r.m.s. roughness (Rq value) on cured body surface of the present invention is preferably below 650nm, is more preferably below 600nm, more preferably below 550nm, is particularly preferably below 500nm, below 550nm, below 500nm, below 450nm, below 400nm, below 350nm or below 300nm.The lower limit of this Rq value is not particularly limited, and is generally more than 10nm, more than 30nm, 50nm with first-class.Arithmetic average roughness (Ra value) and the r.m.s. roughness (Rq value) on roughening cured body surface can use non-contact type surface roughness meter to measure.As the concrete example of non-contact type surface roughness meter, " WYKONT3300 " of Wei Yike precision instrument company limited can be enumerated.

[multilayer body]

The conductor layer that multilayer body of the present invention possesses roughening cured body of the present invention and is formed on the surface of this roughening cured body.

Metal used in conductor layer is not particularly limited, and in a suitable embodiment, conductor layer contains the metal of more than a kind of being selected from gold, platinum, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Conductor layer can be single metal layer or alloy layer, as alloy layer, can enumerate the layer such as formed by the alloy (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) of the metal of more than two kinds being selected from above-mentioned metal.Wherein, the versatility, the cost that are formed from conductor layer, to consider by the viewpoint such as easiness of etching removing, be preferably the alloy layer of the single metal layer of chromium, nickel, titanium, aluminium, zinc, gold and silver or copper or nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, be more preferably the single metal layer of chromium, nickel, titanium, aluminium, zinc, gold and silver or copper or the alloy layer of nickel-chromium alloy, more preferably the single metal layer of copper.

Conductor layer can be single layer structure, also can be the single metal layer comprising different types of metal or alloy of more than 2 layers or alloy layer lamination and the multilayered structure obtained.When conductor layer is multilayered structure, the layer connected with roughening cured body is preferably the single metal layer of chromium, zinc or titanium or the alloy layer of nickel-chromium alloy.

From the viewpoint of the fine wiring of multilayer printed circuit board, the thickness of conductor layer is preferably less than 40 μm, is more preferably 1 ~ 35 μm, more preferably 3 ~ 30 μm.When conductor layer is multilayered structure, also preferably the thickness of conductor layer entirety is above-mentioned scope.

Dry type plating or wet type plating can be utilized to form conductor layer on the surface at roughening cured body.As dry type plating, the known methods such as such as evaporation, sputtering, ion plating can be enumerated.When wet type plating, such as, combination non-electrolytic plating and electrolysis plating form conductor layer.Or also can be formed with conductor layer is the protective layer plating (めっ I レジスト) of opposite pattern, non-electrolytic plating is only utilized to form conductor layer.As the method that wiring pattern is formed, example (subtractive) method, semi-additive process etc. can be subtracted each other as known to the skilled person.

When utilizing semi-additive process to form conductor layer, following operation can be adopted to be formed.First, the surface of roughening cured body utilize non-electrolytic plating to form plating layer (めっ I シー De Layer).Then, on the plating layer formed, corresponding to required wiring pattern, the mask pattern that a part for plating layer is exposed is formed.On the plating layer exposed, after utilizing electrolysis plating to form metal level, removing mask pattern.Then, utilize etching to wait the unwanted plating layer of removing, the conductor layer with required wiring pattern can be formed.

Require that roughening cured body (insulation layer) and conductor layer demonstrate sufficient dhering strength (stripping strength), usually by described adaptation can be obtained because of concavo-convex fastening (anchor) effect brought on roughening cured body surface.But, if roughening cured body surface is concavo-convex larger, then when wiring pattern is formed by etch removing unwanted plating layer when, the kind layer (シー De Layer of jog) be difficult to removing, and when etching under the condition of plating layer that fully can remove jog, the dissolving of wiring pattern is significantly changed, and becomes the obstacle of fine wiring.About this point, the discoveries such as the present inventor, about the cured body containing the high thermal conductivity inorganic filling material be selected from aluminium nitride and silicon nitride, as previously mentioned, utilize roughened, not only its surfaceness sharply increases, although and surfaceness high, result obtains the roughening cured body with the remarkable deterioration of the dhering strength of conductor layer (stripping strength) sometimes.To this, using in the present invention of packing material that high thermal conductivity inorganic filling material silane compound is processed, can advantageously obtain low and good with the dhering strength (stripping strength) of the conductor layer roughening cured body of surfaceness (for roughening cured body surfaceness as previously mentioned).Also complement each other with the effect that can realize abundant thermal diffusivity, multilayer body of the present invention significantly contributes to the thermal diffusivity of multilayer printed circuit board and fine both wiring.

In multilayer body of the present invention, the stripping strength of roughening cured body and conductor layer is preferably more than 0.25kgf/cm, is more preferably more than 0.30kgf/cm, more preferably more than 0.35kgf/cm, be particularly preferably more than 0.40kgf/cm or more than 0.45kgf/cm.The upper limit of stripping strength is not particularly limited, and is generally below 1.0kgf/cm, 0.9kgf/cm is such as the following.Should illustrate, the stripping strength of roughening cured body and conductor layer refers to the stripping strength (90 degree of pull strengths) when peeling conductor layer relative to roughening cured body with vertical direction (90 degree of directions), and stripping strength when peeling conductor layer relative to roughening cured body with vertical direction (90 degree of directions) carries out mensuration to obtain by adopting tensile testing machine.As tensile testing machine, " AC-50C-SL " of (strain) TSE etc. can be enumerated such as.

[multilayer printed circuit board]

Multilayer printed circuit board of the present invention contains cured body of the present invention or roughening cured body.

In one embodiment, multilayer printed circuit board of the present invention contains roughening cured body of the present invention as insulation layer.In other embodiments, multilayer printed circuit board of the present invention contains cured body of the present invention as solder resist.In multilayer printed circuit board of the present invention, comprise cured body of the present invention or roughening cured body according to its concrete purposes as suitable component.

Below, be described for containing cured body of the present invention or the roughening cured body embodiment as the multilayer printed circuit board of insulation layer.

In one embodiment, multilayer printed circuit board of the present invention can use above-mentioned adhesive film to manufacture.In this embodiment, after the mode engaged with circuit substrate with the resin composition layer of adhesive film carries out lamination treatment, implement above-mentioned " preheating " and " thermofixation ", cured body of the present invention can be formed on circuit substrate.Should illustrate, when adhesive film has protective membrane, can for manufacture after removing protective membrane.

The condition of lamination treatment is not particularly limited, and can adopt the known condition used when using adhesive film to form the insulation layer of multilayer printed circuit board.Such as, can implement by pressurizeing from the support side of adhesive film to metal sheets such as the SUS end plates through heating.At this moment, preferably not to metal sheet direct weighting, but pressurize across heat resistant rubber elastomeric material, concavo-convex to make adhesive film fully follow the circuit of circuit substrate.Pressed temperature is preferably the scope of 70 DEG C ~ 140 DEG C, is preferably 1kgf/cm at moulding pressure ²~ 11kgf/cm ²the scope of (0.098MPa ~ 1.079MPa) is carried out, be preferably clamping time 5 second ~ scope of 3 minutes.In addition, lamination treatment is preferably implemented under the following decompression of 20mmHg (26.7hPa).Lamination treatment can use commercially available vacuum laminator to implement.As commercially available vacuum laminator, the vacuum pack system device (バキュー system アップリケーター) etc. that (strain) name mechanism makes made vacuum pressure type laminating machine, ニチゴーモート Application (strain) makes can be enumerated such as.

Should illustrate, in the present invention, " circuit substrate " mainly refers to the circuit substrate being formed with the conductor layer (circuit) having carried out pattern processing on the one or both sides of the substrates such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide substrate.In addition when manufacturing multilayer printed circuit board, the middle internal layer circuit substrate manufacturing thing that will form insulation layer and/or conductor layer is further also contained in the present invention's said " circuit substrate ".

In other embodiments, printed-wiring board (PWB) of the present invention can use above-mentioned resinous varnish to manufacture.In this embodiment, die coating machine etc. is utilized to be coated on equably on circuit substrate by resinous varnish, make it heat, dry, after defining resin composition layer thus on circuit substrate, implement above-mentioned " preheating " and " thermofixation ", thus cured body of the present invention can be formed on circuit substrate.Organic solvent used in resinous varnish and heating, dry condition can with for illustrated same in the manufacture of adhesive film.

Then, for the cured body be formed on circuit substrate, implement above-mentioned " roughened " and after forming roughening cured body, the surface of this roughening cured body form conductor layer.Should illustrate, in the manufacture of multilayer printed circuit board, and then the perforate operation etc. of insulation layer carrying out perforate can be included in.These operations can according to well known to a person skilled in the art various methods used in the manufacture of multilayer printed circuit board to carry out.

[semiconductor device]

Above-mentioned multilayer printed circuit board is used to manufacture semiconductor device.

As this semiconductor device, can enumerate for electric product (such as, computer, mobile telephone, digital camera and televisor etc.) and the various semiconductor devices of the vehicles (such as, motorcycle, automobile, electric car, boats and ships and aircraft etc.) etc.

Embodiment

Specifically describe the present invention by the following examples, but the present invention is not limited to the examples.Should illustrate, in following record, " part " and " % ", if do not recorded in addition, refers to " mass parts " and " quality % " respectively.

< measuring method, evaluation method >

First various measuring method, evaluation method are described.

(preparation of mensuration, evaluation substrate)

(1) base treatment of internal layer circuit substrate

The two sides of the woven fiber glass base material epoxy resin two sides copper-clad laminates (thickness 18 μm of Copper Foil, the thickness 0.3mm of substrate, SUNX (strain) system " R5715ES ") defining internal layer circuit on two sides be impregnated in メッ Network (strain) system " CZ8100 ", carry out the roughened (copper etch quantity 1 μm) on copper surface.

(2) lamination treatment of adhesive film

Use intermittent vacuum pressure level press (name machine (strain) system " MVLP-500 "), in the mode that resin composition layer engages with internal layer circuit substrate, carry out the process adhesive film made in embodiment and comparative example being laminated to internal layer circuit substrate two sides.Lamination treatment is carried out as follows, carries out decompression in 30 seconds and makes after air pressure reaches below 13hPa, 120 DEG C, carry out pressurization in 30 seconds under pressure 0.74MPa.

(3) thermofixation of resin composition layer

After the lamination treatment of resin composition layer, the PET film as supporter is peeled off.Then, after having the internal layer circuit substrate of resin composition layer to carry out preheating for 30 minutes at 100 DEG C to lamination, heat 30 minutes at 180 DEG C, resin composition layer thermofixation is formed cured body.

(4) roughened

By the internal layer circuit substrate that is formed with cured body on two sides, at 60 DEG C, in swelling liquid, (アトテッ Network ジャパ Application (strain) makes " スエリ Application グディップセキュリガ Application ト P ", aqueous sodium hydroxide solution containing diethylene glycol monobutyl ehter) in dipping 5 minutes, then at 80 DEG C, in oxygenant, (アトテッ Network ジャパ Application (strain) makes " コ Application セ Application トレートコ Application パ Network ト CP ", potassium permanganate concentration about 6 quality %, the aqueous solution of naoh concentration about 4 quality %) in dipping 20 minutes, it is last that at 40 DEG C, in neutralizer, (アトテッ Network ジャパ Application (strain) makes " リダ Network ショ Application ソリューショ Application セキュリガ Application ト P ", sulfuric acid aqueous hydroxylamine) in dipping 5 minutes.Then, at 80 DEG C, drying 30 minutes, the two sides of internal layer circuit substrate is formed roughening cured body.

(5) formation of conductor layer

According to semi-additive process, the surface of roughening cured body forms conductor layer.

That is, at 40 DEG C, the internal layer circuit substrate being formed with roughening cured body on two sides be impregnated in containing PdCl ₂electroless plating application solution in 5 minutes, at 25 DEG C, then to impregnated in non-electrolytic copper plating bath 20 minutes, form plating layer on roughening cured body surface.After heating carries out anneal in 30 minutes at 150 DEG C, plating layer arranges erosion shield, by etching, pattern formation is carried out to plating layer.Then carry out copper sulfate bath plating, after forming the conductor layer of thickness 30 μm, at 190 DEG C, carry out 60 minutes anneal, the surface of roughening cured body forms conductor layer.

(mensuration of arithmetic average roughness (Ra value), r.m.s. roughness (Rq value))

The arithmetic average roughness (Ra value) on cured body surface, the arithmetic average roughness (Ra value) on roughening cured body surface and r.m.s. roughness (Rq value), use non-contact type surface roughness meter (society of Wei Yike precision instrument company limited system " WYKONT3300 "), by VSI contact mode, 50 times of lens, measurement range is set to 121 μm × 92 μm, is obtained by the numerical value of gained.For each cured body and roughening cured body, obtain the mean value of 10 of Stochastic choice.

(mensuration of the stripping strength (pull strength) of conductor layer)

The conductor layer evaluating substrate cuts the otch of part of wide 10mm, long 100mm, by its one end strip off, clamp with fixture (Co., Ltd. TSE オートコ system type trier " AC-50C-SL "), measure the load (kgf/cm) at room temperature, when vertically to peel 35mm with the speed of 50mm/ minute, obtain pull strength.

(mensuration of the thermal diffusivity of cured body and evaluation)

The thermal diffusivity of cured body is evaluated by the thermal conductivity measuring cured body according to following operation.That is, the adhesive film made in embodiment and comparative example is heated at 190 DEG C within 90 minutes, make resin composition layer thermofixation.After resin composition layer thermofixation, the PET film as supporter is peeled off, obtains the cured body of sheet.For the cured body of gained, ai-Phase system " ai-PhaseMobile1u " is used to be measured the thermal conductivity of the thickness direction of this cured body by temperature wave analytical method.3 times are carried out for same test film measure, calculating mean value.So the situation by mean value being that the situation of more than 1.5W/m K is evaluated as "○", mean value is more than 1W/m K and is less than 1.5W/m K is evaluated as " △ ", mean value is less than the situation of 1W/m K be evaluated as "×".

< embodiment 1 >

By naphthalene type epoxy resin, (DIC (strain) makes " HP4032SS ", epoxy equivalent (weight) about 144) 12 parts, (DIC (strain) makes " HP6000 " to naphthylidene ether type epoxy, epoxy equivalent (weight) about 250) 6 parts, di-toluene phenol-type epoxy resin (Mitsubishi Chemical's (strain) system " YX4000HK ", epoxy equivalent (weight) about 185) 4 parts, and phenoxy resin (Mitsubishi Chemical's (strain) system " YL7553BH30 ", the methyl ethyl ketone (MEK) of solids component 30 quality % and the 1:1 solution of pimelinketone) 6 parts stir while heating for dissolving is in solvent oil 30 parts.After being cooled to room temperature, (DIC (strain) makes " LA-3018-50P " to mix the cresol novolac resin containing triazine structure wherein, hydroxyl equivalent 151, the 2-methoxy propyl alcoholic solution of solids component 50%) 9 parts, (DIC (strain) makes " HPC8000-65T " to active ester system solidifying agent, active group equivalent about 223, the toluene solution of nonvolatile component 65 quality %) 10 parts, curing catalyst (4-dimethylaminopyridine, " DMAP ", the MEK solution of solids component 5 quality %) 2 parts, with amino silane compounds (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 ", N-phenyl-3-TSL 8330) 0.7 part carried out surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m ²/ g, proportion 3.3g/cm ³) 120 parts, dispersed with high speed rotating mixing machine, prepare resinous varnish.

Then, 30 μm are reached to make the thickness of dried resin composition layer at the release layer side even spread resinous varnish of the PET film (リ Application テッ Network (strain) makes " PET501010 ", thickness 50 μm) of band release layer, under 80 ~ 120 DEG C (average 100 DEG C), drying 4 minutes, makes adhesive film.

< embodiment 2 >

By bisphenol-type epoxy resin (Nippon Steel's chemistry (strain) system " ZX1059 ", the 1:1 melange of bisphenol A-type and bisphenol-f type, epoxy equivalent (weight) about 169) 6 parts, biphenyl type epoxy resin (Japanese chemical drug (strain) system " NC3000H ", epoxy equivalent (weight) about 288) 9 parts, di-toluene phenol-type epoxy resin (Mitsubishi Chemical's (strain) system " YX4000HK ", epoxy equivalent (weight) about 185) 12 parts, fluorenes type epoxy resin (Mitsubishi Chemical's (strain) system " YL7800BH40 ", the methyl ethyl ketone (MEK) of solids component 40 quality % and the 1:1 solution of pimelinketone, epoxy equivalent (weight) about 4100) 6 parts stir while heating for dissolving is in solvent oil 40 parts.After being cooled to room temperature, (DIC (strain) makes " LA-1356 " to mix the phenol resol resins containing triazine structure wherein, hydroxyl equivalent 146) the MEK solution 10 parts of solids component 60%, (DIC (strain) makes " HPC8000-65T " to active ester type solidifying agent, the toluene solution of the nonvolatile component 65 quality % of active group equivalent about 223) 10 parts, curing catalyst (4-dimethylaminopyridine, the MEK solution of solids component 5 quality %) 2 parts, with silane compound (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM103 ", phenyltrimethoxysila,e) 1 part carried out surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m ²/ g, proportion 3.3g/cm ³) 170 parts, dispersed with high speed rotating mixing machine, prepare resinous varnish.Then, adhesive film is prepared in operation similarly to Example 1.

< embodiment 3 >

By naphthalene type epoxy resin, (DIC (strain) makes " HP4032SS ", epoxy equivalent (weight) about 144) 4 parts, biphenyl type epoxy resin (Japanese chemical drug (strain) system " NC3000H ", epoxy equivalent (weight) about 288) 12 parts, di-toluene phenol-type epoxy resin (Mitsubishi Chemical's (strain) system " YX4000HK ", epoxy equivalent (weight) about 185) 6 parts, phenoxy resin (Mitsubishi Chemical's (strain) system " YL7553BH30 ", the methyl ethyl ketone (MEK) of solids component 30 quality % and the 1:1 solution of pimelinketone) 9 parts stir while heating for dissolving is in solvent oil 30 parts.After being cooled to room temperature, (ロ Application ザジャパ Application (strain) makes " BA230S75 " to mix the cyanate ester resin containing triazine structure wherein, cyanate equivalent about 232, the MEK solution of nonvolatile component 75 quality %) 12 parts, (ロ Application ザジャパ Application (strain) makes " PT30S " to phenol novolak type cyanate ester resin, cyanate equivalent about 133, the MEK solution of nonvolatile component 85 quality %) 3 parts, (DIC (strain) makes " HPC8000-65T " to active ester system solidifying agent, the toluene solution of the nonvolatile component 65 quality % of active group equivalent about 223) 12 parts, curing catalyst (4-dimethylaminopyridine, the MEK solution of solids component 5 quality %) 0.4 part, (Tokyo changes into (strain) makes curing catalyst, acetylacetone cobalt (III), the MEK solution of solids component 1 quality %) 3 parts, fire retardant (three light (strain) system " HCA-HQ ", 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, median size 2 μm) 3 parts, with amino silane compounds (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 ", N-phenyl-3-TSL 8330) 0.6 part carried out surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m ²/ g, proportion 3.3g/cm ³) 110 parts, dispersed with high speed rotating mixing machine, prepare resinous varnish.Then, adhesive film is prepared in operation similarly to Example 1.

< embodiment 4 >

Except using 10 parts, naphthols system solidifying agent (the MEK solution of Nippon Steel's chemistry (strain) system " SN-485 ", hydroxyl equivalent 215, solids component 60%) to replace except 10 parts, active ester system solidifying agent (DIC (strain) makes the toluene solution of " HPC8000-65T ", active group equivalent about 223, nonvolatile component 65 quality %), operation is prepared resinous varnish, is made adhesive film similarly to Example 2.

< embodiment 5 >

Except do not add the solids component 60% of the phenol resol resins (DIC (strain) makes " LA-1356 " hydroxyl equivalent 146) containing triazine structure MEK solution 10 parts and by the use level of active ester system solidifying agent (DIC (strain) makes the toluene solution of " HPC8000-65T ", active group equivalent about 223, nonvolatile component 65 quality %) from 10 parts of increments to except 24 parts, resinous varnish is prepared in operation similarly to Example 2, makes adhesive film.

< embodiment 6 >

Surface-treated silicon nitride (electrochemically industry (strain) system " SN-9S ", median size 1.1 μm, specific surface area 7m has been carried out with amino silane compounds (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 ", N-phenyl-3-TSL 8330) 0.7 part except using ²/ g, proportion 3.4g/cm ³) replace having carried out surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m with amino silane compounds (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 ", N-phenyl-3-TSL 8330) 0.7 part ²/ g, proportion 3.3g/cm ³) outside 120 parts, resinous varnish is prepared in operation similarly to Example 1, makes adhesive film.

< comparative example 1 >

By naphthalene type epoxy resin, (DIC (strain) makes " HP4032SS ", epoxy equivalent (weight) about 144) 4 parts, biphenyl type epoxy resin (Japanese chemical drug (strain) system " NC3000H ", epoxy equivalent (weight) about 288) 12 parts, di-toluene phenol-type epoxy resin (Mitsubishi Chemical's (strain) system " YX4000HK ", epoxy equivalent (weight) about 185) 6 parts, phenoxy resin (Mitsubishi Chemical's (strain) system " YL7553BH30 ", the methyl ethyl ketone (MEK) of solids component 30 quality % and the 1:1 solution of pimelinketone) 9 parts stir while heating for dissolving is in solvent oil 30 parts.After being cooled to room temperature, (ロ Application ザジャパ Application (strain) makes " BA230S75 " to mix the cyanate ester resin containing triazine structure wherein, cyanate equivalent about 232, the MEK solution of nonvolatile component 75 quality %) 24 parts, (ロ Application ザジャパ Application (strain) makes " PT30S " to phenol novolak type cyanate ester resin, cyanate equivalent about 133, the MEK solution of nonvolatile component 85 quality %) 3 parts, curing catalyst (4-dimethylaminopyridine, the MEK solution of solids component 5 quality %) 0.4 part, (Tokyo changes into (strain) makes curing catalyst, acetylacetone cobalt (III), the MEK solution of solids component 1 quality %) 3 parts, fire retardant (three light (strain) system " HCA-HQ ", 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, median size 2 μm) 3 parts, do not carry out surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m ²/ g, proportion 3.3g/cm ³) 100 parts, dispersed with high speed rotating mixing machine, prepare resinous varnish.Then, adhesive film is prepared in operation similarly to Example 1.

< comparative example 2 >

Surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m is not carried out except using ²/ g, proportion 3.3g/cm ³) 170 parts replace having carried out surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m with silane compound (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM103 ", phenyltrimethoxysila,e) 1 part ²/ g, proportion 3.3g/cm ³) outside 170 parts, resinous varnish is prepared in operation similarly to Example 5, makes adhesive film.

< comparative example 3 >

Surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m has been carried out with aluminium system coupling agent (monosodium glutamate Off ァイ Application テ Network ノ system " プレ Application ア Network ト AL-M ", acetyl aluminum alkoxide diiso propoxide) 0.7 part except using ²/ g, proportion 3.3g/cm ³) 120 parts replace having carried out surface-treated aluminium nitride ((strain) ト Network ヤマ system " シェイパ Le H ", median size 1.1 μm, specific surface area 2.6m with amino silane compounds (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 ", N-phenyl-3-TSL 8330) 0.7 part ²/ g, proportion 3.3g/cm ³) beyond 120 parts, resinous varnish is prepared in operation similarly to Example 1, makes adhesive film.

Result is shown in table 1.

[table 1]

。

In the embodiment 1 ~ 6 using the resin combination containing the packing material processed by the high thermal conductivity inorganic filling material silane compound be selected from aluminium nitride and silicon nitride, can obtain presenting sufficient thermal diffusivity (thermal conductivity), surfaceness is low and good with the dhering strength (stripping strength) of conductor layer simultaneously cured body, roughening cured body.Wherein, combinationally use in active ester system solidifying agent and the embodiment 1 ~ 3 and 6 containing the solidifying agent of triazine structure, can obtain presenting sufficient thermal diffusivity (thermal conductivity), surfaceness is especially low and especially excellent with the dhering strength (stripping strength) of conductor layer simultaneously cured body, roughening cured body.Comparatively speaking, in the comparative example 1 and 2 using the resin combination containing untreated high thermal conductivity inorganic filling material, although due to the content increase of high thermal conductivity inorganic filling material, the thermal diffusivity of cured body (thermal conductivity) improves (comparative example 1 is with the contrast of comparative example 2), and result obtains surfaceness high and significantly deteriorated with the dhering strength (stripping strength) of conductor layer cured body, roughening cured body.In addition, in the comparative example 3 using the resin combination containing the packing material processed by high thermal conductivity inorganic filling material aluminium system coupling agent, result also obtains surfaceness high and significantly deteriorated with the dhering strength (stripping strength) of conductor layer cured body, roughening cured body.Should illustrate, cured body containing the packing material that high thermal conductivity inorganic filling material silane compound is processed, with contain the cured body of untreated high thermal conductivity inorganic filling material with almost identical content compared with, can confirm to present higher thermal diffusivity (thermal conductivity) (embodiment 3 is with the contrast of comparative example 1 or the contrast of embodiment 5 and comparative example 2).

Claims

1. resin combination, it contains:

(B) epoxy resin and

(C) solidifying agent,

Wherein, (A) composition silane compound is processed.

2. resin combination according to claim 1, wherein, silane compound has phenyl.

3. the resin combination described in claim 1 or 2, wherein, relative to high thermal conductivity inorganic filling material 100 mass parts, the treatment capacity of silane compound is more than 0.05 mass parts.

4. the resin combination according to any one of claims 1 to 3, wherein, (C) composition comprises the first solidifying agent and second solidifying agent different from this first solidifying agent, and the first solidifying agent is active ester system solidifying agent.

5. resin combination according to claim 4, wherein, the second solidifying agent is the solidifying agent containing triazine structure.

6. the resin combination described in claim 4 or 5, wherein, the second solidifying agent is the phenol system solidifying agent containing triazine structure or the cyanate system solidifying agent containing triazine structure.

7. the resin combination according to any one of claim 4 ~ 6, wherein, the first solidifying agent is 0.3 ~ 2 relative to the mass ratio of the second solidifying agent, i.e. the first solidifying agent/the second solidifying agent.

8. make the resin combination thermofixation according to any one of claim 1 ~ 7 and the cured body obtained.

9. cured body according to claim 8, wherein, the arithmetic average roughness (Ra) on surface is below 180nm.

10. the cured body described in claim 8 or 9, wherein, thermal conductivity is more than 1W/m K.

Cured body according to any one of claim 8 ~ 10 is carried out roughened and the roughening cured body obtained by 11..

12. multilayer body, it conductor layer possessing roughening cured body according to claim 11 and be formed on the surface of this roughening cured body.

13. multilayer body according to claim 12, wherein, the stripping strength of roughening cured body and conductor layer is more than 0.25kgf/cm.

14. multilayer printed circuit boards, it contains cured body according to any one of claim 8 ~ 10 or roughening cured body according to claim 11.

15. semiconductor devices, it contains multilayer printed circuit board according to claim 14.