CN107141447A - Poly- (vinyl benzyl) ether compound and its purposes - Google Patents

Poly- (vinyl benzyl) ether compound and its purposes Download PDF

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Publication number
CN107141447A
CN107141447A CN201710105917.1A CN201710105917A CN107141447A CN 107141447 A CN107141447 A CN 107141447A CN 201710105917 A CN201710105917 A CN 201710105917A CN 107141447 A CN107141447 A CN 107141447A
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China
Prior art keywords
resin
vinyl benzyl
poly
composition
hardening
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多田若菜
岩下新
岩下新一
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09D5/18—Fireproof paints including high temperature resistant paints
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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Abstract

The present invention provides a kind of low dielectric tangent met after harsh thermal history, and has heat resistance, anti-flammability, contiguity reliability and processability and resistance to anti-thread breakage poly- (vinyl benzyl) ether compound and its purposes concurrently.A kind of poly- (vinyl benzyl) ether compound and allotment poly- (vinyl benzyl) ether compound represented by following formula (1) and curable resin composition formed by polyfunctional epoxy resin.

Description

Poly- (vinyl benzyl) ether compound and its purposes
Technical field
The present invention relates to poly- (vinyl benzyl) ether compound of one kind, contain poly- (vinyl benzyl) ether compound and epoxy Hardening of resin resin combination, circuit base material varnish, hardening thing, include its composite hardening thing and metal foil Layered product, the metal foil with resin and circuit base material.
Background technology
With the increase of the information traffic in recent years, the information communication in high frequency band starts actively to carry out, and is More excellent electrical characteristics, wherein, in order to reduce transmission loss in high frequency band, and requiring a kind of has low-k With low dielectric tangent, changed small electrically insulating material by the dielectric property after especially harsh thermal history.And then, use these The printed base plate or electronic component of electrically insulating material are exposed in the Reflow Soldering of high temperature when mounted, it is therefore desirable for a kind of heat-resisting Property, anti-flammability it is high, that is, show the material of high glass-transition temperature.Especially, most immediate cause environmental problem and use fusing point it is high Unleaded solder, therefore the requirement of the higher electrically insulating material of heat resistance just uprises.For these requirements, proposed there is one kind in the past Curable resin composition containing the vinyl benzyl ether compound with various chemical constitutions.
As such a curable resin composition, for example, propose there is following curable resin composition, it, which contains, passes through Make to be condensed obtained phenol aralkyl resin and gathering that vinyl benzyl halogen is reacted and obtained with biphenol compound (vinyl benzyl) ether compound (patent document 1).But, poly- (vinyl benzyl) etherificate disclosed in the patent document In terms of the dielectric property of compound not only in the early stage, it is impossible to obtain sufficient characteristic, and it is special for the dielectric of harsh thermal history Property change it is big, heat resistance, anti-flammability and insufficient.
It is used as poly- (vinyl benzyl) ether compound, it has been suggested that poly- (vinyl benzyl) etherificate for there are several specific structures is closed Thing, and carried out suppressing to be attempted by the change of dielectric tangent during harsh thermal history, or lifting heat resistance, anti-flammability Attempt, but the lifting of characteristic is still far from being fully, and expecting further characteristic improves.Therefore, as mounting material, reliable Property and processability in terms of and it is insufficient (patent document 2, patent document 3 and patent document 4).
In addition, in patent document 5 disclose have a kind of curable resin composition, its contain by phenol aralkyl resin, The hydroxyl of naphthols aralkyl resin, biphenyl type phenol resol resins or biphenyl type naphthol novolac varnish gum is subject to vinyl The hardening resin of benzyl etherificate, and intramolecular have the compound of the maleimide base of more than 1.But, The characteristic at initial stage of curable resin composition disclosed in the patent document not only dielectric property is insufficient, and as exhausted Edge material, by the contiguity reliability after damp and hot course and unsatisfactory, in terms of formability, also easily produces shaping not It is good, and it is undesirable.
Announcement has a kind of operability height obtained under unhardened state in patent document 6 and relative dielectric constant is low Hardening thing insulating trip and laminate structure, as the material for forming described and structure, announcement, which has, a kind of contains poly- (second Alkenyl benzyl) ether compound and epoxy resin curable resin composition.It is used as the tool of poly- (vinyl benzyl) ether compound Style, can be enumerated using vinyl benzyl ether to hydroquinones, bisphenol-A, Bisphenol F, bisphenol S, xenol, phenol novolacs Resin, the condensation product of phenol and benzaldehyde or new phenol (Xylok) type phenol resin carry out compound of substitution etc., and then, In embodiment, the vinyl benzyl ether compound for having new phenolic phenol resin is only disclosed.Moreover, disclosed in the patent document Curable resin composition containing poly- (vinyl benzyl) ether compound and epoxy resin by during harsh thermal history The change of dielectric tangent is big, in addition, the contiguity reliability after damp and hot course is also insufficient.
In this way, former poly- (vinyl benzyl) ether compound and its curable resin composition not provides following hard Compound person, the hardening thing has as electrically insulating material purposes, is particularly corresponding to high-frequency electrically insulating material purposes institute The heat resistance, the anti-flammability that meet the low dielectric tangent after harsh thermal history needed, in addition, just contiguity reliability and processability It is also insufficient for viewpoint.
Patent document 7 proposes that one kind makes naphthols aralkyl resin carry out reaction institute with vinyl aromatic halomethyl compounds Poly- (vinyl benzyl) ether compound obtained is used as solution poly- (vinyl benzyl) ether compound the problem of point person.
If however, considering the nearest trend that the miniaturization or slimming, multifunction of e-machine are accelerating, needing Want it is a kind of except the heat resistance of the required low dielectric tangent met after harsh thermal history so far, it is anti-flammability, close Connect beyond reliability and processability, the insulating resin of the circuit board use with new function.For example, working as integrated circuit When (Integrated Circuit, IC) chip is arranged on circuit substrate, if using not enclosing to the encapsulation of IC chip (package) the naked core sheet mode installed in, then compared with former mounting means, can be achieved the small-sized of e-machine Change.In the mode, the insulating resin of circuit board use is heated via solder or copper wiring.Caused by heat described in reason Stress concentration, and there is the anxiety cracked in insulating resin, solder or copper wiring.It is therefore desirable to a kind of resistance to anti-thread breakage excellent Insulating resin.
But, it is described naphthols aralkyl resin and vinyl aromatic halomethyl compounds is reacted gathering of being obtained There is further room for improvement at resistance to anti-thread breakage aspect in (vinyl benzyl) ether compound.
[prior art literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2005-314556 publications
The flat 1-503238 publications of [patent document 2] Japanese Patent Laid
[patent document 3] Japanese Patent Laid-Open 9-31006 publications
[patent document 4] Japanese Patent Laid-Open 2004-323730 publications
[patent document 5] Japanese Patent Laid-Open 2003-306591 publications
[patent document 6] Japanese Patent Laid-Open 2011-124076 publications
[patent document 7] No. WO2014/103926 number
The content of the invention
[invention problem to be solved]
Therefore, the problem of the invention to be solved is to provide a kind of low dielectric tangent met after harsh thermal history, and Have heat resistance, anti-flammability, contiguity reliability and processability and resistance to anti-thread breakage resin material concurrently, and use its circuit substrate material Material.
[technological means for solving problem]
The present inventor et al. has found that the hydroxyl of naphthols aralkyl resin is replaced into vinyl benzyl ether with specific ratio Poly- (vinyl benzyl) ether compound of base is for solving the problem effectively, so as to complete the present invention.
That is, the present invention is a kind of poly- (vinyl benzyl) ether compound, and it is represented by following formula (1).
[changing 1]
Herein, R1The aryl of hydrogen atom, the alkyl of carbon number 1~6, pi-allyl or carbon number 6~10 is separately represented, Ar1Represent the aromatic hydrocarbyl of the divalence of carbon number 6~50, R2Separately represent hydrogen atom, the alkyl of carbon number 1~12 or second Alkenyl benzyl.Wherein, R2In vinyl benzyl ratio for 10 moles of more than %, less than 60 moles of %, the ratio of hydrogen atom For 40 moles of more than %.N is calculated as 1~20 scope with average value, and m is 1~6 number, and r is 1~3 number, but m+r is no more than 6 Or 7.
Poly- (vinyl benzyl) ether compound can be to make the R in formula (1)2For hydrogen atom or hydrogen atom and carbon number 1~ The naphthols aralkyl resin of 12 alkyl is reacted institute winner with vinyl aromatic halomethyl compounds.
In addition, in formula (1), there is the R of more than 1 preferably in 1 molecule2For hydrogen atom or the OR of vinyl benzyl2 Base (Y), and the average OR of every 1 molecule2The quantity of base (Y) is more than 1.1.
And then, the present invention is a kind of curable resin composition, it is characterised in that：Including following (A) compositions and (B) into Point.
(A) composition：Poly- (vinyl benzyl) ether compound；
(B) composition：Have in 1 molecule in the epoxy radicals of more than 2 and the epoxy resin of aromatic structure, 1 molecule There is epoxy radicals and the fat of more than 2 in epoxy resin and 1 molecule with the epoxy radicals of more than 2 and cyanurate structure At least one of epoxy resin of ring structure epoxy resin.
The curable resin composition and then can contain epoxy resin hardener as (C) composition.
Make hardening thing formed by the curable resin composition hardening, comprising described hard in addition, the present invention is one kind Change property resin combination and base material hardening composite or on the one side of metal foil have by the hardening resin group The metal foil with resin of the film of compound formation.And then, the present invention is a kind of layer and metal foil layer with the hardening thing Layered product or use circuit base material formed by the hardening thing.Make the hardening tree in addition, the present invention is one kind Varnish or the varnish for circuit base material formed by oil/fat composition dissolving in a solvent.
[The effect of invention]
Poly- (vinyl benzyl) ether compound of the present invention or allotment have its resin combination to may be provided in harsh heat Also there is the dielectric property (the low dielectric tangent of low-k) of height and in hot and humid inferior harsh ring after course Under border, it may have high contiguity reliability and resistance to anti-thread breakage excellent hardening thing.Therefore, fly in electric and electronic industry, space In the fields such as machine industry, it can suitably be used as dielectric material, insulating materials, heat proof material.One side can be used as particularly suitablely, it is double Face or the printed base plate of multilayer, flexible printing substrate, the circuit base material of increasing layer substrate etc..
Embodiment
Hereinafter, the present invention is described in detail.
Poly- (vinyl benzyl) ether compound of the present invention is represented by the formula (1).
In formula (1), R1Separately represent the virtue of hydrogen atom, the alkyl of carbon number 1~6, pi-allyl or carbon number 6~30 Base.Aryl can further have the alkyl of substituent, such as carbon number 1~6.
For the viewpoint of dissolubility and dielectric property with hardening and the balance of anti-flammability, R1It is preferred that hydrogen atom, carbon number 1 The aryl of~6 alkyl or the aryl, more preferably hydrogen atom, the alkyl of carbon number 1~6 or carbon number 6~10 of carbon number 6~10, it is special It is preferred that the alkyl of hydrogen atom or carbon number 1~3.
R2Separately represent hydrogen atom, the alkyl or vinyl benzyl of carbon number 1~12.Moreover, vinyl benzyl exists R2In shared ratio (mole %) for 10 moles of more than %, less than 60 moles of %, but preferably 15 moles %~59 mole %, more It is preferred that 20 moles of %~55 mole %.And then more preferably 20 moles %~53 mole %.When the ratio of vinyl benzyl is rubbed for 60 During your more than %, polymerization activity point excessively increases, and the flexibility of resin is lost, and is easily cracked in reliability test. On the other hand, when the ratio of vinyl benzyl is less than 10 moles of %, crosslink density declines, and shadow is produced to anti-flammability or heat resistance Carbide growing amount at loud 600 DEG C declines.
When allocating epoxy resin, in order to efficiently carry out the cross-linking reaction with epoxy resin, hydrogen atom is in R2Middle institute Preferably 40 moles more than % of the ratio accounted for.
In formula (1), there is the R of more than 1 preferably in 1 molecule2For hydrogen atom or the OR of vinyl benzyl2Base (Y), And the average OR of every 1 molecule2The quantity of base (Y) is more than 1.1.Herein, by R2For hydrogen atom or the OR of vinyl benzyl2Base Referred to as OR2Base (Y).By OR2Base (Y) is understood as R2For the OR of the base beyond the alkyl of carbon number 1~122Base.More preferably in 1 molecule In there is the OR of more than 12Base (Y), and the average OR of every 1 molecule2The quantity of base (Y) is more than 1.1, it is advantageous that 2.2 More than individual.And then more preferably R2For vinyl benzyl and the OR of hydrogen atom2The quantity of base is more than 1.1 in 1 molecule.Separately Outside, 90 moles of more than % following molecule is preferably comprised, the molecule is R2For vinyl benzyl and the OR of hydrogen atom2Base Quantity is the molecule of more than 1.1 in 1 molecule.Moreover, can the R containing 5 moles of %, preferably 10 moles of more than %22 It is the molecule of vinyl benzyl more than individual.Furthermore, when poly- (vinyl benzyl) ether compound of the present invention is with multiple ethene Base benzyl ether, but with the molecular weight distribution comprising molecules different n resin when, as long as 1 mole of % of all molecules with It is upper that there are multiple vinyl benzyl ethers.
In order to lift toughness, formability and dielectric property, preferably by R2A part be set to alkyl.Alkyl is in R2In it is shared Ratio can be 1 mole of %~10 mole %, preferably 1 mole %~6 mole %, more preferably 1.5 moles %~4 mole %.Separately Outside, can be the alkyl of the alkyl, preferably carbon number 1~6 of carbon number 1~12 as the alkyl.
In formula (1), m represents 1~6 number, but for the viewpoint of dissolubility and the balance of anti-flammability, works as R1For hydrogen with During outer substituent, the number (m) preferably 0~2.
In addition, r represents 1~3 number, but for the viewpoint of dissolubility and toughness, preferably 1~2 number.M+r is 6 or 7. Specifically, in the formula (1), in the naphthalene nucleus represented by the left end in formula, m+r is 7, represented in constitutional repeating unit In naphthalene nucleus, m+r is 6.The m of every 1 naphthalene nucleus and r's and preferably 1~4.
Ar1Represent the aromatic hydrocarbyl of the divalence of carbon number 6~50.It can such as enumerate：Selected from by-Ph- ,-Ph-Ph- ,- Np-、-Np-CH2-Np-、-Ph-CH2-Ph-、-Ph-C(CH3)2-Ph-、-Ph-CH(CH3)-Ph-、-Ph-CH(C6H5)-Ph-、- Ph-Flu-Ph- and-Flu (CH3)2Aromatic hydrocarbyl of carbon number 6~50 in the-group constituted etc..It is preferred that carbon number 6~30 Aromatic hydrocarbyl, more preferably carbon number 6~20 aromatic hydrocarbyl.Herein, Ph represents phenylene (- C6H4-), Np represents sub- naphthalene Base (- C10H6-), Flu represents fluorenyl (- C13H8-).Herein, Ph, Np and Flu can have substituent, for example, alkyl, alkoxy, Phenyl.It is preferred that substituent can enumerate the alkyl of carbon number 1~6.In addition, being used as Ar1, with regard to dissolubility and anti-flammability viewpoint and Speech ,-the Ph- ,-Ph-Ph- or Np- be more preferably unsubstituted, replace through alkyl, replacing through alkoxy or replacing through phenyl.
N represents 1~20 number, preferably 1~10 in terms of average value.If n is more than 20, viscosity rises, just for fine figure It is not preferred for the fillibility decline this point of case.Furthermore, it is number average when with molecular weight distribution.
And then, poly- (vinyl benzyl) ether compound preferably gas chromatography (Gas Chromatography, GC in) determining, the PeakArea (a) based on vinyl aromatic halomethyl compounds is etherified relative to poly- (vinyl benzyl) The PeakArea (a+b) that the PeakArea (b) of compound is added is less than 1.0%.It is preferred that less than 0.5%, more preferably 0.2% with Under.If the PeakArea is more than 1.0%, exists and declined for a long time by the dielectric property after more than 250 DEG C of thermal history Tendency.Herein, the PeakArea (b) of poly- (vinyl benzyl) ether compound refers to be based on meeting the pure of the formula (1) The PeakArea of pure poly- (vinyl benzyl) ether compound.Poly- (vinyl benzyl) ether compound of the present invention is reaction product Or it is carried out to refine and winner, can be containing described in a small amount of be unsatisfactory in addition to pure poly- (vinyl benzyl) ether compound The other compositions as impurity of formula (1).
The present invention the preferred total content of halogen of poly- (vinyl benzyl) ether compound for 600ppm (wt) below.More preferably Below 450ppm, and then more preferably below 200ppm.If total content of halogen is more than 600ppm, in the presence of long-time by 250 DEG C The tendency that dielectric property after thermal history above declines.The halogen is based primarily upon the aromatic series halomethyl chemical combination as raw material Thing, thus it is related to the PeakArea (a).
In addition, if total content of halogen becomes below 600ppm, also result in can avoid warpage or transfer bad grade into This unexpected effect of shape bad phenomenon, therefore it is also preferred that.But, excessively reduce total content of halogen or vinyl aromatic halogen first The content of based compound can be such that refined yield significantly declines.According to experiment, if distinguishing, total content of halogen is more than 2ppm, The problem of will not producing related to industrial implementation as described above, thus more than its refined just refined yield aspect and talk It is not upper favourable.
As described above, as one, naphthols aralkyl resin can be made to be carried out with vinyl aromatic halomethyl compounds anti- Should come obtain the present invention poly- (vinyl benzyl) ether compound.The naphthols aralkyl resin is represented by following formula (2).
[changing 2]
In the formula (1) and formula (2), identical mark has identical implication.Therefore, the R in the formula (2)1、Ar1、 The R of n, m and r implication and the formula (1)1、Ar1, n, m and r it is identical.
The reaction of naphthols aralkyl resin and vinyl aromatic halomethyl compounds represented by the formula (2) has no Especially limitation, for example, can be carried out in the following way：In the liquid phases such as polarity solvent, alkali metal hydroxide is used as dehalogenation Change hydrogen agent to be reacted.In the reaction, phenolic hydroxyl group and the vinyl aromatic halomethylation of naphthols aralkyl resin The CH of compound2X bases carry out condensation reaction, take off and vinyl benzyl ether compound is generated after HX.
In addition, in order to lift toughness, formability and dielectric property, for example can also be according to the publication of Japan Patent 4465257 In described method, in the presence of acidic catalyst, make the phenol of the naphthols aralkyl resin represented by the formula (2) A part for hydroxyl and the alcohols of carbon number 1~12 are reacted, and thus import the alkyl of carbon number 1~12 as in the formula (1) R2A part.
Import alkyl reaction can before the reaction with vinyl aromatic halomethyl compounds, can also with vinyl After the reaction of aromatic series halomethyl compounds, but in order to avoid the polymerization of vinyl, preferably with vinyl aromatic halomethyl Before the reaction of compound.When importing the reaction of alkyl before the reaction with vinyl aromatic halomethyl compounds to be following Method：First a part for the hydrogen atom of synthesis phenolic hydroxyl group is (hereinafter referred to as a part of through alkyl-substituted naphthols aralkyl resin Modified naphthols aralkyl resin), reacted with vinyl aromatic halomethyl compounds thereafter, and obtain part warp Poly- (vinyl benzyl) ether compound of alkylation.When import alkyl reaction with vinyl aromatic halomethyl compounds It is following method when after reaction：Naphthols aralkyl resin is reacted with vinyl aromatic halomethyl compounds, obtain Poly- (vinyl benzyl) ether compound, thereafter, a part for the hydrogen atom of the phenolic hydroxyl group of remaining is alkylated, and is obtained Poly- (vinyl benzyl) ether compound.Herein, a part of modified naphthols aralkyl resin is included in described in this specification Naphthols aralkyl resin in.
In addition, as the raw material of naphthols aralkyl resin part or all, can also use the hydrogen of phenolic hydroxyl group Part or all of atom is set to the hydroxyl naphthalenes of alkyl.
In addition, naphthols aralkyl resin can also be whole hydrogen atoms of phenolic hydroxyl group through alkylation person and phenolic hydroxyl group The mixture of whole hydrogen atom residual persons, it is also contained in a part of modified naphthols aralkyl resin.
As the naphthols aralkyl resin represented by the formula (2), except by the reaction come in addition to obtaining, can also Using commercially available person, for example can suitably using Nippon Steel live in the SN170 of aurification limited company manufacture, SN180, SN190, SN475, SN485, SN495 etc..For dissolubility, toughness and anti-flammability this point, more preferably SN475, SN485, SN495, SN485V、SN495V.For the viewpoint of dielectric property, toughness and formability, particularly preferably SN485V, SN495V.
In addition, by the naphthols aralkyl resin represented by the formula (2) can also be manufactured by known method.It is described Manufacture method is for example in Japanese Patent Laid-Open 2001-213946 publications, Japanese Patent Laid-Open 11-255868 publications, day This patent Unexamined Patent 11-228673 publications, Japanese Patent Laid-Open 08-073570 publications, Japanese Patent Laid-Open 08- There is note in No. 048755 publication, Japanese Patent Laid-Open 10-310634 or Japanese Patent Laid-Open 11-116647 publications etc. Carry.Naphthols aralkyl resin represented by the formula (2) can be used alone, can also and with two or more.
The vinyl aromatic halomethyl compounds are by CH2=CH-Ar2-CH2X is represented.Herein, Ar2For phenylene or The phenylene being substituted.As the substituent in the case of the phenylene being substituted, for example, it can enumerate：Alkyl, alkoxy, benzene Base.Preferably enumerate the alkyl of carbon number 1~6.In addition, being used as Ar2, for the viewpoint of dissolubility and anti-flammability, more preferably The phenylene be unsubstituted, replace through alkyl, replacing through alkoxy or replacing through phenyl.And then more preferably industrially easily make That makes is unsubstituted and through alkyl-substituted phenylene.The vinyl aromatic halomethyl compounds provide R2 vinyl benzyl Base, therefore understands that into vinyl benzyl can on its phenyl ring have substituent the vinyl benzyl being substituted.In addition, X is Halogen, preferably chlorine or bromine.
As preferred vinyl aromatic halomethyl compounds, it can enumerate：To vinyl chloride, a vinyl benzyl Chlorine, the mixture to vinyl chloride and a vinyl chloride, to vinyl benzyl bromide, a vinyl benzyl bromide, to second The mixture of alkenyl benzyl bromide a-bromotoluene and a vinyl benzyl bromide.Wherein, if using to vinyl chloride and a vinyl chloride Mixture, then excellent poly- (vinyl benzyl) ether compound of dissolubility can be obtained, because of the compatibility and work with other materials Industry becomes good, therefore it is preferred that.When using the mixture to vinyl benzyl halogen and a vinyl benzyl halogen, ratio of components has no Especially limitation, but preferred pair body/mesosome=90/10~10/90 (moles/mole), more preferably 70/30~30/70 (mole/rub You), and then more preferably 60/40~40/60 (moles/mole).
When making naphthols aralkyl resin be reacted with vinyl aromatic halomethyl compounds as described, and gathered During (vinyl benzyl) ether compound, there is deviation and reacted with the OH bases of naphthols aralkyl resin in vinyl benzyl, because The quantity of the vinyl benzyl of this every 1 molecule produces deviation.Moreover, the vinyl benzyl of every 1 molecule is more than 2 persons and every 1 The vinyl benzyl of molecule is mixed less than 2 persons, and the vinyl benzyl of every 1 molecule carries out cross-linked polymeric for more than 2 persons To provide hardening resin.The vinyl benzyl of every 1 molecule controls the degree of cross linking less than 2 persons, and assigns the property such as flexibility to resin Matter.Do not join the polymerization of vinyl without vinyl benzyl person, it is therefore desirable that its amount is few, but can be by the way that OH bases are converted into Cyanic acid ester group etc. react etc. making contributions to hardening resin reaction of formation with epoxy resin.
In addition, as be described hereinafter, poly- (vinyl benzyl) ether compound of the invention preferably mixes to be gathered with epoxy resin Close and (be also referred to as crosslinked).In addition, it can also mix to be polymerize with the epoxide beyond epoxy resin, can also Using known method, hydroxyl is subject to cyanic acid esterification, and as cyanate ester resin or double maleimides-triazine tree Fat.By the way that low dielectric and heat resistance, the printed wiring plate material of excellent in flame retardance with upper type, such as can be obtained.
Then, the curable resin composition of the present invention is illustrated.
The curable resin composition of the present invention contains (A) composition and (B) composition.
(A) composition is poly- (vinyl benzyl) ether compound, and (B) composition is that have the epoxy of more than 2 in 1 molecule The polyfunctional epoxy resin of base.As the polyfunctional epoxy resin of the epoxy radicals in 1 molecule with more than 2, have with fragrance The epoxy resin (B1) of race's structure, epoxy resin (B2), the epoxy resin with alicyclic structure with cyanurate structure Or these mixture (B3).Hereinafter, epoxy resin (B1) is also referred to as fragrant family epoxy resin, by epoxy resin (B2) Referred to as cyanurate system epoxy resin, is referred to as alicyclic epoxy resin by the epoxy resin (B3) with alicyclic structure.Ester ring type Epoxy resin can have the alicyclic structure of carbon number 3~12, preferably carbon number 5~10.
As the preferred example of the epoxy resin of (B) composition, it can enumerate：Bisphenol A type epoxy resin, bisphenol F type epoxy Resin, bisphenol-s epoxy resin, alkylphenol phenolic resin varnish type epoxy resin, xylylene modified phenol phenolic varnish type Epoxy resin, xylylene modified alkyl phenol phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, phenols are with having phenol Fragrant family epoxy resin, the isocyanuric acids three such as epoxides, the naphthalene type epoxy resin of condensation product of aromatic aldehyde of property hydroxyl The cyanurate such as ethylene oxidic ester system epoxy resin, hexamethylene type epoxy resin, dicyclopentadiene-type epoxy resin, adamantane type The alicyclic epoxy resins such as epoxy resin.These epoxy resin can be used alone respectively, can also be used in combination of two or more.
As bisphenol f type epoxy resin, for example, it can enumerate：By two contractings of 4,4 '-di-2-ethylhexylphosphine oxide (2,6- xylenol) Epoxy resin of the water glycerin ether as principal component, the diglycidyl ether by 4,4 '-di-2-ethylhexylphosphine oxide (2,3,6-TMP) As the epoxy resin of principal component, by epoxy resin of the diglycidyl ether of 4,4 '-methylene bis-phenol as principal component.Its In, preferably by epoxy resin of the diglycidyl ether of 4,4 '-di-2-ethylhexylphosphine oxide (2,6- xylenol) as principal component.As The bisphenol f type epoxy resin, can be obtained as YSLV-80XY (manufacture of aurification company is lived by Nippon Steel).
As biphenyl type epoxy resin, it can enumerate：4,4 '-diglycidyl biphenyl and 4,4 '-diglycidyl- 3,3 ', 5, the epoxy resin such as 5 '-tetramethyl biphenyl.As the biphenyl type epoxy resin, YX-4000, YL-6121H can be used as (Mitsubishi Chemical Ind's manufacture) and obtain.
As dicyclopentadiene-type epoxy resin, it can enumerate：Dicyclopentadiene and with bicyclopentadiene bone Phenol Novolac epoxy monomer of frame etc..
As naphthalene type epoxy resin, it can enumerate：1,2- diglycidyl naphthalene, 1,5- diglycidyls naphthalene, 1,6- bis- Glycidyl naphthalene, 1,7- diglycidyls naphthalene, 2,7- diglycidyls naphthalene, triglycidyl group naphthalene and 1,2,5,6- Four glycidyl group naphthalene, naphthols aralkyl-type epoxy resin, naphthalene skeleton are modified cresol novolak type epoxy resin, methoxyl group Naphthalene is modified cresol novolak type epoxy resin, naphthylene ether type epoxy, methoxynaphthalene dimethylene type epoxy resin etc. Modified naphthalene type epoxy resin etc..
As adamantane type epoxy resin, it can enumerate：1- (2,4- 2-glycidyl phenyl) adamantane, 1- (2,3, 4- three-glycidyls phenyl) adamantane, double (2, the 4- 2-glycidyl phenyl) adamantane of 1,3-, 1,3- it is double (2,3, 4- three-glycidyls phenyl) adamantane, 2,2- double (2,4- 2-glycidyl phenyl) adamantane, 1- (2,3,4- tri- Hydroxy phenyl) adamantane, double (2, the 4- dihydroxy phenyl) adamantane of 1,3-, double (2,3, the 4- trihydroxy phenyl) adamantane of 1,3-, And double (2, the 4- dihydroxy phenyl) adamantane of 2,2- etc..
Among the epoxy resin, the just viewpoint small with the warpage of the compatibility, dielectric property and formed products of (A) composition For, it can suitably use bisphenol f type epoxy resin, alkylphenol phenolic resin varnish type epoxy resin, phenol aralkyl type epoxy Resin, alkylphenol aralkyl-type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type asphalt mixtures modified by epoxy resin Fat, triglycidyl isocyanurate, hexamethylene type epoxy resin, adamantane type epoxy resin.
(B) weight average molecular weight (Mw) of the epoxy resin of composition is preferably less than 10,000.Preferred Mw is less than 600, And then more preferably more than 200, less than 550.When Mw is less than 200, the volatility that there is (B) composition is uprised, the place of casting film piece The tendency that rationality is deteriorated.On the other hand, if Mw is more than 10,000, there is casting film piece and be easily hardened and crisp, the hardening of casting film piece The tendency that the cementability of thing declines.
Relative to the parts by weight of (A) composition 100, the content preferred lower limit of (B) composition is 5 parts by weight and the upper limit is 100 weight Part.More preferably relative to the parts by weight of (A) composition 100, the preferred lower limit of the content of (B) composition is 10 parts by weight.The opposing party Face, the preferred upper limit is 80 parts by weight, and then the preferred upper limit is 60 parts by weight.If the content of (B) composition meets described It is preferred that lower limit, then can further improve the cementability of the hardening thing of casting film piece.If the content of (B) composition meets described preferred The upper limit, then the casting film piece under unhardened state operability further uprise.
The curable resin composition of the present invention can add epoxy resin hardener as (C) composition.(C) as long as composition Make the epoxy cure person as (B) composition, be then not particularly limited.One kind can be used only in the curing agent, can also be simultaneously With two or more.
(C) the preferred phenol resin of the curing agent of composition or acid anhydrides, these acid with aromatic backbone or alicyclic skeleton The hydride or modifier of acid anhydride.By using these curing agents, it can obtain as heat resistance, anti-flammability, moisture-proof and electric physical property Balancing good hardening thing curable resin composition.
Phenol resin as curing agent is not particularly limited.As the concrete example of the phenol resin, it can enumerate：Phenol novolac It is varnish, o-cresol novolak, paracresol novolaks, t-butylphenol novolac, bicyclopentadiene cresols, poly- to ethene Base phenol, bisphenol A-type novolaks, phenol aralkyl resin, naphthols aralkyl resin, biphenyl type phenol resol resins, Biphenyl type naphthol novolac varnish gum, decahydronaphthalene modified novolac, poly- (two-o-hydroxy-phenyl) methane, a poly- (two-hydroxyl Phenyl) methane and poly- (two-p-hydroxybenzene) methane etc..Wherein, phenol resin with melamine skeleton, with triazine bone The phenol resin of frame or phenol resin with pi-allyl because can further improve the flexibility and anti-flammability of insulating trip and it is preferred that.
As the commercially available product of the phenol resin, it can enumerate：(bright and chemical conversion is public by MEH-8005, MEH-8010 and NEH-8015 Department's manufacture), YLH903 (Japanese epoxy resin (Japan Epoxy Resins) company manufacture), LA-7052, LA-7054, LA- 7751st, LA-1356 and LA-3018-50P (manufacture of DIC (DIC) company), and (group Rong Huaxue is public by PS6313 and PS6492 Department's manufacture) etc..
On the acid anhydrides with aromatic backbone as curing agent, its hydride or modifier, structure is also without special limit It is fixed.It can such as enumerate：Styrene/maleic anhydride copolymer, benzophenone tetracarboxylic anhydride, pyromellitic dianhydride, inclined benzene three Formic anhydride, 4,4 '-epoxide diphthalic anhydrides, phenylene-ethynylene phthalic anhydride, glycerine are double (dehydration trimellitate) Monoacetate, ethylene glycol double (dehydration trimellitate), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, The adjacent benzene of trialkyl tetrabydrophthalic anhydride, methylnadic anhydride (Nadic methyl anhydride), trialkyl tetrahydrochysene Dicarboxylic acid anhydride etc..
As the commercially available product of the acid anhydrides with aromatic backbone, its hydride or modifier, it can enumerate：SMA resins EF30, SMA resin EF40, SMA resin EF60 and SMA resin EF80 (Japanese Sartomer (SartomerJapan) company systems Make), ODPA-M and PEPA (manufacture of Ma Naike (Manac) company), Li Kaxide (Rikacid) MTA-10, Li Kaxide (Rikacid) MTA-15, Li Kaxide (Rikacid) TMTA, Li Kaxide (Rikacid) TMEG-100, Li Kaxide (Rikacid) TMEG-200, Li Kaxide (Rikacid) TMEG-300, Li Kaxide (Rikacid) TMEG-500, Li Kaxi Moral (Rikacid) TMEG-S, Li Kaxide (Rikacid) TH, Li Kaxide (Rikacid) HT-1A, Li Kaxide (Rikacid) HH, Li Kaxide (Rikacid) MH-700, Li Kaxide (Rikacid) MT-500, Li Kaxide (Rikacid) DSDA and Li Kaxide (Rikacid) TDA-100 (new Japan Chemical company manufacture), and Epiclon (EPICLON) B4400, Epiclon (EPICLON) B650 and Epiclon (EPICLON) B570 (manufacture of DIC company) etc..
The modifier of the acid anhydrides with alicyclic skeleton or the acid anhydrides preferably with many alicyclic skeletons acid anhydrides, The acid anhydrides with alicyclic skeleton obtained by the addition reaction of terpene based compound and maleic anhydride or its change Property thing.In the case, the flexibility, moisture-proof or cementability of insulating trip be can further improve.In addition, there is fat as described The acid anhydrides of ring type skeleton or its modifier, can be enumerated：Methylnadic anhydride, the acid anhydrides with bicyclopentadiene skeleton or its change Property thing etc..The alicyclic skeleton is just like skeleton of the bicyclopentadiene skeleton with unsaturated bond and such as cyclopentane framework Skeleton without unsaturated bond, can be any.In addition, can be for the skeleton with unsaturated bond be hydrogenated into what is obtained Hydrogenated acid anhydrides or its modifier, the hydrogenated skeleton can be the skeleton without unsaturated bond or one The part hydride of lease making hydrogenation.Furthermore, the hydride of the acid anhydrides with aromatic backbone is sometimes equivalent to alicyclic ring The acid anhydrides of formula skeleton.
As the commercially available product of the acid anhydrides with alicyclic skeleton, modifier, it can enumerate：Li Kaxide (Rikacid) HNA and Li Kaxide (Rikacid) HNA-100 (new Japan Chemical company manufacture), and a Chinese mugwort mound (Epicure) YH306, Chinese mugwort Mound (Epicure) YH307, a Chinese mugwort mound (Epicure) YH308H and a Chinese mugwort mound (Epicure) YH309 (are Japanese ring above Oxygen tree fat company manufactures) etc..
With regard to for the compatibility and moisture-proof of (A) composition, the viewpoint of cementability, the curing agent as (C) composition is more excellent Select o-cresol novolak, it is paracresol novolaks, t-butylphenol novolac, bicyclopentadiene cresols, poly- to vinyl It is phenol, xylylene modified novolac, poly- (two-o-hydroxy-phenyl) methane, poly- (a two-hydroxy phenyl) methane, poly- (two-p-hydroxybenzene) methane, methylnadic anhydride, trialkyl tetrabydrophthalic anhydride or with bicyclopentadiene bone The modifier of the acid anhydrides of frame or these acid anhydrides.
The present invention curable resin composition in, can add Mw be more than 10,000 high molecular weight resin as (D) into Point.As long as the high molecular weight resin Mw be more than 10,000, then be not particularly limited, can be used only one kind, can also and with two kinds More than.
If enumerating the concrete example of (D) composition, polyphenylene sulfide, polyarylate resin, polysulfone resin, polyether sulfone can be used Resin, polyphenylene oxide resin, polycarbonate resin, polyvinyl acetal resins, polyimide resin, polyamide-imide resin, Polybenzoxazole resin, phenoxy resin, phenylethylene resin series, (methyl) acrylic resin, polycyclopentadiene resins, polycyclic Olefin resin, polyether-ether-ketone resin, polyether ketone resin, or known thermoplastic elastomer (TPE), such as styrene ethylene-propylene are total to Polymers, styrene-ethylene-butadiene copolymer, SB, styrene-isoprene copolymer, hydrogenation of benzene Ethylene-butadiene copolymer, hydrogenated styrene isoprene copolymer etc., or rubber-like, such as polybutadiene, poly- isoamyl two The high molecular weight resins such as alkene.
Among these high molecular weight resins, with regard to for the compatibility of (A) composition, the viewpoint of contiguity reliability, suitably making It is polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, phenoxy resin, polycyclic alkene resin, hydrogenated styrene-fourth two The high molecular weight resins such as alkene copolymer, hydrogenated styrene isoprene copolymer.
(D) the preferred lower limit of the glass transition temperature Tg of the high molecular weight resin of composition is -40 DEG C, it is preferred under 50 DEG C are limited to, most preferred lower limit is 90 DEG C.It is preferred that the upper limit be 250 DEG C, the preferred upper limit be 200 DEG C.If Tg meets institute Preferred lower limit is stated, then resin is difficult to heat deterioration, if Tg meets the preferred upper limit, the phase of (D) composition and other resins Capacitive is uprised.As a result, the operability of the casting film piece under can further improve unhardened state, and casting film piece hardening Heat resistance, the anti-flammability of thing.
The Mw of high molecular weight resin preferred lower limit is 20,000, and preferred lower limit is 30,000, and the upper limit preferably is 100 Ten thousand, the preferred upper limit is 250,000.If Mw meets the preferred lower limit, insulating trip is difficult to heat deterioration, if meeting described excellent The upper limit of choosing, then the compatibility of (D) composition and other resins uprise.As a result, the casting under can further improve unhardened state The operability of diaphragm, and the hardening thing of casting film piece heat resistance, anti-flammability.
When containing (A) composition~(D) composition in the curable resin composition in the present invention, (D) composition is in all trees Shared content is preferred in total 100wt% (percentage by weight) of fat composition (hereinafter also referred to as all resin component X) In the range of 10wt%~60wt%.The content of (D) composition in all resin component X total 100wt% it is preferred Lower limit is 20wt%, and the preferred upper limit is 50wt%.If the content of (D) composition meets the preferred lower limit, one can be entered Step improves the operability of the casting film piece under unhardened state.If the content of (D) composition meets the preferred upper limit, aftermentioned The scattered of the inorganic fill material as (F) composition become easy.Furthermore, all resin component X refer to (A) composition, (B) into Point, (C) composition, (D) composition and optionally and add other resin components summation.Turn into resin after the hardening such as curing agent The composition of composition is calculated as resin component, but without (F) composition inorganic fill material or (G) composition described later it is fire-retardant Agent.
In addition to the composition, curable resin composition of the invention can contain radical polymerization initiation according to expectation Agent (also referred to as catalysts for radical polymerization) is used as (E) composition.For example, the curable resin composition of the present invention passes through as be described hereinafter The methods such as heating and produce cross-linking reaction and harden, but pass through and add (E) composition, it is possible to decrease reaction temperature now promotes The cross-linking reaction of unsaturated group.
If enumerating the typical example of (E) composition, there are benzoyl peroxide, cumene hydroperoxide, 2,5- dimethyl Hexane -2,5- dihydro-peroxidase, 2,5- dimethyl -2,5- bis- (tert-butyl peroxide) hexin -3, di-t-butyl peroxidating Thing, tert-butyl cumyl peroxide, α, α '-bis- (a tert-butyl peroxide-isopropyl) benzene, (peroxide of 2,5- dimethyl -2,5- bis- Change the tert-butyl group) hexane, dicumyl peroxide, two-tert-butyl ester of peroxidating M-phthalic acid, peroxidized t-butyl perbenzoate, 2, Double (tert-butyl peroxide) butane of 2-, 2,2- double (tert-butyl peroxide) octane, (the benzoyl peroxide first of 2,5- dimethyl -2,5- bis- Acyl group) peroxidating such as hexane, two (trimethylsilyl) peroxide, trimethylsilyl tri-phenyl-silane base peroxide Thing, but it is not limited to these examples.In addition, though be not peroxide, but 2,3- dimethyl -2,3- diphenyl butane also may be used For use as radical polymerization initiator (or polymerization catalyst).But, catalyst, freedom for the hardening of this resin combination Base polymerization initiator is not limited to these examples.
If relative to (A) composition, the allotment amount of (E) composition is the scope of the parts by weight of 0.01 parts by weight~10, then will not hinder Hinder sclerous reaction and reacted well.
In addition, optionally, allotment copolymerization can also can be carried out with (A) composition into the curable resin composition of the present invention Other polymerizable monomers hardened.When other described polymerizable monomers of allotment, included in all resin component X.
As other described polymerizable monomers, it can enumerate：Styrene, styrene dimer, α-methylstyrene, Alpha-Methyl Styrene dimer, divinylbenzene, vinyltoluene, t-butyl styrene, chlorostyrene, Dowspray 9, vinyl naphthalene, Vinyl biphenyl, acenaphthene, divinyl benzylic ether, allyl phenyl ether etc..
In addition, in the curable resin composition of the present invention, physical property in order to adjust setting rate or hardening thing etc., Hardening accelerator can be added to be used in combination with (C) composition.
The hardening accelerator is not particularly limited.As the concrete example of hardening accelerator, for example, it can enumerate：Tertiary amine, Diazabicyclo alkenes such as imidazoles, imidazolines, triazines, organic phosphorus series compound, four grades of phosphonium salt classes, acylates etc.. In addition, as the hardening accelerator, can enumerate：Organo-metallic compound class, quarternary ammonium salt class and metal halide etc..As The organo-metallic compound class, can be enumerated：Zinc octoate, tin octoate and acetylacetone,2,4-pentanedione aluminium complex etc..
As hardening accelerator, dystectic imidazole hardening accelerator, dystectic decentralized potentiality can also be used Hardening accelerator, microcapsule-type potentiality hardening accelerator, amine salt type potentiality hardening accelerator and high temperature dissociative type and heat Cationic polymerization type potentiality hardening accelerator etc..One kind can be used only in hardening accelerator, can also and with two or more.
As dystectic decentralized potentiality accelerator, it can enumerate：The addition dicyanodiamine in epoxy monomer etc. (dicyandiamide) and amine amine add-on type accelerator etc..As the microcapsule-type potentiality accelerator, it can arrange Lift：Utilize the microcapsule-type potentiality accelerator on the surface of the accelerator of polymer overmold imidazoles system, phosphorus system or phosphine system.Make For the high temperature dissociative type and hot cationic polymerization type potentiality hardening accelerator, it can enumerate：Lewis acid (Lewis acid) Salt or cloth bear this special sour (bronsted acid) salt etc..
Hardening accelerator preferably organic phosphorus series compound and dystectic imidazoles system hardening accelerator.By using organic Phosphorus series compound and dystectic imidazoles system hardening accelerator, can easily control reaction system, and can more easily adjust casting The setting rate of diaphragm and the physical property of hardening thing of casting film piece etc..Fusing point promotes for more than 100 DEG C of dystectic hardening The treatability of agent is excellent.Therefore, preferably more than 100 DEG C of the fusing point of hardening accelerator.
In total 100wt% of all resin component X, the preferred lower limit of the content of (C) composition is 1wt%, and It is preferred that the upper limit be 40wt%.Preferred lower limit is 5wt%, and the preferred upper limit is 25wt%.If the content of (C) composition expires The foot preferred lower limit, then easily make casting film piece fully harden, if meeting the preferred upper limit, is difficult to produce not The unnecessary curing agent of hardening is participated in, and can be sufficiently carried out the crosslinking of hardening thing.Therefore, it can further improve casting film piece Hardening thing heat resistance, anti-flammability and cementability.
Furthermore, it is known that the function in epoxy radicals and curing agent in the relation preferred epoxy of epoxy resin and curing agent The ratio (equivalent proportion) of base (reactive hydrogen etc.) is 1: 1 or so, also can be with the ratio in the curable resin composition of the present invention Become 0.5~2: 1, the mode for preferably becoming 0.8~1.2: 1 is allocated.In the case, OH bases contained in (A) composition are made For curing agent function, therefore include in the calculating of curing agent (A) composition.
In the curable resin composition of the present invention, obtained to further reduce by the curable resin composition The thermal coefficient of expansion of the insulating barrier obtained, can also add inorganic fill material as (F) composition.As (F) composition, for example, it can enumerate Silica, aluminum oxide, barium sulfate, talcum, clay, mica powder, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, oxidation Magnesium, boron nitride, aluminium borate, barium titanate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, barium zirconate, calcium zirconate etc., this Among a little, particularly suitable is amorphous silica, fused silica, crystalline silica, synthetic silica etc. two Silica.It is used as silica, preferably spherical silica.
(F) composition can also be used in combination of two or more.The average grain diameter of inorganic fill material is not particularly limited, but just For the viewpoint that fine distribution is formed on towards insulating barrier, preferably less than 5 μm, more preferably less than 1 μm, so more preferably 0.7 μm with Under.Furthermore, it is clear when the curable resin composition of the present invention is made into resin if the average particle diameter became of (F) composition is too small During paint, the viscosity that there is varnish rises, the tendency that treatability declines, therefore preferably more than 0.05 μm of average grain diameter.(F) into The average grain diameter divided can be determined by the laser diffraction scattering method according to Michaelis (Mie) scattering theory.Specifically, it can lead to Cross using laser diffraction mode particle size distribution device, make the size distribution of (F) composition with volume reference, and by its central diameter (median diameter) is set to average grain diameter to determine.Determination sample preferably using made by ultrasonic wave (F) composition divide It is dispersed in water and winner.As laser diffraction mode particle size distribution device, hole can be used to make the LA- of institute's (share) manufacture 500 etc..
(F) composition is surface-treated preferably by epoxy silane coupling agent, amino silicane coupling agent, titanate esters system coupling agent etc. Agent is surface-treated to lift its moisture-proof person.Relative to the mass of nonvolatile component 100 of the curable resin composition Part, the scope of the mass parts of addition preferably 20 mass parts of (F) composition~400, the model of the mass parts of more preferably 30 mass parts~350 Enclose, the scope of the mass parts of and then more preferably 40 mass parts~300.If the content of (F) composition is more than 400 mass parts, in the presence of hard The tendency that the tendency or peel strength that compound becomes fragile decline.On the other hand, when the content of (F) composition is less than 20 mass parts, heat The coefficient of expansion will not fully decline.
In the curable resin composition of the present invention, fire retardant work can be contained in the range of lossless effect of the invention For (G) composition.As (G) composition, for example, it can enumerate：Organic phosphorus flame retardant, organic system contain the phosphorus compound of nitrogen, nitrification Thing, silicone flame retardant, metal hydroxides etc..As organic phosphorus flame retardant, it can enumerate：The HCA of three light (share) manufacture, The phenanthrene type phosphorus compound such as HCA-HQ, HCA-NQ, the benzoxazine containing phosphorus such as the HFB-2006M of Showa macromolecule (share) manufacture Compound, the thunder Europe FOX (Reofos) 30 of aginomoto microtechnic (Ajinomoto Fine-Techno) (share) manufacture, 50th, 65,90,110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, northern emerging chemical industry (share) system The Phosphations such as the PX200 of chemical (share) manufacture of the PPQ made, the OP930 of Clariant (Clariant) (share) manufacture, big eight Compound, Dongdu is melted into the epoxy resin containing phosphorus such as FX289, FX305 of (share) manufacture, Dongdu chemical conversion (share) manufacture The phenoxy resin containing phosphorus such as ERF001, the epoxy resin containing phosphorus such as the YL7613 of Japanese epoxy resin (share) manufacture Deng.Contain the phosphorus compound of nitrogen as organic system, can enumerate：The phosphorus such as SP670, SP703 of four countries' chemical conversion industry (share) manufacture Ester amides compound, SPB100, SPE100 of big tomb chemical (share) manufacture, volt is shown in the FP- systems for making institute's (share) manufacture Phosphazene compounds such as row etc..As metal hydroxides, it can enumerate：Space portion material (Ube Material) (share) manufacture The magnesium hydroxides such as UD65, UD650, UD653, bar industry (share) manufacture B-30, B-325, B-315, B-308, B-303, Aluminium hydroxides such as UFH-20 etc..
The curable resin composition of the present invention can be by being dissolved in known solvent, and is used as circuit base material Varnish., can for not reacted with curable resin composition and there is good dissolubility as preferred solvent Enumerate：Toluene, dimethylbenzene, tetrahydrofuran, dioxolane.Furthermore, circuit base material of the invention is using the present invention Hardening thing, composite hardening thing or layered product manufacture.Specifically, it can enumerate：One side, two-sided or multilayer printing base Plate, flexible printing substrate, increasing layer substrate etc..
The hardening thing of the present invention is to make the curable resin composition hardening of the present invention and obtain.The form of hardening thing has no Limitation, may correspond to purposes and is used as article shaped, sandwich, pours casting material, bonding agent, film or film.For example, encapsulating semiconductor material The hardening thing of material, as the method for the hardening thing for obtaining the purposes, can be obtained in the following way to pour casting material or article shaped Obtain hardening thing：Curable resin composition is shaped using casting or metaideophone forming machine, emission forming machine etc., and then 80 DEG C~230 DEG C at heat 0.5 hour~10 hours.Additionally, it would be advantageous to which the hardening thing of circuit board use varnish is sandwich, make For the method for the hardening thing for obtaining the circuit board use varnish, first contain circuit board use varnish and be immersed in glass fibre, carbon In base material known to fiber, polyester fiber, Fypro, alumina fibre, paper etc., and it is thermally dried and is presoaked Body.The prepreg can be made to be stacked on one another or make the prepreg and copper foil etc. metal foil laminated and carry out hot forming and obtain Obtain the hardening thing of the circuit board use varnish.
In addition, by the inorganic high dielectric powder of allotment barium titanate etc. in the curable resin composition to the present invention, Or the inorganic magnetic body such as ferrite (ferrite), and have as electronic component material, particularly high-frequency electronic part material With.
In addition, identical with hardened composite described later, curable resin composition of the invention (can be included with metal foil The implication of metallic plate.It is same as below) fit or be coated in the metal foil to use.
In addition, the curable resin composition of the present invention containing being immersed in known base material by can be made into hardening and be combined Material.Hardening composite is a form of curable resin composition.By the way that hardening composite is made, for example, it can obtain Obtain high mechanical strength, the circuit base material of excellent in dimensional stability.
As the known base material used in hardening composite, woven roving can be individually used The various glass cloth, asbestos such as (roving cloth), cloth, chopped mat (chopped mat), surface felt (surfacing mat) Cloth, metal fiber cloth and other synthesis or natural inorfil cloth, it is fine by fully aromatic polyamide fiber, Wholly aromatic polyester What the liquid crystal fibers such as dimension, polybenzoxazole fibers were obtained weaves cotton cloth or adhesive-bonded fabric, by polyvinyl alcohol fibers, polyester fiber, third What the synthetic fibers such as olefin(e) acid fiber were obtained weaves cotton cloth or adhesive-bonded fabric, the natural fiber cloth such as cotton, burlap, felt, carbon cloth, ox Dry goods, the stationeries such as the natural fiber prime system cloth such as the mixed fine paper of mulberry paper, cotton paper, paper-glass etc., or and with two or more.
Base material ratio shared in hardening composite can be 5wt%~90wt%, preferably 10wt%~80wt%, More preferably 20wt%~70wt%.If base material is less than 5wt%, there is dimensional stability or intensity after the hardening of composite The tendency of decline.If in addition, base material is more than 90wt%, there is the tendency that the dielectric property of composite declines.In the present invention Hardening composite in, the cementability on interface in order to improve resin and base material, optionally can be used coupling agent.As Coupling agent, can be used the general coupling agents such as silane coupler, titanate coupling agent, aluminium system coupling agent, aluminum-zirconium coupling agent.
As the method for manufacturing the hardening composite, the method that can be for example listed below：Make the hardening of the present invention Property resin combination and other compositions optionally be equably dissolved or dispersed in the fragrant family, ketone system etc. solvent or its In mixed solvent, after impregnation in the substrate, it is dried.Impregnation is carried out by impregnating (dipping), coating etc..Impregnation is regarded Needing can also repeatedly, in addition, can also now use composition or the different a variety of solution of concentration to repeat to be impregnated with, finally Desired resin is adjusted to constitute and amount of resin.
The hardening composite hardening can be made to obtain composite hardening thing by using methods such as heating.It is described Composite hardening thing is a form of the hardening thing of the present invention.Its manufacture method is not particularly limited, for example can be hard by multi-disc The property changed composite superposition, thermmohardening is carried out while making each layers cementing under heating pressurization, and obtains desired thickness Composite hardening thing.Alternatively, it is also possible to the hardened composite and hardening composite wood by hardening be once bonded Material combines to obtain the composite hardening thing that new layer is constituted.It is cascading into shape generally to be entered simultaneously using hot pressing etc. with hardening OK, but it is also possible to separately carry out both.That is, it can be handled to make to enter in advance by heat treatment or using other method Row obtained unhardened or semi-harden composite hardening cascading into shape.
Shaping and hardening can be in temperature：80 DEG C~300 DEG C, pressure：0.1kg/cm2~1000kg/cm2, the time：1 minute~ The scope of 10 hours, more preferably temperature：150 DEG C~250 DEG C, pressure 1kg/cm2~500kg/cm2, the time：1 minute~5 hours In the range of carry out.
The layer and the layer of metal foil of hardening thing of the layered product of the present invention comprising the present invention.It is used as metal as used herein Paper tinsel, for example, can enumerate：Copper foil, aluminium foil etc..Its thickness is not particularly limited, but for 3 μm~200 μm, more preferably 3 μm~105 μm Scope.
As the method for the layered product of the manufacture present invention, the method that can be for example listed below：With the layer structure corresponding to purpose It is laminated into by the hardening thing or hardening composite with metal foil, while making each layers cementing under heating pressurization Carry out thermmohardening.In the layered product of the present invention, hardening thing or composite hardening thing are constituted with metal foil with arbitrary layer Stacking.Metal foil can be used as top layer, be also used as intermediate layer., can also be by stacking with hardening repeatedly in addition to described To carry out multiple stratification.
It is bonding with metal foil to use bonding agent.As bonding agent, can enumerate epoxy, acrylic acid series, phenol system, Cyanoacrylate system etc., but it is not particularly limited to these bonding agents.Described cascading into shape and hardening can be combined with described The manufacture of material hardening thing is carried out under the same conditions.
It is membranaceous alternatively, it is also possible to which the curable resin composition of the present invention is configured to.Its thickness is not particularly limited, but For 3 μm~200 μm, more preferably 5 μm~105 μm of scope.
As the method for manufacture film, it is not particularly limited, such as the method that can be listed below：Combine hardening resin Thing is equably dissolved or dispersed in the solvent of fragrant family, ketone system etc. or its mixed solvent with other compositions optionally, is applied Cloth on the resin films such as PET (Polyethylene terephthalate, PET) film after be dried. Coating optionally can also repeatedly, in addition, can also now use composition or the different a variety of solution of concentration to repeat to apply Cloth, final adjustment is constituted and amount of resin into desired resin.
There is the metal foil with resin of the present invention hardening resin by the present invention to combine on the one side of metal foil The film of thing formation.Person identical with the metal foil for constituting layered product of the invention can be used in metal foil as used herein.
As the method for the metal foil with resin of the manufacture present invention, it is not particularly limited, for example, can be listed below Method：Curable resin composition is set equably to be dissolved or dispersed in fragrant family, ketone system etc. with other compositions optionally In solvent or its mixed solvent, coating is dried afterwards on metal foil.Coating optionally can also repeatedly, in addition, this When composition or concentration different a variety of solution can also be used to repeat to be coated with, final adjustment is into desired resin composition and tree Fat amount.
[embodiment]
Hereinafter, the present invention is illustrated by embodiment, but the present invention is not limited by these embodiments.Furthermore, in each example Part be parts by weight.In addition, the measurement result in embodiment is to carry out sample preparation and measure using method as shown below Gained person.
1) structural analysis and constituent analysis of poly- (vinyl benzyl) ether compound
Utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) (eastern Cao's manufacture, HLC- 8120GPC, with solvent：Tetrahydrofuran (Tetrahydrofuran, THF), flow：1.0ml/mm, tubing string temperature：40 μ come real Apply), (forward position of Japanese PerkinElmer (PerkinElmer Japan) manufacture is golden (Frontier Gold) for infrared spectroscopic analysis Fourier transform infrared spectroscopy (Fourier Transform Infrared Spectroscopy, FTIR) system, KBr methods) and 1H- nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) analysis (the JNM-LA600 type nuclear-magnetisms of JEOL's manufacture Resonate light-dividing device, solvent：Chloroform-d1), carry out the confirmation and structural analysis of product.
In addition, passing through elementary analysis (automatic combustion-chromatography of ions, automatic combustion portion：The AQF- of Mitsubishi's chemical conversion manufacture 100, chromatography of ions portion：Sai Mo flies the ICS-1000 of your (Thermo Fisher) manufacture of generation) determine chloride content.In addition, Chloromethane as raw material is confirmed by gas chromatography (GC-2010 that Shimadzu Seisakusho Ltd. manufactures, hydrogen flame ionization detector) The presence of the non-reacted parts of base styrene.
2) tensile strength and elongation
The tensile strength and elongation (tension fracture elongation rate) of hardening thing film are, according to JIS K7161-1994, to use ten thousand Energy testing machine (Toyo Seiki is manufactured, this special Roger's pressgang (Strograph) VES05D) is measured.Elongation is set to breakaway poing Value between elongation divided by chuck obtained by distance.
3) evaluation of anti-flammability
(under thermogravimetric analysis (Thermal Gravimetric Analysis, TGA), stream of nitrogen gas, heated up using thermobalance Speed：10 DEG C/min), determine as the thermal decomposition initial temperature obtained by tangential method and the generation ratio of the carbide at 600 DEG C.
4) resistance to anti-thread breakage evaluation
By glass cloth, (E glass, weight per unit area is 71g/m2) be immersed in curable resin composition and contained Leaching, and the progress drying in 30 minutes in 50 DEG C of air -oven, and make prepreg.
On the prepreg, the copper foil of FR-4 substrates (thickness is 0.8mm) is fully being dissolved into removal using etching Base material two sides on, in the way of thickness after forming becomes about 0.6mm~1.0mm, be superimposed 8 prepregs, and The copper foil that thickness is 18 μm is placed on its two sides, using extrusion moulding machine, in 30kg/cm2, from room temperature with 3 DEG C/min heating, Under conditions of being kept for 60 minutes with 180 DEG C, hardening is formed and layered product is obtained.In order to be formed on the layered product obtained Circuit pattern (outer circuit is left to the shape of 2mm square), with 100 DEG C, 0.5m/min, pressure 0.5MPa condition will etch Resist (H-K425, the manufacture of chemical conversion industry limited company of Hitachi, trade name) is laminated on the copper face of layered product.Thereafter, It is exposed that (light exposure is 80mJ/cm across photomask2).Then, using the developer solution of the aqueous solution of sodium carbonate 1.0%, with 30 DEG C, pressure 0.1MPa, developing time developed within 60 seconds, and then resist peeled off using sodium hydrate aqueous solution, and done It is dry.Then, copper is etched using ferric chloride in aqueous solution and obtains the resistance to anti-thread breakage evaluation figure that outer circuit becomes 2mm square Case.
To the thermal cycling test of resistance to anti-thread breakage -55 DEG C~125 DEG C of the evaluation pattern generating sample implementation obtained in this way, Using the crackle of micro- sem observation easily in the insulating resin that the 2mm square corner of outer circuit is produced, and with until being formed Cyclic test number of times untill crackle is resistance to anti-thread breakage to evaluate.
Embodiment 1
SN495V is added into the four-hole boiling flask for possessing thermoregulator, agitating device, cooling condenser and addition funnel (the naphthols aralkyl resin of aurification company manufacture is lived by Nippon Steel；The OH equivalents of phenolic hydroxyl group are 232g/eq., phenolic hydroxyl group Methoxyl group modification amount：2.7%, the methoxyl content from terephthalyl alcohol dimethyl ether：N.D.) 195 parts, CMS-AM (clear U.S.s The 1-chloro-4-methyl-benzene of chemical (Seimi Chemical) company manufacture) 44 parts, 9.6 parts of four-normal-butyl of bromination ammonium, 2,4- dinitros 0.152 part of base phenol, 255 parts of methyl ethyl ketone simultaneously carry out stirring and dissolving, and liquid temperature is become into 75 DEG C, last 20 minutes and are added dropwise 50% 42 parts of sodium hydrate aqueous solution, and then persistently stirred 4 hours at 75 DEG C.Then, using 10% aqueous hydrochloric acid solution in flask After being neutralized, additional 400 parts of toluene, and cleaned organic layer 3 times using 1500ml water.
By being distilled to the organic phase obtained, and organic phase-change is concentrated into untill 460 parts, add methanol/water =75,/25 1,000 parts of (vol/vol) come make product carry out reprecipitation.By the reprecipitation of the same terms and then it is repeated 2 times.To institute The precipitation of the resin of acquisition carries out filtration drying, and obtains the conduct as SN495V and the reaction product of vinyl chloride 178.1 parts of the vinyl benzyl naphthols aralkyl resin (VBE25-SN495V) of poly- (vinyl benzyl) ether compound.
The confirmation of product is carried out by GPC, 1H NMR spectrum (1H-NMR), results verification is in GPC, in institute In the reaction product of recovery, the crest from raw material is disappeared, and new crest is generated in HMW side, in 1H-NMR, is derived from The resonance heading line off of the proton of 1-chloro-4-methyl-benzene, the resonance near 5.02ppm on the contrary with the proton from benzyl ether Line, the resonance line near 5.25ppm, 5.77ppm and 6.73ppm with the proton from vinyl has near 5.15ppm There is the resonance line of the proton from phenolic hydroxyl group, and confirm and obtain poly- (vinyl benzyl) ether compound (VBE25- SN495V).Moreover, equivalent to the R of formula (1)2Methyl content be 2.6 moles of %, vinyl benzyl content (that is, vinyl benzyl Base ether degree of modification) it is 25.4 moles of %, hydrogen atom is 72 moles of %.In addition, determining chloride content by elementary analysis, as a result For 140ppm.GC measure is carried out, the crest from 1-chloro-4-methyl-benzene is not as a result observed.In addition, using thermobalance (TGA), Under stream of nitrogen gas, with programming rate：10 DEG C/min determines thermal decomposition behavior, as a result originates temperature as the thermal decomposition obtained by tangential method Degree：Carbide growing amount at 346 DEG C, 600 DEG C is 41.8wt%.In addition, the average OR of every 1 molecule2The quantity of base is 10.
Embodiment 2
SN495V is added into the four-hole boiling flask for possessing thermoregulator, agitating device, cooling condenser and addition funnel 195 parts, 86.6 parts of CMS-AM, 9.6 parts of four-normal-butyl of bromination ammonium, 0.152 part of 2,4-DNP, methyl ethyl ketone 255 Part simultaneously carries out stirring and dissolving, and liquid temperature is become into 75 DEG C, lasts 20 minutes and 82.5 parts of 50% sodium hydrate aqueous solution, Jin Er is added dropwise Persistently stirred at 75 DEG C 4 hours.Then, using 10% aqueous hydrochloric acid solution to being neutralized in flask after, additional 400 parts of toluene, And cleaned organic layer 3 times using 1500ml water.
By being distilled to the organic phase obtained, and organic phase-change is concentrated into untill 440 parts, add methanol/water =75,/25 1,000 parts of (vol/vol) come make product carry out reprecipitation.By the reprecipitation of the same terms and then it is repeated 2 times.To institute The precipitation of the resin of acquisition carries out filtration drying, and obtains and be used as SN495V and the ethene of the reaction product of vinyl chloride Benzylation 202.5 parts of the naphthols aralkyl resin (VBE50-SN495V) of base.
The confirmation of product is carried out in the same manner as described, results verification disappears to the crest from raw material, in HMW side The new crest of generation, the resonance heading line off of the proton from 1-chloro-4-methyl-benzene has near 5.02ppm be derived from benzyl on the contrary The resonance line of the proton of ether, the resonance near 5.25ppm, 5.77ppm and 6.73ppm with the proton from vinyl Line, the resonance line near 5.15ppm with the proton from phenolic hydroxyl group, and confirm and obtain vinyl benzyl naphthols Aralkyl resin (VBE50-SN495V).Moreover, equivalent to the R of formula (1)2Methyl content be 2.6%, vinyl benzyl content For 50.2%, hydrogen atom is 47.2 moles of %.It is as a result 152ppm in addition, determining chloride content by elementary analysis.Carry out GC is determined, and the crest from 1-chloro-4-methyl-benzene is not as a result observed.In addition, thermal decomposition initial temperature：At 370 DEG C, 600 DEG C Carbide growing amount is 39.0wt%.In addition, the average OR of every 1 molecule2The quantity of base is 10.
Comparative example 1
SN495V is added into the four-hole boiling flask for possessing thermoregulator, agitating device, cooling condenser and addition funnel 195 parts, 160.1 parts of CMS-AM, 9.6 parts of four-normal-butyl of bromination ammonium, 0.152 part of 2,4-DNP, methyl ethyl ketone 255 Part simultaneously carries out stirring and dissolving, and liquid temperature is become into 75 DEG C, lasts 20 minutes and 160 parts of 50% sodium hydrate aqueous solution, Jin Er is added dropwise Persistently stirred at 75 DEG C 4 hours.Then, using 10% aqueous hydrochloric acid solution to being neutralized in flask after, additional 400 parts of toluene, And cleaned organic layer 3 times using 1500ml water.
By being distilled to the organic phase obtained, and organic phase-change is concentrated into untill 500 parts, add methanol/water =75,/25 1,000 parts of (vol/vol) come make product carry out reprecipitation.By the reprecipitation of the same terms and then it is repeated 2 times.To institute The precipitation of the resin of acquisition carries out filtration drying, and obtains the conduct as SN495V and the reaction product of vinyl chloride 246.7 parts of the vinyl benzyl naphthols aralkyl resin (VBE-SN495V) of poly- (vinyl benzyl) ether compound.
The confirmation of product is carried out, results verification is disappeared to the crest from raw material, and new crest is generated in HMW side, Phenolic hydroxyl group disappears, the resonance heading line off of the proton from 1-chloro-4-methyl-benzene, has near 5.02ppm be derived from benzyl on the contrary The resonance line of the proton of ether, the resonance near 5.25ppm, 5.77ppm and 6.73ppm with the proton from vinyl Line, and confirm and obtain VBE-SN495V.Moreover, equivalent to the R of formula (1)2Methyl content be 2.6%, vinyl benzyl Content is 97.4%, and hydrogen atom is 0 mole of %.I.e., it is impossible to detect phenolic hydroxyl group.In addition, chloride content is 167ppm.Do not see Observe the crest from 1-chloro-4-methyl-benzene.In addition, utilizing differential scanning calorimetry (Differential Scanning Calorimeter, DSC), under stream of nitrogen gas, with programming rate：10 DEG C/min determines hot phase in version behavior, does not as a result observe To the melting crest from crystallization, initial temperature is thermally decomposed：Carbide growing amount at 402 DEG C, 600 DEG C is 36.1wt%.
Embodiment 5
SN495V is added into the four-hole boiling flask for possessing thermoregulator, agitating device, cooling condenser and addition funnel 195 parts, 30.5 parts of CMS-AM, 9.6 parts of four-normal-butyl of bromination ammonium, 0.152 part of 2,4-DNP, methyl ethyl ketone 255 Part simultaneously carries out stirring and dissolving, and liquid temperature is become into 75 DEG C, lasts 20 minutes and 42 parts of 50% sodium hydrate aqueous solution is added dropwise, and then 75 Persistently stirred at DEG C 4 hours.Then, using 10% aqueous hydrochloric acid solution to being neutralized in flask after, additional 400 parts of toluene, and Organic layer is cleaned 3 times using 1500ml water.
By being distilled to the organic phase obtained, and organic phase-change is concentrated into untill 460 parts, add methanol/water 1,000 part of=75/25 (vol/vol) makes the product carry out reprecipitation.By the reprecipitation of the same terms and then it is repeated 2 times.To institute The precipitation of the resin of acquisition carries out filtration drying, and obtains and be used as SN495V and the ethene of the reaction product of vinyl chloride Benzylation 270.0 parts of the naphthols aralkyl resin (VBE15-SN495V) of base.
The confirmation of product is carried out in the same manner as described, results verification disappears to the crest from raw material, in HMW side The new crest of generation, the resonance heading line off of the proton from 1-chloro-4-methyl-benzene has near 5.02ppm be derived from benzyl on the contrary The resonance line of the proton of ether, the resonance near 5.25ppm, 5.77ppm and 6.73ppm with the proton from vinyl Line, the resonance line near 5.15ppm with the proton from phenolic hydroxyl group, and confirm and obtain vinyl benzyl naphthols Aralkyl resin (VBE15-SN495V).Moreover, equivalent to the R of formula (1)2Methyl content be 2.6%, vinyl benzyl content For 15.0%, hydrogen atom is 82.4 moles of %.It is as a result 121ppm in addition, determining chloride content by elementary analysis.Carry out GC is determined, and the crest from 1-chloro-4-methyl-benzene is not as a result observed.In addition, thermal decomposition initial temperature：At 340 DEG C, 600 DEG C Carbide growing amount is 42.6wt%.In addition, the average OR of every 1 molecule2The quantity of base is 10.
Embodiment 7
1- naphthols 288g, 1,5- dichloromethyls naphthalene (1,5- dichloromethane matrix are weighed in 1L four mouthfuls of detachable flasks 95.6%, other dichloromethane matrixes 3.0%, monochloro methyl body 1.4%) 135g and toluene 840g, under stream of nitrogen gas, simultaneously enter Row stirs one side slowly rising temperature for dissolving, is reacted 2 hours at about 116 DEG C when directly being flowed back.Thereafter, simultaneously evaporate Go toluene one side be warming up to 180 DEG C untill, and in this condition react 1 hour.After reaction, evaporated at 200 DEG C by decompression Go to remove after unreacted 1- naphthols and solvent, obtain the resin 224g (multi-hydroxy Resin A) of brown.The polynary hydroxyl obtained The hydroxyl equivalent of base Resin A is 230g/eq..
Polynary hydroxyl is added into the four-hole boiling flask for possessing thermoregulator, agitating device, cooling condenser and addition funnel 195 parts of base Resin A, 44 parts of CMS-AM (1-chloro-4-methyl-benzene of clear beautification company manufacture), four-normal-butyl of bromination ammonium 9.6 Part, 0.152 part of 2,4-DNP, 255 parts of methyl ethyl ketone simultaneously carry out stirring and dissolving, and liquid temperature is become into 75 DEG C, 20 are lasted 42 parts of 50% sodium hydrate aqueous solution is added dropwise in minute, and then is persistently stirred 4 hours at 75 DEG C.Then, 10% hydrochloric acid water is utilized After solution in flask to neutralizing, additional 400 parts of toluene, and cleaned organic layer 3 times using 1500ml water.
By being distilled to the organic phase obtained, and organic phase-change is concentrated into untill 460 parts, add methanol/water =75,/25 1,000 parts of (vol/vol) come make product carry out reprecipitation.By the reprecipitation of the same terms and then it is repeated 2 times.To institute The precipitation of the resin of acquisition carries out filtration drying, and obtains and produced as the reaction of multi-hydroxy Resin A and vinyl chloride The vinyl benzyl naphthol resin (VBE25- multi-hydroxies Resin A) as poly- (vinyl benzyl) ether compound of thing 198.1 part.
The confirmation of product is carried out, results verification is disappeared to the crest from raw material, and new crest is generated in HMW side, Phenolic hydroxyl group disappears, the resonance heading line off of the proton from 1-chloro-4-methyl-benzene, has near 5.02ppm be derived from benzyl on the contrary The resonance line of the proton of ether, the resonance near 5.25ppm, 5.77ppm and 6.73ppm with the proton from vinyl Line, and confirm and obtain VBE- multi-hydroxy Resin As.Moreover, equivalent to the R of formula (1)2Vinyl benzyl content be 25.2%, hydrogen atom is 74.8 moles of %.In addition, chloride content is 138ppm.Not it was observed that the ripple from 1-chloro-4-methyl-benzene Peak.
Following presentation contracted notation.
YDCN-700-3：(aurification (share) manufacture, Albert are lived to cresol novolak type epoxy resin by Nippon Steel (Epotohto)YDCN-700-3)
MEH-7851-S：Biphenyl type phenol resol resins (bright and chemical conversion company manufacture, MEH-7851-S)
XD-1000：Dicyclopentadiene-type epoxy resin (Japanese chemical drug company system is made)
A1535：Hydrogenated styrene butadiene block copolymer (day undergraduate course rise polymer (Kraton Polymer Japan) (share) is manufactured, and (KRATON) A1535, Mw=223,000 rises in section)
Handkerchief storehouse Mill (Percumyl) D：Dicumyl peroxide (You companies manufacture, handkerchief storehouse Mill (Percumyl) D)
AO-60：Pentaerythrite four [3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester] (Ai Dike (Adeka) (stock Part) manufacture, Ai Di Coase tower ripple (Adekastab) AO-60)
SE2050SPE：Amorphous spherical silicon dioxide (the refined all agates handled using phenyl silane coupling agent (Admatechs) company manufactures, SE2050SPE, and average grain diameter is 0.5 μm)
Embodiment 3
Make YDCN-700-3,5g as epoxy resin of VBE25-SN495V, 5g obtained in 40g embodiment 1 MEH-7851-S, 50g as phenol resin A1535,1.0g as thermoplastic elastomer (TPE) as polymerization initiator Handkerchief storehouse Mill (Percumyl) D, 0.4g triphenylphosphine (Triphenylphosphine, TPP) as hardening accelerator, 0.2g's is dissolved in 82.8g dimethylbenzene as the AO-60 of antioxidant, and obtains curable resin composition (varnish A).
By prepared varnish A coatings on a pet film and with 80 DEG C of progress solvent removals, stripped after drying from PET film Film, carries out vacuum pressed extruding in 1 hour to separated casting film under conditions of 180 DEG C, 3MPa, makes its thermmohardening, and obtains Obtain hardening thing film.Various characteristics are determined to the varnish A and hardening thing film obtained.
Embodiment 4, embodiment 6
Divided by the formula shown in table 1 is prepared beyond varnish, tested with condition same as Example 3.
In table 1, in the case of the record without unit, the allotment amount of allotment composition is wt%.In addition, blank represents to be free of The composition.Result of the test is shown in Table 2.
Comparative example 2, comparative example 3
Divided by the formula shown in table 1 is prepared beyond varnish, varnish is prepared with condition same as Example 3, and carry out Experiment.Result of the test is shown in Table 2.
[table 1]
[table 2]
Comparative example 2 Embodiment 3 Embodiment 4 Comparative example 3 Embodiment 6
Carbide generation ratio [%] 31.8 43.3 40.1 36.9 44.5
Tensile strength [MPa] 10.6 14.6 18.5 23.6 12.9
Tension fracture elongation rate [%] 20.6 17.3 14.6 9.6 18.5
Resistance to anti-thread breakage [circulation] ＞ 1000 ＞ 1000 ＞ 1000 300~500 ＞ 1000

Claims (12)

1. a kind of poly- (vinyl benzyl) ether compound, it is represented by following formula (1),
Herein, R1Separately represent the aryl of hydrogen atom, the alkyl of carbon number 1~6, pi-allyl or carbon number 6~10, Ar1Table Show the aromatic hydrocarbyl of the divalence of carbon number 6~50, R2Separately represent hydrogen atom, the alkyl or vinyl of carbon number 1~12 Benzyl；Wherein, R2In vinyl benzyl ratio for 10 moles of more than %, less than 60 moles of %, the ratio of hydrogen atom is 40 Mole more than %；N is calculated as 1~20 scope with average value, and m is 1~6 number, and r is 1~3 number, but m+r is no more than 6 or 7.
2. poly- (vinyl benzyl) ether compound according to claim 1, wherein poly- (vinyl benzyl) etherificate is closed Thing is to make the R in formula (1)2For hydrogen atom or the naphthols aralkyl resin and vinyl aromatic (co) of hydrogen atom and the alkyl of carbon number 1~12 Fragrant race's halomethyl compounds, which are reacted, to be obtained.
3. poly- (vinyl benzyl) ether compound according to claim 1 or 2, wherein in the formula (1), in 1 molecule In there is the R of more than 12For hydrogen atom or the OR of vinyl benzyl2Base (Y), and the average OR of every 1 molecule2The number of base (Y) Measure as more than 1.1.
4. a kind of curable resin composition, it includes：
(A) composition, poly- (vinyl benzyl) ether compound according to any one of claim 1 to 3；And
(B) composition, having in 1 molecule in the epoxy radicals of more than 2 and the epoxy resin of aromatic structure, 1 molecule has 2 There is epoxy radicals and the alicyclic structure of more than 2 in the epoxy resin and 1 molecule of epoxy radicals and cyanurate structure more than individual At least one of epoxy resin epoxy resin.
5. curable resin composition according to claim 4, itself so that including epoxy resin hardener as (C) into Point.
6. a kind of hardening thing, it makes the curable resin composition according to claim 4 or 5 harden and be formed.
7. a kind of hardening composite, it includes the curable resin composition and base material according to claim 4 or 5.
8. a kind of metal foil with resin, it has as the hardening according to claim 4 or 5 on the one side of metal foil Property resin combination formation film.
9. a kind of layered product, it is characterised in that：Layer and metal foil layer including hardening thing according to claim 6.
10. a kind of circuit base material, it is formed using hardening thing according to claim 6.
11. a kind of varnish, it makes the curable resin composition dissolving according to claim 4 or 5 be formed in a solvent.
12. varnish according to claim 11, it is used for circuit base material.
CN201710105917.1A 2016-03-01 2017-02-24 Poly- (vinyl benzyl) ether compound and its purposes Pending CN107141447A (en)

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