CN107400198A

CN107400198A - Composition epoxy resin and its hardening thing

Info

Publication number: CN107400198A
Application number: CN201710360852.5A
Authority: CN
Inventors: 高岛智行; 石原男; 石原一男; 宗正浩
Original assignee: Nippon Steel Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2016-05-20
Filing date: 2017-05-18
Publication date: 2017-11-28
Anticipated expiration: 2037-05-18
Also published as: JP2017206641A; CN107400198B; KR102351752B1; JP6924000B2; KR20170131267A; TW201809130A; TWI724167B

Abstract

The present invention provides a kind of with excellent performances such as heat resistance, dielectric property, adhesion properties, useful composition epoxy resin and its hardening thing in the purposes such as stacking, shaping, casting, bonding.The composition epoxy resin, contain epoxy resin (A) and curing agent (B), the epoxy resin (a) for the Han oxazolidine ketone rings that epoxy resin (A) obtains containing the epoxy resin (c) represented by following formula (1) and isocyanate compound (d), curing agent (B) contain the bisphenol compound (b1) represented by following formula (2) and the novolac phenol compound (b2) represented by following formula (3).X¹、X²For with cycloalkylidene of the alkyl as ring person's number 5~8 of substituent, A¹For phenyl ring, naphthalene nucleus or cyclohexyl biphenyl, T is the crosslinking groups such as methylene [changing 1].

Description

Composition epoxy resin and its hardening thing

Technical field

The present invention relates to a kind of epoxy for obtaining the excellent hardening thing such as low dielectric property, high-fire resistance, high adhesiveness Resin combination and its hardening thing.

Background technology

Because the progressive exception of electric/electronic device is notable, particularly communication equipment is carried out at the high-capacity and high-speed of data Reason, thus be accordingly used in low-k, the low-dielectric loss tangent of the electronic device members such as these printed wiring board, sealing material Requirement etc. dielectric property is increasingly strong.In addition, the distribution of metal foil ensures bonding force by the roughening of bonding plane, but in order to High speed processing, it is necessary to suppress to be roughened and maintain the problem of bonding force it is also apparent that in the presence of.

The portable set of one of purposes as printed wiring board or maintain the infrastructure equipments such as its base station with Information content increase tremendous in recent years, it has been required to the requirement of multifunction.In a portable device, mesh is turned to small-sized And carry out high multiple stratification or fine distribution, in order that substrate thinner and need the material of lower dielectric constant, due to fine Distribution and reduce bonding plane, it is therefore desirable to the material of more high adhesiveness.In the substrate towards base station, in order to suppress high frequency letter Number decay, it is necessary to the more material of low-dielectric loss tangent.

The characteristics such as low-k, low-dielectric loss tangent and high bonding force are largely derived from and are used as printed wiring base The epoxy resin of the matrix resin of plate and the structure of curing agent.

Known composition epoxy resin hardened caused by hydroxyl deteriorate dielectric constant.Set as what hydroxyl tailed off One of meter, being disclosed in patent document 1 has the containing and Sheng Cheng oxazolidone rings by the reaction of epoxy resin and isocyanates The epoxy resin of oxazolidone ring.As raw material epoxy resin, glycidyl is carried out exemplified with to dihydric phenols such as bisphenol-As Compound, three (glycidoxypropyl phenyl) alkanes or para-aminophenol etc. carry out compound etc. of glycidyl, Or the novolaks such as Pyrogentisinic Acid's novolaks class carries out the compound of glycidyl.However, in disclosed epoxy resin And insufficient requirement for meeting the dielectric property based on multifunction in recent years, cementability are also insufficient.

As the ameliorative way of the dielectric property of epoxy resin, such as Clausius-Mosso base of a fruit (Clausius-Mossotti) Formula shown in as, the effectively reduction of mole polarizability and the increase of molal volume.As application, the molal volume increases Effect curing agent, in patent document 2 disclose have dicyclopentadiene phenol resin.Being disclosed in patent document 3 has 4, The cycloalkylidene bisphenols containing substituent such as 4 '-(3,3,5- trimethylcyclohexylene) bis-phenols, but taking off independent of dielectric property Show.

On the other hand, being disclosed in patent document 4, patent document 5 has aromatic modified phenol novolacs as hardening Agent, although heat resistance, dielectric property etc. are excellent, the problem of bonding force is easily insufficient be present.

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 5-43655 publications

[patent document 2] Japanese Patent Laid 2015-535865 publications

[patent document 3] Japanese Patent Laid-Open 2-229181 publications

[patent document 4] Japanese Patent Laid-Open 2010-235819 publications

[patent document 5] Japanese Patent Laid-Open 2012-57079 publications

The content of the invention

[inventing problem to be solved]

Therefore, the problem of the invention to be solved is to provide with the excellent property of low-dielectric, high-fire resistance, high adhesiveness Can, and composition epoxy resin and its hardening thing useful in the purposes such as stacking, shaping, casting, bonding.Additionally, it is provided i.e. Make in the case where allocating fire retardant, also do not make the characteristics such as dielectricity, heat resistance, cementability that there is well fire-retardant with deteriorating The composition epoxy resin and its hardening thing of property.

[technological means for solving problem]

In order to solve the problem, the present inventor has carried out making great efforts to grind to low-k, low-dielectric loss tangent material Study carefully, as a result find, will make that there is the epoxy resin of specific structure to be reacted and the Han oxazolidines of gained with isocyanate compound The epoxy resin of ketone ring (oxazolidone ring) and and with specific bisphenol compound and specific novolac phenol The composition epoxy resin of the hardener combination of compound realizes unexistent low-k, low-dielectric loss tangent now simultaneously With high glass-transition temperature, and then bonding force is also good, so as to complete the present invention.In addition, it is found that even if with fire retardant simultaneously With, do not make yet the characteristics such as dielectricity, heat resistance, cementability deteriorate play excellent anti-flammability.

That is, the present invention is a kind of composition epoxy resin, and it contains epoxy resin (A) and curing agent (B), the asphalt mixtures modified by epoxy resin Oil/fat composition is characterised by：Epoxy resin (A) contains the epoxy resin (c) and isocyanation esterification represented by following formula (1) The epoxy resin (a) of compound (d) and the Han oxazolidine ketone rings of acquisition, curing agent (B) contain the bis-phenol represented by following formula (2) Compound (b1) and the novolac phenol compound (b2) represented by following formula (3).

[changing 1]

In formula, X¹Represent sub- cycloalkanes of the alkyl with least one carbon number 1~20 as ring person's number 5~8 of substituent Base (cycloalkylidene).R¹Separately represent hydrogen atom, halogen atom, carbon number 1~20 halogenation alkyl or can Alkyl with heteroatomic carbon number 1~20.G represents glycidyl.N represents repeat number, and average value is 0~5.

[changing 2]

In formula, X²Represent sub- cycloalkanes of the alkyl with least one carbon number 1~20 as ring person's number 5~8 of substituent Base.R²Separately represent hydrogen atom, halogen atom, carbon number 1~20 halogenation alkyl or can have heteroatomic carbon number 1 ~20 alkyl.

[changing 3]

In formula, A¹Separately represent the aromatic series ring group in phenyl ring, naphthalene nucleus or cyclohexyl biphenyl, these aromatic series Ring group also can with can the alkyl with heteroatomic carbon number 1~49 as substituent, be averagely selected from 0.1~2.5 The aryl of carbon number 6~48, the aryloxy group of carbon number 6~48, the aralkyl of carbon number 7~49 and carbon number 7~49 aralkoxy in Substituent.Times of divalence crosslinking group represented by T expression bivalent aliphatic cyclic hydrocarbon groups or following formula (3a) or following formula (3b) One.K represents 1 or 2.M represents repeat number, and average value is more than 1.5.

[changing 4]

In formula, R³And R⁴Separately represent hydrogen atom or there can be the alkyl of heteroatomic carbon number 1~20.R⁵And R⁶ Separately represent the alkyl of hydrogen atom or carbon number 1~6.A²Represent the aromatic ring in phenyl ring, naphthalene nucleus or cyclohexyl biphenyl Base, these aromatic series ring groups also can with can the alkyl with heteroatomic carbon number 1~20 as substituent.

In the composition epoxy resin, preferred aspects of the invention are to meet more than any one following.

1) scope that bisphenol compound (b1) and the mass ratio of novolac phenol compound (b2) are 5/95~95/5,

2) bisphenol compound (b1) is 4,4 '-(3,3,5- trimethylcyclohexylene) bis-phenols or 4,4 '-(3,3,5,5- tetramethyls Base cyclohexylidene) bis-phenol,

3) novolac phenol compound (b2) is the oxybenzene compound represented by following formula (4), or

4) rubbed relative to 1 mole of the epoxy radicals of epoxy resin (A), the active hydrogen-based of curing agent (B) for 0.2 mole~1.5 You.

[changing 5]

In formula, R⁷Separately represent the alkyl of carbon number 1~6, R⁸For the substituent represented by following formula (4a).P's is flat It is identical with the m implications of formula (3) that average is that 0.1~2.5, q is that 0~2, p+q with average value is calculated as 0.1~3, m.

[changing 6]

In formula, R⁹、R¹⁰And R¹¹Separately represent the alkyl of hydrogen atom or carbon number 1~6.

In addition, the present invention is the epoxy cure thing for forming composition epoxy resin hardening.

[The effect of invention]

The composition epoxy resin of the present invention provides the bonding force for remaining good, and the hardening that glass transition temperature is high Thing.And then the dielectric property of hardening thing of the invention is also excellent, the electronics of low-k, low-dielectric loss tangent is being required Good characteristic is played in material applications.

Embodiment

Hereinafter, embodiments of the present invention are described in detail.

The composition epoxy resin of the present invention contains epoxy resin (A) and curing agent (B).Epoxy resin (A) contains The epoxy resin (a) of oxazolidone ring is as required composition.Curing agent (B) includes bisphenol compound (b1) and novolac phenol Compound (b2) is as required composition.

The epoxide equivalent (g/eq.) of the epoxy resin (a) of Han oxazolidine ketone rings is preferably 200~1000, more preferably 220~700, and then preferably 230~500, particularly preferably 250~400.If epoxide equivalent is low, in the presence of following worry： The content of oxazolidone ring tails off, and the hydroxyl concentration in hardening thing uprises, therefore dielectric constant uprises.In addition, if epoxy is worked as Amount is high, then in the presence of following worry：Content necessity of oxazolidone ring becomes more with Shangdi, due to the raising effect of dielectric property, The harmful effects such as solvent solubility deteriorates or resin viscosity increases become more.It additionally, there are following worry：The crosslinking of hardening thing is close Step-down, therefore modulus of elasticity reduction etc. at a temperature of Reflow Soldering are spent, is turning into problem using upper.

In addition, situation of the softening point of the epoxy resin (a) of Han oxazolidine ketone rings in for prepreg or membrane material Under, preferably 50 DEG C~150 DEG C, more preferably 60 DEG C~135 DEG C, and then preferably 70 DEG C~110 DEG C.If softening point is low, In the presence of following worry：Resin varnish is contained after being immersed in glass cloth, when being thermally dried in an oven, because viscosity is low, Therefore the adhesion amount of resin tails off.If softening point is high, in the presence of following worry：Resin viscosity uprises, containing in prepreg Leaching property deteriorates, or solvent solubility deteriorates, or dilutes in heat drying solvent and non-volatile and remain in resin, therefore Space etc. is produced when plywood is made, is turning into problem using upper.

The epoxy resin (a) of Han oxazolidine ketone rings using the epoxy resin of Han oxazolidines ketone ring described later manufacture Method advantageously obtains, but generally obtains the epoxy resin of the Han oxazolidine ketone rings comprising accessory substance etc..Herein, accessory substance Etc. the implication that may be interpreted as including unreacted reactant.The epoxy resin (a) of Han oxazolidine ketone rings is alternatively comprising the accessory substance etc. Reaction product.

Epoxy resin (c) and isocyanates of the epoxy resin (a) of Han oxazolidine ketone rings represented by by the formula (1) The reaction of compound (d) and obtain.In the reaction, epoxy radicals is reacted and Sheng Cheng oxazolidone rings with NCO.Typical case For, in the case of using the epoxy resin and isocyanate compound of two functions together, turn into as shown in following formula Construction unit person.

-E¹-O-CH₂-Ox¹-Ic¹-Ox¹-CH₂-O-

Herein, E¹For the residue formed from epoxy resin removal glycidyl ether, Ox¹Wei oxazolidone rings, Ic¹For certainly Isocyanates removes the residue that NCO forms.

In formula (1), R¹Separately represent hydrogen atom, halogen atom, carbon number 1~20 halogenation alkyl or can have The alkyl of heteroatomic carbon number 1~20.

In this specification, it can be that a part for alkyl or the carbon for forming alkyl is set into miscellaneous original that can have heteroatomic alkyl Son contains heteroatomic alkyl.It is that a part for the carbon for forming hydrocarbon chain or hydrocarbon ring is set to hetero atom containing heteroatomic alkyl Person, in the case of hydrocarbon chain, end can be may be alternatively located at positioned at centre.As hetero atom, there are oxygen atom, nitrogen-atoms, sulphur atom etc., Preferably oxygen atom.Hetero atom be oxygen atom, its be located at end, in the case that alkyl is alkyl, aryl or aralkyl, can be into For alkoxy, aryloxy group or aralkoxy.In addition, hetero atom can be located in the substituent as hydroxyl.

As halogen atom, can enumerate：Fluorine, chlorine, bromine, iodine.

Halogenation alkyl as carbon number 1~20, it is preferable to enumerate carbon number 1~20, preferably 1~6 halogenated alkyl.

Can be straight-chain, branch's chain state, preferably ring-type, carbon number as the alkyl can with heteroatomic carbon number 1~20 The aromatic hydrocarbyl of 1~20 aliphatic alkyl, the alicyclic alkyl of carbon number 3~20 or carbon number 6~20, more preferably carbon number 1 ~8 alkyl, the alkoxy of carbon number 1~8, the cycloalkyl of carbon number 5~8, the cycloalkyloxy of carbon number 5~8, the virtue of carbon number 6~14 Base, the aryloxy group of carbon number 6~14, the aralkoxy of the aralkyl of carbon number 7~15 or carbon number 7~15.These can be by one of carbon It is divided into hetero atom.

For example, alkyl or alkoxy as carbon number 1~8, can be enumerated：Methyl, ethyl, propyl group, isopropyl, normal-butyl, The tert-butyl group, hexyl, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, tert-butoxy, hexyloxy etc., as carbon number 5~8 cycloalkyl or cycloalkyloxy, can enumerate cyclohexyl, cyclohexyloxy etc., can as the aryl or aryloxy group of carbon number 6~14 Enumerate：Phenyl, tolyl, ortho-xylene base, naphthyl, dihydro indenyl, phenoxy group, naphthoxy etc., the aralkyl as carbon number 7~15 Base or aralkoxy, it can enumerate：Benzyl, phenethyl, 1- phenylethyls, naphthyl methyl, anthrylmethyl, benzyloxy, naphthyl methoxy Base, anthryl methoxyl group etc., but these are not limited to, it may be the same or different respectively.

In the case where needing anti-flammability, it is however preferred to have the halogenation alkyl of halogen atom or carbon number 1~20 is as substitution Base, halogen atom are preferably bromine atoms.As the halogenation alkyl of carbon number 1~20, Diethylaminoethyl etc. can be enumerated.Wherein, aftermentioned Non-halogen flame-retardant epoxy resin omposition in the case of, not comprising the substituent with such a halogen atom.

For the easiness of acquisition and the viewpoint of hardening thing physical property, preferable R¹For hydrogen atom, methyl, methoxyl group, benzene Base, benzyl, 1- phenylethyls or phenoxy group.R¹The position of substitution relative to X¹For the carbon atom of bond for ortho position, contraposition, Any one of meta, preferably ortho position or contraposition, more preferably ortho position.

In formula (1), X¹For the cycloalkylidene of ring person's number 5~8, and the alkyl with least one carbon number 1~20 is as taking Dai Ji.The cycloalkanes hydrocarbon ring for forming cycloalkylidene is any one of pentamethylene ring, cyclohexane ring, cycloheptane ring or cyclooctane ring, excellent Elect pentamethylene ring or cyclohexane ring as.

For the viewpoint of dielectric property, the alkyl as the carbon number 1~20 of substituent is preferably the big structure of molecular weight, And the preferably aralkyl of the alkyl of carbon number 1~8, the cycloalkyl of carbon number 5~8, the aryl of carbon number 6~14 or carbon number 7~15. For example, the alkyl as carbon number 1~8, can be enumerated：Methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, hexyl etc., make For the cycloalkyl of carbon number 5~8, cyclohexyl etc. can be enumerated, as the aryl of carbon number 6~14, can be enumerated：Phenyl, tolyl, neighbour two Tolyl, naphthyl etc., as the aralkyl of carbon number 7~15, it can enumerate：Benzyl, phenethyl, 1- phenylethyls etc., but it is and unlimited Due to these, exist it is multiple in the case of, may be the same or different respectively.The sight of easiness and hardening thing physical property with regard to acquisition For point, preferable substituent is the alkyl or phenyl of carbon number 1~3, more preferably methyl.

In addition, cycloalkylidene is 1,1- cycloalkylidenes, the substituent due to the bond of the carbon of 1 with cycloalkylidene two The three-dimensional repulsion that individual phenyl ring or substituent act on each other acts on and limits the motility of cycloalkane ring, so that dielectric property Improve, while heat resistance also improves.The position of substitution can be then bonded at an arbitrary position if the position that can limit motility, But be preferably bond with the 1 of cycloalkylidene close carbon atom.The position of preferable substituent is 2 in pentamethylene ring Position or the carbon atom of 5.The carbon atom for being 2,3,5 or 6 in cyclohexane ring, the carbon of more preferably 2 or 6 are former Son.The carbon atom for being 2,3,6 or 7 in cycloheptane ring, the carbon atom of more preferably 2 or 7.In cyclooctane ring In be the carbon atom of 2,3,4,6,7 or 8, the carbon atom of more preferably 2,3,7 or 8, Jin Eryou Elect the carbon atom of 2 or 8 as.Wherein, due to the influence of the steric hindrance with adjacent phenyl ring, also exist and be difficult to closest to 1 Carbon atom situation about being substituted, in this case, substituent is adapted to bond on the second near carbon atom.For example, In cyclohexane ring, for the carbon atom of 2 or 6 closest to 1, but due to steric hindrance and in the case of being difficult to substitute, substituent can To be bonded on second near 3 or 5.

In addition, the number of substituent needs at least one, but just heat resistance as hardening thing etc. due to the reason For the viewpoint of physical property, preferably more than three, more preferably three.

In formula (1), n is repeat number, and its average value (number is average) is 0~5, preferably 0~3, more preferably 0~1, is entered And preferably 0~0.5, most preferably 0.Can be the single compound for any one integer that repeat number is 0~5, or n is 0 The mixture of multiple integers in~5.

The epoxide equivalent of epoxy resin (c) is preferably 100~500, and more preferably 125~400, and then preferably 150~ 300.In addition, alcohol hydroxyl group equivalent (g/eq.) is preferably more than 3000, more preferably more than 4000, and then preferably 5000 with On.Alcohol hydroxyl group generates amino-formate bond by being reacted with isocyanates, makes the glass transition point of hardening thing reduce, because This alcohol hydroxyl group equivalent is small without preferred.In addition, the hydroxyl concentration increase in hardening thing, therefore become the dielectric constant of hardening thing Height, thus it is also not preferred.

As epoxy resin (c), the bisphenol compound and table containing cycloalkylidene represented by the formula (2) can be enumerated The epoxy resin that halogenohydrin is obtained.Such as it can enumerate：4,4 '-(2- methylcyclohexylidenes) bis-phenol glycidol ethers, 4,4 '-(3- Methylcyclohexylidene) bis-phenol glycidol ether, 4,4 '-(4- methylcyclohexylidenes) bis-phenol glycidol ethers, 4,4 '-(3,3,5- Trimethylcyclohexylene) bis-phenol glycidol ether, 4,4 '-(3,3,5- trimethylcyclohexylene)-bis--phenylphenol glycidol Ether, 4,4 '-(3,3,5- trimethylcyclohexylene)-bis--xylenol glycidol ether, 4,4 '-(3,3,5- trimethyl Asia rings Hexyl)-bis--tert-butyl phenol glycidol ether etc., but be not limited to these, can be used alone, also can and with two or more.

For the easiness of acquisition and the formedness of hardening thing physical property, epoxy resin (c) be preferably by 4,4 '-(3,3, 5- trimethylcyclohexylenes) epoxy resin (c1) represented by the following formula (5) that is obtained of bis-phenol and epihalohydrins.In addition, formula (5) Middle n is identical with the n implications of formula (1).

[changing 7]

During the epoxy resin (a) of the manufacture ring of ketone containing oxazolidine, epoxy resin (c) and isocyanates chemical combination can be passed through The reaction of thing (d) and obtain the epoxy resin of desired Han oxazolidines ketone ring.As long as the isocyanate compound (d) be One intramolecular has the isocyanate compound of average more than 1.8 NCOs (- N=C=O), is essentially two officials Polyfunctional isocyanate compound more than energy, known usual isocyanate compound can be used.It can also wrap on a small quantity Compound containing monofunctional isocyanates, but it turns into terminal groups, therefore in the purpose for reducing the degree of polymerization effectively, but the degree of polymerization Do not uprise.

Specifically, can enumerate：2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, 3,5- toluene diisocyanates Acid esters, 2,2 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate, 4,4 '-diphenyl methane two are different Cyanate, m xylene diisocyanate, paraxylene diisocyanate, tetramethylxylene diisocyanate, Isosorbide-5-Nitrae-naphthalene two Group diisocyanate, 1,5- naphthalene-diyls diisocyanate, 2,6- naphthalene-diyls diisocyanate, 2,7- naphthalene-diyls diisocyanate, Double (methylene) diisocyanate of naphthalene-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl double (methylene) diisocyanate, the isocyanic acids of isophthalic two Ester, PPDI, biphenyl -4,4 '-diisocyanate, 3,3 '-dimethyl diphenyl -4,4 '-diisocyanate, 2,3 ' - Dimethoxy-biphenyl -4,4 '-diisocyanate, diphenyl methane -4,4 '-diisocyanate, 3,3 '-dimethoxydiphenyl first Alkane -4,4 '-diisocyanate, 4,4 '-dimethoxydiphenyl methane -3,3 '-diisocyanate, sulfurous diphenyl phthalate -4,4 ' - Diisocyanate, diphenyl sulfone -4,4 '-diisocyanate, the bicyclic isocyanic acid of [2.2.1] heptane -2,5- diyl dimethylene two Ester, bicyclic [2.2.1] heptane -2,6- diyl dimethylene diisocyanate, IPDI, 4,4 '-methylene Double (isocyanatomethyl) hexamethylenes of biscyclohexyl diisocyanate, lysine diisocyanate, 1,1-, the double (isocyanic acids of 1,2- METH) hexamethylene, 1,3- double (isocyanatomethyl) hexamethylene, Isosorbide-5-Nitrae-bis- (isocyanatomethyl) hexamethylene, 1,3- Asias rings Hexyl diisocyanate, Isosorbide-5-Nitrae-cyclohexylene diisocyanate, 4- methyl isophthalic acids, 3- cyclohexylene diisocyanates, 2- methyl isophthalic acids, 3- cyclohexylene diisocyanates, 1- methylbenzenes -2,4- diisocyanate, 1- methylbenzenes -2,5- diisocyanate, 1- methyl Benzene -2,6- diisocyanate, 1- methylbenzenes -3,5- diisocyanate, hexamethylene diisocyanate, 2,2,4- trimethyl six are sub- Methyl diisocyanate, 2,4,4- trimethyl hexamethylene diisocyanates, methane diisocyanate, the isocyanide of ethane -1,2- bis- Acid esters, propane -1,3- diisocyanate, butane -1,1- diisocyanate, butane -1,2- diisocyanate, butane-Isosorbide-5-Nitrae-two Isocyanates, 2- butene-1s, 4- diisocyanate, 2- methyl butenes-Isosorbide-5-Nitrae-diisocyanate, 2- methybutanes-Isosorbide-5-Nitrae-two are different Cyanate, pentane -1,5- diisocyanate, 2,2- dimethyl pentanes -1,5- diisocyanate, hexane -1,6- diisocyanate, Heptane -1,7- diisocyanate, octane -1,8- diisocyanate, nonane -1,9- diisocyanate, the isocyanide of decane -1,10- bis- The functional isocyanate compound of acid esters, dimethylsilane diisocyanate, diphenyl silane diisocyanate etc. two, or triphenyl Methane triisocyanate, 1,3,6- hexa-methylene triisocyanates, 1,8- diisocyanate -4- isocyanatometyls octane, two Cycloheptane triisocyanate, three (isocyanate phenyl) thiophosphates, lysine ester triisocyanate, the isocyanic acid of hendecane three Ester, three (4- phenyl isocyanates thiophosphates) -3,3 ', 4,4 '-diphenyl methane tetraisocyanate, polymethylene polyphenyl base The polyfunctional isocyanate compounds such as isocyanates, or the polymer such as the dimer of the isocyanate compound or tripolymer, Or the block type isocyanates sheltered using the block agent such as alcohol or phenol, or double carbamate compound etc., but not It is defined in these.These isocyanate compounds can be used alone, and can also be used in combination two or more combinations.

In these isocyanate compounds, preferably two functional isocyanate compounds or trifunctional isocyanates chemical combination Thing, more preferably two functional isocyanate compounds.If the function radix of isocyanate compound is more, bin stability be present The worry of reduction, if the function radix of isocyanate compound is few, the worry that heat resistance or dielectric property do not improve be present. And then preferable isocyanate compound is selected from by 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, 3,5- first Phenylene diisocyanate, 2,2 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate, 4,4 '-diphenyl Methane diisocyanate, m xylene diisocyanate, paraxylene diisocyanate, tetramethylxylene diisocyanate, Isosorbide-5-Nitrae-naphthalene-diyl diisocyanate, 1,5- naphthalene-diyls diisocyanate, 2,6- naphthalene-diyls diisocyanate, 2,7- naphthalene-diyls two are different Cyanate, 3,3 '-dimethyl diphenyl -4,4 '-diisocyanate, m-benzene diisocyanate, PPDI, hexamethylene - The group diisocyanate of Isosorbide-5-Nitrae-two, hexamethylene -1,3- diyl dimethylene diisocyanate, hexamethylene-Isosorbide-5-Nitrae-diyl dimethylene Diisocyanate, hexamethylene diisocyanate, 2,2,4- trimethyl hexamethylene diisocyanates, 2,4,4- trimethyl six are sub- Methyl diisocyanate, 4,4 '-methylene-bis-cyclohexyl diisocyanate, bicyclic [2.2.1] heptane -2,5- diyl dimethylene Diisocyanate, bicyclic [2.2.1] heptane -2,6- diyl dimethylene diisocyanate and IPDI institute One or more of group of composition.In these, particularly preferred isocyanate compound (d) is selected from different by 2,4- toluene two Cyanate, 2,6- toluene di-isocyanate(TDI)s, 3,5- toluene di-isocyanate(TDI)s, 2,2 '-methyl diphenylene diisocyanate, 2,4 '- Methyl diphenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, the isocyanide of hexamethylene -1,3- diyl dimethylene two One in the group that acid esters, hexamethylene-Isosorbide-5-Nitrae-diyl dimethylene diisocyanate and IPDI are formed More than kind.

The reaction of epoxy resin (c) and isocyanate compound (d) can be carried out using known method.Specific reaction Method has：(1) melt epoxy resin (c), the methods of being rinsed using dry gas or decompression will be set in system and by epoxy Moisture removal in resin, the method then added isocyanate compound (d) and catalyst and reacted；Or (2) will Epoxy resin (c) is pre-mixed with catalyst, and the methods of being rinsed using dry gas or decompression will be set in system is by asphalt mixtures modified by epoxy resin Moisture removal in fat, the method then added isocyanate compound (d) and reacted etc..The moisture in system now Amount is preferably below 0.5 mass %, more preferably below 0.1 mass %, and then preferably below 0.05 mass %.In addition, In arbitrary method, it is high in resin viscosity and in the case of being difficult to stir etc., if it is desired, then can also be used non-reacted molten Matchmaker.The epoxy radicals of epoxy resin (c) and the NCO of isocyanate compound (d) react and Xing Cheng oxazoles in this way Alkanone ring.In addition, in the case where the n of formula (1) is more than 1, comprising alcohol hydroxyl group, the alcohol hydroxyl group and isocyanates chemical combination The NCO of thing (d) carries out addition reaction and forms amino-formate bond.When the n of formula (1) is 0, exist The impurity of addition using the amino-formate bond.The epoxy resin (a) of the Han oxazolidine ketone rings used in the so-called present invention, The not only epoxy resin of the ring of ketone containing oxazolidine, and contain usual unreacted raw material epoxy resin (c).In addition, also may be used Include the impurity that addition reaction is carried out using amino-formate bond.Even if being these mixture, being also contained in the present invention makes In the epoxy resin (a) of Han oxazolidine ketone rings.

In addition, the epoxide equivalent (No) of the epoxy resin (a) of Han oxazolidine ketone rings can according to the species of raw material, load Amount, is predicted according to following calculating formulas.In addition, the ring of the Han oxazolidine ketone rings vice versa for desired epoxide equivalent Oxygen tree fat (a), can be according to the epoxide equivalent (Ne) of epoxy resin (c) and working as the NCO of isocyanate compound (d) Measure (Ni), the charge weight of epoxy resin (c) and isocyanate compound (d) is obtained according to following calculating formulas.In addition, equivalent Unit is g/eq., as long as no special instructions, then following also identical.

[number 1]

Me：The charge weight (g) of epoxy resin (c)

Mi：The charge weight (g) of isocyanate compound (d)

For example, the epoxide equivalent in epoxy resin (c) is 220, the equivalent of the NCO of isocyanate compound (d) In the case of 125, the epoxide equivalent on the epoxy resin (a) of Han oxazolidine ketone rings turns into about 500 charge weight, according to The calculating formula and relative to the mass parts of epoxy resin (c) 100, isocyanate compound (d) is 30 mass parts.

With regard to highly viscous suppression or solvent solubility ensure or the raising of obdurability, cementability, electrical characteristic etc. is seen For point, epoxy resin (a) oxazolidone ring degree of modification of the Han oxazolidine ketone rings used in the present invention is preferably 0.15 ~0.6, more preferably 0.2~0.5, and then preferably 0.25~0.45.Ruo oxazolidone ring degree of modification is big, as macromolecular Or high viscosity is carried out, the worry that solvent solubility reduction be present.In addition, Ruo oxazolidone ring degree of modification is small, it is upright and outspoken and point Son interaction Gao oxazolidone rings are few, and the heat resistance of hardening thing or the raising effect of cementability do not permit point, generate during hardening Free hydroxyl group it is also more, the raising effect of electrical characteristic does not also permit point.In addition , oxazolidones ring degree of modification is substantially by being made The ratio of epoxy radicals and NCO is determined, therefore the bright Shu Zhong oxazolidones ring degree of modification of this Shuo of determined by following formula Justice.

Oxazolidone ring degree of modification=(NCO mol)/(epoxy radicals mol)

For example, oxazolidones in the case of the epoxy resin for the Han oxazolidine ketone rings that the epoxide equivalent is about 500 Ring degree of modification is 0.53.

As non-reacted solvent that can be by the reaction of epoxy resin (c) and isocyanate compound (d) to use, tool For body, it can enumerate：Hexane, heptane, octane, decane, dimethylbutane, amylene, hexamethylene, hexahydrotoluene, benzene, toluene, The hydro carbons such as dimethylbenzene, ethylo benzene, or the ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, or ether, isopropyl Ether, butyl ether, isoamyl ether, methyl phenylate, ethyl phenylate, amyl group phenylate, ethyl benzyl ether, dioxane, methylfuran, tetrahydrochysene furan Mutter, the ethers such as diethylene glycol dimethyl ether, ethylene glycol diethyl ether, Methylethyl carbitol, or methylcellosolve acetate, cellosolve The esters such as acetic acid esters, butyl cellosolve acetate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, diethy-aceto oxalate, Or the amide-type such as METHYLPYRROLIDONE, DMA, DMF, or in gamma-butyrolacton etc. Esters, or the sulfoxide type such as dimethyl sulfoxide (DMSO), or the ureas such as tetramethylurea, or dichloromethane, 1,2- dichloroethanes, the neoprene of Isosorbide-5-Nitrae-two The halogenated hydrocarbons such as alkane, chlorobenzene, o-dichlorohenzene, but these are not limited to, these non-reacted solvents can be used alone, and can also incite somebody to action It is two or more to be used in mixed way.Relative to the mass parts of epoxy resin (c) 100, the usage amounts of these solvents be preferably 1 mass parts~ The mass parts of 900 mass parts, more preferably 5 mass parts~100.

The reaction of epoxy resin (c) and isocyanate compound (d) is preferably to add catalyst and carry out.Catalyst adds Heating degree is preferably the scope of the scope of room temperature~150 DEG C, more preferably room temperature~100 DEG C.

Reaction temperature is preferably 100 DEG C~250 DEG C, more preferably 100 DEG C~200 DEG C, and then preferably 120 DEG C~160 ℃.If reaction temperature is low, a point formation for Jin Hang oxazolidone rings can not be permitted, because the trimerizing of NCO reacts and shape Into isocyanurate ring.In addition, if reaction temperature is high, local molecular weight, the life of indissolubility gel component are produced It is more into becoming.It is therefore preferable that the adding speed of adjustment isocyanate compound (d), appropriate temperature is maintained by reaction temperature.It is logical Cross and suitably control reaction condition, can by the epoxy radicals of epoxy resin (c) and the NCO of isocyanate compound (d) and Substantially quantitatively Sheng Cheng oxazolidones ring.

Reaction time is preferably that the addition of isocyanate compound (d) terminates the scope of latter 15 minutes~10 hours, more excellent Elect 30 minutes~8 hours, and then preferably 1 hour~5 hours as.If the reaction time is short, it is largely residual to there is NCO The worry in product is stayed, if the reaction time is grown, the worry that productivity substantially reduces be present.

If base catalyst, then species is not particularly limited catalyst used in the reaction.Specifically, may be used Enumerate：The lithium compound classes such as lithium chloride, butoxy lithium, boron trifluoride complex salt class, tetramethyl ammonium chloride, 4 bromide, four The quaternary ammonium salts such as ethyl phosphonium bromide ammonium, TBAB, tetramethyl-ammonium iodide, tetraethyl ammonium iodide, tetrabutylammonium iodide, diformazan Base ethylaminoethanol, triethylamine, tri-n-butylamine, benzyldimethylamine, 2,4, N-methylmorpholine, N, N '-lupetazin, Isosorbide-5-Nitrae-diethyl piperazine The phosphine such as the three-level amine such as piperazine, triphenylphosphine, three (2,6- Dimethoxyphenyl) phosphines, the phenyl-bromide Phosphonium of amyl group three, diallyl Diphenyl phosphonium bromide, ethyl triphenyl phosphonium chloride, the phenyl-bromide Phosphonium of second base three, ethyl triphenyl phosphonium iodide, butyl triphenyl chlorine Hua Phosphonium, butyl triphenyl phosphonium bromide, butyl triphenyl phosphonium iodide, tetrabutyl Yi Suan Phosphonium acetic acid complex compound, tetrabutyl Yi Suan Phosphonium, The phosphonium salt classes such as 4-butyl phosphonium chloride, four butyl phosphonium bromides, four butyl phosphonium iodides, the combination of antimony triphenyl and iodine, 2- phenylimidazoles, Imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole etc., but these are not limited to, these catalyst can be used alone, Also can and with two or more.Furthermore, it is also possible to split and fraction time use.

In these catalyst, preferably quaternary ammonium salt, three-level amine, phosphine or phosphonium salt class, in reactivity, reaction Tetramethyl-ammonium iodide is more preferably in selectivity.If the low catalyst of reactivity, then it is elongated and cause to there is the reaction time The worry that productivity reduces, if the low catalyst of the selectivity of reaction, then exist and carry out the mutual polymerisation of epoxy radicals, nothing Method obtains the worry of target properties.

The usage amount of catalyst is not particularly limited, relative to the total of epoxy resin (c) and isocyanate compound (d) It is the mass % of 0.0001 mass %~5 for quality, the mass % of preferably 0.0005 mass %~1, more preferably 0.001 matter Measure the mass % of %~0.5, the mass % of and then preferably 0.002 mass %~0.2.If catalytic amount is more, according to circumstances enter The self-polymeric reaction of row epoxy radicals, therefore resin viscosity uprises.In addition, promote the self-polymeric reaction of isocyanates, Yi oxazolidones The generation of ring.And then following worry be present：Remain as impurity in resin is generated, in a variety of applications where, particularly make For plywood or the material of sealing material in the case of use, insulating properties reduction or moisture-proof is caused to reduce.

Curing agent (B) includes the bisphenol compound (b1) represented by the formula (2) and the phenolic aldehyde represented by the formula (3) is clear Paint oxybenzene compound (b2).Bisphenol compound (b1) and the mixed proportion (b1/b2 of novolac phenol compound (b2)；Quality Than) it is preferably 5/95~95/5, more preferably 10/90~90~10, and then preferably 20/80~80/20, particularly preferably 30/70~70/30.If epoxy resin (A) is only that the epoxy resin (a) of Han oxazolidine ketone rings, curing agent (B) are only bisphenol The mixture of compound (b1) and novolac phenol compound (b2), then the effect of the present invention can be played to greatest extent.In addition, If containing with the combination in composition epoxy resin, compared with situation about not containing, the effect of content can be added, therefore can For a small amount of addition.

The content of the epoxy resin (a) of Han oxazolidine ketone rings in epoxy resin (A) is preferably the matter of 5 mass %~100 Measure the mass % of %, the mass % of more preferably 20 mass %~100, and then preferably 50 mass %~100, particularly preferably 70 matter Measure %~100 mass %, most preferably 100 mass %.Bisphenol compound (b1) and novolac phenol in curing agent (B) The content of the mixture of compound (b2) is preferably the mass % of 5 mass %~100, the mass % of more preferably 20 mass %~100, is entered And preferably 50 mass %~100 mass %, particularly preferably 70 mass %~100 mass %, most preferably 100 mass %. In the case where using the reaction product comprising accessory substance etc. as the epoxy resin (a) of Han oxazolidine ketone rings, except reaction The containing ratio of the epoxy resin (a) of Han oxazolidine ketone rings in product substantially few situation (for example, below 20 mass %) with Outside, can be calculated using the quality of the reaction product as the quality of the epoxy resin (a) of Han oxazolidine ketone rings.

Bisphenol compound (b1) is represented by the formula (2).In formula (2), R²Separately represent that hydrogen atom, halogen are former Sub, carbon number 1~20 halogenation alkyl or the alkyl can with heteroatomic carbon number 1~20.These R with formula (1)¹Middle explanation Person is identical.In addition, X²For the cycloalkylidene of ring person's number 5~8, there is the alkyl of at least one carbon number 1~20 as substituent.This A bit with the X of formula (1)¹Middle expositor is identical.

Bisphenol compound (b1) can be by making annular aliphatic ketone suitable respectively and phenols react to obtain.As double The concrete example of phenolic compounds (b1), can enumerate it is following shown in as the bisphenol compound containing cycloalkylidene, but be not limited to These.Formed in addition, removing two hydroxy phenyls (substituent beyond there is a situation where with hydrogen) from following bisphenol compounds Residue be X², it is also preferable X¹.The substituent for being similarly replaced in two hydroxy phenyls is R², it is also preferable R¹。

[changing 8]

These bisphenol compounds containing cycloalkylidene illustrated are for example using Japanese Patent Laid-Open 4-282334 Method disclosed in publication or Japanese Patent Laid-Open 2015-51935 publications etc. and manufacture, can also be obtained as commercially available product Take, such as can enumerate：BisP-TMC、BisOC-TMC、BisP-MZ、BisP-3MZ、BisP-IPZ、BisCR-IPZ、Bis26X- IPZ, BisOCP-IPZ, BisP-nBZ, BisOEP-2HBP (it is above trade name, Honshu chemical industry limited company system Make) etc..In these, for formedness of the easiness obtained with hardening thing physical property, preferably 4,4 '-(3,3,5- trimethyls Cyclohexylidene) bis-phenol, 4,4 '-(3,3,5,5- tetramethyl cyclohexylidene) bis-phenols, more preferably 4,4 '-(3,3,5- trimethyls are sub- Cyclohexyl) bis-phenol.

Novolac phenol compound (b2) is represented by the formula (3).Preferably represented by the formula (4).

In formula (3), A¹The aromatic series ring group in phenyl ring, naphthalene nucleus or cyclohexyl biphenyl is separately represented, these fragrance Race's ring group also can with can the alkyl with heteroatomic carbon number 1~49 as substituent (R²⁰), the aromatic series ring group has extremely A few substituent (R¹⁸).The substituent (R¹⁸) it is the aryl of carbon number 6~48, the aryloxy group of carbon number 6~48, carbon number 7~49 Any one of the aralkoxy of aralkyl or carbon number 7~49.Substituent (R¹⁸) it is preferably base or benzene represented by the formula (4a) Base, naphthyl, dihydro indenyl, 2- phenylethyls, naphthyl methyl, anthrylmethyl, phenoxy group, naphthoxy, benzyloxy, naphthyl methoxy Base, more preferably benzyl, 1- phenylethyls.By with substituent (R¹⁸), hardening thing physical property can be made good.

Form A¹Aromatic series ring group except required substituent (R¹⁸) beyond, can also have other substituents (R¹⁷).This Place, substituent (R¹⁸) and substituent (R¹⁷) it is understood to substituent (R²⁰) one kind.There is hetero atom in substituent (a1) Carbon number 1~49 alkyl carbon number it is different, in addition, with R¹Middle explanation has heteroatomic alkyl identical.Substitution Base (R¹⁸) with formula (4) in R⁸It is corresponding, substituent (R¹⁷) with formula (4) in R⁷It is corresponding, but as be described hereinafter as further to R⁷ With R⁸It is defined.

These substituent (R¹⁸) importing can be by by phenylphenol, cumyl phenol, styrenated phenol, benzyl benzene Phenol, phenoxy phenyl etc. contain substituent (R¹⁸) phenol raw material is made and is subject to novolaks and obtains.In this feelings Under condition, contain substituent (R¹⁸) phenol substituent (R¹⁸) number be directly becoming substituent (R¹⁸) number be averaged Value.In adjustment substituent (R¹⁸) number in the case of, as long as and with containing substituent (R¹⁸) phenol and be unsubstituted Phenol contains not substituent (R¹⁸) substituent substituted benzene phenols.

In addition, by using aralkyl agent relative to novolac phenol compound, also into substituent (R¹⁸). In this case, the mole of the aralkyl agent used relative to the aromatic ring 1 of novolac phenol compound into For substituent (R¹⁸) number average value.The preferably addition relative to the aromatic ring 1 of novolac phenol compound There is 0.1 mole~2.5 moles of an aralkyl agent, more preferably 0.5 mole~2.0 moles, and then preferably 1.0 moles~ 1.5 mole.

As aralkyl agent, can enumerate：Phenyl methanol compound, phenyl-halide are for methane compounds, naphthyl carbinol chemical combination Thing, naphthyl halide compound and distyryl compound etc..Specifically, can enumerate：Methoxybenzyl chloride, benzylic bromides, Benzyl iodide, adjacent metylbenzyl chloride, a metylbenzyl chloride, to metylbenzyl chloride, to Ethylbenzyl chlorination Thing, p-isopropyl Methoxybenzyl chloride, to t-butylbenzyl chloride, to phenylbenzylchloride, 5- chloromethyls acenaphthene, 2- naphthyl first Base chloride, 1- chloromethyl -2- naphthalenes and these core substitution isomers, α-methylbenzyl chloride, alpha, alpha-dimethylbenzyl chlorine Compound, methyl benzyl ether, adjacent methyl-benzyl methyl ether, a methyl-benzyl methyl ether, to methyl-benzyl methyl ether, to Ethylbenzyl methyl ether and this A little core substitution isomers, benzyl ether, benzyl propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, to methyl-benzyl methyl ether and these Core substitution isomers, benzyl alcohol, adjacent methyl-benzyl alcohol, a methyl-benzyl alcohol, to methyl-benzyl alcohol, to Ethylbenzyl alcohol, right Isopropyl benzyl alcohol, to t-butylbenzyl alcohol, to phenylbenzyl alcohol, Alpha-Naphthyl methanol and these core substitute isomers, α-first Base benzyl alcohol, alpha, alpha-dimethylbenzyl alcohol, styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, α-first Base styrene, Beta-methyl styrene etc..Distyryl compound can also include other a small amount of reacted constituents (for example, divinyl Composition containing unsaturated bond such as benzene, indenes, coumarone, benzothiophene, indoles, vinyl naphthalene etc.).These can individually make With, also can and with two or more.In these, just turn into excellent heat resistance, its dielectric constant and the lower person of dielectric loss tangent and Speech, preferably styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, α-methylstyrene, Beta-methyl benzene Ethene, Methoxybenzyl chloride, benzylic bromides or benzyl alcohol.

Importing the reaction of these aralkyl agents can be carried out in the presence of acid catalyst., can be certainly as the acid catalyst Suitably selected in known inorganic acid, organic acid.For example, it can enumerate：The inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid (mineral Acid), or the organic acid such as formic acid, oxalic acid, trifluoroacetic acid, p-methyl benzenesulfonic acid, dimethyl sulfate, diethyl sulfuric acid, or zinc chloride, The lewis acids such as aluminium chloride, iron chloride, boron trifluoride, or ion exchange resin, atlapulgite, silica-alumina, boiling Solid acids such as stone etc..

In addition, make by the reaction of more than two functions phenols and crosslinking group and the phenol novolacs compound that obtains with The aralkyl agent is reacted in the presence of base catalyst, and thus a part for hydroxyl turns into aralkoxy.As base catalysis Agent, such as can enumerate：The alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, or metallic sodium, lithium metal, sodium carbonate, potassium carbonate Deng inorganic base etc..It is 1 mole~2 moles of scope for 1 mole of aralkyl agent that its usage amount, which is preferably,.

In addition, substituent (R¹⁸) in addition to described, can be aryl, aryloxy group, but on these importing, have in raw material phenol The method of aryloxy group fortified phenol as middle aryl-substituted phenol or phenoxy phenyl using as phenylphenol.

T appoints for the divalence crosslinking group represented by bivalent aliphatic cyclic hydrocarbon group or the formula (3a) or the formula (3b) One.

The carbon number of bivalent aliphatic cyclic hydrocarbon group is preferably 5~15, and more preferably 5~10.Specifically, carbon number can be enumerated 5~12 cycloalkylidene or the bilvalent radical for including the condensed ring as represented by following structural formula, but it is not limited to these.This Outside, the cycloalkylidene of carbon number 5~12 has carbon number or the different situation of ring person's number, in addition to without substituent, can refer to X²In The explanation of the cycloalkylidene of explanation.

[changing 9]

In formula (3a), R³And R⁴Separately represent hydrogen atom or there can be the alkyl of the carbon number 1~20 of miscellaneous original, it is excellent Elect the aromatic hydrocarbon of hydrogen atom, the aliphatic alkyl of carbon number 1~20, the alicyclic alkyl of carbon number 3~20 or carbon number 6~20 as Base.In the case of aromatic ring being present in these substituents, the aromatic ring can have hydroxyl as substituent.

In formula (3b), R⁵And R⁶Separately represent the alkyl of hydrogen atom or carbon number 1~6.A²To include phenyl ring, naphthalene nucleus Or the aromatic series base of cyclohexyl biphenyl.In addition, form A²These rings can through with A¹Same substituent substitution.

K is 1 or 2, represents the number of the hydroxyl of raw material phenols.M represents repeat number, is 1~20.Its average value be 1.5 with On, preferably 1.7~10, more preferably 2.0~5.0, and then preferably 2.2~4.0.

Novolac phenol compound (b2) is preferably the phenol novolacs containing substituent represented by the formula (4) Compound.In formula (4), R⁷Separately represent the alkyl of carbon number 1~6, preferably methyl, the tert-butyl group, phenyl, cyclohexyl Deng more preferably methyl.R⁸Represent the substituent represented by the formula (4a).P be 0~3 integer, tool average value be 0.1~ 2.5 number, preferably 0.5~2.0, more preferably 1.0~1.5.Q is 0~2 integer, and its average value is 0~2 number, preferably For 0~1.In addition, p+q is calculated as 0.1~3 number with average value.

In formula (4a), R⁹、R¹⁰And R¹¹Separately represent hydrogen original in or carbon number 1~6 alkyl, preferably hydrogen atom, Methyl, the tert-butyl group, phenyl, more preferably hydrogen atom or methyl.And then preferably R⁹And R¹⁰One of be hydrogen atom, another one be Methyl.As R⁸Concrete example, can enumerate：Benzyl, methyl-benzyl, Ethylbenzyl, isopropyl benzyl, t-butylbenzyl, hexamethylene Base benzyl, phenylbenzyl, dimethyl benzyl, 1- phenylethyls, 1- tolylethyls, 1- xylyls ethyl, 2- phenyl-propanes- 2- bases, 2- tolyl propane -2- bases, 2- xylyl propane -2- bases etc..

The phenol novolacs compound preferably addition on phenol resol resins represented by the formula (4) has benzene Phenylethene modified novolac resin represented by the following formula (7) of ethene.In formula (7), p and m and p the and m implication phases of formula (4) Together.

[changing 10]

As the raw material phenols to obtain novolac phenol compound (b2) and use, can enumerate：Phenol, cresols, Ethyl -phenol, butylphenol, phenylphenol, styrenated phenol, cumyl phenol, benzylphenol, phenoxy phenyl, naphthols, youngster Tea phenol, resorcinol, naphthalenediol etc., but be not limited to these, these phenols can be used alone, also can and with two or more. In these phenols, preferably single phenols such as phenol or alkylphenol.Alkyl in the case of as alkylphenol, suitably carbon The alkyl of number 1~6.In addition, as described, in phenylphenol, cumyl phenol, styrenated phenol, benzylphenol or phenoxy group In the case of phenol etc., the compound that novolaks have been carried out using crosslinking agent is directly becoming novolac phenol compound (b2).In the case of in addition, it is necessary to using aralkyl agent etc. come to substituents such as the aralkyl containing aromatic ring Carry out addition.

As the T of the formula of offer (3) crosslinking agent, can enumerate：The aldehyde such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, benzaldehyde Class, or the ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetophenone, or the glycol body such as paraxylene glycol, to diformazan The dialkoxy matrix such as Benzenediol dimethyl ether, 4,4 '-dimethoxy-methyl biphenyl, dimethoxy-methyl naphthalenes, or paraxylene two The dichloromethane matrix such as chloride, 4,4 '-dichloromethyl biphenyl, dichloromethyl naphthalenes, or divinylbenzene class, divinyl biphenyls The divinyl matrixes such as class, divinyl naphthalenes, or the loop chain such as cyclopentadiene or bicyclopentadiene diene (alkadiene) class, but Be not limited to these, these crosslinking agents can be used alone, also can and with two or more.The T of formula (3) is using loop chain dienes In the case of, turn into bivalent aliphatic cyclic hydrocarbon group, in the case where using aldehydes or ketone, turn into the friendship represented by formula (3a) Symbasis, in the case where using glycol body or dialkoxy matrix or dichloromethane matrix or divinyl matrix, turn into formula (3b) institute table The crosslinking group shown.In these crosslinking agents, preferably formaldehyde, acetaldehyde, benzaldehyde, acetone, paraxylene dichloride, 4,4 '-two Chloromethyl biphenyl, particularly preferably formaldehyde.As by formaldehyde be used for react when preferred configuration, can enumerate the Formalin aqueous solution, PARA FORMALDEHYDE PRILLS(91,95), trioxanes etc..

The mol ratio of phenols and crosslinking agent is mol ratio (phenols/crosslinking agent) institute relative to 1 mole of crosslinking agent by phenols Represent, and manufactured using the mol ratio as more than 0.1 ratio, in the case where mol ratio is big, generate in large quantities two nucleomes, Three nucleomes, otherwise in the case where mol ratio is small, HMW bodies more than five nucleomes, two nucleomes, three nucleomes are generated in large quantities Tail off.Herein, in the novolac phenol compound (b2) represented by formula (3), the core of so-called two nucleome, three nucleomes etc., it is Refer to the A in the presence of molecule¹Number.That is, so-called i nucleomes, for the compound of the m=i-1 structural formula in formula (3).Phenols Mol ratio (phenols/crosslinking agent) with crosslinking agent is preferably 0.1~10, and more preferably 0.3~6, and then preferably 0.5~4.Separately Outside, low molecular weight compositions are optionally reduced or removed, thus can also obtain the novolac phenol compound of narrow molecular weight distribution. In this case, as the method for reducing or removing low molecular weight compositions, particularly two nucleomes, can enumerate：Using various molten The poor method of the dissolubility of matchmaker, the method being dissolved in alkaline aqueous solution, other known separation methods etc..

As the acidic catalyst to obtain novolac phenol compound (b2) and use, can enumerate：Hydrochloric acid, phosphorus The lewis acid such as the Bronsted acids such as acid, sulfuric acid, nitric acid, toluenesulfonic acid, boron trifluoride, aluminium chloride, stannic chloride, zinc chloride, iron chloride, Oxalic acid, monochloro acetic acid etc., but be not limited to these, these acidic catalysts can be used alone, also can and with two or more.This In a little acidic catalysts, preferably phosphoric acid, toluenesulfonic acid, oxalic acid.

In the range of lossless physical property, in the epoxy resin (A) in composition epoxy resin of the invention also can and with containing Epoxy resin beyond the epoxy resin (a) of oxazolidine ketone ring.Can and Han oxazolidine ketone rings epoxy resin (a) with There is no particular restriction for outer epoxy resin, preferably the polyfunctional epoxy resin containing two or more epoxy radicals.Specifically, may be used Enumerate：Poly epihydric alcohol ether compound, poly epihydric alcohol amines, poly epihydric alcohol ester compounds, alicyclic epoxy close Thing, other modified epoxies etc., but it is not limited to these.These epoxy resin can be used alone, also can and with two kinds with On same system epoxy resin and use, in addition, also the epoxy composite of different system can be used.In epoxy resin (A) in, the usage amount of the epoxy resin beyond the epoxy resin (a) of these Han oxazolidine ketone rings is the matter of 0 mass %~95 Measure %, the mass % of preferably 0 mass %~80 mass %, more preferably 0 mass %~50, and then preferably 0 mass %~30 Quality %.

As poly epihydric alcohol ether compound, specifically, can enumerate：Bisphenol A type epoxy resin, bisphenol F type epoxy tree Fat, tetramethyl bisphenol f type epoxy resin, united phenol-type epoxy resin, hydroquinones type epoxy resin, bisphenol fluorene type ring oxygen tree Fat, naphthalenediol type epoxy resin, bisphenol-s epoxy resin, diphenylsulfide type epoxy resin, diphenyl ether type epoxy resin, Benzenediol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alkyl phenolic varnish type Epoxy resin, aromatic modified phenol novolak type epoxy resin, bis-phenol phenolic resin varnish type epoxy resin, naphthol novolac varnish Type epoxy resin, betanaphthol aralkyl-type epoxy resin, naphthalenediol aralkyl-type epoxy resin, alpha-Naphthol aralkyl type epoxy tree Fat, biphenyl aralkylphenol type epoxy resin, trihydroxy benzene methylmethane type epoxy resin, tetrahydroxy diphenylphosphino ethane type ring oxygen tree Fat, dicyclopentadiene-type epoxy resin, alkane diol type epoxy resin, aliphatic cyclic epoxy resin etc., but it is not limited to this A bit.

As poly epihydric alcohol amines, specifically, can enumerate：Diaminodiphenyl-methane type epoxy resin, The double aminomethyl cyclohexane type epoxy resin of dimethylphenylene diamine type epoxy resin, 1,3-, isocyanurate type epoxy resin, aniline Type epoxy resin, hydantoins type epoxy resin, aminobenzene phenol-type epoxy resin etc., but it is not limited to these.

As poly epihydric alcohol ester compounds, specifically, can enumerate：Dimer acid type epoxy resin, hexahydro O-phthalic Acid type epoxy resin, trimellitic acid type epoxy resin etc., but it is not limited to these.

As cycloaliphatic epoxy, (the Daicel chemical industry share of Sai Luo West Germany (Celloxide) 2021 can be enumerated Co., Ltd manufactures) etc. aliphatic cyclic epoxy resin etc., but be not limited to these.

As other modified epoxies, specifically, can enumerate：Beyond urethane-modified epoxy resin, (a) It is the epoxy resin of the Han oxazolidine ketone rings of skeleton, epoxide modified polybutadiene rubber derivative, CTBN modified epoxies, poly- Vinyl-arene poly oxide (for example, divinylbenzene dioxide, trivinyl naphthalene trioxide etc.), phosphorous epoxy resin Deng, but it is not limited to these.

In the range of lossless physical property, bis-phenol and can be also used in the curing agent (B) in composition epoxy resin of the invention Curing agent beyond compound (b1) and novolac phenol compound (b2).Can and (b1) and (b2) beyond curing agent There is no particular restriction, as long as the person that makes epoxy cure, is then not particularly limited, and can be used phenol system curing agent, acid anhydrides system hard The hardener for epoxy resin such as agent, amine system curing agent, hydrazides system curing agent, active ester system curing agent, phosphorous curing agent.These Curing agent can be used alone, also can and with the curing agent of two or more same systems, in addition, also can be by the hardening of different system Agent is applied in combination.In curing agent (B), the usage amount of the curing agent beyond these (b1) and (b2) is the matter of 0 mass %~95 Measure %, the mass % of preferably 0 mass %~80 mass %, more preferably 0 mass %~50, and then preferably 0 mass %~30 Quality %.

Phenol system curing agent particularly preferably includes a large amount of aromatic backbone persons in molecular structure, such as can enumerate：Phenol Novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin, phenol aralkyl resin, naphthalene Phenol aralkyl resin, naphthol novolac varnish gum, naphthols-phenol cocondensation novolac resin, naphthols-cresols cocondensation novolaks Resin, biphenyl modified phenolic resin, biphenyl are modified naphthol resin, amino triazine modified phenolic resin.In these will it is described with The identical person of formula (3) is considered as (b2), therefore preferably unsubstituted body, alkyl substitution body, cycloalkyl substitution body or alkoxy substitution Body.

In addition, during heating open loop and also serve as curing agent and useful as the benzoxazine compound of phenolic compounds.Specifically For, benzoxazine compound of bisphenol-f type or bisphenol S type etc. can be enumerated, but be not limited to these.

As acid anhydrides system curing agent, specifically, can enumerate：Tetrabydrophthalic anhydride, methyl tetrahydrophthalic acid Acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, the inclined benzene three of hydrogenation Formic anhydride, methylnadic anhydride, succinic anhydride, maleic anhydride etc., or 4,4 '-epoxide diphthalic anhydrides, 4,4 '-two Phthalic anhydride, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,3,4- Pentamethylene tetracarboxylic dianhydride, 5- (2,5- dioxotetrahydro furfuryl group) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, 4- (2,5- Dioxotetrahydro furans -3- bases) -1,2,3,4- naphthane -1,2- dicarboxylic anhydrides etc., but it is not limited to these.

As amine system curing agent, the amines that can be used as the various epoxy resin modification agent can be enumerated.In addition, 2,4,6- tri- (dimethylaminomethyl) phenol or dimer diamines or dicyanodiamine and its derivative or dimeric dibasic acid can be enumerated Condensation product Deng acids and more amines is amine compounds such as daiamid etc., but is not limited to these.

As hydrazides system curing agent, specifically, can enumerate：Adipic dihydrazide, isophthalic dihydrazide, decanedioic acid Two hydrazides, the hydrazides of dodecanedioic acid two etc., but it is not limited to these.

As active ester system curing agent, can enumerate it is described in No. 5152445 publications of Japan Patent as multifunctional phenolate The reaction product of compound and aromatic carboxylic acid, commercially available product have Epiclon (Epiclon) HPC-8000-65T (DICs (DIC) limited company manufactures) etc., but it is not limited to these.

On the ratio of epoxy resin (A) and curing agent (B), for 1 mole of the epoxy radicals of epoxy resin (A), The active hydrogen-based of curing agent (B) is preferably 0.2 mole~1.5 moles.In the active hydrogen-based deficiency for 1 mole of epoxy radicals 0.2 mole or more than 1.5 moles in the case of, exist hardening become load incomplete that good hardening physical property obtains Sorrow.Preferable scope is 0.3 mole~1.5 moles, and preferred scope is 0.5 mole~1.5 moles, and then preferable scope For 0.8 mole~1.2 moles.In addition, relative to Han oxazolidine ketone rings epoxy resin (a) or include Han oxazolidine ketone rings Epoxy resin (a) and accessory substance etc. reaction product (a2) 1 mole of epoxy radicals for, bisphenol compound (b1) and phenolic aldehyde are clear It is preferably 0.8 mole~1.2 moles to paint the total of the phenolic hydroxyl group of oxybenzene compound (b2), and more preferably 0.9 mole~1.1 rub You, and then preferably 0.95 mole~1.05 moles.In composition epoxy resin, and with Han oxazolidine ketone rings epoxy Epoxy resin or bisphenol compound (b1) and novolac phenol compound beyond resin (a) or reaction product (a2) (b2) in the case of the curing agent beyond, preferably consider and epoxy resin or curing agent most preferred allotment amount after Determine allotment amount.For example, and with the case of phenol system curing agent or amine system curing agent or active ester system curing agent, relative to ring Epoxide and allocate substantially equimolar active hydrogen-based, in the case where using acid anhydrides system curing agent, relative to 1 mole of epoxy radicals 0.5 mole~1.2 moles of allotment, preferably 0.6 mole~1.0 moles of anhydride group.

So-called active hydrogen-based (includes tool for the functional group with the reactive reactive hydrogen with epoxy radicals in this specification Have due to hydrolysis etc. and produce the functional group of the potentiality reactive hydrogen of reactive hydrogen or show the functional group of equal induration), Specifically, anhydride group or carboxyl or amino or phenolic hydroxyl group etc. can be enumerated.In addition, on active hydrogen-based, by carboxyl (- COOH) Or phenolic hydroxyl group (- OH) is calculated as 1 mole, by amino (- NH₂) it is calculated as 2 moles.It is in addition, indefinite in active hydrogen-based In the case of, Ahew can be obtained by measure.Such as can be by making known to the epoxide equivalents such as phenyl glycidyl ether Monoepoxy resin reacts with the unknown curing agent of Ahew, determines the amount of the monoepoxy resin of consumption, and obtains and used Curing agent Ahew.

Hardening accelerator is visually needed to use in the composition epoxy resin of the present invention.As hardening accelerator, such as can Enumerate：The phosphorus compounds such as imdazole derivatives, three-level amine, phosphine, metallic compound, lewis acid, amine complex salt (amine Complex salt) etc., but it is not limited to these.These hardening accelerators can be used alone, also can and with two or more.

As imdazole derivatives, as long as the compound with imidazole skeleton, it is not particularly limited.Such as it can arrange Lift：2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole, double -2-ethyl-4-methylimidazole, 1- methyl -2- ethyls Imidazoles, 2 isopropyl imidazole, 2,4- methylimidazoles, 2- heptadecyl imidazoles etc. are through alkyl-substituted imidazolium compounds, or 2- Phenylimidazole, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- ethyl imidazol(e)s, 1- benzyl -2- phenyl Imidazoles, benzimidazole, 2- ethyl -4- methyl isophthalic acids-(2 '-cyano ethyl) imidazoles, 2,3- dihydro -1H- pyrrolo-es [1,2-a] benzo Imidazolium compounds that imidazoles etc. substitutes through the alkyl containing circular structure such as aryl or aralkyl etc., but it is not limited to these.

As three-level amine, such as can enumerate：2- dimethyl aminopyridines, 4-dimethylaminopyridine, 2- (dimethylaminos Ylmethyl) phenol, 1,8- diazas-bicyclic [5.4.0] -7- endecatylenes (1,8-diaza-bicyclo [5.4.0] -7- Undecene, DBU) etc., but it is not limited to these.

As phosphine, such as can enumerate：Triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine triphenylborane etc., but it is and unlimited Due to these.

As metallic compound, such as tin octoate etc. can be enumerated, but be not limited to these.

As amine complex salt, such as can enumerate：Boron trifluoride MEA complex compound, boron trifluoride diethylamide complex compound, Boron trifluoride isopropylamine complex compound, boron trifluoride chlorphenyl amine complex, boron trifluoride benzyl amine complex, boron trifluoride benzene Boron trifluoride complex class such as mixture of amine complex or these complex compounds etc., but it is not limited to these.

In these hardening accelerators, in the case of as increasing layer material applications or circuit substrate purposes, with regard to heat resistance, it is situated between For the excellent aspects such as electrical characteristics, solder resistant, preferably 2- dimethyl aminopyridines, 4-dimethylaminopyridine or imidazoles Class.In addition, in the case of as semiconductor sealing material use way, with regard to hardening, heat resistance, electrical characteristic, moisture-proof reliability For excellent aspect, preferably triphenylphosphine or DBU.

As long as the allotment amount of hardening accelerator suitably selects according to application target, relative to composition epoxy resin In the mass parts of epoxy resin ingredient 100 for, optionally using the mass parts of 0.01 mass parts~15.Preferably 0.01 mass parts The mass parts of~10 mass parts, more preferably 0.05 mass parts~8, the mass parts of and then preferably 0.1 mass parts~5.By using Hardening accelerator, hardening temperature can be reduced, or shorten firm time.

It can be used to adjust viscosity using organic solvent or reactive diluent in composition epoxy resin.

As organic solvent, such as can enumerate：The amide-types such as DMF, DMA, or The ethers such as glycol monoethyl ether, dimethoxy diethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, TRIGLYME Class, or the ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, or methanol, ethanol, 1- methoxy-2-propanols, 2- The alcohols such as ethyl -1- hexanols, benzyl alcohol, ethylene glycol, propane diols, butyl diglycol, pine tar, or butyl acetate, acetic acid methoxy Base butyl ester, methylcellosolve acetate, cellosolve acetate, ethyl diethylene glycol acetic acid esters, propylene glycol methyl ether acetate, card must The acetate esters such as alcohol acetic ester, benzyl alcohol acetic ester, or the benzoates such as methyl benzoate, ethyl benzoate, or methyl are molten The dioxanes such as fine agent, cellosolve, butyl cellosolve, or the carbitol class such as methyl carbitol, carbitol, butyl carbitol, or Benzene,toluene,xylene etc. is aromatic hydrocarbon, or dimethyl sulfoxide (DMSO), acetonitrile, 1-METHYLPYRROLIDONE etc., but is not limited to this A bit.

As reactive diluent, such as can enumerate：Allyl glycidyl ether, butyl glycidyl ether, 2- ethyl hexyls The monofunctional glycidyl ethers such as base glycidol ether, phenyl glycidyl ether, cresyl glycidyl ether, or resorcinol two Glycidol ether, neopentylglycol diglycidyl ether, BDDE, 1,6- hexylene glycol 2-glycidyls The function glycidol ethers of ether, cyclohexanedimethanodiglycidyl diglycidyl ether, propylene glycol diglycidylether etc. two, or glycerine bunching Water glycerin ether, trimethylolpropane polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythrite poly epihydric alcohol Polyfunctional glycidyl ether's class such as ether, or the glycidol esters such as new decane acid glycidyl ester, or phenyl 2-glycidyl amine, The glycidol amines such as tolyl 2-glycidyl amine, but it is not limited to these.

These organic solvents or reactive diluent are preferably to be used alone by below 90 mass % of nonvolatile component Or use is mixed with a variety of persons, its appropriate species or usage amount can suitably select according to purposes.Such as in printing distributing board In purposes, preferably the boiling point such as methyl ethyl ketone, acetone, 1- methoxy-2-propanols is less than 160 DEG C of polarity solvent, and it makes Dosage is preferably the mass % of 40 mass %~80 in terms of nonvolatile component.In addition, in adhesive film purposes, such as be preferably to use Ketone, acetate esters, carbitol class, aromatic hydrocarbon, dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc., Its usage amount is preferably the mass % of 30 mass %~60 in terms of nonvolatile component.

In composition epoxy resin, in order to improve the anti-flammability of obtained hardening thing, the model of reliability is not being reduced In enclosing, usual known various fire retardants can be used.As workable fire retardant, such as can enumerate：Halogen-system fire retardant, phosphorus Flame retardant (phosphorus compound as fire retardant), nitrogenated flame retardant, silicone flame retardant, inorganic flame retardant, organic metal Salt flame retardant etc..For the viewpoint to environment, preferably not halogen-containing fire retardant, particularly preferably phosphorus flame retardant. There is no particular restriction when in use for these fire retardants, can be used alone, and can also use the fire retardant of a variety of same systems, and The flame retardant combination of different system can be used.

Phosphor-included additive can be used inorganic phosphorus series compound, organic phosphorus series compound it is any.As Phos system Compound, such as can enumerate：The ammonium phosphate types such as red phosphorus, MAP, Diammonium phosphate (DAP), triammonium phosphate, ammonium polyphosphate, phosphamide etc. contain The inorganic phosphorus series compound of nitrogen, but it is not limited to these.

As organic phosphorus series compound, such as except phosphate compound, condensed phosphoric acid esters, phosphinic acid compounds, secondary phosphine General organic phosphorus series compound such as acid compound, phosphine oxide compound, carboxy phosphinic acid compound, or nitrogenous organic phosphorus series compound, or Beyond metal phosphinate etc., it can enumerate：With the active hydrogen-based being directly bonded on phosphorus atoms phosphorus compound (such as 9, Miscellaneous -10- phosphines phenanthrene -10- the oxides of 10- dihydro-9-oxies, diphenyl phosphine oxide etc.) or phosphorous phenolic compounds (such as 10- (2,5- bis- Hydroxy phenyl) -10H-9- oxa- -10- phosphine phenanthrene -10- oxides, 10- (2,7- dihydroxy naphthyl) -10H-9- oxa- -10- phosphines Phenanthrene -10- oxides, two phenenyl phosphinyl hydroquinones, two phenenyl phosphinyl-epoxide of Isosorbide-5-Nitrae-two naphthalene, Isosorbide-5-Nitrae-cyclooctylene phosphine oxide Base-Isosorbide-5-Nitrae-phenyl glycol, 1,5- cyclooctylenes phosphinyl-Isosorbide-5-Nitrae-phenyl glycol etc.) etc. organic phosphorus series compound, or have these Derivative that the reaction of the compound such as machine phosphorus series compound and epoxy resin or phenol resin forms etc., but it is not limited to these.

As can and phosphorous epoxy resin, such as can enumerate：Albert (Epotohto) FX-305, FX-289B, TX-1320A, TX-1328 (living the manufacture of aurification limited company above for Nippon Steel) etc., but it is not limited to these.Can And the epoxide equivalent of phosphorous epoxy resin be preferably 200~800, more preferably 300~780, and then preferably 400~ 760.Phosphorus containing ratio is preferably the mass % of 0.5 mass %~6, the mass % of more preferably 2 mass %~5.5, and then preferably 3 matter Measure the mass % of %~5.In addition, as can and phosphorous curing agent, in addition to the phosphorous phenolic compounds, using Japan Manufacture method as shown in No. 4548547 publications of patent spy table 2008-501063 publications or Japanese Patent No., by making phosphorus Compound is reacted with phenolic compounds with aldehydes and obtains phosphorous phenolic compounds.In addition, using Japanese Patent Laid-Open 2013- Manufacture method as shown in No. 185002 publications, further reacts aromatic carboxylic acid, is thus obtained from phosphorous phenolic compounds Obtain the active ester compound containing phosphorus.In addition, obtained using the manufacture method as shown in No. WO2008/010429 containing phosphorus Benzoxazine compound.

Can and the allotment amount of phosphorus compound can be according to the species or phosphorus containing ratio, composition epoxy resin of phosphorus compound Composition, desired anti-flammability degree and suitably select.It is reactive phosphorus compound, i.e. phosphorous asphalt mixtures modified by epoxy resin in phosphorus compound In the case of fat or phosphorous curing agent, there are epoxy resin, hardener for epoxy resin, fire retardant and other fillings relative to allotment For solid constituent (nonvolatile component) in whole composition epoxy resins of material or additive etc., phosphorus containing ratio is preferably Below the mass % of below the mass % of 0.2 mass %~6, more preferably 0.4 mass %~4, and then preferably 0.5 mass %~ Below 3.5 mass %, further particularly preferably below 0.6~3 mass %.If phosphorus containing ratio is few, existing becomes to be difficult to really The worry of environment friendly flame-retardant, if phosphorus containing ratio is excessive, the worry being had undesirable effect to heat resistance be present.It is to add in phosphorus compound In the case of adding the phosphorus flame retardant for being, in the mass parts of solid constituent (nonvolatile component) 100 in composition epoxy resin, Using in the case of red phosphorus, preferably allocated in the range of the mass parts of 0.1 mass parts~2, using organophosphor system chemical combination In the case of thing, preferably again allocated in the range of the mass parts of 0.1 mass parts~10, particularly preferably in 0.5 mass parts Allocated in the range of~6 mass parts.

In addition, in the case where using phosphorus compound as fire retardant, as flame retardant, such as neatly and can be also used Stone, magnesium hydroxide, boron compound, zirconium oxide, calcium carbonate, zinc molybdate etc..

In the present invention, it is preferred to for using phosphorus compound as fire retardant, but can also be used it is following described in fire retardant.

As nitrogenated flame retardant, such as can enumerate：Triaizine compounds, cyanurate compound, isocyanuric acid compound, coffee thiophene Piperazine etc., preferably triaizine compounds, cyanurate compound, isocyanuric acid compound.The allotment amount of nitrogenated flame retardant can be according to nitrogen The species of flame retardant, the other compositions of composition epoxy resin, the degree of desired anti-flammability and suitably select, such as In the mass parts of solid constituent (nonvolatile component) 100 in composition epoxy resin, preferably in the mass of 0.05 mass parts~10 Allocate in the range of part, particularly preferably allocated in the range of the mass parts of 0.1 mass parts~5.In addition, fire-retardant using nitrogen system During agent, also can and with metal hydroxides, molybdenum compound etc..

As silicone flame retardant, if the organic compound containing silicon atom, then can there is no particular restriction that ground uses, example It can such as enumerate：Silicone oil, silicone rubber, silicone resin etc., but it is not limited to these.The allotment amount of silicone flame retardant can root According to the species of silicone flame retardant, the other compositions of composition epoxy resin, the degree of desired anti-flammability and suitably select, Such as in the mass parts of solid constituent (nonvolatile component) 100 in composition epoxy resin, preferably 0.05 mass parts~ Allocated in the range of 20 mass parts.In addition, when using silicone flame retardant, also can and with molybdenum compound, aluminum oxide etc..

As inorganic flame retardant, such as can enumerate：Metal hydroxides, metal oxide, metal carbonate compounds, Metal powder, boron compound, low-melting glass etc., but it is not limited to these.The allotment amount of inorganic flame retardant can be according to inorganic The species of flame retardant, the other compositions of composition epoxy resin, the degree of desired anti-flammability and suitably select, such as Allotment has epoxy resin, hardener for epoxy resin, fire retardant and whole epoxy resin of other filling materials or additive etc. In the mass parts of solid constituent (nonvolatile component) 100 in composition, the scope preferably in the mass parts of 0.05 mass parts~20 Interior allotment, particularly preferably allocated in the range of the mass parts of 0.5 mass parts~15.

As organic metal salt flame retardant, such as can enumerate：Ferrocene, acetylacetone metal complex, organic metal Carbonyls, organic cobalt salt compound, metal organic sulfonate, metallic atom and aromatic compound or heterocyclic compound enter Compound that row ion is bonded or coordination bond forms etc., but it is not limited to these.The allotment of organic metal salt flame retardant Amount can be according to the species of organic metal salt flame retardant, the other compositions of composition epoxy resin, the journey of desired anti-flammability Spend and suitably select, such as have epoxy resin, hardener for epoxy resin, fire retardant and other filling materials or additive in allotment Deng whole composition epoxy resins the mass parts of solid constituent (nonvolatile component) 100 in, preferably in 0.005 mass parts Allocated in the range of~10 mass parts.

In composition epoxy resin, material, thermoplastic resin can be filled if necessary in allotment in the range of lossless characteristic, or Thermosetting resin, silane coupler, antioxidant, releasing agent, defoamer, emulsifying agent, thixotropy beyond epoxy resin are assigned Give other additives such as agent, lubricant, pigment.

As filling material, such as can enumerate：Fused silica, crystalline silica, aluminum oxide, silicon nitride, boron nitride, Aluminium hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talcum, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, The inorganic fillers such as titanium oxide, magnesia, magnesium silicate, calcium silicates, zirconium silicate, barium sulfate, carbon, or carbon fiber, glass fibre, oxygen Change aluminum fiber, aluminosilicate fiber, silicon carbide fibre, polyester fiber, cellulose fibre, aromatic polyamide fibre, ceramic fibre Deng fibrous filler, or particulate rubber etc..In these filling materials, preferably not because the surface coarsening of hardening thing is handled Used in the acidifying such as the aqueous solution of permanganate property compound decompose or dissolving person, particularly fused silica or crystallization Silica is readily available fine particle, therefore preferably.In addition, make filling material allotment amount it is king-sized in the case of, it is excellent Elect as and use fused silica.Broken shape, any one spherical can be used in fused silica, in order to improve melting titanium dioxide The allotment amount of silicon and suppress moulding material melt viscosity rise, more preferably mainly use spherical fused silica.Enter And in order to improve the allotment amount of spherical silicon dioxide, it is preferably the size distribution of appropriate adjustment spherical silicon dioxide.In addition, filling Agent can also carry out organic acid treatment such as silane coupler processing or stearic acid.As generally using the reason of filling material By the impact resistance that can enumerate hardening thing improves the low linear expansion of effect or hardening thing.In addition, using aluminium hydroxide, In the case of the metal hydroxides such as boehmite, magnesium hydroxide, have and worked as flame retardant, make what anti-flammability improved Effect.In the purposes such as electroconductive paste in the case of use, the conductive filler agent such as silver powder or copper powder can be used.

In the case where considering the low linear expansion of hardening thing or anti-flammability, the allotment amount for preferably filling material is high.Phase For the solid constituent (nonvolatile component) in composition epoxy resin, the mass % of preferably 1 mass %~90, more preferably For the mass % of 5 mass %~80, the mass % of and then preferably 10 mass %~60.If allotment amount is more, exists and be used as plywood , hardening thing further be present and become fragile, become that sufficient mechanical properties can not be obtained in the worry that the cementability needed for purposes reduces Worry.In addition, if allotment amount is lacked, in the presence of following worry：Impact resistance raising of hardening thing etc., the not allotment of filler Effect.

In addition, the average grain diameter of inorganic filler is preferably 0.05 μm~1.5 μm, more preferably 0.1 μm~1 μm.If nothing The average grain diameter of machine filler is the scope, then keeps the mobility of composition epoxy resin well.In addition, average grain diameter can Determined using particle size distribution device.

Allotment thermoplastic resin particularly composition epoxy resin is shaped to sheet or it is membranaceous in the case of effectively. As thermoplastic resin, such as can enumerate：It is phenoxy resin, polyurethane resin, polyester resin, polyvinyl resin, poly- Allyl resin, polystyrene resin, ABS resin, AS resins, vinyl chloride resin, vinylite, polymethylacrylic acid Late resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide, TPI tree Fat, polyamide-imide resin, polyflon, polyetherimide resin, polyphenylene oxide resin, modified polyphenylene ether resin, Polyethersulfone resin, polysulfone resin, polyether-ether-ketone resin, polyphenylene sulfide, polyvinyl formal resin etc., but it is not limited to this A bit.With regard to for the aspect of the compatibility of epoxy resin, preferably phenoxy resin is excellent for the aspect of low dielectric property Elect polyphenylene oxide resin or modified polyphenylene ether resin as.

As other additives, such as can enumerate：Phenol resin, melmac, carbamide resin, unsaturated polyester resin, Thermosetting resin beyond the epoxy resin such as alkyd resin, diallyl phthalate resin, thermosetting polyimides, Or the organic pigment such as quinacridone, azo system, phthalocyanine system, or the inorganic face such as titanium oxide, metal foil-like pigment, rust resisting pigment Material, or the ultra-violet absorber such as amine system of being obstructed, enumerate BTA system, benzophenone series, or hindered phenol series, phosphorus system, sulphur system, hydrazides system Deng antioxidant, or the coupling agent such as silane system, titanium system, or the releasing agent such as stearic acid, palmitic acid, zinc stearate, calcium stearate, stream Additives such as flat agent, rheology control agent, pigment dispersing agent, contraction inhibitor, defoamer etc..Relative in composition epoxy resin Solid constituent (nonvolatile component), the allotment amounts of these other additives is preferably the mass % of 0.01 mass %~20 model Enclose.

The composition epoxy resin of the present invention can be by the way that each composition be equably mixed to obtain.Moreover, it can pass through Hardened using the method same with existing known method and be readily available the hardening thing of the present invention.As obtaining The method of hardening thing, the method same with known composition epoxy resin can be used, it is preferable to use：Casting, injection, fill Note, dipping, drippage coating, transfer shaping, compression molding etc., or by the way that resin sheet, the copper foil with resin, prepreg is made Etc. form, the methods of be laminated and heat press quenching and plywood is made.Hardening temperature now is usually 100 DEG C~ 300 DEG C of scope, firm time are usually 10 minutes~5 hours or so.As hardening thing, can enumerate：Sandwich, pour casting material, Article shaped, adhesive linkage, insulating barrier, film etc. shape hardening thing.

As the purposes using composition epoxy resin, can enumerate：Circuit board use material, encapsulant, cast material, Or electroconductive paste, bonding agent etc..As circuit board use material, can enumerate：Prepreg, resin sheet, the metal foil with resin, The circuit board use insulation material such as printing distributing board or flexible wiring substrate resin combination, increasing layer substrate interlayer dielectic Material, increasing layer adhesive film, resist ink etc..In these various uses, printed wiring plate material, circuit board use insulation material Material, increasing layer with adhesive film purposes, can be used as by the passive part such as capacitor or integrated circuit (Integrated circuit, IC) active part such as chip is embedded to that so-called electronic component to substrate is built-in to be used with substrate insulating materials.These are used In way, for the characteristics such as high flame retardant, high-fire resistance, low dielectric property and solvent dissolubility, preferably in printing distributing board Material, flexible wiring substrate use material with resin combination, increasing layer substrate with the circuit substrates such as interlayer dielectic (plywood) And used in semiconductor-encapsulating material.

In the case where composition epoxy resin is made into the tabulars such as plywood, as used filling material, with regard to its chi It is preferably the filling material of threadiness, more preferably glass cloth, glass mat, glass for very little stability, bending strength etc. Glass Coarse Mesh Gauze.

By making composition epoxy resin be impregnated in the enhancing base materials of threadiness, can be made into printing distributing board etc. is made Prepreg.As the enhancing base materials of threadiness, it can be used the inorfil such as glass, or it is polyester resin etc., polyamino resin, poly- The organic matter fiber such as acrylic resin, polyimide resin, aromatic polyamide resin weave cotton cloth or non-woven fabrics, but do not limit In this.

It is not particularly limited, such as can be obtained in the following way by the method for composition epoxy resin manufacture prepreg ：Further allotment organic solvent is made in the composition epoxy resin of varnish shape comprising the organic solvent and is adjusted to suitable When viscosity resin varnish, after the resin varnish is impregnated in the fibrous substrate, is thermally dried and makes tree Fat composition is semi-harden (B-staged).As heating-up temperature, according to the species of used organic solvent, preferably 50 DEG C~200 DEG C, more preferably 100 DEG C~170 DEG C.Heat time used in the species of organic solvent or the hardening of prepreg and It is adjusted, preferably 1 minute~40 minutes, more preferably 3 minutes~20 minutes.Now, used epoxy composite Thing and the mass ratio of enhancing base materials are not particularly limited, it is often preferred that turn into 20 mass % with the resin component in prepreg ~80 mass % mode is adjusted.

In addition, the composition epoxy resin of the present invention can shape as sheet or membranaceous use.In this case, may be used Sheet material or membranization are carried out using existing known method.The method of manufacture resin sheet is not particularly limited, such as can be led to Cross following manner and obtain：And be not dissolved on the brace foundation film of the resin varnish, use inverse roll coater, unfilled corner Coating machine, the coating machine such as die coating machine and coating resin varnish are taken turns, is then thermally dried and makes resin component B-staged.In addition, If necessary in other overlapping brace foundation films on coated face (bond layer) as diaphragm, it is dried, is derived from viscous Connecing has the adhesive sheet of peel ply on two faces of oxidant layer.

As brace foundation film, can enumerate：The polyolefin film such as the metal foils such as copper foil, polyethylene film, polypropylene screen, gather to benzene The polyester films, polycarbonate membrane, silicone film, polyimide film etc. such as dioctyl phthalate second diester film, it is preferably in these brace foundation films The dimensional accuracy that has no the defect such as broken is excellent, cost also excellent polyethylene terephthalate film.Additionally, it is preferred that to make layer The easy metal foil of multiple stratification of lamination, particularly copper foil.The thickness of brace foundation film is not particularly limited, and is just had as branch The intensity of support body, be difficult to produce lamination it is bad for, preferably 10 μm~150 μm, more preferably 25 μm~50 μm.

The thickness of diaphragm is not particularly limited, usually 5 μm~50 μm.In addition, in order to be easily peeled off be molded it is viscous Contact pin, preferably advance with releasing agent and implement surface treatment.In addition, the thickness of coating resin varnish is with dried thickness gauge Preferably 5 μm~200 μm, more preferably 5 μm~100 μm.As heating-up temperature, according to the species of used organic solvent, Preferably 50 DEG C~200 DEG C, more preferably 100 DEG C~170 DEG C.Heat time species of organic solvent or pre- used in Soak the hardening of material and be adjusted, preferably 1 minute~40 minutes, more preferably 3 minutes~20 minutes.

The resin sheet obtained in this way usually becomes the insulation adhesive sheet with insulating properties, but also can be by ring Conductive metal is mixed in epoxy resin composition or is coated with the particulate of metal and obtains conductive adhesive sheet.This Outside, the brace foundation film be after being laminated in circuit substrate, or carry out heat hardening and formed after insulating barrier and Peeled off.If peeling off brace foundation film after by adhesive sheet heat hardening, adhesive dust etc. in cure step can be prevented. Herein, the insulation adhesive sheet is also insulating trip.

The metal foil with resin obtained using composition epoxy resin is illustrated.As metal foil, can make With copper, aluminium, brass, nickel etc. individually, alloy, compound metal foil.Preferably using the metal foil that thickness is 9 μm~70 μm.By The method of metal foil of fire retardant resin composition and the metal foil manufacture with resin formed comprising phosphorous epoxy resin has no It is particularly limited to, such as can obtains in the following way：Using roll coater etc., profit is coated with the one side of the metal foil After the resin varnish for having carried out viscosity adjustment to composition epoxy resin with solvent, it is thermally dried and makes resin component semihard Change (B-staged), form resin bed.When making resin component semi-harden, for example, can at 100 DEG C~200 DEG C heat drying 1 minute ~40 minutes.Herein, it is generally desirable to which the thickness of the resin portion of the metal foil with resin is formed as 5 μm~110 μm.

In addition, when being hardened to prepreg or insulation adhesive sheet, layer during manufacture printing distributing board generally can be used The method for curing of lamination, but it is not limited to this.Such as using prepreg and in the case of forming plywood, by one piece or more The stacking of piece prepreg, the configuration metal foil in unilateral or both sides and form sandwich, pressurized, heated is carried out to the sandwich, thus made Prepreg hardening, integration and obtain plywood.Herein, as metal foil, can be used copper, aluminium, brass, nickel etc. individually, alloy, Compound metal foil.

As the condition for sandwich heat pressurization, as long as suitably being adjusted under conditions of composition epoxy resin hardening It is whole and carry out heating pressurization, if but pressurization pressure amount it is too low, the internal residual bubble of obtained plywood, electricity be present The situation that gas characteristic reduces, it is therefore desirable that being pressurizeed under conditions of mouldability is met.Heating-up temperature is preferably 160 DEG C ~250 DEG C, more preferably 170 DEG C~220 DEG C.Moulding pressure is preferably 0.5MPa~10MPa, more preferably 1MPa~5MPa. It is preferably 10 minutes~4 hours, more preferably 40 minutes~3 hours to heat pressing time.If heating-up temperature is low, existing can not The worry of sclerous reaction is sufficiently carried out, if heating-up temperature is high, the worry for the thermal decomposition for causing hardening thing be present.If pressurization pressure Power is low, then the internal residual bubble of obtained plywood be present, the situation that electrical characteristic reduces, if moulding pressure is high, enter Resin flows before row hardening, the worry for the plywood that can not obtain desired thickness be present.If in addition, heating pressing time Short, then presence can not be sufficiently carried out the worry of sclerous reaction, if heating pressing time length, has the heat point for causing hardening thing The worry of solution.

And then multi-layer sheet can be made using the plywood of the individual layer obtained in this way as internal layer material.In such case Under, first with the formation to plywood implementing circuit such as addition process or subtractive process, using acid solution to the circuit table that is formed Face is handled and implements Darkening process, obtains internal layer material.On the one side of the internal layer material or the circuit forming face of both sides, utilize Prepreg or resin sheet, the insulation adhesive sheet or metal foil with resin form insulating barrier, and formed on the surface of insulating barrier Conductor layer, so as to form multi-layer sheet.

In addition, using prepreg and in the case of forming insulating barrier, the circuit forming face of internal layer material configure one piece or More pieces of prepreg persons are laminated with, and then configures metal foil on the outside of it and forms layered product.And the layered product is heated and pressurizeed And be integrally formed, the hardening thing of prepreg is consequently formed as insulating barrier, and the metal foil formed on the outside of it is as conductor Layer.Herein, as metal foil, the metal foil same with person used in the plywood used as internal layer material can be used.Separately Outside, heating press molding can be carried out under conditions of the shaping with internal layer material is same.It is multilayer laminated what is shaped in this way The surface of plate, and then implement the formation of via hole or the formation of circuit, plastic printing distributing board using addition process or subtractive process. In addition, the engineering method is repeated using the printing distributing board as internal layer material, the multi-layer sheet of multilayer thus can be further formed.

For example, in the case where forming insulating barrier using the adhesive sheet that insulate, in the circuit forming face configuration of more pieces of internal layer materials Insulation adhesive sheet and form sandwich.Or between the circuit forming face and metal foil of internal layer material configuration insulation adhesive sheet and shape Into sandwich.Moreover, heating pressurization to the sandwich and being integrally formed, the hardening thing conduct of insulation adhesive sheet is consequently formed Insulating barrier, and form the multiple stratification of internal layer material.Or formation insulation is Nian Jie between internal layer material and the metal foil as conductor layer The hardening thing of piece and be used as insulating barrier.Herein, as metal foil, can be used with being made in the plywood that is used as internal layer material The same metal foil of user.In addition, heating press molding can be carried out under conditions of the shaping with internal layer material is same.

In addition, on plywood epoxy resin coating composition and in the case of forming insulating barrier, by epoxy composite Thing coating is preferably 5 μm~100 μm of thickness, and 1 point is then carried out at 100 DEG C~200 DEG C, preferably 150 DEG C~200 DEG C Clock~120 minute, it is preferably the heat drying of 30 minutes~90 minutes and is formed as sheet.General utilize is referred to as casting method Method and formed.Preferably dried thickness is formed as 5 μm~150 μm, is preferably 5 μm~80 μm.In addition, just obtain Obtain sufficient thickness, be difficult to for producing application inequality or striped, the viscosity of composition epoxy resin is preferably to be at 25 DEG C 10mPas~40000mPas scope, and then preferably 200mPas~30000mPas.Formed in this way Multilayer laminate surface, and then implement using addition process or subtractive process the formation of via hole or the formation of circuit, can shape Into printing distributing board.In addition, the engineering method is repeated using the printing distributing board as internal layer material, thus can further be formed The plywood of multilayer.

The sealing material obtained using the composition epoxy resin of the present invention there are adhesive tape-like semiconductor chip and use, irrigate The sealing of type liquid is used, underfill is used, semiconductor interlayer dielectric is used etc., can be preferably used in these.For example, as half Conductor is in package shape, can be listed below method：Composition epoxy resin is cast, or uses metaideophone forming machine, injection Composition epoxy resin is formed forming machine etc., so heated 2 hours~10 hours at 50 DEG C~200 DEG C and obtain into Shape thing.

In order to which composition epoxy resin is prepared as into semiconductor sealing material use, method can be listed below：In epoxy resin The blenders such as the inorganic fill material optionally allocated, or the additive such as coupling agent, releasing agent are pre-mixed in composition, is then made With the fully melting mixing such as extruder, kneader, roller until becoming uniform.Now, inorganic filler is usually using silica, In this case, inorganic fill out is allocated with the ratio as the mass % of 70 mass %~95 preferably in composition epoxy resin Fill agent.

In the case where the composition epoxy resin obtained in this way is used as into adhesive tape-like sealing material, can be listed below Method：It is heated and makes semi-harden sheet material, after sealing material adhesive tape is made, the sealing material adhesive tape is positioned over semiconductor On chip, being heated to 100 DEG C~150 DEG C makes it soften and be formed, and makes its fully hardened at 170 DEG C~250 DEG C.Separately Outside, as pouring type liquid sealing material and in the case of use, as long as the composition epoxy resin obtained is optionally molten After solution is in solvent, it is coated on semiconductor chip or electronic component, directly hardens it.

In addition, the composition epoxy resin of the present invention can also be further used as resist ink.In this case, can arrange Lift following method：Allotment has the vinyl monomer of ethene unsaturated double-bond, as curing agent in composition epoxy resin Cationic polymerization catalyst, further add pigment, talcum and filler and be made after resist ink composition, profit It is coated on screen printing mode on printed base plate, resist ink hardening thing is then made.Hardening temperature now is preferred For 20 DEG C~250 DEG C or so of temperature range.

The composition epoxy resin of the present invention is made and hardening thing is evaluated by heat hardening, as a result can be shown The hardening thing of present unexistent low dielectric property and the balancing good of heat resistance, cementability etc..It is in addition, fire-retardant by allocating Agent, it also can show low dielectric property and heat resistance, cementability etc. is assigned anti-flammability with deteriorating.

[embodiment]

Enumerate embodiment and comparative example and the present invention is specifically described, but the present invention is without departing from its purport, then It is not limited to these examples.As long as no special instructions, then part represents mass parts, and % represents quality %.

Analysis method described below, assay method.

(1) epoxide equivalent：Advised according to Japanese Industrial Standards (Japanese Industrial Standard, JIS) K7236 Lattice.

(2) softening point：According to JIS K7234 specifications, ring and ball method and determine.Specifically, using automatic softening point device (sensible limited company of section manufacture, ASP-MG4).

(3) glass transition temperature：According to IPC-TM-650 2.4.25.c specifications, to be determined using Differential Scanning Calorimetry Device (new and high technology limited company of Hitachi manufactures, EXSTAR6000 DSC6200) enters under 20 DEG C/min Elevated Temperature Conditions Row measure when DSCTgm (relative to vitreousness and the tangent line of rubbery state, the medium temperature of variation curve) and represent.

(4) peel strength of copper foil and layers cementing power：It is measured according to JIS C6481 specifications, layers cementing power is Peel off and determine between the 7th layer and the 8th layer.

(5) relative dielectric constant and dielectric loss tangent：According to IPC-TM-650 2.5.5.9 specifications, material analysis is used Instrument (manufacture of Agilent Technologies (AGILENT Technologies) company), frequency 1GHz dielectric constant is obtained using capacitance method And dielectric loss tangent.

(6) anti-flammability：According to UL94, evaluated using normal beam technique.Evaluation is marked with V-0, V-1, V-2.

Synthesis example 1

In the detachable burning of glass system for possessing agitating device, thermometer, nitrogen gatherer, condenser pipe and Dropping feeder In bottle, (aurification limited company is lived to the TX-1468 of 100 parts of loading by the epoxy resin represented by the formula (5), Nippon Steel Manufacture, epoxide equivalent 219), 0.11 part of tetramethyl-ammonium iodide, heated up when putting into nitrogen, by temperature at 120 DEG C Maintain 30 minutes and the moisture in removal system.Secondly, 130 DEG C~140 DEG C of reaction temperature is maintained, while one side is heated up to 60 DEG C, simultaneously spend 3 hours and 11.5 parts of methyl diphenylene diisocyanate (NCO concentration is 34%) is added dropwise.After completion of dropwise addition, simultaneously Maintain mutually synthermal one side and then persistently stir 60 minutes, obtain the epoxy resin (resin 1) of the ring of ketone containing oxazolidine.Obtained The oxazolidone ring degree of modification (Rox) of resin 1 be 0.2, epoxide equivalent 300, softening point be 85 DEG C.

Synthesis example 2

To TX-1468,0.12 part of the tetramethyl-ammonium iodide of the device loading 100 part same with synthesis example 1, simultaneously put into Nitrogen one side heats up, and maintains temperature 30 minutes and the moisture in removal system at 120 DEG C.Secondly, simultaneously maintain 140 DEG C~ 150 DEG C of reaction temperature, simultaneously spend 5 hours be added dropwise toluene di-isocyanate(TDI) (2,4- toluene di-isocyanate(TDI)s (80%) and 2, The mixture of 6- toluene di-isocyanate(TDI)s (20%), NCO concentration are 48%) 17.8 parts.After completion of dropwise addition, phase equality of temperature is simultaneously maintained Degree one side and then persistently stirring 60 minutes, obtain the epoxy resin (resin 2) of Han oxazolidine ketone rings.The resin 2 obtained Degree of modification (Rox) is 0.45, epoxide equivalent 464, and softening point is 125 DEG C.

Synthesis example 3

To TX-1468,0.12 part of the tetramethyl-ammonium iodide of the device loading 100 part same with synthesis example 1, simultaneously put into Nitrogen one side heats up, and maintains temperature 30 minutes and the moisture in removal system at 120 DEG C.Secondly, simultaneously maintain 140 DEG C~ 150 DEG C of reaction temperature, simultaneously spending 5 hours and be added dropwise hexamethylene -1,3- diyl dimethylene diisocyanate, (NCO concentration is 43%) 16.0 parts.After completion of dropwise addition, when remaining mutually synthermal and then persistently stir 60 minutes, acquisition contains oxazolidine The epoxy resin (resin 3) of ketone ring.The degree of modification (Rox) of the resin 3 obtained is 0.36, epoxide equivalent 400, and softening point is 115℃。

In addition, it is 49% that the containing ratio (quality %) of unreacted epoxy resin, which is resin 1, resin 2 is 20%, resin 3 For 33%.

Synthesis example 4

To 4,4 '-(4- methylcyclohexylidenes) bis-phenols, 358 parts of the table chlorine of the device loading 91 part same with synthesis example 1 Alcohol, 4 parts of ion exchange water, 50 DEG C are warming up to when stirring.After uniform dissolution, load 5.3 parts of 49% hydroxide Sodium water solution and carry out 3 hours react.Secondly, after being warming up to 64 DEG C, the degree for the backflow for producing water is decompressed to, spends 3 hours 48 parts of 49% sodium hydrate aqueous solution is added dropwise, the water and epichlorohydrin gone out in the dropwise addition using separating tank separation cohobation, makes Epichlorohydrin is back in reaction vessel, and water is removed to being reacted outside system.After reaction terminates, temperature is improved to 70 DEG C And be dehydrated, temperature is set to 135 DEG C and reclaims the epichlorohydrin of remaining.Recover to normal pressure, the methyl-isobutyl of 204 parts of addition Ketone (Methyl isobutyl ketone, MIBK) and dissolved.127 parts of ion exchange water is added, is stirred standing Salt caused by pair is set to be dissolved in the water and remove it.Secondly, 2.9 parts of 49% sodium hydrate aqueous solution is loaded, at 80 DEG C It is lower to carry out 90 minutes stirring reactions and carry out purification reaction.Additional MIBK, is washed and is removed ionic impurity for several times.Return Receive solvent and obtain the X of the formula (1)¹For 4- methylcyclohexylidenes, R¹The epoxy resin for being 0.05 for H, n (c4).Obtained The epoxide equivalent of epoxy resin (c4) is 206.

Then, the epoxy resin (c4) obtained to the device loading 100 part same with synthesis example 1, the four of 0.12 part Methylpyridinium iodide ammonium, heat up when putting into nitrogen, maintain temperature 30 minutes and the moisture in removal system at 120 DEG C. Secondly, 130 DEG C~140 DEG C of reaction temperature is maintained, while spends 3 hours when being heated up to 60 DEG C and diphenyl methane is added dropwise 12.2 parts of diisocyanate.After completion of dropwise addition, when remaining mutually synthermal and then persistently stir 60 minutes, obtaining to contain has Evil The epoxy resin (resin 4) of oxazolidone ring.The degree of modification (Rox) of the resin 4 obtained is 0.2, epoxide equivalent 290, softening Point is 80 DEG C.

Synthesis example 5

To load with the same device of synthesis example 1 86.5 parts 4,4 '-cyclohexylidene bisphenol, 358 parts of epichlorohydrin, 4 parts Ion exchange water, 50 DEG C are warming up to when stirring.After uniform dissolution, it is water-soluble to load 5.3 parts of 49% sodium hydroxide Liquid and carry out 3 hours react.Secondly, after being warming up to 64 DEG C, the degree for the backflow for producing water is decompressed to, 3 hours is spent and is added dropwise 49% 48 parts of sodium hydrate aqueous solution, the water and epichlorohydrin gone out in the dropwise addition using separating tank separation cohobation, makes table chlorine Alcohol is back in reaction vessel, and water is removed to being reacted outside system.After reaction terminates, temperature is improved to 70 DEG C and entered Row dehydration, temperature is set to 135 DEG C and reclaims the epichlorohydrin of remaining.Recover to add 204 parts of MIBK to normal pressure and carry out molten Solution.127 parts of ion exchange water is added, being stirred standing makes salt caused by pair be dissolved in the water and remove it.Secondly, Load 2.9 parts of 49% sodium hydrate aqueous solution, carry out 90 minutes stirring reactions at 80 DEG C and carry out purification reaction.It is additional MIBK, washed for several times and removed ionic impurity.Recycling design and obtain epoxy resin (c5).Epoxy resin (c5) is The X of the formula (1)¹For 4- cyclohexylidenes, R¹The epoxy resin for being 0.06 for H, n, epoxide equivalent 200.

Then, the epoxy resin (c5) obtained to the device loading 100 part same with synthesis example 1, the four of 0.11 part Methylpyridinium iodide ammonium, heat up when putting into nitrogen, maintain temperature 30 minutes and the moisture in removal system at 120 DEG C. Secondly, 130 DEG C~140 DEG C of reaction temperature is maintained, while spends 3 hours when being heated up to 60 DEG C and diphenyl methane is added dropwise 12.5 parts of diisocyanate.After completion of dropwise addition, when remaining mutually synthermal and then persistently stir 60 minutes, obtaining to contain has Evil The epoxy resin (resin H1) of oxazolidone ring.The resin H1 obtained degree of modification (Rox) is 0.2, and epoxide equivalent 285 is soft It is 85 DEG C to change point.

Synthesis example 6

To the phenol novolacs of the device loading 105 part same with synthesis example 1, (hydroxyl equivalent 105, softening point are 130 DEG C), 0.1 part of p-methyl benzenesulfonic acid, be warming up to 150 DEG C.Simultaneously remain mutually synthermal, simultaneously spend 3 hours and styrene is added dropwise 94 parts, and then persistently stir 1 hour at the same temperature.Then, add 500 parts of MIBK and make contents melting, at 80 DEG C It is lower to carry out 5 washings.Then, MIBK is evaporated under reduced pressure after removing, obtains phenylethene modified novolac phenol compound (APN- A).The APN-A obtained phenolic hydroxyl group equivalent is 199, and softening point is 110 DEG C.In the formula (3), relative to an A¹'s The average substitution number of 1- phenylethyls is 0.9.

Synthesis example 7

To the phenol novolacs of the device loading 105 part same with synthesis example 1, (phenolic hydroxyl group equivalent is 105, softening point For 67 DEG C), 0.13 part of p-methyl benzenesulfonic acid, be warming up to 150 DEG C.Simultaneously remain mutually synthermal, simultaneously spend 3 hours and benzene second is added dropwise 156 parts of alkene, and then persistently stir 1 hour at the same temperature.Then, carry out with after the same processing of synthesis example 6, obtaining benzene second Alkene modified novolac oxybenzene compound (APN-B).The APN-B obtained phenolic hydroxyl group equivalent is 261, softening point 75 ℃.Relative to an A¹1- phenylethyls average substitution number be 1.5.

Synthesis example 8

To the 1- naphthols aralkyl resin of the device loading 210 part same with synthesis example 1, (the limited public affairs of golden share are lived by Nippon Steel Department manufacture, SN-475, phenolic hydroxyl group equivalent be 210, softening point be 77 DEG C), 0.18 part of p-methyl benzenesulfonic acid, be warming up to 150 DEG C. Simultaneously remain mutually synthermal, simultaneously spend 3 hours and 135 parts of styrene is added dropwise, and then persistently stir 1 hour at the same temperature. Then, carry out with after the same processing of synthesis example 6, obtaining phenylethene modified novolac phenol compound (APN-C).Obtained APN-C phenolic hydroxyl group equivalent be 345, softening point be 88 DEG C.Relative to an A¹1- phenylethyls average substitution number For 1.3.

Synthesis example 9

To phenol, 190 parts of the boron trifluoride ether complex of the device loading 500 part same with synthesis example 1, it is warming up to 120℃.Simultaneously remain mutually synthermal, simultaneously spend 6 hours and 176 parts of bicyclopentadiene is added dropwise, and then progress 4 is small at 130 DEG C Shi Fanying.Then, neutralized and carry out phenol recovery.And then add 500 parts of MIBK and make contents melting, at 80 DEG C It is lower to carry out 4 washings.Then, MIBK is evaporated under reduced pressure after removing, obtains bicyclopentadiene/phenol cocondensation resin.

Then, to the bicyclopentadiene the obtained/phenol cocondensation tree for loading 196 parts with the same device of synthesis example 1 Fat, 0.11 part of p-methyl benzenesulfonic acid, are warming up to 150 DEG C.Simultaneously remain mutually synthermal, simultaneously spend 3 hours and styrene 31 is added dropwise Part, and then persistently stir 1 hour at the same temperature.Then, carry out with after the same processing of synthesis example 6, obtaining containing substituted The novolac phenol compound (APN-D) of base.The APN-D obtained phenolic hydroxyl group equivalent is 228, and softening point is 122 DEG C. Relative to an A¹1- phenylethyls average substitution number be 0.3.

Synthesis example 10

To phenol, 9.5 parts of the boron trifluoride ether complex of the device loading 500 part same with synthesis example 1, it is warming up to 120℃.Simultaneously remain mutually synthermal, simultaneously spend 6 hours and 88 parts of bicyclopentadiene is added dropwise, and then carried out 4 hours at 130 DEG C Reaction.Then, neutralized and carry out phenol recovery.And then add 300 parts of MIBK and make contents melting, at 80 DEG C Carry out 4 washings.Then, MIBK is evaporated under reduced pressure after removing, obtains bicyclopentadiene/phenol cocondensation resin.

Then, to the bicyclopentadiene the obtained/phenol cocondensation tree for loading 178 parts with the same device of synthesis example 1 Fat, 0.11 part of p-methyl benzenesulfonic acid, are warming up to 150 DEG C.Simultaneously remain mutually synthermal, simultaneously spend 3 hours and benzyl alcohol 32 is added dropwise Part, and then persistently stir 1 hour at the same temperature.Then, carry out with after the same processing of synthesis example 6, obtaining containing substituted The novolac phenol compound (APN-E) of base.The APN-E obtained phenolic hydroxyl group equivalent is 205, and softening point is 90 DEG C. Relative to an A¹Benzyl average substitution number be 0.3.

The explanation of the contracted notation used in embodiment and comparative example is as following.

(epoxy resin)

(the epoxy resin (a) of 1) Han oxazolidine ketone rings

1~resin of resin 4：Epoxy resin obtained in 1~synthesis example of synthesis example 4

(2) epoxy resin in addition

Resin H1：Epoxy resin obtained in synthesis example 5

TX-1468：It is described

YDPN-638：(manufacture of aurification limited company, Albert live to phenol novolak type epoxy resin in Nippon Steel (Epotohto) YDPN-638, epoxide equivalent 176)

KDCP-130：(national capital chemistry limited company manufactures dicyclopentadiene-type epoxy resin, KDCP-130, epoxy 254) equivalent is

(curing agent)

(1) bisphenol compound (b1)

BisP-TMC：4,4 '-(3,3,5- trimethylcyclohexylene) bis-phenol (Honshu chemical industry limited company systems Make, BisP-TMC, 155) phenolic hydroxyl group equivalent is

BisP-MC：4,4 '-(4- methylcyclohexylidenes) bis-phenols (reagent, phenolic hydroxyl group equivalent)

(2) novolac phenol compound (b2)

APN-A~APN-E：Novolac phenol compound obtained in 6~synthesis example of synthesis example 10

(3) other curing agents

PN：(Showa electrician limited company manufactures phenol resol resins, new Australia (Shonol) BRG-557, phenol Hydroxyl equivalent is 105, and softening point is 80 DEG C)

Bis-Z：4, (Honshu chemical industry limited company manufactures 4 '-cyclohexylidene bisphenol, Bis-Z, and phenolic hydroxyl group is worked as Measure as 134)

DCPD：(group Rong Huaxue limited companies manufacture dicyclopentadiene phenol compound, GDP9140, phenolic hydroxyl group Equivalent is 196, and softening point is 130 DEG C)

(hardening accelerator)

2E4MZ：(chemical conversion industry limited company of four countries manufactures 2-ethyl-4-methylimidazole, Ke Lilu (Curezol) 2E4MZ)

(fire retardant)

SPE-100：Phosphonitrile flame retardant (great mound chemistry limited company manufactures, SPE-100,13%) phosphorus containing ratio is

Embodiment 1

Allocate 100 parts of resin 1 as epoxy resin, BisP-TMC and 29.0 part of 29.0 parts as curing agent APN-A, 0.2 part of the 2E4MZ as hardening accelerator, and be dissolved in and utilize MEK, propylene glycol monomethyl ether, N, N- dimethyl methyls The in the mixed solvent that acid amides is adjusted, obtain composition epoxy resin varnish.

The composition epoxy resin varnish obtained is impregnated in glass cloth in 150 DEG C of heated-air circulation oven to impregnation Glass cloth

The composition epoxy resin varnish obtained is impregnated in glass cloth (ISO7628 types, thickness 0.16mm).Will The glass cloth being impregnated with is dried in 150 DEG C of heated-air circulation oven and obtains prepreg.8 pieces of the prepreg that will be obtained Overlapping copper foil up and down (mining industry limited company of Mitsui Metal Co., Ltd. manufactures, 3EC-III, and thickness is 35 μm), at 130 DEG C × 15 points 2MPa vacuum compacting is carried out under the temperature conditionss of+190 DEG C of clock × 80 minute, obtains the thick plywoods of 1.6mm.By plywood Glass transition temperature, peel strength of copper foil, the result of layers cementing power are shown in Table 1.

In addition, untiing obtained prepreg, the powdery prepreg powder by 100 mesh is made with sieve.This is presoaked Feed powder end is put into fluororesin molding jig, and 2MPa is carried out under the temperature conditionss of+190 DEG C × 80 minutes 130 DEG C × 15 minutes Vacuum compacting, obtain the thick test pieces of 50mm square × 2mm.By the relative dielectric constant of test piece and the result of dielectric loss tangent It is shown in Table 1.

2~embodiment of embodiment 8

Allocated with the allotment amount (part) of table 1, same operation is carried out using device similarly to Example 1, obtained Plywood and test piece.Experiment similarly to Example 1 is carried out, the results are shown in table 1.In addition, " b1/b2 (the equivalents in table Than) " represent bisphenol compound (b1) and the equivalent proportion (mol ratio) of novolac phenol compound (b2).In addition, in all realities Apply in example, comparative example, the equivalent proportion (mol ratio) of epoxy resin (A) and curing agent (B) is 1.0.

1~comparative example of comparative example 7

Allocated with the allotment amount (part) of table 2, same operation is carried out using device similarly to Example 1, obtained Plywood and test piece.Experiment similarly to Example 1 is carried out, the results are shown in table 2.

[table 1]

Embodiment	1	2	3	4	5	6	7	8
									Resin 1	100	100	100	100	100	100	100	100
BisP-TMC	29.0	6.4	47.5	32.4	35.6	30.7	29.4	-
									BisP-MC	-	-	-	-	-	-	-	27.5
APN-A	29.0	58.0	5.3	-	-	-	-	27.5
									APN-B	-	-	-	32.4	-	-	-	-
APN-C	-	-	-	-	35.6	-	-	-
									APN-D	-	-	-	-	-	30.7	-	-
APN-E	-	-	-	-	-	-	29.4	-
									2E4MZ	0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.2
B1/b2 (equivalent proportion)	56/44	12/88	92/8	63/34	69/31	60/40	57/43	59/41
									Glass transition temperature (DEG C)	182	180	183	175	165	186	188	175
Peel strength of copper foil (kN/m)	1.6	1.4	1.8	1.6	1.6	1.4	1.4	1.6
									Layers cementing power (kN/m)	1.5	1.1	2.1	1.5	1.5	1.4	1.4	1.7
Relative dielectric constant	2.9	2.9	2.8	2.8	2.9	2.9	2.8	2.9
									Dielectric loss tangent	0.012	0.011	0.013	0.010	0.011	0.013	0.012	0.013

[table 2]

Comparative example	1	2	3	4	5	6	7
								Resin 1	100	100	100	100	100	100	100
BisP-TMC	51.6	-	-	-	-	20.8	28.8
								BisP-MC	-	47.0	-	-	-	-	-
APN-A	-	-	66.3	-	26.7	-	-
								APN-D	-	-	-	75.9	-	-	-
Bis-Z	-	-	-	-	26.7	-	-
								PN	-	-	-	-	-	20.8	-
DCPD	-	-	-	-	-	-	28.8
								2E4MZ	0.2	0.2	0.2	0.2	0.2	0.2	0.2
Glass transition temperature (DEG C)	184	155	178	188	165	185	186
								Peel strength of copper foil (kN/m)	1.6	1.8	1.3	1.4	1.6	1.7	1.6
Layers cementing power (kN/m)	2.2	2.1	0.7	1.2	1.6	1.7	1.8
								Relative dielectric constant	2.9	2.9	2.9	3.0	2.9	3.0	3.0
Dielectric loss tangent	0.015	0.016	0.011	0.015	0.013	0.016	0.016

9~embodiment of embodiment 12 and 8~comparative example of comparative example 10

Allocated with the allotment amount (part) of table 3, same operation is carried out using device similarly to Example 1, obtained Plywood and test piece.Experiment similarly to Example 1 is carried out, the results are shown in table 3.

[table 3]

13~embodiment of embodiment 16 and comparative example 11

Allocated with the allotment amount (part) of table 4, using device similarly to Example 1 and carry out same operation, obtain Obtain plywood and test piece.Fire retardant is to be allocated with the phosphorus containing ratio of composition epoxy resin as 2.5% amount.Carry out with The same experiment of embodiment 1, the results are shown in table 4.In addition, anti-flammability measure is that the two sides of plywood is carried out with test piece Etch and be made, carry out flame retardant test using its test piece, the results are shown in table 4.

[table 4]

[industrial utilizability]

The composition epoxy resin of the present invention and its heat resistance, cementability, the dielectric property of hardening thing are excellent, can be used as ring The composition epoxy resin of the purposes such as oxygen tree fat hardening thing, prepreg, plywood.In addition, further allotment has the ring of fire retardant Epoxy resin composition and its anti-flammability of hardening thing, heat resistance, cementability, dielectric property are excellent, can be used as and recent Gao Gong The composition epoxy resin of the high functional material purposes such as electronic circuit board material corresponding to energyization requirement.

Claims

1. a kind of composition epoxy resin, it contains epoxy resin (A) and curing agent (B), the spy of the composition epoxy resin Sign is：Epoxy resin (A) obtains containing the epoxy resin (c) represented by following formula (1) and isocyanate compound (d) Han oxazolidine ketone rings epoxy resin (a), curing agent (B) containing the bisphenol compound (b1) represented by following formula (2) with Novolac phenol compound (b2) represented by following formula (3),

In formula, X¹Represent cycloalkylidene of the alkyl with least one carbon number 1~20 as ring person's number 5~8 of substituent；R¹ Separately represent hydrogen atom, halogen atom, carbon number 1~20 halogenation alkyl or can have heteroatomic carbon number 1~20 Alkyl；G represents glycidyl；N represents repeat number, and average value is 0~5；

In formula, X²Represent cycloalkylidene of the alkyl with least one carbon number 1~20 as ring person's number 5~8 of substituent；R² Separately represent hydrogen atom, halogen atom, carbon number 1~20 halogenation alkyl or can have heteroatomic carbon number 1~20 Alkyl；

In formula, A¹The aromatic series ring group in phenyl ring, naphthalene nucleus or cyclohexyl biphenyl is separately represented, these aromatic series ring groups Can with can the alkyl with heteroatomic carbon number 1~49 as substituent, averagely with 0.1~2.5 selected from carbon number 6~ 48 aryl, the aryloxy group of carbon number 6~48, the aralkyl of carbon number 7~49 and carbon number 7~49 aralkoxy in substituent；

Any of divalence crosslinking group represented by T expression bivalent aliphatic cyclic hydrocarbon groups or following formula (3a) or following formula (3b) Person；K represents 1 or 2；M represents repeat number, and average value is more than 1.5；

In formula, R³And R⁴Separately represent hydrogen atom or there can be the alkyl of heteroatomic carbon number 1~20；R⁵And R⁶It is only respectively On the spot represent the alkyl of hydrogen atom or carbon number 1~6；A²The aromatic series ring group in phenyl ring, naphthalene nucleus or cyclohexyl biphenyl is represented, these Aromatic series ring group also can with can the alkyl with heteroatomic carbon number 1~20 as substituent.

2. composition epoxy resin according to claim 1, it is characterised in that：The bisphenol compound (b1) and the phenol The mass ratio of Novolac oxybenzene compound (b2) is 5/95~95/5 scope.

3. composition epoxy resin according to claim 1 or 2, it is characterised in that：The bisphenol compound (b1) is 4, 4 '-(3,3,5- trimethylcyclohexylene) bis-phenols or 4,4 '-(3,3,5,5- tetramethyl cyclohexylidene) bis-phenols.

4. composition epoxy resin according to claim 1 or 2, it is characterised in that：The novolac phenol compound (b2) oxybenzene compound represented by following formula (4),

In formula, R⁷Separately represent the alkyl of carbon number 1~6, R⁸For the substituent represented by following formula (4a)；P is with average value The number that 0.1~2.5, q is 0~2 is calculated as, p+q is calculated as 0.1~3 with average value；M is identical with the m implications of formula (3)；

5. composition epoxy resin according to claim 1 or 2, it is characterised in that：Relative to the epoxy resin (A) 1 mole of epoxy radicals, the active hydrogen-based of the curing agent (B) is 0.2 mole~1.5 moles.

A kind of 6. epoxy cure thing, it is characterised in that：By the epoxy resin according to the small any one of claim 1 to 5 Composition hardening forms.