CN107663273A

CN107663273A - Organo-silicon compound and its manufacture method and solidification compound

Info

Publication number: CN107663273A
Application number: CN201710614721.5A
Authority: CN
Inventors: 山田哲郎; 广神宗直
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2016-07-27
Filing date: 2017-07-26
Publication date: 2018-02-06
Anticipated expiration: 2037-07-26
Also published as: KR102356533B1; JP6642325B2; TW201817769A; TWI660977B; CN107663273B; JP2018016709A; KR20180012701A

Abstract

The present invention relates to organo-silicon compound and its manufacture method and solidification compound, the i.e. effective organo-silicon compound such as the modifier of offer as high frequency substrate material and its manufacture method and the solidification compound comprising the organo-silicon compound.Organo-silicon compound, it is characterised in that represent that (in formula, X represents the organic group of the n valencys comprising polyphenyl ether structure, R by average formula (i)¹The alkyl of unsubstituted or substituted carbon number 1~10 or the aryl of unsubstituted or substituted carbon number 6~10, R are represented independently of each other²The alkyl of unsubstituted or substituted carbon number 1~10 or the aryl of unsubstituted or substituted carbon number 6~10, A are represented independently of each other¹Represent singly-bound or the linker containing heteroatomic divalence, A²The bivalent hydrocarbon radical without heteroatomic, unsubstituted or substituted carbon number 1~20 is represented, m is 1~3 number, and n is 1~10 number.)

Description

Organo-silicon compound and its manufacture method and solidification compound

Technical field

The present invention relates to organo-silicon compound and its manufacture method and solidification compound, in more detail, is related to There are the organo-silicon compound and its manufacture method of polyphenyl ether structure and hydrolization group and siliconated comprising this in molecule The solidification compound and its curing item of compound.

Background technology

Silane coupler is contained simultaneously with the reactive part for inorganic matter (with Si atom keys in 1 intramolecular The hydrolization group of conjunction) and be imbued with reactive, the deliquescent part of compound to(for) organic matter, as inorganic matter with it is organic The bonding additives at the interface of thing play a role, therefore are widely utilized as compound resin modifying agent.

Additionally, it is known that polyphenylene ether compound is dielectric as high-fire resistance and dielectric constant, dielectric loss angle tangent Excellent, particularly brought from MHz excellent to dielectric property, the i.e. high frequency characteristics in the high frequency band (high-frequency region) of GHz bands.

Therefore, the Application Example as polyphenylene ether compound, think that as high frequency be suitable with the utilization of moulding material in recent years Close.Specifically, as being formed in the printing distributing board having in the electronic equipment for the electric signal for utilizing high-frequency region One composition of the baseplate material of base material (copper-clad laminated board), it have studied and be used in combination with epoxy resin etc..

In such purposes, due to the electric signal with high-frequency region easily wiring circuit decay tendency, therefore Think that the good electronic circuit board of transmission characteristic is required.

In order to obtain the good electronic circuit board of transmission characteristic, using as polyphenylene ether compound, dielectric loss angle is being just While cutting small dielectric resin material, make the surface of conductor (metal wiring of copper foil etc.) it is smoothened, by low roughness, Low thickness is come to reduce epidermis resistance be effective.

But for conventional copper-clad laminated board, it is concavo-convex by being set in copper foil surface, show Anchoring Effect, The adaptation of resin material and copper foil is ensured that, therefore in order to which high frequency substrate material described above obtains transmission characteristic like that And make copper foil surface smoothened, then the problem of Anchoring Effect dies down, the adaptation of resin material and copper foil is deteriorated be present.

Therefore, in order to improve adaptation, also studied the use of in general silane coupler, but present situation be still can not be abundant Ground meets its adaptation.

In addition, Patent Document 1 discloses by entering 2 functionality phenylene ether resins and alkoxysilane moiety condensation product Silane-modified phenylene ether resins containing alkoxysilyl obtained from row dealcoholization condensation reaction.

But for the compound of patent document 1, in its preparation method, reactive highest, adaptation is contributed to improve Alkoxysilyl be consumed in dealcoholization condensation reaction, therefore the adaptation of resin material and copper foil and insufficient.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2005-330324 publications

The content of the invention

The invention problem to be solved

The present invention in view of above-mentioned actual conditions and complete the modifier, and it is an object of the present invention to provide as high frequency substrate material Solidification compound etc. effective organo-silicon compound and its manufacture method and comprising the organo-silicon compound.

Means for solving the problems

The present inventor has made intensive studies to solve above-mentioned problem, as a result finds there is polyphenylene oxide knot in the molecule The defined organo-silicon compound and its manufacture method of structure and hydrolization group, and find the combination for including the organo-silicon compound Thing gives the solidfied material that can play dielectric property as good copper foil adaptation and dielectric constant, dielectric loss angle tangent, Therefore it is suitable as being formed the solidification compound of high frequency substrate material, completes the present invention.

That is, the present invention provides：

1. organo-silicon compound, it is characterised in that represented by average formula (i)：

【Change 1】

(in formula, X represents the organic group of the n valencys comprising polyphenyl ether structure, R¹Represent independently of each other unsubstituted or substituted The alkyl of carbon number 1~10 or the aryl of unsubstituted or substituted carbon number 6~10, R²Represent independently of each other The alkyl of unsubstituted or substituted carbon number 1~10 or the aryl of unsubstituted or substituted carbon number 6~10, A¹Table Show singly-bound or the linker containing heteroatomic divalence, A²Expression is free of heteroatomic, unsubstituted or substituted carbon number 1~20 bivalent hydrocarbon radical, m are 1~3 number, and n is 1~10 number.)

2.1 organo-silicon compound, it is represented by average formula (1) or (2)：

【Change 2】

In formula, R¹、R²、A¹、A²Implication same as described above, R are represented with m³Halogen atom is represented independently of each other, is not taken The alkoxy, unsubstituted or take of the alkyl of carbon number 1~12 of generation or substitution, unsubstituted or substituted carbon number 1~12 The alkylthio group of the carbon number 1~12 in generation or the halogenated alkoxy of unsubstituted or substituted carbon number 1~12, R⁴Mutually Independently represent hydrogen atom, halogen atom, the alkyl of unsubstituted or substituted carbon number 1~12, unsubstituted or substituted carbon The alkoxy of atomicity 1~12, the alkylthio group of unsubstituted or substituted carbon number 1~12 or unsubstituted or substituted carbon The halogenated alkoxy of atomicity 1~12, a and b are independently of one another 1~100 number, and c is more than 0 and the number less than 2, and Z is represented The linker represented by following formula (3).

【Change 3】

[(in formula, R⁴Implication same as described above is represented, L represents the linker being selected from following formula (4)~(11).)

【Change 4】

(in formula, R⁵The alkyl of hydrogen atom or carbon number 1~12, R are represented independently of each other⁶Represent that carbon is former independently of each other The alkyl of subnumber 1~12, k represent 1~12 integer, and j represents 1~1,000 number.)]}

3.1 or 2 organo-silicon compound, wherein, above-mentioned A¹-A²Represented by formula (12) or formula (13)：

【Change 5】

The manufacture method of the organo-silicon compound of 4.1~3 any one, it is characterised in that make by average formula (14) Or (15)

【Change 6】

(in formula, R³、R⁴, a, b and Z represent implication same as described above.)

Represent, have hydroxyl polyphenylene ether compound with by formula (16)

【Change 7】

(in formula, R¹、R²、A²Implication same as described above is represented with m.)

Compound reaction represent, with NCO and alkoxysilyl,

The manufacture method of the organo-silicon compound of 5.1~3 any one, it is characterised in that make by average formula (14) Or formula (15)

【Change 8】

Represent, polyphenylene ether compound with hydroxyl and with can be with the functional group of above-mentioned hydroxyl reaction and the change of alkenyl Compound react, after having obtained alkenyl compound, make in the presence of the catalyst containing platinum compounds the alkenyl compound with by Formula (17)

【Change 9】

(in formula, R¹、R²Implication same as described above is represented with m.)

The silane compound of expression carries out hydrosilylation reactions,

6. solidification compound, it contains the organo-silicon compound of 1~3 any one,

The curing item that 7.6 solidification compound solidification forms.

The effect of invention

The organo-silicon compound of the present invention have the hydrolization group of polyphenyl ether structure and high response in the molecule, with Past silane coupler is compared, and has dielectric property as copper foil adaptation and dielectric constant, dielectric loss angle tangent excellent Characteristic.

Composition comprising the organo-silicon compound of the invention having characteristics that can be suitable as curability group Compound, particularly form the solidification compound of high frequency substrate material.

Embodiment

The present invention is specifically described below.

Organo-silicon compound of the present invention are represented by average formula (i).

【Change 10】

Wherein, X represents the organic group of the n valencys comprising polyphenyl ether structure, R¹Represent independently of each other unsubstituted or substituted The alkyl of carbon number 1~10 or the aryl of unsubstituted or substituted carbon number 6~10, R²Represent independently of each other The alkyl of unsubstituted or substituted carbon number 1~10 or the aryl of unsubstituted or substituted carbon number 6~10, A¹Table Show singly-bound or the linker containing heteroatomic divalence, A²Expression is free of heteroatomic, unsubstituted or substituted carbon number 1~20 bivalent hydrocarbon radical, m are 1~3 number, and n is 1~10 number.

As R¹And R²Carbon number 1~10 alkyl, straight-chain, ring-type, the alkyl of branch-like, as its tool Style, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, positive heptan can be included The straight chains such as base, n-octyl, n-nonyl, positive decyl or branch-like alkyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, The cycloalkyl such as cyclooctyl.

As R¹And R²Carbon number 6~10 aryl concrete example, phenyl, Alpha-Naphthyl, betanaphthyl etc. can be included.

In addition, part or all of the hydrogen atom of these each groups can by the alkyl of carbon number 1~10, F, Cl, The halogen atoms such as Br, cyano group etc. substitute, and as the concrete example of such group, can illustrate 3- chloropropyls, 3,3,3- trifluoropropyls Base, 2- cyano ethyls, tolyl, xylyl etc..

In these, as R¹, from the viewpoint of water-disintegrable, the preferred alkyl of the straight chain of carbon number 1~5, more preferably Methyl, ethyl, further preferred methyl.

On the other hand, as R², the preferably alkyl of straight chain, more preferably methyl, ethyl, further preferred methyl.

In addition, m is 1~3 integer, and from the viewpoint of reactivity, preferably 2~3, more preferably 3.

As above-mentioned A¹The linker containing heteroatomic divalence concrete example, ehter bond (- O-), thioether bond can be included (- S-), amino linkage (- NH-), sulfonyl key (- S (=O)₂-), phosphinyl key (- P (=O) OH-), oxo key (- C (=O) -), It is thio key (- C (=S) -), ester bond (- C (=O) O-), thioester bond (- C (=O) S-), thion ester bond (- C (=S) O-), two thio Ester bond (- C (=S) S-), carbonic acid ester bond (- OC (=O) O-), thiocarbonic acid ester bond (- OC (=S) O-), amido link (- C (=O) NH-), thioamides key (- C (=S) NH-), urethane bond (- OC (=O) NH-), S-ethyl thiocarbamate key (- SC (=O) NH-), thion urine Alkane key (- OC (=S) NH-), two thiourethane keys (- SC (=S) NH-), urea bond (- NHC (=O) NH-), thiocarbamide key (- NHC (= S) NH-) etc..

In these, as A¹, preferably ehter bond (- O-) or urethane bond (- OC (=O) NH-).

On the other hand, as A²Bivalent hydrocarbon radical without heteroatomic, unsubstituted or substituted carbon number 1~20 Concrete example, methylene, ethylidene, trimethylene, propylidene, isopropylidene, tetramethylene, isobutylidene, five Asias can be included Methyl, hexa-methylene, heptamethylene, eight methylene, nine methylene, decamethylene, 11 methylene, ten dimethylenes, 13 Methylene, ten tetramethylenes, ten pentamethylenes, ten hexa-methylenes, ten heptamethylenes, 18 methylene, 19 methylene, Asia two The alkylidenes such as ten alkyl；The cycloalkylidenes such as cyclopentylene, cyclohexylidene；Phenylene, α-, arlydene such as β-naphthylene etc..

In these, preferably trimethylene, more preferably eight methylene, trimethylene.

X in formula (i) represents the linker of the n valencys comprising polyphenyl ether structure, wherein can have straight chain structure, branch-like Structure or cross-linked structure.

The n of each molecule average out to 1~10, preferably 1~5, more preferably 1~2.If n is less than 1, due to water-disintegrable base Group's deficiency, therefore reactivity is poor.On the other hand, if n is more than 10, reflecting point excessively increases, therefore the guarantor of compound sometimes Deposit bad stability or easily cracked in solidfied material.

As above-mentioned X, as long as the linker of the n valencys comprising polyphenyl ether structure, then be not particularly limited, if it is considered that carrying High copper foil adaptation and dielectric property, then in the present invention, particularly preferably by the group of following formula expression.

【Change 11】

Therefore, the organo-silicon compound as the present invention, preferably average formula represent organic by formula (1) or formula (2) Silicon compound, by using these compounds, play more good copper foil adaptation and dielectric property.

【Change 12】

During these are various, R¹、R²、A¹、A²Implication same as described above, R are represented with m³Independently of each other represent halogen atom, It is the alkyl of unsubstituted or substituted carbon number 1~12, the alkoxy of unsubstituted or substituted carbon number 1~12, unsubstituted Or the alkylthio group of carbon number 1~12 or the halogenated alkoxy of unsubstituted or substituted carbon number 1~12 of substitution, R⁴ The alkyl, unsubstituted or substituted of hydrogen atom, halogen atom, unsubstituted or substituted carbon number 1~12 is represented independently of each other The alkoxy of carbon number 1~12, the alkylthio group of unsubstituted or substituted carbon number 1~12 or unsubstituted or substituted Carbon number 1~12 halogenated alkoxy, a and b be independently of one another 1~100 number, and c is more than 0 and the number less than 2, Z Represent the linker represented by following formula (3).

【Change 13】

Above-mentioned R⁴Implication same as described above is represented, L represents the linker being selected from following formula (4)~(11).

【Change 14】

Above-mentioned R⁵The alkyl of hydrogen atom or carbon number 1~12, R are represented independently of each other⁶Carbon atom is represented independently of each other The alkyl of number 1~12, k represent 1~12 integer, and j represents 1~1,000 number.

As R³And R⁴Carbon number 1~12 alkyl, straight-chain, ring-type, the alkyl of branch-like, as its tool Style, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, positive heptan can be included The straight chains such as base, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl or branch-like alkyl, cyclopropyl, ring fourth The cycloalkyl such as base, cyclopenta, cyclohexyl, suberyl, cyclooctyl.

As R³And R⁴Carbon number 1~12 alkoxy, straight-chain, ring-type, the alkoxy of branch-like, as Its concrete example, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, just can be included Amoxy, positive hexyloxy, positive epoxide in heptan, n-octyloxy, positive nonyl epoxide, n-decyloxy, n-undecane epoxide, n-dodecane epoxide Deng the cycloalkyloxy such as straight chain or branch-like alkoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyl epoxide, ring octyloxy.

In addition, the one or all of the hydrogen atom of these each groups can be by the halogen atoms such as F, Cl, Br, sulfydryl, cyano group Deng substitution, as the concrete example of such group, 3- chloropropyls, 3 can be illustrated, 3,3- trifluoro propyls, 3- mercaptopropyis, 2- cyanogen Base ethyl etc..

As R³And R⁴Halogen atom, F, Cl, Br etc. can be included.

In these, as R³, from the viewpoint of the easiness of manufacture, preferably methyl, methoxyl group, more preferably methyl.

On the other hand, as R⁴, preferably hydrogen atom, methyl, methoxyl group, more preferably hydrogen atom.

In addition, a and b are independently of one another 1~100 number, but it is special from the copper foil adaptation and dielectric of organo-silicon compound From the viewpoint of property, preferably 3~50, more preferably 5~20.In the case that a and b ratios 1 are small, it is possible to good copper foil can not be obtained Adaptation and dielectric property, in the case that a and b ratios 100 are big, compatibility of the organo-silicon compound in organic resin becomes sometimes Difference.

And then in the present invention, it is used as-A¹-A²- base, preferably there is urethane bond (- OC (=O) by what formula (12) represented NH- trimethylene), the trimethylene with ehter bond (- O-) by formula (13) expression.

【Change 15】

The weight average molecular weight of the organo-silicon compound of the present invention is not particularly limited, if it is considered that making to include the compound The viscosity of solidification compound etc. turn into appropriate scope and improve workability, and the solidfied material to obtaining assigns sufficient copper Paper tinsel adaptation and dielectric property, then preferable weight-average molecular weight 500~50,000, more preferably 1,000~20,000, further preferred 4,000 ~1 ten thousand.It should illustrate, the weight average molecular weight in the present invention is that the polystyrene obtained using gel permeation chromatography (GPC) is converted Value.

Further, the organo-silicon compound of the present invention can use in the state of containing solvent.

As solvent, as long as there is the solvability of the organo-silicon compound represented by formula (i), then it is not particularly limited, From the viewpoint of dissolubility and volatility etc., the preferred fragrant family solvent such as toluene, dimethylbenzene；MEK, methyl-isobutyl The ketone series solvents such as ketone；The ether series solvents such as tetrahydrofuran, wherein more preferably toluene, dimethylbenzene.

Relative to the mass parts of organo-silicon compound 100 represented by formula (i), the addition preferably 100~20,000 of solvent Mass parts, more preferably 200~10,000 mass parts.

A in the organo-silicon compound represented by above-mentioned formula (i)¹Can be by making average formula for the compound of urethane bond There is the compound of the group comprising polyphenyl ether structure and hydroxyl in 1 molecule and by formula by what formula (14) or formula (15) represented (16) what is represented has the reaction of the compound (hereinafter referred to as isocyanato silanes) of NCO and alkoxysilyl And obtain.

More specifically, carry out in the hydroxyl and NCO silicon by average formula (14) or the compound of (15) expression The reaction of urethane bond is formed between the NCO of alkane.

【Change 16】

(in formula, R³、R⁴, a, b and Z it is same as described above.)

【Change 17】

(in formula, R¹、R²、A²It is same as described above with m.)

As the compound by formula (14) and formula (15) expression, commercially available product can be used as to obtain, as such commercially available product, example (strain) SABIC Innovative Plastics PPO (trade mark) SA120-100, PPO (trade mark) SA90-100 can such as be included Deng.

On the other hand, the concrete example as the isocyanato silanes represented by formula (16), can include 3- isocyanates Base propyl trimethoxy silicane, 3- NCO hydroxypropyl methyls dimethoxysilane, 3- NCO propyl-dimethyl first TMOS, 3- NCOs propyl-triethoxysilicane, 3- NCO hydroxypropyl methyls diethoxy silane, 3- isocyanides Perester radical propyl-dimethyl Ethoxysilane etc..

In these, from the viewpoint of water-disintegrable, preferably 3- NCOs propyl-triethoxysilicane, 3- isocyanates Base propyl trimethoxy silicane, more preferably 3- NCOs propyl trimethoxy silicane.

The compound in 1 molecule with the group containing polyphenyl ether structure and hydroxyl represented by formula (14) or formula (15) With the reaction ratio of the isocyanato silanes represented by formula (16), if it is considered that suppress urine alkylation reaction when accessory substance, and Storage stability, the characteristic of obtained organo-silicon compound are improved, then relative to the compound by formula (14) or formula (15) expression In hydroxyl 1mol, preferably by formula (16) represent isocyanato silanes NCO turn into 0.01~1.2mol ratio Example, the more preferably ratio as 0.1~1.1mol, the further preferably ratio as 0.4~1mol.

In addition, the catalyst for improving reaction speed can be used in above-mentioned urine alkylation reaction.

, can be specific as its from typically being properly selected in the catalyst used in urinating alkylation reaction as catalyst Example, can include Dibutyltin oxide, dioctyl tin oxide, double (2 ethyl hexanoic acid) tin (II), dibutyl tin laurate, two Dioctyltin laurate etc..

The usage amount of catalyst is catalytic amount, generally, relative to by formula (14) or formula (15) expression compound and Adding up to for the isocyanato silanes represented by formula (16), is 0.001~1 mass %.

And then in above-mentioned urine alkylation reaction, the nonreactive solvent of raw material with using can be used.

As its concrete example, the hydrocarbon system solvents such as pentane, hexane, heptane, octane, decane, hexamethylene can be included；Benzene, first The fragrant family solvent such as benzene, dimethylbenzene；The ketone series solvents such as acetone, MEK, methyl iso-butyl ketone (MIBK)；Formamide, N, N- dimethyl The acid amides series solvents such as formamide, pyrrolidones, 1-METHYLPYRROLIDONE, ethyl acetate, butyl acetate, gamma-butyrolacton, the third two The ester series solvents such as alcohol -1- monomethyl ether -2- acetic acid esters；Diethyl ether, butyl oxide, cyclopentyl-methyl ether, tetrahydrofuran, 1,4- bis- Evil Ether series solvents such as alkane etc., these can be used alone, and also two or more can be applied in combination.

Reaction temperature during to urine alkylation reaction is not particularly limited, if it is considered that making reaction speed appropriate, is suppressed simultaneously The side reactions such as allophanatization, then preferably 25~90 DEG C, more preferably 40~80 DEG C.

To the reaction time, there is no particular restriction, usually 10 minutes~24 hours.

In addition, by A in the organo-silicon compound of formula (i) expression¹It can be made for the compound of ehter bond by being used as the 1st stage Average formula has the group containing polyphenyl ether structure and hydroxyl by what above-mentioned formula (14) or formula (15) represented in 1 molecule Compound with can be with the reaction of the compound of the functional group of the hydroxyl reaction and alkenyl and after alkenyl compound be made, the 2nd The alkenyl compound for making to obtain in the 1st stage in stage reacts and obtained with the silane compound represented by formula (17).

More specifically, in the 1st stage, make can be with hydroxyl reaction functional group and hydroxyl reaction, will averagely be tied with ehter bond Structure formula is coupled by the compound that formula (14) or formula (15) represent and the compound with alkenyl, in the 2nd stage, is containing platinum The alkenyl compound for making to obtain in the 1st stage in the presence of the catalyst of compound is carried out with the silane compound represented by formula (17) Hydrosilylation, make hydrogen silicyl and alkenyl addition and form carbon-silicon key.

【Change 18】

(in formula, R¹、R²It is same as described above with m.)

As used in the 1st stage have can with the functional group of hydroxyl reaction and the compound of alkenyl possessed by it is above-mentioned Functional group, as long as the functional group selectively reacted with hydroxyl, then be not particularly limited, halogen atom, methanesulfonic acid can be included Ester group, trifluoromethanesulfonic acid ester group, p- tosylate group etc., preferably halogen atom, more preferably chlorine atom, bromine atoms, iodine are former Son.

As the concrete example of the compound (hereinafter referred to as alkenyl halide compound) with halogen atom and alkenyl, can include Allyl chloride, methallyl chloride, butenyl chloride, pentenyl chlorine, hexenyl chlorine, heptenyl chlorine, octenyl chlorine, nonenyl chlorine etc. Alkenyl chlorine compound；Allyl bromide, bromoallylene, methallyl bromide, butylene bromide, amylene bromide, hexene bromide, heptene bromide, octenyl The alkenyl bromine compounds such as bromine, nonene bromide；Allyl iodide, methacrylic iodine, butenyl iodide, pentenyl iodine, hexenyl iodine, heptan Alkenyl iodine compounds such as alkenyl iodine, octenyl iodine, nonenyl iodine etc..

In these, from reactivity and from the viewpoint of obtaining easiness, preferably allyl chloride, hexenyl chlorine, octenyl chlorine, Allyl bromide, bromoallylene, allyl iodide, more preferably allyl chloride, octenyl chlorine, allyl bromide, bromoallylene, further preferred allyl bromide, bromoallylene.

The reaction in the 1st stage can use known in general method to carry out, such as can use in alkaline chemical combination Synthetic method (Williamson's conjunction of the asymmetric ether of the nucleophilic substitution of hydroxyl and alkenyl halide compound etc. is utilized in the presence of thing Into the synthesis of, Williamson's ether) etc..

In this case, the reaction ratio as compound and alkenyl halide compound by formula (14) or formula (15) expression, It is not particularly limited, if it is considered that further reducing unreacted raw material, improves the obtained preservation stabilization of organo-silicon compound Property, each characteristic, then relative to by formula (14) or formula (15) expression compound hydroxyl 1mol, preferably alkenyl halide compound halogen Plain atom turns into 0.1~10mol ratio, the more preferably ratio as 0.2~5mol, further preferably as 0.4~ 1.2mol ratio.

In addition, as above-mentioned alkali compounds, the various alkalescence used in Williamson's synthetic method usually can be used Compound, as long as with by not reacted beyond the hydroxyl of formula (14) or the compound of formula (15) expression, then can be used.

Specifically, the alkali metal such as metallic sodium, lithium metal can be included；The alkaline-earth metal such as calcium metal；Sodium hydride, lithium hydride, The alkali metal hydrides such as hydrofining, cesium hydride；The alkaline earth metal hydrides such as calcium hydride；Lithium hydroxide, sodium hydroxide, hydroxide The alkaline earth metal hydroxide such as the alkali metal hydroxides such as potassium, cesium hydroxide and its aqueous solution, barium hydroxide, calcium hydroxide and its The aqueous solution；The alkali metal such as potassium tert-butoxide, sodium tert-butoxide and alkali earths alkoxide；The alkali metal such as potassium carbonate, sodium carbonate, calcium carbonate and alkali Earth metal carbonate；The alkali metal such as sodium acid carbonate, saleratus and alkali earths bicarbonate；Triethylamine, tri-n-butylamine, N, N- bis- are different Tertiary amine such as propylethylamine, tetramethylethylenediamine, pyridine, N, N- dimethyl -4-aminopyridine etc..

In these, from the viewpoint of reaction efficiency, preferably lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, The hydroxide of the alkali and alkaline earth metal ions such as barium hydroxide, calcium hydroxide or their aqueous solution, more preferably sodium hydroxide The aqueous solution.

The usage amount of alkali compounds is not particularly limited, if it is considered that being sufficiently carried out etherification reaction, prevents original The remaining of material, and prevent the excessive remaining of alkali compounds, the storage stability for the organo-silicon compound for improving to obtain, each spy Property, it is more excellent relative to hydroxyl 1mol, the alkali compounds preferably 0.5~20mol by formula (14) or the compound of formula (15) expression Select 1~10mol, further preferred 2~8mol.

In above-mentioned etherification reaction, the solvent not reacted with the raw material used can be used.

As its concrete example, water outlet can be enumerated；The hydrocarbon system solvents such as pentane, hexane, heptane, octane, decane, hexamethylene；Benzene, The fragrant family solvent such as toluene, dimethylbenzene；The acyls such as formamide, N,N-dimethylformamide, pyrrolidones, 1-METHYLPYRROLIDONE Amine series solvent；The ether series solvents such as diethyl ether, butyl oxide, cyclopentyl-methyl ether, tetrahydrofuran, 1,4- dioxanes；The nitrile such as acetonitrile system Solvent etc., these can be used alone, and also two or more can be applied in combination.

In these, from the viewpoint of reaction efficiency, preferably water, toluene, dimethylbenzene, dimethylformamide, cyclopenta first The mixed solvent of the mixed solvent of base ether, tetrahydrofuran, more preferably water and toluene, water and dimethylbenzene.

Reaction temperature during to etherification reaction is not particularly limited, if it is considered that making reaction speed appropriate while suppressing alkene The volatilization of base halogen compound, preferably 25~90 DEG C, more preferably 40~80 DEG C, further preferred 50~70 DEG C.

In addition, etherification reaction is generally carried out under atmospheric pressure, in order to suppress the volatilization of above-mentioned alkenyl halide compound, improve instead Speed etc. is answered, can be carried out under elevated pressure.

Further, in above-mentioned etherification reaction, in order to improve reaction speed, catalyst can be used.

As catalyst, can be properly selected from the catalyst for typically having been used for Williamson's synthetic method and by formula (14) Or nonreactive catalyst beyond the hydroxyl of the compound of formula (15) expression.

As its concrete example, the crown ethers such as 12-crown-4,15- crown-s 5,18- crown-s 6, dibenzo-18 crown-6 can be included；Four The quaternary ammonium salts such as butyl ammonium chloride, TBAB, tetrabutylammonium iodide, tetrabutylammonium disulfate；KI, sodium iodide etc. Alkali halide etc., these can be used alone, and also two or more can be applied in combination.

In these, from reactivity and from the viewpoint of obtaining easiness, preferably 18- crown-s 6, TBAB, the tetrabutyl Ammonium iodide, tetrabutylammonium disulfate, KI, more preferably tetrabutylammonium iodide, tetrabutylammonium disulfate, KI, enter The preferred tetrabutylammonium disulfate of one step.

Above-mentioned catalyst can be played a role as phase transfer catalyst, or alkenyl halide compound is activated, and make reaction Speed improves.

As long as the usage amount of above-mentioned catalyst is catalytic amount, relative to the compound by formula (14) or formula (15) expression With total, preferably 0.001~10 mass %, more preferably 0.01~1 mass % of alkenyl halide compound.

In 2nd stage, represented as being used in the reaction of the alkenyl compound with being obtained in the 1st stage by formula (17) Silane compound concrete example, can include trimethoxy silane, methyl dimethoxysilane, dimethyl methoxy silane, Triethoxysilane, methyldiethoxysilane, dimethylethoxysilane etc., from the viewpoint of water-disintegrable, preferred front three TMOS, triethoxysilane, more preferably trimethoxy silane.

The catalyst containing platinum compounds used in hydrosilylation to the 2nd stage is not particularly limited, and is used as it Concrete example, chloroplatinic acid, the alcoholic solution of chloroplatinic acid, platinum -1,3- divinyl -1,1,3,3- tetramethyl disiloxane networks can be included The toluene or xylene solution of compound, four (triphenylphosphine) platinum, double (triphenylphosphine) platinum of dichloro, the double acetonitrile platinum of dichloro, dichloro are double Benzonitrile platinum, dichloro cyclooctadiene platinum, platinum-carbon, platinum-aluminum oxide, platinum-silica even load catalyst etc..

In these, from the platinum complex of the aspect, preferably 0 valency of selectivity, more preferably platinum -1,3- divinyl -1, The toluene or xylene solution of 1,3,3- tetramethyl disiloxane complex compounds.

The usage amount of catalyst containing platinum compounds is not particularly limited, from reactivity, productivity ratio aspect, Relative to the silane compound 1mol represented by formula (17), preferably contained pt atom turns into 1 × 10^-7~1 × 10^-2Mol's Amount, more preferably as 1 × 10^-7~1 × 10^-3Mol amount.

In addition, in order to improve the reactivity of hydrosilylation, co-catalyst can be used.As the co-catalyst, can make With the co-catalyst typically used in hydrosilylation, in the present invention, preferably the ammonium salt of inorganic acid, sour amide compound, Carboxylic acid.

As the concrete example of the ammonium salt of inorganic acid, ammonium chloride, ammonium sulfate, Amcide Ammate, ammonium nitrate, phosphoric acid can be included The ammonium of dihydro one, diammonium hydrogen phosphate, triammonium phosphate, diphosphorous acid ammonium, ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfide, ammonium borate, boron fluorination Ammonium etc., wherein, preferably pKa is the ammonium salt of more than 2 inorganic acid, more preferably ammonium carbonate, ammonium hydrogen carbonate.

As the concrete example of sour amide compound, formamide, acetamide, N- methylacetamides, N, N- diformazans can be included Yl acetamide, propionamide, acrylamide, malonamide, succinamide, maleic amide, fumaramide, benzamide, adjacent benzene two Formamide, palmitamide, stearmide etc..

As the concrete example of carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, Methoxy acetic acid, valeric acid, caproic acid, heptan can be included Acid, octanoic acid, lactic acid, glycolic etc., in these, preferably formic acid, acetic acid, lactic acid, more preferably acetic acid.

The usage amount of co-catalyst is not particularly limited, from the viewpoint of reactivity, selectivity, cost etc., relatively In the silane compound 1mol represented by formula (17), preferably 1 × 10^-5~1 × 10^-1Mol, more preferably 1 × 10^-4~5 × 10^- ¹mol。

Further, above-mentioned hydrosilylation reactions are also carried out under solvent-free, but it can also use solvent.

As the concrete example of workable solvent, pentane, hexane, hexamethylene, heptane, isooctane, benzene, first can be included The hydrocarbon system solvents such as benzene, dimethylbenzene；The ether series solvents such as diethyl ether, tetrahydrofuran, dioxanes；The ester such as ethyl acetate, butyl acetate system Solvent；The aprotic polar solvents such as N,N-dimethylformamide；Chloro hydrocarbon system solvent such as dichloromethane, chloroform etc., these are molten Agent can be used alone a kind, can also be used in mixed way two or more.

Reaction temperature in above-mentioned hydrosilylation reactions is not particularly limited, can be entered under heating since 0 DEG C OK, but preferably 0~200 DEG C.

In order to obtain appropriate reaction speed, preferably make its reaction, from such a viewpoint, reaction temperature under heating More preferably 40~110 DEG C, further preferred 40~90 DEG C.

In addition, the reaction time is also not particularly limited, usually 1~60 hour or so, preferably 1~30 hour, more preferably 1 ~20 hours.

The solidification compound of the present invention includes the organo-silicon compound represented by formula (i).

Structure of the organo-silicon compound from the organo-silicon compound represented by formula (i) of the present invention, has with conventional Organic silicon compound is compared, and is carried using the copper foil adaptation and dielectric property of the solidfied material obtained containing its solidification compound It is high.

In the solidification compound of the present invention, the content of organo-silicon compound is not particularly limited, combined in curability In thing, preferably 0.1~10 mass % or so, more preferably 0.5~5 mass %.It should illustrate, organo-silicon compound bag is solvent-laden In the case of, above-mentioned content means the nonvolatile component for not including solvent.

In addition, the solidification compound of the present invention preferably comprises organic resin.

As organic resin, it is not particularly limited, can be according to purposes etc. from epoxy resin, phenolic aldehyde tree as its concrete example Fat, polycarbonate-based and polycarbonate Alloys, acrylic resin, polyester resin, polyamide, polyimide resin, Acrylonitritrile-styrene resin, ABS, Corvic, polystyrene resin, polyphenyl Properly selected in ether resin, the blend of polystyrene and polyphenylene oxide, cellulose acetate-butyrate, polyvinyl resin etc., if It is considered as the baseplate material of printing distributing board having in the electronic equipment using the electric signal of high-frequency region, preferably epoxy Resin, polyphenylene oxide resin or their blend.

In this case, appropriate curing agent, such as the feelings using epoxy resin can be coordinated according to the organic resin used Under condition, the curing agent such as imidazolium compounds can be coordinated.

In addition, as crosslinking component, can mate properly into such as cyanate esters, and then, can according to application target Add the various additions such as cementability modifier, ultra-violet absorber, storage stability modifier, plasticizer, filler, pigment Agent.

Embodiment

It is exemplified below embodiment and comparative example further illustrates to the present invention, but the present invention is not limited to these implementations Example.

It should illustrate, Xia Shuzhong, viscosity is using the measured value at 25 DEG C of Type B rotation viscometer, and molecular weight is to pass through The weight average molecular weight for the polystyrene conversion that GPC (gel permeation chromatography) measure is obtained, nonvolatile component are using on aluminum dish The measured value that heating residual method of the heat drying after 3 hours obtains at 105 DEG C.

[1] synthesis of organo-silicon compound

[embodiment 1-1]The synthesis of organo-silicon compound 1

Load PPO (business in the removable flasks of 200mL for possessing agitator, reflux condenser, dropping funel and thermometer Mark) SA120-100 ((strain) SABIC Innovative Plastics manufactures) 40g, toluene 110g and tin dilaurate dioctyl tin 0.05g, it is heated to 80 DEG C.Input 3- NCO propyl trimethoxy silicane 7.6g are added dropwise thereto, are heated at 80 DEG C Stir 2 hours.Determined by IR and confirm that the absworption peak from NCO of raw material is wholly absent, replaced and generate Absworption peak from urethane bond, it is believed that reaction terminates.

Obtained reaction product is brown transparency liquid, weight average molecular weight 6,700, viscosity 23mm²/ s, it is non-volatile Composition is 34 mass %.

[embodiment 1-2]The synthesis of organo-silicon compound 2

In addition to the quantitative change more 9.2g by 3- NCO propyl-triethoxysilicanes, according to embodiment 1-1 Same step synthesis.

Obtained reaction product is brown transparency liquid, weight average molecular weight 6,800, viscosity 30mm²/ s, it is non-volatile Composition is 30 mass %.

[embodiment 1-3]The synthesis of organo-silicon compound 3

Except by the quantitative change of toluene more 120g, by the quantitative change of 3- NCO propyl trimethoxy silicanes more Beyond 11.1g, synthesized according to the step same with embodiment 1-1.

Obtained reaction product is brown transparency liquid, weight average molecular weight 5,300, viscosity 21mm²/ s, it is non-volatile Composition is 29 mass %.

[embodiment 1-4]The synthesis of organo-silicon compound 4

In addition to the quantitative change more 5.6g by 3- NCO propyl trimethoxy silicanes, according to embodiment 1-1 Same step synthesis.

Obtained reaction product is brown transparency liquid, weight average molecular weight 4,200, viscosity 12mm²/ s, it is non-volatile Composition is 30 mass %.

[embodiment 1-5]The synthesis of organo-silicon compound 5

Load PPO (business in the removable flasks of 200mL for possessing agitator, reflux condenser, dropping funel and thermometer Mark) toner ((strain) SABIC Innovative Plastics manufactures) 40g, toluene 110g and tin dilaurate dioctyl tin 0.05g, it is heated to 80 DEG C.Input 3- NCO propyl trimethoxy silicane 0.5g are added dropwise thereto, are heated at 80 DEG C Stir 2 hours.Then, determined by IR and confirm that the absworption peak from NCO of raw material fully disappears, taken and generation Generate the absworption peak from urethane bond, it is believed that reaction terminate.

Obtained reaction product is brown transparency liquid, weight average molecular weight 102,000, viscosity 1,200mm²/ s, Nonvolatile component is 28 mass %.

[embodiment 1-6]The synthesis of organo-silicon compound 6

Method described in embodiment " PPE-3 " based on Japanese Unexamined Patent Publication 2015-086329 publications, passes through Noryl640-111 ((strain) SABIC Innovative Plastics manufactures) distribution rearranges, and has obtained distribution and has rearranged Polyphenylene oxide.

Load above-mentioned obtain in the removable flasks of 200mL for possessing agitator, reflux condenser, dropping funel and thermometer Polyphenylene oxide 40g, the toluene 110g and tin dilaurate dioctyl tin 0.05g that the distribution arrived rearranges, are heated to 80 DEG C.Drip thereto Add input 3- NCO propyl trimethoxy silicane 27.8g, the heating stirring 2 hours at 80 DEG C.Then, surveyed by IR Surely confirm that the absworption peak from NCO of raw material fully disappears, and replaces and generates the absorption from urethane bond Peak, it is believed that reaction terminates.

Obtained reaction product is brown transparency liquid, weight average molecular weight 6,200, viscosity 49mm²/ s, it is non-volatile Composition is 30 mass %.

[embodiment 1-7]The synthesis of organo-silicon compound 7

Load embodiment in the removable flasks of 200mL for possessing agitator, reflux condenser, dropping funel and thermometer Polyphenylene oxide 40g, the toluene 110g and tin dilaurate dioctyl tin 0.05g of rearrangement are distributed in 1-6, is heated to 80 DEG C.Thereto Input 3- NCO propyl trimethoxy silicane 13.9g are added dropwise, the heating stirring 2 hours at 80 DEG C.Then, IR is passed through Measure confirms that the absworption peak from NCO of raw material fully disappears, and replaces and generates the absorption from urethane bond Peak, it is believed that reaction terminates.

Obtained reaction product is brown transparency liquid, weight average molecular weight 5,000, viscosity 35mm²/ s, it is non-volatile Composition is 30 mass %.

[embodiment 1-8]The synthesis of organo-silicon compound 8

[the 1st stage]

Load PPO (business in the removable flasks of 300mL for possessing agitator, reflux condenser, dropping funel and thermometer Mark) SA120-100 ((strain) SABIC Innovative Plastics manufactures) 50g, toluene 120g, tetrabutylammonium disulfate 0.56g and 30% sodium hydrate aqueous solution 37.6g, is heated to 60 DEG C.Input allyl bromide, bromoallylene 5.7g is added dropwise thereto, at 60 DEG C Heating stirring 6 hours.Then, stand, liquid separation is carried out to the water layer of two layers of separation, in organic layer wash until turning into Property, and then, be concentrated under reduced pressure (80 DEG C, 5mmHg) to organic layer, and volatile ingredient is removed, so as to be obtained as brown solid Corresponding alkenyl compound.

[the 2nd stage]

Load above-mentioned in the removable flasks of 200mL for possessing agitator, reflux condenser, dropping funel and thermometer Alkenyl compound 30g, toluene 70g, the platinum -1,3- divinyl -1,1,3,3- tetramethyl disiloxanes obtained in 1 stage is complexed The toluene solution 0.08g of thing (is 5.0 × 10 in terms of pt atom relative to trimethoxy silane 1mol^-5Mol), inside temperature 75~ After trimethoxy silane 3.5g has been put at 85 DEG C, stirred at 80 DEG C 1 hour.

Obtained reaction product is brown transparency liquid, weight average molecular weight 6,000, viscosity 15mm²/ s, it is non-volatile Composition is 31 mass %.

[embodiment 1-9]The synthesis of organo-silicon compound 9

[the 1st stage]

Load PPO (business in the removable flasks of 300mL for possessing agitator, reflux condenser, dropping funel and thermometer Mark) SA120-100 ((strain) SABIC Innovative Plastics manufactures) 50g, toluene 120g, tetrabutylammonium iodide 0.56g With 30% sodium hydrate aqueous solution 37.6g, 60 DEG C are heated to.Input octenyl chlorine 6.9g is added dropwise thereto, is heated at 60 DEG C Stir 6 hours.Then, standing, liquid separations are carried out to the water layers of two layers of separation, washing are carried out to organic layer until turning into neutrality, And then organic layer is concentrated under reduced pressure (80 DEG C, 5mmHg), volatile ingredient is removed, obtained as brown solid corresponding Alkenyl compound.

[the 2nd stage]

Load above-mentioned in the removable flasks of 200mL for possessing agitator, reflux condenser, dropping funel and thermometer Alkenyl compound 30g, toluene 70g, the platinum -1,3- divinyl -1,1,3,3- tetramethyl disiloxanes obtained in 1 stage is complexed The toluene solution 0.08g of thing (is 5.0 × 10 in terms of pt atom relative to trimethoxy silane 1mol^-5) and acetic acid mol 0.003g, after having put into trimethoxy silane 3.4g at 75~85 DEG C of temperature inside, stirred at 80 DEG C 1 hour.

Obtained reaction product is brown transparency liquid, weight average molecular weight 6,100, viscosity 17mm²/ s, it is non-volatile Composition is 30 mass %.

[embodiment 1-10]The synthesis of organo-silicon compound 10

[the 1st stage]

Load PPO (business in the removable flasks of 300mL for possessing agitator, reflux condenser, dropping funel and thermometer Mark) SA90-100 ((strain) SABIC Innovative Plastics manufactures) 50g, toluene 130g, tetrabutylammonium disulfate 0.58g and 30% sodium hydrate aqueous solution 54.1g, is heated to 60 DEG C.Input allyl bromide, bromoallylene 8.2g is added dropwise thereto, at 60 DEG C Heating stirring 6 hours.Then, stand, liquid separation is carried out to the water layer of two layers of separation, in organic layer wash until turning into Property, and then, be concentrated under reduced pressure (80 DEG C, 5mmHg) to organic layer, and volatile ingredient is removed, and has been obtained pair as brown solid The alkenyl compound answered.

[the 2nd stage]

Load above-mentioned in the removable flasks of 200mL for possessing agitator, reflux condenser, dropping funel and thermometer Alkenyl compound 40g, toluene 60g, the platinum -1,3- divinyl -1,1,3,3- tetramethyl disiloxanes obtained in 1 stage is complexed The toluene solution 0.10g of thing (is 5.0 × 10 in terms of pt atom relative to trimethoxy silane 1mol^-5Mol), inside temperature 75~ After trimethoxy silane 6.3g has been put at 85 DEG C, stirred at 80 DEG C 1 hour.

Obtained reaction product is brown transparency liquid, weight average molecular weight 4,800, viscosity 13mm²/ s, it is non-volatile Composition is 31 mass %.

[embodiment 1-11]The synthesis of organo-silicon compound 11

[the 1st stage]

Load PPO (business in the removable flasks of 300mL for possessing agitator, reflux condenser, dropping funel and thermometer Mark) SA90-100 ((strain) SABIC Innovative Plastics manufactures) 50g, toluene 130g, tetrabutylammonium disulfate 0.54g and 30% sodium hydrate aqueous solution 54.1g, is heated to 60 DEG C.Input allyl bromide, bromoallylene 4.1g is added dropwise thereto, at 60 DEG C Heating stirring 6 hours.Then, stand, liquid separation is carried out to the water layer of two layers of separation, in organic layer wash until turning into Property, and then, be concentrated under reduced pressure (80 DEG C, 5mmHg) to organic layer, and volatile ingredient is removed, and has been obtained pair as brown solid The alkenyl compound answered.

[the 2nd stage]

Load above-mentioned in the removable flasks of 200mL for possessing agitator, reflux condenser, dropping funel and thermometer Alkenyl compound 25g, toluene 75g, the platinum -1,3- divinyl -1,1,3,3- tetramethyl disiloxanes obtained in 1 stage is complexed The toluene solution 0.06g of thing (is 5.0 × 10 in terms of pt atom relative to trimethoxy silane 1mol^-5Mol), inside temperature 75~ After trimethoxy silane 3.7g has been put at 85 DEG C, stirred at 80 DEG C 1 hour.

Obtained reaction product is brown transparency liquid, weight average molecular weight 6,100, viscosity 18mm²/ s, it is non-volatile Composition is 30 mass %.

[comparative example 1-1]The synthesis of organo-silicon compound 12

Load 2 functionality phenylate trees in the reaction unit for possessing agitator, reflux condenser, dropping funel and thermometer Fat (Mitsubishi's gas chemical (strain) manufacture, OPE-1000) 500g, (rub poly- tetramethoxy-silicane chemical (strain) manufacture, M more Silicate 51) 447g, 90 DEG C are heated to, melting mixing, uniform solution is made.The February as catalyst is added thereto Dilaurylate 0.22g, it is set to carry out separating methanol reaction in 15 hours at 90 DEG C, so as to obtain corresponding organosilicon compound Thing.

[comparative example 1-2]The synthesis of organo-silicon compound 13

Load 2 functionality phenylate trees in the reaction unit for possessing agitator, reflux condenser, dropping funel and thermometer Fat (Mitsubishi gas chemical (strain) manufacture, OPE-1000) 71.8g, poly- MTMS (chemical (strain) manufacture that rubs more, MTMS-A) 45.3g, 90 DEG C is heated to, melting mixing, uniform solution is made.The tin dilaurate as catalyst is added thereto Dibutyl tin 0.02g, separating methanol reaction in 15 hours is carried out at 90 DEG C, so as to obtain corresponding organo-silicon compound.

[2] preparation of solidification compound and its curing item

Each composition used during for preparing solidification compound and its curing item illustrates.

[PPE]

(strain) SABIC Innovative Plastics manufacture PPO (trade mark) SA90-100

[epoxy resin]

Epoxy resin 1：DIC (strain) manufacture EPICLON HP7200 (dicyclopentadiene type epoxy compound)

Epoxy resin 2：DIC (strain) manufacture EPICLON 850S (bisphenol A type epoxy resin)

[curing agent]

Four countries' chemical conversion industry (strain) manufacture 2E4MZ (2- ethyl -4- imidazoles)

[cyanate esters]

ロ Application ザジャパ Application (strain) manufacture BADCy (double (4- cyanatephenyls) propane of 2,2-)

[organic metal salt]

DIC (strain) manufacture Cu-NAPHTENATE (copper naphthenate)

[organo-silicon compound]

Organo-silicon compound：The organo-silicon compound obtained in above-described embodiment 1-1~1-11, comparative example 1-1,1-2

[embodiment 2-1]

According to described in table 1,2 mixing ratio (mass parts, wherein, organo-silicon compound be nonvolatile component conversion Value), the organo-silicon compound 1 obtained in PPE, epoxy resin, curing agent and above-described embodiment 1-1 are mixed, it is mixed by what is obtained Close solution and be heated to 60 DEG C.After with the addition of cyanate esters and organic metal salt thereto, stir 30 minutes, fully make it Dissolving, has obtained the solidification compound (resin varnish) of varnish shape.

Then, so as to get resin varnish be impregnated in glass cloth (day east weaving (strain) manufacture, WEA116E, E glass) after, heat drying 10 minutes at 160 DEG C, obtain preimpregnation blank.Now, with the content of resin component Mode as 55 mass % or so is adjusted.

Obtained each preimpregnation blank 6 is opened overlapping, be held on copper foil (Furukawa サーキット Off ォイ Le (strain) GT-MP processed) Stacking, 2 hours at 200 DEG C, pressurization is heated under conditions of pressure 3MPa, so as to obtain the evaluation base as curing item Plate.

[embodiment 2-2~2-11 and comparative example 2-1,2-2]

Except organo-silicon compound 1 are changed into what is obtained in embodiment 1-2~1-11 and comparative example 1-1~1-2 respectively Beyond organo-silicon compound 2~13, solidification compound and its curing item are made in the same manner as embodiment 2-1.

[comparative example 2-3,2-4]

Except organo-silicon compound 1 are changed into γ-glycidoxypropyltrimewasxysilane (KBM-403, SHIN-ETSU HANTOTAI Chemical industry (strain) manufactures) it is used as comparative example 2-3, is changed to phenyltrimethoxysila,e (KBM-103, SHIN-ETSU HANTOTAI's chemical industry (strain) manufactures) it is used as beyond comparative example 2-4, make solidification compound and its curing item in the same manner as embodiment 2-1.

[comparative example 2-5]

Except not use organo-silicon compound 1 in addition to, made in the same manner as embodiment 2-1 solidification compound and its Curing item.

For each evaluation substrate according to above-mentioned step preparation, evaluated using method as shown below.

[dielectric property]

The cavity resonance " CP461 " that (strain) Northeast the development of electronics applied manufactures is used, is determined copper-clad laminated under 2GHz The dielectric constant and dielectric loss angle tangent of plate.Show the result in table 1 below, 2.

[copper foil dhering strength]

The peel strength of the copper foil of copper-clad laminated plate surface is determined using the method according to JIS C 6481, and (copper foil is closely sealed Intensity).Now, wide 20mm, long 100mm test film on form wide 10mm, long 100mm pattern, use cupping machine Copper foil is peeled off with the speed of 50mm/ minutes, peel strength (kgf/cm) now is evaluated as copper foil dhering strength.By result It is shown in table 1 below, 2.

【Table 1】

【Table 2】

As shown in table 1,2, it is known that the organo-silicon compound that are obtained in embodiment 1-1~1-11 and comparative example 1-1, Organo-silicon compound, γ-glycidoxypropyltrimewasxysilane and the phenyltrimethoxysila,e phase obtained in 1-2 Than giving dielectric property as copper foil adaptation and dielectric constant, dielectric loss angle tangent excellent solidfied material.

Claims

In formula, X represents the organic group of the n valencys comprising polyphenyl ether structure, R¹Represent that unsubstituted or substituted carbon is former independently of each other The aryl of the alkyl of subnumber 1~10 or unsubstituted or substituted carbon number 6~10, R²Represent independently of each other unsubstituted Or the alkyl of carbon number 1~10 or the aryl of unsubstituted or substituted carbon number 6~10 of substitution, A¹Expression singly-bound, Or the linker containing heteroatomic divalence, A²Represent without heteroatomic, unsubstituted or substituted carbon number 1~20 Bivalent hydrocarbon radical, m are 1~3 number, and n is 1~10 number.

2. organo-silicon compound according to claim 1, it is represented by average formula (1) or (2)：

In formula, R¹、R²、A¹、A²Implication same as described above, R are represented with m³Halogen atom, unsubstituted or take is represented independently of each other The alkyl of the carbon number 1~12 in generation, the alkoxy of unsubstituted or substituted carbon number 1~12, unsubstituted or substituted carbon The halogenated alkoxy of the alkylthio group of atomicity 1~12 or unsubstituted or substituted carbon number 1~12, R⁴Independently of each other Represent hydrogen atom, halogen atom, the alkyl of unsubstituted or substituted carbon number 1~12, unsubstituted or substituted carbon number 1 The alkylthio group or unsubstituted or substituted carbon number 1 of~12 alkoxy, unsubstituted or substituted carbon number 1~12 ~12 halogenated alkoxy, a and b are independently of one another 1~100 number, and c is more than 0 and the number less than 2, and Z is represented by following formula (3) linker represented,

In formula, R⁴Implication same as described above is represented, L represents the linker being selected from following formula (4)~(11),

In formula, R⁵The alkyl of hydrogen atom or carbon number 1~12, R are represented independently of each other⁶Carbon number 1 is represented independently of each other ~12 alkyl, k represent 1~12 integer, and j represents 1~1,000 number.

3. organo-silicon compound according to claim 1 or 2, wherein, above-mentioned A¹-A²Represented by formula (12) or formula (13)：

4. the manufacture method of the organo-silicon compound according to any one of claims 1 to 3, it is characterised in that make by putting down Polyphenylene ether compound that equal structural formula (14) or (15) represent, with hydroxyl with by formula (16) expression, with isocyanates The compound of base and alkoxysilyl is reacted,

In formula, R³、R⁴, a, b and Z represent implication same as described above,

In formula, R¹、R²、A²Implication same as described above is represented with m.

5. the manufacture method of the organo-silicon compound according to any one of claims 1 to 3, it is characterised in that make by putting down Polyphenylene ether compound that equal structural formula (14) or formula (15) represent, with hydroxyl and with can be with the function of above-mentioned hydroxyl reaction The reaction of the compound of group and alkenyl and after having obtained alkenyl compound, the alkene is made in the presence of the catalyst containing platinum compounds Based compound carries out hydrosilylation reactions with the silane compound represented by formula (17),

In formula, R¹、R²Implication same as described above is represented with m.

6. solidification compound, it contains the organo-silicon compound described in any one of claims 1 to 3.

7. curing item, it is formed by the solidification compound solidification described in claim 6.