CN109415489A

CN109415489A - Resin combination, resin sheet, multilayer printed-wiring board and semiconductor device

Info

Publication number: CN109415489A
Application number: CN201780040121.0A
Authority: CN
Inventors: 喜多村慎也; 铃木卓也; 四家诚司
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2016-06-29
Filing date: 2017-05-12
Publication date: 2019-03-01
Anticipated expiration: 2037-05-12
Also published as: JP6939784B2; CN109415489B; KR20190022517A; WO2018003313A1; JPWO2018003313A1; TWI788292B; TW201821467A; KR102324899B1

Abstract

When providing for multilayer printed-wiring board, film property and excellent heat resistance, the excellent resin combination of plating adaptation, developability, the resin sheet with supporting mass, the multilayer printed-wiring board for having used them, semiconductor device are applied.A kind of resin combination contains dicyclopentadiene type epoxy resin (A), trigger for optical solidification (B) shown in following formula (1), following formula (2) compound represented (C) and the compound (D) with ethylenically unsaturated group being somebody's turn to do other than (C) ingredient.

Description

Resin combination, resin sheet, multilayer printed-wiring board and semiconductor device

Technical field

The present invention relates to resin combination, use its resin sheet, multilayer printed-wiring board and semiconductor device.

Background technique

By the miniaturization of multilayer printed-wiring board, densification, and by plywood used in multilayer printed-wiring board The research of slimming is prevailing.With slimming, insulating layer is also required to be thinned, seeks the resin sheet without containing glass cloth Material.The mainstream of resin combination as insulating layer material is thermosetting resin, is opened for what is be connected between insulating layer Hole usually passes through laser processing and carries out.In addition, for the resin sheet for having used thermosetting resin, as on the insulating layer The method for forming conductor circuit, usually forms the method for conductor circuit using copper facing.

On the other hand, the aperture carried out using laser processing, which is existed, forms the more high-density base board of hole count then process time The problems such as longer.Therefore, seek in recent years by using the resin combination for being solidified using light etc., being dissolved in development, it can Carry out the resin sheet of aperture processing together in developing procedure.In turn, in order to utilize copper facing to form conductor circuit on the insulating layer, Therefore it is required that copper facing adaptation will not remove conductor circuit for insulating layer height.

In resin combination used in this plywood, resin sheet, alkali development type is mainstream, in order to carry out Development, uses the acrylate containing anhydride group, carboxyl.Also, epoxy resin is used for copper facing adaptation.Such as patent A kind of hardening resin composition is described in document 1, it includes the resin containing carboxyl, inorganic filler, contains Malaysia acyl The heat curable component of group with imine moiety and compound with urethane bond, the resin containing carboxyl include to have phenol The resin containing carboxyl of Novolac skeleton.In addition, disclosing a kind of composition epoxy resin in patent document 2, contain ring Oxygen resin, curing agent, silica dioxide granule is surface-treated using silane coupling agent made of silica composition, be free of Have curing accelerator or relative to aforementioned epoxy resins and 100 parts by weight of the total of aforementioned curing agent with 3.5 parts by weight below Content contain curing accelerator, the average grain diameter of aforementioned silicas particle is 1 μm hereinafter, in aforementioned silicas ingredient The surface treatment amount B (g) of the aforementioned silane coupling agent of the every 1g of aforementioned silicas particle, relative to pass through formula (X) (C (g)/bis- Silicon oxide particle 1g=[specific surface area (the m of silica dioxide granule²/ g)/silane coupling agent minimum vertex-covering area (m²/g)]… Formula (X)) calculate the every 1g of silica dioxide granule value C (g) be in 10~80% in the range of.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2016-8267 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2011-174082 bulletin

Summary of the invention

Problems to be solved by the invention

But for having used the solidfied material of previous epoxy resin, it cannot get sufficient physical property, with high It is restricted in the formation of the high protective film of copper facing adaptation and interlayer insulating film while developability.

In addition, for the solidfied material obtained by the resin combination recorded in patent document 1, purposes is limited to printed wiring Etching resist, the welding resist of plate, although gold-plated patience is excellent, when being used as interlayer insulating film, copper facing adaptation It is insufficient.

For the solidfied material obtained by the resin combination recorded in patent document 2, although due to copper facing excellent adhesion, But aperture is limited to laser machine, therefore cannot disposably carry out aperture using developing procedure.

Therefore, the present invention in view of the above problems, when providing for multilayer printed-wiring board, applies film property and excellent heat resistance, Developability, the resin combination of copper facing excellent adhesion, the resin sheet with supporting mass, the multilayer printed circuit for having used them Plate, semiconductor device.

The solution to the problem

The inventors of the present invention's discovery, by using containing dicyclopentadiene type epoxy resin (A), light shown in following formula (1) Curing initiator (B), following formula (2) compound represented (C) and the change with ethylenically unsaturated group being somebody's turn to do other than (C) ingredient The resin combination for closing object (D), can solve the above problem, so as to complete the present invention.

(in formula (1), n indicates 0~15 integer.)

(in formula (2), multiple R₁Each independently represent hydrogen atom or methyl, multiple R₂Each independently represent hydrogen atom or The optionally alkyl of the carbon number 1~22 with substituent group, multiple R₃Each independently represent substituent group shown in following formula (3), under State substituent group or hydroxyl shown in formula (4).)

(in formula (4), R₄Indicate hydrogen atom or methyl.)

That is, the present invention includes content below.

[1] a kind of resin combination contains dicyclopentadiene type epoxy resin (A), photocuring shown in previously described formula (1) There is olefinic not other than initiator (B), previously described formula (2) compound represented (C) and previously described formula (2) compound represented (C) The compound (D) of saturated group.

[2] resin combination according to [1] also contains maleimide compound (E).

[3] resin combination according to [1] or [2] also contains filler (F).

[4] resin combination according to any one of [1]~[3] also contains selected from by cyanate esters, phenol Urea formaldehyde, oxetane resin, benzoxazine compound and with dicyclopentadiene type epoxy resin (A) shown in aforementioned (1) Any one above compound (G) in the group of different epoxy resin compositions.

[5] resin combination according to any one of [1]~[4], wherein previously described formula (2) compound represented (C) Acid value be 30mgKOH/g or more and 120mgKOH/g or less.

[6] resin combination according to any one of [1]~[5], wherein the content of ingredient (A) is relative to resin 100 mass parts of resin solid content in composition be 3 mass parts or more and 50 below the mass.

[7] resin combination according to any one of [1]~[6], wherein aforementioned with ethylenically unsaturated group Compound (D) is for the compound with (methyl) acryloyl group and/or with the compound of vinyl.

[8] resin combination according to [3], wherein aforementioned filler (F) is selected from by silica, boehmite, sulphur Sour barium, silicone powder, fluororesin system filler, polyurethane resin system filler, acrylic resin system filler, polyethylene-based filler, It is more than any one in the group of styrene butadiene ribber and silicon rubber composition.

[9] resin combination according to any one of [1]~[8], also contains thermosetting accelerator (H).

[10] resin combination according to any one of [1]~[9], also contains naphthalene type shown in following formula (5) Epoxy resin,

[11] resin combination according to any one of [1]~[10], wherein aforementioned trigger for optical solidification (B) contains There is phosphine oxide compound shown in following formula (6).

(in formula (6), R₅~R₁₀Each independently represent the alkyl of hydrogen atom or carbon number 1~4, R₁₁Indicate carbon number 1~20 The aryl of alkyl or carbon number 6~20.)

[12] a kind of resin sheet, with supporting mass and any one of [1]~[11] for being configured at the supporting mass surface The resin combination.

[13] a kind of multilayer printed-wiring board, with resin combination described in any one of [1]~[11].

[14] a kind of semiconductor device, with resin combination described in any one of [1]~[11].

The effect of invention

According to the present invention it is possible to provide plating adaptation, apply film property, heat resistance and developability it is excellent, have be suitable for multilayer The resin combination using active energy ray-curable of the physical property of printed wiring board, uses the resin sheet with supporting mass Their multilayer printed-wiring board, semiconductor device.

Specific embodiment

It is described in detail below for mode for carrying out the present invention (hereinafter referred to as " present embodiment ").It is below Present embodiment is for illustrating that illustration of the invention, objective not limit the invention to content below.The present invention is at it It can suitably deform in the range of purport to implement.

It should be noted that " (methyl) acryloyl group " in this specification refer to it is " acryloyl group " and corresponding Both " methylacryloyl ", " (methyl) acrylate " refers to " acrylate " and corresponding " methacrylic acid Both esters ", " (methyl) acrylic acid " refer to both " acrylic acid " and corresponding " methacrylic acid ".In addition, this In embodiment, " resin solid content " or " resin solid content in resin combination " then refers to unless otherwise specified It is the ingredient other than solvent and filler in resin combination, " 100 mass parts of resin solid content " refer to resin group That closes the ingredient other than solvent and filler in object adds up to 100 mass parts.

It is solid that the resin combination of present embodiment contains dicyclopentadiene type epoxy resin (A), light shown in previously described formula (1) Change the compound with ethylenically unsaturated group other than initiator (B), previously described formula (2) compound represented (C) and (C) ingredient (D).It is illustrated below for each ingredient.

Dicyclopentadiene type epoxy resin (A) used in present embodiment (also referred to as ingredient (A)) is with previously described formula (1) structure, compound with dicyclopentadiene skeleton.The solidfied material obtained containing the resin (A) has high development Copper facing adaptation high protective film and interlayer insulating film can be suitably formed while property.

In formula (1), n indicates 0~15 integer.From the viewpoint of developability, preferably 0~5 integer.

In the resin combination of present embodiment, the content of ingredient (A) is not particularly limited, but from improve copper facing From the viewpoint of adaptation, 100 mass parts of total content relative to ingredient (A), ingredient (C) and ingredient (D) are preferably 3 mass parts Above, more than more preferable 4 mass parts, more than further preferred 5 mass parts.In addition, from the viewpoint for sufficiently solidifying, improving heat resistance Consider preferably 90 below the mass, more preferably 89 below the mass, further preferably 88 below the mass.

The content of ingredient (A) in the resin combination of present embodiment is not particularly limited, but is plated from improving It is preferably 3 matter relative to 100 mass parts of resin solid content in resin combination from the viewpoint of copper adaptation and developability Measure part or more, more than more preferable 5 mass parts, more than further preferred 10 mass parts, more than even more preferably 15 mass parts.Separately Outside, from the viewpoint of abundant solidification, improving heat resistance, relative to 100 mass parts of resin solid content in resin combination Preferably 50 below the mass, more preferably 40 below the mass, further preferably 30 below the mass, even more preferably 28 matter Measure part or less.

Commercially available product also can be used in resin (A), can enumerate such as XD-1000 (n=1~3 in formula (1)) (trade name, Nippon Kayaku K. K's system), HP-7200L (n=1~3 in formula (1)) (trade name, Dainippon Ink Chemicals's system) etc..

They also can be used alone or properly mix two or more come using.

Trigger for optical solidification used in present embodiment (B) (also referred to as ingredient (B)) is not particularly limited, still Well known trigger for optical solidification in the usually field used in Photocurable resin composition can be used.

Such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl can be enumerated The benzoin class such as base ether, with benzoyl peroxide, lauroyl peroxide, acetyl peroxide, chloro benzoyl peroxide, two tertiary fourths Base-two crosses the organic peroxide of the illustrations such as phthalate ester, acylphosphine oxide class, acetophenone, 2,2- diethoxy -2- phenyl benzene second Ketone, 2,2- diethoxy -2- phenyl acetophenone, 1,1- dichloroacetophenone, 2- hydroxy-2-methyl-phenyl-propane -1- ketone, diethyl Oxygroup acetophenone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino base-propane-1- ketone, The acetophenones such as 2- benzyl -2- dimethylamino -1- (4- morpholino base phenyl)-butanone -1,2- ethyl hydrazine, 2- tert-butyl anthracene The Anthraquinones such as quinone, 2- chloroanthraquinone, 2- amyl anthraquinone, the thiophenes such as 2,4- diethyl thioxanthones, 2-isopropylthioxanthone, 2-chlorothioxanthone Xanthones, the ketals classes such as acetophenone dimethyl acetal, dibenzoyl dimethyl acetal, benzophenone, 4- benzoyl -4 '-methyldiphenyl Base thioether, 4, the benzophenones such as 4 '-bis- methylamino benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, The phosphinoxides such as bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, 1,2- octanedione, 1- [4- (thiophenyl)-, 2- (O- benzoyl oximes)] etc. the free radical types trigger for optical solidification such as oximes esters, fluorinated phosphonic acid p-methoxyphenyl diazonium salt, hexafluoro phosphine The lewis acidic diazonium salts such as sour N, N- diethylamino Arenediazonium salts, hexafluoro phosphonic acids diphenyl iodine, hexafluoro-antimonic acid hexichol The lewis acidic salt compounded of iodine such as base iodine, the lewis acidic sulfonium salts, six such as hexafluoro phosphonic acids triphenylsulfonium, hexafluoro-antimonic acid triphenylsulfonium The lewis acidic microcosmic salts such as fluorine metaantimmonic acid triphenyl phosphorus, other halide, triazine series initiators, borate-based initiator, with And the cationic systems Photoepolymerizationinitiater initiater such as other photoacid generators.

As acylphosphine oxide class, the following formula such as bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides can be enumerated (6) phosphine oxide compound shown in, 2,4,6- trimethylbenzoy-dipheny-phosphine oxide etc..Especially following formula (6) institute The phosphine oxide compound shown, the UV absorptivity of long wavelength is high, excellent in terms of making inside UV light resin all arrival.It therefore can be with The dicyclopentadiene type epoxy resin (A), compound (C) and compound (D) etc. for making present embodiment suitably react, and can make Make the superior resin sheet of heat resistance and multilayer printed-wiring board.

In formula (6), R₅~R₁₀Each independently represent the alkyl of hydrogen atom or carbon number 1~4, R₁₁Indicate carbon number 1~20 The aryl of alkyl or carbon number 6~20.

As the alkyl of carbon number 1~4, can enumerate for example methyl, ethyl, n-propyl, normal-butyl, isopropyl, isobutyl group, The alkyl of the straight-chains such as sec-butyl, tert-butyl or branched.

As the alkyl of carbon number 1~20, can enumerate for example methyl, ethyl, n-propyl, normal-butyl, n-pentyl, just oneself Base, isopropyl, isobutyl group, sec-butyl, tert-butyl, neopentyl, 1,1- dimethyl propyl, 1,1- diethylpropyl, 1- ethyl -1- The straight-chains such as methyl-propyl, 1,1,2,2- tetramethyl propyl, 1,1- dimethylbutyl, 1,1,3- trimethyl butyl or branched Alkyl.

As the aryl of carbon number 6~20, it can enumerate that phenyl, naphthalene, xenyl, terphenyl, phenanthryl, anthryl etc. are non-to be taken For aryl；The alkyl substituting aromatic bases such as tolyl, 3,5-dimethylphenyl, isopropyl phenyl, tert-butyl-phenyl, di-t-butyl phenyl.

Wherein, from the sight with the reactivity suitable for multilayer printed wiring board-use way, the high reliablity for metallic conductor Point consideration, preferably the benzene second such as acylphosphine oxide class, 2- benzyl -2- dimethylamino -1- (4- morpholino base phenyl)-butanone -1 The free radical type trigger for optical solidification of ketone, as described above, from the viewpoint of further obtaining heat resistance, it is more preferably aforementioned Phosphine oxide compound shown in formula (6), further preferably bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides.

These trigger for optical solidification (B) also can be used alone or properly mix two or more come using, can also will Free base system and cationic system both initiators are applied in combination.

In addition, 2- benzyl -2- dimethylamino -1- (4- morpholino base phenyl)-butanone -1, bis- (2,4,6- trimethylbenzenes Formoxyl)-phenyl phosphine oxide and 2,4,6- trimethylbenzoy-diphenies-phosphine oxide also can be used commercially available product, closes respectively Irgacure (registered trademark) 369 (BASF Japan Ltd. system), 819 (BASF of Irgacure (registered trademark) are used suitablely Japan Ltd. system) and Irgacure (registered trademark) TPO (BASF Japan Ltd. system).

The content of trigger for optical solidification (B) in the resin combination of present embodiment is not particularly limited, still From the viewpoint of making resin combination sufficiently solidify, improve heat resistance using active energy beam, relative to resin combination In ingredient (A), ingredient (C) and ingredient (D) 100 mass parts of total content be preferably 0.1 mass parts or more, more preferable 0.2 matter Measure part or more, more than further preferred 0.3 mass parts.In addition, from hinder photocuring after heat cure, make heat resistance reduce sight Point considers, preferably 30 below the mass, more preferably 25 below the mass, further preferably 20 below the mass.

The content of trigger for optical solidification (B) in the resin combination of present embodiment is not particularly limited, still It is preferably 0.1 mass parts or more, more preferable 0.2 mass parts relative to 100 mass parts of resin solid content in resin combination Above, more than further preferred 0.3 mass parts, more than even more preferably 1 mass parts, even more preferably 1.8 mass parts with On.In addition, from the viewpoint of the heat cure after hindering photocuring reduces heat resistance, relative to the resin in resin combination 100 mass parts of solid component be preferably 30 below the mass, more preferably 25 below the mass, further preferably 20 mass parts with Under, even more preferably 10 below the mass.

Compound used in present embodiment (C) (also referred to as ingredient (C)) is previously described formula (2) compound represented.Change Close object (C) and can be used alone, can also be containing the isomers such as constitutional isomer and stereoisomer or by structure Mutually different compound it is appropriately combined two or more come using.

In previously described formula (2), multiple R₁Each independently represent hydrogen atom or methyl.Wherein, from raising photocuring reaction From the viewpoint of reactivity, hydrogen atom, more preferably whole R are preferably comprised₁For hydrogen atom.

Multiple R₂It each independently represents hydrogen atom or can have the alkyl of the carbon number 1~22 of substituent group.

As alkyl, the straight-chain or branched of carbon number 1~22, preferably 1~14, further preferred 1~10 can be enumerated Aliphatic alkyl；The alicyclic alkyl of carbon number 3~22, preferably 3~14, further preferred 3~10；Carbon number 6~22, preferably 6 ~14, further preferred 6~10 aromatic hydrocarbyl.

As aliphatic alkyl, such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, isopropyl can be enumerated Base, isobutyl group, sec-butyl, tert-butyl, neopentyl, 1,1- dimethyl propyl, 1,1- diethylpropyl, 1- ethyl -1- methyl-prop The alkyl of the straight-chains such as base, 1,1,2,2- tetramethyl propyl, 1,1- dimethylbutyl, 1,1,3- trimethyl butyl or branched； The alkenyl of the straight-chains such as vinyl, allyl, isopropenyl or branched；The straight-chains such as acetenyl, propargyl or branched Alkynyl.

As alicyclic alkyl, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, 1- methyl-1-hexamethylene can be enumerated The cyclic saturated hydrocarbons base such as base, adamantyl；The ring-type unsaturated alkyl such as cyclopentadienyl group, indenyl, fluorenyl.

As aromatic hydrocarbyl, non-such as phenyl, naphthalene, xenyl, terphenyl, phenanthryl, anthryl take can be enumerated For aryl；Alkyl substituting aromatic bases such as tolyl, 3,5-dimethylphenyl, isopropyl phenyl, tert-butyl-phenyl, di-t-butyl phenyl etc. Aryl.

These alkyl can be replaced at least one hydrogen atom by other alkyl.As at least one hydrogen atom by other alkyl Alkyl made of substitution, can enumerate the aryl substituted alkyl such as benzyl, cumyl, and the cyclic saturated hydrocarbons base such as cyclohexyl methyl takes Substituted alkyl.

As the alkyl for the carbon number 1~22 that can have substituent group, the preferably alkyl of straight-chain or branched.

Multiple R₂Methyl, more preferably whole R are preferably comprised from the viewpoint of the heat resistance for improving solidfied material₂For methyl.

Multiple R₃Each independently represent substituent group or hydroxyl shown in substituent group shown in previously described formula (3), previously described formula (4) Base.Wherein, from the viewpoint of improving heat resistance, hydroxyl is preferably comprised.In addition, in present embodiment, from raising developability Viewpoint considers, it is also preferred that using multiple R₃In, the compound (C) containing substituent group shown in previously described formula (3).Present embodiment In, from the viewpoint of improving heat resistance, it is also preferred that using multiple R₃In, the chemical combination containing substituent group shown in previously described formula (4) Object (C).In previously described formula (4),

R₄Indicate hydrogen atom or methyl.Wherein, from the viewpoint of the reactivity for improving photocuring reaction, preferably hydrogen is former Son.

Multiple R₃From the viewpoint of improving developability, preferably whole R₃Substituent group in, shown in previously described formula (3) replace The ratio of base is in 20% or more and 98% or less range, the ratio of substituent group shown in previously described formula (4) is in 5% or more And in 98% or less range, the ratio of hydroxyl be in the (ratio of these substituent groups in 10% or more and 98% or less range The sum of for 100%).Wherein, from the viewpoint of improving developability, particularly preferred multiple R₃In at least one be previously described formula (3) Shown in substituent group.

As compound (C), containing any a kind or more in compound below (C1)~(C5), due to can be improved The reactivity of photocuring reaction, the heat resistance of solidfied material and developability and it is preferred that, more preferably at least contain compound (C1), more excellent Choosing containing in (C1)~(C5) it is any two or more, further preferably in compound (C1) and compound (C2)~(C5) Any a kind or more.As compound (C), it is also preferred that at least containing compound (C2) and (C3).

This compound also can be used commercially available product, can enumerate such as KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR- 6007H, KAYARAD (registered trademark) ZCR-601H (the above trade name, Nippon Kayaku K. K's system) etc..

In the resin combination of present embodiment, the acid value of compound (C) is from the viewpoint of improving developability, preferably 30mgKOH/g or more, from the viewpoint of further increasing developability, further preferably 50mgKOH/g or more.In addition, from From the viewpoint of preventing the dissolution caused by developer solution after being solidified using active energy beam, compound (C) Acid value is preferably 120mgKOH/g hereinafter, from the viewpoint of it can further prevent dissolution, further preferably 110mgKOH/ G or less.It should be noted that " acid value " in present embodiment indicates to measure using the method based on JISK 0070:1992 The value arrived.

In the resin combination of present embodiment, the content of compound (C) is not particularly limited, but is lived from utilizing Property energy-ray make resin combination solidify from the viewpoint of, relative in resin combination ingredient (A), ingredient (C) and at 100 mass parts of total content of point (D) be preferably 1 mass parts or more, it is more than more preferable 2 mass parts, further preferred 3 mass parts with On.In addition, from the viewpoint of sufficiently being solidified using active energy beam, improving heat resistance, preferably 99 mass parts with Under, more preferable 98 below the mass, further preferably 97 below the mass.

In the resin combination of present embodiment, the content of compound (C) is not particularly limited, but is lived from utilizing Property energy-ray make resin combination solidify from the viewpoint of, relative to 100 mass of resin solid content in resin combination Part be preferably 1 mass parts more than, it is more than more preferable 2 mass parts, it is more than further preferred 3 mass parts, even more preferably 10 matter Measure part or more, more than even more preferably 25 mass parts, more than most preferably 30 mass parts.In addition, from active energy beam is utilized It is excellent relative to 100 mass parts of resin solid content in resin combination from the viewpoint of sufficiently being solidified, improving heat resistance Be selected as 99 below the mass, more preferably 98 below the mass, further preferably 97 below the mass, even more preferably 90 mass Part or less, even more preferably 75 below the mass, most preferably 72 below the mass.

The resin combination of present embodiment is in order to improve the reactivity for active energy beam (such as ultraviolet light), mention High-fire resistance contains the compound (D) (also referred to as ingredient (D)) with ethylenically unsaturated group other than (C) ingredient.This implementation Used in mode with ethylenically unsaturated group compound (D) if other than previously described formula (2) compound represented (C), 1 point The compound of ethylenically unsaturated group in son with 1 or more is not particularly limited, and can enumerate for example with (methyl) The compound of acryloyl group, vinyl etc..They can be used alone or properly mix two or more come using.

As the compound with (methyl) acryloyl group, such as (methyl) methyl acrylate, (methyl) third can be enumerated Olefin(e) acid ethyl ester, (methyl) butyl acrylate, (methyl) lauryl acrylate, polyethylene glycol (methyl) acrylate, polyethylene glycol (methyl) acrylate monomethyl ether, (methyl) phenylethyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid Cyclohexyl, (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate, butanediol two (methyl) acrylate, hexylene glycol Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, nonanediol two (methyl) acrylate, two (first of ethylene glycol Base) acrylate, diethylidene two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, three (methyl) acryloyls Oxygroup ethyl isocyanurate, polypropylene glycol two (methyl) acrylate, adipic acid epoxy two (methyl) acrylate, bis-phenol ring Oxidative ethane two (methyl) acrylate, A Hydrogenated Bisphenol A ethylene oxide (methyl) acrylate, bis-phenol two (methyl) acrylate, ε- Modified six (methyl) third of dipentaerythritol of caprolactone modification hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, 6-caprolactone Poly- (methyl) acrylate of the modified dipentaerythritol of olefin(e) acid ester, 6-caprolactone, poly- (methyl) acrylate of dipentaerythritol, three hydroxyls Methylpropane three (methyl) acrylate, (methyl) acrylate of triethylol propane three and its ethylene oxide adduct, season penta (methyl) acrylate of tetrol three and its ethylene oxide adduct, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate and its ethylene oxide adduct etc..

In addition to this, the amino first that same intramolecular has both (methyl) acryloyl group and urethane bond can also be enumerated Acid esters (methyl) esters of acrylic acid, similarly same intramolecular have both polyester (methyl) propylene of (methyl) acryloyl group and ester bond Use this to acid esters, epoxy (methyl) esters of acrylic acid that (methyl) acryloyl group is had both as derived from epoxy resin, plyability The reactive oligomers etc. of a little keys.

Above-mentioned carbamate (methyl) esters of acrylic acid refers to (methyl) acrylate and polyisocyanate cyanogen containing hydroxyl The reactant of acid esters, other alcohols used as needed.Such as (methyl) Hydroxyethyl Acrylate, (methyl) dihydroxypropyl (methyl) the hydroxyalkyl acrylates classes such as propyl ester, (methyl) hydroxy butyl acrylate, glycerol list (methyl) acrylate, glycerol Two (methyl) acrylate etc. glycerol (methyl) esters of acrylic acid, pentaerythrite two (methyl) acrylate, three (first of pentaerythrite Base) sugar alcohols (methyl) such as acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate Esters of acrylic acid, with toluene di-isocyanate(TDI), hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, different Buddhist That ketone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, two rings The reaction such as polyisocyanates such as hexane methylene diisocyanate and their isocyanuric acid ester, biuret reaction object, forms ammonia Carbamate (methyl) esters of acrylic acid.

For above-mentioned polyester (methyl) esters of acrylic acid, such as caprolactone modification 2- hydroxyethyl (methyl) third can be enumerated Olefin(e) acid ester, ethylene oxide and/or epoxy pronane modification phthalic acid (methyl) acrylate, ethylene-oxide-modified succinic acid (methyl) acrylate, caprolactone modification tetrahydrofurfuryl (methyl) acrylate etc. simple functions (poly-) ester (methyl) acrylate Class；Hydroxy new pentane acid ester neopentyl glycol two (methyl) acrylate, two (first of caprolactone modification hydroxy new pentane acid ester neopentyl glycol Base) two (poly-) ester (methyl) esters of acrylic acid such as acrylate, modified phthalic acid two (methyl) acrylate of epichlorohydrin；? The annular lactones such as 6-caprolactone, gamma-butyrolacton, the δ-valerolactone of trimethylolpropane or 1 mole of glycerol, 1 mole of addition or more Close the mono-, di- or three (methyl) acrylate of triol obtained from object.

In turn, it can enumerate in the ε-of pentaerythrite or two 1 mole of (trihydroxy methyl) propane, 1 mole of additions or more in oneself Mono-, di-, three or four (methyl) acrylic acid of triol obtained from the annular lactones compound such as ester, gamma-butyrolacton, δ-valerolactone Ester, in annular lactones chemical combination such as 6-caprolactone, gamma-butyrolacton, the δ-valerolactones of 1 mole of dipentaerythritol, 1 mole of addition or more The list (methyl) of the polyalcohols such as triol, tetrol, pentol or six alcohol of the list of triol obtained from object or poly- (methyl) acrylate Acrylate or poly- (methyl) acrylate.

And it in addition and then can enumerate as (poly-) ethylene glycol, (poly-) propylene glycol, (poly-) tetramethylene glycol, (poly-) fourth Glycol, 3- methyl-1, the glycol components such as 5- pentanediol, hexylene glycol and maleic acid, fumaric acid, succinic acid, adipic acid, adjacent benzene two Between formic acid, M-phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimeric dibasic acid, decanedioic acid, azelaic acid, 5- sodium sulfo group (methyl) acrylate of the polyester polyol of the reactant of the polyacids such as phthalic acid and their acid anhydrides；Include aforementioned two The annular lactone modified poly ester of first alcohol component, polyacid and their acid anhydrides and 6-caprolactone, gamma-butyrolacton, δ-valerolactone etc. Multifunctional (poly-) ester (methyl) esters of acrylic acid such as (methyl) acrylate of glycol etc., but it is not limited to them.

Above-mentioned epoxy (methyl) esters of acrylic acid refers to the carboxylic acid of the compound with epoxy group and (methyl) acrylic acid Ester compounds.Such as phenol novolak-type epoxy (methyl) acrylate, cresol novolak type epoxy (first can be enumerated Base) acrylate, trihydroxy benzene methylmethane type ring oxygen (methyl) acrylate, dicyclopentadiene phenol type epoxy (methyl) propylene Acid esters, bisphenol type epoxy (methyl) acrylate, bisphenol F type epoxy (methyl) acrylate, xenol type ring oxygen (methyl) third Olefin(e) acid ester, bisphenol A novolac type ring oxygen (methyl) acrylate, epoxy (methyl) acrylate containing naphthalene skeleton, second two Aldehyde type ring oxygen (methyl) acrylate, hetero ring type epoxy (methyl) acrylate etc. and their anhydride modified propylene oxide Acid esters etc..

As the compound with vinyl, ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl can be enumerated The vinyl ethers such as base ether, ethylene glycol divinyl ether.As phenylethylene, styrene, methyl styrene, ethyl can be enumerated Styrene, divinylbenzene etc..As other vinyl compounds, Triallyl isocyanurate, trimethyl alkene can be enumerated Propyl isocyanuric acid ester, diallyl nadikimide etc..

Among them, from the viewpoint of heat resistance, it is preferably selected from by pentaerythrite four (methyl) acrylate, two seasons Penta tetrol six (methyl) acrylate, cresol novolak type epoxy (methyl) acrylate, bisphenol type epoxy (methyl) propylene One or more of acid esters, epoxy (methyl) acrylate containing naphthalene skeleton, group of diallyl nadikimide composition, From the viewpoint of further increasing heat resistance, more preferably dipentaerythritol six (methyl) acrylate.By containing this Compound with ethylenically unsaturated group, there are the tendencies that the heat resistance of obtained solidfied material further increases.

In the resin combination of present embodiment, for the compound with ethylenically unsaturated group other than (C) ingredient (D) content is not particularly limited, but from the viewpoint of keeping developability good, relative to the ingredient in resin combination (A), 100 mass parts of total content of ingredient (C) and ingredient (D) be preferably 0.5 mass parts or more, it is more than more preferable 1.0 mass parts, It is more than further preferred 1.5 mass parts.In addition, from make solidfied material heat resistance it is good from the viewpoint of, preferably 90 mass parts Below, more preferably 70 below the mass, further preferably 50 below the mass.

In the resin combination of present embodiment, the content of compound (D) is not particularly limited, but from making to develop From the viewpoint of property is good, relative to 100 mass parts of resin solid content in resin combination, preferably 0.5 mass parts with It is more than upper, more preferable 1.0 mass parts, it is more than further preferred 1.5 mass parts, it is more than even more preferably 5.0 mass parts, it is optimal Select 10 mass parts or more.In addition, from make solidfied material heat resistance it is good from the viewpoint of, relative to the resin in resin combination 100 mass parts of solid component be preferably 90 below the mass, more preferably 70 below the mass, further preferably 50 mass parts with Under, even more preferably 25 below the mass, most preferably 20 below the mass.

In the resin combination of present embodiment, maleimide compound (E) (also referred to as ingredient (E)) can be used. It is described in detail below for maleimide compound (E).

Maleimide compound used in present embodiment (E) if in molecule have more than one maleimide The compound of amido is not particularly limited.As its concrete example, such as N-phenylmaleimide, N- hydroxy benzenes can be enumerated Bis- { 4- (4- the maleimidephenoxy)-phenyl } third of base maleimide, bis- (4- maleimide phenyl) methane, 2,2- Alkane, 4,4- diphenyl methane bismaleimide, bis- (3,5- dimethyl -4- maleimide phenyl) methane, bis- (3- ethyls - 5- methyl -4- maleimide phenyl) methane, bis- (3,5- diethyl -4- maleimide phenyl) methane, phenylmethane Malaysia Acid imide, adjacent phenylene bismaleimide, meta-phenylene bismaleimide, TOPOT 2,2′ p phenylenebis maleimide, adjacent sub- benzene Bis- (4- (the 4- maleimides of base dual-citraconic imide, metaphenylene dual-citraconic imide, TOPOT 2,2′ p phenylenebis citraconimide, 2,2- Amine phenoxy group)-phenyl) propane, 3,3- dimethyl -5,5- diethyl -4,4- diphenyl methane bismaleimide, 4- methyl - 1,3- phenylene bismaleimide, 1,6- bismaleimide-(2,2,4- trimethyl) hexane, 4,4- diphenyl ether span come Bis- (3- maleimidephenoxy) benzene of acid imide, 4,4- diphenyl sulfone bismaleimide, 1,3-, the bis- (Malaysia the 4- acyls of 1,3- Imines phenoxy group) benzene, 4,4- diphenyl methane dual-citraconic imide, bis- [4- (the 4- citraconimide phenoxy group) phenyl] third of 2,2- Alkane, bis- (3,5- dimethyl -4- citraconimide phenyl) methane, bis- (3- ethyl -5- methyl -4- citraconimide phenyl) first Alkane, bis- (3,5- diethyl -4- citraconimide phenyl) methane, polyphenyl methylmethane maleimide, phenolic varnish type Malaysia acyl It is group with imine moiety, biphenyl aralkyl-type maleimide compound, maleimide compound shown in following formula (7), following The prepolymer or maleimide chemical combination of maleimide compound shown in formula (8) and these maleimide compounds Object and the prepolymer of amine compounds etc..

Wherein, particularly preferably phenolic varnish type maleimide compound, biphenyl aralkyl-type maleimide chemical combination Object.In addition, from the viewpoint of obtaining good painting film property, excellent heat resistance, preferably maleimide shown in following formula (7) Maleimide compound shown in amine compounds, following formula (8), maleimide chemical combination shown in more preferable following formula (7) Object.As maleimide compound shown in following formula (7), commercially available product also can use, can enumerate such as BMI-2300 (Daiwa Kasei Industry Co., Ltd.'s system).As maleimide compound shown in following formula (8), also can use commercially available Product can enumerate such as MIR-3000 (Nippon Kayaku K. K's system).

These maleimide compounds (E) also can be used alone or properly mix two or more come using.

(in formula (7), multiple R₅Each independently represent hydrogen atom or methyl.n₁The integer of 1 or more expression preferably indicates 1 ~10 integer, the integer for more preferably indicating 1~5).

(in formula (8), multiple R₆Each independently represent hydrogen atom or methyl.n₂The integer of 1 or more expression preferably indicates 1 ~5 integer).

These maleimide compounds (E) also can be used alone or it is appropriately combined two or more come using.

The content of maleimide compound (E) in the resin combination of present embodiment is not particularly limited, But from making from the viewpoint of resin combination sufficiently solidifies, improves heat resistance, relative in resin combination ingredient (A), 100 mass parts of total content of ingredient (C) and ingredient (D) be preferably 0.01 mass parts or more, it is more than more preferable 0.02 mass parts, into It is more than one step preferably 0.03 mass parts.In addition, from the viewpoint of keeping developability good, preferably 50 below the mass, more excellent It selects 45 below the mass, further preferably 40 below the mass.

In the resin combination of present embodiment, the content of maleimide compound (E) is not particularly limited, phase It is preferably 0.01 mass parts~50 mass parts, more preferable 0.02 mass parts~45 mass for 100 mass parts of resin solid content Part, further preferred 0.03 mass parts~20 mass parts, even more preferably 0.1 mass parts~10 mass parts, most preferably 1 mass Part~7 mass parts.Within the above range by the content of maleimide compound, there are the heat resistance of solidfied material is further The tendency of raising.

In the resin combination of present embodiment, the various characteristics such as film property, heat resistance are applied in order to improve, can also combine makes With filler (F) (also referred to as ingredient (F)).Filler used in present embodiment (F) if being not particularly limited with insulating properties, Such as silica (such as native silicon dioxide, fused silica, amorphous silica, hollow titanium dioxide can be enumerated Silicon etc.), aluminium compound (such as boehmite, aluminium hydroxide, aluminium oxide etc.), magnesium compound (such as magnesia, magnesium hydroxide etc.), Calcium compound (such as calcium carbonate etc.), molybdenum compound (such as molybdenum oxide, zinc molybdate etc.), barium compound (such as barium sulfate, silicic acid Barium etc.), talcum (such as natural talcum, calcination of talc etc.), mica (mica), glass (such as staple fiber shape glass, spherical glass Glass, micropowder glass (such as E glass, T glass, D glass etc.) etc.), silicone powder, fluororesin system filler, polyurethane resin system Filler, acrylic resin system filler, polyethylene-based filler, styrene butadiene ribber and silicon rubber etc..

Wherein, it is preferably selected from by silica, boehmite, barium sulfate, silicone powder, fluororesin system filler, polyurethane The group of resin system filler, acrylic resin system filler, polyethylene-based filler, styrene butadiene ribber and silicon rubber composition One or more of.

These fillers (F) can be surface-treated with aftermentioned silane coupling agent etc..

Especially from the viewpoint of improving the heat resistance of solidfied material, in addition obtaining good painting film property, preferably dioxy SiClx, particularly preferred fused silica.As the concrete example of silica, Denka Company Limited can be enumerated SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C- of SFP-130MC of system etc., ADMATECHS Co., Ltd. MJA etc..

These fillers (F) also can be used alone or properly mix two or more come using.

In the resin combination of present embodiment, the content of filler (F) is not particularly limited, but is solidified from improving From the viewpoint of the heat resistance of object, relative to 100 mass parts of resin solid content in resin combination be preferably 5 mass parts with More than upper, more preferable 10 mass parts, more than further preferred 20 mass parts.In addition, from keeping the developability of resin combination good From the viewpoint of, relative in resin combination 100 mass parts of resin solid content, preferably 400 below the mass, it is more excellent Select 350 below the mass, further preferably 300 below the mass, even more preferably 200 below the mass, most preferably 100 matter Measure part or less.

In the resin combination of present embodiment, in order to improve dispersibility, polymer and/or the resin and filler of filler Silane coupling agent and/or Ricinate can also be applied in combination in adhesive strength.

As these silane coupling agents, silane coupling agent used in the surface treatment if usual inorganic matter is then without spy It does not limit.As concrete example, such as γ aminopropyltriethoxy silane, N- β-(amino-ethyl)-gamma-amino can be enumerated The amino silicone methane series such as propyl trimethoxy silicane；The epoxy silanes such as γ-glycidoxypropyltrime,hoxysilane system；γ-the third The acryl silanes systems such as alkene acryloxypropylethoxysilane trimethoxy silane；N- β-(N- vinylbenzylaminoethyl)-gamma-amino third The cationic silanes systems such as base trimethoxy silane hydrochloride；The silane coupling agent of phenyl silane system.These silane coupling agents can also Be used alone a kind or it is appropriately combined two or more come using.

In the resin combination of present embodiment, the content of silane coupling agent is not particularly limited, but usual phase It is 0.1~10 mass parts for 100 mass parts of resin combination.

As Ricinate, it is not particularly limited if coating dispersion stabilizer used in.As concrete example, DISPERBYK (registered trademark) -110,111,118,180,161, BYK (note of such as BYK Japan K.K. can be enumerated Volume trade mark)-W996, the Ricinates such as W9010, W903.These Ricinates also can be used alone or properly mix Two or more come using.

In the resin combination of present embodiment, the content of Ricinate is not particularly limited, but usual phase It is 0.1~10 mass parts for 100 mass parts of resin combination.

< selected from by cyanate esters, phenolic resin, oxetane resin, benzoxazine compound and with aforementioned (1) Shown in dicyclopentadiene type epoxy resin (A) it is different epoxy resin composition group in any one more than compound (G)>

Compound used in present embodiment (G) (also referred to as ingredient (G)) according to by using ingredient (A) in addition to obtaining Copper facing adaptation etc. except, also according to the resistance for having carried out cured solidfied material required in the field using resin combination The characteristics such as combustion property, heat resistance, thermal expansion character use various compounds (G).Such as in the case where requiring heat resistance, it can enumerate Cyanate esters, benzoxazine compound etc., in addition to this also can be used phenolic resin, oxetane resin etc..Separately Outside, if it is different from epoxy resin (A) using being used while dicyclopentadiene type epoxy resin (A) shown in aforementioned (1) Epoxy resin, the then resin combination of especially available developability and plating excellent adhesion.

In addition, they also can be used alone or properly mix two or more come using.

It is described in detail below for these compounds and/or resin (G).

As cyanate esters, there is the aromatic series instead of at least one cyanato- (cyanic acid ester group) if intramolecular Partial resin is not particularly limited.

Such as general formula (9) compound represented can be enumerated.

In formula (9), Ar₁Group made of expression phenyl ring, naphthalene nucleus or 2 phenyl ring singly bounds.In the case where multiple, It can be mutually identical or different.Ra each independently represents hydrogen atom, the alkyl of carbon number 1~6, the aryl of carbon number 6~12, carbon number Group made of 1~4 alkoxy, the alkyl of carbon number 1~6 are bonded with the aryl of carbon number 6~12.Aromatic rings in Ra can have Substituted base, Ar₁It can choose arbitrary position with the substituent group in Ra.P is indicated and Ar₁The cyanato- number of bonding, respectively independence The integer that ground is 1~3.Q is indicated and Ar₁The Ra number of bonding, Ar₁Q is 4-p, Ar when for phenyl ring₁Q is 6-p, Ar when for naphthalene nucleus₁It is 2 Q is 8-p when group made of a phenyl ring singly bound.T indicate averaged repeating numbers, for 0~50 integer, cyanate esters can Think the mixture of the different compound of t.X each independently represents the divalent of singly-bound, carbon number 1~50 there are in the case where multiple Organic group (hydrogen atom can be exchanged for heteroatoms), nitrogen number 1~10 the organic group of divalent (such as-N-R-N- is (in this R Indicate organic group)), carbonyl (- CO-), carboxyl (- C (=O) O-), carbonylic dioxo base (- OC (=O) O-), sulfonyl (- SO₂), any one in the oxygen atom of the sulphur atom of divalent or divalent.

Alkyl in the Ra of general formula (9) can have the chain structure and cyclic structure (such as naphthenic base of straight chain or branch Deng) in any one.

In addition, the hydrogen atom in aryl in alkyl and Ra in general formula (9) can be by the halogens such as fluorine atom, chlorine atom original Son, the alkoxies such as methoxyl group, phenoxy group or cyano etc. replace.

As the concrete example of alkyl, can enumerate methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, N-pentyl, 1- ethyl propyl, 2,2- dimethyl propyl, cyclopenta, hexyl, cyclohexyl and trifluoromethyl etc..

As the concrete example of aryl, phenyl, xylyl, 2,4,6- trimethylphenyls, naphthalene, phenoxy group benzene can be enumerated Base, ethylphenyl, o-fluorophenyl, fluorophenyl, p-fluorophenyl, dichlorophenyl, dicyano phenyl, trifluorophenyl, methoxybenzene Base, o-tolyl, tolyl, p-methylphenyl etc..In turn, as alkoxy, such as methoxyl group, ethyoxyl, third can be enumerated Oxygroup, isopropoxy, n-butoxy, isobutoxy and tert-butoxy etc..

The concrete example of the organic group of divalent as the carbon number 1~50 in the X of general formula (9), can enumerate methylene, Asia Ethyl, trimethylene, cyclopentylene, cyclohexylidene, trimethylcyclohexylene, biphenyl methylene, dimethylmethylene-Asia benzene Base-dimethylmethylene, fluorenes diyl and benzofuranone diyl etc..Hydrogen atom in the organic group of the divalent can be by fluorine original The halogen atoms such as son, chlorine atom, the alkoxies such as methoxyl group, phenoxy group, cyano etc. replace.

The organic group of divalent as the nitrogen number 1~10 in the X of general formula (9) can enumerate imino group, polyimide-based Deng.

In addition, the organic group as the X in general formula (9), can enumerate such as the following general formula (10) or the following general formula (11) organic group of structure shown in.

In formula (10), Ar₂In the case where indicating that four base of benzene, four base of four base of naphthalene or biphenyl, u are 2 or more, it can be mutually identical Or it is different.Rb, Rc, Rf and Rg each independently represent hydrogen atom, the alkyl of carbon number 1~6, the aryl of carbon number 6~12, trifluoro Methyl or aryl at least one phenolic hydroxyl group.Rd and Re be each independently selected from hydrogen atom, carbon number 1~6 alkyl, The aryl of carbon number 6~12, the alkoxy of carbon number 1~4 or any one in hydroxyl.U indicates 0~5 integer.

In formula (11), Ar₃In the case where indicating that four base of benzene, four base of four base of naphthalene or biphenyl, v are 2 or more, it can be mutually identical Or it is different.Ri and Rj each independently represent hydrogen atom, the alkyl of carbon number 1~6, the aryl of carbon number 6~12, benzyl, carbon number 1~ 4 alkoxy, hydroxyl, trifluoromethyl or the aryl instead of at least one cyanato-.V indicates 0~5 integer, but can also Think the mixture of the different compound of v.

In turn, as the X in general formula (9), divalent group shown in following formula can be enumerated.

Here, z indicates 4~7 integer in formula.Rk each independently represents the alkyl of hydrogen atom or carbon number 1~6.

Ar as general formula (10)₂With the Ar of general formula (11)₃Concrete example, 2 carbon originals shown in general formula (10) can be enumerated Four base of benzene, above-mentioned 2 carbon atoms or the 2 oxygen originals that 2 oxygen atoms shown in son or general formula (11) are bonded with 1,4 or 1,3 Four base of biphenyl and above-mentioned 2 carbon atoms that son is bonded with 4,4 ' positions, 2,4 ' positions, 2,2 ' positions, 2,3 ' positions, 3,3 ' positions or 3,4 ' positions Or four base of naphthalene that 2 oxygen atoms are bonded with 2,6,1,5,1,6,1,8,1,3,1,4 or 2,7.

The definition of Rb, Rc, Rd, Re, Rf and Rg of general formula (10) and alkyl and aryl in Ri, Rj of general formula (11) It is identical as above-mentioned general formula (9).

As the concrete example of cyanato- substituted aromatic compound shown in above-mentioned general formula (9), can enumerate cyanato- benzene, 1- cyanato- -2- methylbenzene, 1- cyanato- -3- methylbenzene, 1- cyanato- -4- methylbenzene, 1- cyanato- -2- methoxybenzene, 1- Cyanato- -3- methoxybenzene, 1- cyanato- -4- methoxybenzene, 1- cyanato- -2,3- dimethyl benzene, 1- cyanato- -2,4- diformazan Base benzene, 1- cyanato- -2,5- dimethyl benzene, 1- cyanato- -2,6- dimethyl benzene, 1- cyanato- -3,4- dimethyl benzene, 1- cyanogen oxygen Base -3,5- dimethyl benzene, cyanato- ethylo benzene, cyanato- butyl benzene, cyanato- octyl benzene, cyanato- nonyl benzene, 2- (4- cyanogen oxygen Base phenyl) -2- phenyl-propane (4- α-cumyl phenol cyanate), 1- cyanato- -4- cyclohexyl benzene, 1- cyanato- -4- ethylene Base benzene, 1- cyanato- -2- chlorobenzene, 1- cyanato- -3- chlorobenzene, 1- cyanato- -2,6- dichloro-benzenes, 1- cyanato- -2- methyl -3- chlorine Benzene, cyanato- nitrobenzene, 1- cyanato- -4- nitro -2- ethylo benzene, 1- cyanato- -2- methoxyl group -4- allyl benzene (clove tree The cyanate of phenol), methyl (4- cyanato- phenyl) thioether, 1- cyanato- -3- trifluoromethylbenzene, 4- cyanato- biphenyl, 1- cyanogen oxygen Base -2- acetophenone, 1- cyanato- -4- acetophenone, 4- cyanato- benzaldehyde, 4- cyanato- methyl benzoate, 4- cyanato- benzene first Acid phenenyl ester, 1- cyanato- -4- acetyl amino phenyl, 4- cyanato- benzophenone, 1- cyanato- -2,6- di-t-butyl benzene, 1,2- bis- Cyanato- benzene, bis- cyanato- benzene of 1,3-, bis- cyanato- benzene of 1,4-, bis- cyanato- -2- tert-butyl benzene of 1,4-, bis- cyanato- of 1,4- - 2,4- dimethyl benzene, bis- cyanato- -2,3,4- dimethyl benzene of 1,4-, bis- cyanato- -2,4,6- trimethylbenzene of 1,3-, 1,3- dicyan Oxygroup -5- methylbenzene, 1- cyanato- naphthalene, 2- cyanato- naphthalene, 1- cyanato- 4- methoxynaphthalene, 2- cyanato- -6- methyl naphthalene, 2- cyanogen Oxygroup -7- methoxynaphthalene, 2,2 '-dicyan Oxy-1s, 1 '-binaphthyl, bis- cyanato- naphthalene of 1,3-, bis- cyanato- naphthalene of 1,4-, 1,5- Two cyanato- naphthalenes, bis- cyanato- naphthalene of 1,6-, bis- cyanato- naphthalene of 1,7-, bis- cyanato- naphthalene of 2,3-, bis- cyanato- naphthalene of 2,6-, 2,7- bis- Cyanato- naphthalene, 2,2 '-two cyanato- biphenyl, 4,4 '-two cyanato- biphenyl, 4,4 '-two cyanato- octafluorobiphenyls, 2,4 '-dicyan Oxygroup diphenyl methane, 4,4 '-two cyanato- diphenyl methanes, bis- (4- cyanato- -3,5- 3,5-dimethylphenyl) methane, 1,1- are bis- Bis- (the 4- cyanato- phenyl) propane of (4- cyanato- phenyl) ethane, 1,1-, bis- (the 4- cyanato- phenyl) propane of 2,2-, 2,2- are bis- Bis- (2- cyanato- -5- xenyl) propane of (4- cyanato- -3- aminomethyl phenyl) propane, 2,2-, 2,2- bis- (4- cyanato- phenyl) Bis- (4- cyanato- -3,5- 3,5-dimethylphenyl) propane of hexafluoropropane, 2,2-, bis- (the 4- cyanato- phenyl) butane of 1,1-, 1,1- are bis- Bis- (the 4- cyanato- phenyl) pentanes of (4- cyanato- phenyl) iso-butane, 1,1-, bis- (4- cyanato- the phenyl) -3- methyl fourths of 1,1- Bis- (4- cyanato- the phenyl) -2- methybutanes of alkane, 1,1-, bis- (4- cyanato- the phenyl) -2,2- dimethylpropanes of 1,1-, 2,2- are bis- Bis- (the 4- cyanato- phenyl) pentanes of (4- cyanato- phenyl) butane, 2,2-, bis- (the 4- cyanato- phenyl) hexanes of 2,2-, 2,2- are bis- Bis- (4- cyanato- the phenyl) -4- methylpentanes of (4- cyanato- phenyl) -3- methybutane, 2,2-, bis- (the 4- cyanato- benzene of 2,2- Base) -3,3- dimethylbutane, bis- (the 4- cyanato- phenyl) hexanes of 3,3-, bis- (the 4- cyanato- phenyl) heptane of 3,3-, 3,3- be bis- Bis- (4- cyanato- the phenyl) -2- methylpentanes of (4- cyanato- phenyl) octane, 3,3-, bis- (4- cyanato- the phenyl) -2- first of 3,3- Bis- (4- cyanato- the phenyl) -2,2- dimethyl pentanes of base hexane, 3,3-, 4,4- bis- (4- cyanato- phenyl) -3- methyl heptanes, 3, Bis- (4- cyanato- the phenyl) -2- methyl heptanes of 3-, bis- (4- cyanato- the phenyl) -2,2- dimethylhexanes of 3,3-, bis- (the 4- cyanogen of 3,3- Phenyl) -2,4- dimethylhexane, bis- (4- cyanato- the phenyl) -2,2,4- trimethylpentanes of 3,3-, bis- (the 4- cyanogen oxygen of 2,2- Base phenyl) -1,1,1,3,3,3- hexafluoropropane, bis- (4- cyanato- phenyl) phenylmethanes, bis- (4- cyanato- the phenyl) -1- of 1,1- Diphenylphosphino ethane, bis- (4- cyanato- phenyl) biphenyl methane, bis- (the 4- cyanato- phenyl) pentamethylene of 1,1-, bis- (the 4- cyanato-s of 1,1- Phenyl) hexamethylene, bis- (4- cyanato- -3- isopropyl phenyl) propane of 2,2-, bis- (3- cyclohexyl -4- cyanato- phenyl) rings of 1,1- Hexane, bis- (4- cyanato- phenyl) diphenyl methanes, bis- (4- cyanato- phenyl) -2,2- dichloroethylene, bis- [2- (the 4- cyanogen of 1,3- Phenyl) -2- propyl] benzene, bis- [2- (4- cyanato- the phenyl) -2- propyl] benzene of 1,4-, bis- (the 4- cyanato- phenyl) -3 of 1,1-, 3,5- trimethyl-cyclohexane, 4- [bis- (4- cyanato- phenyl) methyl] biphenyl, bis- cyanato- benzophenone of 4,4-, the bis- (4- of 1,3- Cyanato- phenyl) -2- propylene -1- ketone, bis- (4- cyanato- phenyl) ethers, bis- (4- cyanato- phenyl) thioethers, bis- (4- cyanato- benzene Base) sulfone, 4- cyanato- benzoic acid -4- cyanato- phenyl ester (4- cyanato- phenyl -4- cyanato- benzoic ether), double-(4- cyanato- Phenyl) carbonic ester, bis- (the 4- cyanato- phenyl) adamantane of 1,3-, bis- (4- cyanato- the phenyl) -5,7- dimethyladamantanes of 1,3-, Bis- (4- cyanato- phenyl) isobenzofuran -1 (3H) -one (cyanate of phenolphthalein) of 3,3-, the bis- (4- cyanato- -3- methyl of 3,3- Phenyl) isobenzofuran -1 (3H) -one (cyanate of o-cresolphthalein), 9,9 '-bis- (4- cyanato- phenyl) fluorenes, the bis- (4- of 9,9- Cyanato- -3- aminomethyl phenyl) fluorenes, bis- (2- cyanato- -5- xenyl) fluorenes of 9,9-, three (4- cyanato- phenyl) methane, 1,1,1- Three (4- cyanato- phenyl) ethane, 1,1,3- tri- (4- cyanato- phenyl) propane, α, α, α '-three (4- cyanato- phenyl) -1- second Base -4- cumene, 1,1,2,2- tetra- (4- cyanato- phenyl) ethane, four (4- cyanato- phenyl) methane, (the N- first of 2,4,6- tri- Base -4- cyanato- anilino-) -1,3,5- triazine, bis- (N- methyl -4- cyanato- the anilino-) -6- (methylphenylamine base)-of 2,4- 1,3,5- triazine, two phthalimide of bis- (N-4- cyanato- -2- aminomethyl phenyls) -4,4 '-oxygroup, bis- (N-3- cyanato- -4- methyl Phenyl) two phthalimide of -4,4 '-oxygroup, two phthalimide of bis- (N-4- cyanato- phenyl) -4,4 '-oxygroup, bis- (N-4- cyanogen oxygen Base -2- aminomethyl phenyl) -4,4 '-(hexafluoroisopropyli,ene base) two phthalimides, three (3,5- dimethyl -4- cyanato- benzyl) isocyanides Bis- (4- cyanato- phenyl) benzo [C] pyrrolones of urea acid esters, 2- phenyl -3,3-, bis- (the 4- cyanogen oxygen of 2- (4- aminomethyl phenyl) -3,3- Base phenyl) benzo [C] pyrrolones, 2- phenyl -3,3- bis- (4- cyanato- -3- aminomethyl phenyl) benzo [C] pyrrolones, 1- methyl - Bis- (the 4- cyanato- phenyl) Indolin-2-ones of 3,3- and bis- (the 4- cyanato- phenyl) Indolin-2-ones of 2- phenyl -3,3-.

These cyanate esters can be used alone or mix two or more come using.

In addition, other concrete examples as cyanate esters shown in above-mentioned general formula (9), can enumerate phenol novolac Varnish gum and cresol novolac resin (by known method, make phenol, alkyl substituted phenol or halogen-substituted phenol and The formaldehyde compounds such as formalin, paraformaldehyde react in an acidic solution), trisphenol novolac resin (make hydroxyl Benzaldehyde and phenol react in the presence of acidic catalysts), fluorenes novolac resin (keep fluorenone compound and 9,9- bis- (hydroxyaryl) fluorenes class is reacted in the presence of acidic catalysts), phenol aralkyl resin, cresols aralkyl resin, naphthalene Phenol aralkyl resin and biphenyl aralkyl resin (by known method, make Ar₄-(CH₂Y)₂(Ar₄Indicate that phenyl, Y indicate halogen Atom.It is identical in the paragraph below) shown in double halogenated methyl chemical combination objects and oxybenzene compound in acidic catalyst or without urging Reaction forms, makes Ar under agent₄-(CH₂OR)₂Shown in bis- (alkoxy methyl) compounds and oxybenzene compound in acidic catalyst Reaction forms or makes Ar in the presence of agent₄-(CH₂OH)₂Shown in bis- (hydroxymethyl) compounds and oxybenzene compound in acidity In the presence of catalyst reaction form or make aromatic aldehyde compound, aralkyl compound and oxybenzene compound polycondensation and At), phenol-modified xylene formaldehyde resin (by known method, urge xylene formaldehyde resin and oxybenzene compound in acidity Reacted in the presence of agent), modified naphthalene formaldehyde resin (by known method, make naphthaldehyde resin and hydroxyl substituted aroma Compounds of group reacts in the presence of acidic catalysts), phenol-modified dcpd resin, have poly- naphthylene ether knot The phenolic resin of structure (by known method, makes the multi-hydroxy naphthalene compound in 1 molecule with 2 or more phenolic hydroxyl group in alkali Property catalyst in the presence of dehydrating condensation form) etc. phenolic resin, cyanic acid is carried out by method same as described above and is esterified Cyanate esters etc. and their prepolymer etc..They are not particularly limited.These cyanate esters can be with Be used alone a kind or mix two or more come using.

Wherein, preferably phenol novolak type cyanate esters, naphthols aralkyl-type cyanate esters composition, biphenyl are fragrant Alkyl type cyanate esters, naphthylene ether type cyanate esters, xylene resin type cyanate esters, adamantane framework Type cyanate esters, naphthols aralkyl-type cyanate esters composition are particularly preferred from the viewpoint of plating adaptation.

It as the manufacturing method of these cyanate esters, is not particularly limited, well known method can be used.As upper The example of preparation method is stated, can enumerate acquisition or synthesis has the compound containing hydroxyl of desired skeleton, utilizes well known hand Method by the hydroxyl modified, carry out cyanic acid esterification method.As the gimmick that hydroxyl is carried out to cyanic acid esterification, can enumerate for example Ian Hamerton,“Chemistry and Technology of Cyanate Ester Resins,”Blackie The gimmick recorded in Academic&Professional.

Use the resin cured matter of these cyanate esters close in glass transition temperature, low heat expansion, plating Conjunction property etc. has excellent characteristic.

In the resin combination of present embodiment, the content of cyanate esters is not particularly limited, but from plating It is preferably 0.01 mass parts~50 mass relative to 100 mass parts of resin solid content from the viewpoint of covering adaptation, heat resistance Part, more preferable 0.05 mass parts~40 mass parts, further preferred 0.1 mass parts~20 mass parts, even more preferably 0.2 matter Measure part~5 mass parts.

As phenolic resin, then usually can be used if the phenolic resin in 1 molecule with 2 or more hydroxyls well known Phenolic resin.Such as bisphenol A type phenolic resin, bisphenol E-type phenolic resin, bisphenol F type phenolic resin, bisphenol S type can be enumerated Phenolic resin, phenol resol resins, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl Base novolak phenolics, biphenyl aralkyl-type phenol resin, cresol novolak type phenolic resin, multifunctional phenolic aldehyde tree Rouge, 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 resin, dicyclopentadiene type phenolic resin, biphenyl Type phenolic resin, polyol type phenolic resin, the phenolic resin containing phosphorus, contains polymerism unsaturation at ester ring type phenolic resin The phenolic resin of alkyl and the organic siliconresin class containing hydroxyl etc., but be not particularly limited.Among these phenolic resin, connection Benzene aralkyl-type phenol resin, naphthols aralkyl-type phenol resin, the phenolic resin containing phosphorus, the organic siliconresin containing hydroxyl Consider from anti-flammability viewpoint preferred.These phenolic resin can be used alone or properly mix two or more come using.

The content of phenolic resin is not particularly limited, is preferably 0.1 matter relative to 100 mass parts of resin solid content Measure part~50 mass parts, more preferable 0.2 mass parts~45 mass parts.Within the above range by the content of phenolic resin, it deposits In the tendency that heat resistance further increases.

As oxetane resin, well known oxetane resin usually can be used.Such as oxa- can be enumerated Cyclobutane, 2- methy oxetane, 2,2- dimethyl oxygen azetidine, 3- methy oxetane, 3,3- dimethyl oxa- The alkyl oxetanes such as cyclobutane, 3- methyl -3- methoxy oxetanes, 3,3- bis- (trifluoromethyl) perfluor oxa- Bis- (chloromethyl) oxetanes of cyclobutane, 2- chloromethyl oxetanes, 3,3-, biphenyl type oxetanes, OXT-101 (East Asia synthesis system, trade name), OXT-121 (East Asia synthesis system, trade name) etc., are not particularly limited.They can individually make With a kind or properly mix two or more come using.

The content of oxetane resin is not particularly limited, it is preferred relative to 100 mass parts of resin solid content For 0.1 mass parts~50 mass parts, more preferable 0.2 mass parts~45 mass parts.It is in by the content of oxetane resin In above range, there are the tendencies that heat resistance further increases.

As benzoxazine compound, then lead to if the compound of the dihydrobenzo oxazines ring in 1 molecule with 2 or more Well known benzoxazine compound often can be used.Can enumerate such as bisphenol A-type benzoxazine BA-BXZ (small westernization length of schooling, Trade name), bisphenol-f type benzoxazine BF-BXZ (small westernization length of schooling, trade name), BS-BXZ (the small westernization of bisphenol S type benzoxazine Length of schooling, trade name), phenolphthalein type benzoxazine etc., but be not particularly limited.They can be used alone or properly mix 2 Kind or more use.

The content of benzoxazine compound is not particularly limited, it is preferred relative to 100 mass parts of resin solid content For 0.1 mass parts~50 mass parts, more preferable 0.2 mass parts~45 mass parts.It is in by the content of benzoxazine compound In above range, there are the tendencies that heat resistance further increases.

In the resin combination of present embodiment, in order to improve the heat resistance of solidfied material, can also be applied in combination with it is aforementioned (1) the different epoxy resin of dicyclopentadiene type epoxy resin (A) shown in.

This epoxy resin if it is different from aforementioned epoxy resins (A), in 1 molecule with the change of 2 or more epoxy groups Object is closed to be not particularly limited.As its concrete example, can enumerate for example bisphenol A type epoxy resin, bisphenol E-type epoxy resin, Bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol phenol Novolac type epoxy resin, cresol novolak type epoxy resin, dimethylbenzene phenolic resin varnish type epoxy resin, multifunctional phenol type Epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthylene ether type epoxy, phenol virtue Alkane type epoxy resin, anthracene type epoxy resin, 3 trifunctional phenol type epoxy resin, 4 trifunctional phenol type epoxy resin, three shrinks are sweet Oil base isocyanuric acid ester, glycidyl esters type epoxy resin, alicyclic epoxy resin, biphenyl phenolic resin varnish type epoxy resin, Phenol aralkyl phenolic resin varnish type epoxy resin, naphthols aralkyl phenolic resin varnish type epoxy resin, aralkyl novolaks type ring Oxygen resin, biphenyl aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin, polyol type epoxy resin, the ring containing phosphorus The double bond of butadiene etc. is carried out compound made of epoxidation, by containing the organic of hydroxyl by oxygen resin, glycidyl group amine The compound and their halide that the reaction of silicones class and epichlorohydrin obtains.

Wherein, it is preferably selected from by biphenyl aralkyl-type epoxy resin, naphthylene ether type epoxy, multifunctional phenol type One or more of group of epoxy resin, naphthalene type epoxy resin composition, more preferable naphthalene type epoxy resin.By containing this epoxy Resin, there are the tendencies that developability and plating adaptation further increase.

As naphthalene type epoxy resin, using resin shown in following formula (5) since developability and plating adaptation are further Improve and it is preferred that.As this epoxy resin, commercially available product can use, can enumerate Dainippon Ink Chemicals's HP-4710 (commodity Name).Naphthalene type epoxy resin shown in following formula (5) is since for low molecule and multifunctional, dissolubility is excellent in developer solution It is different.Therefore, it is considered that by being applied in combination with dicyclopentadiene type epoxy resin (A), available developability also excellent resin group Close object.

These epoxy resin also can be used alone or properly mix two or more come using.

The content of epoxy resin is not particularly limited, but from the viewpoint of further increasing developability, relatively 100 mass parts of resin solid content in resin combination, according to aforementioned epoxy resins (A) and different from epoxy resin (A) Epoxy resin total, it is more than preferably 3 mass parts, it is more than more preferable 5 mass parts, it is more than further preferred 10 mass parts, It is more than even more preferably 15 mass parts.In addition, from the viewpoint of further increasing copper facing adaptation, relative to resin combination 100 mass parts of resin solid content in object, according to aforementioned epoxy resins (A) and the epoxy resin different from epoxy resin (A) Total, preferably 50 below the mass, more preferably 40 below the mass, further preferably 30 below the mass, it is further excellent It selects 28 below the mass.

In addition, the ratio for aforementioned epoxy resins (A) and the epoxy resin different from epoxy resin (A) does not limit especially System, but from the viewpoint of plating adaptation, preferably 1~10:1~3, more preferable 2~4:1~2.

In the resin combination of present embodiment, in the range of will not damage present embodiment characteristic, also it can be used Thermosetting accelerator (H) (also referred to as ingredient (H)).As thermosetting accelerator used in present embodiment (H), without special It limits, can enumerate for example with benzoyl peroxide, lauroyl peroxide, acetyl peroxide, chloro benzoyl peroxide, two uncles Butyl-two crosses the organic peroxide of the illustrations such as phthalate ester；The azo-compounds such as the double nitriles of azo；N, N- dimethyl benzyl amine, N, Accelerine, N, N- dimethyl toluidine, 2-N- ethylo benzene aminoethanol, tri-n-butyl amine, pyridine, quinoline, N- methyl The tertiary amines such as morpholine, triethanolamine, triethylenediamine, tetramethyl butane diamine, N- methyl piperidine；Phenol, dimethlbenzene, first The phenols such as phenol, resorcinol, catechol；Lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, oleic acid tin, dibutyl horse Carry out the organic metal salts such as sour tin, manganese naphthenate, cobalt naphthenate, pentanedione iron；These organic metal salts are dissolved in phenol, double Thermosetting accelerator made of the compounds containing hydroxyl such as phenol；The inorganic metal salts such as stannic chloride, zinc chloride, aluminium chloride；Two is pungent The organo-tin compounds such as base tin oxide, other tin alkyls, alkyl-tin oxide；2-ethyl-4-methylimidazole, 1,2- dimethyl miaow Imidazolium compounds such as azoles, 1- benzyl -2- phenylimidazole, triphenylimidazolyl (TPIZ) etc..Wherein, excellent from the viewpoint of heat resistance Select the imidazoles such as 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 1- benzyl -2- phenylimidazole, triphenylimidazolyl (TPIZ) Close object, the more preferable 2-ethyl-4-methylimidazole from the viewpoint of obtaining superior heat resistance.

These thermosetting accelerators also can be used alone or properly mix two or more come using.

In the resin combination of present embodiment, the content of thermosetting accelerator (H) is not particularly limited, but it is logical It is often 0.01~10 mass parts, preferably 0.05~5 mass relative to 100 mass parts of resin solid content in resin combination Part.

Solvent can be contained in the resin combination of present embodiment as needed.Such as it can be with if using organic solvent Adjust the viscosity when manufacture of resin combination.If the type of solvent can be by a part of the resin in resin combination or complete Portion's dissolution is not particularly limited.As its concrete example, it is not particularly limited, it is molten that such as acetone, methyl ethyl ketone, methyl can be enumerated The ketones such as fine agent；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；The amides such as dimethylformamide；Propylene glycol monomethyl ether and its second Acid esters.

These organic solvents can be used alone or properly mix two or more come using.

In the resin combination of present embodiment, in the range of will not damage present embodiment characteristic, it can also combine Use thermosetting resin, thermoplastic resin and its oligomer, the various macromolecule chemical combination such as elastomer class not enumerated so far Object；The compound for the anti-flammability not enumerated so far；Additive etc..They are not limited especially then if usually used ingredient It is fixed.Such as the compound of anti-flammability, melamine, benzoguanamine etc. can be enumerated and contain nitrogen compound, contain The compound of oxazines ring and phosphate compound, the aromatic condensation phosphate, condensed phosphoric acid esters containing halogen of phosphorus series compound Deng.As additive, ultraviolet absorbing agent, antioxidant, fluorescent whitening agent, photosensitizer, dyestuff, pigment, thickening can be enumerated Agent, lubricant, defoaming agent, surface conditioner, gloss agent, polymerization inhibitor etc..These ingredients also can be used alone or suitably mix Close two or more come using.

In the resin combination of present embodiment, the content of other ingredients is not particularly limited, but it is usually opposite In 100 mass parts of resin combination be respectively 0.1~10 mass parts.

The resin combination of present embodiment is by by dicyclopentadiene type epoxy resin (A), light shown in previously described formula (1) The chemical combination with ethylenically unsaturated group other than curing initiator (B), previously described formula (2) compound represented (C) and (C) ingredient Object (D) and maleimide compound as needed (E), filler (F), compound (G) and other ingredients properly mix to make It makes.The resin combination of present embodiment can suitably serve as varnish when making aftermentioned resin sheet of the invention.

The manufacturing method of the resin combination of present embodiment is not particularly limited, can enumerate for example will be above-mentioned Each ingredient successively matches the method for being mixed in solvent, being sufficiently stirred.

When manufacturing resin combination, the known place carried out for equably dissolving or dispersing each ingredient can according to need It manages (stirring, mixing, mixing process etc.).Specifically, by using the blender with stirring capacity appropriate has been set up Stirred tank is stirred decentralized processing, and inorganic filler (G) can be improved for the dispersibility of resin combination.Above-mentioned stirring, Ultrasonic homogenizer etc. can be used for example to disperse agitating device, triple-roller mill, ball milling as a purpose in mixing, mixing process Machine, ball mill, sand mill etc. are with device well known to mixing arrangement for mixing device as a purpose or revolution or rotation type etc. It is appropriate to carry out.In addition, can according to need when the resin combination of manufacture present embodiment using organic solvent.Organic solvent If type can the resin in dissolving resin composition be not particularly limited, concrete example is as described above.

The resin combination of present embodiment can be used for needing the purposes of the resin combination of insulating properties, not limit especially It is fixed, it can be used for the insulating resins sheet materials such as photosensitive film, the photosensitive film with supporting mass, prepreg, circuit substrate (stacking Plate purposes, multilayer printed wiring board-use way etc.), welding resist, underfill, die bond material, encapsulating semiconductor The purposes such as material, filling perforation resin, element embedment resin.Wherein it is possible to which the insulating layer for suitably serving as multilayer printed-wiring board is used Resin combination, welding resist.

The resin sheet of present embodiment is to have supporting mass and be formed in the supporting mass surface, contain present embodiment Resin combination resin composition layer, above-mentioned resin combination is coated on band made of the one or two sides of supporting mass The resin sheet of supporting mass.Resin sheet can be manufactured by the way that resin combination is coated on supporting mass and is dried.

Supporting mass used in resin sheet for present embodiment is not particularly limited, and well known bearing can be used Body, preferably resin film.As resin film, can enumerate for example Kapton, polyamide film, polyester film, Polyethylene terephthalate (PET) film, polypropylene (PP) film, gathers polybutylene terephthalate (PBT) (PBT) film The resins such as ethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, triacetyl acetate films are thin Film.Wherein, preferably PET film.

Above-mentioned resin film can be used suitably remover being coated on table to be easy to be removed by resin composition layer Resin film made of face.The thickness of resin film be preferably in 5 μm~100 μm in the range of, be more preferably in 10 μm~50 μ In the range of m.When the thickness is less than 5 μm, when there is the supporting mass removing carried out before development, supporting mass is crackly inclines To the tendency that resolution ratio when existing if thickness is more than 100 μm by exposing on supporting mass reduces.

In addition, light when being exposed to reduce using ultraviolet light isoreactivity energy-ray is scattered, resin film is preferred The transparency is excellent.

In turn, in the resin sheet in present embodiment, which can be protected with protective film.

By protecting resin composition layer side with protective film, dust etc. can be prevented to the attached of resin combination layer surface , scratch.As protective film, the film constituted using material identical with above-mentioned resin film can be used.For protection The thickness of film is not particularly limited, it is preferred that in the range of 1 μm~50 μm, being more preferably in 5 μm~40 μm of model In enclosing.When thickness is less than 1 μm, there are the tendencies that the treatability of protective film reduces, and there are cheapness variation if more than 50 μm Tendency.It should be noted that it is preferable to use set for the bonding force of resin composition layer and supporting mass for protective film The small protective film of the bonding force of oil/fat composition layer and protective film.

The manufacturing method of the resin sheet of present embodiment is not particularly limited, can be enumerated for example by by this reality The resin combination for applying mode is coated on the supporting masses such as PET film, is removed organic solvent using dry, and resin sheet is thus manufactured The method etc. of material.

Above-mentioned coating for example can by using roll coater, comma coating machine, gravure coater, die coating machine, bar coater, The known method of die lip coating machine, knife type coater, extrusion coating machine etc. carries out.Above-mentioned drying for example can by 60~ Method that 1~60 minute is heated in 200 DEG C of drying machine etc. carries out.

The residual organic solvent amount viewpoint that organic solvent is spread from the process prevented hereafter in resin composition layer is examined Consider, the gross mass preferably with respect to resin composition layer is 5 mass % or less.For the thickness of the resin composition layer of supporting mass From the viewpoint of improving treatability, according to the resin composition layer thickness of resin sheet, preferably 1.0 μm or more.In addition, from Improve transmitance and from the viewpoint of keeping developability good, preferably 300 μm or less.

The resin sheet of present embodiment may be used as the interlayer insulating film of multilayer printed-wiring board.

The multilayer printed-wiring board of present embodiment can also have the interlayer of the resin combination containing present embodiment Insulating layer, for example by above-mentioned resin sheet 1 open it is above be overlapped and solidify obtain.It can specifically make by the following method It makes.

(laminating process)

The resin composition layer side of the resin sheet of present embodiment is laminated to circuit substrate using vacuum lamination apparatus One or two sides.As circuit substrate, can enumerate for example glass epoxy substrate, metal substrate, ceramic substrate, silicon substrate, Semiconductor sealing resin substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide substrate etc..It needs Illustrate, refers to being formed with the conductor layer processed by pattern in the one or two sides of aforesaid substrate in this circuit substrate The substrate of (circuit).In addition, in multilayer printed-wiring board made of conductor layer and insulating layer are alternately laminated, the printed wiring board Outermost one or two sides forms the substrate of the conductor layer (circuit) by pattern processing, is also contained in so-called circuit herein Substrate.It should be noted that can also be implemented at roughening in advance by blackening process, copper etching etc. for conductor layer surface Reason.In laminating process, in the case that resin sheet has protective film, after protective film removing removal, as needed will Resin sheet and circuit substrate preheating, are crimped on circuit substrate while resin composition layer is pressurizeed and heated.This implementation In the resin sheet of mode, suitably using by vacuum layer platen press, be laminated to the method for circuit substrate under reduced pressure.

The condition of laminating process is not particularly limited, such as is preferably, crimping temperature (laminating temperature) is preferred It is set as 50 DEG C~140 DEG C, crimping pressure is preferably set to 1kgf/cm²~15kgf/cm², will crimping the time be preferably set to 5 seconds~ 300 seconds, be laminated in the case where air pressure is set as 20mmHg decompression below.In addition, laminating process can be intermittent or make With the continous way of roller.Vacuum layer platen press can be used commercially available vacuum lamination apparatus and carry out.As commercially available vacuum lamination apparatus, Such as Nikko-Materials Co., 2 step lamination laminater of Ltd. system etc. can be enumerated.

(exposure process)

By laminating process, after resin sheet is set on circuit substrate, the specified part for resin composition layer is carried out Divide irradiation active energy beam, make the cured exposure process of the resin composition layer of irradiation portion.The irradiation of active energy beam can With by mask pattern, the direct picture of direct irradiation active energy beam also can be used.

As active energy beam, can enumerate such as ultraviolet light, luminous ray, electron beam, X-ray, particularly preferably For ultraviolet light.Ultraviolet irradiation amount substantially 10mJ/cm²~1000mJ/cm².By depositing in the exposure method of mask pattern Keep mask pattern and multilayer printed-wiring board closely sealed the contact exposure method that carries out and not closely sealed and carry out using parallel rays The non-contact exposure method of exposure, can be used any one.In addition, on resin composition layer there are in the case where supporting mass, By exposing on supporting mass or supporting mass can also be removed into post-exposure.

(developing procedure)

After exposure process, on resin composition layer there are in the case where supporting mass, after supporting mass removal, with wet type The part (unexposed portion) of not photocuring is removed, is developed by development, it is possible thereby to form the pattern of insulating layer.

In the case where above-mentioned wet developing, as developer solution, do not limited especially if selectively dissolving out unexposed portion It is fixed, the developer solutions such as alkaline aqueous solution, water system developer solution, organic solvent can be used.In present embodiment, it is particularly preferably utilization The developing procedure that alkaline aqueous solution carries out.These developer solutions may be used singly or in combination of two or m.In addition, conduct Developing method, such as can be impregnated by spraying, shake, is brush, scraping the progress of the known methods such as formula.

For be used as developer solution alkaline aqueous solution be not particularly limited, can enumerate for example potassium hydroxide, sodium hydroxide, Sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate, 4- Boratex, ammonia, amine etc..

The concentration of above-mentioned aqueous alkali is preferably 0.1 mass of mass %~60 % relative to developer solution total amount.In addition, buck The temperature of solution can meet developability to adjust.In turn, these aqueous alkalis can be used alone or combine two or more next It uses.

During the pattern of present embodiment is formed, above-mentioned developing method of more than two kinds can be applied in combination as needed.Development Mode there are impregnation method, paddle mode, spray pattern, high-pressure fog mode, it is brush, scrape formula etc., high-pressure fog mode by In improve resolution ratio and it is preferred that.Atomisation pressure when being taken as spray pattern is preferably 0.02MPa~0.5MPa.

(drying process afterwards)

After above-mentioned developing procedure, process is dried after progress, is formed insulating layer (solidfied material).As rear baking process, can arrange The ultraviolet light irradiation process using high-pressure sodium lamp, the heating process for having used cleaning oven etc. are enumerated, them can also be combined It uses.In the case where irradiating ultraviolet light, it can according to need and adjust its exposure, such as can be with 0.05J/cm²~10J/cm² The exposure of left and right is irradiated.In addition the condition heated is suitable according to type, content of the resin component in resin combination etc. When selection, it is preferred that at 150 DEG C~220 DEG C in the range of 20 minutes~180 minutes, it is 160 DEG C~200 DEG C more preferable It is selected in the range of lower 30 minutes~150 minutes.

(plating process)

Then by dry type plating or wet type plating, conductor layer is formed in surface of insulating layer.As dry type plating, can make The method well known to vapour deposition method, sputtering method, ion plating method etc..Vapour deposition method (vacuum vapour deposition) for example can be by filling supporting mass Enter into vacuum tank, metal film is formed on the insulating layer in METAL HEATING PROCESS evaporation.Sputtering method for example can also be by supporting mass It is encased in vacuum tank, imports the non-active gas such as argon, apply DC voltage, make the non-active gas and target by ionization Metal film is formed on the insulating layer using the metal typed it out in metal bump.

In the case where wet type plating, for being formed by the surface of insulating layer, successively carry out carrying out using swelling solution molten Swollen processing, the roughening treatment carried out using oxidant and the neutralisation treatment carried out using neutralizer, thus by surface of insulating layer Roughening.Using swelling solution carry out swelling treatment by insulating layer is impregnated in swelling solution at 50 DEG C~80 DEG C 1 minute~ It carries out within 20 minutes.As swelling solution, aqueous slkali can be enumerated, as the aqueous slkali, sodium hydroxide solution, hydrogen-oxygen can be enumerated Change potassium solution etc..As commercially available swelling solution, the Appdes (registered trademark) of such as C. Uyemura & Co Ltd can be enumerated MDS-37 etc..

The roughening treatment carried out using oxidant is by being impregnated in oxidizing agent solution 5 at 60 DEG C~80 DEG C for insulating layer Minute~carry out within 30 minutes.As oxidant, aqueous dissolution potassium permanganate, the Gao Meng for example in sodium hydroxide can be enumerated Alkalinity permanganic acid solution, bichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid etc. made of sour sodium.In addition, alkaline permanganic acid is molten The concentration of permanganate in liquid is preferably 5 mass of mass %~10 %.As commercially available oxidant, for example upper village can be enumerated The alkalinity permanganic acid solution such as Industrial Co., Ltd Appdes (registered trademark) MDE-40, Appdes (registered trademark) ELC-SH. It is carried out using the neutralisation treatment that neutralizer carries out by being impregnated in neutralizer at 30 DEG C~50 DEG C 1 minute~10 minutes.Make Appdes (the note of C. Uyemura & Co Ltd can be enumerated as commercially available product for neutralizer, preferably acid aqueous solution Volume trade mark) MDN-62.

Then, chemical plating and electrolytic coating combination are formed into conductor layer.It is opposite with conductor layer alternatively, it is also possible to be formed The plating resist of pattern only forms conductor layer by chemical plating.As the method that pattern hereafter is formed, such as can be with Use subraction, semi-additive process etc..

The semiconductor device of present embodiment has the interlayer insulating film of the resin combination containing present embodiment, specifically For can manufacture by the following method.Pass through the conducting position actual load semiconductor of the multilayer printed-wiring board in present embodiment Chip can manufacture semiconductor device.Here, conducting position refers to the portion of the transmitting electric signal in multilayer printed-wiring board Position, this place can be surface or embedment position, any one is ok.In addition, semiconductor chip is made if with semiconductor It is not particularly limited for the circuit element of material.

If the mounting method semiconductor chip of semiconductor chip when manufacturing the semiconductor device of present embodiment is effectively It functions and is not particularly limited, specifically, wire bonding mounting method, flip-chip mounting method, nothing can be enumerated Mounting method of the protrusion using lamination (BBUL), the mounting method using anisotropic conducting film (ACF), using non-conductive The mounting method etc. of film (NCF).

In addition, by the way that the resin sheet of present embodiment is laminated to semiconductor chip, semiconductor device can also be manufactured. After lamination, method manufacture identical with multilayer printed-wiring board above-mentioned can be used.

Embodiment

The present invention is more particularly described by the following examples, but the present invention is not by any limit of these embodiments It is fixed.

[synthesis example 1]

(synthesis of cyanate esters)

By 1- naphthols aralkyl resin (Nippon Steel & Sumitomo Metal Corporation's system) 300g (OH base convert 1.28 moles) and Triethylamine 194.6g (1.92 moles) (being 1.5 moles relative to 1 mole of hydroxyl) is dissolved in methylene chloride 1800g, as Solution 1.

For cyanogen chloride 125.9g (2.05 moles) (relative to 1 mole of hydroxyl be 1.6 moles), methylene chloride 293.8g, 36% hydrochloric acid 194.5g (1.92 moles) (being 1.5 moles relative to 1 mole of hydroxyl), water 1205.9g, are held in liquid under stiring While -2~-0.5 DEG C of temperature, solution 1 was poured down with 30 minutes.After solution 1 pours down, stir 30 minutes at the same temperature Afterwards, triethylamine 65g (0.64 mole) (being 0.5 mole relative to 1 mole of hydroxyl) was poured down with 10 minutes be dissolved in methylene chloride 65g Made of solution (solution 2).It after solution 2 pours down, stirs 30 minutes at the same temperature, completes reaction.

Then reaction solution is stood, by organic phase and aqueous phase separation.Obtained organic phase is washed 5 times with water 1300g. The conductivity for washing the waste water of the 5th is 5 μ S/cm, is identified through and is washed using water, the ionic compound quilt removed Sufficiently removal.

Organic phase after washing is concentrated under reduced pressure, is finally concentrated and dried 1 hour at 90 DEG C, obtains the naphthols of purpose Cyanate esters (SNCN) (orange gummy object) 331g of aralkyl-type.The matter average molecular weight Mw of obtained SNCN is 600. In addition, the IR spectrum of SNCN shows 2250cm^-1The absorption of (cyanic acid ester group) and the absorption for not showing hydroxyl.

[embodiment 1]

(resin combination and resin sheet be made)

It is compounded the dicyclopentadiene type epoxy resin (formula as dicyclopentadiene type epoxy resin (A) shown in formula (1) (1) n in is 1~3.XD-1000 (trade name), Nippon Kayaku K. K's system) 22.4 mass parts, as trigger for optical solidification (B) 2- benzyl -2- dimethylamino -1- (4- morpholino base phenyl)-butanone -1 (Irgacure (registered trademark) 369, BASF Japan Ltd. system) 6.5 mass parts, as compound (C) TrisP-PA epoxy acrylic ester compounds propylene glycol list first Base ether acetic acid ester (hereinafter sometimes referred to simply as PGMEA) solution (KAYARAD (registered trademark) ZCR-6007H, 65 matter of nonvolatile component Amount %, acid value: 70mgKOH/g, Nippon Kayaku K. K's system) 77.5 mass parts (are scaled 50.4 matter according to nonvolatile component Measure part), as the dipentaerythritol hexaacrylate of the compound (D) with ethylenically unsaturated group other than (C) ingredient (KAYARAD (registered trademark) DPHA, Nippon Kayaku K. K's system) 17.4 mass parts, as maleimide compound (E) Maleimide compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.3 mass parts, as filler (F) methyl ethyl ketone (hereinafter sometimes referred to simply as MEK) slurry of epoxy silane processing silica (SC2050MB (trade name), is put down Equal 0.5 μm of partial size, 70 mass %, ADMATECHS Co., Ltd. system of nonvolatile component) 71.4 mass parts are (according to nonvolatile component It is scaled 50 mass parts), it is stirred with ultrasonic homogenizer, obtains varnish (solution of resin combination).It is filled using automatic coating It sets (PI-1210, TESTER SANGYO CO .LTD. (strain) system) and these varnish is coated on to 38 μm of thickness of PET film On (Unipeel (registered trademark) TR1-38, Unitika Ltd. system, trade name), heat drying 7 minutes, are obtained at 80 DEG C Using PET film as supporting mass, resin composition layer with a thickness of 30 μm of resin sheet.

It should be noted that aforementioned KAYARAD (registered trademark) ZCR-6007H is to contain above compound (C1) and above-mentioned Mixture more than any one in compound (C2)~(C5).

(being made for internal layer circuit substrate)

For being formed with glass cloth base material BT resin two sides copper-clad laminated board (18 μm of the copper thickness, thickness of internal layer circuit 0.2mm, Mitsubishi Gas Chemical Company, Inc. CCL (registered trademark)-HL832NS) two sides, utilize MEC Co., Ltd. CZ8100 carries out the roughening treatment on copper surface, obtains internal layer circuit substrate.

(production that laminated body is used in evaluation)

The resin face of aforementioned resin sheet material is configured on internal layer circuit substrate, vacuum lamination apparatus (Nikko- is used Materials Co., Ltd. system), it carries out 30 seconds after vacuumizing (5.0MPa or less), in pressure 10kgf/cm², under temperature 70 C Carry out 30 seconds cascading into shape.And then in pressure 10kgf/cm², carry out under temperature 70 C 60 seconds it is cascading into shape, thus obtain in Laminated body made of layer circuit substrate, resin composition layer and supporting mass stacking.Implement to irradiate obtained laminated body 200mJ/cm²Ultraviolet light exposure process, supporting mass is removed, is developed with the aqueous sodium carbonate of 1 mass %, and then is implemented Irradiate 1000mJ/cm²Ultraviolet light exposure process, implement after heating 120 minutes rear baking processes at 180 DEG C, as Laminated body is used in evaluation.

(production that solidfied material is used in evaluation)

Implement to irradiate 200mJ/cm for aforementioned resin sheet material²Ultraviolet light, and then irradiate 1000mJ/cm²Ultraviolet light Exposure process removes supporting mass after heating 120 minutes rear baking processes at 180 DEG C of implementation, as evaluation solidification Object.

[embodiment 2]

It is compounded dicyclopentadiene type epoxy resin (XD-1000 (trade name), Japanese chemical drug strain formula meeting as ingredient (A) Society's system) 21.9 mass parts, the 2- benzyl -2- dimethylamino -1- (4- morpholino base phenyl)-as trigger for optical solidification (B) Butanone -1 (Irgacure (registered trademark) 369, BASF Japan Ltd. system) 6.5 mass parts, as compound (C) PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, nonvolatile component 65 of TrisP-PA epoxy acrylic ester compounds Quality %, acid value: 70mgKOH/g, Nippon Kayaku K. K's system) 77.5 mass parts (are scaled 50.4 according to nonvolatile component Mass parts), as the dipentaerythritol hexaacrylate of the compound (D) with ethylenically unsaturated group other than (C) ingredient (KAYARAD (registered trademark) DPHA, Nippon Kayaku K. K's system) 17.4 mass parts, as maleimide compound (E) Maleimide compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.3 mass parts, as filler (F) MEK slurry (SC2050MB (trade name), 0.5 μm of average grain diameter, nonvolatile component of epoxy silane processing silica 70 mass %, ADMATECHS Co., Ltd. systems) 71.4 mass parts (being scaled 50 mass parts according to nonvolatile component), as change 0.5 mass parts of cyanate esters SNCN obtained in the synthesis example 1 of object (G) are closed, are stirred with ultrasonic homogenizer, are obtained clear It paints (solution of resin combination).It will using automatic coating device (PI-1210, TESTER SANGYO CO .LTD. (strain) make) These varnish are coated on 38 μm of thickness PET film (Unipeel (registered trademark) TR1-38, Unitika Ltd. system, commodity Name) on, heat drying 7 minutes at 80 DEG C, obtain using PET film as supporting mass, resin composition layer with a thickness of 30 μm Resin sheet.It obtains evaluating with laminated body and evaluation solidfied material similarly to Example 1 using it.

[embodiment 3]

It is compounded dicyclopentadiene type epoxy resin (XD-1000 (trade name), Japanese chemical drug strain formula meeting as ingredient (A) Society's system) 21.9 mass parts, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides as trigger for optical solidification (B) (Irgacure (registered trademark) 819, BASF Japan Ltd. system) 6.5 mass parts, as the TrisP-PA ring of compound (C) PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, 65 mass % of nonvolatile component, acid of oxypropylene ester compound Value: 70mgKOH/g, Nippon Kayaku K. K's system) 77.5 mass parts (being scaled 50.4 mass parts according to nonvolatile component), work For the dipentaerythritol hexaacrylate (KAYARAD (note of the compound (D) with ethylenically unsaturated group other than (C) ingredient Volume trade mark) DPHA, Nippon Kayaku K. K's system) 17.4 mass parts, as the maleimide of maleimide compound (E) Compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.3 mass parts, as the epoxy silicon of filler (F) Alkane handle silica MEK slurry (SC2050MB (trade name), 0.5 μm of average grain diameter, 70 mass % of nonvolatile component, ADMATECHS Co., Ltd. system) 71.4 mass parts (being scaled 50 mass parts according to nonvolatile component), as compound (G) 0.5 mass parts of cyanate esters SNCN, are stirred with ultrasonic homogenizer obtained in synthesis example 1, obtain varnish (resin group Close the solution of object).Using automatic coating device (PI-1210, TESTER SANGYO CO .LTD. (strain) make) by these varnish It is coated in 38 μm of thickness of PET film (Unipeel (registered trademark) TR1-38, Unitika Ltd. system, trade name), 80 Heat drying 7 minutes at DEG C, obtain using PET film as supporting mass, resin composition layer with a thickness of 30 μm of resin sheet. It obtains evaluating with laminated body and evaluation solidfied material similarly to Example 1 using it.

[embodiment 4]

It is compounded dicyclopentadiene type epoxy resin (XD-1000 (trade name), Japanese chemical drug strain formula meeting as ingredient (A) Society's system) 19.9 mass parts, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides as trigger for optical solidification (B) (Irgacure (registered trademark) 819, BASF Japan Ltd. system) 6.5 mass parts, as the TrisP-PA ring of compound (C) PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, 65 mass % of nonvolatile component, acid of oxypropylene ester compound Value: 70mgKOH/g, Nippon Kayaku K. K's system) 77.5 mass parts (being scaled 50.4 mass parts according to nonvolatile component), work For the dipentaerythritol hexaacrylate (KAYARAD (note of the compound (D) with ethylenically unsaturated group other than (C) ingredient Volume trade mark) DPHA, Nippon Kayaku K. K's system) 17.4 mass parts, as the maleimide of maleimide compound (E) Compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.3 mass parts, as the epoxy silicon of filler (F) Alkane handle silica MEK slurry (SC2050MB (trade name), 0.5 μm of average grain diameter, 70 mass % of nonvolatile component, ADMATECHS Co., Ltd. system) 71.4 mass parts (being scaled 50 mass parts according to nonvolatile component), as compound (G) 0.5 mass parts of cyanate esters SNCN obtained in synthesis example 1 and naphthalene type epoxy resin (HP-4710 (trade name), DIC plants Formula commercial firm system) 2 mass parts, are stirred with ultrasonic homogenizer, obtain varnish (solution of resin combination).It is filled using automatic coating It sets (PI-1210, TESTER SANGYO CO .LTD. (strain) system) and these varnish is coated on to 38 μm of thickness of PET film On (Unipeel (registered trademark) TR1-38, Unitika Ltd. system, trade name), heat drying 7 minutes, are obtained at 80 DEG C Using PET film as supporting mass, resin composition layer with a thickness of 30 μm of resin sheet.Similarly to Example 1 using it It obtains evaluating with laminated body and evaluation solidfied material.

[embodiment 5]

It is compounded dicyclopentadiene type epoxy resin (XD-1000 (trade name), Japanese chemical drug strain formula meeting as ingredient (A) Society's system) 15.8 mass parts, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides as trigger for optical solidification (B) (Irgacure (registered trademark) 819, BASF Japan Ltd. system) 6.5 mass parts, as the TrisP-PA ring of compound (C) PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, 65 mass % of nonvolatile component, acid of oxypropylene ester compound Value: 70mgKOH/g, Nippon Kayaku K. K's system) 77.5 mass parts (being scaled 50.4 mass parts according to nonvolatile component), work For the dipentaerythritol hexaacrylate (KAYARAD (note of the compound (D) with ethylenically unsaturated group other than (C) ingredient Volume trade mark) DPHA, Nippon Kayaku K. K's system) 17.4 mass parts, as the maleimide of maleimide compound (E) Compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.3 mass parts, as the epoxy silicon of filler (F) Alkane handle silica MEK slurry (SC2050MB (trade name), 0.5 μm of average grain diameter, 70 mass % of nonvolatile component, ADMATECHS Co., Ltd. system) 71.4 mass parts (being scaled 50 mass parts according to nonvolatile component), as compound (G) 0.5 mass parts of cyanate esters SNCN obtained in synthesis example 1 and naphthalene type epoxy resin (HP-4710 (trade name), DIC plants Formula commercial firm system) 6.1 mass parts, are stirred with ultrasonic homogenizer, obtain varnish (solution of resin combination).Use automatic coating These varnish are coated on 38 μm of thickness of PET film by device (PI-1210, TESTER SANGYO CO .LTD. (strain) system) On (Unipeel (registered trademark) TR1-38, Unitika Ltd. system, trade name), heat drying 7 minutes, are obtained at 80 DEG C Using PET film as supporting mass, resin composition layer with a thickness of 30 μm of resin sheet.Similarly to Example 1 using it It obtains evaluating with laminated body and evaluation solidfied material.

[embodiment 6]

It is compounded dicyclopentadiene type epoxy resin (XD-1000 (trade name), Japanese chemical drug strain formula meeting as ingredient (A) Society's system) 5.9 mass parts, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides as trigger for optical solidification (B) (Irgacure (registered trademark) 819, BASF Japan Ltd. system) 6.5 mass parts, as the TrisP-PA ring of compound (C) PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, 65 mass % of nonvolatile component, acid of oxypropylene ester compound Value: 70mgKOH/g, Nippon Kayaku K. K's system) 77.5 mass parts (being scaled 50.4 mass parts according to nonvolatile component), work For the dipentaerythritol hexaacrylate (KAYARAD (note of the compound (D) with ethylenically unsaturated group other than (C) ingredient Volume trade mark) DPHA, Nippon Kayaku K. K's system) 17.4 mass parts, as the maleimide of maleimide compound (E) Compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.3 mass parts, as the epoxy silicon of filler (F) Alkane handle silica MEK slurry (SC2050MB (trade name), 0.5 μm of average grain diameter, 70 mass % of nonvolatile component, ADMATECHS Co., Ltd. system) 71.4 mass parts (being scaled 50 mass parts according to nonvolatile component), as compound (G) 0.5 mass parts of cyanate esters SNCN obtained in synthesis example 1 and naphthalene type epoxy resin (HP-4710 (trade name), DIC plants Formula commercial firm system) 16 mass parts, are stirred with ultrasonic homogenizer, obtain varnish (solution of resin combination).Use automatic coating These varnish are coated on 38 μm of thickness of PET film by device (PI-1210, TESTER SANGYO CO .LTD. (strain) system) On (Unipeel (registered trademark) TR1-38, Unitika Ltd. system, trade name), heat drying 7 minutes, are obtained at 80 DEG C Using PET film as supporting mass, resin composition layer with a thickness of 30 μm of resin sheet.Similarly to Example 1 using it It obtains evaluating with laminated body and evaluation solidfied material.

[embodiment 7]

It is compounded dicyclopentadiene type epoxy resin (XD-1000 (trade name), Japanese chemical drug strain formula meeting as ingredient (A) Society's system) 15.8 mass parts, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides as trigger for optical solidification (B) (Irgacure (registered trademark) 819, BASF Japan Ltd. system) 6.5 mass parts, as the TrisP-PA ring of compound (C) PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, 65 mass % of nonvolatile component, acid of oxypropylene ester compound Value: 70mgKOH/g, Nippon Kayaku K. K's system) 77.5 mass parts (being scaled 50.4 mass parts according to nonvolatile component), work For the dipentaerythritol hexaacrylate (KAYARAD (note of the compound (D) with ethylenically unsaturated group other than (C) ingredient Volume trade mark) DPHA, Nippon Kayaku K. K's system) 17.4 mass parts, as the maleimide of maleimide compound (E) Compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.3 mass parts, as the epoxy silicon of filler (F) Alkane handle silica MEK slurry (SC2050MB (trade name), 0.5 μm of average grain diameter, 70 mass % of nonvolatile component, ADMATECHS Co., Ltd. system) 71.4 mass parts (being scaled 50 mass parts according to nonvolatile component), as compound (G) 0.5 mass parts of cyanate esters SNCN obtained in synthesis example 1 and naphthalene type epoxy resin (HP-4710 (trade name), DIC plants Formula commercial firm system) 6.1 mass parts, 2-ethyl-4-methylimidazole (2E4MZ (trade name), four countries as thermosetting accelerator (H) It is melted into Co. Ltd. system) 0.2 mass parts, are stirred with ultrasonic homogenizer, obtain varnish (solution of resin combination).Using certainly These varnish are coated on 38 μm of thickness of PET film by dynamic apparatus for coating (PI-1210, TESTER SANGYO CO .LTD. system) On (Unipeel (registered trademark) TR1-38, Unitika Ltd. system, trade name), heat drying 7 minutes, are obtained at 80 DEG C Using PET film as supporting mass, resin composition layer with a thickness of 30 μm of resin sheet.Similarly to Example 1 using it It obtains evaluating with laminated body and evaluation solidfied material.

[comparative example 1]

Alternative compounds (C) (KAYARAD (registered trademark) ZFR-1553H, are not waved using bisphenol F type epoxy acrylate Hair 68 mass % of ingredient, acid value: 70mgKOH/g, Nippon Kayaku K. K's system) 74.1 mass parts (change according to nonvolatile component Calculating is 50.4 mass parts), varnish is in addition to this manufactured similarly to Example 1, is obtained resin sheet, evaluation laminated body and is commented Valence solidfied material.

It should be noted that KAYARAD (registered trademark) ZFR-1553H does not have structure shown in previously described formula (2).

[comparative example 2]

It substitutes ingredient (A), uses naphthalene type epoxy resin (HP-4710 (trade name), Dainippon Ink Chemicals's system) 22.4 mass Part, varnish is in addition to this manufactured similarly to Example 1, obtains resin sheet, evaluation laminated body and evaluation solidfied material.

[comparative example 3]

It substitutes ingredient (A), uses multifunctional type epoxy resin (1031S (trade name), Mitsubishi chemical Co., Ltd's system) 22.4 mass parts, in addition to this manufacture varnish similarly to Example 1, obtain resin sheet, evaluation laminated body and evaluation and use Solidfied material.

It should be noted that aforementioned multifunctional type epoxy resin (1031S (trade name), Mitsubishi chemical Co., Ltd's system) tool There are structural formula below (12).

[physical property measurement evaluation]

Resin sheet, evaluation laminated body and evaluation are measured with solidfied material using following methods, evaluated.They The results are shown in Table 1.

Finger is pressed lightly in the resin surface end of each resin sheet with supporting mass of A4 size, for finger Stickup degree is evaluated according to following benchmark.

Zero: the stickup almost without discovery for finger.The end of resin sheet with supporting mass is pasted on finger, still It removed, fallen by finger when height is less than 30mm.

×: stickup of the discovery for finger.The end of resin sheet with supporting mass is pasted on finger, levitation height 30mm More than.

It will using DMA device (TA Instruments corporation measurement of dynamic viscoelasticity device DMAQ800 (trade name)) Evaluation solidfied material is heated up with 10 DEG C/min, using the peak position of LossModulus (loss modulus) as glass transition temperature (Tg、℃)。

For the development face of evaluation laminated body, measurement since developing procedure after up to visually observing lower be without residue After time only, (1000 times of multiplying power) is observed using SEM (scanning electron microscope), according to having for following benchmark evaluation residues Nothing.

◎: it is 50 seconds or less, also sees in 30mm after SEM observation until visually observing the lower time without until development residue Without development residue in the range of side, developability is very excellent.

Zero: it is more than 50 seconds until visually observing the lower time without until development residue, but also in 30mm after SEM observation There is no development residue in the range of square, developability is excellent.

×: there are development residue in the range of 30mm square, developability is poor.

The evaluation wet type roughening treatment and conductor layer plating of solidfied material:

For multilayer printed-wiring board obtained in embodiment 1,2 and comparative example 1~3, the chemistry of upper village's industry is utilized Copper-plating technique (uses medical fluid name: MCD-PL, MDP-2, MAT-SP, MAB-4-C, MEL-3-APEA ver.2), implements about 0.8 μm Electroless copper, drying in 1 hour is carried out at 130 DEG C.Then, implement electrolysis plating in a manner of by copper-plated with a thickness of 18 μm Copper carries out drying in 1 hour at 180 DEG C.So production is formed with 18 μm of thickness of conductor layer (copper facing) on the insulating layer Sample, for following evaluation.

Using the sample made through the above steps, copper-plated bonding force measures 3 times according to JIS C6481, finds out average Value.For the sample expanded due to the drying after electrolytic copper plating, evaluated using the part not expanded.

[table 1]

Project

Embodiment 1

Embodiment 2

Embodiment 3

Embodiment 4

Embodiment 5

Embodiment 6

Embodiment 7

Comparative example 1

Comparative example 2

Comparative example 3

Apply film property

○

Heat resistance (Tg (DEG C))

165

168

203

200

202

207

210

133

165

Developability

○

◎

○

Plating adaptation (kN/m)

0.54

0.57

0.52

0.5

0.47

0.43

0.49

0.52

0.18

0.15

As shown in Table 1, for Examples 1 to 7, plating adaptation and excellent heat resistance.Wherein, for embodiment 2 For, heat resistance and plating adaptation are good, and for embodiment 3~7, heat resistance is more excellent.On the other hand, for than For example 1~3, plating adaptation or heat resistance are insufficient.According to the invention it is thus possible to obtain plating adaptation and resistance to Hot excellent resin combination, the resin sheet for having used it, multilayer printed-wiring board and semiconductor device.

Claims

1. a kind of resin combination causes containing dicyclopentadiene type epoxy resin (A) shown in following formula (1), photocuring Have olefinic unsaturated other than agent (B), following formula (2) compound represented (C) and following formula (2) compound represented (C) The compound (D) of group,

In formula (1), n indicates 0~15 integer,

In formula (2), multiple R₁Each independently represent hydrogen atom or methyl, multiple R₂Each independently represent hydrogen atom or optional The alkyl of carbon number 1~22 with substituent group, multiple R₃Each independently represent substituent group, following formula shown in following formula (3) (4) substituent group or hydroxyl shown in,

In formula (4), R₄Indicate hydrogen atom or methyl.

2. resin combination according to claim 1 also contains maleimide compound (E).

3. resin combination according to claim 1 or 2 also contains filler (F).

4. resin combination described in any one of claim 1 to 3 also contains selected from by cyanate esters, phenol Urea formaldehyde, oxetane resin, benzoxazine compound and with dicyclopentadiene type epoxy resin (A) shown in (1) Any one above compound (G) in the group of different epoxy resin compositions.

5. resin combination according to any one of claims 1 to 4, wherein formula (2) compound represented (C) Acid value be 30mgKOH/g or more and 120mgKOH/g or less.

6. resin combination according to any one of claims 1 to 5, wherein the content of ingredient (A) is relative to resin group Closing 100 mass parts of resin solid content in object is 3 mass parts or more and 50 below the mass.

7. resin combination described according to claim 1~any one of 6, wherein described with ethylenically unsaturated group Compound (D) is for the compound with (methyl) acryloyl group and/or with the compound of vinyl.

8. resin combination according to claim 3, wherein the filler (F) be selected from by silica, boehmite, Barium sulfate, fluororesin system filler, polyurethane resin system filler, acrylic resin system filler, polyethylene-based is filled out at silicone powder It is more than any one in the group of material, styrene butadiene ribber and silicon rubber composition.

9. resin combination described according to claim 1~any one of 8 also contains thermosetting accelerator (H).

10. resin combination described according to claim 1~any one of 9 also contains naphthalene type ring shown in following formula (5) Oxygen resin,

11. resin combination described according to claim 1~any one of 10, wherein the trigger for optical solidification (B) is contained Phosphine oxide compound shown in following formula (6),

In formula (6), R₅~R₁₀Each independently represent the alkyl of hydrogen atom or carbon number 1~4, R₁₁Indicate the alkyl of carbon number 1~20 Or the aryl of carbon number 6~20.

12. a kind of resin sheet, with any one of supporting mass and the claim 1~11 for being configured at the supporting mass surface institute The resin combination stated.

13. a kind of multilayer printed-wiring board, with resin combination described in any one of claim 1~11.

14. a kind of semiconductor device, with resin combination described in any one of claim 1~11.