CN110139893A

CN110139893A - Prepreg, plywood, clad with metal foil plywood, printed circuit board and multilayer board

Info

Publication number: CN110139893A
Application number: CN201780081386.5A
Authority: CN
Inventors: 滨岛知树; 山口翔平; 久保孝史; 伊藤环; 志贺英祐
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2016-12-28
Filing date: 2017-12-27
Publication date: 2019-08-16
Anticipated expiration: 2037-12-27
Also published as: JP2019048990A; JP6424992B1; TW201831572A; CN110139893B; KR102026591B1; KR20190026953A; JP6681052B2; TWI725387B; TWI656151B; CN114196204A; TW201920399A; JPWO2018124158A1; WO2018124158A1

Abstract

In order to provide be not present specific glass transition temperature (no Tg) and can sufficiently reduce printed circuit board, particularly multilayered coreless substrate warpage (reaching low warpage) prepreg, plywood, clad with metal foil plywood, printed circuit board and multilayer board, prepreg of the invention include heat-curing resin, packing material and substrate.In addition, prepreg solidfied material obtained from heat cure under conditions of 230 DEG C and 100 minutes is made to meet following formula (1)~(5)；E ' (200 DEG C)/E ' (30 DEG C)≤0.90 ... (1) E ' (260 DEG C)/E ' (30 DEG C)≤0.85 ... (2) E ' (330 DEG C)/E ' (30 DEG C)≤0.80 ... (3) E " max/E ' (30 DEG C)≤3.0% ... (4) E " min/E ' (30 DEG C) >=0.5% ... (5) (E ': storage modulus, E ": loss modulus, E ": loss modulus).

Description

Prepreg, plywood, clad with metal foil plywood, printed circuit board and multi-sheet printed electricity Road plate

Technical field

The present invention relates to prepreg, plywood, clad with metal foil plywood, printed circuit board and multilayer boards.

Background technique

In recent years, with the high function of widely used semiconductor packages in electronic equipment, communication equipment, personal computer etc. Change, miniaturization progress, the highly integrated of each component of semiconductor-sealing-purpose, high-density installation increasingly accelerate in recent years.Therewith, Each characteristic that the printed circuit board of semiconductor-sealing-purpose requires becomes to be increasingly stringenter.The spy required as the printed circuit board Property, for example, it is swollen to enumerate low water absorbable, moisture absorption heat resistance, anti-flammability, low-k, low dielectric loss angle tangent, low-heat Swollen rate, heat resistance, chemical resistance, high plating peel strength etc..In addition, inhibiting printed circuit board, spy in addition to these characteristics Be not multilayered coreless substrate warpage (reaching low warpage) in recent years become important project, taking various countermeasures.

As one of its countermeasure, the low thermal expansion of insulating layer used in printed circuit board can be enumerated.It is to pass through The method for making the coefficient of thermal expansion of printed circuit board and inhibiting close to the coefficient of thermal expansion of semiconductor element warpage, actively grinds now (for example, referring to Patent Documents 1 to 3) in studying carefully.

As inhibit plastic semiconductor encapsulation warpage method, in addition to research printed circuit board low thermal expansion with Outside, the rigidity (high rigidity) of plywood, glass transition temperature (high Tgization) (example of raising plywood also are improved in research Such as, referring to patent document 4 and 5).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2013-216884 bulletin

Patent document 2: No. 3173332 bulletins of Japanese Patent Publication No.

Patent document 3: Japanese Unexamined Patent Publication 2009-035728 bulletin

Patent document 4: Japanese Unexamined Patent Publication 2013-001807 bulletin

Patent document 5: Japanese Unexamined Patent Publication 2011-178992 bulletin

Summary of the invention

But the detailed research of people etc. according to the present invention, even if having the above-mentioned prior art, remaining on sufficiently to subtract The warpage of small printed circuit board, particularly multilayered coreless substrate, it is expected that further improveing.

That is, the object of the present invention is to provide there is no specific glass transition temperature (Tg) (so-called no Tg) and The prepreg of the warpage (reaching low warpage) of printed circuit board, particularly multilayered coreless substrate can sufficiently be reduced, plywood, covered Metal foil layer lamination, printed circuit board and multilayer board.

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, as a result specify, in the past about semiconductor The buckling behavior of the printed circuit board of Plastic Package, it is believed that energy storage mould when bigger heat can be achieved in the solidfied material of prepreg The resin combination of amount and higher elasticity modulus sustainment rate is effectively that but not limited to this.In turn, the inventors of the present invention It has made intensive studies, as a result, it has been found that, for by the specific mechanical property phase in solidfied material obtained from prepreg heat cure The physical parameter of pass is able to solve the above problem by making the numerical value of the physical parameter meet defined condition and range.Send out It is existing: storage modulus when heat in solidfied material obtained from prepreg heat cure and loss modulus being met into specific condition as making Range is able to solve the above problem, so as to complete the present invention.

That is, the present invention is as follows.

〔1〕

A kind of prepreg, contains: heat-curing resin, packing material and substrate,

Make prepreg solidfied material obtained from heat cure under conditions of 230 DEG C and 100 minutes meet following formula (1)~ (5) numberical range of the relevant physical parameter of mechanical property shown in,

E’(200℃)/E’(30℃)≤0.90…(1)

E’(260℃)/E’(30℃)≤0.85…(2)

E’(330℃)/E’(30℃)≤0.80…(3)

E " max/E ' (30 DEG C)≤3.0% ... (4)

E " min/E ' (30 DEG C) >=0.5% ... (5)

(in various, E ' indicate parantheses shown at a temperature of said curing object storage modulus, E " max indicate 30 DEG C The maximum value of the loss modulus of said curing object in~330 DEG C of temperature range, E " min indicate 30 DEG C~330 DEG C of temperature The minimum value of the loss modulus of said curing object in range.).

〔2〕

The prepreg according to (1) also meets mechanical property shown in following formula (6A),

E’(30℃)≤30GPa…(6A)

(in formula, E ' indicate parantheses shown at a temperature of said curing object storage modulus.).

〔3〕

According to prepreg described in (1) or (2), wherein aforementioned substrates are glass baseplate.

〔4〕

The prepreg according to (3), wherein foregoing glass substrate by selected from by E glass, D glass, S glass, T glass, The fiber of the glass of one or more of the group of Q glass, L glass, NE glass and HME glass composition is constituted.

〔5〕

A kind of plywood, with prepreg described in any one of at least 1 or more (1)~(4) being laminated.

〔6〕

A kind of clad with metal foil plywood, includes

Prepreg described in any one of at least 1 or more (1)~(4) being laminated and

It is configured at the metal foil of the one or two sides of the prepreg.

〔7〕

A kind of printed circuit board, includes

Insulating layer that the prepreg as described in any one of (1)~(4) is formed and

It is formed in the conductor layer on the surface of the insulating layer.

〔8〕

A kind of multilayer board, with multiple insulating layers and multiple conductor layers,

The multiple insulating layer includes: prepreg shape described in any one of (1)~(4) being laminated as at least 1 or more At the 1st insulating layer and any one of (1)~(4) that are laminated in the single side direction of aforementioned 1st insulating layer by least 1 or more The 2nd insulating layer that the prepreg is formed,

The multiple conductor layer includes: the 1st conductor layer that is configured between each layer of aforesaid plurality of insulating layer and being configured at 2nd conductor layer on the outermost surface of aforesaid plurality of insulating layer.

The effect of invention

It (is reached according to the present invention it is possible to provide and can sufficiently reduce the warpage of printed circuit board, particularly multilayered coreless substrate At low warpage) prepreg, plywood, clad with metal foil plywood, printed circuit board and multilayer board.

Detailed description of the invention

Fig. 1 is process flow chart (still, the multilayered coreless of an example the step of showing the panel of production multilayered coreless substrate The manufacturing method of substrate is not limited to this.It is same in Fig. 2~Fig. 8 below.).

Fig. 2 is the process flow chart of an example the step of showing the panel of production multilayered coreless substrate.

Fig. 3 is the process flow chart of an example the step of showing the panel of production multilayered coreless substrate.

Fig. 4 is the process flow chart of an example the step of showing the panel of production multilayered coreless substrate.

Fig. 5 is the process flow chart of an example the step of showing the panel of production multilayered coreless substrate.

Fig. 6 is the process flow chart of an example the step of showing the panel of production multilayered coreless substrate.

Fig. 7 is the process flow chart of an example the step of showing the panel of production multilayered coreless substrate.

Fig. 8 is the process flow chart of an example the step of showing the panel of production multilayered coreless substrate.

Fig. 9 is the partial section view for showing the composition of an example of panel of multilayered coreless substrate.

Specific embodiment

Hereinafter, to mode for carrying out the present invention (hereinafter referred to as " present embodiment ".) be described in detail, but this Invention is not limited to this, can carry out various modifications within the scope of its spirit.It should be noted that present embodiment In, for " resin solid content ", unless otherwise specified, just refer to it is in resin combination, in addition to solvent and filling material Ingredient other than material, " 100 mass parts of resin solid content " refer in resin combination other than solvent and packing material Ingredient add up to 100 mass parts.

(prepreg)

The prepreg of present embodiment contains: substrate and infiltration or the aftermentioned resin combination for being coated on the substrate.It is right It in the manufacturing method of prepreg, may be carried out by conventional means, be not particularly limited.For example, present embodiment can be made After resin combination infiltrates or is coated on substrate, heating in 1~30 minute etc. is carried out in 100~200 DEG C of drying machine and makes it Semi-solid preparation (B-staged) thus makes the prepreg of present embodiment.

In addition, for the prepreg of present embodiment, make its under conditions of 230 DEG C and 100 minutes heat cure and obtain Solidfied material meet the numberical range of the relevant physical parameter of mechanical property shown in following formula (1)~(5), preferably satisfy following The numberical range of the relevant physical parameter of mechanical property shown in formula (1A)~(5A).

E’(200℃)/E’(30℃)≤0.90…(1)

E’(260℃)/E’(30℃)≤0.85…(2)

E’(330℃)/E’(30℃)≤0.80…(3)

E " max/E ' (30 DEG C)≤3.0% ... (4)

E " min/E ' (30 DEG C) >=0.5% ... (5)

0.40≤E’(200℃)/E’(30℃)≤0.90…(1A)

0.40≤E’(260℃)/E’(30℃)≤0.85…(2A)

0.40≤E’(330℃)/E’(30℃)≤0.80…(3A)

0.5%≤E " max/E ' (30 DEG C)≤3.0% ... (4A)

3.0% >=E " min/E ' (30 DEG C) >=0.5% ... (5A)

Herein, in various, E ' indicate parantheses shown at a temperature of solidfied material storage modulus, E " max indicate 30 DEG C The maximum value of the loss modulus of solidfied material in~330 DEG C of temperature range, E " min indicate 30 DEG C~330 DEG C of temperature range In solidfied material loss modulus minimum value (E " expression solidfied material loss modulus.).

In the past, about the buckling behavior of printed circuit board, it is believed that can be achieved to store up when bigger heat in the solidfied material of prepreg The resin combination of energy modulus and higher elasticity modulus sustainment rate is effectively that but not limited to this, makes to presoak by allowing Expect the numerical value of the relevant physical parameter of mechanical property of solidfied material obtained from heat cure under conditions of 230 DEG C and 100 minutes In the range of above-mentioned formula (1)~(5), preferred formula (1A)~(5A), so as to sufficiently improve glass transition temperature (Tg), And it can sufficiently reduce the warpage of plywood, clad with metal foil plywood, printed circuit board, particularly multilayered coreless substrate itself Amount.

In other words, the machine of the solidfied material as obtained from allowing and make prepreg heat cure under conditions of 230 DEG C and 100 minutes The numerical value of the relevant physical parameter of tool characteristic is above-mentioned formula (1)~(5), in the range of preferred formula (1A)~(5A), so as to suitable Locality is not present specific glass transition temperature (no Tg) and sufficiently reduces printed circuit board (especially multilayered coreless base Plate) warpage (reaching low warpage).That is, it can be said that meet formula (4) and (5), the preferred formula (4A) and (5A) of loss modulus, and not There are the meaning of specific glass transition temperature (Tg) (no Tg) is identical, but solidfied material only meets formula (4) and (5), preferred formula (4A) and (5A), and when being unsatisfactory for formula (1)~(3), preferred formula (1A)~(3A), loss modulus itself is small to be difficult to extend, But when printed circuit board is made, elongation difficulty becomes trouble, to be difficult to reach low warpage.In contrast, solidfied material is not only Meeting formula (4) and (5), preferred formula (4A) and (5A) has when also meeting formula (1)~(5), preferred formula (1A)~(5A) because of no Tg And it is difficult to extend and becomes easy the tendency for reaching the low warpage of printed circuit board.

In turn, the prepreg of present embodiment preferably satisfies mechanical property shown in following formula (6A), under more preferably meeting State mechanical property shown in formula (6) and/or formula (6B).

E’(30℃)≤30GPa…(6A)

E’(30℃)≤25GPa…(6)

1GPa≤E’(30℃)…(6B)

Herein, in formula, E ' indicate parantheses shown at a temperature of said curing object storage modulus.That is, for this reality The prepreg of mode is applied, E ' (30 DEG C) is preferably 30GPa or less, more preferably 25GPa or less.In addition, its E ' (30 DEG C) Lower limit value is not particularly limited, preferably 1GPa or more.

The mechanical property of the solidfied material as obtained from allowing and make prepreg heat cure under conditions of 230 DEG C and 100 minutes In the range of above-mentioned formula (6), so as to further decrease the warpage of especially multilayered coreless substrate.

The measuring method of the mechanical property (storage modulus E ' and loss modulus E ") of the solidfied material of prepreg does not limit especially It is fixed, for example, can be measured by the following method.That is, 1 prepreg upper and lower surface configuration copper foil (3EC-VLP, 12 μm of Mitsu Mining & Smelting Co., Ltd's system, thickness), with pressure 30kgf/cm², 230 DEG C of temperature be laminated within 100 minutes Shape (heat cure) obtains the copper foil covered lamination of defined thickness of insulating layer.Then, copper foil covered folded by what is obtained with cast-cutting saw After plate is cut into size 5.0mm × 20mm, the copper foil on surface is removed by etching, obtains test sample.Use the measurement With sample, pass through DMA method to mechanical property with dynamic viscoelastic analytical equipment (TA Instruments system) according to JIS C6481 (storage modulus E ' and loss modulus E ") is measured.At this point it is possible to find out the average value of n=3.

Resin combination in aforementioned prepreg is (comprising aftermentioned packing material (H).) content relative to prepreg Total amount is preferably 30~90 volume %, more preferably 35~85 volume %, further preferably 40~80 volume %.By making to set The content of oil/fat composition is in above range, to have the tendency that formability further increases.

It as substrate, is not particularly limited, can be suitable for selecting using various printed circuits according to intended applications, performance Well known substrate used in plate material.As substrate, for example, can enumerate glass baseplate, the inorganic substrate in addition to glass, Organic substrate etc., in these, from the viewpoint of high rigidity and dimensional stability under heat, particularly preferred glass baseplate.As structure It at the concrete example of the fiber of these substrates, is not particularly limited, for glass baseplate, such as can enumerate selected from by E glass, D The fiber of the glass of one or more of the group of glass, S glass, T glass, Q glass, L glass, NE glass, HME glass composition.Separately Outside, for the inorganic substrate other than glass, the quartzy equal inorfil in addition to glass can be enumerated.In turn, for organic group Material can enumerate poly(p-phenylene terephthalamide) (Kevlar (registered trademark), Du Pont Co. Ltd. system), copolymerization to Asia 3,4 ' oxo diphenylene p-phenylenediamine of phenyl (Technora (registered trademark), Teijin Techno Products Limited. make) etc. fully aromatic polyamides；2,6 hydroxy naphthoic acid P-hydroxybenzoic acid (Vectran (registered trademark), KURARAY CO., LTD system), the polyester such as Zxion (registered trademark, KB SEIREN, LTD. system)；Polyparaphenylene benzoxazoles The organic fibers such as (Zylon (registered trademark), Toyo Boseki K.K's system), polyimides.These substrates can be used alone 1 Kind, two or more can also be applied in combination.

As the shape of substrate, be not particularly limited, for example, can enumerate woven fabric, non-woven fabrics, rove, chopped mat, Surface felt etc..It as the weave of woven fabric, is not particularly limited, such as it has been known that there is plain weave, basket weave, twill-weave etc., It can be suitable for selection from weave well known to these according to intended applications, performance and use.Furthermore it is possible to be suitably used to this It is a little carry out fibrillation processing and winner, be surface-treated with silane coupling agent etc. made of glass woven fabric.The thickness of substrate, quality It is not particularly limited, can usually be suitably used 0.01~0.3mm's or so.Especially go out from the viewpoint of intensity and water imbibition Hair, 200 μm of substrate preferred thickness or less, quality 250g/m²Glass woven fabric below, more preferably by E glass, S glass and T glass The glass woven fabric that the glass fibre of glass is formed.

(resin combination)

As long as the resin combination of present embodiment used in above-mentioned prepreg includes heat-curing resin and filling material Material, there is no particular limitation, for example, can be suitable for select containing maleimide compound (A), contain allyl compound (B), And the epoxy resin (C) comprising bisphenol A-type structural unit and hydrocarbon system structural unit, and can be realized above-mentioned formula (1)~(5), The composition of the numberical range of the relevant physical parameter of mechanical property shown in preferred formula (1A)~(5A).It has used and has contained this tree Plywood, clad with metal foil plywood, printed circuit board, the special multilayered coreless substrate of the prepreg of oil/fat composition and substrate have energy Enough tendencies for sufficiently reducing the amount of warpage as caused by the heating of Reflow Soldering etc..

(maleimide compound (A))

As maleimide compound (A), as long as to have the compound of 1 or more dimaleoyl imino in molecule, It is just not particularly limited, such as N-phenylmaleimide, N- hydroxyphenyl-maleimides, the bis- (Malaysia 4- acyls can be enumerated Imines phenyl) methane, bis- { 4- (the 4- maleimidephenoxy)-phenyl } propane of 2,2-, the bis- (Malaysia 3,5- dimethyl -4- acyls Imines phenyl) methane, bis- (3- ethyl -5- methyl -4- maleimide phenyl) methane, bis- (3,5- diethyl -4- maleimides Amine phenyl) methane, maleimide compound, the prepolymer of these maleimide compounds or horse shown in following formula (7) Carry out the prepolymer of imide compound and amine compounds.Wherein, it is preferably selected from by bis- (4- maleimide phenyl) methane, 2,2- Bis- { 4- (4- maleimidephenoxy)-phenyl } propane, bis- (3- ethyl -5- methyl -4- maleimide phenyl) methane and At least one kind of, horse shown in particularly preferred following formula (7) in the group of the composition of maleimide compound shown in following formula (7) Carry out imide compound.By the inclusion of such maleimide compound (A), thus the coefficient of thermal expansion for the solidfied material having It further decreases, the tendency that heat resistance, glass transition temperature (Tg) further increase.

Herein, in formula (7), R₅Hydrogen atom or methyl are each independently represented, preferably expression hydrogen atom.In addition, formula (7) In, n₁Indicate 1 or more integer, preferably 10 integer, more preferably 7 integers below below.

The content of maleimide compound (A) is preferably 10~70 mass relative to 100 mass parts of resin solid content Part, more preferably 20~60 mass parts, further preferably 25~50 mass parts, particularly preferably 35~50 mass parts, more into One step is more preferably 35~45 mass parts.In content above range by making maleimide compound (A), to have To solidfied material coefficient of thermal expansion further decrease, the tendency that heat resistance further increases.

((B) containing allyl compound)

Containing allyl compound (B) as long as, with the compound of 1 or more allyl, not limited especially in molecule It is fixed, it can be also containing the reactive functional groups in addition to allyl.As the reactive functional groups in addition to allyl, without spy It does not limit, for example, cyanic acid ester group (Cyanate group), hydroxyl, epoxy group, amido, isocyanate group, shrink can be enumerated Glyceryl and phosphate.Wherein, it is preferably selected from the group being made of cyanic acid ester group (Cyanate group), hydroxyl and epoxy group In at least one kind of, more preferable cyanic acid ester group (Cyanate group).By with hydroxyl, cyanic acid ester group (Cyanate Group), epoxy group, to have with high bending strength and bending modulus, low dielectric constant, high glass transition temperature The tendency that degree (high Tg), thermal expansion coefficient are low, thermal conductivity further increases.

(B) containing allyl compound can be used singly or in combination of two or more.Being applied in combination has 2 Kind or more reactive functional groups in addition to allyl containing in the case where allyl compound (B), it is anti-in addition to allyl Answering property functional group may be the same or different.Wherein, it is cyanogen that (B) containing allyl compound, which preferably comprises reactive functional groups, Perester radical is epoxy group containing allyl compound containing allyl compound and reactive functional groups.By being applied in combination in this way (B) containing allyl compound, to there is bending strength, bending modulus, glass transition temperature (Tg), thermal conductivity further to mention High tendency.

Among above-mentioned, as containing allyl compound (B), it is preferable to use having reactive functional groups in addition to allyl Replace nadikimide compound (E) containing allyl compound and/or aftermentioned alkenyl.Contain allyl by using such Based compound (B), to have the tendency that glass transition temperature (Tg), coefficient of thermal expansion, thermal conductivity improve.

In addition, particularly preferably using aftermentioned allyl phenol derivative (D) and/or alkene as (B) containing allyl compound Base replaces nadikimide compound (E).By using such (B) containing allyl compound, to there is glass transition The tendency that temperature (Tg), coefficient of thermal expansion, thermal conductivity further increase.

Content containing allyl compound (B) relative to 100 mass parts of resin solid content be preferably 1~90 mass parts, More preferably 10~80 mass parts, further preferably 20~75 mass parts, particularly preferably 25~40 mass parts.By making to contain The content of allyl compound (B) is in above range, thus the flexibility for the solidfied material having, bending strength, bending die The tendency that amount, glass transition temperature (Tg), coefficient of thermal expansion, thermal conductivity and peel strength of copper foil further increase.

(allyl phenol derivative (D))

As allyl phenol derivative (D), as long as there is the compound of allyl and phenolic hydroxyl group for Direct Bonding on aromatic rings And its derivative, there is no particular limitation, for example, the bis-phenol that the hydrogen atom that can enumerate aromatic rings is replaced by allyl, fragrance The hydrogen atom of ring is replaced by allyl and phenolic hydroxyl group is by other than hydroxyl-removal in the above-mentioned reactive functional groups in addition to allyl More specifically modified bisphenol compound made of reactive functional groups are modified can enumerate chemical combination shown in following formula (8) More specifically object can enumerate diallyl bisphenol, the cyanate esters of diallyl bisphenol, diallyl bisphenol Type ring oxide.

In formula (8), Ra each independently represents the reactive substituents in addition to allyl.

It as formula (8) compound represented, is not particularly limited, such as following formula (8a) compound represented can be enumerated And/or following formula (8b) compound represented.By using such allyl phenol derivative (D), to there is bending strength, curved The tendency that bent modulus, glass transition temperature (Tg), coefficient of thermal expansion, thermal conductivity, peel strength of copper foil further increase.

It as above-mentioned bis-phenol, is not particularly limited, for example, bisphenol-A, bisphenol-ap, bisphenol AF, bisphenol b, bis-phenol can be enumerated BP, bisphenol-c, bisphenol-c, bis-phenol E, Bisphenol F, bis-phenol G, bis-phenol M, bisphenol S, bis-phenol P, bis-phenol PH, bis-phenol TMC, bisphenol Z.Wherein, It is preferred that bisphenol-A.

The group number of allyl in 1 molecule of allyl phenol derivative (D) is preferably 1~5, more preferably 2~4, into one Step preferably 2.In group number above range by making the allyl in 1 molecule of allyl phenol derivative (D), to have curved Qu Qiangdu, bending modulus, peel strength of copper foil, glass transition temperature (Tg) further increases, thermal expansion coefficient is low, thermal conductivity Excellent tendency.

The reactive functional groups number in addition to allyl in 1 molecule of allyl phenol derivative (D) is preferably 1~5, more excellent It is selected as 2~4, further preferably 2.By making the reactive official in addition to allyl in 1 molecule of allyl phenol derivative (D) Can roll into a ball number be above range in, thus have bending strength, bending modulus, peel strength of copper foil, glass transition temperature (Tg) into The raising of one step, the tendency that thermal expansion coefficient is low, thermal conductivity is excellent.

The suitable range of the content of allyl phenol derivative (D) is based on the above-mentioned content containing allyl compound (B).

(alkenyl replaces nadikimide compound (E))

Alkenyl replaces nadikimide compound (E) as long as in molecule to there is 1 or more alkenyl to replace nadik acyl The compound of imido grpup, is just not particularly limited.Wherein, preferred following formula (9) compound represented.By using such alkene Base replaces nadikimide compound (E), so that the coefficient of thermal expansion for the solidfied material having further decreases, heat resistance is into one Walk the tendency improved.

In formula (9), R₁Each independently represent the alkyl of hydrogen atom or carbon number 1~6, R₂Indicate the alkylene of carbon number 1~6 Group shown in base, phenylene, biphenylene, naphthylene or following formula (10) or (11).

In formula (10), R₃Indicate methylene, isopropylidene or CO, O, S or SO₂Shown in substituent group.

In formula (11), R₄Each independently represent the alkylidene of carbon number 1~4 or the ring alkylidene of carbon number 5~8.

In addition, alkenyl replaces nadikimide compound (E) to be more preferably shown in following formula (12) and/or (13) Compound.Nadikimide compound (E) is replaced by using such alkenyl, so that the heat for the solidfied material having is swollen The tendency that swollen rate further decreases, heat resistance further increases.

Alkenyl replaces nadikimide compound (E) that commercially available substance also can be used.As commercially available substance, do not have It is particularly limited to, such as BANI-M (Maruzen Petrochemical Co., Ltd.'s system, formula (12) compound represented), BANI-X can be enumerated (Maruzen Petrochemical Co., Ltd.'s system, formula (13) compound represented) etc..These can be used a kind or be applied in combination 2 kinds with On.

Alkenyl replace nadikimide compound (E) content be preferably relative to 100 mass parts of resin solid content 20~50 mass parts, further preferably 20~35 mass parts.In addition, further more preferably allyl phenol derivative (D) and Alkenyl replace total content of nadikimide compound (E) relative to 100 mass parts of resin solid content be preferably 20~ 50 mass parts are even more preferably 35~45 mass parts.By making alkenyl replace the content of nadikimide compound (E) For in above range, so that the coefficient of thermal expansion for the solidfied material having the tendency that further decreases, heat resistance further increases.

(epoxy resin (C) comprising bisphenol A-type structural unit and hydrocarbon system structural unit)

Epoxy resin (C) comprising bisphenol A-type structural unit and hydrocarbon system structural unit is as long as to have 1 or more in molecule The compound of bisphenol A-type structural unit and 1 or more hydrocarbon system structural unit, is just not particularly limited.Wherein, preferred following formula (14) compound represented.By using such epoxy resin comprising bisphenol A-type structural unit and hydrocarbon system structural unit (C), so that the storage modulus E ' when the heating for the solidfied material having the tendency that, which becomes, is suitable for the value that warpage inhibits.

Herein, in formula (14), R₁And R₂Each independently represent hydrogen atom or methyl, R₃~R₆Each independently represent hydrogen Atom, methyl, chlorine atom or bromine atom, X indicate ethyleneoxy group ethyl, two (ethyleneoxy group) ethyls, three (ethylidene oxygen Base) ethyl, propylidene oxygroup propyl, two (propylidene oxygroup) propyl, three (propylidene oxygroup) propyl or carbon number 2~15 Asia Alkyl, n indicate natural number.

Commercially available object also can be used in the above-mentioned epoxy resin (C) comprising bisphenol A-type structural unit and hydrocarbon system structural unit Matter.It as commercially available substance, is not particularly limited, such as EPICLON EXA-4850-150 (Dainippon Ink Chemicals can be enumerated System, the compound with structure shown in formula (14)), (X in Dainippon Ink Chemicals's system, formula (14) is EPICLON EXA-4816 The compound of ethylidene) etc..These can be used a kind or two or more be applied in combination.

The content of epoxy resin (C) comprising bisphenol A-type structural unit and hydrocarbon system structural unit relative to resin solid at Dividing 100 mass parts is preferably 5~25 mass parts, more preferably 5~20 mass parts, further preferably 10~20 mass parts.It is logical It crosses in the content above range for making the epoxy resin (C) comprising bisphenol A-type structural unit and hydrocarbon system structural unit, to have Storage modulus E ' when the heating of the solidfied material arrived becomes the tendency for being suitable for inhibiting the value of warpage.

(cyanate esters (F))

The resin combination of present embodiment can also contain cyanate esters (F).As cyanate esters (F), As long as the cyanate esters in addition to above-mentioned allyl phenol derivative (D), there is no particular limitation, can for example enumerate down State phenolic varnish type cyanate, biphenyl aralkyl shown in naphthols aralkyl-type cyanate, following formula (16) shown in formula (15) Type cyanate, bis- (3,5- dimethyl -4- cyanatophenyl) methane, bis- (4- cyanatophenyl) methane, 1,3- -bis-cyanato benzene, 1,4- -bis-cyanato benzene, 1,3,5- tri-cyanato benzene, 1,3- dicyan acyl-naphthaline, 1,4- dicyan acyl-naphthaline, 1,6- dicyan acyl-naphthaline, 1,8- dicyan acyl-naphthaline, 2,6- dicyan acyl-naphthaline, 2,7- dicyan acyl-naphthaline, 1,3,6- tri-cyanato naphthalene, 4,4 '-two cyanatos connection Benzene, bis- (4- cyanatophenyl) ethers, bis- (4- cyanatophenyl) thioethers, bis- (4- cyanatophenyl) sulfones and 2,2 '-bis- (4- cyanogen Aminosulfonylphenyl) propane；The prepolymer etc. of these cyanates.These cyanate esters (F) can be used alone, can also be with Two or more is applied in combination.

In formula (15), R₆Hydrogen atom or methyl are each independently represented, wherein it is preferred that hydrogen atom.In addition, in formula (15), n₂ Indicate 1 or more integer.n₂Upper limit value be usually 10, preferably 6.

In formula (16), R₇Hydrogen atom or methyl are each independently represented, wherein it is preferred that hydrogen atom.In addition, in formula (16), n₃ Indicate 1 or more integer.n₃Upper limit value be usually 10, preferably 7.

In these, cyanate esters (F) preferably comprise select naphthols aralkyl-type cyanate shown in free style (15), One or more of the group of phenolic varnish type cyanate shown in formula (16) and biphenyl aralkyl-type cyanate composition, is more preferably wrapped Containing the group for selecting phenolic varnish type cyanate shown in naphthols aralkyl-type cyanate shown in free style (15) and formula (16) to form One or more of.By using such cyanate esters (F), thus obtain anti-flammability is more excellent, curability is higher, And the tendency of the lower solidfied material of thermal expansion coefficient.

It as the manufacturing method of these cyanate esters (F), is not particularly limited, can be used as cyanate chemical combination Method well known to the synthetic method of object.As well known method, be not particularly limited, such as can enumerate: make phenolic resin with The method that cyanogen halides reacts in the presence of alkali compounds in nonactive organic solvent；Phenolic aldehyde is formed in the solution containing water The salt of resin and alkali compounds, the method that the salt made thereafter carries out 2 phase system interfacial reactions with cyanogen halides.

For becoming the phenolic resin of the raw material of these cyanate esters (F), it is not particularly limited, for example, can enumerate Naphthols aralkyl-type phenol resin, novolak phenolics shown in following formula (17), biphenyl aralkyl type phenol tree out Rouge.

In formula (17), R₈Hydrogen atom or methyl are each independently represented, wherein it is preferred that hydrogen atom.In addition, in formula (17), n₄ Indicate 1 or more integer.n₄Upper limit value be usually 10, preferably 6.

Naphthols aralkyl-type phenol resin shown in formula (17) can be such that naphthols aralkyl resin is condensed with cyanic acid to obtain. It as naphthols aralkyl-type phenol resin, is not particularly limited, such as can enumerate through aphthols such as alpha-Naphthol and betanaphthols With terephthaldehyde's base glycol, α, the reaction of the benzene class such as α '-dimethoxy paraxylene and 1,4- bis- (2- hydroxyl -2- propyl) benzene And it obtains.Naphthols aralkyl-type cyanate can selected from making the naphthols aralkyl resin that obtains as described above and cyanic acid condensation and Obtained substance.

The content of cyanate esters (F) relative to 100 mass parts of resin solid content be preferably 0.5~45 mass parts, It is even more preferably 10~45 mass parts, more preferably 15~45 mass parts, further preferably 20~35 mass parts.Pass through Make in the content above range of cyanate esters, so that the heat resistance for the solidfied material having and chemical resistance are into one Walk the tendency improved.

(epoxide (G))

The resin combination of present embodiment can include also bisphenol A-type structural unit and hydrocarbon system structure list containing removing above-mentioned Epoxide (G) other than the epoxy resin (C) of member.As the epoxide (G), as long as except aforementioned epoxy resins (C) other than, in 1 molecule with 2 or more epoxy groups compound, there is no particular limitation, for example, bisphenol-A can be enumerated Type epoxy resin, bisphenol E-type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak-type epoxy Resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type asphalt mixtures modified by epoxy resin Rouge, anthracene type epoxy resin, 3 function phenol-type epoxy resins, 4 function phenol-type epoxy resins, glycidyl ester type epoxy resin, phenol Aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, aralkyl phenolic resin varnish type epoxy resin, naphthols aralkyl type ring Oxygen resin, dicyclopentadiene-type epoxy resin, polyol type epoxy resin, containing the epoxy resin of isocyanurate ring or these Halide.It should be noted that epoxide (G) is tool in the case where having epoxy group containing allyl compound (B) There is the compound of epoxy group contained other than allyl compound (B).

The content of epoxide (G) is preferably 2.5~30 mass parts, more relative to 100 mass parts of resin solid content Preferably 5.0~27.5 mass parts, further preferably 7.5~25 mass parts.In content by making epoxide (G) State in range, thus the flexibility for the solidfied material having, peel strength of copper foil, chemical resistance and resistance to de-smear into The tendency that one step improves.

(packing material (H))

The resin combination of present embodiment can also contain packing material (H).As packing material (H), without special It limits, such as inorganic filling material and organic filler material can be enumerated, preferably comprise the inorganic filling material in the two, suitably Be that organic filler material is used together with inorganic filling material.It as inorganic filling material, is not particularly limited, such as can arrange Enumerate native silicon dioxide, fused silica, synthetic silica, amorphous silica, AEROSIL, hollow titanium dioxide Silicon etc. is silica-based；The silicon compounds such as white carbon black；The metal oxides such as titanium white, zinc oxide, magnesia, zirconium oxide；Boron nitride, Assemble the metal nitrides such as boron nitride, silicon nitride, aluminium nitride；The metal sulfates compound such as barium sulfate；Aluminium hydroxide, aluminium hydroxide add Heat treatment product (aluminium hydroxide being heated, substance made of a part of the crystallization water is reduced), boehmite, hydroxide The metal hydrates such as magnesium；The molybdenum compounds such as molybdenum oxide, zinc molybdate；The zinc compounds such as zinc borate, zinc stannate；Aluminium oxide, clay, height Ridge soil, talcum, calcined clay, roasting kaolin, fired talc, mica, E- glass, A- glass, NE- glass, C- glass, L- glass Glass, D- glass, S- glass, M- glass G20, staple glass fibre (include the glass such as E glass, T glass, D glass, S glass, Q glass Micropowder class.), hollow glass, globular glass etc..In addition, being not particularly limited as organic filler material, such as can enumerate The rubber powders such as styrene type powder, butadiene-type powder, acrylic type powder out；Nucleocapsid type rubber powder；Organic siliconresin Powder；Silicone rubber powder；Organosilicon composite powder etc..Packing material (H) can be used alone, and can also combine makes Use two or more.

Wherein, preferably comprise selected from by as the silica of inorganic filling material, aluminium oxide, magnesia, aluminium hydroxide, Boehmite, boron nitride, aggregation boron nitride, silicon nitride and aluminium nitride composition group in it is at least one kind of, more preferably comprising selected from by It is at least one kind of in the group of silica, aluminium oxide and boehmite composition.By using such packing material (H), to have The tendency that the high rigidity of obtained solidfied material, low warpage further increase.

The content of packing material (H) (special inorganic filling material) is preferably relative to 100 mass parts of resin solid content 100~700 mass parts, more preferably 100~450 mass parts, further preferably 120~250 mass parts.By making to fill material The content for expecting (H) is in above range, thus inclining of further increasing of the high rigidity for the solidfied material having, low warpage To.

(silane coupling agent and Ricinate)

The resin combination of present embodiment can also contain silane coupling agent, Ricinate.By the inclusion of silane idol Join agent, Ricinate, to have the dispersibility of above-mentioned packing material (H), resin component, packing material (H) and aftermentioned base The tendency that the adhesive strength of material further increases.

As silane coupling agent, as long as being silane coupling agent used in the surface treatment of usual inorganic matter, without spy It does not limit, for example, γ aminopropyltriethoxy silane, N- β-(amino-ethyl)-gamma-amino propyl trimethoxy can be enumerated The amino silanes based compound such as base silane；The epoxy silanes based compound such as γ-glycidoxypropyltrime,hoxysilane；γ- The acrylic-silanes based compound such as acryloyloxypropyltrimethoxysilane；N- β-(N- vinylbenzylaminoethyl)- The cationic silicons methane series compound such as gamma-amino propyl trimethoxy silicane hydrochloride；Phenyl silane based compound etc..Silane is even Connection agent can be used singly or in combination of two or more.

As Ricinate, as long as dispersion stabilizer used in coating use, there is no particular limitation, for example, can Enumerate DISPERBYK-110,111,118,180,161, BYK-W996, W9010, W903 etc. of BYK Japan KK.

(other resins etc.)

The resin combination of present embodiment as needed can also containing except it is above-mentioned contain allyl compound (B) in addition to , selected from by containing allyl compound (hereinafter also referred to " other contain allyl compound "), phenolic resin, oxetanes tree It is one kind or two or more in the group of rouge, benzoxazine compound and the compound composition with polymerizable unsaturated group.It is logical It crosses comprising other such resins etc., thus the peel strength of copper foil for the solidfied material having, bending strength and bending modulus etc. The tendency further increased.

(other contain allyl compound)

As other contain allyl compound, be not particularly limited, for example, can enumerate allyl chloride, allyl acetate, Allyl ether, propylene, triallylcyanurate, Triallyl isocyanurate, diallyl phthalate, isophthalic diformazan Diallyl phthalate, diallyl maleate etc..

Other contents containing allyl compound relative to 100 mass parts of resin solid content be preferably 0~50 mass parts, It is even more preferably 10~45 mass parts, more preferably 15~45 mass parts, further preferably 20~35 mass parts.Pass through Make in other content above ranges containing allyl compound, thus the bending strength for the solidfied material having, bending modulus, The tendency that heat resistance, chemical resistance further increase.

(phenolic resin)

As phenolic resin, as long as to have the phenolic resin of 2 or more hydroxyls in 1 molecule, so that it may using usually public The substance known, type are not particularly limited.As its concrete example, bisphenol A type phenolic resin, bisphenol E-type phenolic aldehyde can be enumerated Resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol resol resins, bisphenol A novolac type phenolic aldehyde tree Rouge, glycidyl ester type phenolic resin, aralkyl novolak phenolics, biphenyl aralkyl-type phenol resin, cresols phenol Novolac type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac varnish gum, multifunctional naphthol resin, anthracene type Phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthols aralkyl type phenol tree Rouge, dicyclopentadiene type phenol resin, biphenyl type phenolic resin, ester ring type phenolic resin, polyol type phenolic resin, phosphorous phenol Urea formaldehyde, hydroxyl organic siliconresin class etc., are not particularly limited.These phenolic resin, which can be used alone or combine, to be made Use two or more.By the inclusion of such phenolic resin, incline so that the cementability for the solidfied material having, flexibility etc. are superior To.

The content of phenolic resin is preferably 0~99 mass parts, more preferably 1 relative to 100 mass parts of resin solid content ~90 mass parts, further preferably 3~80 mass parts.In content above range by making phenolic resin, to have The further more excellent tendency such as cementability, the flexibility of the solidfied material arrived.

(oxetane resin)

As oxetane resin, generally well-known substance can be used, type is not particularly limited.As its tool Body example can enumerate oxetanes, 2- methy oxetane, 2,2- dimethyl oxygen azetidine, 3- methyl oxa- ring fourth The alkyl oxetanes such as alkane, 3,3- dimethyl oxygen azetidine, 3- methyl -3- methoxy oxetanes, 3,3 '-two Bis- (chloromethyl) oxetanes of (trifluoromethyl) perfluor oxetanes, 2- chloromethyl oxetanes, 3,3-, biphenyl type oxygen Azetidine, OXT-101 (East Asia synthesizes trade name processed), OXT-121 (East Asia synthesizes trade name processed) etc..These oxetanes Resin can be used a kind or two or more be applied in combination.By the inclusion of such oxetane resin, so that is had consolidates The more excellent tendencys such as cementability, the flexibility of compound.

The content of oxetane resin relative to 100 mass parts of resin solid content is preferably 0~99 mass parts, more excellent It is selected as 1~90 mass parts, further preferably 3~80 mass parts.By the content above range for making oxetane resin It is interior, thus the further more excellent tendency such as the adaptation for the solidfied material having, flexibility.

(benzoxazine compound)

As benzoxazine compound, as long as to have the compound of 2 or more dihydrobenzo oxazines rings in 1 molecule, Generally well-known compound can be used, type is not particularly limited.As its concrete example, bisphenol A-type benzo can be enumerated Oxazines BA-BXZ (small westernization length of schooling trade name), bisphenol-f type benzoxazine BF-BXZ (small westernization length of schooling trade name), bisphenol S type Benzoxazine BS-BXZ (small westernization length of schooling trade name) etc..These benzoxazine compounds can be used a kind or be used in mixed way 2 kinds More than.By the inclusion of such benzoxazine compound, thus the anti-flammability for the solidfied material having, heat resistance, low water absorbable, The more excellent tendencys such as low-k.

The content of benzoxazine compound relative to 100 mass parts of resin solid content is preferably 0~99 mass parts, more excellent It is selected as 1~90 mass parts, further preferably 3~80 mass parts.By the content above range for making benzoxazine compound It is interior, thus the further more excellent tendency such as heat resistance for the solidfied material having.

(compound with polymerizable unsaturated group)

As the compound with polymerizable unsaturated group, generally well-known substance can be used, type does not have It is particularly limited to.As its concrete example, the ethylene such as ethylene, propylene, styrene, divinylbenzene, divinyl biphenyls can be enumerated Based compound；(methyl) methyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, poly- third Glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid (methyl) third of 1 yuan of ester, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc. or polyalcohol Olefin(e) acid esters；Epoxies (methyl) propylene such as bisphenol type epoxy (methyl) acrylate, bisphenol F type epoxy (methyl) acrylate Esters of gallic acid；Benzocyclobutane olefine resin；(double) maleimide resin etc..These compounds with unsaturated group can be used It a kind or is mixed with two or more.By the inclusion of such compound with polymerizable unsaturated group, to obtain The more excellent tendencys such as heat resistance, the toughness of solidfied material.

The content of compound with polymerizable unsaturated group is preferably relative to 100 mass parts of resin solid content 0~99 mass parts, more preferably 1~90 mass parts, further preferably 3~80 mass parts.By make to have it is polymerizable not The content of the compound of saturated group is in above range, so that the heat resistance for the solidfied material having, toughness etc. are further more Excellent tendency.

(curing accelerator)

The resin combination of present embodiment can also contain curing accelerator.As curing accelerator, do not limit especially It is fixed, such as the imidazoles such as triphenylimidazolyl can be enumerated；Benzoyl peroxide, lauroyl peroxide, acetyl peroxide, peroxidating To organic peroxides such as chlorobenzoyl, diperoxy phthalic acid di tert butyl carbonates；The azo-compounds such as the double nitriles of azo；N, N- bis- Methylbenzyl amine, N, accelerine, N, N- dimethyl toluidine, N, N- lutidines, 2-N- ethylo benzene aminoethanol, The uncles such as tri-n-butyl amine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethyl butane diamine, N- methyl piperidine Amine；The phenols such as phenol, xylenol, cresols, resorcinol, catechol；Lead naphthenate, lead stearate, zinc naphthenate, octanoic acid The organic metal salts such as zinc, oleic acid tin, dibutyitin maleate, manganese naphthenate, cobalt naphthenate, ferric acetyl acetonade；Keep these organic Dissolving metal salts in hydroxy-containing compounds such as phenol, bis-phenols and winner；The inorganic metal salts such as stannic chloride, zinc chloride, aluminium chloride；Two Organo-tin compounds such as octyl tin oxide, other tin alkyls, alkyl-tin oxide etc..In these, triphenylimidazolyl has promotion solid The excellent tendency of change reaction, glass transition temperature (Tg), coefficient of thermal expansion, therefore particularly preferably.

(solvent)

The resin combination of present embodiment can also contain solvent.By the inclusion of solvent, to there is resin combination The tendency that viscosity decline when preparation, treatability are further increased and further increased to the infiltration of aftermentioned substrate.

As solvent, as long as part or all of the resin component in resin combination can be dissolved, without special It limits, such as the ketones such as acetone, methyl ethyl ketone, methyl cellosolve can be enumerated；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；Dimethyl The amides such as formamide；Propylene glycol monomethyl ether and its acetic acid esters etc..Solvent can be used alone, and can also be applied in combination 2 kinds More than.

(manufacturing method of resin combination)

The manufacturing method of the resin combination of present embodiment is not particularly limited, for example, can enumerate by each ingredient according to It is secondary to be compounded the method into solvent and being sufficiently stirred.At this point, can be stirred to make each ingredient equably dissolve or disperse It mixes, mix, processing well known to mixing process etc..Specifically, by using the stirring with stirring capacity appropriate is attached to The stirred tank of machine is stirred decentralized processing, can be improved dispersibility of the packing material (H) in resin combination.It is above-mentioned to stir It mixes, mix, ball mill can be used for example in mixing process, the device or revolution or rotation type for the purpose of mixing such as ball mill Mixing arrangement etc. well known to device being suitable for progress.

In addition, organic solvent can be used as needed when the preparation of the resin combination of present embodiment.For organic The type of solvent is not particularly limited as long as can dissolve the resin in resin combination.Its concrete example is for example above-mentioned.

(purposes)

Present embodiment meets the relevant physical property ginseng of mechanical property shown in formula (1)~(5), preferred formula (1A)~(5A) The prepreg of several numberical ranges can function properly as insulating layer, plywood, clad with metal foil plywood, printed circuit board or Multilayer board.Hereinafter, (including multilayer board to plywood, clad with metal foil plywood and printed circuit board.) It is illustrated.

(plywood and clad with metal foil plywood)

The plywood of present embodiment has the above-mentioned prepreg of at least 1 or more the present embodiment being laminated.In addition, this The clad with metal foil plywood of embodiment has plywood (i.e. at least 1 or more the present embodiment being laminated of present embodiment Above-mentioned prepreg) and be configured at its plywood one or two sides metal foil (conductor layer).Meet formula by using above-mentioned (1) number of the relevant physical parameter of mechanical property (storage modulus and loss modulus) shown in~(5), preferred formula (1A)~(5A) It is worth the prepreg of range, there is no specific glass transitions so that the plywood of present embodiment and clad with metal foil plywood have Temperature (no Tg) and the tendency that can sufficiently reduce warpage (reaching low warpage).

Conductor layer can be using metal foils such as copper, aluminium.As long as metal foil used herein is to make in printed circuit board material Substance, there is no particular limitation, copper foil well known to preferred rolled copper foil, electrolytic copper foil etc..In addition, the thickness of conductor layer does not have It is particularly limited to, preferably 1~70 μm, more preferably 1.5~35 μm.

Plywood, the manufacturing process of clad with metal foil plywood and its molding condition are not particularly limited, can be using usual Printed circuit board plywood and multiple-plate method and condition.For example, when the forming of plywood or clad with metal foil plywood Multistage press, multi-stage vacuum press, progressive forming machine, autoclave forming machine etc. can be used.In addition, plywood or covering gold In the forming (cascading into shape) for belonging to layers of foil lamination, usually temperature is 100~300 DEG C, pressure is 2~100kgf/cm of face pressure²、 The range that heating time is 0.05~5 hour.In turn, as needed, can also 150~300 DEG C at a temperature of carry out after it is solid Change.In the case where especially with multistage press, from the viewpoint of the solidification for sufficiently promoting prepreg, preferable temperature 200 DEG C~250 DEG C, 10~40kgf/cm of pressure², heating time 80 minutes~130 minutes, 215 DEG C~235 DEG C of more preferable temperature, pressure 25~35kgf/cm of power², heating time 90 minutes~120 minutes.In addition, in by by above-mentioned prepreg and separately making The wiring plate group merging of layer is cascading into shape, and multi-layer board can also be made.

(printed circuit board)

The printed circuit board of present embodiment is the print with insulating layer He the conductor layer on the surface for being formed in the insulating layer Printed circuit board, insulating layer include above-mentioned prepreg.For example, forming rule by the clad with metal foil plywood in above-mentioned present embodiment Fixed wiring pattern, so as to function properly as printed circuit board.As described above, the clad with metal foil plywood of present embodiment Have the tendency that there is no specific glass transition temperature (no Tg) and can sufficiently reduce warpage (reaching low warpage), because This can especially be effective as that the printed circuit board of such performance is required to use.

The printed circuit board of present embodiment specifically can for example be manufactured by the following method.Firstly, preparing Above-mentioned clad with metal foil plywood (copper-clad laminated board etc.).Etching process is implemented to the surface of clad with metal foil plywood and is carried out interior The formation of layer circuit, makes internal substrate.The internal layer circuit surface of the internal substrate is carried out as needed for improving bonding The surface treatment of intensity, then, the above-mentioned prepreg of number needed for being overlapped on the internal layer circuit surface, and then be laminated on the outside The metal foil of outer circuit, heating are pressurizeed and are carried out integrally formed (cascading into shape).In this way, manufacture is in internal layer circuit and outer layer The plywood of the multilayer of insulating layer is formed between the metal foil of circuit, the insulating layer includes substrate and heat-curing resin The solidfied material of composition.Method and its molding condition cascading into shape is same as above-mentioned plywood or clad with metal foil plywood. Then, after the drilling processing for implementing through-hole, via hole to the plywood of the multilayer, in order to be originated from contained in solidified material layer The residue and glue residue of the resin of resin component remove, and carry out de-smear processing.Thereafter the wall surface formation in the hole makes internal layer circuit The plating metal epithelium be connected with the metal foil of outer circuit, and then the shape to the metal foil of outer circuit implementation etching process At outer circuit, printed circuit board is manufactured.

Should in the case where, (substrate and be impregnated in above-mentioned resin combination therein) is constituted exhausted for example, above-mentioned prepreg Edge layer.

In addition, without using in the case where clad with metal foil plywood the conductor as circuit can be formed in above-mentioned prepreg Layer and make printed circuit board.At this point, the method that chemical plating also can be used in the formation of conductor layer.

In turn, the printed circuit board of present embodiment is as shown in Figure 9, it is proper that: there are multiple insulating layers and multiple lead Body layer, the multiple insulating layer includes: the 1st insulating layer (1) that the above-mentioned prepreg being laminated by least 1 or more is formed and The above-mentioned prepreg that the single side direction (illustrating following direction) of 1st insulating layer (1) is laminated by least 1 or more formed the 2nd Insulating layer (2), the multiple conductor layer includes: the 1st conductor layer being configured between each layer of the multiple insulating layer (1,2) (3) and it is configured at outermost 2nd conductor layer (3) of the multiple insulating layer (1,2).The opinion of people etc. is true according to the present invention Accept: common plywood is for example by being laminated another prepreg in the two sides direction of the prepreg as a core substrate come shape At multilayer board, and the prepreg of present embodiment passes through to only in a prepreg of the 1st insulating layer (1) of formation Single side direction be laminated to form another prepreg of the 2nd insulating layer (2) the coreless type that manufactures multilayer board (multilayer without Core substrate) it is particularly effective.

In other words, the prepreg and resin combination of present embodiment can be effective in the case where being used for printed circuit board Ground reduces its amount of warpage, though it is not particularly limited, it is especially effective to multilayered coreless substrate in printed circuit board.That is, common Printed circuit board usually becomes two sides and symmetrically constitutes therefore have the tendency that being not easy warpage, and multilayered coreless substrate easily becomes two The asymmetrical composition in face, therefore have the tendency that easy warpage compared with common printed circuit board.Therefore, by using this implementation The prepreg and resin combination of mode can particularly effectively reduce the multilayered coreless substrate with easy warpage Amount of warpage.

The composition of 2 the 2nd insulating layers (2) is laminated in 1 the 1st insulating layer (1) it should be noted that showing in Fig. 9 (that is, composition that multiple insulating layers are 3 layers), but the 2nd insulating layer (2) can be 1 or 2 or more.Therefore, it the 1st leads Body layer (3) can be 1 layer or 2 layers or more.

In this way, for meet mechanical property shown in above-mentioned formula (1)~(5), preferred formula (1A)~(5A) (storage modulus and Loss modulus) relevant physical parameter numberical range prepreg, the printed circuit of the present embodiment with above-mentioned composition Plate, special multilayered coreless substrate, which are not present specific glass transition temperature (no Tg) and can sufficiently reduce warpage, (to be reached Low warpage), therefore can especially be effective as semiconductor package type printed circuit board and the use of multilayered coreless substrate.

Embodiment

Hereinafter, with Examples and Comparative Examples, more specifically the present invention will be described.But the present invention is not by reality below Apply any restriction of example.

The synthesis of (synthesis example 1) alpha-Naphthol aralkyl-type cyanate esters (SN495VCN)

Make alpha-Naphthol aralkyl resin (SN495V, OH base equivalent: 236g/eq., Nippon Steel's chemistry strain formula in reactor Commercial firm's system: the number of repeat unit n comprising naphthols aralkyl is 1~5.) 0.47 mole (conversion of OH base) be dissolved in chloroform 500ml adds 0.7 mole of triethylamine into the solution.It was dripped into reactor with 1.5 hours when temperature is remained -10 DEG C The chloroformic solution 300g for adding 0.93 mole of cyanogen chloride after completion of dropwise addition, stir within 30 minutes.Thereafter and then by 0.1 mole Triethylamine and the mixed solution of chloroform 30g be added drop-wise in reactor, carry out stirring in 30 minutes and reaction was completed.By the three of by-product The hydrochloride of ethamine in reaction solution after filtering, and after obtained filtrate is cleaned with 0.1N hydrochloric acid 500ml, repeats 4 with water 500ml Secondary cleaning.By it with after sodium sulphate drying, it is evaporated at 75 DEG C, and then carry out decompression degassing at 90 DEG C, thus obtains The alpha-Naphthol aralkyl-type cyanate esters (R in formula shown in the above-mentioned formula (15) of brown solid⁶All hydrogen atoms.). Obtained alpha-Naphthol aralkyl-type cyanate esters are analyzed with infrared absorption spectrum, as a result in 2264cm^-1Nearby really Recognize the absorption of cyanic acid ester group.

(embodiment 1)

By maleimide compound (A) (BMI-2300, Daiwa Kasei Industry Co., Ltd.'s system, maleimide amine equivalent 186g/eq.) 45 mass parts, for containing in allyl compound (B) alkenyl replace nadikimide compound (E) (BANI- M, Maruzen Petrochemical Co., Ltd.'s system, allyl equivalent: 286g/eq.) 34 mass parts, include bisphenol A-type structural unit and hydrocarbon The epoxy resin (C) (EPICLONEXA-4850-150, Dainippon Ink Chemicals's system, epoxide equivalent: 450g/eq.) of architecture unit 10 mass parts, as cyanate esters (F) synthesis example 1 alpha-Naphthol aralkyl-type cyanate esters (SN495VCN, cyanogen Acid esters equivalent: 261g/eq.) 1 mass parts, epoxide (G) (work as by NC-3000FH, Nippon Kayaku K. K's system, epoxy Amount: 320g/eq.) 10 mass parts, slurry silica (SC-2050MB, Admatechs as packing material (H) Company Limited system) 120 mass parts and as packing material (H) organosilicon composite powder (KMP-600, SHIN-ETSU HANTOTAI chemistry Industrial Co., Ltd's system) 20 mass parts, silane coupling agent (Z-6040, Dow Corning Toray Co., Ltd. system) 5 mass Part, Ricinate (DISPERBYK-161, BYK Japan KK system) 1 mass parts and the triphenyl as curing accelerator Imidazoles (Wako Pure Chemical Industries, Ltd.'s system) 0.5 mass parts and zinc octoate (Japanese Chemical Industries strain as curing accelerator Formula commercial firm system) mixing of 0.1 mass parts, it is diluted with methyl ethyl ketone, thus obtains varnish.Varnish infiltration is coated on E glass Woven fabric (Co., Ltd. Makato Koito's system, IPC#2116) carries out 3 minutes heat dryings at 160 DEG C, obtains resin combination Content is the prepreg of 57 volume %.

(embodiment 2)

The infiltration of varnish obtained in embodiment 1 is coated on E glass woven fabric (Unitika Ltd. system, IPC#1030), 160 3 minutes heat dryings are carried out at DEG C, obtain the prepreg that resin composition content is 73 volume %.

(embodiment 3)

By 43 mass parts of maleimide compound (A) (BMI-2300), to take containing the alkenyl in allyl compound (B) For 32 mass parts of nadikimide compound (E) (BANI-M), the ring comprising bisphenol A-type structural unit and hydrocarbon system structural unit Oxygen resin (C) (EPICLONEXA-4816, Dainippon Ink Chemicals's system, epoxide equivalent: 403g/eq.) 10 mass parts, as cyanate 5 mass parts of alpha-Naphthol aralkyl-type cyanate esters (SN495VCN) of the synthesis example 1 of compound (F), epoxide (G) (NC-3000FH, Nippon Kayaku K. K's system, epoxide equivalent: 320g/eq.) 10 mass parts, as the slurry of packing material (H) Expect silica (SC-2050MB) 100 mass parts, as packing material (H) slurry silica (SC-5050MOB, Admatechs Company Limited system) 100 mass parts and the organosilicon composite powder (KMP- as packing material (H) 600) 20 mass parts, 5 mass parts of silane coupling agent (Z-6040), Ricinate (DISPERBYK-111, BYK Japan KK System) 2 mass parts and 1 mass parts of Ricinate (DISPERBYK-161) and the triphenylimidazolyl as curing accelerator 0.5 mass parts and as curing accelerator 0.1 mass parts of zinc octoate mix, be diluted with methyl ethyl ketone, thus obtain varnish. Varnish infiltration is coated on E glass woven fabric (IPC#2116), 3 minutes heat dryings are carried out at 160 DEG C, obtain resin combination Object content is the prepreg of 57 volume %.

(embodiment 4)

The infiltration of varnish obtained in embodiment 3 is coated on E glass woven fabric (IPC#1030), is carried out 3 minutes at 160 DEG C Heat drying obtains the prepreg of 73 volume % of resin composition content.

(comparative example 1)

By 51 mass parts of maleimide compound (A) (BMI-2300), to take containing the alkenyl in allyl compound (B) For 38 mass parts of nadikimide compound (E) (BANI-M), as cyanate esters (F) synthesis example 1 alpha-Naphthol 1 mass parts of aralkyl-type cyanate esters (SN495VCN), 10 mass parts of epoxide (G) (NC-3000FH), as filling out Fill 120 mass parts of slurry silica (SC-2050MB) of material (H) and the organosilicon composite powder as packing material (H) (KMP-600) 20 mass parts, 5 mass parts of silane coupling agent (Z-6040), 1 mass parts of Ricinate (DISPERBYK-161), And 0.5 mass parts of triphenylimidazolyl as curing accelerator and 0.1 mass parts of zinc octoate as curing accelerator mix, It is diluted with methyl ethyl ketone, thus obtains varnish.Varnish infiltration is coated on E glass woven fabric (IPC#2116), at 160 DEG C 3 minutes heat dryings are carried out, the prepreg that resin composition content is 57 volume % is obtained.

(comparative example 2)

The infiltration of varnish obtained in comparative example 1 is coated on E glass woven fabric (IPC#1030), is carried out 3 minutes at 160 DEG C Heat drying obtains the prepreg of 73 volume % of resin composition content.

(comparative example 3)

By 49 mass parts of maleimide compound (A) (BMI-2300), to take containing the alkenyl in allyl compound (B) For 36 mass parts of nadikimide compound (E) (BANI-M), as cyanate esters (F) synthesis example 1 alpha-Naphthol 5 mass parts of aralkyl-type cyanate esters (SN495VCN), 10 mass parts of epoxide (G) (NC-3000FH), as filling out 100 mass parts of slurry silica (SC-2050MB) of filling material (H), the slurry silica (SC- as packing material (H) 5050MOB) 100 mass parts and 20 mass parts of organosilicon composite powder (KMP-600), silane coupled as packing material (H) 5 mass parts of agent (Z-6040), 2 mass parts of Ricinate (DISPERBYK-111) and Ricinate (DISPERBYK-161) 1 mass parts and 0.5 mass parts of triphenylimidazolyl as curing accelerator and 0.1 matter of zinc octoate as curing accelerator Part mixing is measured, is diluted with methyl ethyl ketone, thus obtains varnish.Varnish infiltration is coated on E glass woven fabric (IPC#2116), 3 minutes heat dryings are carried out at 160 DEG C, obtain the prepreg that resin composition content is 57 volume %.

(comparative example 4)

The infiltration of varnish obtained in comparative example 3 is coated on E glass woven fabric (IPC#1030), is carried out 3 minutes at 160 DEG C Heat drying obtains the prepreg that resin composition content is 73 volume %.

(comparative example 5)

By maleimide compound (BMI-70, big and chemical conversion Co. Ltd. system, maleimide amine equivalent: 221g/eq.) 15 mass parts, as cyanate esters (F) synthesis example 1 alpha-Naphthol aralkyl-type cyanate esters (SN495VCN) 35 Mass parts, 50 mass parts of epoxide (G) (NC-3000FH), the slurry silica (SC- as packing material (H) 2050MB) 100 mass parts, as 100 mass parts of slurry silica (SC-5050MOB) of packing material (H) and as filling 20 mass parts of organosilicon composite powder (KMP-600), 5 mass parts of silane coupling agent (Z-6040), Ricinate of material (H) (DISPERBYK-111) 2 mass parts and 1 mass parts of Ricinate (DISPERBYK-161) and as curing accelerator 0.5 mass parts of triphenylimidazolyl and as curing accelerator 0.1 mass parts of zinc octoate mix, be diluted with methyl ethyl ketone, by This obtains varnish.Varnish infiltration is coated on E glass woven fabric (IPC#2116), 3 minutes heat dryings are carried out at 160 DEG C, Obtain the prepreg that resin composition content is 57 volume %.

(comparative example 6)

The infiltration of varnish obtained in comparative example 5 is coated on E glass woven fabric (IPC#1030), is carried out 3 minutes at 160 DEG C Heat drying obtains the prepreg that resin composition content is 73 volume %.

(physical property measurement evaluation)

Using prepreg obtained in Examples 1 to 4 and comparative example 1~6, step system shown in projects below is utilized Be used as the sample of physical property evaluation of measuring, to mechanical property (storage modulus and loss modulus), formula (1)~(5) and formula (1A)~ The relevant physical parameter of mechanical property, glass transition temperature (Tg), amount of warpage (2 kinds) and Reflow Soldering process in (5A) Front-back baseboard shrinking percentage is measured evaluation.The result of embodiment is shown in table 1 together, the result of comparative example is shown in table together 2。

(mechanical property)

Upper and lower surface that the prepreg 1 obtained in Examples 1 to 4 and comparative example 1~6 is opened configuration copper foil (3EC-VLP, 12 μm of Mitsu Mining & Smelting Co., Ltd's system, thickness), with pressure 30kgf/cm², 230 DEG C of temperature be laminated within 100 minutes Shape (heat cure) obtains the copper foil covered lamination of defined thickness of insulating layer.Obtained copper foil covered lamination is cut into sawing After being cut into size 5.0mm × 20mm, the copper foil on surface is removed by etching, obtains test sample.Use the measurement sample Product (store up mechanical property by DMA method with dynamic viscoelastic analytical equipment (TA Instruments system) according to JIS C6481 Energy modulus E ' and loss modulus E ") it is measured (average value of n=3)

(glass transition temperature (Tg))

Upper and lower surface that the prepreg 1 obtained in Examples 1 to 4 and comparative example 1~6 is opened configuration copper foil (3EC-VLP, 12 μm of Mitsu Mining & Smelting Co., Ltd's system, thickness), with pressure 30kgf/cm², 230 DEG C of temperature be laminated within 100 minutes Shape (heat cure) obtains the copper foil covered lamination of defined thickness of insulating layer.Obtained copper foil covered lamination is cut into sawing After being cut into size 12.7mm × 2.5mm, the copper foil on surface is removed by etching, obtains test sample.It is used using the measurement Sample passes through DMA method to glass transition with dynamic viscoelastic analytical equipment (TA Instruments system) according to JIS C6481 Temperature (Tg) is measured (average value of n=3).

(amount of warpage: bimetal leaf method)

Firstly, the upper and lower surface configuration copper foil (3EC- that the prepreg 1 obtained in Examples 1 to 4 and comparative example 1~6 is opened VLP, Mitsu Mining & Smelting Co., Ltd's system, 12 μm of thickness), with pressure 30kgf/cm², 220 DEG C of temperature carry out 120 minutes layers Shape (heat cure) is built up, copper foil covered lamination is obtained.Then, above-mentioned copper foil is removed from obtained copper foil covered lamination.Then, Prepreg obtained in 1 Examples 1 to 4 and comparative example 1~6 is further configured in the single side for the plywood for eliminating copper foil, Two sides is descended to configure above-mentioned copper foil (3EC-VLP, Mitsu Mining & Smelting Co., Ltd's system, 12 μm of thickness), on it with pressure 30kgf/cm², 220 DEG C of temperature carry out 120 minutes (heat cure) cascading into shape, obtain copper foil covered lamination again.In turn, from Obtained copper foil covered lamination removes above-mentioned copper foil, obtains plywood.Then, from obtained plywood cut out 20mm × The strip board of 200mm, the face for the prepreg being laminated using the 2nd is as top, with the warpage at metal scale measurement strip direction both ends The maximum value of amount, using its average value as " amount of warpage " based on bimetal leaf method.

(amount of warpage: multilayered coreless substrate)

Firstly, as shown in Figure 1, two in the prepreg as supporter (a) configure facing towards prepreg side with carrier The carrier copper foil face of ultrathin copper foil (b1) (MT18Ex, Mitsu Mining & Smelting Co., Ltd's system, 5 μm of thickness), on it further Configure prepreg (c1) obtained in Examples 1 to 4 and comparative example 1~6, on it further configuration copper foil (d) (3EC-VLP, 12 μm of Mitsu Mining & Smelting Co., Ltd's system, thickness), with pressure 30kgf/cm², 220 DEG C of temperature be laminated within 120 minutes Shape obtains copper foil covered lamination shown in Fig. 2.

Then, to the above-mentioned copper foil (d) of obtained copper foil covered lamination shown in Fig. 2 for example as shown in Figure 3 with rule Fixed wiring pattern is etched and forms conductor layer (d ').Then, in the plywood shown in Fig. 3 for being formed with conductor layer (d ') Prepreg (c2) obtained in upper configuration Examples 1 to 4 as shown in Figure 4 and comparative example 1~6, on it further configuration Ultrathin copper foil (b2) (MT18Ex, Mitsu Mining & Smelting Co., Ltd's system, 5 μm of thickness) with carrier, with pressure 30kgf/cm²、 230 DEG C of temperature carry out 120 minutes cascading into shape, obtain copper foil covered lamination shown in fig. 5.

Then, in copper foil covered lamination shown in fig. 5, supporter (a) (cured supporter prepreg) will be configured at The ultrathin copper foil (b1) with carrier carrier copper foil and ultrathin copper foil remove, thus as shown in fig. 6, from supporter (a) by 2 Plywood removing, in turn, removes carrier copper foil from the ultrathin copper foil (b2) with carrier on the top of each plywood.It connects , the processing to being carried out on the upper and lower ultrathin copper foil of obtained each plywood using laser machine, as shown in fig. 7, passing through Electroless copper forms defined through-hole (v).As a result, for example as shown in figure 8, being etched with defined wiring pattern and being formed and led Body layer obtains the panel (size: 500mm × 400mm) of multilayered coreless substrate.Then, the 4 of the panel measured with metal scale The amount of warpage at a angle and total 8 positions of 4 side center portions, using its average value " sticking up as the panel of multilayered coreless substrate Song amount ".

(Reflow Soldering process front-back baseboard shrinking percentage)

Upper and lower surface that the prepreg 1 obtained in Examples 1 to 4 and comparative example 1~6 is opened configuration copper foil (3EC-VLP, 12 μm of Mitsu Mining & Smelting Co., Ltd's system, thickness), with pressure 30kgf/cm², 220 DEG C of temperature be laminated within 120 minutes Shape obtains copper foil covered lamination.Then, equably implement 9 points of brill with clathrate to obtained copper foil covered lamination with drill bit After hole machined, above-mentioned copper foil is removed.

Hereafter, firstly, measurement eliminate copper foil plywood hole between distance (distance a).Then, to its plywood, SALAMANDER reflow soldering apparatus is used to implement reflow process as maximum temperature for 260 DEG C.Thereafter, plywood is measured again Distance (distance b) between hole.Then, the distance a measured and distance b are brought into following formula (I)s, found out in reflow process The size changing rate of substrate, using its value as Reflow Soldering process front-back baseboard shrinking percentage.

((distance a)-(distance b))/distance a × 100 ... formula (I)

[table 1]

[table 2]

Industrial availability

The prepreg of present embodiment is as plywood, clad with metal foil plywood, printed circuit board or multilayer printed circuit The material of plate has industrial availability.It should be noted that the application is based on Japan filed on December 28th, 2016 Number of patent application 2016-255270 quotes its contents herein.

Claims

1. a kind of prepreg, contains: heat-curing resin, packing material and substrate,

Prepreg solidfied material obtained from heat cure under conditions of 230 DEG C and 100 minutes is set to meet following formula (1)~(5) Shown in the relevant physical parameter of mechanical property numberical range,

E’(200℃)/E’(30℃)≤0.90…(1)

E’(260℃)/E’(30℃)≤0.85…(2)

E’(330℃)/E’(30℃)≤0.80…(3)

E " max/E ' (30 DEG C)≤3.0% ... (4)

E " min/E ' (30 DEG C) >=0.5% ... (5)

In various, E ' indicate parantheses shown at a temperature of the solidfied material storage modulus, E " max indicate 30 DEG C~330 DEG C temperature range in the solidfied material loss modulus maximum value, E " min indicates in 30 DEG C~330 DEG C of temperature range The solidfied material loss modulus minimum value.

2. prepreg according to claim 1 also meets mechanical property shown in following formula (6A),

E’(30℃)≤30GPa…(6A)

In formula, E ' indicate parantheses shown at a temperature of the solidfied material storage modulus.

3. prepreg according to claim 1 or 2, wherein the substrate is glass baseplate.

4. prepreg according to claim 3, wherein the glass baseplate is by selected from by E glass, D glass, S glass, T The fiber of the glass of one or more of the group of glass, Q glass, L glass, NE glass and HME glass composition is constituted.

5. a kind of plywood has at least 1 or more the prepreg according to any one of claims 1 to 4 being laminated.

6. a kind of clad with metal foil plywood, includes

At least 1 or more the prepreg according to any one of claims 1 to 4 being laminated and

It is configured at the metal foil of the one or two sides of the prepreg.

7. a kind of printed circuit board, includes

The insulating layer that formed by prepreg according to any one of claims 1 to 4 and

It is formed in the conductor layer on the surface of the insulating layer.

8. a kind of multilayer board, with multiple insulating layers and multiple conductor layers,

The multiple insulating layer includes: the prepreg shape according to any one of claims 1 to 4 being laminated by least 1 or more At the 1st insulating layer and the single side direction of the 1st insulating layer by least 1 or more the Claims 1 to 4 being laminated appoint The 2nd insulating layer that prepreg described in one is formed,

The multiple conductor layer includes: the 1st conductor layer that is configured between each layer of the multiple insulating layer and being configured at described more 2nd conductor layer on the outermost surface of a insulating layer.