CN106256862A

CN106256862A - Resin combination

Info

Publication number: CN106256862A
Application number: CN201610423902.5A
Authority: CN
Inventors: 藤岛祥平; 中村茂雄
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2015-06-22
Filing date: 2016-06-16
Publication date: 2016-12-28
Anticipated expiration: 2036-06-16
Also published as: CN106256862B; KR102535432B1; KR20160150587A; TW201710366A; JP6648425B2; TWI701288B; JP2017008204A

Abstract

When the problem of the present invention is to provide for manufacturing printed substrate, the resin combination of arbitrary characteristic all insulating barriers of excellence of circuit imbedibility, dielectric dissipation factor, elongation at break can be formed, employ the adhering film of this resin combination, printed substrate and semiconductor device.The solution of the present invention is a kind of resin combination, and it contains (A) epoxy resin, (B) active ester compound and (C) can have the triphenylimidazolyl of substituent group.

Description

Resin combination

Technical field

The present invention relates to resin combination.Further relate to adhering film, printed substrate and semiconductor device.

Background technology

Manufacturing technology as printed substrate, it is known that utilize stacking (build alternately stacked to insulating barrier and conductor layer Up) manufacture method of mode.In the manufacture method utilizing stack manner, resin composition is generally made to form insulation Layer.

Such as in patent documentation 1, disclose the organo-silicon compound (A) containing hydroxyl, cyanate esters (B) And/or phenolic resin (C) and the resin combination of inorganic filling material (D).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2014-84327 publication.

Summary of the invention

The problem that invention is to be solved

Disclose the resin combination of patent documentation 1 by solidification, the anti-flammability of holding height, thermostability height, the heat in direction, face The coefficient of expansion is low and drill processability excellent.But, it is impossible to meet when manufacturing printed substrate important with good balance Various characteristics, be insufficient.

The problem of the present invention be provide manufacture printed substrate time, can be formed circuit imbedibility, dielectric dissipation factor, The resin combination of the insulating barrier that arbitrary characteristic of elongation at break is all excellent, employ this resin combination adhering film, Printed substrate and semiconductor device.

Solve the means of problem

The present inventor etc. have carried out making great efforts research for above-mentioned problem, found that by by (A) epoxy resin, (B) active ester Compound and (C) can have the triphenylimidazolyl of substituent group and be applied in combination, and can solve above-mentioned problem, thus complete this Bright.

That is, the present invention contains content below:

[1] resin combination, it contains (A) epoxy resin, (B) active ester compound and (C) can have the triphenyl of substituent group Imidazoles；

[2] according to the resin combination described in [1], wherein, when the nonvolatile component in resin combination is set to 100 mass %, (B) content of composition is 1 mass %～30 mass %；

[3] according to the resin combination described in [1] or [2], wherein, the nonvolatile component in resin combination is set to 100 matter During amount %, the content of (C) composition is 0.01 mass %～5 mass %；

[4] according to the resin combination according to any one of [1]～[3], wherein, containing (D) inorganic filling material；

[5] according to the resin combination described in [4], wherein, when the nonvolatile component in resin combination is set to 100 mass %, (D) content of composition is more than 50 mass %；

[6] according to the resin combination described in [4] or [5], wherein, the mean diameter of (D) composition is 0.01 μm～3 μm；

[7] according to the resin combination according to any one of [4]～[6], wherein, (D) composition is silicon dioxide；

[8] according to the resin combination according to any one of [1]～[7], wherein, containing (E) thermoplastic resin；

[9] adhering film, its have supporter and be arranged on this supporter containing tree according to any one of [1]～[8] The resin composition layer of oil/fat composition；

[10] according to the adhering film described in [9], wherein, the lowest melt viscosity of resin composition layer is below 3000 pools；

[11] according to the adhering film described in [9] or [10], wherein, the elongation at break of the resin composition layer of solidification is 1.5% Above；

[12] printed substrate, it is exhausted that its solidfied material containing the resin combination according to any one of utilization [1]～[8] is formed Edge layer；

[13] semiconductor device, it contains the printed substrate described in [12].

The effect of invention

According to the present invention it is possible to provide when manufacturing printed substrate, circuit imbedibility, dielectric dissipation factor, fracture can be formed The resin combination of the insulating barrier that arbitrary characteristic of percentage elongation is all excellent, employ the adhering film of this resin combination, printing Wiring board and semiconductor device.

Detailed description of the invention

Hereinafter, resin combination, adhering film, printed substrate and semiconductor device for the present invention are carried out in detail Explanation.

[resin combination]

The resin combination of the present invention is characterised by, can have containing (A) epoxy resin, (B) active ester compound and (C) The triphenylimidazolyl of substituent group.Hereinafter, for each composition contained in the resin combination of the present invention, it is described in detail.

＜ (A) epoxy resin ＞

The resin combination of the present invention contains (A) epoxy resin (hereinafter also referred to (A) composition).

As epoxy resin, include, for example: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy tree Fat, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, tris phenol type epoxy, naphthol novolac (naphthol Novolak) type epoxy resin, phenol novolac (phenol novolak) type epoxy resin, the tert-butyl group-catechol type asphalt mixtures modified by epoxy resin Fat, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type Epoxy resin, cresol novolac (cresol novolak) type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy tree Fat, there is the epoxy resin of butadiene structure, alicyclic epoxy resin, hetero ring type epoxy resin, the epoxy resin containing volution, ring Hexane diformazan alcohol type epoxy resin, naphthylene ether (naphthylene ether) type epoxy resin, trihydroxy methyl type asphalt mixtures modified by epoxy resin Fat, tetraphenyl ethane type epoxy resin, di-methylphenol (PVC キシレノ Le) type epoxy resin etc..Epoxy resin is permissible One is used alone, it is also possible to be used in combination of two or more.

Preferred epoxy comprises the epoxy resin in a part with two or more epoxy radicals.Preferably with epoxy resin Nonvolatile component be 100 mass % in the case of, at least 50 quality % are above in a part having two or more epoxy radicals Epoxy resin.Wherein, preferably comprise: a part has two or more epoxy radicals and the asphalt mixtures modified by epoxy resin being in a liquid state at temperature 20 DEG C Fat (hereinafter referred to as " liquid-state epoxy resin ") and a part have more than three epoxy radicals and in solid-state at temperature 20 DEG C Epoxy resin (hereinafter referred to as " solid epoxy resin ").By by liquid-state epoxy resin and solid epoxy resin and be used as ring Epoxy resins, can obtain having excellent flexible resin combination.It addition, the fracture strength of the solidfied material of resin combination also carries High.

As liquid-state epoxy resin, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type asphalt mixtures modified by epoxy resin Fat, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolak type epoxy, there is the ester ring type ring of ester skeleton Epoxy resins and there is the epoxy resin of butadiene structure；More preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, bis-phenol AF type epoxy resin and naphthalene type epoxy resin.As the concrete example of liquid-state epoxy resin, can enumerate: DIC (strain) makes " 828US " that " HP4032 ", " HP4032D ", " HP4032SS " (naphthalene type epoxy resin), Mitsubishi Chemical's (strain) make, " jER828EL " (bisphenol A type epoxy resin), " jER807 " (bisphenol f type epoxy resin), " jER152 " (phenol novolak type epoxy Resin), Nippon Steel live " ZX1059 " that aurification (strain) makes (mixing of bisphenol A type epoxy resin and bisphenol f type epoxy resin Product), Nagase ChemteX (strain) " EX-721 " (glycidyl ester type epoxy resin), (strain) contest road made " Celloxide 2021P " (having the alicyclic epoxy resin of ester skeleton), " PB-3600 " (have the epoxy of butadiene structure Resin).These can one be used alone, it is also possible to is used in combination of two or more.

As solid epoxy resin, preferably naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, bicyclopentadiene Type epoxy resin, tris phenol type epoxy, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy, anthracene Type epoxy resin, bisphenol A type epoxy resin, tetraphenyl ethane type epoxy resin；More preferably naphthalene type tetrafunctional epoxy resin, naphthols Type epoxy resin and biphenyl type epoxy resin.As the concrete example of solid epoxy resin, can enumerate: DIC (strain) makes " HP4032H " (naphthalene type epoxy resin), " HP-4700 ", " HP-4710 " (naphthalene type 4 functional epoxy resins), " N-690 " (cresol phenol Aldehyde type epoxy resin), " N-695 " (cresol novolak type epoxy resin), " HP-7200 " (dicyclopentadiene-type epoxy resin), " HP-7200HH ", " EXA7311 ", " EXA7311-G3 ", " EXA7311-G4 ", " EXA7311-G4S ", " HP6000 " (naphthylene Ether type epoxy), Japan chemical medicine (strain) " EPPN-502H " (tris phenol type epoxy), " NC7000L " (naphthol novolac of making Type epoxy resin), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin), Nippon Steel live gold " ESN475V " (naphthol type epoxy resin), " ESN485 " (naphthol novolac type epoxy resin), the Mitsubishi Chemical that chemistry (strain) is made " YX4000H ", " YL6121 " (biphenyl type epoxy resin), " YX4000HK " (di-methylbenzene phenolic asphalt mixtures modified by epoxy resin that (strain) makes Fat), " YX8800 " (anthracene type epoxy resin), Osaka combustion gas chemistry (Osaka ガスケミカ Le) (strain) " PG-100 ", " CG-that make 500 " " jER1010 " (Solid Double that " YL7800 " (fluorenes type epoxy resin) that, Mitsubishi Chemical's (strain) makes, Mitsubishi Chemical's (strain) make Phenol A type epoxy resin), " jER1031S " (tetraphenyl ethane type epoxy resin), " YL7760 " (bisphenol AF type epoxy resin) etc..

As epoxy resin, and with in the case of liquid-state epoxy resin and solid epoxy resin, their amount ratio (liquid ring Epoxy resins: solid epoxy resin) by quality ratio be preferably 1:0.1～1:6 scope.By making liquid-state epoxy resin and solid-state The amount ratio of epoxy resin within the above range, can get following effect: can bring suitably when i) using with the form of adhering film Cohesiveness, ii) when using with the form of adhering film available the most flexible, operability improves, and iii) available There is the solidfied material etc. of sufficient fracture strength.From above-mentioned i)～iii) effect from the viewpoint of, liquid-state epoxy resin is with solid The amount ratio (liquid-state epoxy resin: solid epoxy resin) of state epoxy resin, by quality ratio, the model of more preferably 1:0.3～1:5 Enclose, more preferably the scope of 1:0.6～1:4.

The content of the epoxy resin in resin combination is from obtaining showing good mechanical strength, the insulation of insulating reliability From the point of view of Ceng, more than preferably 5 mass %, more than more preferably 10 mass % and then more than preferably 15 mass %.Epoxy As long as the effect that the upper limit of the content of resin can play the present invention is just not particularly limited, below preferably 50 mass %, more preferably It is below below 30 mass % and then preferably 20 mass %.

Should illustrate, in the present invention, content the expressing as long as no other of each composition in resin combination, be by Nonvolatile component in resin combination is set to value during 100 mass %.

The epoxide equivalent of epoxy resin is preferably 50～5000, more preferably 50～3000 and then preferably 80～2000, And then more preferably 110～1000.By for this scope, the crosslink density of solidfied material becomes abundant, can form rough surface Spend little insulating barrier.Should illustrate, epoxide equivalent can be measured according to JIS K7236, is the epoxy radicals containing 1 equivalent The quality of resin.

The weight average molecular weight of epoxy resin is preferably 100～5000, more preferably 250～3000 so preferably 400～ 1500.Here, the weight average molecular weight of epoxy resin is the weight of the polystyrene conversion utilizing gel permeation chromatography (GPC) method to measure Average molecular weight.

＜ (B) active ester compound ＞

The resin combination of the present invention contains (B) active ester compound (hereinafter also referred to (B) composition).

Active ester compound is the active ester compound in a part with more than one active ester groups.As active ester Compound, preferably has the active ester compound of two or more active ester groups in a part, such as, phenol esters is preferably used (phenol esters), phenylmercaptan. esters (thiophenol esters), N-hydroxylamine esters, the ester of heterocycle hydroxyl compound Classes etc. have the active ester compound of the high ester group of two or more reactivity in a part.Active ester compound can be a kind of It is used alone, it is also possible to be used in combination of two or more.

From the viewpoint of improving thermostability, preferably by carboxylic acid compound and/or thiocarboxylic acid compound and hydroxy compound The active ester compound of the condensation reaction gained of thing and/or mercaptan compound.The most more preferably make carboxylic acid compound and selected from benzene More than one in phenolic compounds, naphthol compound and mercaptan compound carry out reacting and the active ester compound that obtains；Enter one What step preferably made carboxylic acid compound and carries out reacting with the aromatic compound with phenolic hydroxyl group and obtained has two in a part The aromatic compound of individual above active ester groups；Even more preferably make the carboxylic in a part with at least two carboxyl Aromatic compound that acid compound and the aromatic compound with phenolic hydroxyl group carry out reacting and obtain, i.e. have in a part There is the aromatic compound of two or more active ester groups.Active ester compound can be straight-chain, it is also possible to be branched.In addition There is in a part the carboxylic acid compound of at least two carboxyl if the compound containing aliphatic chain, then can carry The high compatibility with resin combination；If having the compound of aromatic rings, then can improve thermostability.

As carboxylic acid compound, include, for example: the fat of carbon number 1～20 (preferably 2～10, more preferably 2～8) Aliphatic carboxylic acid, the aromatic carboxylic acid of carbon number 7～20 (preferably 7～10).As aliphatic carboxylic acid, include, for example: second Acid, malonic acid, succinic acid, maleic acid, itaconic acid etc..As aromatic carboxylic acid, include, for example: benzoic acid, phthalic acid, M-phthalic acid, p-phthalic acid, PMA etc..Wherein, from the viewpoint of thermostability, preferably succinic acid, maleic acid, clothing Health acid, phthalic acid, M-phthalic acid, p-phthalic acid, more preferably M-phthalic acid, p-phthalic acid.

As thiocarboxylic acid compound, have no particular limits, include, for example: thiacetic acid., thiobenzoate etc..

As oxybenzene compound, include, for example: carbon number 6～40 (preferably 6～30, more preferably 6～23, enter One step is preferably 6～22) oxybenzene compound, as suitable concrete example, can enumerate: hydroquinone, resorcinol, bisphenol-A, bis-phenol F, bisphenol S, phenolphthalin, the bisphenol-A that methylates, the Bisphenol F that methylates, the bisphenol S that methylates, phenol, orthoresol, metacresol, paracresol, Catechol, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol (benzene Triol), dicyclopentadiene-type xenol etc..As oxybenzene compound, it be also possible to use phenol novolacs (phenol Novolak), the oligomer containing phosphorus atoms with phenolic hydroxyl group that Japanese Unexamined Patent Publication 2013-40270 publication is recorded.

As naphthol compound, include, for example: carbon number 10～40 (preferably 10～30, more preferably 10～20) Naphthol compound, as suitable concrete example, can enumerate: alpha-Naphthol, betanaphthol, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene etc..As naphthol compound, it be also possible to use naphthol novolac resin.

Wherein, preferably bisphenol-A, Bisphenol F, bisphenol S, the bisphenol-A that methylates, the Bisphenol F that methylates, the bisphenol S that methylates, adjacent benzene two Phenol, alpha-Naphthol, betanaphthol, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxy Benzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type xenol, phenol novolacs, have The oligomer containing phosphorus atoms of phenolic hydroxyl group；More preferably catechol, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy Naphthalene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type Xenol, phenol novolacs, there is the oligomer containing phosphorus atoms of phenolic hydroxyl group；Further preferably 1,5-dihydroxy naphthlene, 1,6- Dihydroxy naphthlene, 2,6-dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, bicyclopentadiene Type xenol, phenol novolacs, there is the oligomer containing phosphorus atoms of phenolic hydroxyl group；Even more preferably 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, dicyclopentadiene-type xenol, phenol novolacs, there is the phosphorous former of phenolic hydroxyl group The oligomer of son；The most more preferably 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, dicyclopentadiene-type biphenyl Phenol, there is the oligomer containing phosphorus atoms of phenolic hydroxyl group；Particularly preferably dicyclopentadiene-type xenol.

As mercaptan compound, have no particular limits, include, for example: dimercaptobenzene, triazine two mercaptan etc..

As the suitable concrete example of active ester compound, can enumerate: containing the work of dicyclopentadiene-type biphenol structural Property ester compounds, the active ester compound containing naphthalene structure, the active ester compound of the acetylate containing phenol novolacs, The active ester compound of the benzoylate containing phenol novolacs, make aromatic carboxylic acid with there is phenolic hydroxyl group containing phosphorus atoms Oligomer reaction obtained by active ester compound；The most more preferably contain the active esterifying of dicyclopentadiene-type biphenol structural Compound, active ester compound containing naphthalene structure, make aromatic carboxylic acid and the oligomer containing phosphorus atoms with phenolic hydroxyl group reacts Obtained by active ester compound.Should illustrate, in the present invention, " dicyclopentadiene-type biphenol structural " represent comprise phenylene- The divalent construction unit of two cyclopentylenes (ジシ Network ロペ Application チレ Application)-phenylene.

As active ester compound, it is usable in Japanese Unexamined Patent Publication 2004-277460 publication, Japanese Unexamined Patent Publication 2013-40270 Active ester compound disclosed in number publication, additionally can also use commercially available active ester compound.As active ester compound Commercially available product, " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000-that such as DIC (strain) makes can be enumerated 65T ", " HPC-8000L-65M " (containing the active ester compound of dicyclopentadiene-type biphenol structural), DIC (strain) make " DC808 " that " EXB9416-70BK " (containing the active ester compound of naphthalene structure), Mitsubishi Chemical's (strain) make is (containing phenol novolac The active ester compound of the acetylate of resin), " YLH1026 " (benzene containing phenol novolacs of making of Mitsubishi Chemical's (strain) The active ester compound of formyl compound), DIC (strain) " EXB9050L-62M " (active ester compound containing phosphorus atoms) made.

The content of the active ester compound in resin combination is preferably more than 1 mass %, and more than more preferably 2 mass %, And then preferably 3 is more than mass %, so more than more preferably 4 mass %, more than 5 mass %, more than 6 mass % or 7 mass % with On.The upper limit of the content of active ester compound is not particularly limited, below preferably 30 mass %, more preferably 25 mass % with Under, and then below preferably 20 mass %, and then below more preferably 15 mass % or below 10 mass %.

During it addition, the epoxy radix of (A) epoxy resin is set to 1, from the angle obtaining the good insulating barrier of mechanical strength Considering, the reaction radix of (B) active ester compound is preferably 0.1～2, more preferably 0.2～1.5, and then preferably 0.3～1. Here, " the epoxy radix of epoxy resin " refers to, for whole epoxy resin, and will be with each epoxy present in resin combination The solid constituent quality of resin divided by the value of epoxide equivalent gained amount to obtained by value.Additionally, " reactive group " refer to Epoxy radicals carries out the functional group reacted, and " the reaction radix of active ester compound " refers to, will live present in resin combination The solid constituent quality of property ester compounds divided by the value of reactive group equivalent gained all amount to obtained by value.

＜ (C) can have the triphenylimidazolyl ＞ of substituent group

The resin combination of the present invention contains (C) can be had the triphenylimidazolyl (hereinafter also referred to (C) composition) of substituent group and make For curing accelerator.

The present inventor etc. find: by resin combination, (B) composition and (C) composition are applied in combination, and are manufacturing print During brush wiring board, the insulating barrier of arbitrary characteristic all excellences of circuit imbedibility, dielectric dissipation factor, elongation at break can be formed. This is presumably because that the phenyl in (C) composition is upright and outspoken substituent group, thus (A) composition be slack-off with the curing reaction of (B) composition, Melt viscosity under the semi-cured state (B-stage) of following resin composition layer is prone to reduce.Conventional curing accelerator exists When increasing the content of inorganic filling material, melt viscosity uprises, and circuit imbedibility is prone to reduce, but in the present invention, by making With (C) composition, melt viscosity can be maintained low degree, it is possible to realize good circuit imbedibility.

In this manual, " can have the triphenylimidazolyl of substituent group " and refer to what its hydrogen atom was not substituted with a substituent Both triphenylimidazolyl that part or all of triphenylimidazolyl and its hydrogen atom is substituted with a substituent.Triphenylimidazolyl When having substituent group, the hydrogen atom that imidazoles is 1 can be substituted with a substituent, and the hydrogen atom of phenyl can be substituted with a substituent.

Alternatively base, is not particularly limited, and can enumerate such as halogen atom ,-OH ,-O-C_1-6Alkyl ,-N (C_1-6Alkane Base)₂、C_1-6Alkyl, C_6-10Aryl ,-NH₂、-CN、-C(O)O-C_1-6Alkyl ,-COOH ,-C (O) H ,-NO₂Deng.

Here, " C_p-q" (p and q is positive integer, meets p ＜ q.) such term records after representing immediately this term The carbon number of organic group is p～q.Such as " C_1-6Alkyl " such expression represents the alkyl of carbon number 1～6.

Above-mentioned substituent group and then can also have substituent group (hereinafter sometimes referred to " secondary substituent group ".).As secondary Substituent group, as long as no recording especially, can use the group identical with above-mentioned substituent group.

Wherein, the hydrogen atom of 1 or the hydrogen atom of phenyl as (C) composition, preferably imidazoles are not replaced base and take The triphenylimidazolyl in generation, more preferably 2,4,5-triphenylimidazolyl.

(C) content of composition is preferably more than 0.01 mass %, and more than more preferably 0.03 mass %, and then preferably 0.05 More than quality % or more than 0.1 mass %.(C) upper limit of the content of composition is not particularly limited, below preferably 5 mass %, more It is preferably below 3 mass %, and then below preferably 2 mass %, below 1 mass %, below 0.5 mass % or below 0.3 mass %.

The content that the nonvolatile component of resin combination is (B) composition in the case of 100 mass % is set to b (matter Amount %), the content of (C) composition is when being set to c (quality %), c/b is preferably 0.001～0.2, more preferably 0.005～0.1, and then It is preferably 0.01～0.05.

＜ (D) inorganic filling material ＞

The resin combination of the present invention is preferably in addition to containing (A)～(C) composition, (following possibly together with (D) inorganic filling material Also referred to as (D) composition).

There is no particular limitation for the material of inorganic filling material, can enumerate such as: silicon dioxide, aluminium oxide, glass, violet are blue or green Stone, Si oxide, barium sulfate, brium carbonate, Talcum, clay, mica powder, zinc oxide, brucite, boehmite, aluminium hydroxide, hydrogen-oxygen Change magnesium, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminium nitride, nitrogenized manganese, Alborex M 12, strontium carbonate, strontium titanates, calcium titanate, titanium Acid magnesium, bismuth titanates, titanium oxide, zirconium oxide, Barium metatitanate., metatitanic acid barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate and phosphoric acid tungsten wire array Deng.Wherein silicon dioxide is specially suitable.It addition, as silicon dioxide, preferably preparing spherical SiO 2.Inorganic filling material can It is used alone with one, it is also possible to be used in combination of two or more.

There is no particular limitation for the mean diameter of inorganic filling material, from the angle obtaining the little insulating barrier of surface roughness Or from the point of view of improving fine wiring formative, the mean diameter of inorganic filling material is preferably below 3 μm, is more preferably Below 2 μm, more preferably below 1 μm.There is no particular limitation for the lower limit of this mean diameter, more than preferably 0.01 μm, More than more preferably 0.1 μm and then more than preferably 0.3 μm.As the inorganic filling material with such mean diameter Commercially available product, can enumerate such as (strain) Admatechs system " YC100C ", " YA050C ", " YA050C-MJE ", " YA010C ", electricity Chemistry industry (strain) system " UFP-30 ", (strain) moral mountain (Tokuyama) system " シ Le Off ィ Le NSS-3N ", " シ Le Off ィ Le NSS- 4N ", " シ Le Off ィ Le NSS-5N ", (strain) Admatechs system " SO-C2 ", " SO-C1 " etc..

The mean diameter of inorganic filling material can utilize laser diffraction-scattering method based on Michaelis (Mie) scattering theory Measure.Specifically, utilize laser diffraction and scattering formula particle size distribution device, make inorganic filling material with volume reference Particle size distribution, is set to mean diameter by its median diameter, thus can measure.Mensuration sample can be preferably used and utilize ultrasound wave Make inorganic filling material be dispersed in water obtained by sample.As laser diffraction and scattering formula particle size distribution device, can make Made " LA-500 " etc. is made with (strain) hole field.

From the viewpoint of improving moisture-proof and dispersibility, inorganic filling material is preferably with amino silicone methane series coupling agent, ring TMOS system coupling agent, hydrosulphonyl silane system coupling agent, alkoxysilane compound containing trialkylsilyl group in molecular structure, organic silazane hydride compounds, titanate esters system The surface conditioning agent of more than a kind of coupling agent etc. processes.As the commercially available product of surface reason agent, such as SHIN-ETSU HANTOTAI can be enumerated Chemical industry (strain) system " KBM403 " (3-glycidoxy-propyltrimethoxy silane), 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), SHIN-ETSU HANTOTAI's chemical industry (strain) system " SZ-31 " (hexamethyldisiloxane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM103 " (phenyltrimethoxysila,e), SHIN-ETSU HANTOTAI's chemistry Industry (strain) system " KBM-4803 " (long-chain epoxy type silane coupler) etc..

The degree that the surface utilizing surface conditioning agent to carry out processes can be by the per unit surface area of inorganic filling material Carbon amounts evaluate.From the viewpoint of the dispersibility improving inorganic filling material, the per unit surface area of inorganic filling material Carbon amounts be preferably 0.02mg/m²Above, it is more preferably 0.1mg/m²Above, more preferably 0.2mg/m²Above.The opposing party Face, from the viewpoint of the melt viscosity from the melt viscosity preventing resin varnish or sheet form rises, preferably 1mg/m² Below, it is more preferably 0.8mg/m²Below, more preferably 0.5mg/m²Below.

The carbon amounts of the per unit surface area of inorganic filling material can measure in the following manner: uses solvent (such as first Base ethyl ketone (MEK)) it is carried out processing to the inorganic filling material after the process of surface, then it is measured.Specifically, may be used Enough MEK are added as solvent in the inorganic filling material after carrying out surface process with surface conditioning agent, super at 25 DEG C Sound wave cleans 5 minutes.Remove supernatant, solid constituent is dried, use the carbon analysis meter per unit to inorganic filling material The carbon amounts of surface area is measured.As carbon analysis meter, it is possible to use (strain) hole field makes made " EMIA-320V " etc..

The content of the inorganic filling material in resin combination from the point of view of obtaining the insulating barrier that thermal coefficient of expansion is low, It is preferably more than more than more than 50 mass %, more preferably 60 mass % and then preferably 70 mass %.In resin combination inorganic The upper limit of the content of packing material, from the point of view of the mechanical strength of insulating barrier, below preferably 95 mass %, is more preferably 90 Below quality % and then below preferably 85 mass % or below 80 mass %.

＜ (E) thermoplastic resin ＞

The resin combination of the present invention is preferably in addition to (A)～(C) composition, possibly together with (E) thermoplastic resin (hereinafter also referred to (E) composition).

As thermoplastic resin, such as phenoxy resin, polyvinyl acetal resin, vistanex can be enumerated, gather Butadiene resin, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, Polyphenylene oxide resin, polycarbonate resin, polyether-ether-ketone resin, polyester resin, preferably phenoxy resin.Thermoplastic resin can be single Solely use a kind, or also two or more can be applied in combination.

The weight average molecular weight of the polystyrene conversion of thermoplastic resin is preferably the scope of 8000～70000, more preferably The scope of 10000～60000, and then the scope of preferably 20000～60000.The weight of the polystyrene conversion of thermoplastic resin Average molecular weight can use gel permeation chromatography (GPC) method to measure.Specifically, the Weight-average molecular of the polystyrene conversion of thermoplastic resin Amount obtains as following, i.e. uses (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as determinator, uses Showa electrician (strain) Shodex processed K-800P/K-804L/K-804L as pillar, use chloroform etc. as flowing phase, make column temperature be 40 DEG C to enter Row measures, and uses the standard curve of polystyrene standard to calculate.

As phenoxy resin, include, for example: have selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol Acetophenone skeleton, phenolic aldehyde (novolak) skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, norborene skeleton, naphthalene bone The phenoxy group tree of more than one the skeleton in frame, anthracene skeleton, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton Fat.The end of phenoxy resin can be the arbitrary functional group such as phenolic hydroxyl group, epoxy radicals.Phenoxy resin can be used alone one Kind, it is also possible to it is used in combination of two or more.As the concrete example of phenoxy resin, can enumerate: Mitsubishi Chemical's (strain) makes " 1256 " and " 4250 " (being the phenoxy resin containing bisphenol A skeleton), " YX8100 " (phenoxy group containing bisphenol S skeleton Resin) and " YX6954 " (containing the phenoxy resin of bis-phenol acetophenone skeleton), other also can be enumerated: aurification is lived by Nippon Steel " YX6954BH30 ", " YX7553 ", " YX7553BH30 " that " FX280 " and " FX293 " that (strain) makes, Mitsubishi Chemical's (strain) make, " YL7769BH30 ", " YL6794 ", " YL7213 ", " YL7290 ", " YL7891BH30 " and " YL7482 " etc..

As polyvinyl acetal resin, such as vinyl-formal resin, polyvinyl butyral resin tree can be enumerated Fat, preferably polyvinyl butyral resin.As the concrete example of polyvinyl acetal resin, can enumerate the most electrochemically " changing Block チラ Le 4000-2 ", " changing Block チラ Le 5000-A ", " the change Block チラ Le that industry (strain) is made 6000-C ", " change Block チラ Le 6000-EP ", hydrops chemical industry (strain) make エスレッ Network BH series, BX series, KS Series, BL series, BM series etc..

As the concrete example of polyimide resin, " リカ U ト SN20 " and " リ that new Japan Chemical (strain) is made can be enumerated カコートPN20”.As the concrete example of polyimide resin, additionally can enumerate make 2 functional hydroxyl groups's end polybutadiene, Wire polyimides obtained by diisocyanate cpd and tetra-atomic acid anhydride reactant (record by Japanese Unexamined Patent Publication 2006-37083 publication Polyimides), polyimides (Japanese Unexamined Patent Publication 2002-12667 publication and Japanese Unexamined Patent Publication containing silicone matrix Polyimides described in 2000-319386 publication etc.) etc. modified polyimide.

As the concrete example of polyamide-imide resin, " the バイロマッ Network ス that Japan's weaving (strain) makes can be enumerated HR11NN " and " バイロマッ Network ス HR16NN ".Concrete example as polyamide-imide resin, it is also possible to enumerate Hitachi The modified polyamide acyls such as " KS9100 ", " KS9300 " (containing the polyamidoimide of silicone matrix) that one-tenth industry (strain) is made Imines.

As the concrete example of polyethersulfone resin, " PES5003P " that Sumitomo Chemical (strain) makes etc. can be enumerated.

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

As the concrete example of polyphenylene oxide resin, oligomeric phenylate-styrene resin that Rhizoma Sparganii ガス chemistry (strain) makes can be enumerated Fat " OPE-2St 1200 " etc..

Wherein, as thermoplastic resin, preferably phenoxy resin, polyvinyl acetal resin.Therefore, suitable one In individual embodiment, (E) composition contains more than one in phenoxy resin and polyvinyl acetal resin.

The content of the thermoplastic resin in resin combination is preferably 0.1 mass %～20 mass %, more preferably 0.5 matter Measure %～10 mass % and then preferably 1 mass %～5 mass %.

＜ other additive ＞

The resin combination of the present invention can contain other additive as required.As other additive, (B) composition can be enumerated Curing accelerator, fire retardant and organic filler material etc. beyond firming agent in addition, (C) composition.

-firming agent beyond (B) composition-

The resin combination of the present invention and then can contain the firming agent (hereinafter also referred to (F) composition) beyond (B) composition.

As (F) composition, making the function of epoxy resin cure just be not particularly limited as long as having, such as benzene can be enumerated Phenol (phenol) is that firming agent, naphthols system firming agent, cyanate system firming agent, benzimidazole dihydrochloride system firming agent, carbodiimide system are solid Agent etc..These firming agent can be used alone one, maybe can two or more be applied in combination.

Wherein, with in the combination of (A) to (C) composition, from obtaining presenting the angle of the insulating barrier of good elongation at break Degree considers, (F) composition is preferably phenol system firming agent, naphthols system firming agent.

As phenol system firming agent and naphthols system firming agent, from the viewpoint of thermostability and resistance to water, preferably there is phenol The phenol system firming agent of aldehyde (ノボラッ Network) structure or there is the naphthols system firming agent of phenolic structure.Additionally, from obtaining and leading From the viewpoint of the insulating barrier that the peel strength of body layer is excellent, the most nitrogenous phenol system firming agent or nitrogenous naphthols system firming agent, More preferably contain the phenol system firming agent of triazine skeleton and the naphthols system firming agent containing triazine skeleton.Wherein, meet from height Thermostability, resistance to water and with the peel strength of conductor layer from the viewpoint of, preferably comprise the phenol novolacs of triazine skeleton With the naphthol novolac resin containing triazine skeleton.As phenol system firming agent and the concrete example of naphthols system firming agent, such as, can arrange Lift: bright and chemical conversion (strain) make " MEH-7700 ", " MEH-7810 ", " MEH-7851 ", Japan chemical medicine (strain) make " NHN ", " CBN ", " GPH ", Nippon Steel live in " SN-170 ", " SN-180 ", " SN-190 ", " SN-475 ", " SN-that aurification (strain) is made 485 " " LA-7052 ", " LA-7054 ", " LA-3018 " that, " SN-495 ", " SN-375 ", " SN-395 ", DIC (strain) make, " LA- 1356 ", " TD2090 " etc..

As cyanate system firming agent, it is not particularly limited, can enumerate such as: phenolic aldehyde (novolac) type (phenol novolac Type, alkylphenol phenol aldehyde type etc.) cyanate system firming agent, dicyclopentadiene-type cyanate system firming agent, bisphenol type (bisphenol A-type, Bisphenol-f type, bisphenol S type etc.) cyanate system firming agent and their part be by the prepolymer etc. of triazine.As Concrete example, can enumerate: bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylene-1,5-phenylenecyanate), 4,4 '- Di-2-ethylhexylphosphine oxide (2,6-3,5-dimethylphenyl cyanate), 4,4 '-ethylidenediphenyl dicyanate, hexafluoro bisphenol-a dicyanate, 2, Double (4-cyanate) phenyl-propane of 2-, 1,1-double (4-cyanate phenylmethane), double (4-cyanate-3,5-3,5-dimethylphenyl) first Double (4-cyanate phenyl-1-(methyl the ethylidene)) benzene of alkane, 1,3-, double (4-cyanate phenyl) thioether and double (4-cyanate benzene Base) ether etc. 2 officials can cyanate ester resins, the multifunctional cyanic acid derivative by phenol novolac and cresol novolac (cresol novolac) etc. Ester resin, a part for these cyanate ester resins is by the prepolymer etc. of triazine.Concrete as cyanate system firming agent Example, can enumerate " PT30 " and " PT60 " (being phenol novolak type multifunctional cyanate ester resin) that Lonza Japan (strain) makes, " BA230 " prepolymer of trimer (part or all of bisphenol A dicyanate become by triazine) etc..

As the concrete example of benzimidazole dihydrochloride system firming agent, can enumerate: " HFB2006M ", the four countries that Showa macromolecule (strain) is made " P-d ", " F-a " that chemical conversion industry (strain) is made.

As the concrete example of carbodiimide system firming agent, " the V-that Nisshinbo Chemical (strain) makes can be enumerated 03 ", " V-07 " etc..

When using (F) composition, the content of this firming agent in resin combination is preferably more than 0.5 mass %, is more preferably More than 0.6 mass % and then more than preferably 0.7 mass % or more than 1 mass %.The upper limit of this content be preferably 10 mass % with Under, below more preferably 8 mass %, below 4 mass %, below 3 mass % or below 2 mass %.

-curing accelerator beyond (C) composition-

The resin combination of the present invention and then can contain the curing accelerator (hereinafter also referred to (G) composition) beyond (C) composition.

As (G) composition, can enumerate such as: phosphorus system curing accelerator, amine system curing accelerator, the solidification of imidazoles system promote Agent, guanidine system curing accelerator, metal system curing accelerator etc., preferably phosphorus system curing accelerator, amine system curing accelerator, (C) Imidazoles system solidification beyond imidazoles system curing accelerator beyond composition, more preferably amine system curing accelerator, (C) composition promotes Agent.Curing accelerator can be used alone a kind, it is also possible to two or more is applied in combination.

As phosphorus system curing accelerator, can enumerate such as: triphenylphosphine, boronic acid compounds, tetraphenyl tetraphenyl boron Hydrochlorate, normal-butyl tetraphenyl borate salts, tetrabutyl caprate, (4-aminomethyl phenyl) triphenyl rhodanate, tetraphenyl Rhodanate, butyl triphenyl rhodanate etc., triphenylphosphine, tetrabutyl caprate.

As amine system curing accelerator, the such as trialkylamine such as triethylamine, tri-butylamine, 4-dimethylamino can be enumerated Yl pyridines, benzyldimethylamine, 2,4,2,4,6-tri-(dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0)-hendecene Deng, preferably 4-dimethylaminopyridine, 1,8-diazabicyclo (5,4,0)-hendecene.

As the imidazoles system curing accelerator beyond (C) composition, such as 2-methylimidazole, 2-undecyl miaow can be enumerated Azoles, 2-heptadecyl imidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-first Base imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1-cyanogen Base Ethyl-2-Methyl imidazoles, 1-cyano ethyl-2-undecyl imidazole, 1-cyano ethyl-2-ethyl-4-methylimidazole, 1-cyanogen Base ethyl-2-phenylimidazole, 1-cyano ethyl-2-undecyl imidazole trimellitate, 1-cyano ethyl-2-phenylimidazole Trimellitate, 2,4-diaminourea-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diaminourea-6-[2'- Undecyl imidazole base-(1')]-ethyl-s-triazine, 2,4-diaminourea-6-[2'-ethyl-4'-methylimidazolyl-(1')]-second Base-s-triazine, 2,4-diaminourea-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid addition product, 2-phenyl Imidazoles isocyanuric acid addition product, 2-phenyl-4,5-bishydroxymethyl imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo-[1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzyl imidazole chloride, 2-methyl miaow The adduct of the imidazolium compoundss such as oxazoline, 2-benzylimidazoline and imidazolium compounds and epoxy resin, preferably 2-ethyl- 4-methylimidazole, 1-benzyl-2-phenylimidazole.

As imidazoles system curing accelerator, commercially available product can be used, " the P200-that such as Mitsubishi Chemical's (strain) makes can be enumerated H50 " etc..

As guanidine system curing accelerator, can enumerate such as: dicyandiamide, 1-methylguanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1- Guanidines, 1-(o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethyl guanidine, pentamethyl guanidine, 1,5,7-tri-nitrogen Miscellaneous dicyclo [4.4.0] ten carbon-5-alkene, 7-methyl isophthalic acid, 5,7-tri-azabicyclo [4.4.0] ten carbon-5-alkene, 1-methyl biguanide, 1- Ethyl biguanide, 1-normal-butyl biguanide, 1-n-octadecane base biguanide, 1,1-dimethylbiguanide, 1,1-diethyl biguanide, 1-cyclohexyl Biguanide, 1-pi-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide etc., preferably dicyandiamide, 1,5,7-tri-azabicyclos [4.4.0] ten carbon-5-alkene.

As metal system curing accelerator, the organic metal network of the metals such as such as cobalt, copper, zinc, ferrum, nickel, manganese, stannum can be enumerated Compound or organic metal salt.As the object lesson of metal-organic complex, acetylacetone cobalt (II), acetylacetone cobalt can be enumerated (III) the organic zinc complexations such as the organic copper complex such as organic cobalt complex, acetylacetone copper (II), zinc acetylacetonate (II) such as Organic nickel complex, the manganese acetylacetonates (II) such as the Organic-iron complexes such as thing, ferric acetyl acetonade (III), nickel acetylacetonate (II) Etc. Organic Manganese complex etc..As organic metal salt, such as zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, hard can be enumerated Fat acid stannum, zinc stearate etc..

The content of (G) composition in resin combination is not particularly limited, preferably with 0.05 mass %～the scope of 3 mass % Use.

-fire retardant-

The resin combination of the present invention can contain fire retardant.As fire retardant, such as organic phosphorus flame retardant, organic system can be enumerated Nitrogenous phosphorus compound, nitrogen compound, silicone flame retardant, metal hydroxides etc..Fire retardant can be used alone with a kind, Can also two or more and use.

As fire retardant, it is possible to use commercially available product, " HCA-HQ ", big eight chemistry works that such as three light (strain) are made can be enumerated " PX-200 " that industry (strain) is made etc..

The content of the fire retardant in resin combination is not particularly limited, preferably 0.5 mass %～20 mass %, more preferably It is 1 mass %～15 mass % and then preferably 1.5 mass %～10 mass %.

-organic filler material-

Resin combination, from the point of view of making percentage elongation improve, and then can contain organic filler material (hereinafter also referred to (H) one-tenth Point).As (H) composition, it is usable in the arbitrary organic filler material that can use during the insulating barrier forming printed substrate, Such as rubber particles, polyamide particles, organosilicon particle etc. can be enumerated.

As rubber particles, commercially available product can be used, such as DOW Chemical (Dow Chemical) Japan (strain) can be enumerated " AC3816N " that " EXL-2655 " of system, AICA industry (strain) make etc..

The content of (H) composition in resin combination be preferably 0.1 mass %～20 mass %, more preferably 0.2 mass %～ 10 mass % and then preferably 0.3 mass %～5 mass % or 0.5 mass %～3 mass %.

Resin combination and then can contain other additive as required, as other additive described, can enumerate example Such as the organo-metallic compounds such as organocopper compound, organic zinc compound and organic cobalt compounds and organic filler, glue The resin additives etc. such as agent, defoamer, levelling agent, adaptation imparting agent and coloring agent.

The glass transition temperature (Tg) of the solidfied material of the resin combination of the present invention is preferably more than 130 DEG C, more preferably It is more than 150 DEG C, and then preferably more than 155 DEG C or more than 160 DEG C.The upper limit is preferably less than 200 DEG C, and then preferably 190 Below DEG C, and then preferably less than 180 DEG C.The glass transition temperature (Tg) of the solidfied material of resin combination can be by using Thermo-mechanical analysis device Thermo Plus TMA8310 ((strain) Rigaku system), carries out heat by tensile load method (JIS K7197) Mechanical analysis measures.

The elongation at break of the solidfied material of the resin combination of the present invention is preferably more than 1.5%, and preferably more than 1.6%, More preferably more than 1.7%, and then preferably more than 1.8%, more than 1.9% or more than 2.0%.The upper limit of elongation at break is the highest Preferred, generally can be 5% such as the following.The elongation at break of the solidfied material of resin combination can be broken by following ＜ Split the mensuration of the percentage elongation method described in ＞ to measure.

The dielectric dissipation factor of the solidfied material of the resin combination of the present invention is preferably less than 0.02, more preferably 0.01 with Under, and then preferably less than 0.009 or less than 0.008.The lower limit of dielectric dissipation factor is the lowest preferred, generally can be 0.001 with first-class.The dielectric dissipation factor of the solidfied material of resin combination can be by the survey of following ＜ dielectric dissipation factor The method described in ＞ of determining measures.

The resin combination of the present invention manufacture printed substrate time, can be formed circuit imbedibility, dielectric dissipation factor, The insulating barrier that arbitrary characteristic of elongation at break is all excellent.Therefore the resin combination of the present invention can be suitably as shape The resin combination (resin compositions for insulating layer of printed substrate) becoming the insulating barrier of printed substrate uses, Ke Yigeng For suitably as the resin combination (interlayer insulating film of printed substrate of the interlayer insulating film for forming printed substrate With resin combination) use.It addition, the resin combination of the present invention can also use suitably as solder resist.

[adhering film]

The adhering film of the present invention is characterised by having: supporter and be arranged on this supporter containing resin group of the present invention The resin composition layer of compound.

From the viewpoint of printed substrate slimming, the thickness of resin composition layer is preferably below 100 μm, more preferably It is below below 80 μm, more preferably 60 μm, is even more preferably below below 50 μm or 40 μm.Resin composition layer The lower limit of thickness there is no particular limitation, more than typically 1 μm, more than 5 μm, 10 μm are with first-class.

From the point of view of obtaining good circuit imbedibility, the lowest melt viscosity of resin composition layer is preferably 3000 Pool (300Pas) below, more preferably 2500 pool (250Pas) below, and then preferably 2000 pool (200Pas) below, 1500 pool (150Pas) below or 1000 pools (100Pas) are below.The lower limit of this lowest melt viscosity is preferably 100 pools (10Pas) more than, more than more preferably 200 pools (20Pas), and then more than preferably 250 pools (25Pas).

The lowest melt viscosity of resin composition layer refers to resin composition layer institute during the resin melting of resin composition layer The minimum viscosity presented.Specifically, when making resin melting with certain programming rate heated resin composition layer, just In stage beginning, while temperature raises, melt viscosity reduces, when exceeding to a certain degree afterwards, while temperature raises, and melt viscosity Raise.Lowest melt viscosity refers to the melt viscosity of described minimal point.The lowest melt viscosity of resin composition layer can utilize Dynamic viscoelastic method measures, such as, can survey according to the method described in the mensuration ＞ of following ＜ lowest melt viscosity Fixed.

As supporter, include, for example: the thin film that is molded of plastic material, metal forming, processing release paper, preferably by plastics material The thin film of material formation, metal forming.

When using the thin film being molded of plastic material as supporter, as plastic material, include, for example: poly-to benzene two Formic acid second diester is (hereinafter sometimes referred to simply as " PET ".), PEN (hereinafter sometimes referred to simply as " PEN ".) etc. poly- The acrylic acid seriess such as ester, Merlon (hereinafter sometimes referred to simply as " PC "), polymethyl methacrylate (PMMA), cyclic polyolefin, Tri acetyl cellulose (TAC), polyether sulfides (PES), polyether-ketone, polyimides etc..Wherein, preferred poly terephthalic acid second Diester, PEN, particularly preferred low-cost polyethylene terephthalate.

When using metal forming as supporter, as metal forming, include, for example Copper Foil, aluminium foil etc., preferably Copper Foil.As Copper Foil, it is possible to use the paper tinsel formed by the monometallic of copper, it is possible to use by copper and other metal (such as, stannum, chromium, silver, magnesium, Nickel, zirconium, silicon, titanium etc.) alloy formed paper tinsel.

The face engaged with resin composition layer of supporter can be implemented delustring (マット) process, sided corona treatment.

It addition, as supporter, it is possible to use there is on the face engaged with resin composition layer the band demoulding of release layer The supporter of layer.As the releasing agent used in the release layer of the supporter of band release layer, include, for example selected from alkyd tree More than one releasing agent in fat, vistanex, polyurethane resin and organic siliconresin.Supporter with release layer can To use commercially available product, include, for example out the PET film, i.e. having using alkyd resin system releasing agent as the release layer of main constituent " SK-1 ", " AL-5 ", " AL-7 " of Lindeke Co., Ltd, east beautiful (strain) system " dew Miller (Le ミラ) T6AM " etc..

There is no particular limitation for the thickness of supporter, preferably 5 μm～the scope of 75 μm, more preferably 10 μm～60 μm Scope.Should illustrate, when using the supporter of band release layer, the thickness that preferably supporter of band release layer is overall is above-mentioned model Enclose.

Adhering film such as can be manufactured by following method: resin combination has been dissolved in preparation in organic solvent Resin varnish, uses chill coating machine etc. to coat on supporter by this resin varnish, and then makes it be dried and form resin Composition layer.

As organic solvent, include, for example: the ketones such as acetone, methyl ethyl ketone (MEK) and Ketohexamethylene, ethyl acetate, Acetate esters, cellosolve and the butyl cards such as butyl acetate, cellosolve acetate, propylene glycol methyl ether acetate and carbitol acetate Must the carbitol class such as alcohol, toluene and dimethylbenzene etc. are aromatic hydrocarbon, dimethylformamide, dimethyl acetylamide (DMAc) and N-first The amide series solvents etc. such as base ketopyrrolidine.Organic solvent can one be used alone, it is also possible to is used in combination of two or more.

It is dried and can be implemented by the known method such as heating, blowing hot-air.Drying condition is not particularly limited so that it is carry out It is dried, so that the content that organic solvent is in resin composition layer reaches below 10 mass %, preferably reaches below 5 mass %. Boiling point according to the organic solvent in resin varnish and different, but such as use containing 30 mass %～the organic solvent of 60 mass % Resin varnish time, by 50 DEG C～150 DEG C be dried 3 minutes～10 minutes, resin composition layer can be formed.

In adhering film, in the face not engaged with supporter of resin composition layer (that is, with supporter opposition side Face) on, can so the protective film that is consistent with supporter of lamination.The thickness of protective film is not particularly limited, for example, 1 μm ～40 μm.By lamination protective film, it is possible to prevent the attachment to the surface of resin composition layer such as dust or prevents scar.Viscous Connect thin film can be rolled into a roll to preserve.When adhering film has protective film, can use by peeling off protective film.

The adhering film of the present invention can be used for being formed the insulating barrier (insulating barrier of printed substrate of printed substrate suitably With), can more suitably be used for being formed the interlayer insulating film (interlayer insulating film of printed substrate is used) of printed substrate.

[printed substrate]

The printed substrate of the present invention is characterised by, the insulation that the solidfied material containing the resin combination utilizing the present invention is formed Layer.

Such as, the printed substrate of the present invention can use above-mentioned adhering film, by containing following (I) and (II) The method of step manufactures,

(I) adhering film is stacked in internal substrate in the way of the resin composition layer of this adhering film engages with internal substrate On step；

(II) resin composition layer heat cure is formed the step of insulating barrier.

" internal substrate " that use in step (I) is primarily referred to as glass epoxy substrate, metal basal board, polyester substrate, polyamides The substrates such as imines substrate, BT resin substrate, heat curing-type polyphenylene oxide substrate or define in the one or two sides of this substrate through figure The circuit substrate of the conductor layer (circuit) of case processing.Additionally, manufacture printed substrate time, be formed further insulating barrier and/ Or the middle internal layer circuit substrate manufacturing thing of conductor layer is also contained in the present invention in described " internal substrate ".Printed wire When plate is parts internal circuit board, the internal substrate having used parts built-in.

The lamination of internal substrate and adhering film such as can be by being crimped on internal layer from support side by adhering film heating Carry out on substrate.(hereinafter also referred to " thermo-compressed structure is added as by the component that adhering film heating is crimped on internal substrate Part "), include, for example heated metallic plate (SUS end plate etc.) or metallic roll (SUS roller) etc..Should illustrate, the most will not add Thermo-compressed component is to adhering film direct weighting, but pressurizes across heat resistant rubber elastomeric material, so that adhering film Fully follow the concave-convex surface of internal substrate.

The lamination of internal substrate and adhering film can utilize vacuum layer platen press to implement.In vacuum layer platen press, add thermo-compressed Temperature is preferably 60 DEG C～160 DEG C, more preferably 80 DEG C～the scope of 140 DEG C, add thermo-compressed pressure be preferably 0.098MPa～ The scope of 1.77MPa, more preferably 0.29MPa～1.47MPa, add the thermo-compressed time be preferably 20 seconds～400 seconds, more excellent Elect 30 seconds～the scope of 300 seconds as.Lamination is preferably implemented under the reduced pressure of below pressure 26.7hPa.

Lamination can use commercially available vacuum laminator to carry out.As commercially available vacuum laminator, include, for example (strain) The vacuum pack system device etc. that name mechanism makees made vacuum pressure type laminating machine, Nikko-Materials (strain) makes.

After lamination, by ambient pressure (under atmospheric pressure), such as, add adding thermo-compressed component from supporting side Pressure, can carry out the smoothing techniques of the adhering film of lamination.The pressurized conditions of smoothing techniques can be and above-mentioned lamination Add the condition that thermo-compressed condition is same.Smoothing techniques can utilize commercially available laminating machine to carry out.Should illustrate, lamination is with smooth Change processes and above-mentioned commercially available vacuum laminator can be used to carry out continuously.

Supporter can be removed between step (I) and step (II), supporter can also be removed after step (II).

In step (II), resin composition layer heat cure is formed insulating barrier.

There is no particular limitation for the heat cure condition of resin composition layer, it is possible to use forms the insulating barrier of printed substrate The condition that Shi Tongchang uses.

Such as, the heat cure condition of resin composition layer according to kind of resin combination etc. and different, but can be as Lower condition: solidification temperature be 120 DEG C～240 DEG C scope (preferably 150 DEG C～the scope of 220 DEG C, more preferably 170 DEG C～ The scope of 200 DEG C), hardening time be scope (preferably 10 minutes～100 minutes, more preferably 15 of 5 minutes～120 minutes Minute～90 minutes).

Before making resin composition layer heat cure, can than under solidification temperature lower temperature to resin composition layer Preheat.Such as, before making resin composition layer heat cure, can be more than 50 DEG C and less than 120 DEG C (preferably 60 More than DEG C and less than 110 DEG C, more preferably more than 70 DEG C and less than 100 DEG C) at a temperature of, resin composition layer is carried out 5 points It is more than clock that (preferably 5 minutes～150 minutes, more preferably 15 minutes～120 minutes) preheats.

Manufacture printed substrate time, it is also possible to and then implement (III) insulating barrier is carried out the step of perforate, (IV) to absolutely Step that edge layer is roughened, (V) form the step of conductor layer.These steps (III) can be according to track to (V) In the manufacture of road plate used, well known to a person skilled in the art that various method is implemented.Should illustrate, after step (II) When removing supporter, the removing of this supporter can be between step (II) and step (III), step (III) and step (IV) Between or step (IV) and step (V) between implement.

Step (III) is the step that insulating barrier carries out perforate, thus can be formed on the insulating layer through hole (via hole), The holes such as open-work (through hole).Step (III) is according to the composition etc. of the resin combination used in the formation of insulating barrier, example As drill bit, laser instrument, plasma etc. can be used to implement.The size in hole, shape can be fitted according to the design of printed substrate Work as decision.

Step (IV) is the step being roughened insulating barrier.Step, condition that roughening processes are the most special Restriction, normally used known step, condition when can use the insulating barrier forming printed substrate.For example, it is possible to depend on Secondary enforcement uses the expansion process of inflation fluid, uses the roughening process of oxidant, the neutralisation treatment of employing neutralizer to come absolutely Edge layer is roughened.As inflation fluid, there is no particular limitation, can enumerate aqueous slkali, surfactant solution etc., excellent Select aqueous slkali, as this aqueous slkali, more preferably sodium hydroxide solution, potassium hydroxide solution.As commercially available inflation fluid, such as may be used Enumerate: " Swelling Dip Securiganth P ", " the Swelling Dip that ATOTECH JAPAN (strain) makes Securiganth SBU " etc..Use inflation fluid expansion process there is no particular limitation, such as can by by insulating barrier 30 DEG C～the inflation fluid of 90 DEG C in impregnate and carry out for 1 minute～20 minutes.Suppress to be suitable from by the expansion of the resin of insulating barrier From the point of view of level, firming body is preferably made to impregnate 5 minutes～15 minutes in the inflation fluid of 40 DEG C～80 DEG C.As oxidant There is no particular limitation, include, for example the alkalescence height having dissolved potassium permanganate, sodium permanganate in the aqueous solution of sodium hydroxide Mangaic acid solution.The roughening using the oxidants such as alkalescence permanganic acid solution processes and preferably insulating barrier is being heated to 60 DEG C～80 DEG C Oxidizing agent solution in impregnate and carry out for 10 minutes～30 minutes.It addition, the concentration of the permanganate in alkalescence permanganic acid solution It is preferably 5 mass %～10 mass %.As commercially available oxidant, include, for example what ATOTECH JAPAN (strain) made The alkalescence permanganic acid solution such as " Concentrate Compact CP ", " Dosing solution Securiganth P ".This Outward, as neutralizer, the aqueous solution of preferred acidic, as commercially available product, include, for example what ATOTECH JAPAN (strain) made “Reduction Solution Securiganth P(リダクションソリューション・セキュリガントP)”.Use The process of neutralizer can be by using oxidant to carry out the process face of roughening process at 30 DEG C～the neutralizer of 80 DEG C Middle dipping is carried out for 5 minutes～30 minutes.From the point of view of operability etc., preferably employing oxidant is carried out at roughening The object of reason impregnates 5 minutes～the method for 20 minutes in the neutralizer of 40 DEG C～70 DEG C.

In one embodiment, the arithmetic average roughness Ra of the surface of insulating layer after roughening processes is preferably Below 400nm, more preferably below 350nm and then preferably below 300nm, below 250nm, below 200nm, 150nm with Under or below 100nm.The arithmetic average roughness (Ra) of surface of insulating layer can use non-contact type surface roughometer to carry out Measure.As the concrete example of non-contact type surface roughometer, Wei Yike precision instrument company limited (Veeco can be enumerated Instruments Inc.) " the WYKO NT3300 " that make.

Step (V) is the step forming conductor layer.

There is no particular limitation for the conductor material used in conductor layer.In suitable embodiment, conductor layer contains choosing More than one metal in gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, ferrum, stannum and indium.Conductor layer is permissible It is single metal layer or alloy-layer, as alloy-layer, include, for example by the alloy of the two or more metal selected from above-mentioned metal The layer that (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) is formed.Wherein, from conductor layer formed versatility, cost, The easiness of patterning angularly considers, preferably the single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or nickel-chrome Alloy, copper-nickel alloy, the alloy-layer of copper-titanium alloy, the more preferably monometallic of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper Layer or the alloy-layer of nickel-chromium alloy, and then the single metal layer of preferably copper.

Conductor layer can be single layer structure, it is also possible to be the Dan Jin comprising different types of metal or alloy of more than two-layer Belong to multiple structure obtained by layer or alloy-layer lamination.When conductor layer is multiple structure, the layer connected with insulating barrier is preferably chromium, zinc Or the single metal layer of titanium or the alloy-layer of nickel-chromium alloy.

The thickness of conductor layer depends on the design of required printed substrate, but generally 3 μm～35 μm, preferably 5 μm ～30 μm.

In one embodiment, conductor layer can utilize plating to be formed.Such as can utilize semi-additive process, entirely add The known technology such as method (Off Le アディティ Block method) carry out plating on the surface of insulating barrier, are formed and have required distribution The conductor layer of pattern.Below, it is shown that utilize semi-additive process to form the example of conductor layer.

First, the surface at insulating barrier utilizes electroless plating conformal one-tenth plating layer (めっ I シ De).Then, in shape On the plating layer become, corresponding to required Wiring pattern, form the mask pattern making a part for plating layer expose.Expose On plating layer, after utilizing plating to form metal level, remove mask pattern.Then, utilize etching etc. to remove unwanted plating layer, The conductor layer with required Wiring pattern can be formed.

[semiconductor device]

The semiconductor device of the present invention is characterised by the printed substrate containing the present invention.The semiconductor device of the present invention can make Manufacture with the printed substrate of the present invention.

As semiconductor device, can list for electric product (such as, computer, mobile phone, digital camera and electricity Depending on machine etc.) and the various semiconductor devices of the vehicles (such as, motorcycle, automobile, electric car, boats and ships and aircraft etc.) etc..

By conducting position installing component (semiconductor chip) at printed substrate, the quasiconductor of the present invention can be manufactured Device." conducting position " refers at " position of the signal of telecommunication in conduction printed substrate ", and its position can be surface or landfill Any one of position.As long as it addition, the component that semiconductor chip is with quasiconductor as material, be not particularly limited.

As long as the installation method of semiconductor chip when manufacturing the semiconductor device of the present invention makes semiconductor chip effectively send out Wave function, be not particularly limited, specifically can enumerate: lead-in wire engage installation method, flip-chip installation method, utilize built-in non- The installation method of buckle layer (バ Le プな PVC Le De アップ, BBUL), utilize the peace of anisotropic conducting film (ACF) Dress method, utilize the installation method etc. of non-conductive film (NCF).Here, " the actual load side of bumpless build up layer (BBUL) is utilized Method " it is " semiconductor chip directly to be filled the recess to printed substrate, makes semiconductor chip and the distribution on printed substrate The installation method connected ".

Embodiment

The present invention is the most more specifically described, but the present invention is not limited to these embodiments.Should say Bright, in following record, " part " and " % " expressing as long as no other, each refer to " mass parts " and " quality % ".

Illustrate firstly for various assay methods, evaluation methodology.

Mensuration ＞ of ＜ lowest melt viscosity

The melt viscosity of the resin composition layer measured in the adhering film of making in embodiment and comparative example.Use the most viscous Elasticity measurement device ((strain) UBM system " Rheosol-G3000 "), amount of resin is 1g, use diameter 18mm parallel-plate, from Beginning temperature 60 C to 200 DEG C, programming rate 5 DEG C/min, measure 2.5 DEG C, temperature interval, vibration 1Hz/deg condition determination under Measure melt viscosity.

Mensuration ＞ of ＜ elongation at break

The adhering film made in embodiment and comparative example is heated 90 minutes at 200 DEG C and makes resin composition layer heat cure After, peel off supporter.The solidfied material of gained is referred to as " evaluation solidfied material ".For evaluation solidfied material, based on Japanese industry Standard (JIS K7127), utilizes Tensilon universal testing machine ((strain) Orientec system " RTC-1250A ") to carry out stretching examination Test, measure elongation at break.

Mensuration ＞ of ＜ glass transition temperature

Evaluation solidfied material is cut into wide about 5mm, is about the test film of 15mm, use thermo-mechanical analysis device ((strain) Rigaku system " Thermo Plus TMA8310 "), utilize tensile load method to carry out thermo-mechanical analysis.Specifically, by test film After being arranged on above-mentioned thermo-mechanical analysis device, load 1g, programming rate 5 DEG C/min condition determination under METHOD FOR CONTINUOUS DETERMINATION Twice.Then, in secondary mensuration, glass transition temperature (Tg is calculated；℃).

Mensuration ＞ of ＜ dielectric dissipation factor

Evaluation solidfied material is cut into wide 2mm, the test film of long 80mm.For this test film, use Dielectric Coefficient dress Put (Agilent Technologies company's system " HP8362B "), utilize Resonant-cavity Method measuring frequency 5.8GHz, measuring temperature Dielectric dissipation factor is measured under conditions of 23 DEG C.Two panels test film is measured, calculates meansigma methods.

＜ embodiment 1 ＞

By bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system " 828US ", epoxide equivalent about 180) 30 parts, biphenyl type epoxy resin (Japan chemical medicine (strain) system " NC3000H ", epoxide equivalent about 269) 30 parts stirs while heating for dissolving is solvent naphtha 55 parts In, it is then cooled to room temperature.In this mixed solution, with amino silicone methane series coupling agent, (SHIN-ETSU HANTOTAI's chemical industry (strain) is made in interpolation " KBM573 ") carry out the preparing spherical SiO 2 (mean diameter 0.5 μm, (strain) Admatechs system " SO-C2 ") that surface processes 260 parts, carry out mixing with 3 rollers so that it is be uniformly dispersed.In this roller dispersion, (DIC (strain) makes mixed active ester compounds " HPC-8000-65T ", active group equivalent about 223, the toluene solution of nonvolatile component 65 mass %) 40 parts, phenoxy resin (three Pedicellus et Pericarpium Trapae chemistry (strain) system " YX6954BH30 ", the methyl ethyl ketone (hereinafter referred to as " MEK ") of solid constituent 30 mass % and Ketohexamethylene 1:1 solution) 20 parts, curing accelerator (Tokyo chemical conversion industry (strain) system " 2,4,5-triphenylimidazolyl ", solid constituent 2.5 matter The 1:1 solution of MEK and the Ketohexamethylene of amount %) 24 parts, MEK10 part, it is uniformly dispersed with high speed rotating blender, prepares resin clear Paint.

As supporter, (Lin get Ke (strain) makes " AL-5 ", thickness to prepare the PET film with alkyd resin system release layer 38μm).On the release layer of this supporter, even spread resin varnish, so that the thickness of dried resin composition layer is 40 μm, are dried 5 minutes at 80～120 DEG C (average 100 DEG C), make adhering film.

＜ embodiment 2 ＞

Except in embodiment 1, in roller dispersion so that the mixing phenol system firming agent containing triazine skeleton (DIC (strain) makes " LA-3018-50P ", hydroxyl equivalent about 151, solid constituent are the 2-methoxy propyl alcoholic solution of 50%) beyond 14 parts, other is with real Execute example 1 and similarly make resin varnish, adhering film.

＜ embodiment 3 ＞

Except in example 2, by biphenyl type epoxy resin (Japan's chemical medicine (strain) system " NC3000H ", epoxide equivalent about 269) 30 Part is changed into beyond naphthol type epoxy resin (aurification (strain) system " ESN475V ", epoxide equivalent 332 are lived by Nippon Steel) 30 parts, its It makes resin varnish, adhering film similarly to Example 2.

＜ embodiment 4 ＞

Except in example 2, by biphenyl type epoxy resin (Japan's chemical medicine (strain) system " NC3000H ", epoxide equivalent about 269) 30 Part change into di-methylbenzene phenol-type epoxy resin (Mitsubishi Chemical's (strain) system " YX4000HK ", epoxide equivalent about 185) 30 parts with Outward, other makes resin varnish, adhering film similarly to Example 2.

＜ embodiment 5 ＞

Except in example 2, in mixed solution and then add acrylic modified butadiene-styrene rubber particle (メタ Network リ Le Block タジエ Application スチレ Application go system particle) beyond (DOW Chemical Japan (strain) system " EXL-2655 ") 3 parts, other and embodiment 2 similarly make resin varnish, adhering film.

＜ comparative example 1 ＞

Except in embodiment 1, by curing accelerator, (Tokyo chemical conversion industry (strain) system " 2,4,5-triphenylimidazolyl ", solid become The MEK of point 2.5 mass % and the 1:1 solution of Ketohexamethylene) 24 parts change into curing accelerator (four countries' chemical conversion (strain) system " 1B2PZ ", 1-benzyl-2-phenylimidazole, the MEK solution of solid constituent 10 mass %) beyond 6 parts, other makes tree similarly to Example 1 Fat varnish, adhering film.

＜ comparative example 2 ＞

Except in embodiment 1, by curing accelerator, (Tokyo chemical conversion industry (strain) system " 2,4,5-triphenylimidazolyl ", solid become The MEK of point 2.5 mass % and the 1:1 solution of Ketohexamethylene) 24 parts change into curing accelerator (" DMAP ", 4-dimethylamino pyrrole Pyridine, the MEK solution of solid constituent 5 mass %) beyond 6 parts, other makes resin varnish, adhering film similarly to Example 1.

＜ comparative example 3 ＞

Except in embodiment 1, by active ester compound (DIC (strain) system " HPC-8000-65T ", active group equivalent about 223, no The toluene solution of volatile ingredient 65 mass %) 40 parts change into phenol novolak type multifunctional cyanate ester resin (Lonza Japan (strain) system " PT30 ", cyanate equivalent 124) beyond 26 parts, other makes resin varnish, adhering film similarly to Example 1.

[table 1]

。

Claims

1. resin combination, it contains (A) epoxy resin, (B) active ester compound and (C) can have the triphenyl of substituent group Imidazoles.

Resin combination the most according to claim 1, wherein, is set to 100 matter by the nonvolatile component in resin combination During amount %, the content of (B) composition is 1 mass %～30 mass %.

Resin combination the most according to claim 1, wherein, is set to 100 matter by the nonvolatile component in resin combination During amount %, the content of (C) composition is 0.01 mass %～5 mass %.

Resin combination the most according to claim 1, wherein, containing (D) inorganic filling material.

Resin combination the most according to claim 4, wherein, is set to 100 matter by the nonvolatile component in resin combination During amount %, the content of (D) composition is more than 50 mass %.

Resin combination the most according to claim 4, wherein, the mean diameter of (D) composition is 0.01 μm～3 μm.

Resin combination the most according to claim 4, wherein, (D) composition is silicon dioxide.

Resin combination the most according to claim 1, wherein, containing (E) thermoplastic resin.

9. adhering film, its have supporter and be arranged on this supporter containing the resin combination described in claim 1 Resin composition layer.

Adhering film the most according to claim 9, wherein, the lowest melt viscosity of resin composition layer be 3000 pools with Under.

11. according to the adhering film described in claim 9 or 10, and wherein, the elongation at break of the resin composition layer of solidification is More than 1.5%.

12. printed substrates, it contains and utilizes the solidfied material of the resin combination according to any one of claim 1～8 to be formed Insulating barrier.

13. semiconductor devices, it contains the printed substrate described in claim 12.