CN104812805B

CN104812805B - Silicone compounds, modified imide resin, compositions of thermosetting resin, prepregs, the film with resin, plywood, multilayer printed-wiring board and semiconductor package part

Info

Publication number: CN104812805B
Application number: CN201380061809.9A
Authority: CN
Inventors: 小竹智彦; 长井骏介; 桥本慎太郎; 安部慎郎; 安部慎一郎; 宫武正人; 高根泽伸; 村井曜
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Lishennoco Co ltd; Resonac Holdings Corp
Priority date: 2012-11-28
Filing date: 2013-11-28
Publication date: 2017-06-30
Anticipated expiration: 2033-11-28
Also published as: JPWO2014084318A1; TWI614286B; JP2014129520A; WO2014084310A1; CN106973490B; JP6747655B2; TWI614262B; TW201428030A; CN104812805A; CN107254049A; KR20150089017A; CN106973490A; JPWO2014084310A1; JP6372071B2; WO2014084318A1; TW201434850A; KR102166235B1; JP6375951B2

Abstract

The present invention provides a kind of silicone compounds of the structure comprising shown in following formulas (1) and following formulas (2).R₁And R₂The alkoxy of hydrogen atom, halogen atom, the alkyl of carbon number 1~3, haloalkyl, mercapto, acetyl group, hydroxyl, sulfonic group, the sulfo group alkoxy of carbon number 1~3 or carbon number 1~3 is represented independently of one another, and x, y are each independently 0~4 integer.A is singly-bound or azomethine base, ester group, amide groups, azoxy, azo group, ethylidene or acetenyl.R₃And R₄Alkyl, phenyl or substituted-phenyl are represented independently of one another, and n is 1~100 integer.

Description

Silicone compounds, modified imide resin, compositions of thermosetting resin, pre-preg Base, the film with resin, plywood, multilayer printed-wiring board and semiconductor package part

Technical field

The present invention relates to being applied to semiconductor package part, the silicone compounds of printed wiring board purposes, having used its Modified imide resin, compositions of thermosetting resin, prepregs, the film with resin, plywood, multilayer printed-wiring board, And semiconductor package part.

Background technology

With the miniaturization of electronic equipment in recent years, the trend of high performance, the wiring density of multilayer printed-wiring board High Level, it is highly integrated push ahead, therewith together, for the raising band of the heat resistance by multilayered printed wiring plywood The requirement that the reliability come is improved is strengthened.In this kind of purposes, particularly in semiconductor package part, it is desirable to have concurrently excellent resistance to Hot, low heat expansion.In addition, also requiring dielectric property corresponding with the high frequency of electric signal.

At this point, Polyester or polyamide-based, polycarbonate-based, polymercaptan system, polyethers system, poly-azomethine system etc. Although known liquid crystal liquid crystal property macromolecule is the thermosetting resin of low heat expansion, dielectric property, excellent heat resistance, but there are Processability, the problem of formability, the problem disposed is difficult to because of low-solubility in organic solvent.

In the middle of these liquid crystal liquid crystal property macromolecules, since G.F.D ' Alelio are had found as the poly- azo first of liquid crystal liquid crystal property oligomer Since alkali (with reference to non-patent literature 1), it is reported that the example of many resins about using poly-azomethine is (with reference to patent excessively Document 1~7).

There are various poly-azomethines disclosed in patent document 1, have with ad hoc structure disclosed in patent document 2~7 Poly-azomethine.In addition, having the thermosetting poly-azomethine resin containing unsaturated group, root disclosed in patent document 8,9 According to records, high-fire resistance is shown using these resins.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Application 51-138800 publications

Patent document 2：Japanese Unexamined Patent Application 60-181127 publications

Patent document 3：Japanese Unexamined Patent Application 60-101123 publications

Patent document 4：Japanese Unexamined Patent Publication 2003-073470 publications

Patent document 5：Japanese Unexamined Patent Application 63-193925 publications

Patent document 6：Japanese Unexamined Patent Publication 01-069631 publications

Patent document 7：Japanese Unexamined Patent Publication 01-079233 publications

Patent document 8：Japanese Unexamined Patent Publication 05-140067 publications

Patent document 9：Japanese Unexamined Patent Publication 2011-195476 publications

Non-patent literature

Non-patent literature 1：Polymer Sci.Tech., Wiley-Interscience, NewYork, 1969, Vol.10, pp.659-670

The content of the invention

Invent problem to be solved

However, the poly-azomethine described in patent document 1~7 is as copper-clad laminated board or interlayer dielectic application In the case of, have the not enough situation of heat resistance, formability.

In addition, the improvement of the heat resistance, obdurability of thermosetting poly-azomethine resin described in patent document 8 is still not Foot, when using them as copper-clad laminated board or interlayer dielectic application, also has heat resistance or reliability, processability etc. no The situation of foot.

Additionally, the thermosetting poly-azomethine resin described in patent document 9 is forthright in low cure shrinkage, low-thermal-expansion Aspect it is unsatisfactory.

The present invention is in view of this kind of present situation, it is therefore intended that, there is provided can realize playing excellent when various uses is applied to Low cure shrinkage and low heat expansion, good dielectric property, the silica of the compositions of thermosetting resin of high elastic modulus Hydride compounds, modified imide resin, compositions of thermosetting resin, the prepregs for having used it, the film with resin, stacking Plate, multilayer printed-wiring board and semiconductor package part.

For the method for solve problem

The present inventor etc. have been repeated further investigation to reach the purpose, as a result find, by using with virtue The modified silicone com of fragrant race's azomethine can reach above-mentioned purpose, so as to complete the present invention.The present invention is base In the invention of the opinion.

That is, the present invention provides following silicone compounds, modified imide resin, compositions of thermosetting resin, preimpregnation Stain base, the film with resin, plywood, multilayer printed-wiring board and semiconductor package part.

[1] a kind of silicone compounds, it includes the structure shown in following formulas (1) and following formulas (2).

[changing 1]

In formula, R₁And R₂Hydrogen atom, halogen atom, the alkyl of carbon number 1~3, haloalkyl, mercaptan are represented independently of one another The alkoxy of base, acetyl group, hydroxyl, sulfonic group, the sulfo group alkoxy of carbon number 1~3 or carbon number 1~3, x, y are each independently 0~4 integer.A is singly-bound or azomethine base, ester group, amide groups, azoxy, azo group, ethylidene or acetenyl (アセチレ Application base).

[changing 2]

In formula, R₃And R₄Alkyl, phenyl or substituted-phenyl are represented independently of one another, and n is 1~100 integer.

[2] silicone compounds according to described in [1], wherein, also contain aromatic azo methine.

[3] silicone compounds according to described in [2], it is to make have at least 2 virtues of primary amino radical in 1 molecule Fragrant race's amines (A), there is in 1 molecule the aromatic aldehyde compound (B) of at least 2 aldehyde radicals and in molecular end tool There are at least 2 silicone compounds of amino (C) reactions and obtain.

[4] silicone compounds according to described in [2], it is to make have at least 2 virtues of primary amino radical in 1 molecule Fragrant race's amines (A), there are at least 2 aromatic aldehyde compounds (B) reactions of aldehyde radical in 1 molecule after, make in molecule End has at least 2 silicone compounds of amino (C) reactions and obtains.

[5] silicone compounds according to described in [2], it is to make have at least 2 fragrance of aldehyde radical in 1 molecule Race's aldehyde compound (B), after molecular end has the reaction of at least 2 silicone compounds of amino (C), make in 1 molecule Obtained with least 2 aromatic amines compound of primary amino radical (A) reactions.

[6] a kind of modified imide resin, it has makes [1]~any one of [5] silicone compounds for recording and There is aromatic series idol obtained by least 2 maleimide compound (D) reactions of N- substituted maleimide amidos in 1 molecule N-formyl sarcolysine alkali.

[7] the modified imide resin according to described in [6], it also has acidic substituent, and the acidic substituent comes from The acidic substituent of the amines (E) shown in following formulas (3).

[changing 3]

In formula, R₅Hydroxyl, carboxyl or the sulfonic group of acidic substituent, R are denoted as independently of one another₆Table independently of one another Show the aliphatic alkyl or halogen atom of hydrogen atom, carbon number 1~5, x is 1~5 integer, y is 0~4 integer, and x and y And be 5.

[8] a kind of compositions of thermosetting resin, its contain any one of [1]~[5] record silicone compounds and There are at least 2 maleimide compounds (D) of N- substituted maleimide amidos in 1 molecule.

[9] according to the compositions of thermosetting resin described in [8], its also containing shown in following formulas (3) with acid Property substitution base amines (E).

[changing 4]

[10] compositions of thermosetting resin according to described in [8] or [9], it also contains thermoplastic elastomer (TPE) (F).

[11] compositions of thermosetting resin recorded according to any one of [8]~[10], it is also containing selected from epoxy resin And at least one thermosetting resin (G) in cyanate ester resin.

[12] compositions of thermosetting resin recorded according to any one of [8]~[11], it also contains inorganic filling material (H)。

[13] compositions of thermosetting resin recorded according to any one of [8]~[12], it also contains curing accelerator (I)。

[14] a kind of prepregs, it is the compositions of thermosetting resin for recording any one of [8]~[13] to base material Infiltration is formed.

[15] a kind of film with resin, it is that the compositions of thermosetting resin that any one of [8]~[13] are recorded exists Forming layer is formed on supporting mass.

[16] a kind of plywood, it is to obtain the prepregs described in [14] are cascading into shape.

[17] a kind of plywood, it is to obtain the film with resin described in [15] is cascading into shape.

[18] a kind of multilayer printed-wiring board, it is manufactured using the plywood described in [16] or [17].

[19] a kind of semiconductor package part, it is the semiconductor element mounted thereon on the multilayer printed-wiring board described in [18] Form.

The effect of invention

According to the present invention it is possible to provide can realize being played when various uses is applied to excellent low cure shrinkage, And it is low heat expansion, good dielectric property, the silicone compounds of the compositions of thermosetting resin of high elastic modulus, modified Imide resin, compositions of thermosetting resin, the prepregs for having used it, the film with resin, plywood, multi-sheet printed cloth Line plate and semiconductor package part.

Particularly, by the thermosetting resin containing the modified silicone com with aromatic azo methine of the invention Composition on base material infiltrate, coating obtained by prepregs, on supporting mass coating obtained by with resin film and pass through Plywood that the is prepregs are cascading into shape and manufacturing has especially low cure shrinkage, low heat expansion, excellent Jie Electrical characteristics, high elastic modulus, it is useful as multilayer printed-wiring board, semiconductor package part.

Specific embodiment

Hereinafter, the present invention is described in detail.

(silicone compounds)

Silicone compounds of the invention include the structure shown in following formulas (1) and following formulas (2).The configuration example Can by the compound of the structure as shown in making comprising following formulas (1) with comprising following formulas (2) as shown in structure Compound reaction obtain.

[changing 5]

In formula, R₁And R₂Hydrogen atom, halogen atom, the alkyl of carbon number 1~3, haloalkyl, mercaptan are represented independently of one another The alkoxy of base, acetyl group, hydroxyl, sulfonic group, the sulfo group alkoxy of carbon number 1~3 or carbon number 1~3, x, y are each independently 0~4 integer.A is singly-bound or azomethine base, ester group, amide groups, azoxy, azo group, ethylidene or acetenyl.

[changing 6]

In addition, silicone compounds of the invention preferably comprise aromatic azo methine.

Herein, so-called aromatic azo methine, refers to that to be bonded at least one on schiff bases (- N=CH-) aromatic Material.

Hereinafter, silicone compounds of the invention are described in detail.

Silicone compounds of the invention are to make have at least 2 aromatic amines compounds of primary amino radical in 1 molecule (A) (hereinafter sometimes referred to as aromatic amines compound (A)), there are in 1 molecule the aromatic aldehyde compounds of at least 2 aldehyde radicals (B) (hereinafter sometimes referred to as aromatic aldehyde compound (B)) and molecular end have at least 2 silicone compounds of amino (C) (hereinafter sometimes referred to as silicone compounds (C)) react and obtain.

There are at least 2 aromatic amines compounds of primary amino radical (A) in 1 molecule as of the invention, for example can be with Enumerate p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 3- methyl isophthalic acids, 4- diaminobenzenes, 2,5- dimethyl-Isosorbide-5-Nitrae-diaminobenzene, 4, 4 '-diaminodiphenyl-methane, 4,4 '-diaminourea -3,3 '-dimethyl diphenyl methane, 4,4 '-diaminourea -3,3 '-diethyl Base-diphenyl methane, 4,4 '-diamino-diphenyl ether, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4, 4 '-diamino-diphenyl ketone, benzidine, 3,3 '-dimethyl -4,4 '-benzidine, 2,2 '-dimethyl -4,4 '-diaminourea Biphenyl, 3,3 '-dihydroxybiphenyl amine, 2,2- double (3- amino-4-hydroxylphenyls) propane, 3,3- dimethyl -5,5- diethyl -4, Double (4- aminophenyls) propane of 4- diphenylmethanediamiands, 2,2-, 2,2- double (4- (4- amino-benzene oxygens) phenyl) propane, 1,3- Double (3- amino-benzene oxygens) benzene, 1,3- double (4- amino-benzene oxygens) benzene, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygens) benzene, 4,4 '-bis- (4- ammonia Phenoxyl) biphenyl, double (4- (4- amino-benzene oxygens) phenyl) sulfones, double (4- (3- amino-benzene oxygens) phenyl) sulfones, the double (4- of 9,9- Aminophenyl) fluorenes, 4,4 '-diaminobenzene formailide, double (4- aminophenyls) terephthalamides, 4- -4 '-ammonia of aminophenyl Yl benzoic acid ester, 3,5- diaminourea benzyl benzoate, 4,4 '-chrysoidine, 3,3 '-diaminourea -2,2 '-dimethyl oxygen Change azobenzene, (E) -4,4 '-diamino-stilbene, (Z) -4,4 '-diamino-stilbene, 4,4 '-diamino-stilbene -2,2 '-disulfonic acid, 1,3- are double (4- amino-benzene oxygens) -5- (2- phenylene-ethynylenes) benzene etc..They can be used alone, it is also possible to be mixed with two or more.

In the middle of them, such as reactivity when reaction is high, more high-fire resistance can be realized from the aspect of, more preferably 4, 4 '-diaminodiphenyl-methane, 3,3 '-dimethyl -4,4 '-benzidine, 4,4 '-diaminourea -3,3 '-dimethyl-hexichol Methylmethane, 4,4 '-diaminourea -3,3 '-diethyl-diphenyl methane, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, double (4- (4- Amino-benzene oxygen) phenyl) propane etc..Additionally, from from the aspect of cheap, in a solvent deliquescent, preferably 4,4 '-diaminourea Diphenyl methane, 3,3 '-dimethyl -4,4 '-benzidine, 4,4 '-diaminourea -3 are 3 '-diethyl-diphenyl methane, double (4- (4- amino-benzene oxygens) phenyl) propane.Additionally, from from the aspect of low heat expansion, dielectric property, particularly preferred 4,4 '- Diaminourea -3,3 '-diethyl-diphenyl methane, double (4- (4- amino-benzene oxygens) phenyl) propane.In addition, it is also preferred that can be with height P-phenylenediamine, m-phenylene diamine (MPD), 3- methyl isophthalic acids that springform quantifies, 4- diaminobenzenes, 2,5- dimethyl-Isosorbide-5-Nitrae-diaminobenzene.

There are at least 2 aromatic aldehyde compounds (B) of aldehyde radical in 1 molecule as of the invention, for example, can lift Go out terephthalaldehyde, m-terephthal aldehyde, OPA, 2,2 '-bipyridyl -4,4 '-dicarbaldehyde etc..It is in the middle of them, such as special Not preferably can more low-thermal-expansion, reaction when reactivity it is high, solvent solubility is also excellent, be commercially also readily available Terephthalaldehyde.

It is of the invention in molecular end to there are at least 2 silicone compounds of amino (C) to include with following formulas (2) The structure of expression.

[changing 7]

In the formula of formula (2), n is 1~100 integer, more preferably 2~50 integer.

There are at least 2 silicone compounds of amino (C) as in molecular end, it is also possible to use commercially available product.As Commercially available product, for example, can enumerate " KF-8010 " (amino equivalent 430), " X-22-161A " (amino equivalent 800), " X-22- 161B " (amino equivalent 1500), " KF-8012 " (amino equivalent 2200), " KF-8008 " (amino equivalent 5700), " X-22- 9409 " (amino equivalent 700), " X-22-1660B-3 " (amino equivalent 2200) (are above Shin-Etsu Chemial Co., Ltd System), " BY-16-853U " (amino equivalent 460), " BY-16-853 " (amino equivalent 650), " BY-16-853B " (amino equivalent 2200) (being above eastern beautiful DOW CORNING Co. Ltd. system) etc..They can be used alone, it is also possible to be mixed with two or more.

In the middle of them, such as from the aspect of reactive high and low thermal expansivity when synthesis, preferably X-22-161A, X- 22-161B, KF-8012, X-22-1660B-3, BY-16-853B, from intermiscibility it is excellent, can with high elastic modulus in terms of examine Consider, particularly preferred X-22-161A, X-22-161B.

In the present invention, as the reaction for obtaining silicone compounds, for example, following method can be enumerated.

Reaction method a：By making in 1 molecule with least 2 aromatic amines compounds of primary amino radical (A), at 1 There is the aromatic aldehyde compound (B) of at least 2 aldehyde radicals in molecule and there are at least 2 siloxanes of amino in molecular end Compound (C) reacts, and can obtain silicone compounds (i).

Reaction method b：First, by make to have in 1 molecule at least 2 aromatic amines compounds of primary amino radical (A), Reacted with least 2 aromatic aldehyde compounds (B) of aldehyde radical with 1 molecule, and obtained in 1 molecule with least 1 aromatic azo methine compound of aldehyde radical.Then, by making the compound and there are at least 2 ammonia in molecular end The silicone compounds (C) of base carry out dehydration condensation in organic solvent, can obtain with aromatic azo methine Modified silicone com (ii).

Reaction method c：First, by the aromatic aldehyde compound (B) that makes there is at least 2 aldehyde radicals in 1 molecule and There are at least 2 silicone compounds of amino (C) reactions in molecular end, and obtain that there is at least one aldehyde in 1 molecule The modified silicone com of base and azomethine base (- N=CH-).Then, by making the compound and in 1 molecule With at least 2 aromatic amines compound of primary amino radical (A) reactions, the modified silica with aromatic azo methine can be obtained Hydride compounds (iii).

Silicone compounds of the invention can be obtained using any one reaction method of above-mentioned a, b, c, for example, reaction The operation of method a is especially easy, especially has in the case of the solvent solubility deficiency of modified silicone com of the invention Effect.In addition, reaction method b has is easily controlled in the molecule of silicone compounds of the invention, aromatic azo methine The feature of molecular weight, the high elastic modulusization for the resin combination containing it are especially effective.Additionally, reaction method c has The feature of the molecular weight of in the molecule of silicone compounds of the invention, siloxanes is easily controlled, for the resin containing it The low-thermal-expansion rateization of composition is effective.

First, reaction method a is described in detail.In reaction method a, by making that there are at least 2 in 1 molecule The aromatic amines compound (A) of primary amino radical, the aromatic aldehyde compound (B) in 1 molecule with least 2 aldehyde radicals and Molecular end has at least 2 silicone compounds of amino (C) reactions, can obtain silicone compounds (i) of the invention.

Herein, for having at least 2 aromatic amines compounds of primary amino radical (A) in 1 molecule, in 1 molecule There are at least 2 silicone compounds of amino (C) with least 2 aromatic aldehyde compounds (B) of aldehyde radical, in molecular end Usage amount, preferably so that the primaquine radix (aromatic amines compound of aromatic amines compound (A) and silicone compounds (C) (A) usage amount/silicone compound of the primary amino radical equivalent of usage amount/aromatic amines compound (A)+silicone compounds (C) The primary amino radical equivalent of thing (C)) it is the aldehyde radical number (usage amount/fragrance of aromatic aldehyde compound (B) of aromatic aldehyde compound (B) The aldehyde radical equivalent of race's aldehyde compound (B)) 1.0~10.0 times of the mode of scope use.By being set to more than 1.0 times, will There is the trend that can suppress deliquescent reduction in a solvent.In addition, by being set to less than 10.0 times, just having to suppress The trend of the reduction of the heat resistance of the thermosetting resin containing the modified silicone com (i) with aromatic azo methine.

Organic solvent can be used in the reaction.As organic solvent used, it is not particularly limited, but for example may be used To enumerate the alcohol series solvents such as ethanol, propyl alcohol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, first and second The virtues such as the ether series solvents such as the ketone series solvents such as ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, tetrahydrofuran, toluene, dimethylbenzene, mesitylene The solvents containing nitrogen-atoms such as fragrant family solvent, dimethylformamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, diformazan are sub- Ester series solvents such as the solvent containing sulphur atom such as sulfone, gamma-butyrolacton etc..They using a kind or can be mixed with two or more. In the middle of them, for example, from the aspect of deliquescent, preferably propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, two Methylacetamide, gamma-butyrolacton.Additionally, being difficult to what is remained as residual solvent during, manufacture in prepregs high from volatility From the aspect of, more preferably propylene glycol monomethyl ether, toluene.Further, since the reaction is dehydration condensation, therefore as accessory substance Generation water.For the purpose as the water of accessory substance is removed, for example, preferably it is azeotroped off using with fragrant family solvent As accessory substance water while reacted.

For the usage amount of organic solvent, such as in aromatic amines compound (A), aromatic aldehyde compound (B) and silica In every 100 mass parts of summation of the solid constituent conversion of hydride compounds (C), 25~2000 mass parts are preferably set to, more preferably set It is 40~1000 mass parts, is particularly preferably set to 40~500 mass parts.If the usage amount of organic solvent be 25 mass parts with On, then having can suppress deliquescent not enough trend.In addition, if for below 2000 mass parts, then the reaction time is suitable.

In the reaction, catalysts can be as needed used.Catalysts used are not particularly limited.As Catalysts, for example, can enumerate the amines such as the acidic catalysts such as p-methyl benzenesulfonic acid, triethylamine, pyridine, tri-n-butylamine, methyl miaow Phosphorus series catalysts such as the imidazoles such as azoles, phenylimidazole, triphenylphosphine etc..They using a kind or can be mixed with two or more. In order that dehydration condensation is effectively carried out, such as the acidic catalyst such as preferred p-methyl benzenesulfonic acid.

By above-mentioned raw material, organic solvent, the catalysts for using as needed add reactor in, as needed While heated, be incubated, stir 0.1 hour to 10 hours, be allowed to carry out dehydration condensation, it is hereby achieved that silica Hydride compounds (i).

Reaction temperature is for example preferably 70~150 DEG C, is preferably reacted while the water as accessory substance is removed, instead Temperature is answered to be more preferably 100~130 DEG C.If temperature is less than 70 DEG C, reaction speed is slack-off, if temperature is less than 150 DEG C, High boiling solvent is not needed in reaction dissolvent then, when prepregs are manufactured, it is difficult to remain residual solvent, can suppress heat-resisting The reduction of property.

Below, reaction method b is described in detail.In reaction method b, first, by making in 1 molecule with extremely Lack 2 aromatic amines compounds of primary amino radical (A) and there are at least 2 aromatic aldehyde compounds of aldehyde radical in 1 molecule (B) react, and obtain the aromatic azo methine compound with least one aldehyde radical in 1 molecule.Then, by making State compound and there are at least 2 silicone compounds of amino (C) reactions in molecular end, can obtain with aromatic series The modified silicone com (ii) of azomethine.

In reaction method b, organic solvent used in reaction and the catalysts for using as needed can appoint Meaning ground is used and reaction method a identical materials.

First, by making there are at least 2 aromatic amines compounds of primary amino radical (A) in 1 molecule and at 1 point The aromatic aldehyde compound (B) with least 2 aldehyde radicals carries out dehydration condensation in organic solvent in son, and obtains 1 Aromatic azo methine compound with least one aldehyde radical in individual molecule.

Herein, for having at least 2 aromatic amines compounds of primary amino radical (A) and in 1 molecule in 1 molecule With at least 2 usage amounts of the aromatic aldehyde compound (B) of aldehyde radical, such as preferably so that the primary of aromatic amines compound (A) Amino number (the primary amino radical equivalent of the usage amount/aromatic amines compound (A) of aromatic amines compound (A)) is aromatic aldehyde chemical combination 0.1 times of the aldehyde radical number (the aldehyde radical equivalent of the usage amount of aromatic aldehyde compound (B)/aromatic aldehyde compound (B)) of thing (B)~ The mode of 5.0 times of scope is used.By being set to more than 0.1 times, the aromatic series that can suppress to obtain using this reaction is just had The trend of the reduction of the molecular weight of azomethine compounds.In addition, by being set to less than 5.0 times, it is possible to suppress in a solvent Deliquescent reduction.

In addition, for the usage amount of organic solvent, for example, relative to aromatic amines compound (A), aromatic aldehyde compound (B) mass parts of summation 100 of resinous principle, are preferably set to 25~2000 mass parts, are more preferably set to 40~1000 mass parts, Particularly preferably it is set to 40~500 mass parts.If the usage amount of organic solvent is more than 25 mass parts, just having can suppress molten The not enough trend of solution property.In addition, if for below 2000 mass parts, then the reaction time is suitable.

By above-mentioned raw material, organic solvent, the catalysts for using as needed add reactor in, as needed While heated, be incubated, stir 0.1 hour to 10 hours, be allowed to carry out dehydration condensation, it is hereby achieved that 1 Aromatic azo methine compound with least one aldehyde radical in individual molecule.

Reaction temperature is for example preferably 70~150 DEG C, more preferably 100~130 DEG C.Additionally, it is preferred that removing as secondary Reacted while the water of product.If temperature is more than 70 DEG C, the trend that reaction speed will not be excessively slow is just had.If anti- Answer temperature for less than 150 DEG C, then high boiling solvent is not needed in reaction dissolvent, when prepregs are manufactured, it is difficult to remain residual Remaining solvent, can suppress the reduction of heat resistance.

Then, the aromatic azo first with least one aldehyde radical in 1 molecule by making to be obtained using above-mentioned reaction Alkali cpd and molecular end have at least 2 silicone compounds of amino (C) carry out dehydrating condensation in organic solvent Reaction, can obtain the modified silicone com (ii) with aromatic azo methine.

Herein, for aromatic azo methine compound and the usage amount of silicone compounds (C), such as preferably so that silicon The primaquine radix (the primary amino radical equivalents of the usage amount/silicone compounds (C) of silicone compounds (C)) of siloxane compound (C) It is the aldehyde radical number (usage amount of aromatic azo methine compound/aromatic azo methine of aromatic azo methine compound The aldehyde radical equivalent of compound) 1.0~10.0 times of the mode of scope use.By being set to more than 1.0 times, just having to suppress The trend of deliquescent reduction in a solvent.In addition, by being set to less than 10.0 times, just having can suppress containing with virtue The trend of the reduction of the elastic modelling quantity of the thermosetting resin of the modified silicone com (ii) of fragrant race's azomethine.

In addition, for the usage amount of organic solvent, such as relative to the fragrance with least one aldehyde radical in 1 molecule The mass parts of summation 100 of the resinous principle of race's azomethine compounds and silicone compounds (C), are preferably set to 25~2000 Mass parts, are more preferably set to 40~1000 mass parts, are particularly preferably set to 40~500 mass parts.If the use of organic solvent Measure and can suppress the not enough trend of dissolubility more than 25 mass parts, just to have.In addition, if being below 2000 mass parts, then Reaction time is suitable.

By above-mentioned raw material, organic solvent, the catalysts for using as needed add reactor in, as needed While heated, be incubated, stir 0.1 hour to 10 hours, be allowed to carry out dehydration condensation, it is hereby achieved that having The modified silicone com (ii) of aromatic azo methine.

Reaction temperature is for example preferably 70~150 DEG C, more preferably 100~130 DEG C.Additionally, it is preferred that removing as secondary Reacted while the water of product.If reaction temperature is more than 70 DEG C, the trend that reaction speed will not be excessively slow is just had.Such as Fruit reaction temperature is less than 150 DEG C, then high boiling solvent is not needed in reaction dissolvent, when prepregs are manufactured, it is difficult to residual Residual solvent is stayed, the reduction of heat resistance can be suppressed.

Below, reaction method c is described in detail.In reaction method c, first, by making in 1 molecule with extremely The aromatic aldehyde compound (B) of few 2 aldehyde radicals and have at least 2 silicone compounds of amino (C) anti-in molecular end Should, and obtain the modified silicone com in 1 molecule with least one aldehyde radical and azomethine base (- N=CH-).So Afterwards, by making the compound and in 1 molecule with least 2 aromatic amines compounds of primary amino radical (A) reactions, can To obtain the modified silicone com (iii) with aromatic azo methine.

In reaction method c, organic solvent used in reaction and the catalysts for using as needed can appoint Meaning ground is used and reaction method a and b identical material.

Have by the aromatic aldehyde compound (B) for making there is at least 2 aldehyde radicals in 1 molecule and in molecular end At least 2 silicone compounds of amino (C) dehydration condensation in organic solvent, and obtain having extremely in 1 molecule The modified silicone com of few 1 aldehyde radical and azomethine base (- N=CH-).

Herein, have for the aromatic aldehyde compound (B) in 1 molecule with least 2 aldehyde radicals and in molecular end There are at least 2 usage amounts of the silicone compounds of amino (C), such as preferably so that the primaquine radix of silicone compounds (C) (the primary amino radical equivalents of the usage amount/silicone compounds (C) of silicone compounds (C)) are the aldehyde of aromatic aldehyde compound (B) The model of 0.1 times~5.0 times of radix (the aldehyde radical equivalent of the usage amount of aromatic aldehyde compound (B)/aromatic aldehyde compound (B)) The mode enclosed is used.By being set to more than 0.1 times, deliquescent reduction in a solvent can be suppressed.In addition, by being set to Less than 5.0 times, can suppress that there is at least one aldehyde radical and azomethine base (- N=in 1 molecule using what this reaction was obtained The reduction of the molecular weight of modified silicone com CH-).

In addition, for the usage amount of organic solvent, such as relative to aromatic aldehyde compound (B), silicone compounds (C) Resinous principle the mass parts of summation 100, be preferably set to 25~2000 mass parts, be more preferably set to 40~1000 mass parts, it is special 40~500 mass parts are not preferably set to.If the usage amount of organic solvent is more than 25 mass parts, dissolubility will not be not enough, In addition, if for below 2000 mass parts, then the reaction time is suitable.

By above-mentioned raw material, organic solvent, the catalysts for using as needed add reactor in, as needed While heated, be incubated, stir 0.1 hour to 10 hours, be allowed to carry out dehydration condensation, it is hereby achieved that 1 There is the modified silicone com of at least one aldehyde radical and azomethine base (- N=CH-) in individual molecule.

Then, by make using above-mentioned reaction obtain have in 1 molecule at least one aldehyde radical and azomethine base (- N=CH- modified silicone com) and there are at least 2 aromatic amines compounds of primary amino radical (A) to exist in 1 molecule Dehydration condensation is carried out in organic solvent, it is possible to obtain the modified silicone com with aromatic azo methine (iii)。

Herein, for modified silicone com and the usage amount of aromatic amines compound (A), such as preferably so that fragrance The primaquine radix of race's amines (A) (work as by the primary amino radical of the usage amount/aromatic amines compound (A) of aromatic amines compound (A) Amount) it is the aldehyde radical number (aldehyde radical of the usage amount/modified silicone com of modified silicone com of modified silicone com Equivalent) 1.0~10.0 times of the mode of scope use.By being set to more than 1.0 times, just having can suppress containing with virtue The trend of the reduction of the low heat expansion of the thermosetting resin of the modified silicone com (iii) of fragrant race's azomethine.In addition, By being set to less than 10.0 times, just having can suppress the trend of deliquescent reduction in a solvent.

In addition, for the usage amount of organic solvent, such as relative to having at least one aldehyde radical and azo in 1 molecule The mass of summation 100 of the resinous principle of the modified silicone com and aromatic amines compound (A) of methine base (- N=CH-) Part, 25~2000 mass parts are preferably set to, 40~1000 mass parts are more preferably set to, particularly preferably it is set to 40~500 mass parts. If the usage amount of organic solvent is more than 25 mass parts, just having can suppress deliquescent not enough trend.In addition, if Below 2000 mass parts, then the reaction time is suitable.

By above-mentioned raw material, organic solvent, the catalysts for using as needed add reactor in, as needed While heated, be incubated, stir 0.1 hour to 10 hours, be allowed to carry out dehydration condensation, it is hereby achieved that having The modified silicone com (iii) of aromatic azo methine.

The modified silicone com of the invention obtained using above-mentioned reaction method a, b, c can be by carrying out IR surveys It is fixed to confirm.Determined by using IR, confirm the 1620cm caused by azomethine base (- N=CH-) occur^-1Peak, in addition, Confirm there is the 3440cm caused by primary amino radical^-1And 3370cm^-1Neighbouring peak, it is possible thereby to confirm that reaction is carried out well, Required compound is obtained.In addition, weight average molecular weight (Mw) such as preferably 1000~300000, particularly preferably 6000~ 150000.If weight average molecular weight (Mw) is more than the lower limit, low cure shrinkage, low heat expansion are improved, if Below the upper limit, then intermiscibility, elastic modelling quantity are improved.And, weight average molecular weight (Mw) is to utilize gel permeation chromatography (GPC) it is measured, the value converted using the calibration curve made using polystyrene standard.For example, can be in following condition Under carry out.Used as device is determined, using automatic sampler (Tosoh Co. Ltd. system AS-8020), chromatographic column baking oven, (day is well-behaved Light Co. Ltd. system 860-C0), RI detectors (Japan Spectroscopy Corporation 830-RI), (the Japanese light splitting of UV/VIS detectors Co. Ltd. system 870-UV), HPLC pumps (Japan Spectroscopy Corporation 880-PU).

In addition, conduct uses chromatographic column, it is possible to use Tosoh Co. Ltd. system TSKgel SuperHZ2000,2300, make It is condition determination, can be measured by being set to 40 DEG C of temperature of the measurement, flow 0.5ml/min, solvents tetrahydrofurane.

(modified imide resin)

Modified imide resin of the invention be by make already described of the invention amino modified silicone compounds and There is material obtained by least 2 maleimide compound (C) reactions of N- substituted maleimide amidos in 1 molecule.

Additionally, modified imide resin is preferably with acidic substituent and the acidic substituent comes from following formulas (3) resin of the acidic substituent of the amines (D) shown in.The acidic substituent can be by making amines (D) anti- Should import.By the way that with the acidic substituent, good low heat expansion can be obtained.

[changing 8]

In formula (3), R₁Hydroxyl, carboxyl or the sulfonic group of acidic substituent, R are denoted as independently of one another₂Independently of one another Represent hydrogen atom, the aliphatic alkyl or halogen atom of carbon number 1~5, x is 1~5 integer, y is 0~4 integer, and x with Y's and be 5.

And, the further details to amines (D) are described below.In addition, so-called " come from amines (D) resin of acidic substituent ", refer to the acidic substituent of amines (D) in itself and the tree containing the acidic substituent Fat.

Manufacture in " pre-reaction " during the compositions of thermosetting resin that modified imide resin can be stated after fabrication.

(compositions of thermosetting resin)

Compositions of thermosetting resin of the invention is containing modified silicone com of the invention and in 1 molecule With at least 2 compositions of the maleimide compound (D) of N- substituted maleimide amidos.

As there is in 1 molecule at least 2 N- substituted maleimide amidos maleimide compounds (D) (with Maleimide compound (D) is sometimes referred to as down), can for example enumerate double (4- maleimide phenyls) methane, polyphenylene first Alkane maleimide, double (4- maleimide phenyls) ethers, double (4- maleimide phenyls) sulfones, 3,3- dimethyl -5,5- bis- Ethyl -4,4- diphenyl methanes BMI, 4- methyl isophthalic acids, 3- phenylenes BMI, metaphenylene span come Double (4- (4- maleimidephenoxies) phenyl) propane of acid imide, 2,2- etc..These maleimide compounds both can be single Solely use, it is also possible to be mixed with two or more.

In the middle of them, such as preferred reactive is high, can realize double (4- maleimide phenyls) first of more high-fire resistance Alkane, double (4- maleimide phenyls) sulfones, 2,2- double (4- (4- maleimidephenoxies) phenyl) propane, from a solvent From the aspect of deliquescent, the double (4- (4- maleimidephenoxies) of more preferably double (4- maleimide phenyls) methane, 2,2- Phenyl) propane, from from the aspect of cheap, particularly preferably double (4- maleimide phenyls) methane.

In compositions of thermosetting resin of the invention, the usage amount for silicone compounds of the invention (coordinates Amount), such as in every 100 mass parts of summation of resinous principle, 1~30 mass parts are preferably set to, from Copper Foil cementability, drug-resistant From the aspect of property, 5~20 mass parts are more preferably set to.

It is for the usage amount of maleimide compound (D), such as excellent in every 100 mass parts of summation of resinous principle Choosing is set to 30~99 mass parts, from from the aspect of low heat expansion, high elastic modulus, is more preferably set to 40~95 mass parts.

Compositions of thermosetting resin of the invention is that have containing silicone compounds of the invention and in 1 molecule At least 2 compositions of the maleimide compound (D) of N- substituted maleimide amidos, but above-mentionedization can also be made Compound pre-reaction and used as with the modified imide resin of aromatic azo methine.By carrying out this kind of pre-reaction, just Molecular weight can be controlled, further low cure shrinkage, low heat expansion can be carried out and improved.

While the pre-reaction preferably carries out heating and thermal insulation in organic solvent, make silicone compounds of the invention and Maleimide compound (D) reacts and synthesis modification imide resin.

Reaction temperature example when in organic solvent reacting modified silicone com, maleimide compound (D) Preferably such as 70~150 DEG C, more preferably 100~130 DEG C.Reaction time is for example preferably 0.1~10 hour, more preferably 1 ~6 hours.

In the pre-reaction, for maleimide compound (D) and the usage amount of silicone compounds of the invention, for example Preferably so that the maleimide radix (usage amount/Malaysia of maleimide compound (D) of maleimide compound (D) The dimaleoyl imino equivalent of imide compound (D)) be silicone compounds of the invention primaquine radix (silicon of the invention The primary amino radical equivalent of the usage amount of siloxane compound/silicone compounds of the invention) 2.0~10.0 times of scope.Pass through More than 2.0 times are set to, the trend of the reduction that can suppress gelation and heat resistance is just had.In addition, by be set to 10.0 times with Under, just have the trend of the reduction that can suppress dissolubility and heat resistance in organic solvent.

For the usage amount of the maleimide compound (D) in pre-reaction, while relation as described above is maintained, The mass parts of resinous principle 100 for example relative to silicone compounds of the invention are preferably 50~3000 mass parts, more preferably It is 100~1500 mass parts.By being set to more than 50 mass parts, the trend of the reduction that can suppress heat resistance is just had.In addition, By being set to below 3000 mass parts, it is possible to which low heat expansion is kept into good.

Organic solvent used in the pre-reaction can for example enumerate ethanol, propyl alcohol, butanol, methyl cellosolve, butyl The ketone series solvents such as the alcohol series solvents such as cellosolve, propylene glycol monomethyl ether, acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, acetic acid The fragrant families such as ether series solvent, toluene, dimethylbenzene, the mesitylene such as the ester series solvent such as ethyl ester or gamma-butyrolacton, tetrahydrofuran are molten The solvent containing nitrogen-atoms such as agent, dimethylformamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide etc. contain Solvent of sulphur atom etc..They using a kind or can be mixed with two or more.

In the middle of these organic solvents, such as from the aspect of deliquescent, preferably cyclohexanone, propylene glycol monomethyl ether, first Base cellosolve, gamma-butyrolacton, from hypotoxicity, volatility is high, be difficult to as residual solvent remain from the aspect of, particularly preferably Cyclohexanone, propylene glycol monomethyl ether, dimethylacetylamide.

For the usage amount of organic solvent, such as relative to silicone compounds of the invention, maleimide compound (D) mass parts of summation 100 of resinous principle, are preferably set to 25~2000 mass parts, are more preferably set to 40~1000 mass parts, Particularly preferably it is set to 40~500 mass parts.If the usage amount of organic solvent is more than 25 mass parts, dissolubility will not Foot, in addition if 2000 mass parts below, then the reaction time is suitable.

In addition, can arbitrarily use catalysts in the pre-reaction.Catalysts are not particularly limited, but The phosphorus such as the imidazoles such as the amines such as triethylamine, pyridine, tri-n-butylamine, methylimidazole, phenylimidazole, triphenylphosphine system can for example be enumerated Alkali metal amides such as catalyst, lithium acid amides, sodium acid amides, potassium acid amides etc..They using a kind or can be mixed with two or more.

In addition, the use of the modified imide resin with aromatic azo methine for being obtained using above-mentioned pre-reaction Amount, such as in every 100 mass parts of summation of resinous principle, be preferably set to 50~100 mass parts, is more preferably set to 60~100 Mass parts.It is set to more than 50 mass parts by by the use level of the modified imide resin with aromatic azo methine, so that it may To obtain low heat expansion, high elastic modulus.

Make that there are at least 2 N- substituted maleimide amidos containing silicone compounds of the invention and in 1 molecule Maleimide compound (D) compositions of thermosetting resin and above-claimed cpd pre-reaction, gained with fragrance The modified imide resin of race's azomethine is used alone can also have good heat cure reactivity, but can also be according to need Want and use curing agent and radical initiator.By using curing agent and radical initiator, heat resistance, bonding can be improved Property, mechanical strength.

As curing agent, can for example enumerate dicyandiamide, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino The aromatic amines such as base -3,3 '-diethyl-diphenyl methane, 4,4 '-diamino diphenyl sulfone, phenylenediamine, dimethylphenylene diamine, Guanamines compounds such as aliphatic amine, melamine, the benzoguanamines such as hexamethylene diamine, 2,5- dimethylhexanediamines etc..

In addition, as above-mentioned radical initiator, be not particularly limited, however for example can using acyl peroxide, The organic peroxies such as hydroperoxides, ketone peroxide, the organic peroxide with the tert-butyl group, the peroxide with cumyl Thing etc..They can be used alone, it is also possible to be mixed with two or more.In the middle of them, for example, from good reactive, heat-resisting From the aspect of property, optimization aromatic amine.

Additionally, compositions of thermosetting resin of the invention can contain replacing with acidity shown in following formulas (3) The amines (E) of base.

[changing 9]

In formula (3), R₅Hydroxyl, carboxyl or the sulfonic group of acidic substituent, R are denoted as independently of one another₆Independently of one another Represent hydrogen atom, the aliphatic alkyl or halogen atom of carbon number 1~5, x is 1~5 integer, y is 0~4 integer, and x with Y's and be 5.

As the amines (E) with acidic substituent, for example, can enumerate m-aminophenol, para-aminophenol, neighbour It is amino-phenol, p-aminobenzoic acid, gavaculine, ortho-aminobenzoic acid, orthanilic acid, metanilic acid, right Aminobenzenesulfonic acid, 3,5- dihydroxy aniline, 3,5- dicarboxyanylines etc..In the middle of them, for example, from dissolubility, synthesis yield From the aspect of, preferably m-aminophenol, para-aminophenol, o-aminophenol, p-aminobenzoic acid, gavaculine and 3,5- dihydroxy aniline, from from the aspect of heat resistance, more preferably m-aminophenol and para-aminophenol.

For the usage amount of the amines (E) with acidic substituent, for example, in every 100 matter of summation of resinous principle In amount part, 0.5~30 mass parts are preferably set to, from from the aspect of low heat expansion, are more preferably set to 1~20 mass parts.

Compositions of thermosetting resin of the invention can also be containing modified silicone com of the invention, in 1 molecule In there are maleimide compound (D), the amines with acidic substituent of at least 2 N- substituted maleimide amidos (E), make above-claimed cpd pre-reaction, make as the modified imide resin with acidic substituent and aromatic azo methine With.By carrying out this kind of pre-reaction, molecular weight can be controlled, further low cure shrinkage and low-thermal-expansion can be carried out The raising of property.

While the pre-reaction preferably carries out heating and thermal insulation in organic solvent, make silicone compounds of the invention, horse Come imide compound (D), the amines (E) with acidic substituent to react and synthesize the modified acyl with acidic substituent Imide resin.

Make silicone compounds of the invention, maleimide compound (D) in organic solvent, with acidic substituent Amines (E) react when reaction temperature for example be preferably 70~150 DEG C, more preferably 100~130 DEG C.Reaction time For example it is preferably 0.1~10 hour, more preferably 1~6 hour.

In the pre-reaction, replace for maleimide compound (D), silicone compounds of the invention and with acidity The usage amount of the amines (E) of base, such as preferably so that the maleimide radix (Malaysia of maleimide compound (D) The dimaleoyl imino equivalent of the usage amount/maleimide compound (D) of imide compound (D)) it is silica of the invention Hydride compounds and the amines (E) with acidic substituent primaquine radix (usage amount of silicone compounds of the invention/ The usage amount of the primary amino radical equivalent of silicone compounds of the invention+amines (E) with acidic substituent/there is acidity Replace the primary amino radical equivalent of the amines (E) of base) 2.0~10.0 times of scope.By being set to more than 2.0 times, just have The trend of the reduction of gelation and heat resistance can be suppressed.In addition, by being set to less than 10.0 times, it is possible to suppress organic molten Dissolubility, heat resistance reduction in agent.

For the usage amount of the maleimide compound (D) in pre-reaction, while relation as described above is maintained, The mass parts of resinous principle 100 for example relative to silicone compounds of the invention are preferably 50~3000 mass parts, more preferably It is 100~1500 mass parts.By being set to more than 50 mass parts, the reduction of heat resistance can be suppressed.In addition, by being set to 3000 Below mass parts, low heat expansion can be kept good.

In addition, the usage amount of the amines (E) with acidic substituent in for pre-reaction, such as relative to this hair The mass parts of resinous principle 100 of bright silicone compounds are preferably 1~1000 mass parts, more preferably 5~500 mass parts. By being set to more than 1 mass parts, the reduction of heat resistance can be suppressed, in addition, by being set to below 1000 mass parts, can will be low Thermal expansivity keeps good.

Organic solvent used in the pre-reaction is not particularly limited, but can for example enumerate ethanol, propyl alcohol, fourth The alcohol series solvents such as alcohol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, MEK, methyl iso-butyl ketone (MIBK), hexamethylene The ether series solvents such as the ester series solvents such as the ketone series solvents such as ketone, ethyl acetate or gamma-butyrolacton, tetrahydrofuran, toluene, dimethylbenzene, The fragrant family such as trimethylbenzene solvent, dimethylformamide, dimethylacetylamide, 1-METHYLPYRROLIDONE etc. contain the molten of nitrogen-atoms Solvent containing sulphur atom such as agent, dimethyl sulfoxide etc..They using a kind or can be mixed with two or more.

In the middle of these organic solvents, such as cyclohexanone, propylene glycol monomethyl ether, methyl are preferably from the aspect of deliquescent Cellosolve, gamma-butyrolacton, from hypotoxicity, volatility is high, be difficult to as residual solvent remain from the aspect of, particularly preferred ring Hexanone, propylene glycol monomethyl ether, dimethylacetylamide.

For the usage amount of organic solvent, such as relative to silicone compounds of the invention, maleimide compound (D) mass parts of summation 100 of the resinous principle of amines (E), with acidic substituent, are preferably set to 25~2000 mass Part, 40~1000 mass parts are more preferably set to, particularly preferably it is set to 40~500 mass parts.If the usage amount of organic solvent is More than 25 mass parts, then having can suppress deliquescent not enough trend.In addition, if being below 2000 mass parts, then instead It is suitable between seasonable.

In addition, in the pre-reaction, can arbitrarily use catalysts.Catalysts are not particularly limited, so And can for example enumerate the phosphorus such as the imidazoles such as the amines such as triethylamine, pyridine, tri-n-butylamine, methylimidazole, phenylimidazole, triphenylphosphine Alkali metal amides such as series catalysts, lithium acid amides, sodium acid amides, potassium acid amides etc..They using a kind or can be mixed with two or more.

In addition, the modified acyl with acidic substituent and aromatic azo methine for being obtained using above-mentioned pre-reaction is sub- The usage amount of polyimide resin, such as in every 100 mass parts of summation of resinous principle, be preferably set to 50~100 mass parts, more preferably It is set to 60~100 mass parts.By by the cooperation with acidic substituent and the modified imide resin of aromatic azo methine Amount is set to more than 50 mass parts, can obtain low heat expansion, high elastic modulus.

Make containing the modified silicone com with aromatic azo methine of the invention, in 1 molecule with extremely Few 2 maleimide compounds (D) of N- substituted maleimide amidos, the amines (E) with acidic substituent are formed Compositions of thermosetting resin and above-claimed cpd pre-reaction, the changing with acidic substituent and aromatic azo methine of gained Property imide resin be used alone also and can have good heat cure reactivity, but can as needed and with curing agent and oneself By base initiator.By using curing agent and radical initiator, heat resistance or cementability, mechanical strength can be improved.

In addition, as above-mentioned radical initiator, such as acyl peroxide, hydroperoxides, ketone peroxide can be used Organic peroxides such as compound, the organic peroxide with the tert-butyl group, the peroxide with cumyl etc..They can be independent Use, it is also possible to be mixed with two or more.In the middle of them, for example, from from the aspect of good reactivity, heat resistance, preferably Aromatic amine.

Additionally, compositions of thermosetting resin of the invention can contain thermoplastic elastomer (TPE) (F).

As thermoplastic elastomer (TPE) (F), for example, can enumerate styrene series elastomer, olefin-based elastomer, polyurethane series Elastomer, polyester-based elastomer, polyamide-based elastomer, acrylic elastomer, silicone based elastomers or derivatives thereof.They Contain hard section composition and soft section composition, it is however generally that the former contributes to heat resistance and intensity, the latter contributes to flexibility and tough Property.They can be used alone, or be mixed with two or more.

In addition, as these elastomers, it is possible to use the bullet with reactive functional groups in molecular end or strand Gonosome.As reactive functional groups, for example, can enumerate epoxy radicals, hydroxyl, carboxyl, amino, amide groups, NCO, third Enoyl-, methylacryloyl, vinyl etc..By having these reactive functional groups in molecular end or strand, Intermiscibility in resin will be improved, and be produced during the solidification that can more effectively reduce compositions of thermosetting resin of the invention Internal stress.As a result, the warpage of substrate can be significantly decreased.

In the middle of these elastomers, such as from from the aspect of heat resistance, insulating reliability, optimization styrene based elastomers, Olefin-based elastomer, polyamide-based elastomer and silicone based elastomers, from from the aspect of dielectric property, particularly preferred benzene second Alkene based elastomers and olefin-based elastomer.

In addition, for the reactive functional groups having in the molecular end or strand of these elastomers, for example from From the aspect of the adaptation of metal foil, preferably epoxy radicals, hydroxyl, carboxyl, amino and amide groups are reliable from heat resistance, insulation From the aspect of property, particularly preferred epoxy radicals, hydroxyl and amino.

It is for the usage amount of thermoplastic elastomer (TPE) (F) composition, such as excellent relative to the mass parts of summation 100 of resinous principle Elect 0.1~50 mass parts as, from the intermiscibility of resin it is good, can effectively show the low cure shrinkage of solidfied material, low From the aspect of thermal expansivity, excellent dielectric property, more preferably 2~30 mass parts.

Additionally, compositions of thermosetting resin of the invention can containing selected from epoxy resin and cyanate ester resin at least A kind of thermosetting resin (G).

As epoxy resin, for example, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy Resin, phenol novolak type epoxy, cresol novolak type epoxy resin, bisphenol-A phenolic type epoxy resin, bisphenol F phenolic type ring Oxygen tree fat, stilbene type epoxy resin, the epoxy resin containing triazine skeleton, the epoxy resin containing fluorene skeleton, triphenol methylmethane type Epoxy resin, biphenyl type epoxy resin, xylol type epoxy resin, xenyl aralkyl-type epoxy resin, naphthalene type epoxy resin, Two shrinks of the Ppolynuclear aromatic classes such as dicyclopentadiene type epoxy resin, alicyclic epoxy resin, multifunctional phenol and anthracene are sweet Oily ether compound and to epoxy resin containing phosphorus that phosphorus compound has been imported in them etc..They can be used alone, and also may be used To be mixed with two or more.In the middle of them, such as from from the aspect of heat resistance, anti-flammability, preferred xenyl aralkyl-type ring Oxygen tree fat and naphthalene type epoxy resin.

In addition, as cyanate ester resin, for example, can enumerate Novolac Cyanate Ester Resins, bisphenol A cyanate ester resin, double Bisphenol type cyanate ester resins such as phenol E types cyanate ester resin, tetramethyl bisphenol F cyanate resin and by their part triazines Prepolymer etc..They can be used alone, it is also possible to be mixed with two or more.In the middle of them, such as from heat resistance, fire-retardant From the aspect of property, preferred Novolac Cyanate Ester Resins.

In these thermosetting resins (G), curing agent can be used as needed.As the example of curing agent, for example may be used To enumerate multifunctional phenolic compounds, dicyandiamide, the diamino-diphenyls such as phenol novolac, cresol novolac, amino triazine phenolic resin The amines such as methane, diamino diphenyl sulfone, phthalic anhydride, pyromellitic dianhydride, maleic anhydride, maleic anhydride Acid anhydrides such as thing etc..Their a kind is can be used alone, or is mixed with two or more.

As the usage amount of thermosetting resin (G), such as in every 100 mass parts of summation of resinous principle, it is preferably set to 1 ~50 mass parts, from from the aspect of heat resistance, resistance to chemical reagents, more preferably 3~30 mass parts.

Compositions of thermosetting resin of the invention can contain inorganic filling material (H).As inorganic filling material, for example Silica, aluminum oxide, talcum, mica, kaolin, aluminium hydroxide, boehmite, magnesium hydroxide, Firebrake ZB, stannic acid can be enumerated The glass such as zinc, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminium borate, potassium titanate, E glass or T glass, D glass Powder or hollow glass bead etc..They can be used alone, it is also possible to be mixed with two or more.

In these inorganic filling materials, for example from from the aspect of dielectric property, heat resistance, low heat expansion, especially It is preferred that silica.As silica, can for example enumerate using the moisture content of damp process manufacture sedimentation silica high, The dry process silica being practically free of with reference to water etc. manufactured using dry process.As dry process silica, can be with Difference according to autofrettage enumerates broken silica, fumed silica, melting spherical silicon dioxide etc..In the middle of them, from Low heat expansion and high fluidity when being filled into resin consider, preferred molten spherical silicon dioxide.

In the case where melting spherical silicon dioxide is used as inorganic filling material, for example its average grain diameter is preferably 0.1~10 μm, more preferably 0.3~8 μm.More than 0.1 μm is set to by by the average grain diameter of the melting spherical silicon dioxide, just Mobility when can high density be filled into resin keeps good, in addition by being allowed to be less than 10 μm, it is possible to reduce Oversize grain is mixed into probability, suppresses the bad generation that oversize grain causes.Herein, so-called average grain diameter, refers to by particle Cumulative volume when being set to 100% and obtaining the accumulation number of degrees distribution curve based on particle diameter, equivalent to the particle diameter of the point of volume 50%, Can be determined using particle size distribution device for having used laser diffraction and scattering method etc..

For the content of inorganic filling material, such as mass parts of summation 100 relative to resinous principle are preferably 20~500 Mass parts, more preferably 50~350 mass parts.By making the content of inorganic filling material relative to the summation 100 of resinous principle Mass parts are 20~500 mass parts, the formability of resin combination and low heat expansion can be kept into good.

In addition, when inorganic filling material is coordinated in resin combination, such as it is also preferred that the inorganic filling material is used The surface conditioning agents such as coupling agent, the silicone oligomers such as silane system, titanate esters system carry out pre-treatment or overall blending treatment.

Compositions of thermosetting resin of the invention can contain curing accelerator (I).As curing accelerator, for example can be with Enumerate zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bis-acetylacetonate cobalt (II), praseodynium cobalt (III) etc. organic Organic phosphorus series compound, secondary amine class, tertiary amines and the quaternary ammonium salt such as slaine, imidazoles and its derivative, phosphine and phosphonium salt etc.. Their a kind is can be used alone, or is mixed with two or more.

In the middle of them, such as from from the aspect of facilitation effect and storage stability, preferably zinc naphthenate, imidazole derivatives Wu, phosphonium salts.

For the content of curing accelerator, such as mass parts of summation 100 relative to resinous principle are preferably 0.01~3.0 Mass parts, more preferably 0.05~1.5 mass parts.By making the content of curing accelerator relative to the summation 100 of resinous principle Mass parts are 0.01~3.0 mass parts, facilitation effect and storage stability can be kept into good.

In the present invention, can not violating in the range of its purpose, arbitrarily using known thermoplastic resin, organic fill out Fill material, fire retardant, ultra-violet absorber, antioxidant, Photoepolymerizationinitiater initiater, fluorescent whitening agent and cementability accelerator etc.. They can be used alone, or be mixed with two or more.

As thermoplastic resin, can for example enumerate polyphenylene oxide resin, phenoxy resin, polycarbonate resin, polyester resin, Polyamide, polyimide resin, xylene resin, Petropols and silicone resin etc..

As organic filler material, for example, can enumerate comprising polyethylene, polypropylene, polystyrene, polyphenylene oxide resin, silicon The resin filler of ketone resin, TFE etc.；With comprising acrylic ester resin, methacrylate ester resin, The sandwich layer of the rubbery state of conjugated diene resin etc. and comprising acrylic ester resin, methacrylate ester resin, fragrance Resin filler of core shell structure of shell of vitreousness of race's vinyl resin, vinyl cyanide base system resin etc. etc..

As fire retardant, can for example enumerate containing bromine, chlorine containing halogen-system fire retardant, triphenyl phosphate, tripotassium phosphate Phosphorus flame retardant, Guanidine Sulfamate 99, the sulfuric acid melamines such as phenyl ester, three (dichlorophenyl) phosphates, phosphate based compound, red phosphorus Phosphonitrile flame retardant, three such as the nitrogenated flame retardants such as amine, polyphosphoric acid melamine, melamine cyanurate, ring phosphonitrile, polyphosphazene Inorganic flame retardants such as antimony oxide etc..

In addition, enumerate BTA system ultra-violet absorber can be enumerated as the example of ultra-violet absorber, as anti- The example of oxidant can enumerate hindered phenol series or by histamine system antioxidant, can be enumerated as the example of Photoepolymerizationinitiater initiater Benzophenone, benzil ketals class, the Photoepolymerizationinitiater initiater of thioxanthones system, stilbene can be enumerated as the example of fluorescent whitening agent The fluorescent whitening agent of derivative, the urea compounds such as urea silane or silane can be enumerated as the example of cementability accelerator Coupling agents such as system, titanate esters system, Aluminate system etc..

Compositions of thermosetting resin containing silicone compounds of the invention is due to being used in prepregs therefore excellent Choosing is finally made the state of the varnish being dissolved or dispersed in each composition in organic solvent.

As organic solvent now used, for example, can enumerate methyl alcohol, ethanol, propyl alcohol, butanol, methyl cellosolve, fourth The ketone series solvents such as the alcohol series solvents such as base cellosolve, propylene glycol monomethyl ether, acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, second The ether series solvents such as the ester series solvents such as acid butyl ester, propylene glycol methyl ether acetate, tetrahydrofuran, toluene, dimethylbenzene, mesitylene etc. The solvent containing nitrogen-atoms such as fragrant family solvent, dimethylformamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, diformazan Solvent containing sulphur atom such as sulfoxide etc..They can be used alone, or be mixed with two or more.

In the middle of them, for example, from the aspect of deliquescent, preferably MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, methyl Cellosolve, propylene glycol monomethyl ether, more preferably methyl iso-butyl ketone (MIBK), cyclohexanone, propylene glycol monomethyl ether from from the aspect of hypotoxicity.

Resinous principle in the varnish for finally giving for example is preferably 40~90 mass % of whole varnish, more preferably 50 ~80 mass %.By making the content of the resinous principle in varnish be 40~90 mass %, it is possible to which coating is kept into good, The prepregs of suitable resinous principle adhesion amount can be obtained.

Herein, it is so-called in this specification " resinous principle ", refer to silicone compounds, modified imide resin (including tool There is the modified acid imide of the acidic substituent of the acidic substituent for coming from the amines (D) shown in already described formula (3) Resin), maleimide compound (C), the amines (D) with acidic substituent, thermoplastic elastomer (TPE) (E), thermosetting Resin (F) and their product.In addition, so-called " compositions of thermosetting resin ", refers to contain in above-mentioned resinous principle The composition of inorganic filling material and curing accelerator etc..

(prepregs)

Prepregs of the invention are the things that described compositions of thermosetting resin of the invention is infiltrated to base material Matter.Hereinafter, prepregs of the invention are described in detail.

Prepregs of the invention can be incited somebody to action compositions of thermosetting resin of the invention to base material infiltration, using heating etc. Its semi-solid preparation (second rank) and manufacture.As compositions of thermosetting resin of the invention is no special to the method that base material infiltrates Limit, however can for example enumerate base material is immersed in resin varnish method, using various coating machines be coated with method, borrow Help spraying method of spraying etc..In the middle of them, base material is preferably immersed in the method in resin varnish.Thus, it is possible to improve Infiltration of the resin combination to base material.

As base material of the invention, for example, can use known material used in various electrically insulating material plywoods Material.As the example of its material, the inorganic matter fibers such as E glass, D glass, S glass and Q glass, polyimides can be enumerated, gathered The organic fiber such as ester and tetrafluoroethene and their mixture etc..In other purposes, such as if fibre strengthening base Material, then can also use carbon fiber etc..

These base materials for example have weave cotton cloth, the shape of non-woven fabrics, rove, chopped mat and surface felt, and material and shape can With the purposes of the molding according to target, performance select, as needed, can be used alone or combine material of more than two kinds and Shape.The thickness of base material can for example use about 0.03~0.5mm, from from the aspect of heat resistance or moisture-proof, processability, fit It is combined into the base material being surface-treated with silane coupler etc. or the base material for mechanically implementing fibrillation treatment.

Prepregs of the invention can for example be obtained as follows, i.e. according to making compositions of thermosetting resin on the substrate Adhesion amount in the way of the containing ratio of the compositions of thermosetting resin of dried prepregs is calculated as 20~90 mass %, to After infiltrating or be coated with base material, generally in 100~200 DEG C of temperature heat drying 1~30 minute, semi-solid preparation (second rank) is allowed to And obtain.

(film with resin)

Film with resin of the invention is that forming layer is formed on supporting mass by compositions of thermosetting resin of the invention Film.As the compositions of thermosetting resin that will be obtained in the present invention on supporting mass cambial method, be not particularly limited, But the compositions of thermosetting resin that will can be for example obtained in the present invention is made the state of varnish, is coated with using various coating machines On supporting mass, then it is allowed to dry using heating or heat blow etc. and forms resin composition layer.Like this using heating The film with resin of the invention can be just manufactured etc. semi-solid preparation (second rank) is carried out.It is preferred that the semi-cured state is to carry When the film of resin is with circuit substrate stacking, solidification, may insure the resin composition layer and circuit substrate of the film with resin The state of bonding force, in addition, can be to ensure the state to the imbedibility (mobility) in circuit substrate.

Compositions of thermosetting resin of the invention is coated on into coating machine used when on supporting mass to be not particularly limited, so And for example can be using die coating machine, comma coating machine, bar coater, kiss painting machine, roll coater etc..They can be according to resin combination The thickness of layer is properly selected.In addition, as drying means, it is possible to use heating or heat blow etc..

Drying condition after for compositions of thermosetting resin is coated on supporting mass, for example, so that organic solvent exists Content in the resin composition layer be common below 10 mass %, be preferably below 5 mass % mode be allowed to drying.Though So organic solvent amount in varnish, the boiling point of organic solvent and it is different, but for example pass through that 30~60 mass % will be contained Organic solvent varnish in 50~150 DEG C of dryings 3~10 minutes or so, and form resin composition layer.Drying condition is preferred Simple experiment is advanced with rightly to set suitable drying condition.

The thickness of the resin composition layer being formed on supporting mass is typically set to the thickness of the conductor layer that circuit substrate has It is more than degree.Such as preferably 5~70 μm of the thickness of conductor layer, it is more excellent in order to realize compactization of multilayer printed-wiring board Elect 5~50 μm, more preferably 5~30 μm as.

Supporting mass in film with resin can for example enumerate comprising the polyolefin such as polyethylene, polypropylene, polyvinyl chloride, Polyethylene terephthalate is (hereinafter sometimes referred to simply as " PET ".), the polyester such as PEN, makrolon, The metal foils such as film and processing release paper or Copper Foil, the aluminium foil of polyimides etc..And, for supporting mass and diaphragm described later, In addition to implementing delustring treatment, sided corona treatment, demoulding treatment can also be implemented.

The thickness of supporting mass is for example preferably 10~150 μm, more preferably 25~50 μm.Can be in resin composition layer The one side of supporting mass is not provided with, then is laminated the diaphragm for copying supporting mass.The thickness of diaphragm is, for example, 1~40 μm.Pass through Stacked guard film, can prevent foreign matter to be mixed into.

Film with resin is stored after can also being wound into a roll tubular.

(plywood)

Plywood of the invention is that the foregoing film with resin is cascading into shape and obtains.For example, can be by that will carry The film of resin is laminated to the one or both sides of circuit substrate, prepregs and base material etc. using vacuum laminator, and as needed Solidified using heating and manufactured.As substrate used in circuit substrate, for example, can enumerate glass epoxy substrate, metal Substrate, polyester substrate, polyimide substrate, BT resin substrates, thermohardening type polyphenylene oxide substrate etc..And, described electricity herein Base board, refers to be formed with the substrate of circuit pattern in the one or both sides of substrate as described above.In addition, by conductor layer and In the printed wiring board of the alternately laminated multi-laminate of insulating barrier, formed in the outermost one or both sides of the printed wiring board The printed wiring board for having circuit pattern is also incorporated herein in the circuit substrate described in place.And conductor layer surface can also be utilized Darkening process etc. implements roughening treatment in advance.

In above-mentioned lamination, in the case where the film with resin has diaphragm, after the diaphragm is removed, according to need By film and the circuit substrate preheating with resin, circuit substrate is crimped on while the film with resin is pressurizeed and heated On.In the dielectric film with supporting mass of the invention, it is adapted to use using vacuum layer platen press under reduced pressure on circuit substrate The method of lamination.For lamination, for example, crimping temperature (laminating temperature) is preferably set to 70~140 DEG C, pressure will be crimped It is preferably set to 0.1~1.1MPa, is preferably laminated under the following decompressions of air pressure 20mmHg (26.7hPa).In addition, layer The method of pressure both can be batch-type, or the continous way using roller.

After film layer with resin is pressed on circuit substrate, near room temperature is cooled to, is then peeling off the feelings of supporting mass Peeled off under condition, thus heat cure can just form insulating resin layer on circuit substrate.As long as the condition of heat cure is according to resin Species, content of resinous principle in composition etc. are properly selected, but it is preferred that 20 minutes at 150 DEG C~220 DEG C ~180 minutes, the selection in the range of 30~120 minutes more preferably at 160 DEG C~200 DEG C.

After insulating resin layer is formed, in the case of not peeling off supporting mass before curing, peeled off at this moment.So Afterwards, as needed, carry out perforate in the insulating barrier being formed on circuit substrate and form via (viahole), through hole (through hole).Perforate for example can using the known method such as drill bit, laser, plasma, according further to need by These Combination of Methods are carried out, but are methods most commonly by the perforate of the lasers such as carbonic acid gas laser, YAG laser.

Then, conductor layer is formed on insulating resin layer using dry type plating or wet type plating.As dry type plating, can be with Use the known methods such as evaporation, sputtering, ion plating.In the case of wet type plating, first, the insulating resin group that will be have cured Surface permanganate (potassium permanganate, sodium permanganate etc.), bichromate, ozone, hydrogen peroxide/sulfuric acid, the nitric acid of compound layer Roughening treatment is carried out Deng oxidant, the anchor (anchor) of convex-concave is formed.As oxidant, permanganic acid is particularly preferably used The sodium hydrate aqueous solution (the alkaline permanganic acid aqueous solution) of potassium, sodium permanganate etc..Then, using being combined with non-electrolytic plating and electricity The method of plating forms conductor layer.The platedresist with conductor layer opposite pattern can also be formed in addition, merely with electroless plating It is conformal into conductor layer.As the method that pattern thereafter is formed, for example can using known subtractive process (subtractive), Semi-additive process (Semi-Additive) etc..

Plywood of the invention is that foregoing prepregs of the invention are cascading into shape and obtains.Can be by by the present invention Prepregs be for example laminated 1~20, with cascading into shape in the composition of the metal foil of its one or both sides configuration copper or aluminium etc. To manufacture.

Molding condition during manufacture plywood can for example apply electrically insulating material plywood and multiple-plate method, example Multi-stage ram, multi-stage vacuum punching press, progressive forming, autoclave forming machine are such as used, in 100~250 DEG C of temperature, pressure 0.2 ~10MPa, shaping in the range of 0.1~5 hour heat time.Alternatively, it is also possible to prepregs of the invention and internal layer are used Wiring plate is combined, and carries out cascading into shape, manufacture plywood.

(multilayer printed-wiring board)

Multilayer printed-wiring board of the invention is manufactured using the plywood.For example, can be by stacking of the invention The conductor layer of plate carries out wiring processing and obtains circuit substrate using common etching method.Hereafter, foregoing pre-preg will be utilized The plywood stacking that base has carried out wiring processing is multiple, by carrying out heating punch process and disposal multi-layer.Thereafter, pass through By Drilling operation, the formation of the through hole of Laser Processing or blind hole and by plating or the shape of the interlayer wiring of electric conductivity paste Achievement can manufacture multilayer printed-wiring board.

(semiconductor package part)

Semiconductor package part of the invention is that semiconductor element mounted thereon is formed on the multilayer printed-wiring board.The present invention Semiconductor package part be to carry semiconductor chip, the semiconductor element such as memory in the position of the regulation of the printed wiring board And manufacture.

Embodiment

Below, using following embodiments, the present invention will be described in more detail, but the present invention is not limited to this A little embodiments.

And, cure shrinkage is surveyed using following method using the resin plate obtained in each embodiment and comparative example It is fixed, evaluate, in addition using copper-clad laminated board to glass transition temperature, coefficient of thermal expansion, Copper Foil cementability, cupric solder heat resistance, curved Modulus in elasticity in bending, dielectric property are determined using following method, evaluated.

(1) measure of the cure shrinkage of resin plate

Make 5mm square resin plate (thickness 1mm), using TMA experimental rigs (TA Instrument company systems, Q400) thermo-mechanical analysis has been carried out using compression method.After resin plate is installed on such devices along Z-direction, loading is set to 5g, programming rate are set to 45 DEG C/min, using 20 DEG C (being kept for 5 minutes)~260 DEG C (being kept for 2 minutes)~20 DEG C of (5 points of holdings Clock) Temperature Distribution be determined.Initial stage size and heat up 20 DEG C before starting and 20 DEG C after intensification according to resin plate Under size changing amount have rated the cure shrinkage of resin plate.

Specifically, using following formula, the cure shrinkage of resin plate is calculated.

Cure shrinkage (%)=(intensification starts 20 DEG C after first 20 DEG C of size (mm)-intensification of size (mm))/heat up Start first 20 DEG C of size (mm) } × 100

(2) measure of glass transition temperature (Tg)

The evaluation base of the 5mm square for eliminating Copper Foil is produced by the way that copper-clad laminated board is immersed in copper etchant solution Plate, thermo-mechanical analysis has been carried out using TMA experimental rigs (TA Instrument company systems, Q400) using compression method.To evaluate After substrate is installed on such devices along Z-direction, continuously surveyed under loading 5g, the condition determination of 10 DEG C/min of programming rate It is fixed 2 times.The Tg represented with the intersection point of the different tangent line of the thermal dilatometry in secondary measure is obtained, be have rated heat-resisting Property.

(3) measure of coefficient of thermal expansion

The evaluation base of the 5mm square for eliminating Copper Foil is produced by the way that copper-clad laminated board is immersed in copper etchant solution Plate, thermo-mechanical analysis has been carried out using TMA experimental rigs (TA Instrument company systems, Q400) using compression method.To evaluate After substrate is installed on such devices along Z-direction, continuously surveyed under loading 5g, the condition determination of 10 DEG C/min of programming rate It is fixed 2 times.The average coefficient of thermal expansion of 30 DEG C to 100 DEG C in secondary measure is calculated, as the value of coefficient of thermal expansion.

(4) evaluation of Copper Foil cementability (peel strength of copper foil)

Copper-clad laminated board is immersed in copper etchant solution, 3mm Copper Foils wide is consequently formed and is produced evaluation substrate, used The stretching test machine determination cementability of Copper Foil (peel strength).

(5) evaluation of cupric solder heat resistance

The evaluation substrate of 25mm square is made by copper-clad laminated board, in the solder bath of 288 DEG C of temperature, floats evaluation substrate It is floating 120 minutes, cupric solder heat resistance is have rated by observing outward appearance.

(6) modulus of elasticity in static bending

The evaluation of the 25mm × 50mm for eliminating Copper Foil is produced by the way that copper-clad laminated board is immersed in copper etchant solution Substrate, using 5 tons of Tensilon of Orientech company systems, is determined with crosshead speed 1mm/min, span 20mm.

(7) dielectric property (dielectric constant and dielectric loss angle tangent)

The evaluation of the 100mm × 2mm for eliminating Copper Foil is produced by the way that copper-clad laminated board is immersed in copper etchant solution Substrate, using empty resonance machine device (Co., Ltd.'s Northeast the development of electronics applied system), the dielectric determined under frequency 1GHz is normal Number and dielectric loss angle tangent.

Manufacture embodiment 1：The manufacture of silicone compounds (i-1)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 3,3 '-dimethyl -4,4 '-benzidine are added：0.27g, terephthalaldehyde：0.33g、X-22- 161B：199.4g, propylene glycol monomethyl ether：300.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and utilizes normal pressure concentration It is dehydrated, is obtained the solution (Mw containing the modified silicone com (i-1) with aromatic azo methine：30000th, set Fat composition：90 mass %).

Manufacture embodiment 2：The manufacture of silicone compounds (i-2)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 4,4 '-diaminobenzene formailide are added：0.27g, terephthalaldehyde：0.31g、X-22-161B： 199.4g, propylene glycol monomethyl ether：300.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is taken off using normal pressure concentration Water, obtains the solution (Mw containing the modified silicone com (i-2) with aromatic azo methine：31000th, resinous principle： 90 mass %).

Manufacture embodiment 3：The manufacture of silicone compounds (i-3)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 4- -4 '-Aminobenzoates of aminophenyl are added：0.27g, terephthalaldehyde：0.31g、X-22- 161B：199.4g, propylene glycol monomethyl ether：300.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and utilizes normal pressure concentration It is dehydrated, is obtained the solution (Mw containing the modified silicone com (i-3) with aromatic azo methine：31000th, set Fat composition：90 mass %).

Manufacture embodiment 4：The manufacture of silicone compounds (i-4)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 4,4 '-chrysoidine are added：0.27g, terephthalaldehyde：0.31g、X-22-161B：199.4g、 Propylene glycol monomethyl ether：300.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, is obtained Solution (Mw containing the modified silicone com (i-4) with aromatic azo methine：30000th, resinous principle：90 matter Amount %).

Manufacture embodiment 5：The manufacture of silicone compounds (i-5)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 3,3 '-diethyl -4,4 '-diaminodiphenyl-methane are added：0.18g, terephthalaldehyde：0.19g、 KF-8012：199.6g, propylene glycol monomethyl ether：300.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and utilizes normal pressure dense Indentation row dehydration, obtains the solution (Mw containing the modified silicone com (i-5) with aromatic azo methine：50000、 Resinous principle：90 mass %).

Manufacture embodiment 6：The manufacture of silicone compounds (ii-1)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 3,3 '-diethyl -4,4 '-diaminodiphenyl-methane are added：12.9g, terephthalaldehyde：17.1g、 Propylene glycol monomethyl ether：45.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, is obtained Solution (resinous principle containing aromatic azo methine compound：60 mass %).

Then, in above-mentioned reaction solution, X-22-161B is added：325.5g, propylene glycol monomethyl ether：513.3g, 115 After DEG C reaction 4 hours, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aromatic azo methine Solution (the Mw of modified silicone com (ii-1)：30000th, resinous principle：90 mass %).

Manufacture embodiment 7：The manufacture of silicone compounds (ii-2)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 2,5- dimethyl-Isosorbide-5-Nitrae-diaminobenzene is added：8.7g, terephthalaldehyde：21.3g, propane diols list first Ether：45.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing aromatic series Solution (the resinous principle of azomethine compounds：60 mass %).

Then, in above-mentioned reaction solution, X-22-161B is added：413.8g, propylene glycol monomethyl ether：645.7g, 115 After DEG C reaction 4 hours, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aromatic azo methine Solution (the Mw of modified silicone com (ii-2)：25000 resinous principles：90 mass %).

Manufacture embodiment 8：The manufacture of silicone compounds (ii-3)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 4,4 '-diaminobenzene formailide are added：12.1g, terephthalaldehyde：17.9g, propylene glycol monomethyl ether： 45.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing aromatic azo Solution (the resinous principle of methine compound：60 mass %).

Then, in above-mentioned reaction solution, X-22-161B is added：342.1g, propylene glycol monomethyl ether：538.1g, 115 After DEG C reaction 4 hours, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aromatic azo methine Solution (the Mw of modified silicone com (ii-3)：31000th, resinous principle：90 mass %).

Manufacture embodiment 9：The manufacture of silicone compounds (ii-4)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 4- -4 '-Aminobenzoates of aminophenyl are added：12.2g, terephthalaldehyde：17.9g, propane diols list Methyl ether：45.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing fragrance Solution (the resinous principle of race's azomethine compounds：60 mass %).

Then, in above-mentioned reaction solution, X-22-161B is added：341.6g, propylene glycol monomethyl ether：537.3g, 115 After DEG C reaction 4 hours, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aromatic azo methine Solution (the Mw of modified silicone com (ii-4)：31000th, resinous principle：90 mass %).

Manufacture embodiment 10：The manufacture of silicone compounds (ii-5)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, 4,4 '-chrysoidine are added：11.6g, terephthalaldehyde：18.4g, propylene glycol monomethyl ether： 45.0g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing aromatic azo Solution (the resinous principle of methine compound：60 mass %).

Then, in above-mentioned reaction solution, X-22-161B is added：352.1g, propylene glycol monomethyl ether：553.1g, 115 After DEG C reaction 4 hours, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aromatic azo methine Solution (the Mw of modified silicone com (ii-5)：30000th, resinous principle：90 mass %).

Manufacture embodiment 11：The manufacture of silicone compounds (iii-1)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, terephthalaldehyde is added：5.2g、X-22-161A：24.8g, propylene glycol monomethyl ether：45.0g, at 115 DEG C After reaction 4 hours, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aldehyde radical and azomethine base Solution (the resinous principle of modified silicone com：60 mass %).

Then, in above-mentioned reaction solution, pair (4- (4- amino-benzene oxygens) phenyl) propane are added：13.0g, propane diols list Methyl ether：44.4g, after 115 DEG C of reactions 4 hours, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, is obtained containing having Solution (the Mw of the modified silicone com (iii-1) of aromatic azo methine：40000th, resinous principle：90 mass %).

Manufacture embodiment 12：The manufacture of silicone compounds (iii-2)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, terephthalaldehyde is added：3.0g、X-22-161B：27.0g, propylene glycol monomethyl ether：45.0g, at 115 DEG C After reaction 4 hours, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aldehyde radical and azomethine base The solution (60 mass %) of modified silicone com.

Then, in above-mentioned reaction solution, 3,3 '-diethyl -4,4 '-diaminodiphenyl-methane are added：4.6g, the third two Alcohol monomethyl ether：31.9g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, is contained Solution (the Mw of the modified silicone com (iii-2) with aromatic azo methine：70000th, resinous principle：90 matter Amount %).

Manufacture embodiment 13：The manufacture of silicone compounds (iii-3)

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, terephthalaldehyde is added：3.0g、X-22-161B：27.0g, propylene glycol monomethyl ether：45.0g, at 115 DEG C After reaction 4 hours, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aldehyde radical and azomethine base Solution (the resinous principle of modified silicone com：60 mass %).

Then, in above-mentioned reaction solution, 4,4 '-diaminobenzene formailide are added：4.1g, propylene glycol monomethyl ether： 31.2g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, is obtained containing with aromatic series Solution (the Mw of the modified silicone com (iii-3) of azomethine：69000th, resinous principle：90 mass %).

Manufacture embodiment 14：The manufacture of silicone compounds (iii-4)

Then, in above-mentioned reaction solution, 4- -4 '-Aminobenzoates of aminophenyl are added：4.5g, propane diols list first Ether：31.2g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, is obtained containing with virtue Solution (the Mw of the modified silicone com (iii-4) of fragrant race's azomethine：69000th, resinous principle：90 mass %).

Manufacture embodiment 15：The manufacture of silicone compounds (iii-5)

Then, in above-mentioned reaction solution, 4,4 '-chrysoidine are added：3.9g, propylene glycol monomethyl ether：30.8g, After being reacted 4 hours at 115 DEG C, it is warmed up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing with aromatic azo first Solution (the Mw of the modified silicone com (iii-5) of alkali：68000th, resinous principle：90 mass %).

Manufacture embodiment 16：The manufacture of the modified imide resin (j-1) with aromatic azo methine

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube Rise reaction vessel in, add containing with aromatic azo methine modified silicone com (i-1) solution (resin into Point：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.4g, 2,2-：243.9g, propane diols list first Ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic azo Solution (the resinous principle of the modified imide resin (j-1) of methine：60 mass %).

Manufacture embodiment 17：The manufacture of the modified imide resin (j-2) with aromatic azo methine

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube Rise reaction vessel in, add containing with aromatic azo methine modified silicone com (i-2) solution (resin into Point：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.5g, 2,2-：243.8g, propane diols list first Ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic azo Solution (the resinous principle of the modified imide resin (j-2) of methine：60 mass %).

Manufacture embodiment 18：The manufacture of the modified imide resin (j-3) with aromatic azo methine

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, the solution (resin containing the modified silicone com (ii-1) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.5g, 2,2-：243.7g, propane diols list first Ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic azo Solution (the resinous principle of the modified imide resin (j-3) of methine：60 mass %).

Manufacture embodiment 19：The manufacture of the modified imide resin (j-4) with aromatic azo methine

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, the solution (resin containing the modified silicone com (ii-3) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.3g, 2,2-：243.9g, propane diols list first Ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic azo Solution (the resinous principle of the modified imide resin (j-4) of methine：60 mass %).

Manufacture embodiment 20：The manufacture of the modified imide resin (j-5) with aromatic azo methine

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, the solution (resin containing the modified silicone com (iii-2) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.5g, 2,2-：243.8g, propane diols list first Ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic azo Solution (the resinous principle of the modified imide resin (j-5) of methine：60 mass %).

Manufacture embodiment 21：The manufacture of the modified imide resin (j-6) with aromatic azo methine

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, the solution (resin containing the modified silicone com (iii-3) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 61.7g, 2,2-：244.4g, propane diols list first Ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic azo Solution (the resinous principle of the modified imide resin (j-6) of methine：60 mass %).

Manufacture embodiment 22：The system of the modified imide resin (k-1) with acidic substituent and aromatic azo methine Make

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube Rise reaction vessel in, add containing with aromatic azo methine modified silicone com (i-1) solution (resin into Point：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.5g, 2,2-：238.1g, para-aminophenol： 5.7g, propylene glycol monomethyl ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, is contained There is the solution (resinous principle of the modified imide resin (k-1) with acidic substituent and aromatic azo methine：60 matter Amount %).

Manufacture embodiment 23：The system of the modified imide resin (k-2) with acidic substituent and aromatic azo methine Make

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube Rise reaction vessel in, add containing with aromatic azo methine modified silicone com (i-2) solution (resin into Point：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.6g, 2,2-：238.0g, para-aminophenol： 5.7g, propylene glycol monomethyl ether：443.7g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, is contained There is the solution (resinous principle of the modified imide resin (k-2) with acidic substituent and aromatic azo methine：60 matter Amount %).

Manufacture embodiment 24：The system of the modified imide resin (k-3) with acidic substituent and aromatic azo methine Make

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, the solution (resin containing the modified silicone com (ii-1) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.5g, 2,2-：238.0g, p-aminophenyl Phenol：5.7g, propylene glycol monomethyl ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains Contain the solution (resinous principle with acidic substituent and the modified imide resin (k-3) of aromatic azo methine：60 matter Amount %).

Manufacture embodiment 25：The system of the modified imide resin (k-4) with acidic substituent and aromatic azo methine Make

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, the solution (resin containing the modified silicone com (ii-3) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.3g, 2,2-：238.2g, p-aminophenyl Phenol：5.7g, propylene glycol monomethyl ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains Contain the solution (resinous principle with acidic substituent and the modified imide resin (k-4) of aromatic azo methine：60 matter Amount %).

Manufacture embodiment 26：The system of the modified imide resin (k-5) with acidic substituent and aromatic azo methine Make

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, the solution (resin containing the modified silicone com (iii-2) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.6g, 2,2-：238.0g, p-aminophenyl Phenol：5.7g, propylene glycol monomethyl ether：443.7g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains Contain the solution (resinous principle with acidic substituent and the modified imide resin (k-5) of aromatic azo methine：60 matter Amount %).

Manufacture embodiment 27：The system of the modified imide resin (k-6) with acidic substituent and aromatic azo methine Make

To the volume 2 that can be heated and cool down with thermometer, agitating device, the water and basis weight device with reflux condensing tube In the reaction vessel for rising, the solution (resin containing the modified silicone com (iii-3) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 61.8g, 2,2-：238.6g, p-aminophenyl Phenol：5.7g, propylene glycol monomethyl ether：443.8g, after being reacted 4 hours at 115 DEG C, is warmed up to 130 DEG C and carries out normal pressure concentration, obtains Contain the solution (resinous principle with acidic substituent and the modified imide resin (k-6) of aromatic azo methine：60 matter Amount %).

Embodiment 1~39 and comparative example 1~12

Contain the modified silicone com with aromatic azo methine using what is obtained in manufacture embodiment 1~15 Obtained in the solution of (i-1~i-5, ii-1~ii-5, iii-1~iii-5), manufacture embodiment 16~21 containing with fragrance Obtained in the solution of the modified imide resin (j-1~j-6) of race's azomethine and manufacture embodiment 22~27 containing having The solution and aromatic amines compound as shown below of the modified imide resin of acidic substituent and aromatic azo methine (A), aromatic aldehyde compound (B), silicone compounds (C), maleimide compound (D), the amine with acidic substituent Compound (E), thermoplastic elastomer (TPE) (F), thermosetting resin (G), inorganic filling material (H), curing accelerator (I) and conduct The MEK of retarder thinner, resinous principle as 65 matter is obtained by mixing with the mixing ratio (mass parts) shown in 1~table of table 9 Measure the varnish of %.

Then, above-mentioned varnish is used into film applicator (Tester industries in the way of making dried resin thickness be 35 μm Co. Ltd. system, PI-1210) it is coated in 16 μm of polyethylene terephthalate masking, in 160 DEG C of 10 points of heat dryings Clock, obtains the resin-oatmeal of semi-solid preparation thing.As supporting mass, it is not particularly limited, it is possible to use general material, in addition, conduct As long as the method for coating using common desk-top coating machine it is not also specifically limited, be coated with.

By in the template of resin-oatmeal input Teflon (registration mark) sheet material, 12 μm of electrolytic copper foil is being configured up and down Glassy surface, after carrying out punching press in 60 minutes at pressure 2.0MPa, 240 DEG C of temperature, removes electrolytic copper foil and obtains resin plate.

In addition, the infiltration of above-mentioned varnish is coated on the E glass cloth of thick 0.1mm, obtained in 160 DEG C of heat dryings 10 minutes To the prepregs of the mass % of resin content 48.

The prepregs are laminated 4,12 μm of electrolytic copper foil are being configured up and down, at pressure 3.0MPa, 240 DEG C of temperature Punching press in 60 minutes is carried out, copper-clad laminated board is obtained.

The measure of the resin plate of gained and copper-clad laminated board, evaluation result are shown in 1~table of table 9.

Aromatic amines compound (A)

·KAYAHARD A-A：3,3 '-diethyl -4,4 '-diaminodiphenyl-methane (Nippon Kayaku K. K's system, Trade name)

4,4 '-diaminobenzene formailide (Tokyo HuaCheng Industry Co., Ltd's system, trade name)

- 4 '-Aminobenzoate of 4- aminophenyls (Changzhou Sunlight Pharmaceutical Co., Ltd.'s system, trade name)

Aromatic aldehyde compound (B)

·TPAL：Terephthalaldehyde (Toray Fine Chemicals Co., Ltd.'s system, trade name)

Silicone compounds (C)

·X-22-161B：Two terminal amino group modified siloxanes (Shin-Etsu Chemial Co., Ltd's system, trade name)

Maleimide compound (D)

·BMI：Double (4- maleimide phenyls) methane (KI chemical conversions Co. Ltd. system, trade name)

·BMI-4000：2,2- double (4- (4- maleimidephenoxies) phenyl) propane (big and chemical conversion industry strain formula meetings Society's system, trade name)

Amines (E) with acidic substituent

Para-aminophenol (Kanto Kagaku K. K.'s system, trade name)

Thermoplastic elastomer (TPE) (F)

·Tuftec H1043：Hydrogenated styrene-butadiene copolymer resins (Asahi Chemical Corp's system, trade name)

·Epofriend CT-310：Epoxide modified styrene butadiene copolymers resin (Co., Ltd. Daicel systems, business The name of an article)

Thermosetting resin (G)

·PT-30：Novolac Cyanate Ester Resins (Lonza Japan Co. Ltd. systems, trade name)

·NC-7000L：Alpha-Naphthol/cresol novolak type epoxy resin (Nippon Kayaku K. K's system, trade name)

Inorganic filling material (H)

·SC2050-KNK：Fused silica (Co., Ltd. Admatex systems, trade name)

Zinc molybdate (Sherwin-Williams company systems, trade name：KEMGARD1100〕

Curing accelerator (I)

The petroleum solvent oil solution of zinc naphthenate (II) 8% (Tokyo HuaCheng Industry Co., Ltd's system, trade name)

·G-8009L：Isocyanates shelters imidazoles (Di-ichi Kogyo Seiyaku Co., Ltd.'s system, trade name)

·TPP-MK：The ptolylboronic acid salt of tetraphenylphosphoniphenolate four (Hokko Chemical Industry Co., Ltd.'s system, trade name)

Hereinafter, the solution containing silicone compounds (i-1)~(iii-5) of table 1~4, containing with aromatic azo The solution of modified imide resin (j-1)~(j-6) of methine and containing with acidic substituent and aromatic azo methine The solid constituent that the use level (mass parts) of the solution of modified imide resin (k-1)~(k-6) is shown resinous principle is changed The value of calculation.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

[table 9]

From 1~table of table 9 it will already have become clear that in embodiments of the invention, the cure shrinkage of resin plate is small and low solid Change shrinkage excellent, in addition, in terms of the characteristic of plywood, coefficient of thermal expansion, Copper Foil cementability, elastic modelling quantity, dielectric property It is excellent.

And on the other hand, the cure shrinkage of the resin plate of comparative example is big, in addition, in terms of the characteristic of plywood, heat is swollen Swollen rate, Copper Foil cementability, elastic modelling quantity, dielectric property are compared with embodiment, and any one characteristic is all poor.

Industrial applicability

By the compositions of thermosetting resin containing silicone compounds of the invention to pre- obtained by base material infiltration or coating Dipping base, the layer manufactured to the film obtained by coating on supporting mass with resin and by the way that the prepregs are cascading into shape Lamination has especially low cure shrinkage, especially low thermal expansivity, Copper Foil cementability, high elastic modulus, especially excellent Dielectric property, it is useful as the semiconductor package part or electronic equipment multilayer printed-wiring board that have been highly integrated.

Claims

1. a kind of silicone compounds of the structure comprising shown in following formulas (1) and following formulas (2)；

In formula, R₁And R₂Hydrogen atom, halogen atom, the alkyl of carbon number 1~3, haloalkyl, mercapto, second are represented independently of one another The alkoxy of acyl group, hydroxyl, sulfonic group, the sulfo group alkoxy of carbon number 1~3 or carbon number 1~3, x, y are each independently 0~4 Integer；A is singly-bound or azomethine base, ester group, amide groups, azoxy, azo group, ethylidene or acetenyl；

In formula, R₃And R₄Alkyl, phenyl or substituted-phenyl are represented independently of one another, and n is 1~100 integer,

Described silicone compounds also contain aromatic azo methine,

Described silicone compounds are to make in 1 molecule with least 2 aromatic amines compounds of primary amino radical (A), 1 There are at least 2 aromatic aldehyde compounds (B) of aldehyde radical in molecule, there are at least 2 siliconizations of amino in molecular end Compound (C) reacts and obtains.

2. a kind of silicone compounds of the structure comprising shown in following formulas (1) and following formulas (2)；

Described silicone compounds also contain aromatic azo methine,

Described silicone compounds are to make in 1 molecule with least 2 aromatic amines compounds of primary amino radical (A), 1 After there are at least 2 aromatic aldehyde compound (B) reactions of aldehyde radical in individual molecule, make that there are at least 2 amino in molecular end Silicone compounds (C) reaction and obtain.

3. a kind of silicone compounds of the structure comprising shown in following formulas (1) and following formulas (2)；

Described silicone compounds also contain aromatic azo methine,

Described silicone compounds are to make to have at least 2 aromatic aldehyde compounds (B) of aldehyde radical in 1 molecule, dividing After sub- end has the reaction of at least 2 silicone compounds of amino (C), make to have in 1 molecule at least 2 primary amino radicals Aromatic amines compound (A) reacts and obtains.

4. silicone compounds according to any one of claims 1 to 3, wherein having at least 2 aldehyde in 1 molecule The aromatic aldehyde compound (B) of base is terephthalaldehyde, m-terephthal aldehyde, OPA or '-two of 2,2 '-bipyridyl -4,4 Formaldehyde.

5. a kind of modified imide resin, it has makes silicone compounds any one of claims 1 to 3 and 1 There is aromatic series idol obtained by least 2 maleimide compound (D) reactions of N- substituted maleimide amidos in individual molecule N-formyl sarcolysine alkali.

6. modified imide resin according to claim 5, it also has acidic substituent, and the acidic substituent is derived from The acidic substituent of the amines (E) shown in following formulas (3)；

In formula, R₅Hydroxyl, carboxyl or the sulfonic group of acidic substituent, R are denoted as independently of one another₆Hydrogen is represented independently of one another The aliphatic alkyl or halogen atom of atom, carbon number 1~5, x is 1~5 integer, and y is 0~4 integer, and x with y's and It is 5.

7. a kind of compositions of thermosetting resin, it contains silicone compounds any one of claims 1 to 3 and 1 There are at least 2 maleimide compounds (D) of N- substituted maleimide amidos in individual molecule.

8. compositions of thermosetting resin according to claim 7, its also containing shown in following formulas (3) with acidity Replace the amines (E) of base；

9. compositions of thermosetting resin according to claim 7, it also contains thermoplastic elastomer (TPE) (F).

10. compositions of thermosetting resin according to claim 7, it is also containing selected from epoxy resin and cyanate ester resin At least one thermosetting resin (G).

11. compositions of thermosetting resin according to claim 7, it also contains inorganic filling material (H).

12. compositions of thermosetting resin according to claim 7, it also contains curing accelerator (I).

A kind of 13. prepregs, it is that the compositions of thermosetting resin any one of claim 7~12 is soaked to base material Ooze and form.

A kind of 14. films with resin, it is in branch by the compositions of thermosetting resin any one of claim 7~12 Forming layer on body is held to form.

A kind of 15. plywoods, it is to obtain the prepregs described in claim 13 are cascading into shape.

A kind of 16. plywoods, it is to obtain the film with resin described in claim 14 is cascading into shape.

A kind of 17. multilayer printed-wiring boards, its usage right requires the plywood described in 15 or 16 and manufactures.

A kind of 18. semiconductor package parts, it is the semiconductor element mounted thereon on the multilayer printed-wiring board described in claim 17 Form.