CN109072018A - The adhesive film of multilayer printed circuit board - Google Patents

Abstract

Even if the present invention provide it is a kind of make silica filler height fillingization, the adhesive film of concave-convex imbedibility also excellent multilayer printed circuit board.A kind of adhesive film specifically adhesive film of multilayer printed circuit board, it has resin composition layer made of resin combination forming layer on supporting mass film, the novolac type phenolic resin that dispersion ratio (Mw/Mn) of the resin combination comprising (A) weight average molecular weight (Mw) and number-average molecular weight (Mn) is 1.05~1.8, (B) epoxy resin shown in general formula (1), (C) inorganic filling material, the average grain diameter of (C) inorganic filling material in the resin composition layer is 0.1 μm or more, (C) content of inorganic filling material is 20~95 mass % in resin solid content.

Description

The adhesive film of multilayer printed circuit board

Technical field

The present invention relates to the adhesive films of multilayer printed circuit board.

Background technique

In recent years, for multilayer printed circuit board used in electronic equipment, communication equipment etc., not only it is strongly required small-sized The densification of change, lighting and wiring is also strongly required the high speed of calculation process speed.Along with the requirement, as more The manufacturing method of layer printed wiring board is focusing on the wiring layer of circuit substrate insulating layer, lamination between replacing stack layer The manufacturing technology of mode.

In the manufacturing technology of lamination mode, as the manufacturing method of interlayer insulating film and wiring layer, the side of conventional Method is to be formed to be routed by so-called " subtractive process ", the subtractive process are as follows: will be used to form the resin combination of interlayer insulating film (hereinafter also referred to " interlayer insulating film resin combination ") and it is used to form the copper foil of wiring layer with pressure setting at high temperature It pressurizes for a long time, thus makes interlayer insulating film resin combination heat cure, obtain the interlayer insulating film with copper foil, so The via hole (Japanese: ビ ア ホ ー Le) for forming interlayer connection using boring method, laser method etc. as needed afterwards, then passes through erosion Copper foil is removed and retains necessary part by quarter.

In addition, being wanted along with the miniaturization of multilayer printed circuit board as described above, lighting, densification of wiring etc. It asks, so-called " addition process " gradually causes to pay close attention to, the addition process are as follows: by interlayer insulating film resin combination and copper foil with very Dead level press is after the short time pressurizeed at high temperature, with drying machine etc. at high temperature by interlayer insulating film resin combination heat Solidification forms the via hole of interlayer connection with boring method, laser method etc. as needed, is formed by plating in necessary part Wiring layer.

As the interlayer insulating film resin combination used in lamination mode, main use is by aromatic system asphalt mixtures modified by epoxy resin Rouge, with curing agent (such as phenol system curing agent, amine system curing agent, the carboxylic serials curing agent with the reactive hydrogen for epoxy resin Deng) the organic insulation resin that is combined with.Although flat using these curing agent and for the use of solidfied material physical property obtained by solidifying it Weigh excellent, but the high hydroxyl of polarity generated due to epoxy group and reacting for reactive hydrogen, thus exist cause water absorption rate to rise, phase The problem of to the decline of the electrical characteristics such as dielectric constant, dielectric loss angle tangent.In addition, being generated in the case where using these curing agent The impaired problem of the storage stability of resin combination.

On the other hand, it is known that the cyanate esters with cyanato of Thermocurable can provide the excellent solidification of electrical characteristics Object.But cyanato for example needs 230 DEG C, 120 minutes or more etc of height by the reaction that heat cure forms s-triazine ring The solidification of warm lower long period, therefore the interlayer insulating film as the multilayer printed circuit board made by above-mentioned lamination mode It is not appropriate for resin combination.

Method as the solidification temperature for reducing cyanate esters, it is known that and with cyanate esters and epoxy resin, And make its cured method using curing catalysts (for example, referring to patent document 1 and 2).

In addition, for laminated layer, the demand of the amount of warpage after processing dimension stability, reduction semiconductor installation, It is required that low thermal coefficient of expansion (low CTEization), and take the behave suitable for low CTEization (for example, referring to patent document 3~5). As the method for most mainstream, mostly by making silica filler height fillingization (for example, making the 40 mass % or more in laminated layer For silica filler) realize the low CTEization of laminated layer.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2013-40298 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2010-90237 bulletin

Patent document 3: Japanese Unexamined Patent Application Publication 2006-527920 bulletin

Patent document 4: Japanese Unexamined Patent Publication 2007-87982 bulletin

Patent document 5: Japanese Unexamined Patent Publication 2009-280758 bulletin

Summary of the invention

Problems to be solved by the invention

Lamination is difficult to be utilized if making silica filler height fillingization to realize the low CTEization of laminated layer in [a] Material is embedded to the concave-convex tendency of the wiring pattern of internal layer circuit.Furthermore, it desired to be embedded to through-hole (Japanese: ス using lamination material ル ー ホ ー Le) etc internal layer circuit, to reduce bumps.If making silica to realize the low CTEization of lamination material Filler height fillingization then has the tendency that being difficult to meet these requirements.

1st invention is completed to solve such project, even if it is intended that providing makes silica filler The adhesive film of the imbedibility also excellent multilayer printed circuit board of high fillingization, bumps.

[b] is in addition, for the interlayer insulating film resin combination of previous multilayer printed circuit board, it is difficult to make While heat resistance and high insulating reliability, keep operability when film excellent.

2nd invention is completed to solve such project, is combined it is intended that providing using thermosetting resin Interlayer insulating film resin film and multi-layer resinous film with the interlayer insulating film resin film and supporting mass that object is formed, with And multilayer printed circuit board and its manufacturing method, above-mentioned compositions of thermosetting resin are that heat resistance and insulating reliability are high, simultaneously Operational excellent compositions of thermosetting resin when film.

The means used to solve the problem

Further investigation has been repeated in order to solve above-mentioned 1st project in [a] the inventors of the present invention, as a result, it has been found that, by making With the resin combination comprising specific novolac type phenolic resin, specific epoxy resin and specific inorganic filling material Object, and it is able to solve above-mentioned 1st project, so that the invention was completed.That is, the 1st invention provides following adhesive film.

(1) a kind of adhesive film of multilayer printed circuit board has resin combination forming layer on supporting mass film Made of resin composition layer, above-mentioned resin combination includes: the dispersion ratio of (A) weight average molecular weight Mw and number-average molecular weight Mn Novolac type phenolic resin that Mw/Mn is 1.05~1.8, epoxy resin shown in (B) the following general formula (1) and (C) is inorganic fills out Fill material, wherein the average grain diameter of (C) inorganic filling material in the resin composition layer is 0.1 μm or more, and (C) is inorganic to be filled out The content of material is filled for 20 mass of mass %~95 % in resin solid content.

[changing 1]

(in formula, p indicates 1~5 integer.)

[b] the inventors of the present invention are furtherd investigate repeatedly in order to solve above-mentioned 2nd project, as a result, it has been found that: by In compositions of thermosetting resin containing epoxy resin, curing agent, inorganic filling material and antioxidant, specific solidification is combined Agent and specific antioxidant, so as to solve above-mentioned 2nd project, so that completing the present invention.Still further, it was discovered that: pass through In the compositions of thermosetting resin containing epoxy resin, curing agent, inorganic filling material and specific compound, combine specific Curing agent and specific compound, also can solve above-mentioned 2nd project so that complete the present invention.

That is, the 2nd invention provides following [1]~[23].

[1] a kind of interlayer insulating film resin film, be using containing (a) epoxy resin, (b) curing agent, (c) is inorganic fills out The interlayer insulating film resin film for filling the compositions of thermosetting resin of material and (d) antioxidant and being formed,

Above-mentioned (b) curing agent includes to contain selected from (b1) active ester system curing agent, (b2) cyanate system's curing agent and (b3) It is at least one kind of in the phenol novolak system curing agent of triazine ring, and (d) antioxidant is hindered phenolic antioxidant.

[2] the interlayer insulating film resin film according to above-mentioned [1], wherein, above-mentioned hindered phenolic antioxidant includes It is at least one kind of in compound and the following general formula (dII) compound represented with group shown in the following general formula (dI).

[changing 2]

(in formula (dI), R^d1、R^d2And R^d3Separately indicate the alkyl of hydrogen atom or carbon number 1~8.Wherein, R^d1And R^d2 In at least one indicate carbon number 1~8 alkyl.)

[changing 3]

(in formula (dII), R^d4And R^d5Separately indicate the alkyl of carbon number 1~8.R^d6、R^d7And R^d8Independently earth's surface Show the alkyl of hydrogen atom or carbon number 1~8.Wherein, R^d6、R^d7And R^d8In at least one indicate carbon number 1~8 alkyl.)

[3] the interlayer insulating film resin film according to above-mentioned [2], wherein there is base shown in above-mentioned general formula (dI) The compound of group is any of the following general formula (dI-1)~(dI-3) compound represented.

[changing 4]

(in formula (dI-1) and (dI-2), R^d11、R^d12、R^d13、R^d21、R^d22And R^d23Separately indicate hydrogen atom or The alkyl of carbon number 1~8.Wherein, R^d11And R^d12In at least one and R^d21And R^d22In at least one indicate carbon number 1~8 Alkyl.X¹And X²Separately indicate the organic group of 1~trivalent.n¹And n²It is separately 1~3 integer.)

[changing 5]

(in formula (dI-3), R^d31And R^d32Separately indicate the alkyl of carbon number 1~8.Y expression-COOCH₂,- COOCH₂CH₂?.)

[4] the interlayer insulating film resin film according to above-mentioned [3], wherein, above-mentioned hindered phenolic antioxidant is choosing From at least one kind of in above-mentioned general formula (dI-1) compound represented and above-mentioned general formula (dI-2) compound represented, and molecule Amount is 1,500 or less.

[5] a kind of interlayer insulating film resin film is comprising (a) epoxy resin, (b) curing agent, (c) inorganic fill material Material and (d ') are selected from the compound and the following general formula (dII) compound represented with group shown in the following general formula (dI) At least one kind of interlayer insulating film resin film,

Above-mentioned (b) curing agent includes to contain selected from (b1) active ester system curing agent, (b2) cyanate system's curing agent and (b3) It is at least one kind of in the phenol novolak system curing agent of triazine ring.

[changing 6]

(in formula (dI), R^d1、R^d2And R^d3Separately indicate the alkyl of hydrogen atom or carbon number 1~8.Wherein, R^d1And R^d2 In at least one indicate carbon number 1~8 alkyl.)

[changing 7]

(in formula (dII), R^d4And R^d5Separately indicate the alkyl of carbon number 1~8.R^d6、R^d7And R^d8Independently earth's surface Show the alkyl of hydrogen atom or carbon number 1~8.Wherein, R^d6、R^d7And R^d8In at least one indicate carbon number 1~8 alkyl.)

[6] the interlayer insulating film resin film according to above-mentioned [5], wherein there is base shown in above-mentioned general formula (dI) The compound of group is any of the following general formula (dI-1)~(dI-3) compound represented.

[changing 8]

(in formula (dI-1) and (dI-2), R^d11、R^d12、R^d13、R^d21、R^d22And R^d23Separately indicate hydrogen atom or The alkyl of carbon number 1~8.Wherein, R^d11And R^d12In at least one and R^d21And R^d22In at least one indicate carbon number 1~8 Alkyl.X¹And X²Separately indicate the organic group of 1~trivalent.n¹And n²It is separately 1~3 integer.)

[changing 9]

(in formula (dI-3), R^d31And R^d32Separately indicate the alkyl of carbon number 1~8.Y expression-COOCH₂,- COOCH₂CH₂?.)

[7] the interlayer insulating film resin film according to above-mentioned [6], wherein there is base shown in above-mentioned general formula (dI) The compound of group is in above-mentioned general formula (dI-1) compound represented and above-mentioned general formula (dI-2) compound represented It is at least one kind of, and molecular weight is 1,500 or less.

[8] the interlayer insulating film resin film according to any one of above-mentioned [1]~[7], wherein above-mentioned (b) solidification The functional group of agent sum relative to (a) epoxy resin epoxy group sum ratio [functional group of (b) curing agent it is total The sum of the epoxy group of number/(a) epoxy resin] it is 0.2~2.

[9] the interlayer insulating film resin film according to any one of above-mentioned [1]~[8], wherein (a) epoxy resin With selected from bisphenol A type epoxy resin, naphthalene type epoxy resin, the aralkyl novolac type epoxy resin with biphenyl backbone, It is at least one kind of in cresol novolac type epoxy resin.

[10] the interlayer insulating film resin film according to any one of above-mentioned [1]~[9], wherein above-mentioned (b) solidification Agent includes (b2) cyanate system curing agent.

[11] the interlayer insulating film resin film according to any one of above-mentioned [1]~[9], wherein above-mentioned (b) solidification Agent includes at least 1 in (b1) active ester system's curing agent and the phenol novolak system curing agent of (b3) containing triazine ring Kind.

[12] the interlayer insulating film resin film according to above-mentioned [1]~any one of [9] and [11], wherein (b3) Phenol novolak system curing agent containing triazine ring is comprising the phenol novolaks containing triazine ring and contains triazine ring At least one of cresol novolaks.

[13] the interlayer insulating film resin film according to any one of above-mentioned [1]~[12], wherein (c) is inorganic to be filled out Filling the content of material relative to the solid component of compositions of thermosetting resin is 30~90 mass %.

[14] the interlayer insulating film resin film according to any one of above-mentioned [1]~[13], wherein (c) is inorganic to be filled out It includes at least one kind of in spherical silicon dioxide and fused silica for filling material, and volume average particle size is 0.01~5 μ m。

[15] the interlayer insulating film resin film according to any one of above-mentioned [1]~[14], wherein thermosetting resin Composition also contains (e) phenoxy resin.

[16] the interlayer insulating film resin film according to above-mentioned [15], wherein (e) phenoxy resin has ester ring type Structure.

[17] the interlayer insulating film resin film according to any one of above-mentioned [1]~[16] is multi-sheet printed line Road plate is used.

[18] the interlayer insulating film resin film according to any one of above-mentioned [1]~[16] is multi-sheet printed line The laminated layer of road plate, which is formed, to be used.

[19] a kind of multi-layer resinous film, with interlayer insulating film resin described in any one of above-mentioned [1]~[16] Film and supporting mass.

[20] the multi-layer resinous film according to above-mentioned [19], wherein above-mentioned supporting mass is organic resin film, organic tree Adipose membrane with a thickness of 10~70 μm, and above-mentioned interlayer insulating film resin film with a thickness of 1~80 μm.

[21] a kind of multilayer printed circuit board, using selected from layer insulation described in any one of above-mentioned [1]~[16] At least one kind of in multi-layer resinous film described in layer resin film and above-mentioned [19] or [20] and obtain.

[22] a kind of semiconductor package body is to carry semiconductor element on the multilayer printed circuit board described in above-mentioned [21] Made of part.

[23] a kind of manufacturing method of multilayer printed circuit board is using described in any one of above-mentioned [1]~[16] The manufacturer of the multilayer printed circuit board of multi-layer resinous film described in interlayer insulating film resin film and above-mentioned [19] or [20] Method has process below:

(1) above-mentioned interlayer insulating film resin film and above-mentioned multi-layer resinous film are laminated in the one or two sides of circuit substrate Process.

(2) the resin film heat cure that will be laminated in process (1), the process for forming insulating layer.

(3) process that aperture is carried out to the circuit substrate for foring insulating layer in process (2).

(4) process of desmearing is removed.

(5) process that the surface of the insulating layer obtained in process (4) forms conductor layer by plating.

(6) by semi-additive process, in the process that conductor layer forms circuit.

Invention effect

[a] is according to the 1st invention, even if can provide makes silica filler height fillingization, concave-convex imbedibility is also excellent Multilayer printed circuit board adhesive film.

[b] according to the 2nd invention, can provide using compositions of thermosetting resin formed interlayer insulating film resin film, And multi-layer resinous film and multilayer printed circuit board and its manufacturer with the interlayer insulating film resin film and supporting mass Method, operational excellent thermosetting property tree when which is heat resistance and insulating reliability height while being film-made Oil/fat composition.

Specific embodiment

[a] the 1st invention

The adhesive film of multilayer printed circuit board of the invention have on supporting mass film by resin combination (hereinafter, Referred to as " adhesive film resin combination ") resin composition layer made of forming layer, which includes (A) Weight-average molecular Measure novolac type phenolic resin that the dispersion ratio (Mw/Mn) of (Mw) and number-average molecular weight (Mn) are 1.05~1.8 (hereinafter, Be only called " (A) novolac type phenolic resin "), epoxy resin shown in (B) above-mentioned general formula (1) is (hereinafter, be also only called " (B) Epoxy resin ") and (C) inorganic filling material, the average grain diameter of (C) inorganic filling material in the resin composition layer is 0.1 μm or more, the content of (C) inorganic filling material is 20~95 mass % in resin solid content.

[adhesive film resin combination]

Adhesive film resin combination includes (A) novolac type phenolic resin, (B) epoxy resin and (C) inorganic fill Material.Hereinafter, being illustrated to these each ingredients.

< (A) novolac type phenolic resin >

(A) novolac type phenolic resin is used as the curing agent of epoxy resin, and weight average molecular weight (Mw) is divided equally with number The range that the dispersion ratio (Mw/Mn) of son amount (Mn) is 1.05~1.8.

Such (A) novolac type phenolic resin for example can be by recording in No. 4283773 bulletins of Japanese Patent No. Manufacturing method manufacture.

That is, used as the phenolic compounds and aldehyde compound of raw material, as the phosphate cpd of acid catalyst, as reaction The non-reacted Aqueous organic solvent of secondary solvent, by the two separate state formed by these using such as mechanical stirring, Ultrasonic wave etc. is stirred mixing, and the multiphase reaction system for forming the gonorrhoea shape of two layers of (organic phase with water phase) blending (mutually separates Reaction), propulsion phenolic compounds is reacted with aldehyde compound, so as to synthetic condensation agent object (resin).

Then, for example, addition mixing water-insoluble organic solvent (such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.) dissolution is above-mentioned Condensation product, stopping are stirred and stand, and are separated into organic phase (organic solvent phase) and water phase (phosphate aqueous solution phase), remove water It mutually realizes recycling, on the other hand, after organic phase is carried out hot water wash and/or neutralized, is distilled to recover organic solvent, thus may be used With manufacture (A) novolac type phenolic resin.

The manufacturing method of above-mentioned novolac type phenolic resin is due to being utilized mutually separation reaction, and stirring efficiency is extremely It is important, from reaction efficiency aspect, it is generally desirable to miniaturize the two-phase in reaction system, increase the surface at interface as far as possible Product, thus can promote conversion of the phenolic compounds to resin.

As the phenolic compounds that may be used as raw material, for example, can enumerate: phenol；O-cresol；Metacresol；Paracresol；Two Cresols；Bisphenol compound；Ortho position substitution phenolic compounds of the ortho position with 3 or more carbon number, the alkyl of preferably carbon number 3~10；It is right Position has 3 or more carbon number, p-Substituted residue compound of alkyl of preferably carbon number 3~18 etc..These can be used alone, Also two or more kinds may be used.

Here, as bisphenol compound, for example, can enumerate: bisphenol-A, Bisphenol F, bis- (2- methylphenol) A, bis- (2- Methylphenol) F, bisphenol S, bis-phenol E, bisphenol Z etc..

As ortho position substitution phenolic compounds, for example, can enumerate: 2- propylphenol, 2- isopropyl-phenol, 2- Zhong Ding Base phenol, 2-TBP, 2- phenylphenol, 2- cyclohexylphenol, 2- nonyl phenol, 2- naphthalene phenol etc..

As p-Substituted residue compound, for example, can enumerate: 4- propylphenol, 4- isopropyl-phenol, 4- Zhong Ding Base phenol, 4-TBP, 4- phenylphenol, 4- cyclohexylphenol, 4- nonyl phenol, 4- naphthalene phenol, 4- ten Dialkyl group phenol, 4- octadecylphenol etc..

As the aldehyde compound that may be used as raw material, for example, can enumerate: formaldehyde, formalin, paraformaldehyde, trimerization Formaldehyde, acetaldehyde, para-acetaldehyde, propionic aldehyde etc..Among these, from the viewpoint of reaction speed, preferred paraformaldehyde.These can be with It is used alone a kind, also two or more kinds may be used.

The cooperation molar ratio (F/P) of aldehyde compound (F) and phenolic compounds (P) are preferably 0.33 or more, more preferably 0.40 It~1.0, is more preferably 0.50~0.90.It is available excellent by the way that molar ratio (F/P) will be cooperated to be set as in above range Yield.

Phosphate cpd performance as acid catalyst is formed in presence of water, between phenolic compounds mutually to be separated instead The important function in the place (Japanese: mutually separating anti-ying field) answered.As phosphate cpd, it is, for example, possible to use 89 mass % The aqueous solutions types such as phosphoric acid, 75 mass % phosphoric acid.Alternatively, it is also possible to as needed using such as polyphosphoric acid, phosphoric anhydride.

From the viewpoint of controlling phase separating effect, the content of phosphate cpd is for example relative to 100 mass of phenolic compounds Part is 5 mass parts or more, is preferably 25 mass parts or more, more preferably 50~100 mass parts.It should be noted that using 70 In the case where phosphate cpds more than mass parts, initial reaction stage is preferably inhibited by the investment in batches into reaction system Heat release, it is ensured that safety.

Non-reacted Aqueous organic solvent as reaction secondary solvent is particularly important to promoting mutually separation reaction to play Effect.As reaction secondary solvent, it is preferable to use being selected from alcoholic compound, polyalcohol system ether, cyclic ether compound, polyalcohol system At least one of ester, ketone compound, sulfoxide compound compound.

As alcoholic compound, for example, can enumerate: the monohydric alcohols such as methanol, ethyl alcohol, propyl alcohol；Butanediol, pentanediol, oneself two Alcohol, ethylene glycol, propylene glycol, trimethylene, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol etc. Dihydric alcohol；Trihydroxylic alcohols such as glycerol etc..

As polyalcohol system ether, for example, can enumerate: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, Ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, glycol dimethyl ether, ethylene glycol methyl ether, ethylene glycol glycol ethers etc..

As cyclic ether compound, for example, 1,3- dioxanes, Isosorbide-5-Nitrae-dioxanes etc. can be enumerated, as polyalcohol system Ester, for example, glycol ester compounds such as Ethylene glycol acetate etc. can be enumerated.As ketone compound, for example, can enumerate acetone, Methyl ethyl ketone (hereinafter also referred to as " MEK "), methyl iso-butyl ketone (MIBK) etc., as sulfoxide compound, for example, can enumerate dimethyl sulfoxide, Diethyl sulfoxide etc..

Among these, preferably glycol monoethyl ether, polyethylene glycol, Isosorbide-5-Nitrae-dioxanes.

Reaction secondary solvent be not limited to above-mentioned illustration, as long as with above-mentioned speciality and react when be in a liquid state it is anti- Secondary solvent is answered, then or solid, can be used individually, or two or more kinds may be used.

It as the use level of reaction secondary solvent, is not particularly limited, for example, being 5 relative to 100 mass parts of phenolic compounds It is more than mass parts, preferably 10~200 mass parts.

By also using surfactant in above-mentioned heterogeneous reaction process, so as to promote mutually to separate reaction, shorten Reaction time, moreover it is possible to facilitate yield raising.

As surfactant, for example, can enumerate: soap, alpha-alkene sulfonate, alkyl benzene sulphonate and its salt, alkyl sulfide The yin such as acid esters salt, alkyl ether sulphate salts, phenyl ether-ether salt, polyoxyethylene alkyl ether sulfuric acid, ether sulfonate, ether carboxylate Ionization series surfactant；Polyoxyethylene alkyl phenyl ether, polyoxyethylene styrene phenol ether, gathers at polyoxyalkylene alkyl Ethylene oxide alkyl amino ether, polyethylene glycol fatty race ester, aliphatic monoglyceride, sorbitane fatty race ester, pentaerythrite The nonionic surfactants such as aliphatic ester, polyoxyethylene polypropylene glycol, aliphatic alkanolamide；Monoalkyl ammonium chloride, two Cationic systems surfactants such as object etc. are closed in alkyl ammomium chloride, amino acid salinization (Japanese: ア ミ Application acid salt).

The use level of surfactant is not particularly limited, for example, being 0.5 mass relative to 100 mass parts of phenolic compounds Part or more, preferably 1~10 mass parts.

The amount of water in reaction system impacts phase separating effect, production efficiency, is generally calculated as 40 with quality criteria Quality % or less.By the amount of water is set as 40 mass % hereinafter, and can keep production efficiency well.

Phenolic compounds is different according to type, reaction condition of phenolic compounds etc. from the reaction temperature of aldehyde compound, does not have It is particularly limited to, usually 40 DEG C or more, preferably 80 DEG C~reflux temperature, more preferably reflux temperature.If reaction temperature is 40 DEG C or more, then sufficient reaction speed can be obtained.Reaction time is according in reaction temperature, the use level of phosphoric acid, reaction system Water content etc. and it is different, usually 1~10 hour or so.

In addition, as reaction environment, usually normal pressure, from the viewpoint of maintaining the features of the present invention, i.e. heterogeneous reaction, It can also be reacted under elevated pressure or under decompression.Such as under the pressurization of 0.03~1.50MPa, can be improved reaction speed, It is furthermore possible to use the low boiling point solvents such as methanol as reaction secondary solvent.

By the manufacturing method of above-mentioned (A) novolac type phenolic resin, weight average molecular weight (Mw) can be manufactured and number is equal The novolac type phenolic resin that the dispersion ratio (Mw/Mn) of molecular weight (Mn) is 1.05~1.8

Although also different according to the type of phenolic compounds, rubbed according to aldehyde compound (F) and the cooperation of phenolic compounds (P) Available for example following such (A) the novolac type phenolic resin of your range than (F/P).

Cooperate molar ratio (F/P) be 0.33 more than and less than 0.80 in the range of, can be manufactured with high yield following Novolac type phenolic resin: in the measuring method of the area-method based on gel permeation chromatography (GPC), the monomer of phenolic compounds at Point content be, for example, 3 mass % or less, preferably 1 mass % hereinafter, the content of the dimer ingredient of phenolic compounds be, for example, 5~ 95 mass %, preferably 10~95 mass %, point of weight average molecular weight (Mw) and number-average molecular weight (Mn) furthermore based on GPC measurement Dissipating than (Mw/Mn) is 1.05~1.8, preferably 1.1~1.7.

As (A) novolac type phenolic resin, commercially available product can be used, for example, " PAPS-PN2 " (rising sun can be enumerated Organic material Industrial Co., Ltd system, trade name), " PAPS-PN3 " (Asahi Organic Chem Ind's system, trade name) etc..

Adhesive film resin combination can be in a range that does not hinder the effect of the present invention and with (A) novolac type phenol Epoxy curing agent (being also only called " epoxy curing agent " below) other than urea formaldehyde.

As epoxy curing agent, for example, can enumerate: the various phenol in addition to (A) novolac type phenolic resin Urea formaldehyde compound, anhydride compound, amine compounds, hydrazide compound etc..As phenolic resin compound, for example, can lift Novolac type phenolic resin in addition to (A) novolac type phenolic resin, resol type phenol resin etc. out；As acid anhydrides Object is closed, for example, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methylnadic anhydride etc. can be enumerated.In addition, conduct Amine compounds, for example, dicyandiamide, diaminodiphenyl-methane, dicyandiamidines etc. can be enumerated.

In these epoxy curing agents, from the viewpoint of improving reliability, (A) novolac type phenolic aldehyde tree is preferably removed Novolac type phenolic resin other than rouge.

In addition, going out from the viewpoint of the peel strength of the non-electrolytic plating after the peel strength and chemistry roughening for improving metal foil Hair, preferably comprises the novolac type phenolic resin and dicyandiamide of triazine ring.

Novolac type phenolic resin in addition to (A) novolac type phenolic resin, can be used commercially available product, for example, Phenol novolaks such as " TD2090 " (Dainippon Ink Chemicals's systems, trade name), " KA-1165 " (DIC plants of formula meetings can be enumerated Society's system, trade name) etc. cresol novolaks etc..In addition, the city as the novolac type phenolic resin containing triazine ring Product are sold, for example, " Phenolite LA-1356 " (Dainippon Ink Chemicals's system, trade name), " Phenolite can be enumerated LA7050 series " (Dainippon Ink Chemicals's system, trade name) etc., as the commercially available product of the cresol novolaks containing triazine, example Such as, " Phenolite LA-3018 " (trade name, Dainippon Ink Chemicals's system) etc. can be enumerated.

< (B) epoxy resin >

(B) epoxy resin is epoxy resin shown in the following general formula (1).

[changing 10]

(in formula, p indicates 1~5 integer.)

As (B) epoxy resin, commercially available product can be used.As (B) epoxy resin of commercially available product, for example, can enumerate: " NC-3000 " (epoxy resin that the p in formula (1) is 1.7), " NC-3000-H " (asphalt mixtures modified by epoxy resin that the p in formula (1) is 2.8 Rouge) (being Nippon Kayaku K. K's system, trade name) etc..

Adhesive film resin combination can in a range that does not hinder the effect of the present invention comprising remove (B) epoxy resin with The epoxy resin etc. of the polymer types such as outer epoxy resin, phenoxy resin.

< curing accelerator >

From the viewpoint of the reacting of quickening (A) novolac type phenolic resin and (B) epoxy resin, adhesive film resin Composition may include curing accelerator.As curing accelerator for example, can enumerate: 2- phenylimidazole, 2- ethyl -4- The imidazolium compounds such as methylimidazole, 1- cyano ethyl -2- phenyl trimellitic acid imidazoles；The organic phosphorus compounds such as triphenylphosphine； The salt such as Peng Suan Phosphonium；The amines such as 1,8- diazabicyclo endecatylene；3- (3,4- dichlorophenyl) -1,1- dimethyl urea Deng.These can be used alone or two or more kinds may be used.

< (C) inorganic filling material >

Adhesive film resin combination includes (C) inorganic filling material that average grain diameter is 0.1 μm or more.

As (C) inorganic filling material, for example, can enumerate: silica, aluminium oxide, barium sulfate, talcum, clay, cloud Female powder, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesia, boron nitride, aluminium borate, barium titanate, strontium titanates, metatitanic acid Calcium, bismuth titanates, titanium oxide, barium zirconate, calcium zirconate etc..These can be used alone or two or more kinds may be used.These In, from the viewpoint of reducing the thermal expansion coefficient of interlayer insulating film for being solidified to form adhesive film, preferred silica.

(C) shape of inorganic filling material is not particularly limited, from be easy to will be formed in through-hole that internal layer circuit is formed and It is preferably spherical from the perspective of the concave-convex embedment of circuit pattern.

(C) average grain diameter of inorganic filling material is 0.1 μm or more, excellent from the viewpoint of obtaining excellent imbedibility It is selected as 0.2 μm or more, more preferably 0.3 μm or more.

From the viewpoint of imbedibility, the content of inorganic filling material of the average grain diameter less than 0.1 μm is in terms of solid component Preferably 3vol% hereinafter, more preferably 1vol% hereinafter, further preferably being filled out without containing inorganic less than 0.1 μm of average grain diameter Fill material.It should be noted that (C) inorganic filling material can be used alone or two or more kinds may be used, in addition, The inorganic filling material of different average grain diameters can be used in mixed way.

As (C) inorganic filling material, commercially available product can be used.As (C) inorganic filling material of commercially available product, for example, It can enumerate: " SO-C1 " (average grain diameter: 0.25 μm), " SO-C2 " (average grain diameter: 0.5 μ as spherical silica M), " SO-C3 " (average grain diameter: 0.9 μm), " SO-C5 " (average grain diameter: 1.6 μm), " SO-C6 " (average grain diameter: 2.2 μm) (all Co., Ltd. Admatechs systems) etc..

(C) surface treatment has can be implemented in inorganic filling material.For example, use silica as (C) inorganic fill In the case where material, as surface treatment, it is possible to implement silane coupling agent processing.As silane coupling agent, for example, can lift Out: amino silicane coupling agent, vinyl silicane coupling agent, epoxy silane coupling agent etc..In these, preferably it is coupled with amino silane Agent implements the silica of surface treatment.

Adhesive film is defined in the following way with the amount of (C) inorganic filling material in resin combination.Firstly, will be Cambial resin combination is 30 minutes dry with 200 DEG C on supporting mass film, removes solvent contained in resin combination, measurement Weight (solid component) after removing solvent.The amount of (C) inorganic filling material contained in the solid component is defined as resin The amount of (C) inorganic filling material in solid component.

In addition, the measuring method as (C) inorganic filling material, if precalculating (C) the inorganic fill material to be cooperated The amount of the solid component of material then can easily find out the ratio in solid component.It is described below to use (C) that is scattered in solvent Calculated example when inorganic filling material (hereinafter also referred to " (C) inorganic filling material dispersion liquid ").

About the solid component of (C) inorganic filling material in (C) inorganic filling material dispersion liquid, with 200 DEG C dry 30 It is calculated after minute, result is 70 mass %.Match compound resin composition using (C) the inorganic filling material dispersion liquid 40g As a result, the total amount of obtained resin combination be 100g.The resin combination of 100g is 30 minutes dry with 200 DEG C, it surveys The weight of solid component after fixed drying, result 60g.The amount of (C) inorganic filling material contained in solid component be 40g × 70 mass %=28g, therefore the amount of (C) inorganic filling material in resin solid content can be in the hope of for 28/60=47 matter It measures % (46.6 mass %).

From the viewpoint of the thermal expansion coefficient for reducing the interlayer insulating film after heat cure, in adhesive film resin combination (C) inorganic filling material amount it is more how the more preferred, but from the bumps for the wiring pattern that will be formed by internal layer circuit substrate and From the perspective of through-hole embedment, there are inorganic filling material amounts appropriate.From such a viewpoint, (C) inorganic filling material Content in resin solid content be 20~95 mass %, preferably 30~90 mass %, more preferably 50~90 mass %. If the content of (C) inorganic filling material is 20 mass % or more, thermal expansion coefficient can reduce；If 95 mass % hereinafter, Imbedibility can be then kept well.

< fire retardant >

Adhesive film resin combination can also contain fire retardant.

It as fire retardant, is not particularly limited, for example, inorganic fire retardants, resin fire retardant etc. can be enumerated.

As inorganic fire retardants, for example, can enumerate: aluminium hydroxide, the hydrogen-oxygen illustrated as (C) inorganic filling material Change magnesium etc..

It can be halogen system resin as resin fire retardant, or non-halogen resin, but in view of environment is negative Load, then it is preferable to use non-halogen resins.The substance that resin fire retardant can both have been cooperated in the form of packing material, can also be with For the substance with the functional group reacted with heat-curing resin.

Commercially available product can be used in resin fire retardant.As in the form of packing material come the commercially available of the resin fire retardant that cooperates Product, for example, can enumerate: as aromatic phosphoric ester flame retardant " PX-200 " (Daihachi Chemical Industry Co., Ltd.'s system, Trade name), as " ExolitOP930 " (the Clariant Japan Co. Ltd. system, trade name) of polyphosphate compounds etc..

As the commercially available product of the resin fire retardant with the functional group reacted with heat-curing resin, epoxy can be enumerated Phosphonium flame retardant, phenol system phosphonium flame retardant etc..As epoxy phosphonium flame retardant, for example, can enumerate: " FX-305 " (new day Iron lives aurification Co. Ltd. system, trade name) etc.；As phenol system phosphonium flame retardant, for example, " HCA-HQ " (three light can be enumerated Co. Ltd. system, trade name), " XZ92741 " (DOWCHEMICAL corporation, trade name) etc..These can be used alone, Also two or more kinds may be used.

< solvent >

From the viewpoint of being efficiently formed layer, adhesive film preferably comprises solvent with resin combination.As solvent, example Such as, it can enumerate: the ketone compounds such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Ethyl acetate, butyl acetate, cellosolve The acetate compounds such as acetic acid esters, propylene glycol methyl ether acetate, carbitol acetate；Cellosolve, methyl carbitol, butyl card It must the carbitols compound such as alcohol；The aromatic hydrocarbon compounds such as toluene, dimethylbenzene；Dimethylformamide, dimethyl acetamide, N- Methyl pyrrolidone, diethylene glycol dimethyl ether, propylene glycol monomethyl ether etc..These can be used alone, and also can be used together 2 kinds More than.

< residual solvent amount >

Residual solvent amount in adhesive film of the invention different, preferably 1~20 mass % according to used material, More preferably 2~15 mass %, further preferably 2~10 mass %.If residual solvent amount is 1 mass % or more, it is bonded The operability of film improves, for example, being able to suppress when being cut off with cutter powder falling occurs, rupture occurs etc..On the other hand, if 20 Quality % is hereinafter, then inhibit tacky, batching for film becomes easy with uncoiling.In addition, in order to uncoiling, mostly after the drying viscous The varnish applicator surface setting protective film for connecing film, if residual solvent amount be 20 mass % hereinafter, if protective film with it is of the invention bonding Removing between film becomes easy.

In addition, since residual solvent can be removed in the process of production multilayer printed circuit board by dry and heat cure It goes, therefore from the viewpoint of meeting environment, it is preferably less, it is also excellent in order to reduce the Thickness Variation before and after dry and heat cure It selects less.

It should be noted that when manufacturing adhesive film of the invention, preferably according to the side for the residual solvent amount for reaching target Formula determines drying condition.Type, amount of solvent of drying condition solvent according to contained in above-mentioned resin combination etc. without Together, therefore preferably grope after condition to determine again in advance by each applying device.

Here, the residual solvent amount in the present invention refers to: the ratio of solvent contained in the resin composition layer of supporting mass film Example (quality %), can be such as definition of getting off.

Firstly, weight (the W of measurement supporting mass film_a), measurement is formed on the weight (W after resin composition layer_b).So Afterwards, supporting mass film and the resin composition layer being formed on are placed 10 minutes in 200 DEG C of drying machine, after measurement is dry Weight (W_c).Obtained weight (W can be used_a)~(W_c) calculated by following formula.

The ratio (quality %) of solvent=(1- ((W_c)-(W_a))/((W_b)-(W_a)))×100

The other ingredient > of <

Adhesive film of the invention can contain other ingredients in a range that does not hinder the effect of the present invention.As it is other at Point, it can be cited for example that: the thickeners such as ORBEN, bentonite (Japanese: ベ Application ト Application)；The ultraviolet radiation absorptions such as thiazole system, triazole system Agent；Silane coupling agent etc. touches imparting agent；The colorants such as phthalocyanine blue, phthalocyanine green, iodine is green, dual-azo yellow, carbon black；It is other than the above Any resin component etc..

[supporting mass film]

Supporting mass film in the present invention refers to: as the film of the supporting mass when manufacturing adhesive film of the invention, manufacturing When multilayer printed circuit board, usually finally it is stripped or removes.

It as supporting mass film, is not particularly limited, for example, can enumerate: organic resin film, metal foil, processing release paper etc..

It as the material of organic resin film, can enumerate: the polyolefin such as polyethylene, polyvinyl chloride；Poly terephthalic acid second The polyester such as diol ester (hereinafter also referred to " PET "), polyethylene naphthalate；Polycarbonate, polyimides etc..In these, From the viewpoint of price and operability, preferably PET.

As metal foil, copper foil, aluminium foil etc. can be enumerated.In the case where using copper foil as supporting mass, can also incite somebody to action Copper foil is directly as conductor layer and forms circuit.In this case, as copper foil, calendering copper, electrolytic copper foil etc. can be used.Separately Outside, the thickness of copper foil is not particularly limited, it is, for example, possible to use the copper foils of the thickness with 2~36 μm.Using thickness compared with In the case where thin copper foil, from the viewpoint of improving workability, the copper foil with carrier can be used.

Demoulding processing, corona treatment, sided corona treatment etc. can be implemented to these supporting mass films and aftermentioned protective film Surface treatment.It handles, can enumerate as demoulding: based on organic siliconresin system release agent, alkyd resin system release agent, fluororesin It is the demoulding processing etc. of release agent etc..

The thickness of supporting mass film is not particularly limited, it is preferably 10~120 μm, more excellent from the viewpoint of operability It is selected as 15~80 μm, further preferably 15~70 μm.

Supporting mass film is not necessarily to be as described above single component, can also use the difference of multilayer (2 layers or more) Material is formed.

If showing the example that supporting mass film is 2 layers of structure, for example, can enumerate: being made using above-mentioned cited supporting mass film For the 1st layer of supporting mass film, and have by the layer of the formation such as epoxy resin, the curing agent of epoxy resin, packing material as the 2nd The structure of layer.Material used in 2nd layer can also use material cited in material used in adhesive film of the invention Material.

The layer (the 2nd layer and after, can be 2 layers or more of multilayer) formed on the 1st layer of supporting mass film is intended to tax The layer for giving function and making, for example, can be for raising with copper-plated cementability the purpose of and use.

It as the 2nd layer of forming method, is not particularly limited, for example, following methods can be enumerated: will dissolve in a solvent And varnish obtained by each material is dispersed with coated on the 1st layer of supporting mass film and dry method.

In the case that supporting mass film is formed by multilayer, the thickness of the 1st layer of supporting mass film is preferably 10~100 μm, more excellent It is selected as 10~60 μm, further preferably 13~50 μm.

The thickness for being formed in the layer on the 1st layer of supporting mass film (the 2nd layer and after, can be 2 layers or more of multilayer) is excellent It is selected as 1~20 μm.If 1 μm or more, then the function of wanting performance can be played, in addition, if 20 μm hereinafter, then as bearing The economy of body film is excellent.

In the case where supporting mass film is formed with multilayer, when removing supporting mass film, also can be separated into and the present invention Adhesive film be formed together in multilayer printed circuit board side and remaining layer (can be 2 layers or more) and to remove or remove Layer (can be 2 layers or more).

[protective film]

Adhesive film of the invention can have protective film.Protective film be arranged in adhesive film be equipped with supporting mass face phase The film in the face of anti-side is used for preventing foreign matter etc. to be attached to adhesive film and the purpose scratched.Passing through lamination, hot pressing Protective film is removed Deng before adhesive film of the invention is layered in circuit substrate etc..

It as protective film, is not particularly limited, material same as supporting mass film can be used.Do not have to the thickness of protective film It is particularly limited to, it is, for example, possible to use the protective films of the thickness with 1~40 μm.

[manufacturing method of adhesive film]

Adhesive film of the invention can be manufactured by applying adhesive film resin combination and drying on supporting mass film. Obtained adhesive film can coil into web-like to save and store.More specifically, for example, can manufacture in the following way: After dissolving above-mentioned each resin component in above-mentioned organic solvent, mixes (C) inorganic filling material etc. and prepare adhesive film resin The varnish is coated on supporting mass film by composition, through the dry organic solvent such as heating, heat blow, on supporting mass film Form resin composition layer.

It should be noted that the resin composition layer being formed on supporting mass film can be to make in adhesive film of the invention Uncured state obtained from it is dried, or the state of semi-solid preparation (second rank).

As the method for applying varnish on supporting mass film, it is not particularly limited, such as can be coated with using comma The method that applying device well known to machine, bar coater, kiss painting machine, roll coater, gravure coater, die coating machine etc. is applied.Coating Device is suitably selected according to target film thickness.

[b] the 2nd invention

Then, to the interlayer insulating film resin film of the 2nd invention, multi-layer resinous film and multilayer printed circuit board and its Manufacturing method is illustrated.

[interlayer insulating film resin film]

Compositions of thermosetting resin [hereinafter referred to as layer used in the formation of interlayer insulating film resin film of the invention Between resin compositions for insulating layer.] contain as previously described: (a) epoxy resin (hereinafter also referred to as " (a) ingredient "), (b) are following Specific curing agent (hereinafter also referred to as " (b) ingredient "), (c) inorganic filling material (hereinafter also referred to as " (c) ingredient ") and (d) following specific antioxidants (hereinafter also referred to as " (d) ingredient ") or (d ') following specific compounds (hereinafter also referred to as " (d ') ingredient ").

It should be noted that in general interlayer insulating film is otherwise referred to as interlayer dielectric with resin film.

< interlayer insulating film resin combination >

((a) epoxy resin)

(a) it is used as epoxy resin, is not particularly limited, for example, can preferably enumerate in 1 molecule with more than two The epoxy resin of epoxy group.

It as such (a) epoxy resin, can enumerate: epoxy resin, the glycidol amine of glycidol ether type Epoxy resin, epoxy resin of glycidyl ester-type of type etc..Among these, the preferred asphalt mixtures modified by epoxy resin of glycidol ether type Rouge.

(a) epoxy resin can also classify according to the difference of main framing, in the epoxy resin of above-mentioned each type, It can also classify are as follows: bisphenol A type epoxy resin (preferably bisphenol A-type liquid epoxy resin), bisphenol f type epoxy resin, bisphenol S The bisphenol-type epoxy resins such as type epoxy resin；Phenol novolak type epoxy resin, alkylphenol novolac type epoxy resin, Cresol novolac type epoxy resin, naphthols alkylphenol are copolymerized novolac type epoxy resin, bisphenol A novolac type ring oxygen The novolac type epoxy resins such as resin, Bisphenol F novolac type epoxy resin, aralkyl novolac type epoxy resin；Stilbene Type epoxy resin；Epoxy resin containing triazine skeleton；Epoxy resin containing fluorene skeleton；Naphthalene type epoxy resin；Triphenyl first Alkane type epoxy resin；Biphenyl type epoxy resin；Xylylene type epoxy resin；The ester ring types such as dicyclopentadiene-type epoxy resin Epoxy resin etc..(a) epoxy resin can be used alone or two or more kinds may be used.

As above-mentioned aralkyl novolac type epoxy resin, the aralkyl cresols copolymerization with naphthols skeleton can be enumerated Novolac type epoxy resin, aralkyl novolac type epoxy resin with biphenyl backbone etc. preferably have biphenyl backbone Aralkyl novolac type epoxy resin.

Among these, operability when heat resistance, insulating reliability and film, it is preferably selected from double It is at least one kind of in phenol-type epoxy resin and novolac type epoxy resin, more preferably it is selected from bisphenol A type epoxy resin, cresols At least 1 in novolac type epoxy resin, aralkyl novolac type epoxy resin and bisphenol A novolac type epoxy resin Kind.In addition, as the aralkyl novolac type epoxy resin, more preferably with the aralkyl novolac type of biphenyl backbone Epoxy resin.

In the case where being used in combination of two or more (a) epoxy resin, preferably bisphenol A type epoxy resin and aralkyl line style phenolic aldehyde The combination of type epoxy resin (especially with the aralkyl novolac type epoxy resin of biphenyl backbone) or cresol novolac The combination of type epoxy resin and bisphenol A novolac type epoxy resin.

(especially there is biphenyl containing bisphenol A type epoxy resin and aralkyl novolac type epoxy resin in combination The aralkyl novolac type epoxy resin of skeleton) in the case where, content ratio (bisphenol A type epoxy resin/aralkyl line style Phenol aldehyde type epoxy resin) from the viewpoint of heat resistance, insulating reliability and film when operability, preferably 15/85~ 50/50, more preferably 15/85~45/55, further preferably 20/80~40/60.

In addition, in being applied in combination with cresol novolac type epoxy resin and bisphenol A novolac type epoxy resin In the case of, content ratio (cresol novolac type epoxy resin/bisphenol A novolac type epoxy resin) from heat resistance, absolutely From the perspective of operability when edge reliability and film, preferably 50/50~85/15, more preferably 45/55~85/15, Further preferably 55/45~75/25.

Here, the aralkyl novolac type epoxy resin with biphenyl backbone refers to, biphenyl derivatives are contained in molecule Aromatic ring aralkyl novolac type epoxy resin, can enumerate comprising structural unit shown in the following general formula (a1) Epoxy resin etc..

[changing 11]

In general formula (a1), R^a1Indicate hydrogen atom or methyl.

In epoxy resin comprising structural unit shown in general formula (a1), structural unit shown in general formula (a1) content Operability when heat resistance, insulating reliability and film, preferably 50~100 mass %, more preferably 70 ~100 mass %, further preferably 80~100 mass %.

As the epoxy resin comprising structural unit shown in general formula (a1), for example, the following general formula (a1-1) can be enumerated Shown in epoxy resin.

[changing 12]

In general formula (a1-1), R^a1With above-mentioned just as m¹Indicate 1~20 integer.More than two R^a1It each other can be identical It can also be different, but preferably identical.

In addition, bisphenol A novolac type epoxy resin can be indicated by the following general formula (a2).

[changing 13]

In general formula (a2), m²Indicate 1~10 integer.

In addition, (a) epoxy resin can contain and have family from the viewpoint of improving the operability of interlayer insulating film resin film The lower epoxy resin for liquid of temperature is (hereinafter, sometimes referred to simply as liquid-state epoxy resin.).As liquid-state epoxy resin, without special Limitation, can enumerate the liquid-state epoxy resin etc. of 2 function such as bisphenol A-type liquid epoxy resin.Contain liquid in (a) epoxy resin In the case where epoxy resin, content is from the viewpoint of improving the operability of interlayer insulating film resin film, relative to (a) ring Oxygen resin is preferably 10~60 mass %, more preferably 10~50 mass %, further preferably 10~40 mass %.

As (a) epoxy resin, commercially available product can be used.As (a) epoxy resin of commercially available product, can enumerate: " NC- 3000-H ", " NC-3000-L ", " NC-3100 ", " NC-3000 " (more than, Nippon Kayaku K. K's system, trade name, Aralkyl novolac type epoxy resin with biphenyl backbone), " NC-7000-L " (Nippon Kayaku K. K's system, commodity Name, naphthols novolac type epoxy resin), " jER828 " (Mitsubishi chemical Co., Ltd's system, trade name, bisphenol type epoxy tree Rouge), " jER157S70 " (Mitsubishi chemical Co., Ltd's system, trade name, bisphenol A novolac type epoxy resin) etc..

(a) operability of the epoxide equivalent of epoxy resin when heat resistance, insulating reliability and film, Preferably 150~500g/eq, more preferably 150~400g/eq, further preferred 170~350g/eq, particularly preferably 200 ~320g/eq, and it is possible to be 170~230g/eq, or 250~320g/eq.

Here, epoxide equivalent is the quality (g/eq) of the resin of per unit epoxy group, it can be according to JISK7236 (2001 Year) as defined in method measure.Specifically, it acquires in the following manner: using M Co., Ltd. itsubishi Chemical The automatic titration device " GT-200 type " of Analytech weighs epoxy resin 2g in 200ml beaker, and methyl ethyl ketone is added dropwise 90ml adds glacial acetic acid 10ml and cetrimonium bromide 1.5g, with 0.1mol/L's after ultrasonic cleaner dissolution Perchloric acid/acetic acid solution is titrated.

The content of (a) epoxy resin in interlayer insulating film resin combination is from heat resistance, insulating reliability and is film-made When operability from the perspective of, relative to interlayer insulating film resin combination solid component (here, remove (c) it is inorganic Packing material.) 100 mass parts are preferably 20~80 mass parts, more preferably 30~70 mass parts, further preferably 35~60 Mass parts.

Here, " solid component " in the present invention is unless otherwise specified, then refers to and remove the volatility such as organic solvent Nonvolatile component after ingredient, expression non-volatile and remaining ingredient when keeping compositions of thermosetting resin dry, also includes room temperature It is down liquid, malt sugar shape and wax-like ingredient.Here, room temperature indicates 25 DEG C in this specification.

((b) curing agent)

In the present invention, (b) curing agent includes selected from (b1) active ester system curing agent, (b2) cyanate system's curing agent and (b3) It is at least one kind of in phenol novolak system curing agent containing triazine ring.Use the feelings of more than two kinds in above-mentioned (b1)~(b3) It under condition, is not particularly limited, but operability when heat resistance, insulating reliability and film, preferably (b1) is living Property the ester system curing agent and combination of (b2) cyanate system curing agent, (b1) active ester system's curing agent and the benzene of (b3) containing triazine ring The combination of phenol line style phenolic aldehyde system curing agent.

Furthermore it is possible to which above-mentioned (b1) that is used in combination of two or more, above-mentioned (b2) that also two or more kinds may be used, can also be used in combination Above-mentioned (b3) of more than two kinds.

< (b1) active ester system curing agent >

(b1) as long as active ester system curing agent is functioned as the curing agent of (a) epoxy resin and active ester, It is not particularly limited.If containing (b1) active ester system curing agent, has the tendency that dielectric loss angle tangent reduction.

As (b1) active ester system curing agent, phenol esters, benzenethiol esters, N- hydroxylamine esters, heterocycle can be used Ester compounds of hydroxy kind etc. with ester group with high reactivity, the compound of solidification with epoxy resin etc..

As (b1) active ester system curing agent, there is the compound of more than two active ester groups in preferably 1 molecule, it is more excellent There is two or more in 1 molecule that choosing is obtained by the compound with polybasic carboxylic acid and the aromatic compound with phenolic hydroxyl group Active ester groups aromatic compound, further preferably by 1 molecule at least two carboxylic acid compound and It is that aromatic compound with phenolic hydroxyl group obtains, in molecule with more than two ester groups aromatic compound.In addition, (b1) in active ester system curing agent, straight-chain or highly branched chain shape macromolecule be may include.

Compound in above-mentioned 1 molecule at least two carboxylic acid is if the compound comprising aliphatic chain, then The intermiscibility that can be improved (a) epoxy resin Yu (b2) cyanate ester resin can then be mentioned if the compound with aromatic ring High-fire resistance.Especially from the viewpoint of heat resistance etc., (b1) active ester system's curing agent is preferably by carboxylic acid compound and phenol The active ester compound that compound or naphthol compound obtain.

As carboxylic acid compound, can enumerate: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), pyromellitic acid etc..Among these, from the viewpoint of heat resistance, preferably succinic acid, Malaysia Acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), more preferable M-phthalic acid, terephthalic acid (TPA).

As thiocarboxylic acid compound, thioacetic acid, thiobenzoate etc. can be enumerated.

It as phenolic compounds or naphthol compound, can enumerate: quinhydrones, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenol Phthalein quinoline (Japanese: Off ェ ノ ー Le Off タ リ Application), methylation bisphenol-A, methylation Bisphenol F, methylation bisphenol S, phenol, o-cresol, Metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy Base naphthalene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, bicyclopentadiene Biphenol, phenol novolak (Japanese: Off ェ ノ ー Le ノ ボ ラ ッ Network) etc..Among these, from heat resistance and deliquescent sight Point sets out, preferably bisphenol-A, Bisphenol F, bisphenol S, methylation bisphenol-A, methylation Bisphenol F, methylation bisphenol S, catechol, 1, 5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxy Benzophenone, phloroglucin, benzenetriol, bicyclopentadiene biphenol, phenol novolak, more preferable catechol, 1,5- bis- Hydroxyl naphthalene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxy hexichol first Ketone, phloroglucin, benzenetriol, bicyclopentadiene biphenol, phenol novolak, further preferred 1,5- dihydroxy naphthlene, 1, 6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, two rings penta Diene biphenol, phenol novolak, particularly preferred dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, Bicyclopentadiene biphenol, phenol novolak, highly preferred bicyclopentadiene biphenol, phenol novolak, most preferably two rings Pentadiene biphenol.

As mercaptan compound, dimercaptobenzene, two mercaptan of triazine etc. can be enumerated.

As (b1) active ester system curing agent, activity disclosed in Japanese Unexamined Patent Publication 2004-277460 bulletin can be used Ester system curing agent, furthermore it is also possible to use commercially available product.

As (b1) the active ester system curing agent of commercially available product, can enumerate: the change comprising bicyclopentadiene biphenol structure Object, the acetylate of phenol novolak, benzoylate of phenol novolak etc. are closed, preferably includes two among these The compound of cyclopentadiene biphenol structure.It specifically, can be with as the compound comprising bicyclopentadiene biphenol structure It enumerates: " EXB9451 " (active ester groups equivalent: about 220g/eq), " EXB9460 ", " EXB9460S-65T ", " HPC-8000- 65T " (active ester groups equivalent: about 223g/eq) (the above are Dainippon Ink Chemicals's systems, trade name), the second as phenol novolak Acylate can enumerate " DC808 " (Mitsubishi chemical Co., Ltd's system, active ester groups equivalent: about 149g/eq), as phenol line The benzoylate of type phenolic aldehyde can enumerate " YLH1026 " (Mitsubishi chemical Co., Ltd's system, active ester groups equivalent: about 200g/ Eq) etc..

(b1) manufacturing method of active ester system curing agent is not particularly limited, and can be manufactured by well known method.Specifically For, carboxylic acid compound and/or thiocarboxylic acid compound, the condensation with hydroxy compounds and/or mercaptan compound can be passed through It reacts and obtains.

((b2) cyanate system curing agent)

As (b2) cyanate system curing agent, well known cyanate ester resin can be used, as the cyanate ester resin, example Such as, it can preferably enumerate: with the cyanate ester resin of more than two cyanatos in 1 molecule.

Can specifically enumerate as (b2) cyanate system curing agent: 2,2- bis- (4- cyanatophenyl) propane are [double Phenol A type cyanate ester resin], bis- (4- cyanatophenyl) ethane [bisphenol E-type cyanate resin], bis- (3,5- dimethyl -4- cyanogen Acyl phenyl) methane [tetramethyl bisphenol F cyanate resin], bis- (4- the cyanatophenyl) -1,1,1,3,3,3- hexafluoros of 2,2- The bisphenol types cyanate ester resins such as propane [hexafluoro bisphenol-a type cyanate ester resin]；The cyanate of phenol addition bicyclopentadiene polymer The dicyclopentadiene-types cyanate ester resin such as compound；Phenol novolak type cyanate esters, cresol novolac type cyanic acid The novolac types cyanate ester resin such as ester compounds；α, α '-bis- (4- cyanatophenyl)-diisopropyl benzenes；These cyanates Prepolymer (hereinafter also referred to as " cyanate prepolymer ") of resin etc..These can be used alone, also can be used together 2 kinds with On.

Among these, operability when heat resistance, insulating reliability and film, preferred the following general formula (b2-I) cyanate ester resin shown in cyanate ester resin, the following general formula shown in (b2-IV) and their prepolymer, it is more excellent Select cyanate ester resin and its prepolymer shown in the following general formula (b2-I).

[changing 14]

In general formula (b2-I), R^b1Indicate the alkylidene of carbon number 1~3 being optionally substituted with halogen atoms, sulphur atom, following Divalent group shown in general formula (b2-II) or the following general formula (b2-III).R^b2And R^b3Indicate the alkane of hydrogen atom or carbon number 1~4 Base.Two R^b2Each other or two R^b3It identical respectively can also be different each other, but preferably identical.

[changing 15]

In general formula (b2-II), R^b4Indicate the alkylidene of carbon number 1~3.Two R^b4It can be the same or different each other, But it is preferred that identical.

[changing 16]

[changing 17]

In general formula (b2-IV), R^b5Indicate the alkyl of hydrogen atom or the carbon number 1~3 that can be substituted with halogen atoms.N is indicated 1 or more integer.More than two R^b5It can be the same or different each other, but preferably identical.

In above-mentioned general formula (b2-I), as R^b1The alkylidene of represented carbon number 1~3, can enumerate: methylene, sub- second Base, 1,2- propylidene, 1,3- propylidene, 2,2- propylidene (- C (CH₃)₂) etc..Among these, from heat resistance, insulation can From the perspective of operability when by property and film, preferred methylene or 2,2- propylidene (- C (CH₃)₂), more preferable 2, 2- propylidene (- C (CH₃)₂).

As the halogen atom that the alkylidene to above-mentioned carbon number 1~3 is replaced, fluorine atom, chlorine atom, bromine can be enumerated Atom, iodine atom etc..

In above-mentioned general formula (b2-II), as R^b4The alkylidene of represented carbon number 1~3, can enumerate: methylene, Asia Ethyl, 1,2- propylidene, 1,3- propylidene, 2,2- propylidene (- C (CH₃)₂) etc..

These R^b1Among represented group, the viewpoint of operability when from heat resistance, insulating reliability and being film-made goes out Hair, preferably methylene or 2,2- propylidene (- C (CH₃)₂), more preferable 2,2- propylidene (- C (CH₃)₂).

In above-mentioned general formula (b2-I), as R^b2Or R^b3The alkyl of represented carbon number 1~4, can enumerate methyl, second Base, propyl, butyl etc..

In above-mentioned general formula (b2-IV), as R^b5The alkyl of represented carbon number 1~3, can enumerate methyl, ethyl, third Base etc..

As the halogen atom that the alkyl to above-mentioned carbon number 1~3 is replaced, it is former that fluorine atom, chlorine atom, bromine can be enumerated Son, iodine atom etc..

In general formula (b2-IV), n indicates 1 or more integer, operability when from heat resistance, insulating reliability and being film-made From the perspective of, preferably 1~7, more preferably 1~4.

Above-mentioned cyanate prepolymer refers to that cyanate ester resin forms the polymer of triazine ring each other by cyclization, main It wants to enumerate: 3,5,7,9,11 aggressiveness of cyanate esters etc..In the cyanate prepolymer, the conversion ratio of cyanato does not have It is particularly limited to, but from the viewpoint of obtaining relative to the good dissolubility of organic solvent, preferably 20~70 mass %, more Preferably 30~65 mass %.

As cyanate prepolymer, can enumerate: the prepolymer of cyanate ester resin shown in above-mentioned general formula (b2-I), on State the prepolymer etc. of cyanate ester resin shown in general formula (b2-IV).Among these, from heat resistance, insulating reliability and film When operability from the perspective of, in preferably 1 molecule have there are two cyanato dicyanate compound prepolymer, it is more excellent It is selected as the prepolymer of cyanate ester resin shown in above-mentioned general formula (b2-I), further preferably 2,2- bis- (4- cyanatophenyls) At least part of propane is become the prepolymer of tripolymer by triazine (referring to following formula (b2-V)).

[changing 18]

The weight average molecular weight (Mw) of cyanate prepolymer is not particularly limited, but from relative to organic solvent dissolubility and From the perspective of workability, preferably 500~4,500, more preferably 600~4,000, further preferably 1,000~4, 000, particularly preferably 1,500~4,000.If the weight average molecular weight (Mw) of cyanate prepolymer is 500 or more, there is cyanate The crystallization of prepolymer is suppressed, becomes good tendency relative to the dissolubility of organic solvent, in addition, if 4,500 hereinafter, Then have the tendency that the increase of viscosity is suppressed, workability is excellent.

It should be noted that weight average molecular weight (Mw) is using gel permeation chromatography (GPC) (Tosoh strain formula in the present invention Commercial firm's system), and measured using the calibration curve of standard polystyren, be specifically according to the method that embodiment is recorded and Measurement.

Cyanate prepolymer can be above-mentioned cyanate ester resin pre-polymerization materialization in the presence of mono-functional phenols compound and Obtain person.When manufacturing cyanate prepolymer, by cooperating mono-functional phenols compound, so as in the solidfied material that reduces not The cyanato of reaction, therefore have the tendency that moisture-proof and electrical characteristics are excellent.

As above-mentioned mono-functional phenols compound, can enumerate: nonylphenol, p-tert-butylphenol, p-tert-amylphenol, To the alkyl substituted benzenes phenol system compound such as tert-octyl phenol；To (α-cumyl) phenol, mono- (α-methylbenzyl) phenol, two- Phenol based compound shown in the following general formula (b2-VI) such as (α-methylbenzyl) phenol or three-(α-methylbenzyl) phenol Deng.These can be used alone or two or more kinds may be used.

[changing 19]

In general formula (b2-VI), R^b6And R^b7Separately indicate that hydrogen atom or methyl, m indicate 1~3 integer.M is 2 Or 3 integer in the case where, more than two R^b6Each other or R^b7It identical respectively can also be different each other, but preferred phase Together.

The usage amount of mono-functional phenols compound is preferably set to make phenolic hydroxyl group possessed by mono-functional phenols compound and cyanic acid The equivalent proportion (hydroxyl/cyanato) of cyanato possessed by ester resin becomes 0.01~0.30 amount, is more preferably set as becoming 0.01~0.20 amount is further preferably set as the amount as 0.01~0.15.If the usage amount of mono-functional phenols compound is upper It states in range, then not only has the tendency that obtaining the substantially low substance of the dielectric loss angle tangent of especially high frequency band, but also having can To obtain the tendency of good moisture-proof.

It as the manufacturing method of cyanate prepolymer, is not particularly limited, well known manufacturing method can be applied.

Cyanate prepolymer for example can be by reacting above-mentioned dicyanate compound with above-mentioned mono-functional phenols compound Suitably to manufacture.By reacting for dicyanate compound and mono-functional phenols compound, and formed have-O-C (= NH) the compound (i.e. iminocarbonic ester) of group shown in-O- is further carried out instead by the iminocarbonic ester each other It answers or the iminocarbonic ester is reacted with dicyanate compound, so that mono-functional phenols compound is detached from, on the other hand Obtain the cyanate prepolymer with triazine ring.Above-mentioned reaction can for example carry out as follows: by above-mentioned dicyanate compound with Above-mentioned mono-functional phenols compound is mixed and is dissolved in the presence of toluene equal solvent, is maintained at 80~120 DEG C on one side, on one side basis Need to add the reaction promoters such as zinc naphthenate to carry out.

As cyanate ester resin, commercially available product can be used.As the cyanate ester resin of commercially available product, there is the cyanate of bisphenol type Part or all of resin, the cyanate ester resin of novolac type, these cyanate ester resins become tripolymer by triazine Prepolymer etc..

The commercially available product of cyanate ester resin as bisphenol A-type (2,2- bis- (4- hydroxy phenyl) propanes), can be used " Primaset BADCy " (Lonza corporation, trade name), " Arocy B-10 " (Huntsman corporation, trade name) etc.. In addition, the commercially available product of the cyanate ester resin as bisphenol E-type (1,1- bis- (4- hydroxy phenyl) ethane types), can be used " Arocy L10 " (Huntsman corporation, trade name), " Primaset LECy " (Lonza corporation, trade name) etc., as The commercially available product of the cyanate ester resin of 2,2 '-bis- (4- cyanate -3,5- aminomethyl phenyl) ethane types, can be used " Primaset METHYLCy " (Lonza corporation) etc..

The cyanate as phenol novolak type can be used in the commercially available product of cyanate ester resin as novolac type " Primaset PT30 " (the Lonza corporation, trade name) of resin etc..

The commercially available product of prepolymer as cyanate ester resin can be used the cyanate ester resin pre-polymerization materialization of bisphenol A-type " Primaset BA200 " (Lonza corporation, trade name), " Primaset BA230S " (Lonza corporation, trade name) Deng " Primaset BA3000 " etc. also can be used.

In addition to this, " Arocy XU-371 " (Huntsman corporation, trade name) can be used, as containing two rings " Arocy XP71787.02L " (the Huntsman corporation, trade name) of the cyanate ester resin of pentadiene structure, " Primaset DT-4000 " (Lonza corporation, trade name), " Primaset DT-7000 " (Lonza corporation, trade name) etc..

(the phenol novolak system curing agent of (b3) containing triazine ring)

Phenol novolak system curing agent as (b3) containing triazine ring, in the line style for the curing agent for being used as epoxy resin Among novolac type phenolic resin, the phenol novolak system curing agent containing triazine ring can be used.Line style containing triazine ring Novolac type phenolic resin be amino triazine ring structure and phenol structure via methylene randomly-bonded obtained resin.As containing The phenol novolak system curing agent of triazine ring preferably the phenol novolaks containing triazine ring and contains triazine ring At least one of cresol novolaks.

Novolac type phenolic resin containing triazine ring for example can be by utilizing Japanese Unexamined Patent Publication 2002-226556 The manufacturing method that bulletin is recorded manufactures.I.e., it is possible to make phenolic compounds, amino triazine compound and aldehyde compound in alkylamine etc. In the presence of alkalescent catalyst or without being manufactured near neutral by the way that copolycondensation occurs under catalyst.

It as the phenolic compounds for being used as raw material, can enumerate: phenol, o-cresol, metacresol, paracresol, dimethlbenzene, double Phenolic compounds, ortho position have carbon number with 3 or more carbon number, the ortho position substitution phenolic compounds of the alkyl of preferably carbon number 3~10, contraposition 3 or more, the preferred p-Substituted residue compound etc. of the alkyl of carbon number 3~18.These can be used alone, and also can be used together 2 Kind or more.

Here, can be enumerated as bisphenol compound: bisphenol-A, Bisphenol F, bis- (2- methylphenol) A, bis- (2- methyl Phenol) F, bisphenol S, bis-phenol E, bisphenol Z etc..

It as ortho position substitution phenolic compounds, can enumerate: 2- propylphenol, 2- isopropyl-phenol, 2- sec-butylbenzene Phenol, 2-TBP, 2- phenylphenol, 2- cyclohexylphenol, 2- nonyl phenol, 2- naphthalene phenol etc..

It as p-Substituted residue compound, can enumerate: 4- propylphenol, 4- isopropyl-phenol, 4- sec-butylbenzene Phenol, 4-TBP, 4- phenylphenol, 4- cyclohexylphenol, 4- nonyl phenol, 4- naphthalene phenol, 4- dodecane Base phenol, 4- octadecylphenol etc..

As the amino triazine compound for being used as raw material, melamine, benzoguanamine, acetylguanamine etc. can be enumerated.

As be used as raw material aldehyde compound, can enumerate: formaldehyde, formalin, paraformaldehyde, metaformaldehyde, acetaldehyde, Para-acetaldehyde, propionic aldehyde etc..Among these, from the viewpoint of reaction speed, preferred paraformaldehyde.These can be used alone 1 Kind, also two or more kinds may be used.

The cooperation molar ratio (F/P) of aldehyde compound (F) and phenolic compounds (P) are preferably 0.33 or more, more preferably 0.40 It~1.0, is more preferably 0.50~0.90.It is available excellent by the way that molar ratio (F/P) will be cooperated to be set as in above range Yield.

In addition, the nitrogen atom content in the phenol novolak system curing agent of (b3) containing triazine ring be preferably 8~30%, More preferably 8~20%.

Phenol novolak system curing agent as (b3) containing triazine ring, can be used commercially available product, can enumerate: " PAPS-PN2 " (Asahi Organic Chem Ind's system, trade name), " PAPS-PN3 " (Asahi Organic Chem Ind System, trade name), " Phenolite LA-1356 " (Dainippon Ink Chemicals's system, trade name), " Phenolite LA-7054 " (contain Have phenol novolaks, Dainippon Ink Chemicals's system, trade name of triazine), " Phenolite LA-3018 " (containing triazine Cresol novolaks, Dainippon Ink Chemicals's system, trade name) etc..

Interlayer insulating film used in the present invention is not hindering effect of the invention with (b) of resin combination curing agent It, can be containing the epoxy curing agent other than the curing agent of above-mentioned (b1)~(b3) (hereinafter, being also only called " epoxy in range Resin curing agent ").

As epoxy curing agent, can enumerate: the phenolic resin without containing triazine ring, the phenolic compounds containing phosphorus, Anhydride compound, amine compounds, hydrazide compound etc..

As the phenolic resin for not containing triazine ring, can enumerate: novolac type phenolic resin, resol type phenol resin Deng.Phenolic compounds containing phosphorus be with more than two phenolic hydroxyl group and containing the compound of phosphorus atoms, can enumerate 10- (2, 5- dihydroxyphenyl) -9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide [HCA-HQ or HCA-HQ- HS (Sanko Co., Ltd.'s system, trade name)] etc..It as anhydride compound, can enumerate: phthalic anhydride, benzophenone four Carboxylic acid dianhydride, methyl nadic acid etc..In addition, can be enumerated as amine compounds: dicyandiamide, diaminodiphenyl-methane, amidine Base urea etc..

Among these epoxy curing agents, from the viewpoint of improving reliability, the phenolic aldehyde of triazine ring is not preferably contained Resin, the phenolic compounds containing phosphorus, from the viewpoint of anti-flammability, the further preferably phenolic compounds of phosphorus.

It should be noted that also there are other functions while for having the function as curing agent in the present invention Substance, using have as the case where function of curing agent be it is preferential, be classified as " curing agent ".For example, the above-mentioned phenolate containing phosphorus While closing object has the function as curing agent, also there is the function as fire retardant, be classified as curing agent.

(b) curing agent may include (b2) cyanate system curing agent, also may include selected from (b1) active ester system curing agent It is at least one kind of in the phenol novolak system curing agent of (b3) containing triazine ring.In particular, if comprising being selected from (b1) active ester Be it is at least one kind of in curing agent and the phenol novolak system curing agent of (b3) containing triazine ring, then inhibit aftermentioned containing phosphorus Phenolic compounds brought by easily gelation effect it is big thus preferably.That is, it is desirable to which using has as curing agent When also having the effect of the phenolic compounds containing phosphorus of anti-flammability while effect, by and with solidify selected from (b1) active ester system It is at least one kind of in agent and the phenol novolak system curing agent of (b3) containing triazine ring, it is able to suppress gelation, and protect well Hold operability when film.From the same viewpoint, (b) curing agent preferably comprises the phenol phenol of (b3) containing triazine ring Aldehyde system curing agent.

(b) (b1) the active ester system curing agent in curing agent, (b2) cyanate system's curing agent and (b3) contain triazine ring The respective content of phenol novolak system curing agent is not particularly limited, be applied in combination (b1) ingredient, with (b2) ingredient or (b3) in the case where ingredient, from the viewpoint of dielectric property, relative to the total amount of used (b1)~(b3) ingredient, (b1) Ingredient is preferably 40~70 mass %, more preferably 50~65 mass %.

(b) mass ratio of the total amount of above-mentioned (b1)~(b3) ingredient in curing agent from heat resistance, insulating reliability and is made From the perspective of operability when film, preferably 20 mass % or more, more preferably 40 mass % or more, further preferably 50 Quality % or more.Upper limit value is not particularly limited, and can be 100 mass %, or 90 mass % can also be 80 matter Measure %.

The content ratio of (a) epoxy resin in interlayer insulating film resin combination and (b) curing agent from heat resistance, absolutely Edge reliability and film when operability from the perspective of, preferably according to the functional group of above-mentioned (b) curing agent sum relative to (a) epoxy group of epoxy resin sum ratio [epoxy group of sum/(a) epoxy resin of the functional group of (b) curing agent Sum] it is adjusted as 0.2~2 mode.If the ratio is 0.2 or more, having can be reduced in obtained interlayer insulating film Unreacted epoxy group amount tendency, if 2 hereinafter, then the use level of (b) curing agent will not become excessively, having can press down The tendency of the rising of solidification temperature processed.From the same viewpoint, which is more preferably 0.4~1.5.

((c) inorganic filling material)

Interlayer insulating film resin combination used in the present invention also contains (c) inorganic filling material.From to by interlayer When resin compositions for insulating layer heat cure and the interlayer insulating film formed are laser machined, prevent the dispersing of resin, can From the perspective of the shape for adjusting laser processing, (c) inorganic filling material is important.In addition, from oxidant that interlayer is exhausted When the roughing in surface of edge layer, appropriate roughening face is formed, the viewpoint of the excellent conductor layer of adhesive strength is capable of forming by plating It sets out and is important, preferably select from such a viewpoint.

As (c) inorganic filling material, can enumerate: silica, aluminium oxide, barium sulfate, talcum, clay, mica powder, Aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesia, boron nitride, aluminium borate, barium titanate, strontium titanates, calcium titanate, titanium Sour bismuth, titanium oxide, barium zirconate, calcium zirconate etc..Among these, from thermal expansion coefficient, the operability of varnish and insulating reliability Viewpoint is set out, preferably silica, especially spherical silicon dioxide, fused silica.Inorganic filling material can individually make With a kind, also two or more kinds may be used.

(c) inorganic filling material is from the viewpoint of forming fine wiring, the small inorganic filling material of preferable particle size.From same From the perspective of sample, (c) the preferred specific surface area of inorganic filling material is 3m²/ g or more can be 3~200m²/ g, can for 3~ 130m²/ g can be 3~50m²/ g can be 3~20m²/g.It is low that specific surface area can use the low temperature based on inactive gas The BET method of wet physical absorption is found out.Specifically, the absorption occupied area such as nitrogen can be made known under liquid nitrogen temperature Molecular Adsorption is found out the specific surface area of powder particle by its adsorbance in powder particle surface.

In addition, (c) viewpoint of the volume average particle size of inorganic filling material from the imbedibility for obtaining good circuit substrate From the perspective of insulating reliability, preferably 0.01~5 μm, more preferable 0.1~2 μm, further preferred 0.2~1 μm.Volume is flat Equal partial size refers to: when the total volume of particle being set as 100% and finding out the cumulative frequency distribution curve based on partial size, being equivalent to body The partial size of the point of product 50% can be measured by the particle size distribution device etc. using laser diffraction scattering method.

As (c) inorganic filling material, commercially available product can be used, can enumerate: as pyrogenic silica " AEROSIL (registered trademark) R972 " (Japanese Aerosil Co. Ltd. system, trade name, 110 ± 20m of specific surface area²/ g) and " AEROSIL (registered trademark) R202 " (Japanese Aerosil Co. Ltd. system, trade name, 100 ± 20m of specific surface area²/ g), make For " PL-1 " (Fukawa Chemical Industries Co., Ltd.'s system, trade name, specific surface area 181m of colloidal silicon dioxide²/ g) and " PL- 7 " (Fukawa Chemical Industries Co., Ltd.'s system, trade name, specific surface area 36m²/ g) etc..

It can be used from the viewpoint of the moisture-proof for improving obtained interlayer insulating film as (c) inorganic filling material The inorganic filling material being surface-treated with surface treating agents such as silane coupling agents.

As the inorganic filling material being surface-treated with surface treating agent, commercially available product can be used, can enumerate: " SO-C2 " (Co., Ltd.'s Admatechs system, commodity as the silica filler for implementing amino silicane coupling agent processing Name), as the silica filler for implementing phenyl silane coupling agent treatment " YC100C " (Co., Ltd.'s Admatechs system, Trade name), as " Sciqas series " (the Sakai chemical industry strain for the silica filler for implementing epoxy silane coupling agent processing Formula commercial firm system, trade name, 0.1 μm of grade) etc..

The content of (c) inorganic filling material in interlayer insulating film resin combination swashs from obtained interlayer insulating film Light processability and with the solid component from the perspective of the adhesive strength of conductor layer, relative to interlayer insulating film resin combination It (also include (c) inorganic filling material itself.) it is preferably 30~90 mass %, more preferably 30~70 mass % are further excellent It is selected as 40~60 mass %.If (c) content of inorganic filling material relative to interlayer insulating film resin combination solid at It is divided into 30 mass % or more, then has the tendency that obtaining good laser processing property, if 90 mass % hereinafter, then there is and passing through plating The excellent tendency of the adhesive strength for the conductor layer that the method for applying is formed.

((d) antioxidant)

(d) antioxidant contained by interlayer insulating film resin combination is hindered phenolic antioxidant.Hindered phenolic Antioxidant is that have substituent group person at the ortho position of phenolic hydroxyl group, in particular, there is finger to have tert-butyl and trimethyl silyl Etc. the compound of the big substituent group of steric hindrances tendency.

Interlayer insulating film resin combination is containing unimpeded phenol it is not necessary to containing unimpeded phenolic antioxidant In the case where being antioxidant, the content of unimpeded phenolic antioxidant is preferably 30 matter of the content of hindered phenolic antioxidant % is measured hereinafter, more preferably 15 mass % are hereinafter, further preferred 5 mass % or less, or 0 mass %.

By making (d) antioxidant hindered phenolic antioxidant, so that operability when being film-made is enhanced.

It as hindered phenolic antioxidant, can enumerate: 2,6-di-tert-butyl p-cresol (trade name: Yoshinox BHT), 4,4 '-butylidenebis-(6- tert-butyl -3- methylphenol) (trade name: Yoshinox BB), 2,2 '-methylenes Base pair-(4- methyl-6-tert-butylphenol) (trade name: Yoshinox 2246G), 2,2 '-di-2-ethylhexylphosphine oxides-(4- second Base -6- tert-butyl phenol) (trade name: Yoshinox 425), 2,6- di-t-butyl -4- ethyl -phenol (trade name: Yoshinox 250), 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane (trade name: Yoshinox 930), n-octadecane base -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester (trade name: Tominox SS, IRGANOX1076, IRGANOX1076FD), [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of pentaerythrite base ■ tetra- Ester] (trade name: Tominox TT；IRGANOX1010, IRGANOX1010FF), bis- (3- (the 3- tert-butyls-of triethylene glycol 4- hydroxy-5-methyl base phenyl) propionic ester) (trade name: Tominox 917；IRGANOX245, IRGANOX245FF), three (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester (trade name: Yoshinox 314；IRGANOX3114), 1,6- Hexylene glycol-bis- [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic ester] (trade names: IRGANOX259), 2,4- be bis- - (n-octyl sulfenyl) -6- (4- hydroxyl -3,5- di-tert-butyl amido) -1,3,5- triazine (trade name: IRGANOX565, IRGANOX565DD), 2,2- it is thio-di ethylene bis [3- (3,5- di-t-butyl -4- hydroxy benzenes Base) propionic ester] (trade name: IRGANOX1035FF), N, N '-hexamethylene bis [3- (3,5- di-t-butyl -4- hydroxyl Phenyl) propionic acid] (trade name: IRGANOX1098), three (3,5- di-t-butyl-of 1,3,5- trimethyl -2,4,6- 4- hydroxybenzyl) benzene (trade name: IRGANOX1330), bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester) calcium It is bis- [(octylthio) methyl] o-cresols (trade name: IRGANOX1520L) of (trade name: IRGANOX1425WL), 2,4-, different Octyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester (trade name: IRGANOX1135) etc..

As hindered phenolic antioxidant, preferably comprise selected from group shown in the following general formula (dI) compound and It is at least one kind of in the following general formula (dII) compound represented.It should be noted that having group shown in the following general formula (dI) Compound may include the following general formula (dII) compound represented.

[changing 20]

(in formula (dI), R^d1、R^d2And R^d3Separately indicate the alkyl of hydrogen atom or carbon number 1~8.Wherein, R^d1And R^d2 In at least one indicate carbon number 1~8 alkyl.)

[changing 21]

(in formula (dII), R^d4And R^d5Separately indicate the alkyl of carbon number 1~8.R^d6、R^d7And R^d8Independently earth's surface Show the alkyl of hydrogen atom or carbon number 1~8.Wherein, R^d6、R^d7And R^d8In at least one indicate carbon number 1~8 alkyl.)

In formula (dI), as R^d1、R^d2And R^d3The alkyl of represented carbon number 1~8, can enumerate: methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-hexyl, n-octyl etc..Among these, the preferred alkyl of carbon number 1~6, more It is preferred that the alkyl of carbon number 1~4, further preferred methyl, ethyl, n-propyl, tert-butyl, particularly preferred methyl, ethyl, tertiary fourth Base.

R^d1And R^d2In at least one indicate carbon number 1~8 alkyl.It can be R^d1Alkyl, R for carbon number 1~8^d2For hydrogen The combination of atom, can be R^d1For hydrogen atom, R^d2It, can also be with R for the combination of the alkyl of carbon number 1~8^d1And R^d2Both sides are carbon numbers 1 ~8 alkyl.

In formula (dII), as R^d4、R^d5、R^d6、R^d7And R^d8The alkyl of represented carbon number 1~8, with above-mentioned R^d1、R^d2With R^d3The case where similarly illustrate, preferred example is also identical.

R^d6、R^d7And R^d8In at least one indicate carbon number 1~8 alkyl, preferably two expression carbon number 1~8 alkyl.It can To be R^d6For hydrogen atom, R^d7For hydrogen atom and R^d8For the combination of the alkyl of carbon number 1~8, R can be^d6For hydrogen atom, R^d7For carbon The alkyl and R of number 1~8^d8For the combination of hydrogen atom, R can be^d6Alkyl, R for carbon number 1~8^d7For hydrogen atom and R^d8For hydrogen original The combination of son, can be R^d6Alkyl, R for carbon number 1~8^d7For hydrogen atom and R^d8For the combination of hydrogen atom, R can be^d6For carbon Alkyl, the R of number 1~8^d7For the alkyl and R of carbon number 1~8^d8For the combination of hydrogen atom, R can be^d6For carbon number 1~8 alkyl, R^d7For hydrogen atom and R^d8For the combination of the alkyl of carbon number 1~8, R can be^d6For hydrogen atom, R^d7For carbon number 1~8 alkyl and R^d8For the combination of the alkyl of carbon number 1~8.R^d6、R^d7And R^d8It can be with the alkyl of all carbon numbers 1~8.

Compound with group shown in above-mentioned general formula (dI) is preferably to appoint in the following general formula (dI-1)~(dI-3) One compound represented.

[changing 22]

(in formula (dI-1) and (dI-2), R^d11、R^d12、R^d13、R^d21、R^d22And R^d23Separately indicate hydrogen atom or The alkyl of carbon number 1~8.Wherein, R^d11And R^d12In at least one and R^d21And R^d22In at least one indicate carbon number 1~8 Alkyl.X¹And X²Separately indicate the organic group of 1~trivalent.n¹And n²It is separately 1~3 integer.)

For the alkyl of carbon number 1~8, with above-mentioned R^d1、R^d2And R^d3The case where similarly illustrate, preferred example is also identical.

R^d11And R^d12In at least one indicate carbon number 1~8 alkyl.It can be R^d11Alkyl, R for carbon number 1~8^d12For The combination of hydrogen atom, can be R^d11For hydrogen atom, R^d12For the combination of the alkyl of carbon number 1~8, R can be^d11And R^d12Both sides are The alkyl of carbon number 1~8.It is preferred that R^d11And R^d12Both sides are tert-butyl, R^d13For the combination of hydrogen atom.

It is also preferable to R^d11For hydrogen atom, R^d12Alkyl, R for carbon number 1~8^d13For the combination of the alkyl of carbon number 1~8, More preferable R^d11For hydrogen atom, R^d12For tert-butyl, R^d13For the combination of methyl.

R^d21And R^d22In at least one indicate carbon number 1~8 alkyl.It can be R^d21Alkyl, R for carbon number 1~8^d22For The combination of hydrogen atom, can be R^d21For hydrogen atom, R^d22For the combination of the alkyl of carbon number 1~8, R can be^d21And R^d22Both sides are The alkyl of carbon number 1~8.It is preferred that R^d21For tert-butyl, R^d22For ethyl, R^d23For the combination of hydrogen atom.

It should be noted that R^d13For hydrogen atom and do not have substituent R^d13It is synonymous.In addition, R^d23For hydrogen atom with do not have Substituted base R^d23It is synonymous.

As X¹And X²The organic group of 1 represented~trivalent, is not particularly limited, and can enumerate: aliphatic alkyl contains There are group, aromatic hydrocarbyl, heteroaromatic alkyl and the group formed by their combination of amido bond.

As aliphatic alkyl, the preferably aliphatic alkyl of carbon number 1~10, the aliphatic alkyl of more preferable carbon number 1~6, The aliphatic alkyl of further preferred carbon number 1~4.Aliphatic alkyl can be straight-chain, or branched.

As the group containing amido bond ,-(CH can be enumerated₂)₂- C (=O)-NH- (CH₂)₆- NH-C (= O)-(CH₂)₂Etc..

As aromatic hydrocarbyl, the preferably aromatic hydrocarbyl of carbon number 6~10, the aromatic hydrocarbyl of more preferable carbon number 6.

As heteroaromatic alkyl, the group etc. containing isocyanuric acid ester skeleton can be enumerated.

As the group formed by their combination, specifically, aliphatic alkyl-aromatic hydrocarbyl etc. can be enumerated.

n¹And n²Separately indicate 1~3 integer, all can be 1, can be 2, or 3.

[changing 23]

(in formula (dI-3), R^d31And R^d32Separately indicate the alkyl of carbon number 1~8.Y expression-COOCH₂,- COOCH₂CH₂?.)

As R^d31And R^d32The alkyl of represented carbon number 1~8, with above-mentioned R^d1、R^d2And R^d3The case where similarly illustrate, Preferred example is also identical.Wherein, particularly preferred tert-butyl.

As the compound with group shown in above-mentioned general formula (dI), preferably: it is selected from above-mentioned general formula (dI-1) institute At least one kind of and molecular weight in compound and above-mentioned general formula (dI-2) compound represented shown is 1,500 or less.It is more excellent Choosing: it is at least 1 in above-mentioned general formula (dI-1) compound represented and above-mentioned general formula (dI-2) compound represented Kind and molecular weight are 1,000 hereinafter, further preferably molecular weight is 500 hereinafter, particularly preferably 400 or less.

((d ') following specific compounds)

Interlayer insulating film can replace above-mentioned (d) ingredient containing (d ') ingredient with resin combination.(d ') ingredient be selected from It is at least one kind of in compound and above-mentioned general formula (dII) compound represented with group shown in above-mentioned general formula (dI).General formula (dI) each group and in general formula (dII) is as defined above, and preferred example is also identical.

In particular, the compound with group shown in general formula (dI) is preferably in above-mentioned general formula (dI-1)~(dI-3) Any one compound represented.Additionally, it is preferable that: the compound with group shown in general formula (dI) is selected from above-mentioned general formula (dI-1) at least one kind of and molecular weight in compound represented and above-mentioned general formula (dI-2) compound represented be 1,500 with Under.It is even more preferred that it is the chemical combination shown in above-mentioned general formula (dI-1) compound represented and above-mentioned general formula (dI-2) At least one kind of and molecular weight in object be 1,000 hereinafter, further preferably molecular weight be 500 hereinafter, particularly preferably 400 with Under.

Operability when heat resistance, insulating reliability and film, interlayer insulating film resin combination In (d) ingredient or (d ') ingredient content relative to the solid component of interlayer insulating film resin combination be preferably 0.01~ 10 mass %, more preferably 0.05~5 mass %, further preferably 0.05~2 mass %, particularly preferably 0.05~1 matter Measure %.

((e) phenoxy resin)

Interlayer insulating film preferably comprises (e) phenoxy resin with resin combination.

Here, " phenoxy resin " refers to that main chain is the addition polymerization knot of aromatic diol and aromatic series diglycidyl ether The high molecular general name of structure in this specification, refers to that weight average molecular weight is 10,000 or more phenoxy resin.It needs to illustrate It is that there are the feelings of epoxy group in the macromolecule for the addition polymerization structure that main chain is aromatic diol and aromatic series diglycidyl ether Under condition, weight average molecular weight 10,000 or more is classified as (e) phenoxy resin, and weight average molecular weight is classified as less than 10,000 (a) epoxy resin.

From the viewpoint of operability when improving film, (e) phenoxy resin preferably comprises ester ring type structure.Here, " ester ring type structure " refers to: after removing aromatic compound among the organic compound of the structure of carbon atom bonding synthesis of cyclic Part ".Among these, it is preferably selected from cricoid saturated hydrocarbons (cycloalkane) and in ring comprising the cricoid insatiable hunger of 1 double bond One or more of with hydrocarbon (cycloolefin).

As (e) phenoxy resin, can enumerate: the phenoxy resin containing cyclohexane structure contains 3-methyl cyclohexanol The phenoxy resin of alkyl structure, phenoxy resin containing terpene structures etc..Among these, from operability when improving film Viewpoint is set out, more excellent preferably containing the phenoxy resin selected from one or more of terpene structures and 3-methyl cyclohexanol alkyl structure It is selected as the phenoxy resin containing 3-methyl cyclohexanol alkyl structure.

It as the phenoxy resin containing 3-methyl cyclohexanol alkyl structure, can enumerate: in Japanese Unexamined Patent Publication 2006-176658 It is the phenoxy group tree of raw material with bis-phenol TMC (bis- (4- hydroxy phenyl) -3,3,5- trimethyl-cyclohexanes) disclosed in number bulletin Rouge etc..

As the phenoxy resin containing terpene structures, for example, can enumerate: in Japanese Unexamined Patent Publication 2006-176658 public affairs In phenoxy resin disclosed in report, bis- (4- hydroxy phenyls) -3,3,5- trimethyl-cyclohexane conduct is replaced using terpene diphenol 2 yuan of phenolic compounds of raw material and the phenoxy resin etc. synthesized.

(e) phenoxy resin can be used alone or two or more kinds may be used.

(e) weight average molecular weight of phenoxy resin preferably 10,000~60,000, more preferable 12,000~50,000, into one Step preferably 15,000~45,000, particularly preferred 17,000~40,000, highly preferred 20,000~37,000.If (e) phenoxy group The weight average molecular weight of resin is above-mentioned lower limit value or more, then has the tendency that obtaining the excellent peel strength with conductor layer, if Above-mentioned upper limit value is hereinafter, can then prevent the increase of the increase and coefficient of thermal expansion of rugosity.

Weight average molecular weight is can to pass through reality using the value of gel permeation chromatography (GPC) method (polystyrene conversion) measurement Apply the method measurement of example record.

As the manufacturing method of (e) phenoxy resin, for example, can be manufactured in the following way: front three will be contained The bisphenol compound of butylcyclohexane structure or the bisphenol compound for containing terpene structures and 2 functional epoxy resins as raw material, according to According to the preparation method of well known phenoxy resin, the equivalent proportion (phenolic hydroxyl group/epoxy group) of phenolic hydroxyl group and epoxy group for example as Make its reaction in the range of 1/0.9~1/1.1.

(e) commercially available product can be used in phenoxy resin.As (e) phenoxy resin of commercially available product, preferably are as follows: containing coming from Biphenyl type epoxy resin and containing 3-methyl cyclohexanol alkyl structure bisphenol compound (bis- (the 4- hydroxy phenyls) -3,3 of 1,1-, 5- trimethyl-cyclohexane) skeleton " YX7200B35 " (Mitsubishi chemical Co., Ltd's system, trade name).

In the case where interlayer insulating film resin combination contains (e) phenoxy resin, content is exhausted relative to interlayer The solid component of edge layer resin combination is (here, remove (c) inorganic filling material.) 100 mass parts are preferably 0.2~30 matter Measure part, more preferably 1~20 mass parts, further preferably 3~20 mass parts.If (e) content of phenoxy resin is 0.2 matter Measure part or more, then while having the tendency that flexible, operability is excellent, the peel strength of conductor layer it is excellent, if 20 mass parts with Under, then while having the tendency that storage stability, mobility are excellent, obtain rugosity appropriate.

((f) curing accelerator)

Interlayer insulating film from the viewpoint of it can carry out the solidification of short time with low temperature, can be contained with resin combination (f) curing accelerator.

As (f) curing accelerator, metal system curing accelerator, organic system curing accelerator etc. can be enumerated.

(metal system curing accelerator)

As metal system curing accelerator, it is, for example, possible to use organic metal system curing accelerators.The solidification of organic metal system The facilitation and (a) epoxy resin and (b) curing agent that there is promotor the auto polymerization of (b2) cyanate system curing agent to react The facilitation of reaction.

As organic metal system curing accelerator, transition metal, the organic metal salt of 12 race's metals and organic can be enumerated Metal complex etc..As metal, copper, cobalt, manganese, iron, nickel, zinc, tin etc. can be enumerated.

As organic metal salt, carboxylate can be enumerated, as its concrete example, can be enumerated: cobalt naphthenate, zinc naphthenate The 2 ethyl hexanoic acids salt such as equal naphthenates, 2 ethyl hexanoic acid cobalt, 2 ethyl hexanoic acid zinc, zinc octoate, tin octoate, stearic acid tin, Zinc stearate etc..

As metal-organic complex, the chelate complexes such as acetylacetonate complex can be enumerated, it as its concrete example, can To enumerate: organic cobalt complex such as acetylacetone cobalt (II), acetylacetone cobalt (III)；The organic coppers networks such as acetylacetone copper (II) Close object；The organozinc complexes such as zinc acetylacetonate (II)；The Organic-iron complexes, nickel acetylacetonate such as ferric acetyl acetonade (III) (II) organic nickel complex such as；Organic manganese complexs such as manganese acetylacetonate (II) etc..Among these, from curability and deliquescent Viewpoint is set out, preferably acetylacetone cobalt (II), acetylacetone cobalt (III), zinc acetylacetonate (II), ferric acetyl acetonade (III), ring Alkanoic acid zinc, cobalt naphthenate, more preferable zinc naphthenate.These can be used alone or two or more kinds may be used.

In the case where interlayer insulating film resin combination contains metal system curing accelerator, content from reactivity and It is preferably 1~500 mass ppm relative to (b2) cyanate system curing agent from the perspective of storage stability, more preferably 10~ 500 mass ppm, further preferably 50~400 mass ppm, particularly preferably 150~300 mass ppm.Metal system solidification promotees It can cooperate once or several times into agent.

(organic system curing accelerator)

(above-mentioned organic metal system curing accelerator wherein, is free of as organic system curing accelerator.), it can enumerate: have The amine compounds such as machine phosphorus compound, imidazolium compounds, secondary amine, tertiary amine；Quaternary ammonium salt etc..These can be used alone, can also To be used in combination of two or more.Among these, from the viewpoint of the brill dirt removability in via hole, preferably organic phosphorus compound, imidazoles Close object, amine compound, more preferable organic phosphorus compound.Organic system curing accelerator can cooperate once or several times.

It as organic phosphorus compound, can enumerate: ethyl phosphine, propyl phosphine, butyl phosphine, Phenylphosphine, trimethyl-phosphine, triethyl group Phosphine, tributylphosphine, tri octyl phosphine, triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine/triphenylborane complex compound, tetraphenyl boron four Phenylphosphine etc..Among these, triphenylphosphine.

As imidazolium compounds, 2- phenyl -4-methylimidazole, the inclined benzene of 1- cyano ethyl -2- phenyl can be enumerated Three imidazole acids etc..

In the case where interlayer insulating film resin combination contains organic system curing accelerator, content from reactivity and It is preferably 0.01~5 mass parts relative to 100 mass parts of (a) epoxy resin, more preferably from the perspective of storage stability 0.01~3 mass parts, further preferably 0.01~2 mass parts.

< others ingredient >

Interlayer insulating film in a range that does not hinder the effect of the present invention, can contain above-mentioned each ingredient with resin combination Ingredient in addition.As other ingredients, the resin component other than above-mentioned each ingredient can be enumerated (hereinafter also referred to as " other Resin component "), additive, fire retardant etc..

(other resin components)

It as other resin components, can enumerate: the polymer of bismaleimide compound and diamine compound, double Maleimide compound, diallyl nadikimide (Japanese: ビ ス ア リ Le Na ジ イ ミ De resin) resin, benzo are disliked Piperazine compound etc..

(additive)

It as additive, can enumerate: the thickeners such as ORBEN, bentonite；Imidazoles system, thiazole system, triazole system, silane are even Join the contiguity imparting agent such as agent；Rubber particles；Colorant etc..

(fire retardant)

As fire retardant, inorganic fire retardants, resin fire retardant etc. can be enumerated.As inorganic fire retardants, hydrogen can be enumerated Aluminium oxide, magnesium hydroxide etc..Resin fire retardant can be halogen system resin, or non-halogen resin, but to environment The considerations of load, sets out, preferably non-halogen resin.

Interlayer insulating film resin combination can by by (a)~(d) ingredient, (e) ingredient as needed, (f) at Divide and other ingredients are mixed and manufactured.As mixed method, well known method can be applied, for example, mixing using ball mill etc. ?.

The thickness G T.GT.GT of < interlayer insulating film resin film

The thickness of interlayer insulating film resin film can be determined by the thickness of the conductor layer formed in such as printed wiring board It is fixed.The thickness of conductor layer is usually 5~70 μm, therefore the thickness of interlayer insulating film resin film is preferably 1~100 μm, from energy From the perspective of being enough thinned multilayer printed circuit board, preferably 1~80 μm, more preferably 1~70 μm, more preferably 15~ 70 μm, further preferably 20~50 μm.

< supporting mass >

Interlayer insulating film of the invention can be the resin film formed on supporting mass with resin film.

As supporting mass, organic resin film, metal foil, processing release paper etc. can be enumerated.It is not particularly limited, but as bearing The preferred organic resin film of body.

It as the material of organic resin film, can enumerate: the polyolefin such as polyethylene, polyvinyl chloride；Poly terephthalic acid second The polyester such as diol ester (hereinafter also referred to as " PET "), polyethylene naphthalate；Polycarbonate, polyimides etc..These it In, from the viewpoint of price and operability, preferably PET.

As metal foil, copper foil, aluminium foil etc. can be enumerated.It, can also be by copper in the case where using copper foil to supporting mass Foil forms circuit directly as conductor layer.In this case, calendering copper, electrolytic copper foil etc. can be used as copper foil.In addition, The thickness of copper foil for example can be set to 2~36 μm.In the case where using the thin copper foil of thickness, go out from the viewpoint for improving workability Hair, can be used the copper foil with carrier.

As a scheme of the invention, can enumerate with above-mentioned interlayer insulating film resin film and above-mentioned supporting mass Multi-layer resinous film.As the multi-layer resinous film, preferably: above-mentioned supporting mass be organic resin film, the organic resin film with a thickness of 10~70 μm and above-mentioned interlayer insulating film resin film with a thickness of 1~80 μm of multi-layer resinous film.

The multi-layer resinous film can have layer (the interlayer insulating film resin group formed by interlayer insulating film resin film Close nitride layer) while, also there is bonding auxiliary layer.

For these supporting masses and aftermentioned protective film, it is possible to implement demoulding processing, corona treatment, sided corona treatment etc. Surface treatment.It handles, can enumerate as demoulding: based on organic siliconresin system release agent, alkyd resin system release agent or fluorine tree Demoulding processing of rouge system release agent etc. etc..

The thickness of supporting mass is from the viewpoint of operability and economy, and preferably 10~120 μm, more preferable 10~70 μm, More preferable 15~70 μm, further preferred 25~60 μm.

Supporting mass is usually finally stripped or removes when manufacturing multilayer printed circuit board.

< protective film >

On the face with supporting mass opposite side of interlayer insulating film resin film of the invention, protective film can be configured. Protective film is arranged on the face with the face opposite side for being equipped with supporting mass of interlayer insulating film resin film, different for preventing Object etc. is used to the purpose of attachment and the scuffing of interlayer insulating film resin film.Protective film is by interlayer insulating film resin film It is stripped before being laminated in circuit substrate etc. by lamination, hot pressing etc..

As protective film, material same as supporting mass can be used.The thickness of protective film can be used for example with 1~ The protective film of 40 μm of thickness.

The manufacturing method > of < interlayer insulating film resin film

Interlayer insulating film of the invention can for example apply interlayer insulating film resin combination with resin film on supporting mass It is dried and manufactures after object.At this point, interlayer insulating film with resin combination preferably in organic solvent dissolve and/or disperse and Form the state of varnish.

(organic solvent)

It as organic solvent, can enumerate: acetone, methyl ethyl ketone (hereinafter also referred to as " MEK "), methyl iso-butyl ketone (MIBK), hexamethylene The ketone series solvents such as ketone；Ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether, carbitol acetate Equal acetic acid ester series solvent；The carbitols series solvent such as cellosolve, butyl carbitol；The aromatic hydrocarbon series solvents such as toluene, dimethylbenzene；Two Acid amides series solvents such as methylformamide, dimethyl acetamide, N-Methyl pyrrolidone etc..These can be used alone, Two or more kinds may be used.Among these, from the viewpoint of dissolubility, preferred ketone series solvent, more preferable MEK, methyl-isobutyl Ketone.

It, can be using comma coater, bar coater, kiss as the method for coating interlayer resin compositions for insulating layer The method that applying device well known to painting machine, roll coater, gravure coater, die coating machine etc. is applied.Applying device is according to target Film thickness suitably selects.

As the drying condition after coating interlayer resin compositions for insulating layer, preferably used according to obtained interlayer insulating film The content of organic solvent in resin film becomes 10 mass % modes below and is dried, more preferably according to as 5 mass % Mode below is dried.

Drying condition difference according to the amount and type of the organic solvent in varnish, for example, if 20~80 matter are included Measure the varnish of the organic solvent of %, then it is 1~10 minute dry with 50~150 DEG C.

[multilayer printed circuit board]

Multilayer printed circuit board of the invention, which uses, is selected from interlayer insulating film resin film and multi-layer resinous film of the invention In it is at least one kind of and obtain.That is, interlayer insulating film of the invention uses the resin film to be as multilayer printed circuit board purposes Useful.In turn, interlayer insulating film of the invention uses resin film as multilayer printed circuit board, particularly the layer of lamination wiring plate It is also useful that lamination, which forms purposes,.

Multilayer printed circuit board of the invention can be for example, by including that [wherein, process (3) is appointed for following processes (1)~(6) Meaning.] manufacturing method manufacture, supporting mass can be removed or be removed after process (1), (2) or (3).

It should be noted that hereinafter, refer in the case where being only called " resin film " " interlayer insulating film resin film " and Both " multi-layer resinous film ".

(1) process [the hereinafter referred to as laminating process of resin film of the invention is laminated in the one or two sides of circuit substrate (1)]。

(2) the resin film heat cure that will be laminated in process (1) forms process [the hereinafter referred to as insulating layer shape of insulating layer At process (2)].

(3) on the circuit substrate for foring insulating layer in process (2) aperture process [hereinafter referred to as aperture process (3)]。

(4) except the process of desmearing [hereinafter referred to as except the dirty process (4) of brill].

(5) after except dirty process (4) is bored, the process of conductor layer is formed [hereinafter referred to as by plating on the surface of insulating layer Conductor layer formation process (5)].

(6) by semi-additive process, the process [hereinafter referred to as circuit formation process (6)] of circuit is formed in conductor layer.

Laminating process (1) is that resin film layer of the invention is pressed in the single side or two of circuit substrate using vacuum laminator The process in face.It as vacuum laminator, can enumerate: the vacuum pack system machine of Nichigo-Morton Co. Ltd. system, strain formula meeting Society's name mechanism makees roll-type dry type coating machine, the Hitachi of made vacuum pressure type laminating machine, Hitachi Co., Ltd The vacuum laminator etc. of Kasei Electronics Co. Ltd. system.

, can be after it will protect film stripping or remove in the case where resin film is equipped with protective film, layer according to the invention Between the interlayer insulating film of insulating layer resin film or multi-layer resinous film of the invention contacted with resin composition layer with circuit substrate Mode, be crimped on circuit substrate while pressurizeing and heating and be laminated.

The lamination for example can be after being preheated resin film and circuit substrate, in crimping temperature 60 as needed ~140 DEG C, 0.1~1.1MPa of crimping pressure (9.8 × 10⁴~107.9 × 10⁴N/m²), air pressure 20mmHg (26.7hPa) with Under decompression under implement.In addition, the method for lamination can be intermittent, it is also possible to the continous way using roller.

In insulating layer formation process (2), firstly, the resin film for being laminated to circuit substrate in laminating process (1) is cooled to Near room temperature.

In the case where removing supporting mass, after removing, the resin film for being laminated to circuit substrate is made to be heating and curing and be formed Insulating layer, the insulating layer for becoming " interlayer insulating film " later.The case where using the multi-layer resinous film containing bonding auxiliary layer Under, the insulating layer being here formed as becomes the solidfied material of solidfied material and bonding auxiliary layer by interlayer insulating film resin composition layer The layer of composition.

Being heating and curing can be carried out with 2 stages, and as its condition, for example, can enumerate: the 1st stage is with 100~200 DEG C It carries out 5~30 minutes, the 2nd stage was carried out 20~80 minutes with 140~220 DEG C.Using the supporting mass for implementing demoulding processing In the case where, supporting mass can be removed after heat cure.

After forming insulating layer by above-mentioned method, it can according to need via aperture process (3).Aperture process (3) is: Aperture, shape are carried out by the methods of drill bit, laser, plasma, their combination on circuit substrate and the insulating layer of formation At the process of via hole, through-hole etc..As laser, carbon dioxide gas volumetric laser, YAG laser, UV laser, quasi-molecule can be used and swash Light etc..

It is so-called by being generated whens forming via hole, through-hole etc. on insulating layer and circuit substrate except boring in dirty process (4) " boring dirty " is removed by oxidant.At this point it is possible to carry out roughening treatment by surface of the oxidant to insulating layer.That is, The roughening treatment and the removing for boring dirt can carry out simultaneously.

As above-mentioned oxidant, can enumerate: permanganate (potassium permanganate, sodium permanganate etc.), bichromate, ozone, Hydrogen peroxide, sulfuric acid, nitric acid etc..In these, it can be used as the insulation using lamination technique manufacture multilayer printed circuit board When layer roughening general oxidant, (such as the sodium hydroxide of potassium permanganate, sodium permanganate is water-soluble for alkaline permanganic acid solution Liquid).

By roughening treatment, concave-convex anchoring is formed on the surface of insulating layer.

In conductor layer formation process (5), formd in the roughening treatment by removing progress simultaneously in the dirty process (4) of brill recessed The surface of the insulating layer of convex anchoring forms conductor layer by plating.

As method for plating, electroless plating method, galvanoplastic etc. can be enumerated.As long as the metal of plating application is that can be used in The metal of plating is then not particularly limited.Plate application metal can from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminium, tungsten, iron, titanium, Chromium or comprising being selected at least one kind of alloy in these metallic elements, preferably copper, nickel, more preferably copper.

It should be noted that can also be with the following method: being pre-formed and conductor layer (wiring pattern) opposite pattern Plating resist, it is thereafter, only conformal at conductor layer (wiring pattern) by electroless plating.

After the formation of conductor layer, it can implement to make annealing treatment for 20~120 minutes with 150~200 DEG C.By implementing at annealing Reason, has the adhesive strength between interlayer insulating film and conductor layer to further increase and stabilized tendency.Furthermore it is possible to by should Annealing, and promote the solidification of interlayer insulating film.

In circuit formation process (6), as the method for carrying out pattern processing to conductor layer and forming circuit, half addition is utilized Method (SAP:SemiAdditive Process).It is formed in the conductor layer (seed layer) formed in conductor layer formation process (5) After the pattern of resist, carrying out the platings such as electrolytic copper plating grows circuit.Thereafter, plating resist is removed, then between circuit Seed layer be etched to completing wiring plate.

It can be by the roughing in surface (Darkening process) of the conductor layer so made (circuit).By the way that the surface of conductor layer is thick Change, thus the tendency that is improved of adhesion with the resin of contact conductor layer.In order to conductor layer to be roughened, can be used as having " CZ-8100 " of machine acid system micro-etching agent, " CZ-8101 ", " CZ-5480 " (all MEC Corp.'s systems, trade name) Deng.

It as circuit substrate used in multilayer printed circuit board of the invention, can enumerate: in expoxy glass, Metal Substrate The one or two sides of the substrates such as plate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate forms The substrate of conductor layer (circuit) through pattern processing.

It is formed in addition, conductor layer is alternately carried out layer with insulating layer, there is the conductor processed through pattern in one or two sides The multilayer printed circuit board of layer (circuit)；Have in the one or two sides of foregoing circuit substrate and is formed by resin film of the invention Interlayer insulating film has the circuit substrate for the conductor layer (circuit) processed through pattern in its one or two sides；Make it is of the invention The one or two sides for the solidfied material that resin film is sticked together and is solidified to form has the conductor layer (circuit) processed through pattern In the circuit substrate that circuit substrate etc. is also included in the present invention.

From the viewpoint of interlayer insulating film to the cementability of circuit substrate, for example preceding institute in the surface of the conductor layer of circuit substrate Roughening treatment can be implemented by Darkening process etc. in advance by stating.

[semiconductor package body]

Semiconductor package body of the invention is on multilayer printed circuit board of the invention made of semiconductor element mounted thereon. Semiconductor package body of the invention can be by carrying semiconductor core in the defined position of multilayer printed circuit board of the invention The semiconductor elements such as piece, memory manufacture.Furthermore, it is possible to pass through sealing resin etc. for semiconductor element encapsulation.

Embodiment

Then, by embodiment the 1st invention is further described in [a], but the 1st invention is not limited by these examples.

Embodiment 1

As epoxy resin, cooperate " NC-3000-H " (Japanese chemical drug strain as biphenyl novolac type epoxy resin Formula commercial firm system, trade name, 100 mass % of solid component concentration) 25.8 mass parts,

As novolac type phenolic resin, cooperate " PAPS-PN2 " (Asahi Organic Chem Ind's system, trade name, 100 mass %, Mw/Mn=1.17 of solid component concentration) 6.3 mass parts,

As epoxy curing agent, cooperate " LA-1356-60M " as triazine modified phenol linear phenol-aldehyde resin (Dainippon Ink Chemicals's system, trade name, solvent: MEK, 60 mass % of solid component concentration) 4.9 mass parts,

As inorganic filling material, with share amino silicane coupling agent to " SO-C2 " (Co., Ltd.'s Admatechs system, Trade name, average grain diameter；0.5 μm) surface handled, and further make its be scattered in the silica in MEK (solid at Divide 70 mass % of concentration) 92.9 mass parts,

As curing accelerator, cooperate " 2E4MZ " (four countries' chemical conversion industry strain formula as 2-ethyl-4-methylimidazole Commercial firm's system, trade name, 100 mass % of solid component concentration) 0.026 mass parts,

As additional solvent, cooperate MEK13.1 mass parts, implements mixing and ball mill decentralized processing and made adhesive film With resin composition Chinese varnish 1.

(Di Ren Du Pont is thin by the PET for using resin composition Chinese varnish 1 to be coated on as supporting mass film adhesive film obtained above Film Co. Ltd. system, trade name: G2, film thickness: 50 μm) on after, be dried, formed resin composition layer.It should be noted that Applied thickness is set as 40 μm, and drying carries out in such a way that the residual solvent in resin composition layer becomes 8.0 mass %.It is dry Afterwards, polyethylene film (TAMAPOLY Co. Ltd. system, trade name: NF-13, thickness: 25 μ is laminated in resin composition layer surface side M) it is used as protective film.Thereafter, obtained film roll is taken into web-like, obtains adhesive film 1.

Embodiment 2~6,8, comparative example 1~4

In embodiment 1, raw material composition, manufacturing condition are recorded according to table 1 and is changed, in addition to this, similarly to Example 1 Ground obtains adhesive film 2~6,8~12.

Embodiment 7

Prepare that the resin varnish A made according to the following steps is coated on as bearing in the way of as 10 μm of film thickness On the PET (Supreme Being people's DuPont Film Co. Ltd. system, trade name: G2, film thickness: 50 μm) of body film and 60 μ m-thicks obtained from drying Supporting mass film 2.

The above-mentioned resin varnish A used makes according to following step.

As epoxy resin, cooperate " NC-3000-H " (Japanese chemical drug strain as biphenyl novolac type epoxy resin Formula commercial firm system, trade name, 100 mass % of solid component concentration) 63.9 mass parts,

As epoxy curing agent, cooperate " LA-1356-60M " as triazine modified phenol linear phenol-aldehyde resin (Dainippon Ink Chemicals's system, trade name, solvent；MEK, 60 mass % of solid component concentration) 18.0 mass parts,

Cooperate " EXL-2655 " (Rohm and Haas Electronics Materials Co., Ltd system, quotient as Core-shell rubber particles The name of an article) 15.2 mass parts,

As inorganic filling material, cooperate " the Aerosil R972 " as pyrogenic silica (Aerosil plants Japanese Formula commercial firm system, trade name, average grain diameter；0.02 μm, 100 mass % of solid component concentration) 8.8 mass parts,

As curing accelerator, cooperate " 2E4MZ " (four countries' chemical conversion industry strain formula as 2-ethyl-4-methylimidazole Commercial firm's system, trade name, 100 mass % of solid component concentration) 1.28 mass parts,

As additional solvent, cooperate 226.1 mass parts of cyclohexanone, implements mixing and ball mill decentralized processing and made tree Rouge varnish A.

By resin varnish A obtained above coated in the PET as supporting mass film in the way of as 10 μm of film thickness It after in (Supreme Being people's DuPont Film Co. Ltd. system, trade name: G2, film thickness: 50 μm), is dried, obtains the branch that film thickness is 60 μm Hold body film 2.

Then, it is formed, under manufacturing condition in the raw material that table 1 is recorded, is produced on branch obtained above similarly to Example 1 Hold the adhesive film resin composition Chinese varnish applied on body film 2.

Using supporting mass film 2 and adhesive film resin composition Chinese varnish, adhesive film 7 is obtained similarly to Example 1.

[evaluation method]

Obtained adhesive film 1~12 is evaluated by the following method.

(the operability test of the adhesive film production and test method of sample)

Obtained adhesive film 1~12 is cut into the size of 500mm × 500mm, makes the operability test of adhesive film With sample 1~12.

The operability test sample 1~12 of the adhesive film of use production, is evaluated by the method for (1) below~(3) Operability, using person bad in any test as " operability bad ", using in any test nothing but bad person as " operational Well ".

(1) for the operational test sample 1~12 of adhesive film, firstly, removing protective film.When will remove protective film, Resin a part after coating and drying is attached to the sample of protective film side or the sample of powder falling occurs as operational bad.

(2) 2 points of the central end of holding film (in the way of becoming 500mm × 250mm, holding 2 points of end), will be coated with It is bad as operability that rupture person occurs with the resin after drying.

(3) for implementing " the MCL-E- of the copper-clad laminated board of melanism and reduction treatment as the copper foil to surface 679FG (R) " (Hitachi Chemical Co., Ltd.'s system, copper foil thick 12 μm, plate thickness 0.41mm), uses intermittent vacuum pressure type layer Press " MVL-500 " (Co., Ltd. Mingji Koito's system, trade name) be laminated being laminated.Vacuum degree at this time is 30mmHg hereinafter, temperature be set as 90 DEG C, pressure be set as 0.5MPa.After being cooled to room temperature, supporting mass film is removed (for adhesive film 7 For, among supporting mass film 2, removed between the resin layer that is formed in PET and thereon).At this point, generation powder falling or PET are existed The material ruptured on the way is bad as operability.

(production and test method of MEASURING THE THERMAL EXPANSION COEFFICIENT sample)

Obtained adhesive film 1~12 is cut into the size of 200mm × 200mm respectively, protective film is removed, in the copper of 18 μ m-thicks On foil, passed through using intermittent vacuum pressure type laminating machine " MVL-500 " (Co., Ltd. Mingji Koito's system, trade name) It is laminated.Vacuum degree at this time be 30mmHg hereinafter, temperature be set as 90 DEG C, pressure be set as 0.5MPa.

After being cooled to room temperature, removing supporting mass film is (for adhesive film 7, among supporting mass film 2, in PET and thereon Removed between the resin layer of formation), solidify 120 minutes in 180 DEG C of drying machine.Thereafter, copper foil is removed with chlorination iron liquid, it will The material of wide 3mm, long 8mm are cut out as MEASURING THE THERMAL EXPANSION COEFFICIENT sample 1~12.

The MEASURING THE THERMAL EXPANSION COEFFICIENT of use production sample 1~12, measures thermal expansion coefficient by the following method.

Obtained MEASURING THE THERMAL EXPANSION COEFFICIENT sample 1~12 is used into the heat of Seiko Instruments Co. Ltd. system Mechanical analysis device obtains after being warming up to 240 DEG C with 10 DEG C/min of heating rate, be cooled to -10 DEG C, with heating rate 10 The change curve of swell increment when DEG C/min being warming up to 300 DEG C, finds out being averaged for 0~150 DEG C of the change curve of the swell increment Thermal expansion coefficient.

(production and test method of imbedibility evaluation substrate)

It is as follows that imbedibility evaluates internal layer circuit used in substrate.Be 12 μm as copper foil thickness, plate thickness be 0.15mm (packet Containing copper foil thickness) copper-clad laminated board " MCL-E-679FG (R) " (Hitachi Chemical Co., Ltd.'s system, trade name) on, according to The through-hole that diameter is 0.15mm is made by drill bit aperture legal system as the mode of 25 × 25 groups in the interval 5mm.Then, implement Except dirty and non-electrolytic plating is bored, implement to be electroplated in through-holes using plating.

As a result, obtaining being 0.2mm, with diameter be 0.1mm comprising plate thickness of the copper including thick and being divided into the 25 of 5mm The circuit substrate of a × 25 through-holes.

Then, the adhesive film 1~12 of protective film will have been removed according to the circuit surface side of resin composition layer and circuit substrate Opposed mode uses intermittent vacuum laminator " MVL-500 " (Co., Ltd. Mingji Koito's system, commodity with postponing Name) by being laminated.Vacuum degree at this time be 30mmHg, temperature be set as 90 DEG C, pressure be set as 0.5MPa.

After being cooled to room temperature, the circuit substrate with through-hole that two sides has adhesive film is clipped with the aluminium sheet of 2 1mm thickness, It is laminated using above-mentioned vacuum laminator.Vacuum degree at this time be 30mmHg, temperature be set as 90 DEG C, pressure be set as 0.7MPa.

After being cooled to room temperature, removing supporting mass film is (for adhesive film 7, among supporting mass film 2, in PET and thereon Removed between the resin layer of formation), solidify 120 minutes in 180 DEG C of drying machine.In this way, obtain imbedibility evaluation substrate 1~ 12。

The imbedibility of use production evaluates substrate 1~12, evaluates imbedibility by the following method.

Use the surface roughness meter " SV2100 " (trade name) of the contact of M Co., Ltd. ITUTOYO, measurement embedment Property evaluation substrate 1~12 throughhole portions surface difference of height.In such a way that the central part on the surface of through-hole is included in 10 Difference in height is measured, the average value of 10 recess is calculated.

[table 1]

The ingredient of table 1 is shown in following.

[epoxy resin]

NC-3000-H: biphenyl novolac type epoxy resin (Nippon Kayaku K. K's system, trade name, solid at Divide 100 mass % of concentration)

N-673-80M: cresol novolac type epoxy resin (Dainippon Ink Chemicals's system, trade name, solvent；MEK, consolidate 80 mass % of body constituent concentration)

[novolac type phenolic resin]

PAPS-PN2: novolac type phenolic resin (Asahi Organic Chem Ind's system, trade name, solid component 100 mass %, Mw/Mn=1.17 of concentration)

PAPS-PN3: novolac type phenolic resin (Asahi Organic Chem Ind's system, trade name, solid component 100 mass %, Mw/Mn=1.50 of concentration)

HP-850: using hydrochloric acid rather than novolac type phenolic resin (Hitachi Chemical Co., Ltd. of phosphoric acid production System, trade name, 100 mass % of solid component concentration)

[triazine modified phenol linear phenol-aldehyde resin]

LA-1356-60M: triazine modified phenol linear phenol-aldehyde resin (Dainippon Ink Chemicals's system, trade name, solvent； MEK, 60 mass % of solid component concentration)

[inorganic filling material]

SO-C2: by silica " SO-C2 " (trade name, average grain diameter of Co., Ltd. Admatechs；0.5μ M) surface is handled with amino silicane coupling agent, the silica (solid component concentration being further scattered in MEK solvent 70 mass %)

SO-C6: by silica " SO-C6 " (trade name, average grain diameter of Co., Ltd. Admatechs；2.2μ M) surface is handled with amino silicane coupling agent, the silica (solid component concentration being further scattered in MEK solvent 70 mass %)

Aerosil R972: (Japanese Aerosil Co. Ltd. system, trade name, solid component are dense for pyrogenic silica Spend 100 mass %, specific surface area: 100m²/g)

[curing accelerator]

(Shikoku Chem's system, trade name, solid component are dense for 2E4MZ:2- ethyl -4-methylimidazole Spend 100 mass %)

As shown in Table 1, the operability of adhesive film of the invention is good, is by the available thermal expansion of adhesive film of the invention The interlayer insulating film that number is low, imbedibility is excellent.

On the other hand, in the case where not using adhesive film of the invention, times of operability, thermal expansion coefficient, imbedibility Meaning person is poor.

I.e., it is known that: according to the 1st invention, it is capable of providing the bonding that thermal expansion coefficient is low, imbedibility is excellent, operability is excellent Film is capable of providing the low interlayer insulating film of the thermal expansion coefficient after solidifying.

[b] then, is further described in detail the 2nd invention, but the 2nd invention is not limited by these examples.

[production of interlayer insulating film resin film]

Examples 1 to 9 and comparative example 1~4

According to shown in table 2~4, with being combined into, [numerical value in table is the mass parts of solid component, and solution (removes organic molten Agent) or dispersion liquid in the case where be solid component conversion amount.] mix each ingredient, stirring.Thereafter, by ball mill process into Row dispersion, obtains the interlayer insulating film resin combination of varnish shape.

Use resin combination that die coating machine is used to be coated in 38 μ of thickness as supporting mass interlayer insulating film obtained above 1.5 minutes dry with 100 DEG C on the PET film of m, it is the more of 40 μm of interlayer insulating film resin film that thus obtaining, which has film thickness, Layer resin film, carries out each evaluation by the following method.Show the result in table 2~4.

(evaluation of (1) insulating reliability)

Insulating reliability is evaluated by high temperature and humidity bias test.In evaluation device TEG (Test Element Group) on the combed copper electrode of (trade name: WALTS-KIT EM0101JY, WALTS corporation, L/S=10 μm/10 μm), 40 μm of thickness obtained in each example of multi-layer resinous film is used into lamination with the direction that interlayer insulating film is located at combed copper electrode side Machine is bonded at 110 DEG C.Thereafter, the PET film as supporting mass is removed, is heated 2 hours, is cooled to room temperature with 190 DEG C of baking ovens, Obtain measurement sample.

In the electrode portion of the TEG of obtained measurement sample, lead is installed with solder, carries out high temperature and humidity bias test [voltage；5V (direct current), test period；200 hours, 130 DEG C, 85%RH (using high temperature and humidity machine (ESPEC corporation))].

In test period 200 hours, if resistance value keeps 1.0 × 10⁷Ω or more, it can be said that insulating reliability is excellent.

(evaluation of (2) operability)

It is exhausted with interlayer on supporting mass after multi-layer resinous film obtained in each example is placed 5 days under room temperature (25 DEG C) In the state of edge layer resin film, it is that outside (inside is in PET film side) bends 180 ° using interlayer insulating film with resin film side, passes through The presence or absence of visual confirmation rupture.Equally, 20 multi-layer resinous films are confirmed, with " the number of the multi-layer resinous film ruptured The form of amount/20 " indicates.

(measurement (evaluation of heat resistance) of (3) glass transition temperature (Tg))

For glass transition temperature (Tg), the multi-layer resinous film stripping supporting mass obtained in each example and only forming layer Between insulating layer resin film, make by 5 resin films be laminated laminated body at 190 DEG C heat cure 120 minutes, solidified Object.

The solidfied material is cut out into vertical 40mm (X-direction), horizontal 4mm (Y-direction), 200 μm of thickness (Z-direction) conduct evaluation bases Plate carries out the evaluation substrate using thermo-mechanical analysis device (TA Instrument corporation, Q400) using compression method Thermo-mechanical analysis.Specifically, after above-mentioned evaluation substrate being installed on above-mentioned apparatus along draw direction (direction x-y), in load METHOD FOR CONTINUOUS DETERMINATION twice, finds out the thermal dilatometry in second of measurement under 5mg, 10 DEG C/min of heating rate of determination condition Tg shown in the intersection point of different tangent lines, the index as heat resistance.

[table 2]

Table 2

* 1 indicates the sum of the total functional group relative to (a) epoxy resin of the functional group of (b) curing agent.

* 2 indicate the content of hindered phenolic compound or unimpeded phenol system compound.

[table 3]

Table 3

* 1 indicates the sum of the total functional group relative to (a) epoxy resin of the functional group of (b) curing agent.

[table 4]

Table 4

* 1 indicates the sum of the total functional group relative to (a) epoxy resin of the functional group of (b) curing agent.

The ingredient recorded in table 2~4 is shown in following.

[(a) epoxy resin]

N-673: cresol novolac type epoxy resin (Dainippon Ink Chemicals's system " EPICLON (registered trademark) N-673 ", 100 mass % of solid component concentration, epoxide equivalent: 210g/eq)

JER 157S70: bisphenol A novolac type epoxy resin (Mitsubishi chemical Co., Ltd's system, epoxide equivalent: 210g/eq, 100 mass % of solid component concentration)

NC-3000-H: the aralkyl novolac type epoxy resin (Nippon Kayaku K. K with biphenyl backbone System, 100 mass % of solid component concentration, epoxide equivalent: 289g/eq)

JER828: liquid-state epoxy resin (the Mitsubishi chemical Co., Ltd's system, 100 matter of solid component concentration of bisphenol A-type Measure %, epoxide equivalent: 185g/eq)

[(b) curing agent]

BA230S: prepolymer (Lonza corporation " Primaset BA230S "), (b2) of bisphenol A cyanate ester resin Ingredient

HPC-8000-65T: active ester resin (Dainippon Ink Chemicals's system " EPICLON (registered trademark) HPC- 8000-65T ", 65 mass % of solid component concentration, remove toluene product), (b1) ingredient

LA-7054: phenol novolaks (Dainippon Ink Chemicals's system " Phenolite (registrar containing triazine Mark) LA-7054 "), (b3) ingredient

PAPS-PN2: containing triazine phenol novolaks (Asahi Organic Chem Ind's system, solid at Point 100 mass %, Mw/Mn=1.17 of concentration), (b3) ingredient

LA3018-50P: cresol novolaks (Dainippon Ink Chemicals's system " Phenolite (registration containing triazine Trade mark) LA3018-50P "), (b3) ingredient

(other curing agent)

HCA-HQ-HS: phosphorous phenolic compounds (Sanko Co., Ltd.'s system), 10- (2,5- dihydroxy phenyl) -9, Miscellaneous -10- phospho hetero phenanthrene -10- the oxide of 10- dihydro-9-oxy

[(c) inorganic filling material]

SO-C2: implement amino silicane coupling agent processing spherical silicon dioxide (Co., Ltd.'s Admatechs system, 0.5 μm of volume average particle size, 100 mass % of solid component concentration)

[(d) (d ') hindered phenolic compound]

Yoshinox BB:4,4 '-butylidenebis-(6- tert-butyl -3- methylphenol) (Mitsubishi Chemical's strain formula meeting Society's system)

BHT:2,6- di-t-butyl-paracresol (Tokyo Chemical Industry Co., Ltd's system)

Yoshinox 425:2,2 '-di-2-ethylhexylphosphine oxide-(4- ethyl -6- tert-butyl phenol) (Mitsubishi Chemical's strain formula Commercial firm's system)

(unimpeded phenol system compound)

Bisphenol-A: Tokyo Chemical Industry Co., Ltd's system

[(e) phenoxy resin]

YX7200B35: phenoxy resin (Mitsubishi chemical Co., Ltd's system " jER (registered trademark) YX7200B35 ", ring Oxygen equivalent: 3,000~16,000g/eq, 35 mass % of solid component concentration, MEK is removed)

[(f) curing accelerator]

TPP: triphenylphosphine (Kanto Kagaku K. K.'s system), organic system curing accelerator

Zinc naphthenate: (Wako Pure Chemical Industries, Ltd.'s system, 8 mass % of solid component concentration, benzin solution), gold Category system curing accelerator

2PZ-CNS-PW:1- cyano ethyl -2- phenyl trimellitic acid imidazoles (Shikoku Chem System)

[additional organic solvent]

Cyclohexanone: Co., Ltd.'s GODO system

By table 2~4 it is found that the heat resistance of the interlayer insulating film resin film of Examples 1 to 9 and insulating reliability are high, and And operability is also excellent.

On the other hand, obtained in the comparative example 1~4 for interlayer insulating film resin film, insulating reliability or operation The arbitrary characteristic of property is poor, cannot take into account.

Claims (1)

1. a kind of adhesive film of multilayer printed circuit board, having will be made of resin combination forming layer on supporting mass film Resin composition layer,

The resin combination includes:

(A) the novolac type phenolic aldehyde tree that the dispersion ratio Mw/Mn of weight average molecular weight Mw and number-average molecular weight Mn is 1.05~1.8 Rouge,

(B) epoxy resin shown in the following general formula (1) and

(C) inorganic filling material,

Wherein, the average grain diameter of (C) inorganic filling material in the resin composition layer is 0.1 μm or more,

(C) content of inorganic filling material is the 20 mass % of mass %~95 in resin solid content,

In formula, p indicates 1~5 integer.