CN104292749A

CN104292749A - Resin composition

Info

Publication number: CN104292749A
Application number: CN201410340425.7A
Authority: CN
Inventors: 渡边真俊; 中村茂雄; 佐川幸一郎
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2013-07-19
Filing date: 2014-07-17
Publication date: 2015-01-21
Also published as: KR20150010624A; TW201518390A; JP6582366B2; JP2015038197A; TWI629306B; JP6801736B2; JP2019104941A

Abstract

The invention provides a resin composition, a cured product which is low in linear thermal expansion coefficient, low in roughness, and high in stripping strength, and a sheet-shaped laminated material which is excellent in lamination property. The resin composition comprises (A) epoxy resin, (B) a curing agent, and (C) filling with an average linear thermal expansion coefficient below 300 ppb/DEG C between 30-150 DEG C.

Description

Resin combination

Technical field

The present invention relates to resin combination.

Background technology

Multilayer printed circuit board is widely used in various electronic machine, electronic unit.As the manufacturing technology of multilayer printed circuit board, the known manufacture method that make use of stacking (PVC Le De アップ) mode of alternately lapped insulation layer and conductor layer on the internal layer circuit substrate possessing circuit conductor.

The manufacture method that make use of stack manner is implemented with following step usually.First resin composition layer is set on internal layer circuit substrate, makes this resin composition layer be solidified to form insulation layer.Then, after making surface of insulating layer swelling with swelling liquid, carry out roughening with oxygenant, form minute asperities at surface of insulating layer.Then, according to known methods such as semi-additive process, the conductor layer with regulation line pattern is formed at surface of insulating layer.

In recent years, when manufacturing multilayer printed circuit board, the known splitting that causes in order to the thermal expansion difference prevented because of insulation layer and conductor layer or rupture of line, low coefficient of linear thermal expansion is required to interlayer dielectic, and fill filler in a large number in the resin combination used in the formation of insulation layer, realize low coefficient of linear thermal expansion (such as, patent documentation 1, patent documentation 2) thus.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2005-38821 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2006-4854 publication.

Summary of the invention

The problem that invention will solve

The present inventor has found the increase along with loading level when utilizing filler in the past to study, melt viscosity, surfaceness also rise, and the formation of microfine circuit easily becomes difficult such problem.

Problem of the present invention is to provide resin combination, and it brings low coefficient of linear thermal expansion, low roughness and the high cured article of stripping strength, and has the platy layer laminate materials of excellent laminated property.

For the method for dealing with problems

The present inventor furthers investigate repeatedly in view of above-mentioned problem, found that by using following resin combination, above-mentioned problem can be solved, thus completing the present invention, described resin combination contains: the average thermal linear expansion coefficient between (A) epoxy resin, (B) solidifying agent, (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C.

Namely, the present invention comprises following content:

[1] resin combination, it contains: the average thermal linear expansion coefficient between (A) epoxy resin, (B) solidifying agent, (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C;

[2] resin combination described in [1], wherein, when the nonvolatile component in resin combination is set to 100 volume %, the average thermal linear expansion coefficient between (C) containing 5 ~ 80 volumes 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C;

[3] [1] or the resin combination described in [2], wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the median size of the filler of less than 300ppb/ DEG C is 0.01 ~ 10 μm;

[4] resin combination according to any one of [1] ~ [3], wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the proportion of the filler of less than 300ppb/ DEG C is 1 ~ 7g/cm ³;

[5] resin combination according to any one of [1] ~ [4], wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is spherical inorganic filler or disintegrated mineral filler;

[6] resin combination according to any one of [1] ~ [5], wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is be selected from the filler of more than a kind in glass filler and zirconium phosphate system filler;

[7] resin combination according to any one of [1] ~ [6], wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is titanium doped type glass filler ;

[8] resin combination according to any one of [1] ~ [7], wherein, (B) solidifying agent is selected from the solidifying agent of more than a kind in active ester system solidifying agent, cyanate system solidifying agent, phenol system solidifying agent (Off ェノー Le system sclerosis drug) and naphthols system solidifying agent;

[9] resin combination according to any one of [1] ~ [8], wherein, (A) epoxy resin is bisphenol A type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylidene ether type epoxy or their mixture of more than two kinds

(B) solidifying agent is active ester system solidifying agent,

(C) average thermal linear expansion coefficient between 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is titanium doped type glass filler;

[10] resin combination according to any one of [1] ~ [9], wherein, the average thermal linear expansion coefficient of 25 DEG C to 150 DEG C of the cured article of this resin combination is below 20ppm,

The Ra on the cured article surface of cured article after roughened of this resin combination is below 400nm, and

Form the cured article of this resin combination, the cured article surface after the roughened of this cured article forms conductor layer by plating, and this cured article surface is more than 0.4kgf/cm with the plating stripping strength of this conductor layer;

[11] resin combination according to any one of [1] ~ [10], it is for the insulation layer of multilayer printed circuit board;

[12] adhering film, it contains [1] ~ [11] according to any one of resin combination;

[13] adhering film described in [12], wherein, the melt viscosity of resin composition layer at 100 DEG C of this adhering film is below 35000 pools;

The cured article of the resin combination [14] according to any one of [1] ~ [11];

[15] cured article described in [14], wherein, the average thermal linear expansion coefficient of 25 DEG C to 150 DEG C is below 20ppm;

[16] [14] or the cured article described in [15], wherein, the Ra on the cured article surface after roughened is below 400nm;

[17] cured article according to any one of [14] ~ [16], wherein, when cured article surface after the roughened of cured article forms conductor layer by plating, this cured article surface is more than 0.4kgf/cm with the plating stripping strength of this conductor layer;

[18] multilayer printed circuit board, it has [14] ~ [17] according to any one of cured article;

[19] semiconductor device, is characterized in that, uses the multilayer printed circuit board described in [18];

[20] resin compositions for insulating layer of multilayer printed circuit board, the average thermal linear expansion coefficient between it contains (A) epoxy resin, (B) solidifying agent, (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C, wherein,

Should (A) epoxy resin be bisphenol A type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylidene ether type epoxy or their mixture of more than two kinds,

Should (B) solidifying agent be active ester system solidifying agent,

The average thermal linear expansion coefficient be somebody's turn to do between (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is titanium doped type glass filler,

The average thermal linear expansion coefficient of 25 DEG C to 150 DEG C of the cured article of this resin combination is below 20ppm,

Form the cured article of this resin combination, the cured article surface after the roughened of this cured article forms conductor layer by plating, and this cured article surface is more than 0.4kgf/cm with the plating stripping strength of this conductor layer.

Invention effect

According to the present invention, can provide resin combination, it brings low thermal coefficient of expansion, low roughness and the high cured article of stripping strength, and has the platy layer laminate materials of excellent laminated property.

Embodiment

Resin combination of the present invention contains: the average thermal linear expansion coefficient between (A) epoxy resin, (B) solidifying agent, (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C.

< (A) epoxy resin >

As " epoxy resin " that uses in the present invention, can enumerate such as: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol (trisphenol) epoxy resin, naphthol novolac epoxy resin (Na フトー Le ノボラッ Network エ Port キシ Trees fat), novolac type epoxy resin (Off ェノー Le ノボラッ Network type エ Port キシ Trees fat), tert-butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthalene four functional-type epoxy resin, naphthol type epoxy resin, naphthylidene ether type epoxy, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresoform type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl-type epoxy resin, linear aliphatic race epoxy resin, there is the epoxy resin of butadiene structure, alicyclic epoxy resin, hetero ring type epoxy resin, containing the epoxy resin of volution, cyclohexanedimethanol type epoxy resin, naphthylidene ether type epoxy and trishydroxymethyl type epoxy resin etc.Wherein, preferred bisphenol A type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylidene ether type epoxy and their mixture of more than two kinds.Epoxy resin can a kind be used alone, or and use two or more.

Epoxy resin preferably is contained in the epoxy resin in 1 molecule with more than 2 epoxy group(ing).During using the nonvolatile component of epoxy resin as 100 quality %, preferably more than at least 50 quality % are the epoxy resin in 1 molecule with more than 2 epoxy group(ing).

In addition, preferably also to be contained at temperature 20 DEG C as liquid epoxy resin (hereinafter referred to as " liquid-state epoxy resin ") and to be solid-state epoxy resin (hereinafter referred to as " solid epoxy resin ") at temperature 20 DEG C.As epoxy resin, by also with liquid-state epoxy resin and solid epoxy resin, can obtain that there is excellent flexible resin combination.In addition, the breaking tenacity of the insulation layer formed by resin composition also improves.

As liquid-state epoxy resin, preferred bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac type epoxy resin or naphthalene type epoxy resin, more preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin or naphthalene type epoxy resin.As the concrete example of liquid-state epoxy resin, can enumerate: " ZX1059 " (melange of bisphenol A type epoxy resin and bisphenol f type epoxy resin) etc. that " jER828EL " (bisphenol A type epoxy resin) that " HP4032 ", " HP4032D ", " EXA4032SS " that DIC (strain) makes, " HP4032SS " (naphthalene type epoxy resin), Mitsubishi Chemical's (strain) make, " jER807 " (bisphenol f type epoxy resin), " jER152 " (novolac type epoxy resin), Nippon Steel's chemistry (strain) are made.As liquid-state epoxy resin, particularly preferably " HP4032SS " (naphthalene type epoxy resin), " ZX1059 " (melange of bisphenol A type epoxy resin and bisphenol f type epoxy resin).Liquid-state epoxy resin can a kind be used alone, or and use two or more.

As solid epoxy resin, preferably 4 officials' energy naphthalene type epoxy resin, cresoform type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin or naphthylidene ether type epoxy, more preferably 4 officials can naphthalene type epoxy resin, biphenyl type epoxy resin or naphthylidene ether type epoxy, further preferred biphenyl type epoxy resin.As the concrete example of solid epoxy resin, can enumerate: " HP-4700 " that DIC (strain) makes, " HP-4710 " (4 officials' energy naphthalene type epoxy resin), " N-690 " (cresoform type epoxy resin), " N-695 " (cresoform type epoxy resin), " HP-7200 ", " HP7200H ", " HP7200K-65I " (dicyclopentadiene-type epoxy resin), " EXA7311 ", " EXA7311-G3 ", " EXA7311-G4 ", " HP6000 " (naphthylidene ether type epoxy), " EPPN-502H " (trisphenol epoxy resin) that Japan's chemical drug (strain) makes, " NC7000L " (naphthol novolac epoxy resin), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin), " ESN475V " (naphthol novolac type epoxy resin) that Nippon Steel's chemistry (strain) is made, " ESN485 " (naphthol novolac type epoxy resin), " YX4000H " that Mitsubishi Chemical's (strain) makes, " YL6121 " (biphenyl type epoxy resin), " YX4000HK " (di-first phenol-type epoxy resin) etc." HP7200H " (dicyclopentadiene-type epoxy resin) that " YX4000HK " (di-first phenol-type epoxy resin), " NC3000L " (biphenyl type epoxy resin), DIC (strain) that particularly preferably Japanese chemical drug (strain) is made make.Solid epoxy resin can a kind be used alone, or and use two or more.

As epoxy resin, when also with liquid-state epoxy resin and solid epoxy resin, their amount is preferably the scope of 1: 0.1 ~ 1: 4 by quality ratio than (liquid-state epoxy resin: solid epoxy resin).By making the amount of liquid-state epoxy resin and solid epoxy resin than being above-mentioned scope, can obtain: the cementability bringing appropriateness when i) using with the form of adhering film; Sufficient flexibility is obtained and operability raising when ii) using with the form of adhering film; And iii) effects such as the insulation layer with sufficient breaking tenacity can be obtained.From the view point of above-mentioned i) ~ iii) effect, the amount of liquid-state epoxy resin and solid epoxy resin is more preferably the scope of 1: 0.3 ~ 1: 3.5 by quality ratio than (liquid-state epoxy resin: solid epoxy resin), the more preferably scope of 1: 0.6 ~ 1: 3, is particularly preferably the scope of 1: 0.8 ~ 1: 2.5.

During using the nonvolatile component in resin combination as 100 quality %, the content of the epoxy resin in resin combination is preferably 20 quality % ~ 50 quality %, is more preferably 25 quality % ~ 45 quality %, more preferably 30 quality % ~ 40 quality %.

The epoxy equivalent (weight) of epoxy resin is preferably 50 ~ 3000, is more preferably 80 ~ 2000, more preferably 110 ~ 1000.By being this scope, the cross-linking density that can form cured article fully and the low insulation layer of surfaceness.Should illustrate, epoxy equivalent (weight) can measure according to JIS K7236, and it is the quality of the resin containing 1 equivalent epoxy group(ing).

< (B) solidifying agent >

As solidifying agent, as long as have, the function of epoxy resin cure is not particularly limited, can enumerates such as: active ester system solidifying agent, cyanate system solidifying agent, phenol system solidifying agent, naphthols system solidifying agent, benzoxazine system solidifying agent etc.Wherein, the solidifying agent of more than a kind be selected from active ester system solidifying agent, cyanate system solidifying agent, phenol system solidifying agent and naphthols system solidifying agent is preferably used, more preferably active ester system solidifying agent.Solidifying agent can a kind be used alone, or and use two or more.

Active ester system solidifying agent is not particularly limited, and generally can preferably use the ester class etc. of phenolic ester class (phenol esters), thiophenol ester (thiophenol esters) class, N-hydroxylamine esters, heterocycle hydroxyl compound in 1 molecule, have the compound of the high ester group of more than 2 reactive behavioies.This active ester system solidifying agent preferably by carboxylic acid cpd and/or thiocarboxylic acid compound and oxy-compound and/or mercaptan compound condensation reaction and obtain.Particularly from the view point of raising thermotolerance, the active ester system solidifying agent preferably obtained by carboxylic acid cpd and oxy-compound, the active ester system solidifying agent more preferably obtained by carboxylic acid cpd and oxybenzene compound and/or naphthol compound.As carboxylic acid cpd, can enumerate such as: phenylformic acid, acetic acid, succsinic acid, toxilic acid, methylene-succinic acid, phthalic acid, m-phthalic acid, terephthalic acid, Pyromellitic Acid etc.As oxybenzene compound or naphthol compound, can enumerate such as: quinhydrones, Resorcinol, dihydroxyphenyl propane, Bisphenol F, bisphenol S, phenolphthalin, the dihydroxyphenyl propane that methylates, the Bisphenol F that methylates, the bisphenol S that methylates, phenol, ortho-cresol, meta-cresol, p-cresol, catechol, naphthyl alcohol, 2-Naphthol, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlenes, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, Phloroglucinol, benzene triol, dicyclopentadienyl biphenol, lacquer resins (phenol novolac) etc.

Particularly; the active ester compound of the active ester compound preferably containing dicyclopentadiene-type biphenol fused structure, the active ester compound containing naphthalene structure, the active ester compound of the acetylate containing lacquer resins, the benzoylate containing lacquer resins; wherein, the active ester compound more preferably containing dicyclopentadiene-type biphenol fused structure.

As the active ester solidifying agent containing dicyclopentadiene-type biphenol fused structure, the compound shown in following formula (1) more specifically can be enumerated.

In formula (1), 2 R are phenyl or naphthyl independently of each other.K represents 0 or 1.N is the average of repeating unit and is 0.05 ~ 2.5.

From the view point of making dielectric loss tangent reduce, make thermotolerance improve, R is preferably naphthyl.K is preferably 0.In addition, n is preferably 0.25 ~ 1.5.

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

As cyanate system solidifying agent, can enumerate such as: bisphenol A dicyanate, polyphenol cyanate (oligomeric (3-methylene radical-1, 5-phenylenecyanate)), 4, 4'-methylene-bis (2, 6-3,5-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluoro bisphenol-a dicyanate, 2, two (4-cyanate) phenyl-propane of 2-, 1, 1-two (4-cyanate phenylmethane), two (4-cyanate-3, 5-3,5-dimethylphenyl) methane, 1, two (4-cyanate phenyl-1-(methyl the ethylidene)) benzene of 3-, two (4-cyanate phenyl) thioether, can cyanate ester resins with two (4-cyanate phenyl) ether etc. 2 officials, the multifunctional cyanate ester resin derivative by lacquer resins (phenol novolac) and Cresol Formaldehyde Resin (cresol novolac) etc., a part for these cyanate ester resins is by the prepolymer etc. of triazine.As the preferred concrete example of cyanate system solidifying agent, can enumerate: " PT30 " and " PT60 " (being novalac-type multifunctional cyanate ester resin) that ロ Application ザジャパ Application (strain) makes, " BA230 " (part or all of bisphenol A dicyanate is formed trimerical prepolymer by triazine) etc.

As phenol system solidifying agent and naphthols system solidifying agent, from the view point of thermotolerance, preferably there is the phenol system solidifying agent of lacquer resins structure (ノボラッ Network Agencies makes) or there is the naphthols system solidifying agent of lacquer resins structure.In addition, from the view point of the adaptation with conductor layer (circuit-line), be preferably nitrogenous phenol system solidifying agent, be more preferably the phenol system solidifying agent containing triazine skeleton.Wherein, from the view point of thermotolerance and the adaptation (stripping strength) with conductor layer, preferably use the lacquer resins containing triazine skeleton as solidifying agent.

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

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

As long as epoxy resin cure can be not particularly limited by the amount of the solidifying agent in resin combination, during using the nonvolatile component in resin combination as 100 quality %, such as, be 15 ~ 50 quality %, be preferably 20 ~ 45 quality %, be more preferably 25 ~ 40 quality %.

Average thermal linear expansion coefficient between < (C) 30 DEG C to 150 DEG C is the filler > of less than 300ppb/ DEG C

As the measuring method of the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C of filler, such as, by utilizing the thermal dilatometer of laser interferometer test samples elongation or being measured by known methods such as X-ray diffraction methods.

As " average thermal linear expansion coefficient between 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C ", average thermal linear expansion coefficient between being preferably 30 DEG C to 150 DEG C is the mineral filler of less than 300ppb/ DEG C, the average thermal linear expansion coefficient be more preferably between 30 DEG C to 150 DEG C is spherical inorganic filler, the disintegrated mineral filler of less than 300ppb/ DEG C, and the average thermal linear expansion coefficient more preferably between 30 DEG C to 150 DEG C is the spherical inorganic filler of less than 300ppb/ DEG C.As concrete example, can enumerate: the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C be less than 300ppb/ DEG C glass filler, zirconium phosphate system filler, trichroite system filler, the system filler that silicifies, tungsten wire array system filler and manganese nitride system filler etc.Wherein, be that the viewpoint of low roughness maybe can make the melt viscosity of adhering film reduce from the view point of cured article can be made, preferably use more than a kind that is selected from glass filler and zirconium phosphate system filler.As glass filler, be preferably titanium doped type glass filler, be more preferably titanium doped type globular glass filler.

As above-mentioned titanium doped type glass filler, can enumerate such as: by by TiO ₂-SiO ₂the glass of glass forms raw material TiCl ₄and SiCl ₄the mixing of each autopneumatolysis laggard row and in oxyhydrogen flame heating hydrolysis (flame hydrolysis) and the TiO that obtains ₂-SiO ₂fine glass particle.The method manufacture of above-mentioned titanium doped type glass filler by recording in No. 2010/134449th, International Publication, as the example of commercially available product, can enumerate: " AZ filler " (thermal linear expansion coefficient (mean value of 30-150 DEG C): the titanium doped type globular glass filler of 0.2ppm/ DEG C) that Asahi Glass (strain) is made.As the example of the commercially available product of above-mentioned zirconium phosphate system filler, can enumerate: found " ZWP " (thermal linear expansion coefficient (mean value of 30-150 DEG C) :-0.3ppm/ DEG C) that マテリア Le (strain) makes altogether.As the example of the commercially available product of above-mentioned disintegrated glass filler, can enumerate: " DL7400 " (thermal linear expansion coefficient (mean value of 30-150 DEG C) :-1.1ppm/ DEG C) that NEG (strain) is made.

(C) average thermal linear expansion coefficient between 30 DEG C to 150 DEG C is the median size of the filler of less than 300ppb/ DEG C, be low roughness from the view point of making cured article and the viewpoint of microfine circuit can be formed or improve the mobility of resin combination laminated property is improved, the scope being preferably 0.01 μm ~ 10 μm, the scope being more preferably 0.05 μm ~ 8 μm, the scope of more preferably 0.1 μm ~ 5 μm, the further preferably scope of 0.2 μm ~ 3 μm.The median size of this filler is by the laser diffraction-scattering method based on Michaelis (Mie) scattering theory.Particularly, utilize laser diffraction and scattering formula particle size distribution device, make the size-grade distribution of this filler with volume reference, using its median diameter as median size, can measure thus.Working sample preferably can use the sample be scattered in by ultrasonic wave by this filler in water.As laser diffraction and scattering formula particle size distribution device, (strain) hole field can be used to make made LA-500 etc.

(C) average thermal linear expansion coefficient between 30 DEG C to 150 DEG C is the proportion of the filler of less than 300ppb/ DEG C, from the view point of the Homogenizing of composition prevented in the separation of varnish, film, is preferably 1g/cm ³~ 7g/cm ³scope, be more preferably 1g/cm ³~ 5g/cm ³scope, more preferably 1.5g/cm ³~ 3g/cm ³scope.

(C) average thermal linear expansion coefficient between 30 DEG C to 150 DEG C is the content of the filler of less than 300ppb/ DEG C, using the nonvolatile component in resin combination as 100 volume % time, from the view point of the low-thermal-expansion of cured article, be preferably 5 more than volume %, be more preferably 10 more than volume %, more preferably 15 more than volume %.In addition, from the view point of the mobility of resin combination, be preferably 80 below volume %, be more preferably 70 below volume %, more preferably 65 below volume %.

In resin combination of the present invention, in the scope playing effect of the present invention, the filler outside it can also be contained as required while being the filler of less than 300ppb/ DEG C containing the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C.

Be the filler outside the filler of less than 300ppb/ DEG C as the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C, can enumerate such as: the silicon-dioxide of the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C more than 300ppb/ DEG C, aluminum oxide, barium sulfate, talcum, clay, mica powder, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, barium zirconate and calcium zirconate etc.Among them, the particularly preferably silicon-dioxide such as soft silica, fused silica, crystalline silica, synthetic silica, hollow silica.In addition silicon-dioxide is preferably spherical silicon dioxide.Filler can a kind be used alone, also can combine two or more use.Commercially available spheroidal fused silicon-dioxide can be enumerated: (strain) ア De マテッ Network ス system " SOC2 " (average thermal linear expansion coefficient between 30 DEG C to 150 DEG C: 0.5ppm/ DEG C), " SOC1 " (average thermal linear expansion coefficient between 30 DEG C to 150 DEG C: 0.5ppm/ DEG C).

(C) average thermal linear expansion coefficient between 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is such as 100: 0 ~ 10: 90 with the volume ratio of the filler except this filler, is preferably 100: 0 ~ 20: 80, is more preferably 100: 0 ~ 30: 70.

In resin combination of the present invention, the content (average thermal linear expansion coefficient between 30 DEG C to 150 DEG C is the total content of the filler of less than 300ppb/ DEG C and the filler outside it) of whole filler, during using the nonvolatile component in resin combination as 100 volume %, from the view point of the low-thermal-expansion of cured article, be preferably 40 more than volume %, be more preferably 50 more than volume %.In addition, from the view point of mobility during resin combination laminated, be preferably 80 below volume %, be more preferably 70 below volume %, more preferably 65 below volume %.

In order to make wet fastness, dispersed raising, above-mentioned filler preferably uses the surface treatment agent such as silane coupling agent (epoxy radicals silicone hydride system coupling agent, amino silicone methane series coupling agent, hydrosulphonyl silane system coupling agent etc.), titanic acid ester system coupling agent, silicon nitrogen silane compound to carry out surface treatment.They can one kind or two or morely combinationally use.

As epoxy radicals silicone hydride system coupling agent, can enumerate such as: glycidoxypropyltrime,hoxysilane, glycidoxypropyl group triethoxyl silane, glycidoxypropyl diethoxy silane, glycidyl butyl trimethoxy silane, (3, 4-expoxycyclohexyl) ethyl trimethoxy silane etc., as amino silicone methane series coupling agent, can enumerate such as: aminopropyl methoxysilane, aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-(2-amino-ethyl) TSL 8330 etc., as hydrosulphonyl silane system coupling agent, can enumerate such as: mercaptopropyi Trimethoxy silane, Mercaptopropyltriethoxysilane etc.They can one kind or two or morely combinationally use.As commercially available coupling agent, can enumerate such as: SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 " (3-glycidoxypropyltrime,hoxysilane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM803 " (3-mercaptopropyi Trimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBE903 " (APTES), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 " (N-phenyl-3-TSL 8330) etc.

Other following composition can be contained further in resin combination of the present invention, such as, the additives such as thermoplastic resin, curing catalyst and fire retardant.

-thermoplastic resin-

As thermoplastic resin, can enumerate such as: phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide-imide resin, polyethersulfone resin and polysulfone resin etc.Thermoplastic resin can a kind be used alone, or and use two or more.

The weight-average molecular weight of the polystyrene conversion of thermoplastic resin be preferably 8000 ~ 70000 scope, be more preferably 10000 ~ 60000 scope, more preferably 20000 ~ 60000 scope.The weight-average molecular weight of the polystyrene conversion of thermoplastic resin measures by gel permeation chromatography (GPC) method.Particularly, the weight-average molecular weight of the polystyrene conversion of thermoplastic resin can use (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as determinator, uses Showa electrician (strain) Shodex K-800P/K-804L/K-804L processed as pillar, use chloroform as moving phase, measure under the column temperature of 40 DEG C, use the working curve of polystyrene standard to calculate.

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

As the concrete example of polyvinyl acetal resin, can enumerate: the エスレッ Network BH that Electricityization Block チラー Le 4000-2,5000-A, 6000-C, 6000-EP, Plot water chemistry industry (strain) that electrochemically industry (strain) is made makes is serial, BX is serial, KS is serial, BL is serial, BM is serial.

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

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

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

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

The content of the thermoplastic resin in resin combination, when the nonvolatile component in resin combination is set to 100 quality %, is preferably 0.1 quality % ~ 20 quality %, is more preferably 0.5 quality % ~ 10 quality %.By making the content of thermoplastic resin be above-mentioned scope, the viscosity of resin combination becomes appropriateness, can form the resin combination that thickness, volume proterties are homogeneous.

-curing catalyst-

As curing catalyst, can enumerate such as: phosphorus system curing catalyst, amine system curing catalyst, imidazoles system curing catalyst, guanidine system curing catalyst, metal system curing catalyst etc., preferred amines system curing catalyst, imidazoles system curing catalyst, metal system curing catalyst.

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

As amine system curing catalyst, can enumerate such as: the trialkylamine such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyl dimethyl amine, 2,4,6-tri-(dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0]-undecylene etc., preferred 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0]-undecylene.

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

As guanidine system curing catalyst, can enumerate such as: Dyhard RU 100, 1-methylguanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-guanidines, 1-(o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylammonium guanidine, tetramethyl guanidine, pentamethyl-guanidine, 1, 5, 7-tri-azabicyclo [4.4.0] ten carbon-5-alkene, 7-methyl isophthalic acid, 5, 7-tri-azabicyclo [4.4.0] ten carbon-5-alkene, 1-methyl biguanides, 1-ethyl biguanides, 1-normal-butyl biguanides, 1-Octadecane base biguanides, 1, 1-dimethylbiguanide, 1, 1-diethyl biguanides, 1-cyclohexyl biguanides, 1-allyl group biguanides, 1-phenyl biguanide, 1-(o-tolyl) biguanides etc., preferred Dyhard RU 100, 1, 5, 7-tri-azabicyclo [4.4.0] ten carbon-5-alkene.

As metal system curing catalyst, be not particularly limited, can enumerate such as: the organometallic complex of the metals such as cobalt, copper, zinc, iron, nickel, manganese, tin or organic metal salt.As the concrete example of organometallic complex, can enumerate: the Organic Manganese complex compounds etc. such as the organic nickel complex compounds such as the Organic-iron complexes such as the organozinc complex such as the organic copper complex such as the organic cobalt complex compounds such as acetylacetone cobalt (II), acetylacetone cobalt (III), acetylacetone copper (II), zinc acetylacetonate (II), ferric acetyl acetonade (III), acetylacetonate nickel (II), manganese acetylacetonate (II).As organic metal salt, can enumerate such as: zinc octoate, stannous octoate, zinc naphthenate, cobalt naphthenate, stearic acid tin, Zinic stearas etc.They can one kind or two or morely combinationally use.As metal system curing catalyst, preferably use organic cobalt complex compound, particularly preferably use acetylacetone cobalt (III).

Curing catalyst can a kind be used alone, also can combine two or more use.During using the nonvolatile component in resin combination as 100 quality %, the content of curing catalyst preferably uses with the scope of 0.01 quality % ~ 3 quality %.

-fire retardant-

As fire retardant, can enumerate such as: organic phosphorus flame retardant, organic system Nitrogen-and Phosphorus-containing compound, nitrogen compound, silicone flame retardant, metal hydroxides etc.Fire retardant can a kind be used alone, or and use two or more.The content of fire retardant is not particularly limited, and during using the nonvolatile component in resin combination as 100 quality %, is preferably 0.5 quality % ~ 10 quality %, is more preferably 1 quality % ~ 9 quality %, more preferably 1.5 quality % ~ 8 quality %.

Resin combination of the present invention can be suitable for mixing mentioned component, in addition, undertaken mixing by whipping apptss such as the kneading devices such as three-roller, ball mill, ball mill, sand mill or super stirrer, planetary stirrers as required or stir, thus as the form manufacture of resinous varnish.

The purposes of resin combination of the present invention is not particularly limited, and can be widely used in the purposes that the platy layer such as adhering film, prepreg laminate materials, circuit substrate (plywood purposes, multilayer printed circuit board purposes etc.), solder resist, underfill, die-bond material, semiconductor-encapsulating material, filling perforation resin, parts potting resin etc. need resin combination.Wherein, resin combination of the present invention can be preferably used as the resin compositions for insulating layer of multilayer printed circuit board, can more preferably be used as to form the resin combination (being formed the resin compositions for insulating layer of the multilayer printed circuit board of conductor layer by plating) of conductor layer or the stack layer formation resin combination of multilayer printed circuit board by plating.Resin combination of the present invention can be coated circuit substrate with varnish state and form insulation layer, also can use with the form of the platy layer such as adhering film, prepreg laminate materials.

< platy layer laminate materials >

(adhering film)

Adhering film is the person that is formed with resin composition layer on supporter.This adhering film is by well known to a person skilled in the art method, such as, resin combination is dissolved in the resinous varnish of organic solvent by preparation, use mould coating machine etc., this resinous varnish is coated supporter, and then forms resin composition layer to manufacture by dry organic solvents such as heating or blowing hot-airs.

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

Drying conditions is not particularly limited, and preferably carries out drying in the mode making the content of the organic solvent in resin composition layer reach below 10 quality %, preferably below 5 quality %.Although different according to the boiling point of the organic solvent amount in varnish, organic solvent, such as, by making the varnish of the organic solvent containing 30 ~ 60 quality % 50 ~ 150 DEG C of dryings about 3 ~ 10 minutes, resin composition layer can be formed.This resin composition layer also referred to as B rank film (B ステージ Off ィ Le system), is do not solidify completely sometimes, and the material that solidification is carried out further and obtained.

Melt viscosity at 100 DEG C of this resin composition layer, from the view point of obtaining laminated property or the good adhering film of packaging effects, be preferably 35000 pools following, be more preferably below 20000 pools, more preferably 15000 pools following, be further preferably below 10000 pools, from the viewpoint of suppressing the concavo-convex difference of surface of insulating layer, improving microfine circuit formative, be particularly preferably below 8000 pools, 7000 pools be following, 6000 pools are following, 5000 moor below.In addition, from the view point of oozing out when preventing laminated, be preferably 500 pools above, be more preferably more than more than 1000 pools, more preferably 1500 pools.When resin composition layer is laminated, owing to usually carrying out near 100 DEG C, the laminated property of adhering film thus can be evaluated by the melt viscosity value at 100 DEG C.

Melt viscosity at 100 DEG C of resin composition layer of the present invention measures by dynamic viscoelastic method.Particularly, at amount of resin 1g, use the parallel plate of diameter 18mm, to start temperature 60 C until 200 DEG C, heat-up rate 5 DEG C/min, measure 2.5 DEG C, temperature interval, vibration 1Hz/deg condition determination under carry out Measurement of Dynamic Viscoelasticity, the melt viscosity at 100 DEG C of resin composition layer can be measured thus.As above-mentioned Measurement of Dynamic Viscoelasticity device, can enumerate such as: (strain) ユービーエ system model Rheosol-G3000.

The thickness of the resin composition layer formed in adhering film is preferably more than the thickness of conductor layer.The thickness of the conductor layer that circuit substrate has is generally the scope of 5 ~ 70 μm, and thus resin composition layer preferably has the thickness of 10 ~ 100 μm.From the view point of filming, more preferably 15 ~ 80 μm, further preferably 20 ~ 50 μm.

As supporter, can enumerate: the various plastic film such as film, polycarbonate membrane, polyimide film of the polyester such as the polyolefinic film such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (below sometimes referred to as " PET "), PEN.Also can use release paper or the tinsel such as Copper Foil, aluminium foil etc. in addition.Wherein, from the view point of versatility, preferred plastic film, more preferably polyethylene terephthalate film.The surface treatments such as delustring process, corona treatment can be implemented to supporter and aftermentioned protective membrane.In addition, demoulding process can also be implemented with releasing agents such as silicone resin system releasing agent, Synolac system releasing agent, fluoro-resin system releasing agents.

The thickness of supporter is not particularly limited, and from the view point of raising operability, is preferably more than 10 μm, is more preferably more than 20 μm, more preferably more than 30 μm.In addition, from the view point of improving cost performance or effectively can carrying out perforate when supporter carries out perforate, be preferably less than 150 μm, be more preferably less than 100 μm, more preferably less than 50 μm.

In the closely sealed face having the opposition side in the face of supporter of resin composition layer, can the stacked protective membrane conformed to supporter further.Now, adhering film comprises: supporter, the protective membrane being formed at the resin composition layer on this supporter and being formed on this resin composition layer.The thickness of protective membrane is not particularly limited, such as, be 1 ~ 40 μm.By stacked guard film, attachment or the scuffing of the dust on the surface of resin composition layer etc. can be prevented.Adhering film can also be rolled into web-like storage.

(prepreg)

Prepreg is infiltrated in sheet reinforcement base material by making resin combination of the present invention with hot melt process or solvent method, and heating makes it semicure to manufacture.That is, the prepreg that resin combination of the present invention is infiltrated in the state in sheet reinforcement base material can be made as.As sheet reinforcement base material, can use such as by the fibrous sheet reinforcement base material being commonly used for the prepreg such as woven fiber glass or Kevlar fiber.Then, preferably on supporter, prepreg is formed with.

Hot melt process resin combination need not be dissolved in organic solvent, and it first to be coated on supporter and itself and sheet reinforcement base material is laminated, or directly coat by mould coating machine the method that sheet reinforcement base material etc. manufactures prepreg.In addition, solvent method be identically with adhering film by resin dissolves in organic solvent to prepare resinous varnish, and sheet reinforcement base material to be impregnated in this varnish, resinous varnish is infiltrated in sheet reinforcement base material, then carries out dry method.In addition, also can by carrying out that Continuous Heat is laminated to be prepared from the sandwich heating adhering film of sheet reinforcement base material, under an increased pressure.Supporter or protective membrane etc. also can use identically with adhering film.

< uses the multilayer printed circuit board > of platy layer laminate materials

Then, the example using the platy layer laminate materials manufactured as mentioned above to manufacture the method for multilayer printed circuit board is described.

First, by laminated for platy layer laminate materials vacuum laminator (stacked) in the one or two sides of circuit substrate.As the substrate for circuit substrate, can enumerate such as: glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide substrate etc.Should illustrate, circuit substrate refers to the substrate being formed with the conductor layer (circuit) through pattern processing in the one or two sides of substrate described above herein.In addition, in conductor layer and the alternately laminated multilayer printed circuit board of insulation layer, conductor layer (circuit) person that the outermost one or two sides of this multilayer printed circuit board is formed through pattern processing is also contained in circuit substrate as herein described.Should illustrate, roughened is implemented in advance by Darkening process, copper etching etc. in conductor layer surface.

When platy layer laminate materials has protective membrane, after removing this protective membrane, as required platy layer laminate materials and circuit substrate are preheated, platy layer laminate materials is carried out pressurizeing and heating, while laminated with circuit substrate.In a preferred embodiment, by vacuum lamination method under reduced pressure by laminated for platy layer laminate materials in circuit substrate.Laminated condition is not particularly limited, and such as, makes crimping temperature (laminated temperature) be preferably 70 ~ 140 DEG C, makes crimping pressure (laminated pressure) be preferably 1 ~ 11kgf/cm ²(9.8 × 10 ⁴~ 107.9 × 10 ⁴n/m ²), make the crimping time (lay-up time) be preferably for 5 ~ 180 seconds, preferably carry out laminated under the following decompression of air pressure 20mmHg (26.7hPa).In addition, laminated method can be intermittent type, also can be the continous way utilizing roller.Vacuum is laminated can be used commercially available vacuum laminator to carry out.As commercially available vacuum laminator, can enumerate such as: ニチゴーモート Application (strain) vacuum attaching machine processed, (strain) name mechanism make made vacuum pressure type laminator, (strain) Hitachi イ Application ダストリイズ roll-type dry type coating machine, Hitachi エーアイーシー (strain) vacuum laminator processed etc.

By laminated for platy layer laminate materials after circuit substrate, after being cooled near room temperature, then peeling off when peeling off supporter, resin combination thermofixation is formed cured article.By this, insulation layer can be formed on circuit substrate.The condition of thermofixation can according to suitable selections such as the kind of the resinous principle in resin combination, content, and at preferably 150 DEG C ~ 220 DEG C, at 20 ~ 180 minutes, more preferably 160 DEG C ~ 210 DEG C, the scope of 30 ~ 120 minutes is selected.After forming insulation layer, before curing during unstripped supporter, can peel off at this moment as required.

In addition, can also use vacuum pressed machine that platy layer laminate materials is laminated in the one or two sides of circuit substrate.The lamination process carrying out heating and pressurize under decompression can use common vacuum hotpressing machine to carry out.Such as, by carrying out from metal sheets such as the SUS plate of support body layer side pressurization through heating.Pressurized conditions makes degree of decompression be usual 1 × 10 ^-2below MPa, preferably 1 × 10 ^-3under the decompression of below MPa.Heating and pressurization can be carried out with 1 stage, but ooze out from the view point of control resin, preferably condition are divided into 2 stages more than to carry out.Such as, preferably temperature be 70 ~ 150 DEG C, pressure is 1 ~ 15kgf/cm ²scope carry out the pressurization in the 1st stage, temperature be 150 ~ 200 DEG C, pressure is 1 ~ 40kgf/cm ²scope carry out the pressurization in the 2nd stage.The time in preferred each stage carries out 30 ~ 120 minutes.By as mentioned above by resin composition layer thermofixation, insulation layer can be formed on circuit substrate.As commercially available vacuum hotpressing machine, can enumerate such as: MNPC-V-750-5-200 ((strain) name mechanism is done made), VH1-1603 (Beichuan essence machine (strain) system) etc.

In resin combination of the present invention, the average thermal linear expansion coefficient of 25 DEG C to 150 DEG C of its cured article is preferably below 20ppm, is preferably below 17ppm, more preferably below 14ppm.Lower value does not limit, and is generally more than 4ppm.Thermal linear expansion coefficient can use (strain) リガ Network to heat mechanical analytical equipment (Thermo Plus TMA8310), by carrying out thermo-mechanical analysis to measure with tension load method.

In addition, by laminated for platy layer laminate materials of the present invention in circuit substrate and when making cured article by thermofixation, the concavo-convex difference (fluctuatings) preferably less than 3 μm on the surface outside on the cured article surface on circuit and circuit.This concavo-convex difference can use non-contact type surface roughness meter (PVC ーコイ Application スツルメン Star society WYKO NT3300) to measure.

Then, perforate processing is carried out to the insulation layer be formed on circuit substrate, form through hole (via hole), open-work (through hole).Perforate processing by known methods such as such as drill bit, laser, plasma bodys, and combines these methods to carry out as required.Wherein, the perforate processing utilizing the laser such as carbon dioxide laser, YAG laser is the most general method.In addition, preferably by platy layer laminate materials being laminated in circuit substrate, resin composition layer thermofixation being formed insulation layer and carries out perforate processing to the insulation layer be formed on circuit substrate and form through hole to manufacture multilayer printed circuit board from supporter, preferably after perforate processing, peel off supporter.So, form through hole by carrying out perforate processing from supporter, the generation of spot can be suppressed.In addition, in order to tackle the slimming of multilayer printed circuit board, the footpath, top (diameter) of through hole is preferably 15 ~ 70 μm, is more preferably 20 ~ 65 μm, more preferably 25 ~ 60 μm.

Then, the roughened of surface of insulating layer is carried out.The roughened of dry type can enumerate Cement Composite Treated by Plasma etc., and the roughened of wet type can be enumerated and carry out utilizing the swelling process of swelling liquid successively, utilizes the roughened of oxygenant and utilize the method for neutralizing treatment of neutralizer.The arbitrary roughened in dry type, wet type can be adopted, from the view point of forming the anchor (anchor) of convex-concave and the spot removed in through hole at surface of insulating layer, the roughened of preferred wet type.(preferably 55 ~ 70 DEG C at 8 ~ 15 minutes) carries out by insulation layer be impregnated in swelling liquid 5 ~ 20 minutes at 50 ~ 80 DEG C to utilize the swelling process of swelling liquid.As swelling liquid, alkaline solution, surfactant soln etc. can be enumerated, preferred bases solution.As this alkaline solution, can enumerate such as: sodium hydroxide solution, potassium hydroxide solution etc.As commercially available swelling liquid, can enumerate such as: スウェリ Application グディップセキュリガ Application ス P (Swelling Dip Securiganth P) that アトテッ Network ジャパ Application (strain) makes, スウェリ Application グディップセキュリガ Application ス SBU (Swelling Dip Securiganth SBU) etc.(preferably 70 ~ 80 DEG C at 15 ~ 25 minutes) carries out by insulation layer be impregnated in oxidizing agent solution 10 ~ 30 minutes at 60 ~ 80 DEG C to utilize the roughened of oxygenant.As oxygenant, can enumerate such as: the alkaline permanganic acid solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid etc. that dissolve potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide.In addition, the concentration of the permanganate in alkaline permanganic acid solution is preferably 5 ~ 10 % by weight.As commercially available oxygenant, can enumerate such as: the alkaline permanganic acid solutions such as the コ Application セ Application トレートコ Application パ Network ト CP, ドージ Application グソリューショ Application セキュリガ Application ス P that アトテッ Network ジャパ Application (strain) makes.(preferably 35 ~ 45 DEG C at 3 ~ 8 minutes) carries out by insulation layer to be impregnated in neutralizer 3 ~ 10 minutes at 30 ~ 50 DEG C to utilize the neutralizing treatment of neutralizer.As neutralizer, be preferably the acid aqueous solution, as commercially available product, can enumerate: the リダ Network ショ Application ソリューシ Application セキュリガ Application ト P that アトテッ Network ジャパ Application (strain) makes.

From the view point of forming microfine circuit, the Ra (arithmetic average roughness) on the cured article surface after the roughened of cured article of the present invention is preferably below 400nm, more preferably below 300nm, is further preferably below 200nm, is particularly preferably below 100nm.Lower value does not limit, and is generally more than 20nm.The arithmetic average roughness (Ra value) on cured article surface can use non-contact type surface roughness meter to measure.As the concrete example of non-contact type surface roughness meter, can enumerate: " the WYKO NT3300 " of PVC ーコイ Application スツルメン Star society.

Then, conductor layer is formed on the insulating layer by dry type plating or wet type plating.As dry type plating, the known methods such as evaporation, sputtering, ion plating can be used.As wet type plating, can enumerate: combination non-electrolytic plating and electrolysis plating, to form the method for conductor layer, are formed and the protective layer plating (めっ I レジスト) of conductor layer opposite pattern, the method etc. only being formed conductor layer by non-electrolytic plating.As pattern formation method afterwards, can adopt and such as well known to a person skilled in the art subtractive process (subtractive), semi-additive process etc.Then, by repeatedly repeating above-mentioned series of processes, can manufacture multilayer printed circuit board stacked for stack layer multistage.

The stripping strength of the plated conductor layer of the cured article obtained by resin composition of the present invention is preferably more than 0.4kgf/cm, is more preferably more than 0.5kgf/cm.Higher limit does not limit, and is generally below 1.0kgf/cm.For the stripping strength of plated conductor layer, forming conductor layer by being plated on the surface of the cured article after roughened, measuring the plating stripping strength of this cured article surface and this conductor layer.As tensile testing machine, can enumerate such as: " AC-50C-SL " of (strain) TSE etc.

< semiconductor device >

The multilayer printed circuit board of the application of the invention can manufacture semiconductor device.Semiconductor device is manufactured by the conduction position mounting semiconductor chip at multilayer printed circuit board of the present invention." conduction position " refers to the position of conducting electrical signals " in the multilayer printed circuit board can ", and this position can be surface also can be the position be embedded.In addition, as long as semi-conductor chip is not particularly limited using semi-conductor as the electrical circuit components of material.

As long as the installation method of semi-conductor chip when manufacturing semiconductor device of the present invention makes semi-conductor chip effectively play function, be not particularly limited, specifically can enumerate: wire-bonded installation method, flip-chip installation method, the installation method utilizing bumpless build up layer (バ Le プな PVC Le De アップ Layer, BBUL), the installation method etc. that utilizes the installation method of anisotropic conductive film (ACF), utilize non-conductive film (NCF).

[embodiment]

Below, further illustrate the present invention by embodiment, but the present invention does not limit by these embodiments.Should illustrate, in below recording, if be not particularly limited, then " part " and " % " means " mass parts " and " quality % " respectively.

< measuring method-evaluation method >

First various measuring method, evaluation method are described.

The evaluation > of < thermal linear expansion coefficient

Gained adhering film in embodiment and comparative example is carried out heating in 90 minutes at 190 DEG C, makes resin composition layer thermofixation.Its cured article is cut to wide about 5mm, test film that length is about 15mm, use (strain) リガ Network to heat mechanical analytical equipment (Thermo Plus TMA8310), carry out thermo-mechanical analysis with tension load method.After test film is loaded into aforementioned means, carries out 2 times continuously with the condition determination of loading 1g, heat-up rate 5 DEG C/min and measure.In measuring for 2nd time, calculate second-order transition temperature and the average thermal linear expansion coefficient from 25 DEG C to 150 DEG C.

The preparation > of < arithmetic average roughness (Ra value) and stripping strength test sample

(1) substrate processing of internal layer circuit substrate

Carry out 1 μm of etching on the two sides of the copper foil covered lamination in woven fiber glass base material epoxy resin two sides (thickness 18 μm of Copper Foil, substrate thickness 0.3mm, SUNX (strain) R5715ES processed) defining internal layer circuit by メッ Network (strain) CZ8100 processed, roughened is carried out to copper surface.

(2) adhering film is laminated

By laminated in the two sides of internal layer circuit substrate for adhering film intermittent vacuum pressurization laminator MVLP-500 (name machine (strain) system) made in embodiment and comparative example.Laminated by carry out decompression in 30 seconds make air pressure be below 13hPa, then with 100 DEG C, pressure 0.74MPa crimps and carried out 30 seconds.

(3) solidification of resin combination

By through laminated adhering film at 100 DEG C, 30 minutes, and then by resin composition under the condition of cure of 180 DEG C, 30 minutes, form insulation layer.Then PET film is peeled off.

(4) roughened

The internal layer circuit substrate defining insulation layer is contained in the スエリ Application グディップセキュリガ Application ト P of diethylene glycol monobutyl ehter what make as アトテッ Network ジャパ Application (strain) of swelling liquid, flood 10 minutes, then at the コ Application セ Application トレートコ Application パ Network ト P (KMnO that アトテッ Network ジャパ Application (strain) as roughening liquid makes at 60 DEG C ₄: the aqueous solution of 60g/L, NaOH:40g/L) in, flood 20 minutes at 80 DEG C, in the リダ Network ショ Application ソリューシ Application セキュリガ Application ト P finally made at アトテッ Network ジャパ Application (strain) as neutralizer, 40 DEG C of dippings 5 minutes.At 80 DEG C after dry 30 minutes, the surface of insulating layer after this roughened is carried out to the mensuration of arithmetic average roughness (Ra value), r.m.s. roughness (Rq value).

(5) plating of half adding technology is utilized

In order to form circuit at surface of insulating layer, internal layer circuit substrate is being contained PdCl ₂electroless plating application solution in, 40 DEG C dipping 5 minutes, then in non-electrolytic copper plating solution, 25 DEG C dipping 20 minutes.After 150 DEG C of heating carry out anneal in 30 minutes, form resistant layer, after utilization etching forms pattern, carry out copper sulfate bath plating, form conductor layer with the thickness of 25 μm.Then, 30 minutes anneal are carried out at 180 DEG C.This circuit substrate is carried out to the mensuration of the pull strength (stripping strength) of plated conductor layer.

The mensuration > of the arithmetic average roughness (Ra value) after < roughened

Use non-contact type surface roughness meter (PVC ーコイ Application スツルメン Star society WYKO NT3300), make measurement range be that 121 μm × 92 μm numerical value obtained obtain Ra value according to by VSI contact mode, 50 times of lens.Then, the mean value by obtaining at 10 is used as measured value.

The mensuration > of the pull strength (stripping strength) of < plated conductor layer

The conductor layer of circuit substrate cuts the otch of wide 10mm, long 100mm, its one end is peeled, clamp with fixture ((strain) ティーエスイー, オートコ system type trier AC-50CSL), measure the loading (kgf/cm) when at room temperature vertically peeling off 35mm with the speed of 50mm/ minute.

< melt viscosity measures >

The melt viscosity of 100 DEG C of the resin composition layer in the adhering film made in embodiment and comparative example is measured.Use (strain) ユービーエ system model Rheosol-G3000, amount of resin be 1g, use the parallel plate of diameter 18mm, be 2.5 DEG C by beginning temperature 60 C to 200 DEG C, heat-up rate 5 DEG C/min, mensuration temperature interval, vibrate be the condition determination of 1Hz/deg under measure melt viscosity.

< laminated property test >

By adhering film intermittent vacuum pressurization laminator MVLP-500 (name machine (strain) system) made in embodiment and comparative example, on the conductive pattern of the laminated comb teeth-shaped in conductor thick 35 μm and L (line: circuit is wide)/S (space: interval is wide)=160/160 μm.Laminated by carry out decompression in 30 seconds make air pressure be below 13hPa, then with 100 DEG C, pressure 0.74MPa pressurizes and carried out 30 seconds.PET film is peeled off from through laminated adhering film, by resin composition under the condition of cure of 100 DEG C, 30 minutes and then 180 DEG C, 30 minutes, forms insulation layer.On conductor in insulation layer with its outside the value of concavo-convex difference (Rt: maximum peak valley) of part be use non-contact type surface roughness meter (PVC ーコイ Application スツルメン Star society WYKO NT3300), make measurement range be that the numerical value that 1.2mm × 0.91mm obtains is obtained according to by VSI contact mode, 10 times of lens.Should illustrate, by laminated rear conductor with its outside the concavo-convex difference of part be that the situation of less than 3.0 μm is evaluated as zero, by laminated rear conductor with its outside the concavo-convex difference of the part situation that is greater than 3.0 μm be evaluated as ×.

[embodiment 1]

By liquid bisphenol A type epoxy resin (epoxy equivalent (weight) 190, ジャパ Application エ Port キシレジ Application (strain) makes " jER828US ") 5 parts, biphenyl aralkyl-type epoxy resin (epoxy equivalent (weight) 291, Japan's chemical drug (strain) system " NC3000H ") 8 parts, naphthol type epoxy resin (epoxy equivalent (weight) 332, aurification (strain) system " ESN-475V " is lived by Nippon Steel) 8 parts, with the phenoxy resin resin solution of 30 quality % (ジャパ Application エ Port キシレジ Application (strain) to be made mass ratio that " YX6954BH30 " (weight-average molecular weight 38000) be dissolved in MEK and pimelinketone be nonvolatile component in the mixed solvent of 1: 1 be) 8 parts, MEK8 part, stir while heating for dissolving in pimelinketone 8 parts.Wherein, 26 parts, mixed active ester system solidifying agent (toluene solution, the DIC (strain) of active group equivalent 223, nonvolatile component 65 quality % make " HPC8000-65T "), as curing catalyst 1-benzyl-2-phenylimidazole (four countries change into industry (strain) system " 1B2PZ ") 1 part, by spherical silicon dioxide, (ア De マテッ Network ス (strain) system " SOC1 " (has carried out hexamethyldisilazane process, median size 0.25 μm, proportion 2.2g/m ³)) carried out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system, " KBM573 ") and obtain product 84 parts, be that (Asahi Glass (strain) makes " AZ filler " (line style thermal expansivity (mean values of 30 ~ 150 DEG C): titanium doped type globular glass filler, median size 0.2 μm, the proportion 2.2g/m of 0.2ppm/ DEG C for the globular glass filler of less than 300ppb/ DEG C by the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C ³) carry out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") and the product that obtains )36 parts, with the homogeneous dispersion of high speed rotating stirrer, make resinous varnish.Then, on polyethylene terephthalate (thickness 38 μm, hereinafter referred to as " PET "), be coated with the mode mould coating machine that the thickness of dried resin combination is 40 μm, at 80 ~ 120 DEG C (average 100 DEG C) dry 6 minutes (residual solvent amount about 2 quality %).Then, the surperficial coating thickness 15 μm of resin composition layer polypropylene screen and batch with web-like.The adhering film of web-like is cut with wide 507mm, obtains the sheet adhering film of 507mm × 336mm size thus.

[embodiment 2]

By liquid bisphenol A type epoxy resin (epoxy equivalent (weight) 190, ジャパ Application エ Port キシレジ Application (strain) makes " jER828US ") 5 parts, biphenyl aralkyl-type epoxy resin (epoxy equivalent (weight) 291, Japan's chemical drug (strain) system " NC3000H ") 8 parts, naphthol type epoxy resin (epoxy equivalent (weight) 332, aurification (strain) system " ESN-475V " is lived by Nippon Steel) 8 parts, with the phenoxy resin resin solution of 30 quality % (ジャパ Application エ Port キシレジ Application (strain) to be made mass ratio that " YX6954BH30 " (weight-average molecular weight 38000) be dissolved in MEK and pimelinketone be nonvolatile component in the mixed solvent of 1: 1 be) 8 parts, MEK10 part, stir while heating for dissolving in pimelinketone 10 parts.Wherein, 26 parts, mixed active ester system solidifying agent (toluene solution, the DIC (strain) of active group equivalent 223, nonvolatile component 65 quality % make " HPC8000-65T "), as curing catalyst 1-benzyl-2-phenylimidazole (four countries change into industry (strain) system " 1B2PZ ") 1 part, by spherical silicon dioxide, (ア De マテッ Network ス (strain) system " SOC1 " (has carried out hexamethyldisilazane process, median size 0.25 μm, proportion 2.2g/m ³)) carried out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system, " KBM573 ") and obtain product 84 parts, by the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C be less than 300ppb/ DEG C zirconium phosphate system filler (stand altogether マテリア Le (strain) make " ZWP " (line style thermal expansivity (mean values of 30 ~ 150 DEG C) :-0.3ppm/ DEG C, median size 2.3 μm, disintegrated, proportion 3.8g/m ³)) carry out surface-treated product 62 parts by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system, " KBM573 "), with the homogeneous dispersion of high speed rotating stirrer, make resinous varnish.Then, obtain adhering film identically with embodiment 1.

[embodiment 3]

By liquid bisphenol A type epoxy resin (epoxy equivalent (weight) 190, ジャパ Application エ Port キシレジ Application (strain) makes " jER828US ") 5 parts, biphenyl aralkyl-type epoxy resin (epoxy equivalent (weight) 291, Japan's chemical drug (strain) system " NC3000H ") 8 parts, naphthol type epoxy resin (epoxy equivalent (weight) 332, aurification (strain) system " ESN-475V " is lived by Nippon Steel) 8 parts, with the phenoxy resin resin solution of 30 quality % (ジャパ Application エ Port キシレジ Application (strain) to be made mass ratio that " YX6954BH30 " (weight-average molecular weight 38000) be dissolved in MEK and pimelinketone be nonvolatile component in the mixed solvent of 1: 1 be) 8 parts, MEK10 part, stir while heating for dissolving in pimelinketone 10 parts.Wherein, 26 parts, mixed active ester system solidifying agent (toluene solution, the DIC (strain) of active group equivalent 223, nonvolatile component 65 quality % make " HPC8000-65T "), as curing catalyst 1-benzyl-2-phenylimidazole (four countries change into industry (strain) system " 1B2PZ ") 1 part, by spherical silicon dioxide, (ア De マテッ Network ス (strain) system " SOC1 " (has carried out hexamethyldisilazane process, median size 0.25 μm, proportion 2.2g/m ³)) carried out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system, " KBM573 ") and obtain product 84 parts, by the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C be less than 300ppb/ DEG C disintegrated glass filler (NEG (strain) make " DL7400 " (line style thermal expansivity (mean values of 30 ~ 150 DEG C) :-1.1ppm/ DEG C, median size 4.8 μm, proportion 2.5g/m ³) carried out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system, " KBM573 ") and the product that obtain) 41 parts, with the homogeneous dispersion of high speed rotating stirrer, making resinous varnish.Then, obtain adhering film identically with embodiment 1.

[embodiment 4]

By liquid bisphenol A type epoxy resin (epoxy equivalent (weight) 190, ジャパ Application エ Port キシレジ Application (strain) makes " jER828US ") 10 parts, biphenyl aralkyl-type epoxy resin (epoxy equivalent (weight) 291, Japan's chemical drug (strain) system " NC3000H ") 18 parts, naphthalene type epoxy resin (epoxy equivalent (weight) 144, DIC (strain) makes " EXA4032SS ") 3 parts, naphthalene type 4 functional epoxy resins (epoxy equivalent (weight) 162, DIC (strain) makes " HP-4700 ") 5 parts, the phenoxy resin resin solution of 30 quality % (ジャパ Application エ Port キシレジ Application (strain) to be made mass ratio that " YX6954BH30 " (weight-average molecular weight 38000) be dissolved in methyl ethyl ketone (hereinafter referred to as " MEK ") and pimelinketone be nonvolatile component in the mixed solvent of 1: 1 be) 18 parts, MEK12 part, stir while heating for dissolving in pimelinketone 12 parts.Wherein, mix 9 parts, naphthols aralkyl base system solidifying agent (aurification (strain) system " SN485 " is lived by phenolic hydroxyl group equivalent 215, Nippon Steel), 15 parts, lacquer resins system solidifying agent (the MEK solution of the solids component 60% of phenolic hydroxyl group equivalent 120, DIC (strain) system " LA7052 "), as curing catalyst 4-dimethylaminopyridine 0.2 part, by spherical silicon dioxide, (ア De マテッ Network ス (strain) makes " SOC1 " and (has carried out hexamethyldisilazane process, median size 0.25 μm, proportion 2.2g/m ³)) carried out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system, " KBM573 ") and obtain product 119 parts, be that (Asahi Glass (strain) makes " AZ filler " (line style thermal expansivity (mean values of 30 ~ 150 DEG C): titanium doped type globular glass filler, median size 0.2 μm, the proportion 2.2g/m of 0.2ppm/ DEG C for the globular glass filler of less than 300ppb/ DEG C by the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C ³)) carry out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") and the product 51 parts that obtain, with the homogeneous dispersion of high speed rotating stirrer, making resinous varnish.Then, obtain adhering film identically with embodiment 1.

[embodiment 5]

By liquid bisphenol A type epoxy resin (epoxy equivalent (weight) 190, ジャパ Application エ Port キシレジ Application (strain) makes " jER828US ") 6 parts, naphthol type epoxy resin (epoxy equivalent (weight) 332, aurification (strain) system " ESN-475V " is lived by Nippon Steel) 16 parts, naphthalene type epoxy resin (epoxy equivalent (weight) 144, DIC (strain) makes " EXA4032SS ") 9 parts, naphthylidene ether type epoxy (epoxy equivalent (weight) 266, DIC (strain) makes " EXA7311 ") 6 parts, with the phenoxy resin resin solution of 30 quality % (ジャパ Application エ Port キシレジ Application (strain) to be made mass ratio that " YX6954BH30 " (weight-average molecular weight 38000) be dissolved in MEK and pimelinketone be nonvolatile component in the mixed solvent of 1: 1 be) 5 parts, MEK15 part, stir while heating for dissolving in pimelinketone 15 parts.Wherein, prepolymer (the cyanate equivalent 235 of mixing bisphenol A dicyanate, the MEK solution of nonvolatile component 75 quality %, ロ Application ザジャパ Application (strain) " BA230S75 ") 20 parts, novalac-type multifunctional cyanate ester resin (cyanate equivalent 124, the MEK solution of nonvolatile component 80 quality %, ロ Application ザジャパ Application (strain) makes " PT30 ") 8 parts, active ester system solidifying agent (active group equivalent 223, the toluene solution of nonvolatile component 65 quality %, DIC (strain) makes " HPC8000-65T ") 12 parts, as the 4-dimethylaminopyridine 0.02 part of curing catalyst, acetylacetone cobalt (III) (East capital changes into (strain) system) the MEK solution 4 parts of 1 quality %, by spherical silicon dioxide, (ア De マテッ Network ス (strain) system " SOC1 " (has carried out hexamethyldisilazane process, median size 0.25 μm, proportion 2.2g/m ³)) use N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system, " KBM573 " )carried out surface treatment and obtain product 140 parts, be globular glass filler (Asahi Glass (strain) system " AZ filler " (line style thermal expansivity (mean values of 30 ~ 150 DEG C): titanium doped type globular glass filler, median size 0.2 μm, the proportion 2.2g/m of 0.2ppm/ DEG C of less than 300ppb/ DEG C by the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C ³)) carry out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") and the product 60 parts that obtain, with the homogeneous dispersion of high speed rotating stirrer, making resinous varnish.Then, obtain adhering film identically with embodiment 1.

[embodiment 6]

By liquid bisphenol A type epoxy resin (epoxy equivalent (weight) 190, ジャパ Application エ Port キシレジ Application (strain) makes " jER828US ") 5 parts, biphenyl aralkyl-type epoxy resin (epoxy equivalent (weight) 291, Japan's chemical drug (strain) system " NC3000H ") 8 parts, naphthol type epoxy resin (epoxy equivalent (weight) 332, aurification (strain) system " ESN-475V " is lived by Nippon Steel) 8 parts, with the phenoxy resin resin solution of 30 quality % (ジャパ Application エ Port キシレジ Application (strain) to be made mass ratio that " YX6954BH30 " (weight-average molecular weight 38000) be dissolved in MEK and pimelinketone be nonvolatile component in the mixed solvent of 1: 1 be) 8 parts, MEK8 part, stir while heating for dissolving in pimelinketone 8 parts.Wherein, mixed active ester system solidifying agent (active group equivalent 223, the toluene solution of nonvolatile component 65 quality %, DIC (strain) makes " HPC8000-65T ") 26 parts, as the 1-benzyl-2-phenylimidazole (four countries change into industry (strain) system " 1B2PZ ") 1 part of curing catalyst, it is globular glass filler (Asahi Glass (strain) system " AZ filler " (line style thermal expansivity (mean values of 30 ~ 150 DEG C): the titanium doped type globular glass filler of 0.2ppm/ DEG C of less than 300ppb/ DEG C by the average thermal linear expansion coefficient between 30 DEG C to 150 DEG C, median size 0.2 μm, proportion 2.2g/m ³)) carry out surface treatment by N-phenyl-3-TSL 8330 (SHIN-ETSU HANTOTAI's chemistry (strain) system " KBM573 ") and the product 105 parts that obtain, with the homogeneous dispersion of high speed rotating stirrer, making resinous varnish.Then, obtain adhering film identically with embodiment 1.

[comparative example 1]

By liquid bisphenol A type epoxy resin (epoxy equivalent (weight) 190, ジャパ Application エ Port キシレジ Application (strain) makes " jER828US ") 5 parts, biphenyl aralkyl-type epoxy resin (epoxy equivalent (weight) 291, Japan's chemical drug (strain) system " NC3000H ") 8 parts, naphthol type epoxy resin (epoxy equivalent (weight) 332, aurification (strain) system " ESN-475V " is lived by Nippon Steel) 8 parts, with the phenoxy resin resin solution of 30 quality % (ジャパ Application エ Port キシレジ Application (strain) to be made mass ratio that " YX6954BH30 " (weight-average molecular weight 38000) be dissolved in MEK and pimelinketone be nonvolatile component in the mixed solvent of 1: 1 be) 8 parts, MEK12 part, stir while heating for dissolving in pimelinketone 12 parts.Wherein, 26 parts, mixed active ester system solidifying agent (toluene solution, the DIC (strain) of active group equivalent 223, nonvolatile component 65 quality % make " HPC8000-65T "), as curing catalyst 1-benzyl-2-phenylimidazole (four countries change into industry (strain) system " 1B2PZ ") 1 part, by spherical silicon dioxide, (ア De マテッ Network ス (strain) system " SOC1 " (has carried out hexamethyldisilazane process, median size 0.25 μm, proportion 2.2g/m ³)) by N-phenyl-3-TSL 8330, (product 150 parts that SHIN-ETSU HANTOTAI's chemistry (strain) system, " KBM573 " have carried out surface treatment and obtained, with the homogeneous dispersion of high speed rotating stirrer, makes resinous varnish.Then, obtain adhering film identically with embodiment 1.

[table 1]

。

From this result, resin combination of the present invention can provide the resin combination bringing low coefficient of linear thermal expansion, low roughness and the high cured article of stripping strength and then bring the platy layer laminate materials with excellent laminated property.

Claims

1. resin combination, it contains: the average thermal linear expansion coefficient between (A) epoxy resin, (B) solidifying agent, (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C.

2. resin combination according to claim 1, wherein, when the nonvolatile component in resin combination is set to 100 volume %, the average thermal linear expansion coefficient between (C) containing 5 ~ 80 volumes 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C.

3. resin combination according to claim 1, wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the median size of the filler of less than 300ppb/ DEG C is 0.01 ~ 10 μm.

4. resin combination according to claim 1, wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the proportion of the filler of less than 300ppb/ DEG C is 1 ~ 7g/cm ³.

5. resin combination according to claim 1, wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is spherical inorganic filler or disintegrated mineral filler.

6. resin combination according to claim 1, wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is be selected from the filler of more than a kind in glass filler and zirconium phosphate system filler.

7. resin combination according to claim 1, wherein, the average thermal linear expansion coefficient between (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is titanium doped type glass filler.

8. resin combination according to claim 1, wherein, (B) solidifying agent is selected from the solidifying agent of more than a kind in active ester system solidifying agent, cyanate system solidifying agent, phenol system solidifying agent and naphthols system solidifying agent.

9. resin combination according to claim 1, wherein, (A) epoxy resin is bisphenol A type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylidene ether type epoxy or their mixture of more than two kinds

(B) solidifying agent is active ester system solidifying agent,

(C) average thermal linear expansion coefficient between 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C is titanium doped type glass filler.

10. resin combination according to claim 1, wherein, the average thermal linear expansion coefficient of 25 DEG C to 150 DEG C of the cured article of this resin combination is below 20ppm,

11. resin combinations according to claim 1, it is for the insulation layer of multilayer printed circuit board.

12. adhering films, it contains the resin combination according to any one of claim 1 ~ 11.

13. adhering films according to claim 12, wherein, the melt viscosity of resin composition layer at 100 DEG C of this adhering film is below 35000 pools.

The cured article of the resin combination according to any one of 14. claims 1 ~ 11.

15. cured articles according to claim 14, wherein, the average thermal linear expansion coefficient of 25 DEG C to 150 DEG C is below 20ppm.

16. cured articles according to claim 14, wherein, the Ra on the cured article surface after roughened is below 400nm.

17. cured articles according to claim 14, wherein, when the cured article surface after the roughened of cured article forms conductor layer by plating, this cured article surface is more than 0.4kgf/cm with the plating stripping strength of this conductor layer.

18. multilayer printed circuit boards, it has cured article according to claim 14.

19. semiconductor devices, is characterized in that, use the multilayer printed circuit board described in claim 18.

The resin compositions for insulating layer of 20. multilayer printed circuit boards, the average thermal linear expansion coefficient between it contains (A) epoxy resin, (B) solidifying agent, (C) 30 DEG C to 150 DEG C is the filler of less than 300ppb/ DEG C, wherein,

Should (B) solidifying agent be active ester system solidifying agent,