CN107254049A

CN107254049A - Silicone compounds, modified imide resin, compositions of thermosetting resin, prepregs, film and plywood with resin

Info

Publication number: CN107254049A
Application number: CN201710407622.XA
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: Showa Denko Materials Co ltd
Priority date: 2012-11-28
Filing date: 2013-11-28
Publication date: 2017-10-17
Also published as: KR102166235B1; CN106973490B; JP6747655B2; CN104812805B; WO2014084318A1; JP6375951B2; JPWO2014084318A1; TWI614262B; TW201428030A; JPWO2014084310A1; TW201434850A; CN106973490A; KR20150089017A; CN104812805A; WO2014084310A1; TWI614286B; JP6372071B2; JP2014129520A

Abstract

The present invention provides a kind of silicone compounds of the structure comprising shown in following formulas (1) and following formulas (2).[changing 1]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.[changing 2]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, film and plywood with resin

The application is applicant in November 28 2013 applying date is submitting, international application no is PCT/JP2013/ 082072nd, into National Phase in China Application No. 201380061809.9, entitled " silicone compounds, modification Imide resin, compositions of thermosetting resin, prepregs, the film with resin, plywood, multilayer printed-wiring board and partly lead The divisional application of the application for a patent for invention of body packaging part ".

Technical field

The present invention relates to suitable for semiconductor package part, the silicone compounds of printed wiring board purposes, 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 such a 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 The problem of processability, formability, the problem of be difficult to because of low-solubility in organic solvent disposal.

Among these liquid crystal liquid crystal property macromolecules, since G.F.D ' Alelio have found the poly- azo first as 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 disclosed in patent document 2~7 with specific structure 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 being used 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 of thermosetting poly-azomethine resin described in patent document 8, obdurability is still not Foot, when they are applied as copper-clad laminated board or interlayer dielectic, also has heat resistance or reliability, processability etc. no The situation of foot.

In addition, 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 such a present situation, it is therefore intended that there is provided can realize to play excellent when applied to various uses 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.

Method for solving problem

Further investigation has been repeated in order to reach the purpose in the present inventor etc., as a result finds, 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 Base, acetyl group, hydroxyl, sulfonic group, the alkoxy of 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 containing aromatic azo methine.

[3] silicone compounds according to described in [2], it is the virtue for making to have in 1 molecule at least two primary amino radical Fragrant race's amines (A), in 1 molecule with least two aldehyde radical aromatic aldehyde compound (B) and molecular end tool The silicone compounds (C) for having at least two amino react and obtained.

[4] silicone compounds according to described in [2], it is the virtue for making to have in 1 molecule at least two primary amino radical Fragrant race's amines (A), in 1 molecule with least two aldehyde radical aromatic aldehyde compound (B) reaction after, make in molecule The silicone compounds (C) that end has at least two amino react and obtained.

[5] silicone compounds according to described in [2], it is the fragrance for making to have in 1 molecule at least two aldehyde radical Race's aldehyde compound (B), molecular end have at least two amino silicone compounds (C) react after, make in 1 molecule Aromatic amines compound (A) with least two primary amino radical reacts and obtained.

[6] a kind of modified imide resin, its have make any one of [1]~[5] record silicone compounds, with Aromatic series obtained by maleimide compound (D) reaction with least two N- substituted maleimide amidos in 1 molecule Azomethine.

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

[changing 3]

In formula, R₅The hydroxyl, carboxyl or 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 for 5.

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

[9] according to the compositions of thermosetting resin described in [8], it, which also contains shown in following formulas (3), has acid The amines (E) of property substituent.

[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, which also contains, is selected from epoxy resin And at least one of cyanate ester resin thermosetting resin (G).

[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, its be will the record of any one of [8]~[13] compositions of thermosetting resin to base material Infiltration is formed.

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

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

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

[18] a kind of multilayer printed-wiring board, it uses the plywood described in [16] or [17] to manufacture.

[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 played when applied to various uses excellent low cure shrinkage, And low heat expansion, good dielectric property, the silicone compounds of the compositions of thermosetting resin of high elastic modulus, modification 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 for containing the modified silicone com with aromatic azo methine of the present invention Prepregs obtained by composition to infiltration on base material, coating, to the film obtained by coating on supporting mass with resin and pass through The prepregs are cascading into shape and plywood that manufacture 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.

Embodiment

Hereinafter, the present invention is described in detail.

(silicone compounds)

The silicone compounds of the present invention include the structure shown in following formulas (1) and following formulas (2).The configuration example Can by make the compound comprising the structure as shown in following formulas (1) with comprising following formulas (2) as shown in structure Compound react and 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 Base, acetyl group, hydroxyl, sulfonic group, the alkoxy of 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, the silicone compounds of the present invention preferably comprise aromatic azo methine.

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

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

The silicone compounds of the present invention are the aromatic amines compounds for making to have in 1 molecule at least two primary amino radical (A) (hereinafter sometimes referred to as aromatic amines compound (A)), the aromatic aldehyde compound with least two aldehyde radical in 1 molecule (B) (hereinafter sometimes referred to as aromatic aldehyde compound (B)) and there are the silicone compounds of at least two amino in molecular end (C) (hereinafter sometimes referred to as silicone compounds (C)) react and obtained.

, for example can be with as the aromatic amines compound (A) in 1 molecule with least two primary amino radical of the present invention Enumerate p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 3- methyl isophthalic acids, 4- diaminobenzenes, 2,5- dimethyl-Isosorbide-5-Nitrae-diamino Base benzene, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminourea -3,3 '-dimethyl diphenyl methane, 4,4 '-diamino Base -3,3 '-diethyl-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 '-benzidine, 3,3 '-dihydroxybiphenyl amine, 2,2- are double (3- amino-4-hydroxylphenyls) Double (4- aminophenyls) propane of propane, 3,3- dimethyl -5,5- diethyl -4,4- diphenylmethanediamiand, 2,2-, 2,2- double (4- (4- amino-benzene oxygens) phenyl) propane, double (3- amino-benzene oxygens) benzene of 1,3-, double (the 4- amino of 1,3- Phenoxy group) benzene, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygens) benzene, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, double (4- (4- amino Phenoxy group) phenyl) sulfone, double (4- (3- amino-benzene oxygens) phenyl) sulfones, 9,9- double (4- aminophenyls) fluorenes, 4,4 '-diamino Base benzanilide, double (4- aminophenyls) terephthalamides, -4 '-Aminobenzoate of 4- aminophenyls, 3,5- Diaminourea benzyl benzoate, 4,4 '-chrysoidine, 3,3 '-diaminourea -2,2 '-dimethyl azobenzene, (E) -4,4 '-diaminourea Stilbene, (Z) -4,4 '-diaminourea Stilbene, 4,4 '-diaminourea Stilbene -2,2 '-disulfonic acid, 1,3- are double (4- amino-benzene oxygens) -5- (2- phenylene-ethynylenes) benzene etc..They can be used alone, and can also be used in mixed way 2 kinds More than.

Among them, for example from reactivity during reaction it is high, can realize more high-fire resistance from the aspect of, more preferably 4, 4 '-diaminodiphenyl-methane, 3,3 '-dimethyl -4,4 '-benzidine, 4,4 '-diaminourea -3,3 '-diformazan Base-diphenyl methane, 4,4 '-diaminourea -3,3 '-diethyl-diphenyl methane, 4,4 '-bis- (4- amino-benzene oxygens) Biphenyl, double (4- (4- amino-benzene oxygens) phenyl) propane etc..In addition, from the aspect of cheap, in a solvent deliquescent, It is preferred that 4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl -4,4 '-benzidine, 4,4 '-diaminourea -3, 3 '-diethyl-diphenyl methane, double (4- (4- amino-benzene oxygens) phenyl) propane.In addition, from low heat expansion, dielectric From the aspect of characteristic, particularly preferred 4,4 '-diaminourea -3,3 '-diethyl-diphenyl methane, double (4- (4- amino Phenoxy group) phenyl) propane.In addition, it is also preferred that can with the p-phenylenediamine of high elastic modulus, m-phenylene diamine (MPD), 3- methyl isophthalic acids, 4- diaminobenzenes, 2,5- dimethyl-Isosorbide-5-Nitrae-diaminobenzene.

As the aromatic aldehyde compound (B) in 1 molecule with least two aldehyde radical of the present invention, for example, it can lift Go out terephthalaldehyde, m-terephthal aldehyde, OPA, 2,2 '-bipyridyl -4,4 '-dicarbaldehyde etc..Among them, for example Particularly preferably can more low-thermal-expansion, reaction when reactivity it is high, solvent solubility is also excellent, be commercially also readily available Terephthalaldehyde.

The silicone compounds (C) for having at least two amino in molecular end of the present invention are included 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.

As the silicone compounds (C) in molecular end with least two amino, commercially available product can also be used.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 HANTOTAI's chemical industry 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, and can also mix Conjunction uses two or more.

Among them, such as from the aspect of reactive high and low thermal expansivity during synthesis, preferably X-22-161A, X-22-161B, KF-8012, X-22-1660B-3, BY-16-853B, from intermiscibility it is excellent, can be with high elastic modulus From the aspect of changing, 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 make in 1 molecule with least two primary amino radical aromatic amines compound (A), at 1 There is the aromatic aldehyde compound (B) of at least two aldehyde radical in molecule and there is the siloxanes of at least two amino in molecular end Compound (C) is reacted, and can obtain silicone compounds (i).

Reaction method b：First, by make in 1 molecule with least two primary amino radical aromatic amines compound (A), Reacted with the aromatic aldehyde compound (B) in 1 molecule with least two aldehyde radical, and obtain having at least in 1 molecule The aromatic azo methine compound of 1 aldehyde radical.Then, by making the compound and there is at least two 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 make in 1 molecule with least two aldehyde radical aromatic aldehyde compound (B) and The silicone compounds (C) for having at least two amino in molecular end react, and obtain having 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 In have at least two primary amino radical aromatic amines compound (A) react, the modified silicon with aromatic azo methine can be obtained Siloxane compound (iii).

The silicone compounds of the present invention can use above-mentioned a, b, c any one reaction method to obtain, for example, reaction Method a operation is especially easy, especially has in the case where the solvent solubility of the modified silicone com of the present invention is not enough Effect.In addition, reaction method b, which has, is easily controlled in the molecule of the silicone compounds of the present invention, aromatic azo methine The feature of molecular weight, the high elastic modulusization for the resin combination containing it is especially effective.In addition, reaction method c has The feature of the molecular weight of in the molecule of the silicone compounds of the present 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 is at least two in 1 molecule The aromatic amines compound (A) of primary amino radical, in 1 molecule with least two aldehyde radical aromatic aldehyde compound (B) and The silicone compounds (C) that molecular end has at least two amino react, and can obtain the silicone compounds (i) of the present invention.

Herein, for having the aromatic amines compound (A) of at least two primary amino radical in 1 molecule, in 1 molecule Aromatic aldehyde compound (B) with least two aldehyde radical, the silicone compounds (C) in molecular end with least two amino 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)) be aromatic aldehyde compound (B) aldehyde radical number (usage amount/fragrance of aromatic aldehyde compound (B) The aldehyde radical equivalent of race's aldehyde compound (B)) the mode of 1.0~10.0 times of scope use., will by being set to more than 1.0 times 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 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, dimethyl acetamide, 1-METHYLPYRROLIDONE, diformazan are sub- Ester series solvents such as the solvent containing sulphur atom such as sulfone, gamma-butyrolacton etc..They can use a kind or be mixed with two or more. Among them, for example, from the aspect of deliquescent, preferably propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, two Methylacetamide, gamma-butyrolacton.In addition, from volatility is high, manufacture in prepregs when be difficult to remain as residual solvent From the aspect of, more preferably propylene glycol monomethyl ether, toluene.Further, since the reaction is dehydration condensation, therefore it is used as by-product Thing generates water.For the purpose as the water of accessory substance is removed, for example, preferably removed using the azeotropic with fragrant family solvent Go to be reacted while the water as accessory substance.

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, are more preferably set For 40~1000 mass parts, 40~500 mass parts are particularly preferably set to.If the usage amount of organic solvent be 25 mass parts with On, then deliquescent not enough trend can be suppressed by having.In addition, if for below 2000 mass parts, then the reaction time is suitable.

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

Above-mentioned raw material, organic solvent, the catalysts used as needed are added in reactor, 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 manufacturing prepregs, 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 to have extremely in 1 molecule The aromatic amines compound (A) of few 2 primary amino radicals and the aromatic aldehyde compound in 1 molecule with least two aldehyde radical (B) react, and obtain the aromatic azo methine compound with least one aldehyde radical in 1 molecule.Then, by making State compound and reacted in the silicone compounds (C) that molecular end has at least two amino, can be obtained with aromatic series The modified silicone com (ii) of azomethine.

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

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

Herein, for the aromatic amines compound (A) in 1 molecule with least two primary amino radical and in 1 molecule The usage amount of aromatic aldehyde compound (B) with least two aldehyde radical, such as preferably so that the primary of aromatic amines compound (A) Amino number (the primary amino radical equivalent of 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 resin component, 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.

Above-mentioned raw material, organic solvent, the catalysts used as needed are added in reactor, 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 aromatic azo methine compound of at 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, just having reaction speed will not slow trend excessively.If anti- It is less than 150 DEG C to answer temperature, then high boiling solvent is not needed in reaction dissolvent, when manufacturing prepregs, it is difficult to remain residual Remaining solvent, can suppress the reduction of heat resistance.

Then, the aromatic azo first in 1 molecule with least one aldehyde radical by making to obtain using above-mentioned reaction Alkali cpd and dehydrating condensation is carried out in organic solvent in the silicone compounds (C) that molecular end has at least two amino 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 usage amount/silicone compounds (C) of silicone compounds (C)) of siloxane compound (C) For 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) the mode of 1.0~10.0 times 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 modulus of elasticity 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 in 1 molecule with least one aldehyde radical The mass parts of summation 100 of the resin component 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 The not enough trend of dissolubility can be suppressed more than 25 mass parts, just to have by measuring.In addition, if being below 2000 mass parts, then Reaction time is suitable.

Above-mentioned raw material, organic solvent, the catalysts used as needed are added in reactor, 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, just having reaction speed will not slow trend excessively.Such as Fruit reaction temperature is less than 150 DEG C, then high boiling solvent is not needed in reaction dissolvent, when manufacturing prepregs, 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 to have extremely in 1 molecule The aromatic aldehyde compound (B) of few 2 aldehyde radicals and have the silicone compounds (C) of at least two amino anti-in molecular end Should, and obtain the modified silicone com with least one aldehyde radical and azomethine base (- N=CH-) in 1 molecule. Then, by making the compound and aromatic amines compound (A) reaction with least two primary amino radical in 1 molecule, The modified silicone com (iii) with aromatic azo methine can be obtained.

In reaction method c, organic solvent used in reaction and the catalysts used 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 two aldehyde radical in 1 molecule and in molecular end The silicone compounds (C) of at least two amino 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 two aldehyde radical and in molecular end There is the usage amount of the silicone compounds (C) of at least two amino, such as preferably so that the primaquine radix of silicone compounds (C) (the primary amino radical equivalents of usage amount/silicone compounds (C) of silicone compounds (C)) are the aldehyde of aromatic aldehyde compound (B) 0.1 times~5.0 times of model 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, it can suppress that there is at least one aldehyde radical and azomethine base (- N in 1 molecule using what this reaction was obtained =CH-) modified silicone com molecular weight reduction.

In addition, for the usage amount of organic solvent, such as relative to aromatic aldehyde compound (B), silicone compounds (C) Resin component 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.

Above-mentioned raw material, organic solvent, the catalysts used as needed are added in reactor, 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 making that there is at least one aldehyde radical and azomethine base in 1 molecule using what above-mentioned reaction was obtained The modified silicone com of (- N=CH-) and the aromatic amines compound in 1 molecule with least two primary amino radical (A) dehydration condensation is carried out in organic solvent, it is possible to obtain the modified siloxane chemical combination with aromatic azo methine Thing (iii).

Herein, for the usage amount of modified silicone com and 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 usage amount/aromatic amines compound (A) of aromatic amines compound (A) Amount) be modified silicone com the aldehyde radical number (aldehyde radical of usage amount/modified silicone com of modified silicone com Equivalent) the mode of 1.0~10.0 times 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, the trend of deliquescent reduction in a solvent can be suppressed by just having.

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 matter of summation 100 of the resin component of the modified silicone com and aromatic amines compound (A) of methine base (- N=CH-) Part is measured, 25~2000 mass parts is preferably set to, is more preferably set to 40~1000 mass parts, be particularly preferably set to 40~500 mass Part.If the usage amount of organic solvent is more than 25 mass parts, deliquescent not enough trend can be suppressed by just having.In addition, Below 2000 mass parts, then the reaction time is suitable.

Above-mentioned raw material, organic solvent, the catalysts used as needed are added in reactor, 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 as caused by azomethine base (- N=CH-) occur^-1Peak, separately Outside, confirm there is the 3440cm as caused by primary amino radical^-1And 3370cm^-1Neighbouring peak, it is possible thereby to confirm that reaction is entered well OK, required compound has been obtained.In addition, weight average molecular weight (Mw) is for example 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 carried Height, below the upper limit, then intermiscibility, modulus of elasticity are improved.Moreover, weight average molecular weight (Mw) is to utilize gel infiltration Chromatography (GPC) is measured, the value converted using the calibration curve made using polystyrene standard.For example, can with Carried out under the conditions of lower.As device is determined, automatic sampler (Tosoh Co. Ltd. system AS-8020), chromatographic column baking oven are used (Japan Spectroscopy Corporation 860-C0), RI detectors (Japan Spectroscopy Corporation 830-RI), UV/VIS detectors (Japan Spectroscopy Corporation 870-UV), HPLC pumps (Japan Spectroscopy Corporation 880-PU).

In addition, as chromatographic column is used, Tosoh Co. Ltd. system TSKgel SuperHZ2000,2300 can be used, make For condition determination, it can be measured by being set to determine 40 DEG C of temperature, flow 0.5ml/min, solvents tetrahydrofurane.

(modified imide resin)

The modification imide resin of the present invention be by make already described amino modified silicone compounds of the invention and Material obtained by maleimide compound (C) reaction with least two N- substituted maleimide amidos in 1 molecule.

In addition, 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- It should import.By the way that with the acidic substituent, good low heat expansion can be obtained.

[changing 8]

In formula (3), R₁The hydroxyl, carboxyl or 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 be 1~5 integer, y be 0~4 integer, and x with Y's and for 5.

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

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

(compositions of thermosetting resin)

The compositions of thermosetting resin of the present invention is containing modified silicone com of the invention and in 1 molecule The composition of maleimide compound (D) with least two N- substituted maleimide amidos.

As in 1 molecule with least two N- substituted maleimide amidos maleimide compound (D) (with Maleimide compound (D) is sometimes referred to as down), it 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- diethyl -4,4- diphenyl methanes BMI, 4- methyl isophthalic acids, 3- phenylenes BMI, an Asia Double (4- (4- maleimidephenoxies) phenyl) propane of phenyl-bismaleimide, 2,2- etc..These maleimations Compound both can be used alone, and can also be mixed with two or more.

Among them, for example preferred reactive is high, can realize double (4- maleimide phenyls) first of more high-fire resistance Double (4- (4- maleimidephenoxies) phenyl) propane of alkane, double (4- maleimide phenyls) sulfones, 2,2-, from solvent In it is deliquescent from the aspect of, double (4- (the 4- maleimides of more preferably double (4- maleimide phenyls) methane, 2,2- Amine phenoxy group) phenyl) propane, from the aspect of cheap, particularly preferably double (4- maleimide phenyls) methane.

In the compositions of thermosetting resin of the present invention, the usage amount for the silicone compounds of the present invention (coordinates Amount), such as in every 100 mass parts of summation of resin component, 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 maleimide compound (D) usage amount, such as excellent in every 100 mass parts of summation of resin component Choosing is set to 30~99 mass parts, from the aspect of low heat expansion, high elastic modulus, is more preferably set to 40~95 mass parts.

The compositions of thermosetting resin of the present invention is the silicone compounds containing the present invention and had in 1 molecule The composition of the maleimide compound (D) of at least two N- substituted maleimide amidos, but can also make above-mentioned Compound pre-reaction and used as with the modification imide resin of aromatic azo methine.By carrying out such a pre-reaction, Molecular weight can be just controlled, further low cure shrinkage, low heat expansion can be carried out and improved.

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

Make reaction temperature example when modified silicone com, maleimide compound (D) reaction in organic solvent 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 present invention silicone compounds usage amount, for example Preferably so that maleimide radix (usage amount/Malaysia of maleimide compound (D) of maleimide compound (D) The dimaleoyl imino equivalent of imide compound (D)) for the present invention silicone compounds primaquine radix (silicon of the invention The primary amino radical equivalent of the silicone compounds of usage amount/present invention of siloxane compound) 2.0~10.0 times of scope.Pass through More than 2.0 times are set to, the trend for 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 for 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 resin component 100 for example relative to the silicone compounds of the present invention are preferably 50~3000 mass parts, more preferably For 100~1500 mass parts.By being set to more than 50 mass parts, the trend for 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 The solvent containing nitrogen-atoms such as solvent, dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide etc. contain There is solvent of sulphur atom etc..They can use a kind or be mixed with two or more.

Among 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 from the aspect of being remained as residual solvent, particularly preferably Cyclohexanone, propylene glycol monomethyl ether, dimethyl acetamide.

For the usage amount of organic solvent, such as silicone compounds, maleimide compound relative to the present invention (D) mass parts of summation 100 of resin component, 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 system such as the imidazoles such as amine, methylimidazole, phenylimidazole, triphenylphosphine such as can enumerate triethylamine, pyridine, tri-n-butylamine Alkali metal amides such as catalyst, lithium acid amides, sodium acid amides, potassium acid amides etc..They can use a kind or be mixed with two or more.

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

Make the silicone compounds containing the present invention and there is at least two N- substituted maleimide amine in 1 molecule The compositions of thermosetting resin of the maleimide compound (D) of base and above-claimed cpd pre-reaction, having for gained are fragrant The modification imide resin of fragrant race's azomethine, which is used alone, can also have good heat cure reactivity, but can also basis Need and use curing agent and radical initiator.By using curing agent and radical initiator, heat resistance, bonding can be improved Property, mechanical strength.

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

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

In addition, the compositions of thermosetting resin of the present invention, which can contain shown in following formulas (3), has acid substitution The amines (E) of base.

[changing 9]

In formula (3), R₅The hydroxyl, carboxyl or 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 be 1~5 integer, y be 0~4 integer, and x with Y's and for 5.

As the amines (E) with acidic substituent, for example, it 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..Among them, for example, from dissolubility, synthesis receipts From the aspect of rate, preferably m-aminophenol, para-aminophenol, o-aminophenol, p-aminobenzoic acid, gavaculine, And 3,5- dihydroxy aniline, 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 resin component Measure in part, be preferably set to 0.5~30 mass parts, from the aspect of low heat expansion, be more preferably set to 1~20 mass parts.

The compositions of thermosetting resin of the present invention can also be containing modified silicone com of the invention, in 1 molecule In have at least two N- substituted maleimide amidos maleimide compound (D), the amine compounds with acidic substituent Thing (E), makes above-claimed cpd pre-reaction, makes as the modification imide resin with acidic substituent and aromatic azo methine With.By carrying out such a 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, the horse of the present invention Come imide compound (D), the amines (E) with acidic substituent to react and synthesize the modification acyl with acidic substituent Imide resin.

Make silicone compounds of the invention, maleimide compound (D) in organic solvent, with acidic substituent Amines (E) reaction 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, for maleimide compound (D), the silicone compounds of the present invention and with acidity substitution 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 usage amount/maleimide compound (D) of imide compound (D)) it is silica of the invention Hydride compounds and amines (E) with acidic substituent primaquine radix (usage amount of silicone compounds of the invention/ The primary amino radical equivalent of the silicone compounds of the present invention+usage amount with the amines (E) of acidic substituent/has acidity The primary amino radical equivalent of the amines (E) of substituent) 2.0~10.0 times of scope.By being set to more than 2.0 times, just have The trend of gelation and the reduction of 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 resin component 100 for example relative to the silicone compounds of the present invention are preferably 50~3000 mass parts, more preferably For 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, for the usage amount of the amines (E) with acidic substituent in pre-reaction, such as relative to this hair The mass parts of resin component 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, can will be low in addition, by being set to below 1000 mass parts 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, dimethyl acetamide, 1-METHYLPYRROLIDONE etc. contain nitrogen-atoms Solvent containing sulphur atom such as solvent, dimethyl sulfoxide etc..They can use a kind or be mixed with two or more.

Among these organic solvents, such as it is preferably cyclohexanone, propylene glycol monomethyl ether, methyl from the aspect of deliquescent Cellosolve, gamma-butyrolacton, from hypotoxicity, volatility is high, be difficult to from the aspect of being remained as residual solvent, particularly preferred ring Hexanone, propylene glycol monomethyl ether, dimethyl acetamide.

For the usage amount of organic solvent, such as silicone compounds, maleimide compound relative to the present invention (D) mass parts of summation 100 of the resin component of amines (E), with acidic substituent, are preferably set to 25~2000 mass Part, 40~1000 mass parts are more preferably set to, 40~500 mass parts are particularly preferably set to.If the usage amount of organic solvent is More than 25 mass parts, then deliquescent not enough trend can be suppressed by having.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 the phosphorus such as the imidazoles such as amine, methylimidazole, phenylimidazole, triphenylphosphine such as can enumerate triethylamine, pyridine, tri-n-butylamine Alkali metal amides such as series catalysts, lithium acid amides, sodium acid amides, potassium acid amides etc..They can use a kind or be mixed with two or more.

In addition, sub- for the modification acyl with acidic substituent and aromatic azo methine obtained using above-mentioned pre-reaction The usage amount of polyimide resin, such as in every 100 mass parts of summation of resin component, 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 modification imide resin of aromatic azo methine Amount is set to more than 50 mass parts, can obtain low heat expansion, high elastic modulus.

Make the modified silicone com with aromatic azo methine containing the present invention, have extremely in 1 molecule Maleimide compound (D), the amines (E) with acidic substituent of few 2 N- substituted maleimide amidos are formed Compositions of thermosetting resin and above-claimed cpd pre-reaction, gained has changing for acidic substituent and aromatic azo methine 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 peroxide such as compound, the organic peroxide with the tert-butyl group, peroxide with cumyl etc..They can be independent Use, can also be mixed with two or more.Among them, for example, from the aspect of good reactivity, heat resistance, preferably Aromatic amine.

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

As thermoplastic elastomer (TPE) (F), for example, it 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 segment 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, the bullet in molecular end or strand with reactive functional groups can be used Property body.As reactive functional groups, for example, it 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 for the compositions of thermosetting resin that can more effectively reduce the present invention Internal stress.As a result, the warpage of substrate can be significantly decreased.

Among these elastomers, such as from the aspect of heat resistance, insulating reliability, optimization styrene based elastomers, Olefin-based elastomer, polyamide-based elastomer and silicone based elastomers, 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 excellent for the usage amount of thermoplastic elastomer (TPE) (F) composition, such as mass parts of summation 100 relative to resin component 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, it is low From the aspect of thermal expansivity, excellent dielectric property, more preferably 2~30 mass parts.

In addition, the compositions of thermosetting resin of the present invention can contain in epoxy resin and cyanate ester resin at least A kind of thermosetting resin (G).

As epoxy resin, for example, it 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, The two of the Ppolynuclear aromatic classes such as dicyclopentadiene type epoxy resin, alicyclic epoxy resin, multifunctional phenol and anthracene are shunk sweet Oily ether compound and epoxy resin containing phosphorus of phosphorus compound etc. is imported into them.They can be used alone, and also may be used To be mixed with two or more.Among them, such as 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, it 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, and can also be mixed with two or more.Among 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 thermosetting resin (G) usage amount, such as in every 100 mass parts of summation of resin component, it is preferably set to 1 ~50 mass parts, from the aspect of heat resistance, resistance to chemical reagents, more preferably 3~30 mass parts.

The compositions of thermosetting resin of the present 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, and can also be mixed with two or more.

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

In the case where using melting spherical silicon dioxide as inorganic filling material, for example its average grain diameter is preferably 0.1~10 μm, more preferably 0.3~8 μm.By the way that the average grain diameter of the melting spherical silicon dioxide is set into more than 0.1 μm, just High density can be filled into mobility when in resin and keep good, in addition by being allowed to as less than 10 μm, it is possible to reduce Oversize grain is mixed into probability, suppresses generation bad caused by oversize grain.Herein, so-called average grain diameter, refers to 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 using having used particle size distribution device of laser diffraction and scattering method etc. to determine.

For the content of inorganic filling material, for example the mass parts of summation 100 relative to resin component 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 resin component Mass parts are 20~500 mass parts, the formability of resin combination and low heat expansion can be kept into good.

In addition, when coordinating inorganic filling material into 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 processing.

The compositions of thermosetting resin of the present invention can contain curing accelerator (I)., for example can be with as curing accelerator 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 metal salt, imidazoles and its derivative, phosphine and phosphonium salt etc.. Their a kind is can be used alone, or is mixed with two or more.

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

For the content of curing accelerator, for example the mass parts of summation 100 relative to resin component 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 resin component Mass parts are 0.01~3.0 mass parts, facilitation effect and storage stability can be kept into good.

In the present invention, can in the range of its purpose is not violated, 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, it 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 include 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, for example, it can enumerate and contain halogen-system fire retardant, triphenyl phosphate, tripotassium phosphate containing bromine, chlorine 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..

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

As organic solvent now used, for example, it can enumerate methanol, 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, dimethyl acetamide, 1-METHYLPYRROLIDONE, diformazan Solvent containing sulphur atom such as sulfoxide etc..They can be used alone, or be mixed with two or more.

Among 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 the aspect of hypotoxicity.

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

Herein, it is so-called in this specification " resin component ", refer to silicone compounds, modified imide resin (including tool There is the modification acid imide of the acidic substituent for 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 reaction product.In addition, so-called " compositions of thermosetting resin ", refers to contain in above-mentioned resin component The composition of inorganic filling material and curing accelerator etc..

(prepregs)

The prepregs of the present invention are the things for infiltrating described compositions of thermosetting resin of the invention to base material Matter.Hereinafter, the prepregs of the present invention are described in detail.

The compositions of thermosetting resin of the present invention can be infiltrated, be incited somebody to action using heating etc. by the prepregs of the present invention to base material Its semi-solid preparation (second rank) and manufacture.It is not special as the method for infiltrating the compositions of thermosetting resin of the present invention to base material Limit, but can for example enumerate the method being immersed in base material in resin varnish, the method being coated with using various coating machines, borrow Help spraying method of spraying etc..Among 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 the base material of the present invention, for example, it 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 are for example with weaving 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 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 mechanically implements the base material of fibrillation processing.

The prepregs of the present 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 for carrying resin)

The film with resin of the present invention is that forming layer is formed on supporting mass by the compositions of thermosetting resin of the present invention Film.As by the compositions of thermosetting resin obtained in the present invention on supporting mass cambial method, be not particularly limited, But the compositions of thermosetting resin obtained in the present invention can be for example made to the state of varnish, it 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.Heating is utilized like this The film with resin of the present invention can be just manufactured Deng semi-solid preparation (second rank) is carried out.It is preferred that the semi-cured state is to carry The film of resin is laminated with circuit substrate, solidification when, may insure the resin composition layer and circuit substrate of the film with resin The state of bonding force, in addition, being the state that may insure the imbedibility (mobility) into circuit substrate.

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

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 is common below 10 mass %, preferably below 5 mass % mode is allowed to drying.Though So organic solvent amount in varnish, the boiling point of organic solvent and it is different, but for example by the way that 30~60 mass % will be contained The varnish of organic solvent dried 3~10 minutes or so at 50~150 DEG C, and form resin composition layer.Drying condition is preferred Simple experiment is advanced with rightly to set suitable drying condition.

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

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

(plywood)

The plywood of the present invention is that the foregoing film with resin is cascading into shape and obtain.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 and manufactured using heating.As substrate used in circuit substrate, for example, it can enumerate glass epoxy substrate, metal Substrate, polyester substrate, polyimide substrate, BT resin substrates, thermohardening type polyphenylene oxide substrate etc..Moreover, described electricity herein Base board, refers to that the one or both sides in substrate as described above are formed with the substrate of circuit pattern.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 that place is said.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 Film with resin and circuit substrate are preheated, circuit substrate is crimped on while the film with resin is pressurizeed and heated On.In the dielectric film with supporting mass of the present invention, it is adapted to using utilization 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, then the feelings of supporting mass are being peeled off 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 resin component in composition etc. are properly selected, but it is preferred that 20 minutes at 150 DEG C~220 DEG C ~180 minutes, the more preferably selection in the range of 30~120 minutes 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 such as can utilize drill bit, laser, plasma known to method, 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., can be with as dry type plating Use method known to evaporation, sputtering, ion plating etc..In the case of wet type plating, first, by the insulating resin group that 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, particularly preferably using permanganic acid 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 formation conductor layer of plating.The platedresist with conductor layer opposite pattern can also be formed in addition, merely with electroless plating It is conformal into conductor layer.As thereafter pattern formation method, can for example use known subtractive process (subtractive), Semi-additive process (Semi-Additive) etc..

The plywood of the present invention is that foregoing prepregs of the invention are cascading into shape and obtain.Can be by by the present invention Prepregs such as being laminated 1~20, it is cascading into shape to configure the composition of copper or the metal foil aluminium in its one or both sides To manufacture.

Molding condition when manufacturing 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 which the prepregs of the present invention are used with internal layer Wiring plate is combined, and carries out cascading into shape, manufacture plywood.

(multilayer printed-wiring board)

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

(semiconductor package part)

The semiconductor package part of the present invention is that semiconductor element mounted thereon is formed on the multilayer printed-wiring board.The present invention Semiconductor package part be that semiconductor chip, the semiconductor element such as memory are carried in the defined position 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.

Moreover, being surveyed using the resin plate obtained in each embodiment and comparative example to cure shrinkage using following method 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, utilize 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.According to resin plate initial stage size and heating start before 20 DEG C and heating after 20 DEG C 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 (%)=(heating starts 20 DEG C after first 20 DEG C of size (mm)-heating of size (mm))/liter Temperature starts first 20 DEG C of size (mm) } × 100

(2) measure of glass transition temperature (Tg)

By the evaluation base for copper-clad laminated board being immersed in copper etchant solution and being produced the 5mm square for eliminating copper foil Plate, thermo-mechanical analysis has been carried out using TMA experimental rigs (TA Instrument company systems, Q400) using compression method.It will 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 lines of the thermal dilatometry in secondary measure is obtained, be have rated heat-resisting Property.

(3) measure of coefficient of thermal expansion

By the evaluation base for copper-clad laminated board being immersed in copper etchant solution and being produced the 5mm square for eliminating copper foil Plate, thermo-mechanical analysis has been carried out using TMA experimental rigs (TA Instrument company systems, Q400) using compression method.It will 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.30 DEG C to 100 DEG C of average coefficient of thermal expansion 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, the wide copper foils of 3mm is consequently formed and produces evaluation substrate, use 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, it have rated cupric solder heat resistance by observing outward appearance.

(6) modulus of elasticity in static bending

By the evaluation for copper-clad laminated board being immersed in copper etchant solution and being produced the 25mm × 50mm for eliminating copper foil 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)

By the evaluation for copper-clad laminated board being immersed in copper etchant solution and being produced the 100mm × 2mm for eliminating copper foil 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 risen, 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 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and utilizes normal pressure Concentration is dehydrated, and obtains the solution (Mw containing the modified silicone com (i-1) with aromatic azo methine： 30000th, resin component：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 risen, 4,4'- diaminobenzene formailides are added：0.27g, terephthalaldehyde：0.31g, X-22-161B： 199.4g, propylene glycol monomethyl ether：300.0g, after 115 DEG C are reacted 4 hours, is warming 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, resin into Point：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 risen, 4- -4 '-Aminobenzoates of aminophenyl are added：0.27g, terephthalaldehyde：0.31g, X- 22-161B：199.4g, propylene glycol monomethyl ether：300.0g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and utilizes normal pressure Concentration is dehydrated, and obtains the solution (Mw containing the modified silicone com (i-3) with aromatic azo methine： 31000th, resin component：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 risen, 4,4 '-chrysoidine are added：0.27g, terephthalaldehyde：0.31g, X-22-161B： 199.4g, propylene glycol monomethyl ether：300.0g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and is taken off using normal pressure concentration Water, obtains the solution (Mw containing the modified silicone com (i-4) with aromatic azo methine：30000th, resin into Point：90 mass %).

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 risen, 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 115 DEG C of reactions 4 hours, is warming up to 130 DEG C and sharp It is dehydrated with normal pressure concentration, obtains the solution containing the modified silicone com (i-5) with aromatic azo methine (Mw：50000th, resin component：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 risen, 3,3 '-diethyl -4,4 '-diaminodiphenyl-methane are added：12.9g, terephthalaldehyde： 17.1g, propylene glycol monomethyl ether：45.0g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and is taken off using normal pressure concentration Water, obtains the solution (resin component containing aromatic azo methine compound：60 mass %).

Then, into above-mentioned reaction solution, X-22-161B is added：325.5g, propylene glycol monomethyl ether：513.3g, After 115 DEG C are reacted 4 hours, it is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing with aromatic azo methine Modified silicone com (ii-1) solution (Mw：30000th, resin component：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 risen, 2,5- dimethyl-Isosorbide-5-Nitrae-diaminobenzene is added：8.7g, terephthalaldehyde：21.3g, propane diols list Methyl ether：45.0g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtained containing fragrance Solution (the resin component of race's azomethine compounds：60 mass %).

Then, into above-mentioned reaction solution, X-22-161B is added：413.8g, propylene glycol monomethyl ether：645.7g, After 115 DEG C are reacted 4 hours, it is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing with aromatic azo methine Modified silicone com (ii-2) solution (Mw：25000 resin components：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 risen, 4,4'- diaminobenzene formailides are added：12.1g, terephthalaldehyde：17.9g, propane diols list first Ether：45.0g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtained containing aromatic series Solution (the resin component of azomethine compounds：60 mass %).

Then, into above-mentioned reaction solution, X-22-161B is added：342.1g, propylene glycol monomethyl ether：538.1g, After 115 DEG C are reacted 4 hours, it is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing with aromatic azo methine Modified silicone com (ii-3) solution (Mw：31000th, resin component：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 risen, 4- -4 '-Aminobenzoates of aminophenyl are added：12.2g, terephthalaldehyde：17.9g, the third two Alcohol monomethyl ether：45.0g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and is dehydrated using normal pressure concentration, contained Solution (the resin component of aromatic azo methine compound：60 mass %).

Then, into above-mentioned reaction solution, X-22-161B is added：341.6g, propylene glycol monomethyl ether：537.3g, After 115 DEG C are reacted 4 hours, it is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing with aromatic azo methine Modified silicone com (ii-4) solution (Mw：31000th, resin component：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 risen, 4,4 '-chrysoidine are added：11.6g, terephthalaldehyde：18.4g, propylene glycol monomethyl ether： 45.0g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtained containing aromatic azo Solution (the resin component of methine compound：60 mass %).

Then, into above-mentioned reaction solution, X-22-161B is added：352.1g, propylene glycol monomethyl ether：553.1g, After 115 DEG C are reacted 4 hours, it is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing with aromatic azo methine Modified silicone com (ii-5) solution (Mw：30000th, resin component：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 risen, terephthalaldehyde is added：5.2g, X-22-161A：24.8g, propylene glycol monomethyl ether：45.0g, 115 After DEG C reaction 4 hours, it is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aldehyde radical and azomethine base Modified silicone com solution (resin component：60 mass %).

Then, into above-mentioned reaction solution, double (4- (4- amino-benzene oxygens) phenyl) propane are added：13.0g, propane diols Monomethyl ether：44.4g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtained containing tool There is the solution (Mw of the modified silicone com (iii-1) of aromatic azo methine：40000th, resin component：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 risen, terephthalaldehyde is added：3.0g, X-22-161B：27.0g, propylene glycol monomethyl ether：45.0g, 115 After DEG C reaction 4 hours, it is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aldehyde radical and azomethine base Modified silicone com solution (60 mass %).

Then, into above-mentioned reaction solution, 3,3 '-diethyl -4,4 '-diaminodiphenyl-methane are added：4.6g、 Propylene glycol monomethyl ether：31.9g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtained Solution (Mw containing the modified silicone com (iii-2) with aromatic azo methine：70000th, resin component：90 matter Measure %).

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 risen, terephthalaldehyde is added：3.0g, X-22-161B：27.0g, propylene glycol monomethyl ether：45.0g, 115 After DEG C reaction 4 hours, it is warming up to 130 DEG C and is dehydrated using normal pressure concentration, obtains containing having aldehyde radical and azomethine base Modified silicone com solution (resin component：60 mass %).

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

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

Then, into above-mentioned reaction solution, 4- -4 '-Aminobenzoates of aminophenyl are added：4.5g, propane diols list Methyl ether：31.2g, after 115 DEG C of reactions 4 hours, is warming 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-4) of aromatic azo methine：69000th, resin component：90 mass %).

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

Then, into above-mentioned reaction solution, 4,4 '-chrysoidine are added：3.9g, propylene glycol monomethyl ether：30.8g, After 115 DEG C are reacted 4 hours, it is warming 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, resin component：90 mass %).

Manufacture embodiment 16：The manufacture of modification 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 In the reaction vessel risen, the solution (resin containing the modified silicone com (i-1) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.4g, 2,2-：243.9g, propane diols Monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic series Solution (the resin component of the modification imide resin (j-1) of azomethine：60 mass %).

Manufacture embodiment 17：The manufacture of modification 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 In the reaction vessel risen, the solution (resin containing the modified silicone com (i-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 Monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic series Solution (the resin component of the modification imide resin (j-2) of azomethine：60 mass %).

Manufacture embodiment 18：The manufacture of modification 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 risen, 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 Monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic series Solution (the resin component of the modification imide resin (j-3) of azomethine：60 mass %).

Manufacture embodiment 19：The manufacture of modification 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 risen, 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 Monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtains containing with aromatic series Solution (the resin component of the modification imide resin (j-4) of azomethine：60 mass %).

Manufacture embodiment 20：The manufacture of modification 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 risen, the solution (tree containing the modified silicone com (iii-2) with aromatic azo methine is added Fat composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.5g, 2,2-：243.8g, the third two Alcohol monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtains containing with fragrance Solution (the resin component of the modification imide resin (j-5) of race's azomethine：60 mass %).

Manufacture embodiment 21：The manufacture of modification 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 risen, the solution (tree containing the modified silicone com (iii-3) with aromatic azo methine is added Fat composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 61.7g, 2,2-：244.4g, the third two Alcohol monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtains containing with fragrance Solution (the resin component of the modification imide resin (j-6) of race's azomethine：60 mass %).

Manufacture embodiment 22：The system of modification 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 In the reaction vessel risen, the solution (resin containing the modified silicone com (i-1) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.5g, 2,2-：238.1g, to amino Phenol：5.7g, propylene glycol monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtain To containing the solution (resin component with acidic substituent and the modification imide resin (k-1) of aromatic azo methine：60 Quality %).

Manufacture embodiment 23：The system of modification 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 In the reaction vessel risen, the solution (resin containing the modified silicone com (i-2) with aromatic azo methine is added Composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.6g, 2,2-：238.0g, to amino Phenol：5.7g, propylene glycol monomethyl ether：443.7g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtain To containing the solution (resin component with acidic substituent and the modification imide resin (k-2) of aromatic azo methine：60 Quality %).

Manufacture embodiment 24：The system of modification 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 risen, 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, to amino Phenol：5.7g, propylene glycol monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtain To containing the solution (resin component with acidic substituent and the modification imide resin (k-3) of aromatic azo methine：60 Quality %).

Manufacture embodiment 25：The system of modification 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 risen, 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, to amino Phenol：5.7g, propylene glycol monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, obtain To containing the solution (resin component with acidic substituent and the modification imide resin (k-4) of aromatic azo methine：60 Quality %).

Manufacture embodiment 26：The system of modification 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 risen, the solution (tree containing the modified silicone com (iii-2) with aromatic azo methine is added Fat composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 62.6g, 2,2-：238.0g, to ammonia Base phenol：5.7g, propylene glycol monomethyl ether：443.7g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, Obtain containing the solution (resin component with acidic substituent and the modification imide resin (k-5) of aromatic azo methine： 60 mass %).

Manufacture embodiment 27：The system of modification 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 risen, the solution (tree containing the modified silicone com (iii-3) with aromatic azo methine is added Fat composition：90 mass %)：Double (4- (4- maleimidephenoxies) phenyl) propane of 61.8g, 2,2-：238.6g, to ammonia Base phenol：5.7g, propylene glycol monomethyl ether：443.8g, after 115 DEG C are reacted 4 hours, is warming up to 130 DEG C and carries out normal pressure concentration, Obtain containing the solution (resin component with acidic substituent and the modification imide resin (k-6) of aromatic azo methine： 60 mass %).

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 tool Obtained in the solution and manufacture embodiment 22~27 that have the modification imide resin (j-1~j-6) of aromatic azo methine Contain solution and aromatic amine as shown below with acidic substituent and the modification imide resin of aromatic azo methine Compound (A), aromatic aldehyde compound (B), silicone compounds (C), maleimide compound (D), with acidity substitution The amines (E) of base, thermoplastic elastomer (TPE) (F), thermosetting resin (G), inorganic filling material (H), curing accelerator (I), And as the MEK of retarder thinner, using the mixing ratio (mass parts) shown in 1~table of table 9 be obtained by mixing resin component as 65 mass % varnish.

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

In the template that the resin-oatmeal is put into Teflon (registration mark) sheet material, in the electrolytic copper foil of 12 μm of configuration up and down Glassy surface, is carried out after punching press in 60 minutes at pressure 2.0MPa, 240 DEG C of temperature, is removed electrolytic copper foil and is obtained resin plate.

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

The prepregs are laminated 4, in the electrolytic copper foil of 12 μm of configuration 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 System, trade name)

4,4'- diaminobenzene formailides (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 strains Formula commercial firm 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, commodity Name)

Epofriend CT-310：Epoxide modified styrene butadiene copolymers resin (Co., Ltd.'s Daicel systems, Trade name)

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.'s 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 even with aromatic series Modification imide resin (j-1)~(j-6) of n-formyl sarcolysine alkali solution and containing with acidic substituent and aromatic azo first The solid of resin component is shown in the use level (mass parts) of modification imide resin (k-1)~(k-6) of alkali solution The value of composition conversion.

[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, modulus of elasticity, 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, modulus of elasticity, dielectric property are compared with embodiment, and any one characteristic is all poor.

Industrial applicability

The compositions of thermosetting resin containing silicone compounds of the present invention is infiltrated to base material or obtained by being coated with it is pre- Impregnate 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, it includes aromatic azo methine, and with from the aromatic amine with primary amino radical The construction unit of compound (A), the construction unit from the aromatic aldehyde compound (B) with aldehyde radical, from molecule End has the construction unit of the silicone compounds (C) of amino,

The construction unit and the construction unit from aromatic aldehyde compound (B) from aromatic amines compound (A) In at least one include the structure shown in following formulas (1), and the construction unit from silicone compounds (C) Include the structure shown in 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 Acyl group, hydroxyl, sulfonic group, the alkoxy of 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；

2. silicone compounds according to claim 1, wherein the aromatic aldehyde compound (B) with aldehyde radical for pair Phthalaldehyde, m-terephthal aldehyde, OPA or 2,2 '-bipyridyl -4,4 '-dicarbaldehyde.

3. a kind of modification imide resin with aromatic azo methine, it has from the silicon described in claim 1 or 2 The construction unit of siloxane compound, the knot with deriving from the maleimide compound (D) with N- substituted maleimide amidos Structure unit.

4. the modification imide resin according to claim 3 with the even oxygen methine of aromatic series, it, which also has, derives from down State the acidic substituent of the amines (E) shown in formula (3)；

In formula, R₅The hydroxyl, carboxyl or 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 be 1~5 integer, y be 0~4 integer, and x and y's and For 5.

5. a kind of compositions of thermosetting resin, it contains the modification acyl with aromatic azo methine described in claim 3 or 4 Imide resin.

6. compositions of thermosetting resin according to claim 5, it also contains thermoplastic elastomer (TPE) (F).

7. the compositions of thermosetting resin according to claim 5 or 6, it, which also contains, is selected from epoxy resin and cyanate ester resin At least one of thermosetting resin (G).

8. the compositions of thermosetting resin according to claim 5 or 6, it also contains inorganic filling material (H).

9. the compositions of thermosetting resin according to claim 5 or 6, it also contains curing accelerator (I).

10. a kind of prepregs, it is to soak the compositions of thermosetting resin any one of claim 5~9 to base material Ooze and form.

11. a kind of film with resin, it is in branch by the compositions of thermosetting resin any one of claim 5~9 Forming layer on body is held to form.

12. a kind of plywood, it is obtains the prepregs described in claim 10 are cascading into shape.

13. a kind of plywood, it is obtains the film with resin described in claim 11 is cascading into shape.

14. a kind of multilayer printed-wiring board, its usage right requires the plywood described in 12 or 13 and manufactured.

15. a kind of semiconductor package part, it is the semiconductor element mounted thereon on the multilayer printed-wiring board described in claim 14 Form.