CN104650539B

CN104650539B - Resin combination

Info

Publication number: CN104650539B
Application number: CN201410661022.2A
Authority: CN
Inventors: 中村茂雄; 渡边真俊
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2013-11-22
Filing date: 2014-11-19
Publication date: 2019-06-07
Anticipated expiration: 2034-11-19
Also published as: JP6237155B2; JP2015101626A; CN104650539A; KR102234057B1; KR20150059607A; TW201529703A; TWI635130B

Abstract

The present invention provides resin combination, which can get the low solidfied material of dielectric loss tangent, and the solidfied material is carried out aperture processing, and the stain in roughened treated through-hole can be inhibited.Resin combination of the invention contains epoxy resin, active ester compound and the resin selected from one or more of alkylated melamine resins and alkoxyalkylation phenolic resin.

Description

Resin combination

Technical field

The present invention relates to resin combinations.Further relate to sheet laminated material, multilayer printed circuit board, semiconductor device.

Background technique

In recent years, the miniaturization of electronic equipment, high performance are developing, and in multilayer printed circuit board, seek wiring Miniaturization and densification.And then in order to reduce transmission loss, the insulation material low using dielectric loss tangent is required in insulating layer Material.

Manufacturing technology as multilayer printed circuit board, it is known that replace lapped insulation layer and conductor layer on circuit substrate The manufacturing method of (the ビ Le De アップ) mode of stacking.In the manufacturing method of stack manner, insulation layers are following to be formed: being made Keep resin combination hot in the layer of circuit substrate superimposed layer resin combination with the sheet laminated material containing resin combination Solidification.Then, aperture processing is carried out on the insulating layer of formation and form through-hole (via hole) (for example, patent document 1).

Existing technical literature

Patent document

[patent document 1] Japanese Unexamined Patent Publication 2008-37957 bulletin.

Summary of the invention

Subject to be solved by the invention

When carrying out aperture processing to insulating layer, gum residue (stain (スミア)) is generated in through-hole, is needed by coarse Change is handled to remove stain.However, the inventors of the present invention have found, in the tree using the low dielectric loss tangent containing active ester compound When oil/fat composition makes multilayer printed circuit board, even if to being roughened in through-hole after the aperture processing of insulating layer, Also it is difficult to remove the stain in through-hole.

Therefore, the subject to be solved by the invention is to provide resin combination, the available medium attenuations of the resin combination The low solidfied material of factor, and aperture processing is carried out to the solidfied material, the stain in through-hole after roughened processing can obtain To inhibition.

[means for solving project]

The inventors of the present invention are conscientiously studied in order to solve the above problems, as a result, it has been found that, in addition to containing epoxy resin, Except active ester compound, the also specific resin group containing alkylated melamine resins and/or alkoxyalkylation phenolic resin Object is closed, can solve the above subject, so as to complete the present invention.

That is, the present invention includes content below；

[1] resin combination contains:

(A) epoxy resin,

(B) active ester compound and

(C) resin selected from one or more of alkylated melamine resins and alkoxyalkylation phenolic resin；

[2] resin combination recorded in [1], wherein by the total amount of (A) ingredient and (B) ingredient in resin combination When being set as 100 mass %, the content of (C) ingredient is 0.1 mass of mass %~30 %；

[3] resin combination recorded in [1] or [2], wherein the non-volatile component in resin combination is set as 100 When quality %, the content of (B) ingredient is 1 mass of mass %~30 %；

[4] resin combination that any one of [1]~[3] are recorded, wherein alkylated melamine resins are containing by following formula (1) melamine resin of the structural unit indicated,

[in formula,

X¹、X²、X³、X⁴、X⁵And X⁶Each independently represent hydrogen atom, by formula :-CH₂OH indicate group, by formula :-CH₂- O-R¹The group of expression or by formula-CH₂The group that-* is indicated, wherein R¹It is chemical bond for alkyl, *；Wherein, X¹、X²、X³、X⁴、X⁵ And X⁶At least one of for by formula :-CH₂-O-R¹The group of expression.]；

[5] any one of [1]~[4] record resin combination, wherein alkoxyalkylation phenolic resin be containing By following formula (2) indicate structural unit phenolic resin,

[in formula,

Y indicates hydrogen atom or by formula :-R²The group that-* is indicated, wherein R²For alkylidene or singly-bound, * is chemical bond,

Z¹It indicates by formula :-CH (R³)-O-R⁴The group of expression, wherein R³For hydrogen atom, alkyl, phenyl or hydroxyphenyl, R⁴For Alkyl,

Z²It indicates by formula :-R⁵- * indicate group or by formula :-R⁶(-*)₂The group of expression, wherein R⁵For alkylidene or list Key, R⁶For three base of alkane (ア Le カ Application トリイ Le base), * is chemical bond,

Z³Indicate alkyl optionally with substituent group,

L, m and n is satisfaction 2≤l+m+n≤5 and the integer of 1≤l.]；

[6] resin combination that any one of [1]~[5] are recorded, further contains (D) inorganic filling material；

[7] resin combination recorded in [6], wherein the average grain diameter of (D) inorganic filling material is 0.01 μm~5 μ m；

[8] resin combination recorded in [6] or [7], wherein the non-volatile component in resin combination is set as 100 When quality %, the content of (D) ingredient is 50 mass of mass %~85 %；

[9] resin combination that any one of [1]~[8] are recorded, is the insulating layer resin of multilayer printed circuit board Composition；

[10] resin combination that any one of [1]~[9] are recorded, is the stack layer tree of multilayer printed circuit board Oil/fat composition；

[11] sheet laminated material contains the resin combination of any one of [1]~[10] record；

[12] multilayer printed circuit board contains the solidfied material for the resin combination recorded by any one of [1]~[10] The insulating layer of formation；

[13] semiconductor device contains the multilayer printed circuit board recorded in [12]；

[14] manufacturing method of multilayer printed circuit board, wherein the sheet recorded in circuit substrate superimposed layer [11] is folded Resin combination heat cure is formed insulating layer by layer material, and aperture is carried out on the insulating layer being formed on circuit substrate and is added Work and form through-hole.

Invention effect

Resin combination according to the present invention, the low solidfied material of available dielectric loss tangent, and to the solidfied material Aperture processing is carried out, the stain in through-hole after roughened processing can be inhibited.

Specific embodiment

[ resin combination ]

Resin combination of the invention is characterized in that, is contained: (A) epoxy resin, (B) active ester compound and (C) choosing The resin of one or more of self-alkylation melamine resin and alkoxyalkylation phenolic resin.

< (A) ingredient >

(A) ingredient contained in resin combination of the invention is epoxy resin.As epoxy resin, do not limit particularly It is fixed, there is the epoxy resin of 2 or more epoxy groups preferably in 1 molecule.Specifically, it can enumerate: bisphenol A type epoxy resin, Bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, novolac type (Off ェノー Le ノボラッ Network type) epoxy resin, tert butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type Epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, Cresol formaldehyde type (Network レゾー Le ノボラッ Network type) epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear fat Race's epoxy resin, the epoxy resin with butadiene structure, alicyclic epoxy resin, hetero ring type epoxy resin, containing whorled Epoxy resin, cyclohexanedimethanol type epoxy resin, trihydroxy methyl type epoxy resin, halogenated epoxy resin etc..Epoxy resin can It is used alone with a kind or two or more is applied in combination.

Wherein, from the viewpoint of the adaptation for improving heat resistance, raising insulating reliability, raising and conductor layer, preferably Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, Biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthylene ether type epoxy, glycidyl ester type epoxy tree Rouge, anthracene type epoxy resin, the epoxy resin with butadiene structure.Specifically, it such as can enumerate: bisphenol A type epoxy resin (three Water chestnut chemistry (strain) make " jER828EL ", " YL980 "), bisphenol f type epoxy resin (Mitsubishi Chemical's (strain) make " jER806H ", " YL983U "), bisphenol AF type epoxy resin (Nippon Steel live aurification (strain) system " ZX1059 "), 2 functional epoxy resins of naphthalene type (DIC (strain) makes " HP4032 ", " HP4032D ", " HP4032SS "), 4 functional epoxy resins of naphthalene type (DIC (strain) system " HP4700 ", " HP4710 "), naphthol type epoxy resin (Dongdu be melted into (strain) system " ESN-475V "), the epoxy resin with butadiene structure (ダイセ Le chemical industry (strain) makes " PB-3600 "), biphenyl type epoxy resin (Japanese chemical drug (strain) system " NC3000H ", " NC3000L ", " NC3100 ", Mitsubishi Chemical's (strain) make " YX4000 ", " YL6121 "), double diformazan phenolic (ビキシレノー Le Type) epoxy resin (Mitsubishi Chemical's (strain) makes " YX4000H ", " YX4000HK "), dicyclopentadiene type epoxy resin (DIC (strain) makes " HP-7200HH "), anthracene type epoxy resin (Mitsubishi Chemical's (strain) make " YX8800 "), naphthylene ether type epoxy (DIC (strain) make " EXA-7310 ", " EXA-7311 ", " EXA-7311L ", " EXA7311-G3 ", " EXA7311-G4 ", " EXA7311-G4S "), glycidyl ester type epoxy resin (Na ガセケ system テッ Network ス (strain) make " EX711 ", " EX721 ", (strain) プリ Application テッ Network system " R540 ") etc..

Wherein, liquid-state epoxy resin and solid epoxy resin is preferably used in combination, more preferably containing " with 2 in 1 molecule A above epoxy group, be at 20 DEG C of temperature liquid aromatic system epoxy resin (hereinafter referred to as " liquid-state epoxy resin ".)" " in 1 molecule with 3 or more epoxy group, at 20 DEG C of temperature be solid aromatic system epoxy resin (hereinafter referred to as " solid epoxy resin ".) " mode.It should be noted that aromatic system epoxy resin described in the present invention refers in its intramolecular Epoxy resin with aromatic ring structure.In the case where as epoxy resin and with liquid-state epoxy resin and solid epoxy resin, When resin combination is used in the form of sheet laminated material with it is appropriate it is flexible in terms of, the solidfied material of resin combination From the aspect of breaking strength appropriate, mixing ratio (liquid-state epoxy resin: solid epoxy resin) is excellent by quality ratio Be selected as 1:0.1~1:6 range, more preferably 1:0.1~1:5 range, further preferably 1:0.3~1:4.5 range, It is even more preferably the range of 1:0.6~1:4.

In resin combination of the invention, mentioned from the mechanical strength and insulating reliability of the solidfied material for making resin combination From the viewpoint of height, the content of (A) ingredient is preferably 3 mass of mass %~40 %, more preferably 5 mass of mass %~35 %, into one Step is preferably 10 mass of mass %~30 %.

It should be noted that the content of each ingredient in resin combination refers to resin unless otherwise indicated in the present invention The total amount of non-volatile component in composition is set as value when 100 mass %.

The epoxide equivalent of epoxy resin is preferably 50~3000, more preferably 80~2000, further preferably 110~ 1000.By making epoxide equivalent in the range, so that the crosslink density of solidfied material becomes sufficiently, it is low to obtain surface roughness Insulating layer.It should be noted that epoxide equivalent can be measured according to JIS K7236, refer to the resin of the epoxy group containing 1 equivalent Quality.

The weight average molecular weight of epoxy resin is preferably 100~5000, more preferably 250~3000, further preferably 400 ~1500.Here, the weight average molecular weight of epoxy resin is converted using the polystyrene of gel permeation chromatography (GPC) method measurement Weight average molecular weight.

< (B) ingredient >

(B) ingredient contained in resin combination of the invention is active ester compound.Active ester compound is in 1 molecule In the compound with 1 or more active ester groups, the dielectric loss tangent of resin combination can be reduced.Active ester compound The r.m.s. roughness Rq on the solidfied material surface after being roughened the solidfied material of resin combination can also be reduced.It is living Property ester compounds can be reacted with epoxy resin etc., with the compound of 2 or more active ester groups preferably in 1 molecule.Make For active ester compound, it is usually preferred to use phenol esters (phenol esters), benzenethiol ester (thiophenol Esters) class, N- hydroxylamine esters, esters of heterocycle hydroxyl compound etc. have 2 or more reactivities high in 1 molecule The compound of ester group.Active ester compound can be used alone with a kind or two or more is applied in combination.

From the viewpoint of improving heat resistance, preferably pass through carboxylic acid compound and/or thiocarboxylic acid compound and hydroxylating Close active ester compound obtained by the condensation reaction of object and/or mercaptan compound.Wherein, more preferably by carboxylic acid compound be selected from Active ester compound obtained from the compound reaction of one or more of oxybenzene compound, naphthol compound and mercaptan compound； Obtained from further preferably being reacted as carboxylic acid compound with the aromatic compound with phenolic hydroxyl group, have 2 in 1 molecule The aromatic compound of a above active ester groups；Carboxylic with carboxyl more than at least two still more preferably in 1 molecule Aromatic compound obtained from acid compound is reacted with the aromatic compound with phenolic hydroxyl group, and the aromatic compound There is the aromatic compound of 2 or more active ester groups in 1 molecule of object.Active ester compound can be straight-chain, can also To be branched.In addition, carboxylic acid compound with carboxyl more than at least two in 1 molecule is if it is containing aliphatic chain Compound, then the compatibility with resin combination can be improved, if it is the compound with aromatic rings, then can be improved resistance to It is hot.

As carboxylic acid compound, such as carbon atom number 1~20 (preferably 2~10, the aliphatic of more preferable 2~8) can be enumerated The aromatic carboxylic acid of carboxylic acid, carbon atom number 7~20 (preferably 7~10).As aliphatic carboxylic acid, such as acetic acid, the third two can be enumerated Acid, succinic acid, maleic acid, itaconic acid etc..As aromatic carboxylic acid, such as benzoic acid, phthalic acid, isophthalic diformazan can be enumerated Acid, terephthalic acid (TPA), Pyromellitic Acid etc..Wherein, from the viewpoint of heat resistance, preferably succinic acid, maleic acid, itaconic acid, Phthalic acid, M-phthalic acid, terephthalic acid (TPA), more preferable M-phthalic acid, terephthalic acid (TPA).

As thiocarboxylic acid compound, be not particularly limited, such as thioacetic acid, thiobenzoate can be enumerated etc..

As oxybenzene compound, for example, can enumerate carbon atom number 6~40 (preferably 6~30, it is more preferable 6~23, further excellent Select 6~22) oxybenzene compound, as preferred concrete example, can enumerate quinhydrones, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, Phenolphthalin, methylation bisphenol-A, methylation Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, catechol, Dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type connection Phenol (ジシ Network ロペ Application タジエ Application type ジ Off ェノー Le) etc..As oxybenzene compound, line style phenolic aldehyde can also be used Resin (phenol novolac).

As naphthol compound, such as carbon atom number 10~40 (preferably 10~30, the naphthalenes of more preferable 10~20) can be enumerated Phenolic compounds can enumerate alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- as preferred concrete example Dihydroxy naphthlene etc..Naphthol novolac resin (naphthol novolac) also can be used as naphthol compound.

Wherein, from the viewpoint of improving heat resistance, improving dissolubility, preferably bisphenol-A, Bisphenol F, bisphenol S, methylation Bisphenol-A, methylation Bisphenol F, methylation bisphenol S, catechol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, two Polycyclopentadithio.henes ene-type xenol, linear phenol-aldehyde resin；More preferably catechol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- Dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, two polycyclics Pentadiene type xenol, linear phenol-aldehyde resin；Further preferably 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy Naphthalene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type xenol, line style phenolic aldehyde Resin；It is still more preferably 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dicyclopentadiene type biphenyl Phenol, linear phenol-aldehyde resin；Especially preferably 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dicyclopentadiene Type xenol；Particularly preferably dicyclopentadiene type xenol.

As mercaptan compound, be not particularly limited, such as dimercaptobenzene, two mercaptan of triazine can be enumerated etc..

As the suitable concrete example of active ester curing agent, the work containing dicyclopentadiene type biphenol structural can be enumerated Property ester compounds, the active ester compound containing naphthalene structure, the acetylate containing linear phenol-aldehyde resin active ester compound, The active ester compound of benzoylate containing linear phenol-aldehyde resin, wherein the active ester chemical combination of further preferably naphthalene structure Object, the active ester compound containing dicyclopentadiene type biphenol structural.It should be noted that in the present invention, " dicyclopentadiene Type biphenol structural " indicates the divalent structure list comprising-two ring pentalene of phenylene (ジシ Network ロペ Application タレ Application)-phenylene Member.

As the active ester compound containing dicyclopentadiene type biphenol structural, following formula (a) can be more specifically enumerated Compound.

(a)

(in formula, R is phenyl, naphthalene, and k indicates 0 or 1, and n is calculated as 0.05~2.5 with the average of repetitive unit.).

From the viewpoint of reducing dielectric loss tangent, improving heat resistance, it is preferably 0, n excellent that R, which is preferably naphthalene, k, It is selected as 0.25~1.5.

As (B) ingredient, active ester compound disclosed in Japanese Unexamined Patent Publication 2004-277460 bulletin can be used, Commercially available active ester compound can be used.For commercially available active ester compound, as containing dicyclopentadiene xenol The active ester system curing agent of structure can enumerate EXB9451, EXB9460, EXB9460S, HPC-8000-65T (DIC (strain) system)； As the active ester system curing agent containing naphthalene structure, EXB9416-70BK (DIC (strain) system) can be enumerated；As containing novolak The active ester system curing agent of the acetylate of resin can enumerate DC808 (Mitsubishi Chemical's (strain) system)；As tree containing novolak The active ester system curing agent of the benzoylate of rouge can enumerate YLH1026 (Mitsubishi Chemical's (strain) system) etc..

From the viewpoint of improving heat resistance and then stain inhibited to occur, the content of (B) ingredient be preferably 30 mass % with Under, more preferably 20 mass % or less, further preferably 15 mass % or less.On the other hand, from the viewpoint for improving peel strength Consider, the lower limit of the content of (B) ingredient is preferably 1 mass % or more, more preferably 3 mass % or more, further preferably 5 matter Measure % or more.

In addition, the epoxy radix of (A) epoxy resin is set as from the viewpoint of the mechanical property for improving resin combination When 1, the reaction radix of (B) active ester compound is preferably 0.2~2, more preferably 0.3~1.5, further preferably 0.4~ 1.Here, " the epoxy radix of epoxy resin " refers to, for whole epoxy resin, will use each ring present in resin combination Value obtained by the solid component quality of oxygen resin is amounted to divided by the resulting value of epoxide equivalent.In addition, " reactive group " refers to energy With the functional group of epoxy reaction, " the reaction radix of active ester compound " refers to, will use activity present in resin combination Value obtained by the solid component quality of ester compounds is all amounted to divided by the resulting value of reactive group equivalent.

< (C) ingredient >

(C) ingredient contained in resin combination of the invention is selected from alkylated melamine resins and alkoxyalkylation phenol The resin of one or more of urea formaldehyde.By using (C) ingredient, thus even if using low Jie containing active ester compound The resin combination of matter attenuation factor when making multilayer printed circuit board, is also able to suppress the solidfied material of the resin combination Carry out aperture processing, the stain in roughened treated through-hole.Here, " inhibiting stain, (stain is pressed down in the present invention System) " include any meaning below: it reduces the amount of the stain generated when aperture processing and is easier in roughening treatment Remove stain.

Alkylated melamine resins-

Alkylated melamine resins can obtain as follows: react melamine with formaldehyde, by a part of the hydrogen atom of amino or entirely Portion is replaced into after methylol, and then reacts it with alcoholic compound, part or all for making methylol is converted into alkoxy Methyl.

Alkylated melamine resins have by formula :-N (- CH₂-O-R¹)₂The functional group of expression, by formula :-N (- CH₂-O-R¹) CH₂OH indicate functional group, by formula :-N (- CH₂-O-R¹) H indicate functional group in 1 or more.Here, in above-mentioned functional group R¹For alkyl, suitable example is as be described hereinafter.For example, R¹When for methyl, referred to as methylated melamines resin；R¹When for butyl, referred to as Butylated melamine resins.

In one embodiment, alkylated melamine resins are the melamine trees containing the structural unit indicated by following formula (1) Rouge；

[in formula, X¹、X²、X³、X⁴、X⁵And X⁶Each independently represent hydrogen atom, by formula :-CH₂OH indicate group, by Formula :-CH₂-O-R¹The group of expression or by formula-CH₂The group that-* is indicated, here R¹It is chemical bond for alkyl, *.Wherein, X¹、 X²、X³、X⁴、X⁵And X⁶In at least 1 for by formula :-CH₂-O-R¹The group of expression.].

By formula :-CH₂-O-R¹In the group of expression, R¹For alkyl, the preferably alkyl of carbon atom number 1~20, more preferably The alkyl of carbon atom number 1~10, the alkyl of further preferably carbon atom number 1~6 are still more preferably carbon atom number 1~4 Alkyl, the alkyl of carbon atom number 1~2 or the alkyl of carbon atom number 1.The alkyl can be straight-chain, be also possible to branch Shape.As the suitable example of the alkyl, for example, can enumerate methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl group, Tert-butyl.

In formula (1), X¹、X²、X³、X⁴、X⁵And X⁶In at least 1 for by formula :-CH₂-O-R¹The group of expression.Suitable In embodiment, X¹、X²、X³、X⁴、X⁵And X⁶In, preferably 2 or more, more preferable 3 or more, further preferred 4 the above are by Formula :-CH₂-O-R¹The group of expression.There are multiple R in formula (1)¹When, their carbon atom number can it is mutually the same can also be with that This is different.

In a suitable embodiment, alkylated melamine resins contain to be made by the structural unit that following formula (1-1) is indicated For basic framework.Here " contain ... as basic framework " includes the following two kinds situation: alkylated melamine resins are containing under The situation of the melamine resin (monomer) for the structural unit that formula (1-1) indicates；And alkylated melamine resins be 2 or more by The structural unit that following formula (1-1) indicates carries out polycondensation and the situation of melamine resin (polycondensation polymer) that is formed, further includes the list The mixture of body and the polycondensation polymer.Hereinafter, being expressed as " containing ... as basic framework " for the structural unit of resin When be also same meaning；

[in formula, R ' indicates alkyl.].

In formula (1-1), the carbon atom number for the alkyl that R ' is indicated is preferably 1~20, is more preferably 1~10, is further preferred For 1~6, be still more preferably 1~4,1~2 or 1.As the suitable example of the R ' alkyl indicated, methyl, second can be enumerated Base, propyl, isopropyl, butyl, sec-butyl, isobutyl group, tert-butyl.The carbon atom number of multiple R ' can it is mutually the same can also be with that This is different.

In other one suitable embodiments, alkylated melamine resins contain the structure list indicated by following formula (1-2) Member is used as basic framework；

[in formula, R ' indicates meaning same as described above.].

In other one suitable embodiments, alkylated melamine resins contain the structure list indicated by following formula (1-3) Member is used as basic framework；

[in formula, R ' indicates meaning same as described above.].

In other one suitable embodiments, alkylated melamine resins contain the structure list indicated by following formula (1-4) Member is used as basic framework；

[in formula, R ' indicates meaning same as described above.].

It should be noted that alkylated melamine resins can be containing in the structural unit indicated by above-mentioned formula (1-1)~formula (1-4) 2 or more be used as basic framework.Therefore, in a suitable embodiment, alkylated melamine resins contain selected from by upper 1 or more structural unit in the structural unit that formula (1-1)~formula (1-4) indicates is stated as basic framework.

The weight average molecular weight of alkylated melamine resins is preferably 300 or more, is more preferably 350 or more, is more preferably 400 or more, it is still more preferably 450 or more, is particularly preferably 500 or more.The upper limit of the weight average molecular weight is preferably 10000 Below, be more preferably 5000 or less, further preferably 3000 or less, still more preferably be 2000 or less.It is alkylated melamine The weight average molecular weight of resin for example can be used gel permeation chromatography (GPC) method (polystyrene conversion) and be measured.

Commercially available product can be used in alkylated melamine resins.As the commercially available product of methylated melamines resin, such as can enumerate " the ニカラッ Network MW-390 " of (strain) three and ケミカ Le, " ニカラッ Network MW-100LM " and " ニカラッ Network MX- 750LM"；The " スーパーベッカミ Application ELM-754 of DIC (strain) system ", オ Le ネ Network スジャパ Application (strain) make " サイメ Le Series " etc..As the commercially available product of butylated melamine resins, such as the " スーパーベッカミ Application ELM- of DIC (strain) system can be enumerated 753".As the commercially available product of isobutyl melamine resin, such as the " スーパーベッカミ Application ELM- of DIC (strain) system can be enumerated 752”、“スーパーベッカミンE-2125”。

Alkoxyalkylation phenolic resin-

Alkoxyalkylation phenolic resin is comprising having by formula :-CH (R³)-O-R⁴Expression functional group (in formula, R³For Hydrogen atom, alkyl, phenyl or hydroxyphenyl；R⁴For alkyl) phenol (phenol) skeleton phenolic resin.Here, above-mentioned functional group In R³And R⁴Suitable example it is as be described hereinafter.For example, R³When for hydrogen atom, referred to as aikoxymethytated phenolic resin.

In one embodiment, alkoxyalkylation phenolic resin is containing the structural unit indicated by following formula (2) Phenolic resin；

[in formula,

Z²It indicates by formula :-R⁵- * indicate group or by formula :-R⁶(-*)₂The group of expression, wherein R⁵For alkylidene or list Key, R⁶For three base of alkane, * is chemical bond,

Z³Indicate alkyl optionally with substituent group,

L, m and n is satisfaction 2≤l+m+n≤5 and the integer of 1≤l].

In formula (2), Y indicates hydrogen atom or by formula :-R²The group that-* is indicated.Wherein, R²For alkylidene or singly-bound, being of * Learn key.R²The alkylidene of expression can be straight-chain, be also possible to branched.R²The carbon atom number of the alkylidene of expression is preferably 1 ~10, be more preferably 1~6, further preferably 1~4, still more preferably be 1 or 2.

In a suitable embodiment, Y is hydrogen atom.

In formula (2), Z¹It indicates by formula :-CH (R³)-O-R⁴The group of expression.Wherein R³For hydrogen atom, alkyl, phenyl or hydroxyl Phenyl, R⁴For alkyl.R³The alkyl of expression can be straight-chain, be also possible to branched.R³The carbon atom number of the alkyl of expression is excellent It is selected as 1~3, more preferably 1 or 2.As R³, preferably hydrogen atom or the alkyl of carbon atom number 1~3, more preferably hydrogen atom. R⁴The alkyl of expression can be straight-chain, be also possible to branched.R⁴The carbon atom number of the alkyl of expression is preferably 1~20, more excellent Be selected as 1~10, further preferably 1~6, be still more preferably 1~4,1~2 or 1.

In formula (2), Z²It indicates by formula :-R⁵- * indicate group or by formula :-R⁶(-*)₂The group of expression.Wherein R⁵For Asia Alkyl or singly-bound, R⁶For three base of alkane, * is chemical bond.R⁵The alkylidene of expression can be straight-chain, be also possible to branched.R⁵ The carbon atom number of the alkylidene of expression is preferably 1~10, more preferably 1~6, further preferably 1~4, still more preferably It is 1 or 2.R⁶Three base of alkane of expression can be straight-chain, be also possible to branched.R⁶The carbon atom number of three base of alkane of expression Preferably 1~10, be more preferably 1~6, further preferably 1~4, still more preferably be 1 or 2.

In formula (2), Z³Indicate alkyl optionally with substituent group.Z³In alkyl can be straight-chain, be also possible to branch Shape.Z³In alkyl carbon atom number be preferably 1~20, more preferably 1~10, further preferably 1~6, it is further excellent It is selected as 1~4.The carbon atom number does not include the carbon atom number of substituent group.

Z³In, as the substituent group that alkyl optionally has, there is no particular limitation, such as can enumerate naphthenic base, aryl, by The structural unit that formula (2) indicates.

The carbon atom number of naphthenic base as substituent group is preferably 3~20, more preferably 3~12, further preferably 3~ 6.As the naphthenic base, such as cyclopropyl, cyclobutyl, cyclopenta and cyclohexyl can be enumerated.

Aryl as substituent group is from the group after 1 hydrogen atom removed on aromatic rings in aromatic hydrocarbon.As taking The carbon atom number of the aryl of Dai Ji is preferably 6~24, more preferably 6~18, further preferably 6~14, still more preferably It is 6~10.As the aryl, such as phenyl, naphthalene and anthryl can be enumerated.

Z³In, alkyl can have multiple substituent groups.Under the situation, 2 adjacent substituent groups can be mutually bonded and be formed Ring.For example, Z³When being the methyl with 2 phenyl as substituent group, 2 phenyl can be mutually bonded and form 9H- fluorenes -9- base Group.

Above-mentioned substituent group can further have substituent group (hereinafter sometimes referred to " secondary substituent group ".).As secondary Group identical with above-mentioned substituent group can be used in the case where no especially record in substituent group.

In formula (2), l, m and n are satisfaction 2≤l+m+n≤5 and the integer of 1≤l.The upper limit of the value of l+m+n is preferably 4 or less.L is preferably 1,2 or 3, more preferably 1 or 2.M is preferably 0,1,2 or 3, more preferably 0,1 or 2.N be preferably 0,1 or 2, more preferably 0 or 1.

In a suitable embodiment, in formula (2),

A) l=1, m=1, n=0, Y are hydrogen atom, Z²For by formula :-R⁶(-*)₂The group of expression；Or

B) l=1, m=2, n=1, Y are hydrogen atom, Z²For by formula :-R⁵The group that-* is indicated；Or

C) l=2, m=0, n=1, Y are hydrogen atom；Or

D) l=1, m=2, n=0, Y are hydrogen atom, Z²For by formula :-R⁵The group that-* is indicated；Or

E) l=1, m=1, n=1, Y are hydrogen atom, Z²For by formula :-R⁵The group that-* is indicated；Or

F) l=2, m=1, n=0, Y are by formula :-R²The group that-* is indicated, Z²For by formula :-R⁵The group that-* is indicated.

Alkoxyalkylation phenolic resin can also contain other other than containing the structural unit indicated by formula (2) Structural unit.As other structural unit, there is no particular limitation, such as can enumerate the structure list indicated by formula (3) Member, the structural unit indicated by formula (4)；

[in formula, Y, Z²、Z³, n and m indicate meaning same as described above.]；

[in formula, Z²、Z³, n and m indicate meaning same as described above.].

When alkoxyalkylation phenolic resin also contains the structural unit other than the structural unit indicated by formula (2), by alkane When the gross mass of oxygroup alkylated phenolics is set as 100 mass %, the content of the structural unit indicated by formula (2) is preferably 10 Quality % or more, more preferably 20 mass % or more, further preferably 30 mass % or more, still more preferably for 40 mass % with Above, 50 mass % or more, 60 mass % or more, 70 mass % or more, 80 mass % or more or 90 mass % or more are particularly preferably.By The upper limit of the content for the structural unit that formula (2) indicates is not particularly limited, and can be 100 mass %.

Molecular weight when distribution (have be weight average molecular weight) of alkoxyalkylation phenolic resin is preferably 200 or more, more Preferably 250 or more.The upper limit of the molecular weight is preferably 20000 or less, is more preferably 10000 or less, is more preferably 5000 or less.The measurement of gel permeation chromatography (GPC) method such as can be used in the molecular weight of alkoxyalkylation phenolic resin.

Alkoxyalkylation phenolic resin can be manufactured using known any means.Alternatively, alkoxyalkylation Commercially available product can be used in phenolic resin.The commercially available product of alkoxyalkylation phenolic resin, for example, can from group's honor chemical industry (strain), The supplying party of the organic material of Honshu chemical industry (strain), the rising sun industrial (strain) etc obtains.

From the viewpoint of the reduction for preventing from solidifying physical property, the total amount of (A) ingredient He (B) ingredient is being set as 100 mass % When, the content of (C) ingredient in resin combination of the invention be preferably 30 mass % or less, more preferably 25 mass % or less, It further preferably 20 mass % or less, is still more preferably 15 mass % or less.In addition, from stain rejection ability is improved Viewpoint considers that, when the total amount of (A) ingredient He (B) ingredient is set as 100 mass %, the content of (C) ingredient is preferably 0.1 mass % Above, be more preferably 0.5 mass % or more, further preferably 1 mass % or more, still more preferably for 1.5 mass % or more, Particularly preferably 2 mass % or more, 2.5 mass % or more or 3 mass % or more.

< (D) inorganic filling material >

The purpose of stain removability when for the purpose for reducing coefficient of linear thermal expansion and improving roughening treatment, the present invention Resin combination can also contain (D) inorganic filling material.As inorganic filling material, such as silica, oxygen can be enumerated Change aluminium, glass, cordierite, Si oxide, barium sulfate, talcum, clay, mica powder, aluminium hydroxide, magnesium hydroxide, calcium carbonate, carbon Sour magnesium, magnesia, boron nitride, aluminium nitride, nitrogenized manganese, aluminium borate, barium titanate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, oxygen Change titanium, barium zirconate, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array.Wherein preferred silica.As silica, preferably without fixed Shape silica crushes silica, fused silica, crystalline silica, synthetic silica, hollow silica Deng more preferable fused silica.In addition, as silica, preferably spherical silica (preparing spherical SiO 2).They It can be used alone with a kind or two or more is applied in combination.As commercially available spherical fused silica, (strain) ア can be enumerated De マテッ Network ス system " SO-C2 ", " SO-C1 ".

There is no particular limitation for the average grain diameter of inorganic filling material, from the sight for carrying out fine wiring formation on the insulating layer Point, by make inorganic filling material total surface area increase come when aperture being inhibited to process stain generate from the viewpoint of, it is inorganic The average grain diameter of packing material is preferably 5 μm or less, more preferably 3 μm or less, is more preferably 1 μm or less, further Preferably 0.7 μm or less, especially be more preferably 0.5 μm or less, particularly preferably 0.4 μm or less, especially preferably 0.3 μm with Under.On the other hand, when resin combination is formed as varnish, from the viewpoint for preventing the viscosity of varnish from rising, operability reduces Consider, the lower limit value of the average grain diameter of inorganic filling material is preferably 0.01 μm or more, is more preferably 0.03 μm or more, is further Preferably 0.05 μm or more, especially more preferably 0.07 μm or more, particularly preferably 0.1 μm or more.Above-mentioned inorganic filling material Average grain diameter can be by being measured based on the laser diffraction-scattering method of Michaelis (Mie) scattering theory.Specifically, using sharp Optical diffraction scatters formula particle size distribution device, and the size distribution of inorganic filling material is made with volume reference, its intermediate value is straight Diameter is set as average grain diameter, it is possible thereby to measure.Sample can it is preferable to use disperse inorganic filling material using ultrasonic wave for measurement Sample obtained by water.As laser diffraction and scattering formula particle size distribution device, it is made that the production of (strain) hole field can be used LA-500,750,950 etc..

The content of inorganic filling material is not particularly limited, from preventing from being formed as resin combination into sheet laminated material Form when it is flexible reduce from the viewpoint of, it is inorganic to fill out when the non-volatile component in resin combination is set as 100 mass % The content for filling material is preferably 85 mass % or less, more preferably 80 mass % or less, further preferably 75 mass % or less.This Outside, inhibit aperture from the viewpoint for the thermal expansion coefficient for reducing insulating layer, by increasing the total surface area of inorganic filling material It, will be non-volatile in resin combination from the viewpoint of stain when processing generates, is easy to remove stain in roughening treatment When at being divided into 100 mass %, the content of inorganic filling material be preferably 50 mass % or more, more preferably 55 mass % or more, into One step is preferably 60 mass % or more, is still more preferably 65 mass % or more.

From the viewpoint of improving moisture-proof, dispersibility, inorganic filling material preferably uses amino silicone methane series coupling agent, urea groups (ウレイ De) silane series coupling agent, epoxy radicals silicone hydride system coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, ethylene Base silane system coupling agent, styryl silane series coupling agent, acrylate silane system coupling agent, the coupling of isocynate silane system The surface treating agents such as agent, sulfidesilane system coupling agent, organic silazane hydride compounds, titanate esters system coupling agent carry out at surface Reason.Wherein, table is carried out after inorganic filling material being surface-treated with organic silazane hydride compounds and then with silane coupling agent Surface treatment, it is possible thereby to further increase the moisture-proof of inorganic filling material, dispersibility.They can be with a kind of exclusive use or 2 kinds Combination of the above uses.

It as surface treating agent, such as can enumerate: 3- TSL 8330,3- aminopropyl triethoxysilicane Alkane, 3- aminopropyl diethoxymethylsilane, N- phenyl -3- TSL 8330, N- dimethylaminopropyl three Methoxy silane, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- aminopropyl two The ureido silanes system coupling agents such as the amino silicone methane series coupling agent of methoxy methyl base silane etc., 3- ureidopropyltriethoxysilane； 3- glycidoxypropyltrimewasxysilane, 3- glycidoxypropyl triethoxysilane, 3- glycidoxypropyl Hydroxypropyl methyl diethoxy silane, 3- glycidoxypropyl (dimethoxy) methyl-monosilane, glycidyl butyl front three The epoxy silanes system coupling agents such as oxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane；3- mercaptopropyi front three Oxysilane, 3- Mercaptopropyltriethoxysilane, 3- mercapto propyl methyl dimethoxy silane, 11- mercapto-undecanoic base three The hydrosulphonyl silanes such as methoxy silane system coupling agent；Methyltrimethoxysilane, octadecyl trimethoxysilane, phenyl trimethoxy Base silane, methacryloxy (メタ Network ロキシ) propyl trimethoxy silicane, imidizole silane, triazine silane, tert-butyl The silane series coupling agents such as trimethoxy silane；Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl methyl two The vinyl silanes such as Ethoxysilane system coupling agent；To the styryls silane series coupling agent such as styryltrimethoxysilane； 3- acryloyloxypropyltrimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl Base propyldimethoxy-silane, 3- methacryloxypropyl, 3- methacryloxypropyl diethyl The acrylate silanes such as oxysilane system coupling agent；The coupling of the isocynate silanes such as 3- isocyanate propyl trimethoxysilane system Agent；Bis- (triethoxysilylpropyltetrasulfide) disulphide, bis- (triethoxysilylpropyltetrasulfide) tetrasulfide sulfides Silane series coupling agent；Hexamethyldisilazane, 1,3- divinyl -1,1,3,3- tetramethyl-disilazane, two silicon nitrogen of hexaphenyl Alkane, three silazane, cyclotrisilazane, 2,2,4,4,6,6- hexamethyl cyclotrisilazane, octamethylcyclotetrasilazane, six butyl two Silazane, six octyl disilazanes, 1,3- diethyltetramethyldisilazane, 1,3- di-n-octyl tetramethyl-disilazane, 1, 3- diphenyltetramethyldisilazane, 1,3- dimethyl tetraphenyl disilazane, 1,3- diethyltetramethyldisilazane, 1,1, 3,3- tetraphenyl -1,3- dimethyl disilazane, 1,3- dipropyl tetramethyl-disilazane, hexamethyl cyclotrisilazane, diformazan It is the organic silazane hydride compounds of base amino trimethyl silicane azane, tetramethyl-disilazane etc., tetra-n-butyl titanate esters dimer, different Propoxyl group ethohexadiol acid titanium, tetra-n-butyl titanate, ethohexadiol titanium, bis- (triethanolamine) diisopropoxy titaniums, dilactic acid dihydroxy Bis- (ammonium lactate) titaniums of titanium, dihydroxy, bis- (dioctyl pyrophosphate) ethylene titanates, bis- (dioctyl pyrophosphate) glycolic acid metatitanic acids Ester, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, metatitanic acid four (2- ethylhexyl) ester, bis- (dioctyl phosphites) Tetraisopropyl titanate, bis- four monooctyl esters of (phosphorous acid two (tridecyl) ester) metatitanic acid, bis- (phosphorous acid two (tridecyl) ester) metatitanic acids It is four (2,2- diene propoxy methyl -1- butyl) esters, three caprylyl isopropyl titanates, isopropyl tricumylphenyltitanate, three different hard Fatty acyl group isopropyl titanate, two acryloyl isopropyl titanate of isostearoyl base, Dimethylacryloyl isostearoyl metatitanic acid isopropyl Ester, isopropyl tri(dioctyl phosphate)titanate, three (dodecyl benzenesulfonyl) isopropyl titanates, three (dioctyl pyrophosphate) titaniums Titanate esters system coupling agents such as isopropyl propionate, three (N- amide ethyl-aminoethyl) isopropyl titanates etc..Wherein, amino silicone methane series are even Join agent since moisture-proof, dispersibility, the characteristic of solidfied material etc. are excellent and preferred；Organic silazane hydride compounds are due in resin varnish Dispersibility improve aspect it is excellent and preferred.As the commercially available product of surface treating agent, SHIN-ETSU HANTOTAI's chemical industry (strain) system can be enumerated " KBM403 " (3- glycidoxypropyltrimewasxysilane), SHIN-ETSU HANTOTAI's chemical industry (strain) make " KBM803 " (3- sulfydryl third Base trimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry (strain) make " KBE903 " (3-aminopropyltriethoxysilane), SHIN-ETSU HANTOTAI's chemistry work Industry (strain) makes " KBM573 " (N- phenyl -3- TSL 8330) etc..

With the degree for the surface treatment that surface treating agent carries out, the per unit surface area of inorganic filling material can be passed through Carbon amounts is evaluated.From the r.m.s. roughness for making the dispersibility of inorganic filling material improve, make solidfied material after roughening treatment From the viewpoint of stabilization, the carbon amounts of the per unit surface area of inorganic filling material is preferably 0.02mg/m²Above, more preferably 0.1mg/m²It above, is more preferably 0.2mg/m²More than.On the other hand, from preventing the melt viscosity of resin varnish, sheet folded From the viewpoint of melt viscosity under the form of layer material rises, the carbon amounts of the per unit surface area of inorganic filling material is preferably 1mg/m²Below, it is more preferably 0.8mg/m²It below, is more preferably 0.5mg/m²Below.

The carbon amounts of the per unit surface area of inorganic filling material can be by the inorganic filling material solvent after surface treatment (for example, methyl ethyl ketone (MEK)) is measured after carrying out carrying out washing treatment.Specifically, the MEK of sufficient amount is added as solvent Into the inorganic filling material being surface-treated with surface treating agent, in 25 DEG C of progress, 5 minutes ultrasonic washings.In removing Clear liquid can measure the carbon amounts of the per unit surface area of inorganic filling material using carbon analysis meter after keeping solid component dry.Make For carbon analysis meter, hole field can be used and make made " EMIA-320V " etc..

< (E) curing accelerator >

It is solid that the purpose of resin combination of the invention is in order to adjust curing time and solidification temperature can further contain (E) Change promotor.As curing accelerator, there is no particular limitation, can enumerate imidazoles system curing accelerator, amine system curing accelerator, Organic phosphine compound, organophosphonium salt compound etc..They may be used singly or in combination of two or more.

It as imidazoles system curing accelerator, can enumerate: 2-methylimidazole, 2- undecyl imidazole, 2- heptadecyl miaow Azoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl miaow Azoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2- methyl miaow Azoles, 1- cyano ethyl -2- undecyl imidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenyl miaow Azoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acid salt, 1- cyano ethyl -2- phenylimidazole trimellitic acid salt, 2, 4- diamino -6- [2'- methylimidazolyl-is (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- undecyl imidazole base - (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- ethyl -4'- methylimidazolyl-is (1')]-ethyl-s-triazine, 2,4- Diamino -6- [2'- methylimidazolyl-is (1')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid add At object, 2- phenyl -4,5- bishydroxymethyl imidazoles, -5 hydroxymethylimidazole of 2- phenyl -4- methyl, 2,3- dihydro -1H- pyrrolo- [1,2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazole chloride, 2-methylimidazole quinoline, 2- phenylimidazole The adduct of the imidazolium compounds such as quinoline and imidazolium compounds and epoxy resin.They can be with a kind of exclusive use or two or more group It closes and uses.

It as amine system curing accelerator, can enumerate: the trialkylamines such as triethylamine, tri-butylamine, 4- dimethylamino pyrrole Pyridine, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) phenol, 1,8- diazabicyclo [5.4.0]-endecatylene Amine compounds such as (hereinafter referred to as DBU) etc..They may be used singly or in combination of two or more.

As organic phosphine compound, organophosphonium salt compound, can enumerate: TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, TPTP-SCN (emerging chemical industry (strain) trade name in north) etc..They can be used alone with a kind or two or more combination makes With.

It, will be non-volatile in resin combination from the viewpoint of from the storage stability, cured efficient activity of resin varnish When at being divided into 100 mass %, the content of curing accelerator is preferably 0.01 mass of mass %~3 %, more preferably 0.05 mass % ~2 mass %.

< (F) thermoplastic resin >

Resin combination of the invention can further contain (F) thermoplastic resin.By containing thermoplastic resin, thus Scratching for solidfied material can be improved by the viscosity-adjusting agent of the resin varnish obtained by the resin combination to suitable range Property.As thermoplastic resin, there is no particular limitation, can enumerate: phenoxy resin, polyvinyl acetal resin, polyimides tree Rouge, polyamide-imide resin, polyamide, polyethersulfone resin, polysulfone resin etc., polyolefin resin, gather polyphenylene oxide resin Butadiene resin, ABS resin etc..Wherein, from improve solidfied material flexibility, help to examine with the viewpoint of the adaptation of conductor layer Consider, preferably phenoxy resin, polyvinyl acetal resin, more preferable phenoxy resin.They can with a kind be used alone or two or more It is applied in combination.The glass transition temperature of thermoplastic resin is preferably 80 DEG C or more.

The weight average molecular weight of thermoplastic resin be preferably 5000~800000 range, more preferably 10000~200000 Range, further preferably 15000~150000 range, still more preferably be 20000~100000 range.Pass through The weight average molecular weight for making thermoplastic resin within the above range, mentions so as to give full play to film shaped ability and mechanical strength The compatibility with epoxy resin can be improved in high effect.It should be noted that the weight average molecular weight in the present invention can be seeped with gel Saturating chromatography (GPC) method (polystyrene conversion) is measured.The weight average molecular weight measured using GPC method, can specifically be calculated as follows, (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A is used as measurement device, uses Showa electrician (strain) society system as column Shodex K-800P/K-804L/K-804L uses chloroform etc. as mobile phase, is measured at 40 DEG C of column temperature, using mark The standard curve of quasi- polystyrene calculates.

It as phenoxy resin, can enumerate: have selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol acetophenone Skeleton, linear phenol-aldehyde resin skeleton, biphenyl backbone, fluorene skeleton, dicyclopentadiene skeleton, enb skeleton, naphthalene skeleton, anthracene The phenoxy resin of the skeleton of one or more of skeleton, adamantane framework, terpenes skeleton, trimethyl-cyclohexane skeleton.Phenoxy resin Two or more can be used in mixed way.The end of phenoxy resin can be the arbitrary functional group such as phenolic hydroxyl group, epoxy group.As Commercially available product, such as Mitsubishi Chemical (strain) system 1256,4250 (phenoxy resins containing bisphenol A skeleton), Mitsubishi Chemical can be enumerated (strain) YX8100 processed (phenoxy resin containing bisphenol S skeleton), Mitsubishi Chemical (strain) YX6954 processed (contain bis-phenol acetyl benzene skeleton Phenoxy resin).As commercially available product, Nippon Steel can be enumerated and live in aurification (strain) FX280, FX293 processed, Mitsubishi Chemical's (strain) system YL7553, YL6954, YL6794, YL7213, YL7290, YL7482 etc..

As the concrete example of polyvinyl acetal resin, electrochemically industrial (strain) system, electrochemical Block チラー Le can be enumerated 4000-2,5000-A, 6000-C, 6000-EP, ponding chemical industry (strain) エスレッ Network BH processed are serial, BX is serial, KS is serial, BL series, BM series etc..As the concrete example of polyimide resin, polyimides " the リカ of new Japan Chemical (strain) system can be enumerated コート SN20 " and " リカコート PN20 ".Furthermore, it is possible to which enumerating makes 2 functional hydroxyl groups end polybutadiene, diisocyanate Threadiness polyimides obtained by compound and quaternary anhydride reaction (substance that Japanese Unexamined Patent Publication 2006-37083 bulletin is recorded) contains Polyimides (Japanese Unexamined Patent Publication 2002-12667 bulletin, Japanese Unexamined Patent Publication 2000-319386 bulletin etc. of polysiloxane skeleton The substance of middle record) etc. modified polyimides.As the concrete example of polyamide-imide resin, Japan's weaving (strain) system can be enumerated Polyamidoimide " バイロマッ Network ス HR11NN " and " バイロマッ Network ス HR16NN ".In addition, Hitachi can be enumerated It is sub- at the modified polyamides such as the polyamidoimide " KS9100 " containing silicone matrix of industrial (strain) system, " KS9300 " acyl Amine.As the concrete example of polyethersulfone resin, the polyether sulfone " PES5003P " etc. of Sumitomo Chemical (strain) system can be enumerated.As polysulfones tree The concrete example of rouge can enumerate polysulfones " P1700 ", " P3500 " of ソ Le ベ Application ア De バ Application スト Port リマーズ (strain) system etc..

There is no particular limitation for the content of thermoplastic resin, melt viscosity, resin varnish viscosity from sheet laminated material Adjusting from the viewpoint of, when the non-volatile component in resin combination is set as 100 mass %, the content of thermoplastic resin is excellent It is selected as 0.5 mass of mass %~30 %, more preferably 1 mass of mass %~20 %.

< (G) curing agent >

Resin combination of the invention can further contain (G) curing agent (wherein except (B) ingredient.).By containing Curing agent, so as to improve the insulating reliability of solidfied material, the peel strength, mechanical property of resin combination.As solidification Agent, there is no particular limitation, such as can enumerate phenol system curing agent, cyanate system curing agent, benzoxazine system curing agent, acid anhydrides system Curing agent etc..They may be used singly or in combination of two or more.Wherein, from raising stain removability, raising dielectric From the viewpoint of performance, preferably phenol system curing agent, cyanate system curing agent.

It as phenol system curing agent, is not particularly limited, linear phenol-aldehyde resin, the line style phenol containing triazine skeleton can be enumerated Urea formaldehyde, naphthol novolac resin, naphthols aralkyl-type resin, the naphthol resin containing triazine skeleton, biphenyl aralkyl type phenol Resin etc..For example, " MEH-7700 ", " MEH-7810 ", " MEH-7851 " can be enumerated as biphenyl aralkyl-type phenol resin (bright and chemical conversion (strain) system), " NHN ", " CBN ", " GPH " (Japanese chemical drug (strain) system)；As naphthols aralkyl-type resin, can arrange Lift " SN170 ", " SN180 ", " SN190 ", " SN475 ", " SN485 ", " SN495 ", " SN375 ", " SN395 " (Dongdu chemical conversion (strain) system)；As linear phenol-aldehyde resin, " TD2090 " (DIC (strain) system) can be enumerated；As the line style phenolic aldehyde containing triazine skeleton Resin can enumerate " LA3018 ", " LA7052 ", " LA7054 ", " LA1356 " (DIC (strain) system) etc..Phenol system curing agent can be with a kind It is used alone or two or more is applied in combination.

It as cyanate system curing agent, is not particularly limited, phenolic resin type (ノボラッ Network type) (line style can be enumerated Phenolic resin type, alkyl novalac-type etc.) cyanate system curing agent, dicyclopentadiene type cyanate system curing agent, Bisphenol type (bisphenol A-type, bisphenol-f type, bisphenol S type etc.) cyanate system curing agent and they with a portion of triazine Prepolymer etc..The weight average molecular weight of cyanate system curing agent, there is no particular limitation, preferably 500~4500, more preferably 600~3000.As the concrete example of cyanate system curing agent, such as bisphenol A dicyanate, polyphenol cyanate (widow (3- can be enumerated Methylene -1,5- phenylenecyanate)), 4,4' methylene bis (2,6- 3,5-dimethylphenyl cyanate), 4,4'- ethylidene hexichol Bis- (4- cyanate) phenyl-propanes of base dicyanate, hexafluoro bisphenol-a dicyanate, 2,2-, bis- (the 4- cyanate phenyl first of 1,1- Alkane), it is bis- (4- cyanate -3,5- 3,5-dimethylphenyl) methane, bis- (4- cyanate phenyl -1- (methyl the ethylidene)) benzene of 1,3-, double The 2 function cyanate ester resins such as (4- cyanate phenyl) thioether, bis- (4- cyanate phenyl) ethers, by linear phenol-aldehyde resin, cresols first Multifunctional cyanate ester tree derived from urea formaldehyde (cresol novolac), phenolic resin containing dicyclopentadiene structure etc. Rouge, the prepolymer etc. that with a portion of triazine of these cyanate ester resins.They can with a kind be used alone or two or more It is applied in combination.As commercially available cyanate ester resin, novalac-type multifunctional cyanate ester resin (ロ Application ザジャ can be enumerated パ Application (strain) system, PT30, cyanate equivalent 124), bisphenol A dicyanate part or all carry out triazine and become three The prepolymer (ロ Application ザジャパ Application (strain) system, BA230, cyanate equivalent 232) of aggressiveness contains dicyclopentadiene structure Cyanate ester resin (ロ Application ザジャパ Application (strain) system, DT-4000, DT-7000) etc..

It as benzoxazine system curing agent, is not particularly limited, can specifically enumerating F-a, P-d, (four countries are melted into (strain) System), HFB2006M (Showa macromolecule (strain) system) etc..

There is no particular limitation for the content of curing agent, will from the viewpoint of preventing the solidfied material of resin combination from becoming fragile When non-volatile component in resin combination is set as 100 mass %, the content of curing agent is preferably 0.5 mass of mass %~10 %, more Preferably 1 mass of mass %~6 %.

The other ingredient > of <

Within the scope of the effect of the invention, resin combination of the invention can also contain other ingredients.Make For other ingredients, for example, maleimide compound can be enumerated, diallyl receives enlightening acid imide (ビスアリ Le Na ジイミ De) heat curable components such as compound, vinyl benzyl resin, vinylbenzyl ether resins；Si powder, nylon powder, fluorine powder Equal organic fillers；The thickeners such as オ Le ベ Application, ベ Application ト Application；Organic silicon-type, fluorine system, macromolecular defoaming agent or levelling agent； The adaptations imparting agents such as imidazoles system, thiazole system, triazole system, silane coupling agent；The fire retardants such as phosphorus series compound, metal hydroxides Deng.

Resin combination of the invention can be by properly mixing mentioned component, and uses mixing facilities (example as needed Such as, three rollers, ball mill, ball mill, sand mill etc.) or mixing plant (for example, super mixer, planetary stirring machine etc.) progress It is kneaded or mixes, to be manufactured as resin varnish.The available dielectric loss tangent of resin combination of the invention is low to be consolidated Compound, and aperture processing is carried out to the solidfied material, the stain in through-hole after roughened processing can be inhibited.

The dielectric loss tangent of the solidfied material of resin combination of the invention can pass through the aftermentioned [survey of dielectric loss tangent It is fixed] in the method recorded measure.Specifically, resonant cavity perturbation method (empty resonator feeding moves method) can be used in frequency 5.8GH Z, it is measured under conditions of 23 DEG C of measuring temperature.From the sight of the fever, reduction signal delay and signal noise that prevent under high frequency Point considers, dielectric loss tangent is preferably 0.05 or less, more preferably 0.04 or less, further preferably 0.03 or less, more into One step is preferably 0.02 or less, is especially more preferably 0.01 or less.On the other hand, the lower limit value of dielectric loss tangent is not special Limitation, preferably 0.001 or more.

The arithmetic average roughness Ra of the solidfied material of resin combination of the invention can pass through aftermentioned [arithmetic mean roughness Spend (Ra) and r.m.s. roughness (Rq) measurement] in record method be measured.For the insulating layer after roughening treatment Surface, from the viewpoint of reducing electric signal loss, it is expected that concave-convex surface is smaller.Specifically, by resin combination solidification and Insulating layer is formed, the arithmetic average roughness Ra of the surface of insulating layer after roughening treatment has been carried out to the surface of insulating layer Preferably 400nm or less, more preferably 350nm or less, further preferably 300nm or less, still more preferably for 250nm with Under, especially be more preferably 200nm or less.In addition, arithmetic average is thick from the viewpoint of obtaining the good adaptation with conductor layer The lower limit value of rugosity Ra is preferably 5nm or more, more preferably 10nm or more, further preferably 15nm or more.

The r.m.s. roughness Rq of the solidfied material of resin combination of the invention can pass through aftermentioned [arithmetic mean roughness Spend (Ra) and r.m.s. roughness (Rq) measurement] in record method be measured.For the insulating layer after roughening treatment Surface, from the viewpoint of reducing electric signal loss, it is expected that concave-convex surface is fine.Bumps as performance surface of insulating layer Compactness index, have r.m.s. roughness Rq.It is not that the simple of the bumps of understanding surface of insulating layer is put down using the index Mean value, but know whether surface of insulating layer forms fine and close concaveconvex shape.Specifically, the shape by resin combination solidification At insulating layer, the r.m.s. roughness Rq that the surface of insulating layer after roughening treatment has been carried out to the surface of insulating layer is preferred For 500nm or less, more preferably 400nm or less, further preferably 300nm or less, be still more preferably 250nm or less, Especially it is more preferably 200nm or less.In addition, from the viewpoint of obtaining the good adaptation with conductor layer, r.m.s. roughness The lower limit value of Rq is preferably 7nm or more, more preferably 15nm or more, further preferably 20nm or more.

The coefficient of linear thermal expansion of the solidfied material of resin combination of the invention can pass through the aftermentioned [survey of coefficient of linear thermal expansion The method recorded in calmly] is measured.Specifically, tensile load method, which can be used, carries out thermo-mechanical analysis, 25 DEG C are thus measured The coefficient of mean linear thermal expansion of in-plane at~150 DEG C.It is low that resin combination of the invention can get coefficient of linear thermal expansion Solidfied material, can effectively inhibit crackle caused by the difference of the thermal expansion coefficient due to insulating layer and conductor layer, circuit become Shape.The solidfied material of resin combination of the invention can preferably show 25ppm coefficient of linear thermal expansion below.Coefficient of linear thermal expansion Lower limit be not particularly limited, usually 1ppm or more.

The peel strength of the solidfied material of resin combination of the invention can pass through the aftermentioned [pull-off strength of plated conductor layer The measurement of (peel strength)] in record method be measured.Specifically, resin combination is solidified to form insulating layer, When carrying out plating to roughened treated the surface of insulating layer and form conductor layer, the stripping of resulting conductor layer and insulating layer It is preferably 0.4kgf/cm or more, more preferably 0.45kgf/cm or more, further preferably 0.5kgf/cm or more from intensity.Separately On the one hand, upper limit value is not particularly limited, usually 1.2kgf/cm or less.

There is no particular limitation for the purposes of resin combination of the invention, can be used for the following resin combination that needs Extensive scope of use: the sheets such as adhering film, prepreg laminated material, circuit substrate (laminated plate purposes, multilayered printed circuit Plate purposes etc.), solder resist, bottom filling material (アンダー Off ィ Le material), chip weld material, encapsulating semiconductor material, filling perforation tree Rouge (burying め resin in cave), component potting resin (component Mai め Write body resin) etc..In resin combination of the invention, it can press down Solidfied material is carried out aperture processing, the stain in roughened treated through-hole by system.Whereby, the plating in through-hole can be improved Closing force prevents the hole (void) in through-hole from occurring, it is hereby ensured that the multistage formed multilayer printed circuit board it is exhausted Conducting reliability between edge layer.Therefore, resin combination of the invention is preferably used as in the manufacture of multilayer printed circuit board, It is used to form the resin combination (resin compositions for insulating layer of multilayer printed circuit board) of insulating layer, it may be more preferable to effect In the resin combination (the stack layer resin combination of multilayer printed circuit board) for forming stack layer, can further preferably be used as Resin combination for forming conductor layer using plating (forms the insulating layer of the multilayer printed circuit board of conductor layer using plating With resin combination).From the viewpoint of the plyability of aftermentioned sheet laminated material, the softening point of resin combination is preferably 40~150 DEG C.

< sheet laminated material >

Resin combination of the invention can be with varnish state be coated on circuit substrate and forms insulating layer, but in industry On generally preferably in the form of the sheets laminated material such as adhering film, prepreg use.That is, sheet laminated material of the invention contains There is resin combination of the invention.

(adhering film)

In one embodiment, sheet laminated material of the invention is adhering film.The adhering film contains: support Body and the resin composition layer formed on the supporter.The adhering film can manufacture as follows: public using those skilled in the art The method known, such as the resin varnish for having dissolved resin combination of the invention in organic solvent is prepared, it is applied using metal mold Resin varnish is coated on supporter by material machine (ダイコーター) etc., and then makes organic solvent using heating or blowing hot-air etc. It dries and forms resin composition layer.

As organic solvent, such as the ketones such as acetone, methyl ethyl ketone, cyclohexanone can be enumerated；Ethyl acetate, acetic acid fourth The acetate esters such as ester, cellosolve acetate, propylene glycol monomethyl ether, carbitol acetate；Cellosolve, butyl carbitol Equal carbitols class；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；Dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone etc. Acid amides series solvent etc..Organic solvent may be used singly or in combination of two or more.

There is no particular limitation for drying condition, is preferably dried, so that the organic solvent in resin composition layer contains Amount reaches 10 mass % or less, preferably reaches 5 mass % or less.Drying condition is according to the organic solvent amount in varnish, organic solvent Boiling point and it is different, such as can by will the varnish containing the organic solvent of 30 mass of mass %~60 % at 50 DEG C~150 DEG C Lower drying 3 minutes~10 minutes or so forms resin composition layer.

The thickness of resin composition layer is preferably the thickness of conductor layer or more.The thickness of conductor layer possessed by circuit substrate Usually 5 μm~70 μm of range, therefore the thickness of resin composition layer is preferably 10 μm~100 μm of range.From the thin of layer From the viewpoint of type, the thickness of resin composition layer is more preferably 15 μm~80 μm of range.

As supporter, such as the film of the polyolefin such as polyethylene, polypropylene, polyvinyl chloride, poly terephthalic acid can be enumerated Film, polycarbonate membrane, the polyimide film of the polyester such as second diester (hereinafter sometimes referred to simply as " PET "), polyethylene naphthalate Etc. various plastic foils.Additionally as supporter, metal foils such as processing release paper or copper foil, aluminium foil etc. also can be used.Wherein, from general From the viewpoint of property, supporter is preferably plastic foil, more preferably polyethylene terephthalate film.Can also to supporter and Aftermentioned protective film implements the surface treatment such as delustring processing, sided corona treatment.In addition it is also possible to organic siliconresin system release agent, The release agents such as alkyd resin system release agent, fluororesin system release agent implement demoulding processing to supporter and aftermentioned protective film.

There is no particular limitation for the thickness of supporter, when from by carrying out aperture processing on supporter, even if in laser irradiation The biggish situation of energy under from the viewpoint of gum residue is also difficult to remain, can inhibit the generation of stain, the thickness of supporter Preferably 10 μm or more, more preferably 20 μm or more, further preferably 30 μm or more.In addition, from improve the ratio of performance to price, From the viewpoint of can be effectively carried out aperture when by carrying out aperture on supporter, the thickness of supporter is preferably 150 μm or less, more Preferably 100 μm or less, further preferably 50 μm or less.

On the face that resin composition layer is not contacted with supporter (that is, face of the opposite side in the face contacted with supporter), It can the further protective film that is consistent with supporter of lamination.At this point, adhering film includes: supporter is formed on the supporter Resin composition layer and the protective film that is formed on the resin composition layer.The thickness of protective film is not particularly limited, such as It can be 1 μm~40 μm.By lamination protective film, the attachment of dust on the surface of resin composition layer etc. can be prevented or drawn Wound.Adhering film can be rolled into a roll to store.

(prepreg)

In one embodiment, sheet laminated material of the invention is prepreg.The prepreg can be by using hot melt Or solvent method is impregnated with resin combination of the invention in flake reinforcement substrate, heating is allowed to semi-solid preparation to manufacture.That is, preimpregnation Resin combination of the invention can be impregnated in flake reinforcement substrate by material to be formed.As flake reinforcement substrate, can make It is used as the common substance of the prepregs substrate such as glass cloth, aramid nonwoven fabric, liquid crystal polymer non-woven fabrics.Prepreg It is preferred that the use of the state of the prepreg to be arranged on supporter.

Hot melt is following method: resin combination not being dissolved in organic solvent, but is temporarily coated on supporter On, it is laminated to flake reinforcement substrate or is directly coated on flake reinforcement substrate etc. with chill coating machine, from And prepreg is made.Solvent method is following method: it is same as adhering film, resin is dissolved in organic solvent to prepare resin Flake reinforcement substrate is impregnated in the varnish by varnish, is impregnated with resin varnish into flake reinforcement substrate, then makes it dry It is dry.In addition, prepreg can also by heating, under pressurized conditions by adhering film continuously on the two sides of flake reinforcement substrate It is prepared by heat lamination.For supporter, protective film, object same as substance described in adhering film is directed to also can be used Matter.

< uses the multilayer printed circuit board > of sheet laminated material

Then, illustrate one that manufactures the method for multilayer printed circuit board using sheet laminated material of the invention to show Example.

Firstly, using vacuum laminator by sheet laminated material lamination (lamination) in the one or both sides of circuit substrate.In detail For thin, sheet laminated material is laminated to the one or both sides of circuit substrate, so that resin composition layer or prepreg and electricity Base board engagement.As the substrate used in circuit substrate, such as glass epoxy substrate, metal substrate, polyester base can be enumerated Plate, polyimide substrate, BT resin substrate, heat curing type polyphenylene oxide substrate etc..It should be noted that circuit substrate refers to such as above-mentioned The one or both sides of substrate are formed with the substance for having carried out the conductor layer (circuit) of pattern processing.In addition by conductor layer and insulation Layer alternative stacked is come when manufacturing multilayer printed circuit board, outermost one or both sides have the conductor layer for having carried out pattern processing The multilayer printed circuit board of (circuit) is also contained in circuit substrate.It should be noted that melanism can be implemented in advance in conductor layer surface The roughening treatments such as processing, copper etching.

When sheet laminated material has protective film, after which is removed, as needed by sheet laminated material and electricity Base board preheating, is laminated to circuit substrate while pressurizeing and heating for sheet laminated material.In a suitable embodiment party In formula, under reduced pressure using vacuum layer platen press, sheet laminated material of the invention is laminated to circuit substrate.The condition of lamination does not have There is special limitation, such as be preferably, crimping temperature (laminating temperature) is preferably 70 DEG C~140 DEG C, crimping pressure (lamination pressure Power) it is preferably 1kgf/cm²~11kgf/cm²(0.098MPa~1.078MPa), crimping time (lamination times) is preferably 5 seconds~ It 180 seconds, is laminated in the case where air presses 20mmHg (26.7hPa) decompression below.In addition, the method for lamination can be in batches Formula is also possible to use the continous way of roller.Vacuum lamination can be used commercially available vacuum laminator and carry out.As commercially available true Dead level press can enumerate such as ニチゴーモート Application (strain) vacuum pack system device processed, ニチゴーモート Application (strain) system Stack laminating machine, (strain) name mechanism makees made vacuum pressure type laminating machine, (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..

After lamination, preferably by under normal pressure (under atmospheric pressure), such as hot pressing is carried out to sheet laminated material, from And carry out the smoothing techniques of laminated sheet laminated material.The condition of smoothing techniques can be the heating with above-mentioned lamination The identical condition of crimping condition.Smoothing techniques can be carried out using commercially available laminating machine.It should be noted that lamination treatment is peaceful Cunningization processing can be used above-mentioned commercially available vacuum laminator and continuously carry out.

After sheet laminated material is laminated to circuit substrate, be cooled to room temperature near, when then supporter being removed, into Row removing, and resin combination heat cure is formed into insulating layer.It is possible thereby to form insulating layer on circuit substrate.Heat cure Condition can suitably be selected according to type, content of the resin component in resin combination etc., preferably at 150 DEG C~220 DEG C Lower 20 minutes~180 minutes, more preferably selected in the range of 30 minutes~120 minutes at 160 DEG C~210 DEG C.Here, thermosetting Change temperature to be not necessarily intended to be fixed on temperature fixed in above-mentioned temperature range, as long as can finally form suitable insulating layer, so that it may Timely to change, multiple stages can be divided under different solidification temperatures to be solidified.After foring insulating layer, Before solidification in the case where no removing supporter, it can according to need and remove at this moment.

In addition it is possible to use sheet laminated material is stacked on the one or both sides of circuit substrate by vacuum pressed machine.Subtracting Depressing the lamination procedure being heated and pressurizeed can also be used common vacuum hotpressing machine to carry out.Such as lamination procedure can pass through It is pressurizeed to metal plates such as heated SUS plates from support body layer side to carry out.As pressurized conditions, it is set as keeping vacuum degree usual 1×10^-2MPa or less, preferably 1 × 10^-3Under MPa decompression below.Being heated and pressurizeed can also carry out within a stage, but from From the viewpoint of the exudation for controlling resin, it is more than the stage to be preferably divided into two for condition to carry out.For example, the first stage adds Pressure is preferably 70 DEG C~150 DEG C, pressure 1kgf/cm in temperature²~15kgf/cm²Range under conditions of carry out, second The pressurization in stage is preferably 150 DEG C~200 DEG C, pressure 1kgf/cm in temperature²~40kgf/cm²Range under conditions of It carries out.The time in each stage is preferably 30 minutes~120 minutes ranges.Resin combination is subjected to heat cure in this way, Insulating layer can be formed on circuit substrate.As commercially available vacuum hotpressing machine, it can be mentioned, for example MNPC-V-750-5-200 ((strain) name mechanism is made made), VH1-1603 (Beichuan essence machine (strain) system) etc..

Then, aperture processing is carried out to the insulating layer being formed on circuit substrate, forms through-hole (via hole), open-work (through hole).Aperture processing such as can by method well known to drill bit, laser, plasma, can also basis It needs to combine these methods to carry out.Wherein, using the aperture of the lasers such as carbon dioxide gas laser, YAG laser Processing is most conventional methods.In addition, sheet laminated material of the invention is stacked on circuit substrate, by resin combination thermosetting Change and form insulating layer, forms through-hole by carrying out aperture processing on supporter on the insulating layer being formed on circuit substrate, Thus it manufactures multilayer printed circuit board, preferably removes supporter after aperture processing.In this way, by enterprising by supporter Row aperture processes and forms through-hole, so as to inhibit the generation of stain.In addition, in order to cope with the slim of multilayer printed circuit board Change, the top diameter (diameter) of through-hole is preferably 15 μm~70 μm, more preferably 20 μm~65 μm, further preferably 25 μm~60 μ m。

Then, the roughening treatment of surface of insulating layer is carried out.The roughening treatment of dry type can enumerate corona treatment etc., The roughening treatment of wet type can enumerate swelling process, the roughening treatment and benefit using oxidant successively carried out using swelling liquid With the method for the neutralisation treatment of neutralizer.It can be using dry type, any roughening treatment in wet type, from can be in insulating layer table Face forms the anchor (anchor) of convex-concave and from the perspective of removing the stain in through-hole, preferably the roughening treatment of wet type.Benefit With the swelling process of swelling liquid by the way that insulating layer to be impregnated in (preferably 55 DEG C of swelling liquid 5 minutes~20 minutes at 50 DEG C~80 DEG C 8 minutes~15 minutes at~70 DEG C) Lai Jinhang.As swelling liquid, such as can enumerate: aqueous slkali, surfactant solution etc., it is excellent Select aqueous slkali.It as the aqueous slkali, such as can enumerate: sodium hydroxide solution, potassium hydroxide solution etc..As commercially available swelling Liquid, such as can enumerate: the スウェリ Application グディップセキュリガ Application ス P of アトテッ Network ジャパ Application (strain) system (Swelling Dip Securiganth P)、スウェリング・ディップ・セキュリガンスSBU(Swelling Dip Securiganth SBU) etc..Using the roughening treatment of oxidant by the way that insulating layer is impregnated in oxidant at 60 DEG C~80 DEG C Solution 10 minutes~30 minutes (at preferably 70 DEG C~80 DEG C 15 minutes~25 minutes) Lai Jinhang.As oxidant, such as can arrange It lifts: dissolving alkalinity permanganic acid solution made of potassium permanganate or sodium permanganate, bichromate, smelly in the aqueous solution of sodium hydroxide Oxygen, hydrogen peroxide/sulfuric acid, nitric acid etc..In addition, the concentration of the permanganate in alkaline permanganic acid solution is preferably 5 weight %~10 Weight %.It as commercially available oxidant, such as can enumerate: the U Application セ Application トレート U Application of アトテッ Network ジャパ Application (strain) system The alkalinity permanganic acid solution such as パ Network ト CP, ドージ Application グソリューショ Application セキュリガ Application ス P.Using in neutralizer With processing by the way that insulating layer to be impregnated in in neutralizer 3 minutes~10 minutes at 30 DEG C~50 DEG C (3 points at preferably 35 DEG C~45 DEG C Clock~8 minute) Lai Jinhang.As neutralizer, preferably acid aqueous solution can enumerate アトテッ Network ジャ as commercially available product The リダ Network ショ Application ソリューショ Application セキュリガ Application ト P of パ Application (strain) system.

Then, conductor layer is formed on the insulating layer by dry type plating or wet type plating.As dry type plating, can be used Method well known to vapor deposition, sputtering, ion plating etc..As wet type plating, can enumerate: combination non-electrolytic plating and electrolysis plating carry out shape At the method for conductor layer, formed and the plating (めっ I レジスト) of conductor layer opposite pattern, only conformal by electroless plating At the method etc. of conductor layer.As circuit pattern forming method, it can be used for example that well known to a person skilled in the art subtractive process (subtractive), semi-additive process etc..Then, it by the way that above-mentioned series of processes is repeated several times, can manufacture stack layer is multistage The multilayer printed circuit board of section lamination.In the present invention, due to inhibiting the generation of stain, it can be ensured that the conducting reliability of interlayer. Therefore, sheet laminated material of the invention can be for preferably forming the stack layer of multilayer printed circuit board.What is manufactured in this way is more Layer printed wiring board contains the insulating layer formed using the solidfied material of resin combination of the invention.

< semiconductor device >

Semiconductor device can be manufactured by using multilayer printed circuit board of the invention.It can be by being printed in multilayer of the invention The conduction position of brush wiring board installs semiconductor chip to manufacture semiconductor device." conduction position " refers to " multilayered printed circuit The position of electric signal can be conducted in plate ", which can be the position that surface is also possible to be embedded.In addition, semiconductor core As long as electrical circuit components of the piece using semiconductor as material are not particularly limited.Semiconductor device of the invention includes this The multilayer printed circuit board of invention specifically includes: multilayer printed circuit board of the invention and to be installed on this multi-sheet printed The semiconductor chip of the conduction position of wiring board.

As long as the installation method of semiconductor chip when manufacturing semiconductor device of the invention sends out semiconductor chip effectively Function is waved, is not particularly limited, it is specific enumerable: wire bonding installation method, flip-chip installation method, using built-in non- The installation method of buckle layer (プ layers of バ Le プなビ Le De アッ, BBUL) utilizes the installation of anisotropic conductive film (ACF) Method utilizes installation method of non-conductive film (NCF) etc..

[embodiment]

Hereinafter, the present invention is described in more detail using embodiment, but the present invention is not limited by these embodiments.It should say Bright, below in record, if not otherwise stated, then " part " and " % " is respectively intended to mean " mass parts " and " quality % ".

< measurement, evaluation method >

It is illustrated firstly for the measurement of evaluation of physical property, evaluation method in this specification.

[preparation that substrate is used in measurement, evaluation]

(1) the ground processing of circuit substrate

Glass cloth base material epoxy resin two-sided copper foil covered laminated plate (18 μm of the thickness of copper foil, the substrate of circuit will be formed with Thickness 0.3mm, パ Na ソニッ Network (strain) make " R1515A ") two sides using Micro etching agent (メッ Network (strain) make " CZ8100 ") 1 μm of thickness of etching, to carry out the roughening treatment on copper surface.

(2) lamination of adhering film

The adhering film removing protective film made from embodiment and comparative example.By the bonding of the exposing of resin composition layer Film uses batch-type vacuum pressed laminating machine (2 stage of (strain) ニチ go ーモート Application system stacks laminating machine " CVP700 "), In a manner of engaging resin composition layer with circuit substrate, it is laminated to the two sides of circuit substrate.Lamination is implemented as follows: carrying out 30 The decompression of second after making air pressure reach 13hPa or less, carries out crimping for 30 seconds under conditions of 110 DEG C, pressure 0.74MPa.It connects , by laminated adhering film under atmospheric pressure, 110 DEG C, to carry out hot pressing in 60 seconds under conditions of pressure 0.5MPa flat to carry out Cunningization.

(3) solidification of resin composition layer

By laminated adhering film 30 minutes at 100 DEG C, then at 180 DEG C under 30 minutes conditions of cure by resin Composition layer solidification, forms insulating layer.

(4) formation of through-hole

Use CO₂Laser machine (Hitachi ビアメカニ Network ス (strain) makes " LC-2E21B/1C "), in mask diameter 1.60mm, defocus bias (フォーカスオ Off セット value) 0.050,25 μ s of pulse width, power 0.66W, aperture 13, hair It penetrates under conditions of number 2, burst mode and aperture is carried out to insulating layer, form through-hole.The top diameter (diameter) of the through-hole of surface of insulating layer It is 50 μm.After through-hole is formed, PET film is removed.

(5) roughening treatment

The circuit substrate of insulating layer will be formd in swelling liquid (アトテッ Network ジャパ Application (strain) system " スエリ Application グディップセキュリガ Application ト P ", the aqueous solution containing diethylene glycol monobutyl ehter and sodium hydroxide) in impregnated at 60 DEG C 10 minutes, In roughening liquid, (アトテッ Network ジャパ Application (strain) makes " U Application セ Application トレート U Application パ Network ト CP ", KMnO₄: 60g/L, The aqueous solution of NaOH:40g/L) in impregnated at 80 DEG C 20 minutes, finally neutralizer (アトテッ Network ジャパ Application (strain) make " リダ Network ショ Application ソリューショ Application セキュリガ Application ト P ", aqueous sulfuric acid) in impregnated at 40 DEG C after five minutes, at 80 DEG C Lower drying 30 minutes.Resulting substrate is set as evaluation substrate A.

(6) using the formation of the conductor layer of half adding technology

According to following sequences, it is formed in the conductor layer that surface of insulating layer has required circuit pattern.

Evaluation substrate A is being contained into PdCl₂Non-electrolytic plating solution in, in 40 DEG C impregnate 5 minutes, then in electroless plating It is impregnated 20 minutes in copper liquid in 25 DEG C.Resulting substrate is heated 30 minutes after being made annealing treatment at 150 DEG C, is formed anti- Erosion resisting coating.After underseal is formed pattern by etching, copper sulphate plating is carried out, conductor layer is formed with 30 μm of thickness.It will The substrate for foring conductor layer heats 60 minutes at 190 DEG C to be made annealing treatment.Resulting substrate is set as evaluation substrate B.

[measurement of arithmetic average roughness (Ra) and r.m.s. roughness (Rq)]

For evaluating substrate A, non-contact type surface roughness meter (ビー U イ Application スツルメン Star society system is used " WYKO NT3300 "), using VSI contact mode, 50 times of lens, numerical value is obtained in 121 μ m, 92 μm of measurement range, by this Numerical value acquires Ra value and Rq value.As measured value and acquiring randomly selected 10 points of average value respectively.

[measurement of the pull-off strength (peel strength) of plated conductor layer]

The notch that the part of width 10mm, long 100mm are cut in the conductor layer of evaluation substrate B, one end is peeled off, with folder Tool (Co., Ltd.'s ティーエスイー, オート U system type testing machine " AC-50C-SL ") clamp, measurement at room temperature, with 50mm/ minutes speed vertically removes the load (kgf/cm) when 35mm.Evaluation criteria is as follows.

Evaluation criteria:

Zero: peel strength is more than 0.45kgf/cm

△: peel strength is 0.4kgf/cm or more and 0.45kgf/cm or less

×: peel strength is less than 0.4kgf/cm.

[evaluation of the stain of via bottoms]

Around scanning electron microscope (SEM) observation via bottoms, via bottoms are come from by resulting determining image Wall surface maximum stain length.Evaluation criteria is as follows.

Evaluation criteria:

Zero: maximum stain length is less than 3 μm

×: maximum stain length is 3 μm or more.

[measurement of coefficient of linear thermal expansion]

The adhering film made in embodiment and comparative example is heated 90 minutes at 200 DEG C, thus makes resin composition layer After heat cure, removes PET film and obtain the solidfied material of sheet.The solidfied material is cut into the test film of wide 5mm, long 15mm, is made With thermo-mechanical analysis device ((strain) リガ Network system " Thermo Plus TMA8310 "), thermomechanically divided using tensile load method Analysis.After test film is assembled in above-mentioned apparatus, load 1g, 5 DEG C/min of heating rate of determination condition METHOD FOR CONTINUOUS DETERMINATION 2 are utilized It is secondary.Calculate 25 DEG C~150 DEG C of the coefficient of mean linear thermal expansion (ppm) in the 2nd measurement.Evaluation criteria is as follows.

Evaluation criteria:

Zero: the coefficient of mean linear thermal expansion is 25ppm or less

×: the coefficient of mean linear thermal expansion is greater than 25ppm.

[measurement of dielectric loss tangent]

Make the adhering film made in embodiment and comparative example carry out heating for 90 minutes at 200 DEG C, makes resin composition layer After heat cure, PET film is removed, obtains the solidfied material of sheet.The solidfied material is cut into the test film of wide 2mm, long 80mm, is made With resonant cavity perturbation method dielectric constant measurement device (Northeast applying electronic develops (strain) system " CP521 ") and Network Analyzer (アジレ Application トテ Network ノロジー (strain) makes " E8362B "), medium attenuation is carried out in measurement frequency 5.8GHz using Resonant-cavity Method The measurement of factor (tan δ).2 test films are measured, average value is calculated.

[preparation example 1] (preparation of resin varnish 1)

By bisphenol-type epoxy resin (Nippon Steel live aurification (strain) system " ZX1059 ", epoxide equivalent about 169, bisphenol A-type and The 1:1 melange of bisphenol-f type) 5 parts, double diformazan phenolic (ビキシレノー Le type) epoxy resin (Mitsubishi Chemical's (strain) system (Japanese chemical drug (strain) makes " NC3000L ", epoxide equivalent for about 185) 10 parts of " YX4000HK ", epoxide equivalent, biphenyl type epoxy resin 269) 5 parts, 5 parts of dicyclopentadiene type epoxy resin (DIC (strain) makes " HP-7200HH ", epoxide equivalent 280) and phenoxy (Mitsubishi Chemical's (strain) makes the cyclohexanone of " YL7553BH30 ", 30 mass % of solid component: the 1:1 of methyl ethyl ketone (MEK) is molten for rouge Liquid) 8 parts dissolved by heating while stirring in 30 parts of solvent naphtha.After being cooled to room temperature, mixed active ester compounds thereto (DIC (strain) make " HPC8000-65T ", active group equivalent about 223 65 mass % of non-volatile component toluene solution) 35 parts, alkane Base melamine resin ((strain) three and ケミカ Le system " ニカラッ Network MX-750LM ", 82 mass % of non-volatile component, methylation honey Polyimide resin, content of monomer 35~45%) 5 parts, curing accelerator (4-dimethylaminopyridine (DMAP), 5 mass % of solid component MEK solution) 2 parts, 1 part of curing accelerator (the MEK solution of 1- benzyl -2- phenylimidazole (1B2PZ), 10 mass % of solid component), (three light (strain) make " HCA-HQ ", 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxidation to fire retardant 2 μm of object, average grain diameter) 2 parts, carried out at surface with amino silicone methane series coupling agent (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 ") Preparing spherical SiO 2 ((strain) ア De マテッ Network ス system " SOC1 ", 0.24 μm of average grain diameter, the carbon amounts of per unit surface area of reason 0.36mg/m²) 125 parts, it is uniformly dispersed with high speed rotation mixing machine, prepares resin varnish 1.

[preparation example 2] (preparation of resin varnish 2)

Using alkylated melamine resins (DIC (strain) " スーパーベッカミ Application ELM-752 processed ", weight average molecular weight about 1500,60 mass % of non-volatile component, isobutyl melamine resin) 3 parts replace alkylated melamine resins ((strain) three and ケミカ Le system " ニカラッ Network MX-750LM ", 82 mass % of non-volatile component) 5 parts, in addition to this resin is prepared as with preparation example 1 Varnish 2.

[preparation example 3] (preparation of resin varnish 3)

Using alkoxyalkylation phenolic resin (bis- (the methoxy)-phenol of 4- (1,1- dimethyl ethyl) -2,6-, The methyl isobutyl ketone solution of 65 mass % of solid component, the aikoxymethytated phenolic resin with the structure being expressed from the next) 10 parts replace alkylated melamine resins ((strain) three and ケミカ Le system " ニカラッ Network MX-750LM ", 82 matter of non-volatile component Measure %) 5 parts, in addition to this resin varnish 3 is prepared as with preparation example 1.

[preparation example 4] (preparation of resin varnish 4)

It is ((strain) three and ケミカ Le system " ニカラッ Network MX-750LM ", non-volatile in addition to not adding alkylated melamine resins 82 mass % of ingredient) except 5 parts, resin varnish 4 is prepared as with preparation example 1.

[preparation example 5] (preparation of resin varnish 5)

Using alkylation benzoguanamine resin, (DIC (strain) makes " スーパーベッカミ Application E-1128 ", non-volatile component 60 Quality %, isobutyl benzoguanamine resin) 3 parts replace alkylated melamine resins ((strain) three and ケミカ Le system " ニカラッ Network MX-750LM ", 82 mass % of non-volatile component) 5 parts, in addition to this resin varnish 5 is prepared as with preparation example 1.

1 > of < embodiment (production of adhering film 1)

Preparing the PET film with alkyd resin system release layer as supporter, (リ Application テッ Network (strain) makes " AL5 ", 38 μ of thickness m).Resin varnish 1 is equably coated on the release layer of the supporter, so that the thickness of the resin composition layer after dry reaches 25 μm, keep it 4 minutes dry under 80~120 DEG C (100 DEG C average).Then, protective film (king is bonded on resin composition layer The special paper (strain) of son makes " ア Le Off ァ Application MA-411 ", 15 μm of thickness, polypropylene screen) smooth surface side, production have protective film/ The adhering film 1 of resin composition layer/supporter layer structure.

2 > of < embodiment (production of adhering film 2)

Using resin varnish 2, adhering film 2 is made similarly to Example 1.

3 > of < embodiment (production of adhering film 3)

Using resin varnish 3, adhering film 3 is made similarly to Example 1.

1 > of < comparative example (production of adhering film 4)

Using resin varnish 4, adhering film 4 is made similarly to Example 1.

2 > of < comparative example (production of adhering film 5)

Using resin varnish 5, adhering film 5 is made similarly to Example 1.

Evaluation result is shown in table 1.

[table 1]

As shown in Table 1, it can confirm that the resin combination of Examples 1 to 3 can obtain the solidfied material of low dielectric loss tangent, Inhibit the excellent of the stain in through-hole.It may also confirm that the resin combination of Examples 1 to 3 can obtain coefficient of linear thermal expansion Low solidfied material.On the other hand, although the resin combination of comparative example 1 and 2 can obtain the solidfied material of low dielectric loss tangent, But result remains stain in through-hole.As for the resin combination of comparative example 2, as a result, the coefficient of linear thermal expansion of solidfied material It is deteriorated.

Industrial feasibility

The present invention can provide resin combination, which can get the low solidfied material of dielectric loss tangent, and Solidfied material is subjected to aperture processing, the stain in roughened treated through-hole can be inhibited.In addition, using the resin group Close object, it is possible to provide sheet laminated material, multilayer printed circuit board, semiconductor device.And then the meter for being equipped with these can also be provided The vehicles such as the electrical articles such as calculation machine, mobile phone, digital camera, TV and motorcycle, automobile, electric car, ship, aircraft.

Claims

1. resin combination contains:

(A) epoxy resin,

(B) active ester compound and

(C) resin selected from one or more of alkylated melamine resins and alkoxyalkylation phenolic resin,

Alkylated melamine resins are that have by formula :-N (- CH₂-O-R¹)₂The functional group of expression, by formula :-N (- CH₂-O-R¹)CH₂OH The functional group of expression, by formula :-N (- CH₂-O-R¹) H indicate functional group in 1 or more functional group alkylated melamine resins； R in formula¹For the alkyl of carbon atom number 1~6,

Alkoxyalkylation phenolic resin is that have by formula :-CH (R³)-O-R⁴The phenolic aldehyde comprising phenol skeleton of the functional group of expression Resin；In formula, R³For hydrogen atom, the alkyl of carbon atom number 1~3, phenyl or hydroxyphenyl, R⁴For the alkyl of carbon atom number 1~6.

2. resin combination described in claim 1, wherein set the total amount of (A) ingredient and (B) ingredient in resin combination When for 100 mass %, the content of (C) ingredient is 0.1 mass of mass %~30 %.

3. resin combination described in claim 1, wherein the non-volatile component in resin combination is set as 100 mass % When, the content of (B) ingredient is 1 mass of mass %~30 %.

4. resin combination described in claim 1, wherein alkylated melamine resins are containing the structure indicated by following formula (1) The melamine resin of unit,

In formula,

X¹、X²、X³、X⁴、X⁵And X⁶Each independently represent hydrogen atom, by formula :-CH₂OH indicate group, by formula :-CH₂-O-R¹ The group of expression or by formula-CH₂The group that-* is indicated, wherein R¹It is chemical bond for alkyl, the * of carbon atom number 1~6；Wherein, X¹、X²、X³、X⁴、X⁵And X⁶At least one of for by formula :-CH₂-O-R¹The group of expression.

5. resin combination described in claim 1, wherein alkoxyalkylation phenolic resin is containing by following formula (2) expression Structural unit phenolic resin,

In formula,

Z¹It indicates by formula :-CH (R³)-O-R⁴The group of expression, wherein R³For hydrogen atom, the alkyl of carbon atom number 1~3, phenyl or Hydroxyphenyl, R⁴For the alkyl of carbon atom number 1~6,

Z²It indicates by formula :-R⁵- * indicate group or by formula :-R⁶(-*)₂The group of expression, wherein R⁵For alkylidene or singly-bound, R⁶ For three base of alkane, * is chemical bond,

Z³Indicate the alkyl of the optionally carbon atom number 1~6 with substituent group,

L, m and n is satisfaction 2≤l+m+n≤5 and the integer of 1≤l.

6. resin combination described in claim 1 further contains (D) inorganic filling material.

7. resin combination as claimed in claim 6, wherein the average grain diameter of (D) inorganic filling material is 0.01 μm~5 μm.

8. resin combination as claimed in claim 6, wherein the non-volatile component in resin combination is set as 100 mass % When, the content of (D) ingredient is 50 mass of mass %~85 %.

9. resin combination described in claim 1 is the resin compositions for insulating layer of multilayer printed circuit board.

10. resin combination described in claim 1 is the stack layer resin combination of multilayer printed circuit board.

11. sheet laminated material contains resin combination according to any one of claims 1 to 10.

12. multilayer printed circuit board contains the solidfied material using resin combination according to any one of claims 1 to 10 It is formed by insulating layer.

13. semiconductor device contains the multilayer printed circuit board described in claim 12.

14. the manufacturing method of multilayer printed circuit board, wherein the sheet lamination described in circuit substrate superimposed layer claim 11 Resin combination heat cure is formed insulating layer by material, on the insulating layer formed on circuit substrate carry out aperture processing and Form through-hole.