CN110194843A

CN110194843A - Phosphorous phenoxy resin, resin combination, circuit board use material and hardening thing

Info

Publication number: CN110194843A
Application number: CN201910142063.3A
Authority: CN
Inventors: 佐藤洋; 军司雅男
Original assignee: Nippon Steel Chemical and Materials Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2018-02-26
Filing date: 2019-02-26
Publication date: 2019-09-03
Anticipated expiration: 2039-02-26
Also published as: KR20190103039A; TWI786271B; JP7055664B2; KR102662809B1; CN110194843B; JP2019147863A; TW201938639A

Abstract

The present invention relates to phosphorous phenoxy resin, resin combination, circuit board use material and hardening things.The present invention provides the resin combination of a kind of phosphorous phenoxy resin and the phenoxy resin for having used this phosphorous, wherein the safety of the phosphorous phenoxy resin, anti-flammability, adhesiveness, processability, excellent heat resistance.Solution is phenoxy resin phosphorous shown in a kind of following formula (1), weight average molecular weight 10,000 to 200,000.Wherein, X is the divalent base containing base (X1) shown in formula (2), and Y is each independently hydrogen atom or glycidyl, and n is 25 to 500.A is phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring, and Z is group phosphorous shown in formula (3).

Description

Phosphorous phenoxy resin, resin combination, circuit board use material and hardening thing

Technical field

The present invention relates to anti-flammability, adhesiveness is excellent and has the phosphorous phenoxy resin of high-fire resistance, and is related to Resin combination and its hardening thing containing the phosphorous phenoxy resin and hardening resin ingredient.

Background technique

Epoxy resin is due to there is mechanical property of excellent electrical insulating property, electrical characteristics, adhesiveness, hardening thing etc. and with electric exhausted It is widely used centered on edge material.For the level of safety, high flame retardant is required to these electrically insulating materials, and simultaneously Given flame-retarded with halogen-system fire retardant, antimonial or phosphorus flame retardant etc..However, in recent years, from environmental pollution, toxicity Level for, the regulation of material used in these fire retardants is gradually increased.Wherein especially with organic halogens such as dioxins The toxicity of substance, carcinogenicity become problem, and are strongly required reduction containing halogen species, eliminate.In addition, from the carcinogenicity of antimony The requirement for for problem, reducing, eliminating antimonial is also increasing.Under such situation, just in motion, self-criticism with the resistance of phosphorus system Agent is fired to replace.

In addition, certain on the way, epoxy resin in various ways molecular weight and assign film formation property, and be used as Phenoxy resin.In particular, for performance required by the phenoxy resin to electrically insulating material purposes, can enumerate anti-flammability and High-fire resistance etc..In order to which environmental problem without the use of halogen and shows anti-flammability, though the benzene containing phosphorus atoms is disclosed in certain documents Oxygroup resin, but its water imbibition, due tos the solvent made it dissolve is limited etc. solvent solubility etc. it is bad (patent document 1, 2).In addition, though the method for having improvement water imbibition and solvent solubility is disclosed, because largely using aliphatic skeleton, if therefore not making The containing ratio of phosphorus atoms is more, is unable to ensure anti-flammability (patent document 3,4).

[existing technical literature]

[patent document]

[patent document 1] Japanese Unexamined Patent Publication 2001-310939 bulletin

[patent document 2] Japanese Unexamined Patent Publication 2002-3711 bulletin

[patent document 3] Japanese Unexamined Patent Publication 2015-196719 bulletin

[patent document 4] Japanese Unexamined Patent Publication 2015-196720 bulletin.

Summary of the invention

[the problem of invention is to be solved]

It is an object of the present invention to provide solving described problem, and it can be applied to electrical property/electronic field excellent in flame retardance, resistance to The resin combination of hot high and excellent low water absorbable phosphorous phenoxy resin, the phenoxy resin for having used this phosphorous, Circuit board use material and its hardening thing.In addition, it is an object of the present invention to provide with anti-flammability, high-fire resistance and low water suction Property and balance has low linear expansion well, prolongs Asia property, high-termal conductivity, solvent solubility, low-k, low-dielectric loss The phosphorous phenoxy resin of angle tangent etc..

[to the means solved the problems, such as]

That is, the present invention proposes phosphorous phenoxy resin shown in following formula (1), weight average molecular weight 10,000 to 200,000。

In formula (1), X is divalent base, but at least part in X is base (X1) shown in following formula (2).Y is separately For hydrogen atom or glycidyl.N is number of repetition and its average value is 25 to 500.

In formula (2), A is the aromatic series ring group selected from phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring, these aromatic series ring groups can have The alkyl of carbon number 1 to 8, the alkoxy of carbon number 1 to 8, the naphthenic base of carbon number 5 to 8, the aryl of carbon number 6 to 10, carbon number 7 to 11 Any of aralkyl oxy of aralkyl, the aryloxy group of carbon number 6 to 10 or carbon number 7 to 11 is used as substituent group.Z is following Phosphorous-containigroups groups shown in formula (3).

In formula (3), R¹And R²For that can have the alkyl of heteroatomic carbon number 1 to 20, and it is identical to distinguish phase exclusive or, can be Straight-chain, branched, ring-type.In addition, R¹With R²It can also be bonded and become cyclic structure position.K1 and k2 independently is 0 or 1.

Phosphorous-containigroups groups shown in the preferred following formula of phosphorous-containigroups groups (3a) or (3b).

In formula (3a) and (3b), R³And R⁴It is separately the alkyl of carbon number 1 to 11.M1 is separately 0 to 4 Integer, m2 are separately 0 to 5 integer.

The X is preferably comprised the base (X1), and the molal quantity relative to X entirety, with the range of 25 to 75 moles of % Contain the not phosphorous-containigroups groups (X2) not containing phosphorus.

The not phosphorous-containigroups groups (X2) are preferably at least containing any base in divalent base shown in 1 following formula (4a) to (4c) Group.

In formula (4a), R⁵To be directly bonded or alkyl ,-CO- ,-O- ,-S- ,-SO selected from carbon number 1 to 20₂And-C (CF₃)₂Divalent base.

Formula (4a) is into (4c), R⁶、R⁷And R⁸It is separately the alkyl of carbon number 1 to 11.M3 and m4 are separately 0 to 4 integer, the integer that m5 is 0 to 6.

Phosphorus containing ratio preferably 1 to 10 quality %.

In addition, the present invention is to deploy resin combination made of hardening resin ingredient in the phosphorous phenoxy resin Object.The hardening resin ingredient is preferably selected from epoxy resin, acrylate, melamine resin, isocyanate resin And at least one of phenol resin.

In addition, the present invention is by the resulting circuit board use material of the resin combination, and for the resin combination Hardening thing.

[The effect of invention]

Though phosphorous phenoxy resin of the invention is halogen-free but still to show good anti-flammability and high-fire resistance, and can be because Application and balance have that solvent solubility, low linear expansion, to prolong Asia property, high-termal conductivity, low water absorbable, low dielectric normal well The characteristics such as number, low-dielectric loss angle tangent.Therefore, phosphorous phenoxy resin of the invention or contain the phosphorous phenoxy group tree It is each that the resin combination of rouge can be applied to insulating materials of adhesive, coating, building construction material, electrical property/electronic component etc. The field of formula various kinds is used especially for as insulation injection molded material, stacking material, the sealing material etc. in electrical property/electronic field.

Specific embodiment

Implementation form of the invention described further below.Shown in for example described formula (1) of phosphorous phenoxy resin of the invention And the weight average molecular weight (Mw) as measured by gel permeation chromatography (GPC) is 10,000 to 200,000, preferably 20,000 to 150, 000, more preferable 25,000 to 100,000, even more preferably 30,000 to 80,000.When Mw is low, the film formation property of film prolongs Asia property not Good, when Mw is excessively high, the operability of resin is significant to be deteriorated.Furthermore the measuring method of GPC is carried out according to condition documented by embodiment.

In formula (1), X is divalent base, and is used as essential component containing base (X1) shown in the formula (2).Here, base (X1) Containing aromatic ring, oxygen atom and Z, and because Z is the base containing phosphorus, therefore base (X1) is the base containing phosphorus.

X is not particularly limited if containing the oxygen-containing group (X1), but is preferably had oxygen-containing group (X1) simultaneously and do not contained phosphorus Not phosphorous-containigroups groups (X2) base shown in described formula (4a) to (4c) etc. can be enumerated for not phosphorous-containigroups groups (X2).In addition, can contain There is the base containing P (X3) other than the base (X1) as the base containing phosphorus.

Y is separately hydrogen atom or glycidyl.

N is number of repetition and its average value is 25 to 500, preferably 40 to 400, more preferable 50 to 350, even more preferably 70 to 300.N is relevant with the Mw.

In the formula (2), A indicates the aromatic series ring group selected from phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring.Also, these aromatic series Ring group can have the alkyl of carbon number 1 to 8, the alkoxy of carbon number 1 to 8, the naphthenic base of carbon number 5 to 8, the aryl of carbon number 6 to 10, carbon Any of aralkyl oxy of the aralkyl of number 7 to 11, the aryloxy group of carbon number 6 to 10 or carbon number 7 to 11 is as substitution Base.For example, methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl, hexyl can be enumerated for the alkyl of carbon number 1 to 8 Deng for the naphthenic base of carbon number 5 to 8, cyclohexyl etc. can be enumerated, for the aryl of carbon number 6 to 10 or aryloxy group, can be enumerated Phenyl, naphthalene, phenoxy group, naphthoxy etc. can enumerate benzyl, benzene for the aralkyl of carbon number 7 to 11 or aralkyl oxy Ethyl, 1- phenylethyl, benzyl oxygroup, naphthyl methyl oxygroup etc..Preferred A are as follows: phenyl ring, the methyl substitute of phenyl ring, benzene The 1- phenylethyl substituent of ring, naphthalene nucleus, the methyl substitute of naphthalene nucleus or naphthalene nucleus 1- phenylethyl substituent.Just with greater need for For the purposes of solvent solubility, the preferred 1- phenylethyl substituent of phenyl ring, the methyl substitute of phenyl ring, phenyl ring is just more needed For wanting anti-flammability, the purposes of heat resistance, the preferred 1- phenylethyl substituent of naphthalene nucleus, the methyl substitute of naphthalene nucleus or naphthalene nucleus.

In the formula (2), Z is phosphorous-containigroups groups shown in the formula (3).

In formula (3), R¹And R²Indicate there can be the alkyl of heteroatomic carbon number 1 to 20, and it is identical to distinguish phase exclusive or, it can For straight-chain, branched, ring-type.In addition, R¹With R²It can also be bonded and become cyclic structure position.Particularly preferably aromatic series ring group. R¹And R²When for aromatic series ring group, can have the alkyl of carbon number 1 to 8, the alkoxy of carbon number 1 to 8, the naphthenic base of carbon number 5 to 8, carbon The aralkyl oxy conduct of the aryl of number 6 to 10, the aralkyl of carbon number 7 to 11, the aryloxy group of carbon number 6 to 10 or carbon number 7 to 11 Substituent group.For hetero atom, such as oxygen atom is illustrated, may be included with and constitute between hydrocarbon chain or the carbon of hydrocarbon ring.

N1 and n2 is 0 or 1, and can be identical or different.

For the phosphorous-containigroups groups shown in formula (3), base shown in the formula (3a) or (3b) can be enumerated.

In formula (3a) and formula (3b), R³And R⁴It is separately the alkyl of carbon number 1 to 11, specifically methyl, second Base, tert-butyl, cyclohexyl, phenyl, tolyl, benzyl can enumerate methyl, cyclohexyl, phenyl, tolyl, benzyl, preferably Methyl, phenyl, benzyl.

M1 is separately 0 to 4 integer, preferably 0 to 2, more preferable 0 or 1.M2 be separately 0 to 5 it is whole It counts, preferably 0 to 2, more preferable 0 or 1.

For other preferences of the phosphorous-containigroups groups shown in the formula (3), it can enumerate shown in following formula (a1) to (a10) Phosphorous-containigroups groups.

The base (X1) can give the phosphorous phenoxy resin of anti-flammability, excellent heat resistance.It is phosphorous compared to previous Phenoxy resin in phosphorous atomic framework structure (such as structure shown in aftermentioned formula (5)), the structure of base (X1) The outspoken nature of chemical structure is higher, can more strongly restrain molecular motion, therefore heat resistance more improves, and volume is bigger, hydrophobic Property and it is upright and outspoken, therefore speculate heat resistance can be improved and reduce water imbibition.On the other hand, though the promotion of other characteristics is phosphorous to import Structure other than base is advisable, but due to base (X1) even if can still play desired effect on a small quantity, therefore can import more other knots Structure, and be easy to assign other characteristics.

In formula (1), at least part of X is base (X1).Relative to whole X, base (X1) is 1 to 100 mole of %, preferably 2 to 75 moles of %, more preferable 5 to 50 moles of %, even more preferably 10 to 40 moles of %, particularly preferably 15 to 35 moles of %.Also, 1 Averagely with 1 or more base (X1) in molecule.

For the preferred structure of the base (X1), structure shown in following formula (2a) to (2f) can be enumerated, but be not limited to These.Particularly preferably structure shown in following formula (2a ') to (2f ').

In addition, X contains other bases containing P (X3) containing phosphorus atoms other than base (X1).For base containing P (X3), It is preferred that divalent base shown in the following formula (5) with a Z can be enumerated.

In the formula (5), A and Z are synonymous with the A and Z of the formula (2) respectively.

It, should not be excellent for phosphorous-containigroups groups (X2) in addition, the X of formula (1) is containing not phosphorous-containigroups groups (X2) not containing phosphorus atoms Choosing can enumerate divalent base shown in the formula (4a) to (4c).

In formula (4a), R⁵To be directly bonded or alkyl ,-CO- ,-O- ,-S- ,-SO selected from carbon number 1 to 20₂-、-C (CF₃)₂Divalent base.For the alkyl, it can enumerate :-CH₂-、-CH(CH₃)-、-C₂H₄-、-C(CH₃)₂, cyclohexylidene, Sub- ring dodecyl, cyclopentylene, methylcyclo-pentylene, trimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene, trimethyl Cyclohexylidene, tetramethyl cyclohexylidene, cyclooctylene, sub- ring dodecyl, sub- bicyclic [4.4.0] decyl, sub- connection cyclohexyl, sub- benzene Base, sub- xyxylene, phenylmethylene, diphenylmethylene, 9H- fluorenes -9- subunit or sub- norcamphanyl, sub- adamantyl, Asia four Hydrogen dicyclopentadienyl, has norcamphane structure, tetrahydro bicyclopentadiene structure, tetrahydro tricyclic at three cyclopentadienyl group of sub- tetrahydro The divalent base of pentadiene structure.Among these, preferably directly it is bonded ,-CH₂-、-CH(CH₃)-、-C(CH₃)₂-、-CO-、-O-、- S-、-SO₂, cyclohexylidene, trimethylcyclohexylene, cyclooctylene, sub- ring dodecyl, sub- connection cyclohexyl, 9H- fluorenes -9- subunit Or the divalent base with tetrahydro bicyclopentadiene structure, it is more preferably directly bonded ,-CH₂-、-C(CH₃)₂-、-CO-、-SO₂, front three Base cyclohexylidene, 9H- fluorenes -9- subunit or the divalent base with tetrahydro bicyclopentadiene structure.

R⁵When to be directly bonded, though biphenyl backbone can be 2,2 '-biphenyl backbones, 2,3 '-biphenyl backbones, 2,4 '-biphenyl Skeleton, 3,3 '-biphenyl backbones, 3,4 '-biphenyl backbones, 4, any one of 4 '-biphenyl backbones, but preferably 4,4 '-biphenyl backbones. In addition, R⁵When for other than being directly bonded, though binding site for aromatic rings can for 2,2 ' positions, 2,3 ' positions, 2,4 ' positions, 3,3 ' positions, 3,4 ' positions, 4,4 ' positions it is any, but preferably 4,4 ' positions.

R⁶It is separately the alkyl of carbon number 1 to 11, the preferably R with formula (3a)³Identical base.M3 is separately 0 To 4 integer, preferably 0 to 2, more preferable 0 or 1.

In formula (4b), formula (4c), R⁷、R⁸With the R⁶Explanation it is identical.The integer that m4 is 0 to 4, preferably 0 to 2, more preferably 0 or 1.The integer that m5 is 0 to 6, preferably 0 to 2, more preferable 0 or 1.

In the X of formula (1), by importing not phosphorous-containigroups groups (X2), the characteristic such as solvent facilitated other than anti-flammability dissolves It is the improvement of property, low linear expansion, extensibility, high-termal conductivity, low-k, low-dielectric loss angle tangent etc. and heat resistance, low Water imbibition is promoted again, therefore it is preferred that determines import volume in response to purpose.Relative to the molal quantity of X entirety, not phosphorous-containigroups groups (X2) Content preferably 25 to 75 moles of %.

" not phosphorous-containigroups groups (X2) " is referred to as base (X2) sometimes below, " phosphorous-containigroups groups " are referred to as base (X3).

Can have base (X1), base (X2) and base (X3) in X, but there must be the base in base (X1) and 1 molecule containing 1 or more (X1).From the viewpoint of not, 1 mole of % or more can be contained.

Base (X3) and base (X1) can equally promote anti-flammability, but base (X1) is greater than base (X3) due to effect, therefore a small amount of i.e. aobvious Show sufficient effect.However, base (X3) is imported with commercially available product, therefore there is handy advantage.

Base (X2) can promote the characteristic different from characteristic possessed by base (X1) and base (X3).According to purposes, phenoxy resin To be advisable with characteristic as mentioned, therefore desired characteristic can be assigned by type, the amount of base (X2).If base (X1) and base (X3) effect can be played on a small quantity, then can contain sufficient base (X2), and gives sufficient desired property.

For example, situation of the thermoplastic resin in the purposes as fire retardant, does not preferably include not phosphorous-containigroups groups (X2) and only has Base (X1) and base (X3), from the viewpoint of anti-flammability, preferred only base (X1), but from the viewpoint of productivity, preferably base (X1) with the mixing of base (X3).

In addition, in previous phosphorous phenoxy resin as made of not phosphorous-containigroups groups (X2) and base (X3), in order to new special The imparting of property, the promotion of certain characteristic and base (X2) must be increased, but when anti-flammability does not have ampleness, so far in addition to abandoning phenoxy group The characteristic of resin itself is assigned and is had nothing for it except corresponding to other allotment.In such case, by by base (X3) Part or all is set as base (X1) and anti-flammability is made to have ampleness, therefore can import base (X2), phenoxy resin itself can be made to have Necessary characteristic.

The structure of phosphorous-containigroups groups (X2) is not selected according to the characteristic to be assigned.For example, in order to further enhance heat resistance, Divalent base or 9H- fluorenes -9- subunit etc. with sub- norcamphanyl, sub- adamantyl etc. can be enumerated.With regard to solvent solubility promotion and Speech, can enumerate biphenylene, di-2-ethylhexylphosphine oxide tolyl, di-2-ethylhexylphosphine oxide xylyl etc. with methyl substituents.With regard to dielectric spy For the improvement purposes of property, can enumerate divalent base with tetrahydro bicyclopentadiene structure, three cyclopentadiene structure of tetrahydro etc. or Divalent base with trifluoromethyl, benzyl substituent group, 1- phenylethyl substituent group etc..For the promotion of moisture-absorption characteristics, it can arrange Lift the divalent base with trifluoromethyl or 9H- fluorenes -9- subunit etc..

From the point of view of such viewpoint, the preferably described range of content of the base (X1) in X.

Not phosphorous-containigroups groups (X2) though content it is different according to purposes, be 0 to 99 mole of %, the preferably described range, more preferable 45 To 55 moles of %.

The content of base (X3) preferably 0 to 50 mole of %, more preferable 20 to 40 moles of %.

Also, be originated from constitute phenoxy resin X phosphorus containing ratio, be scaled phosphorus atoms, can for phenoxy resin 1 to 10 mass % preferably can be the range of 1 to 8 quality %.

Epoxy group end, phenolic hydroxyl group end or its mixed style can be used in phenoxy resin of the invention.In general, benzene Oxygroup resin does not consider the reaction in epoxy group, therefore does not define necessity of epoxide equivalent (g/eq.) specially, but can be 5,000 More than.When not up to 5,000, film formation property, the extensibility of film are bad, and it is not preferable.In addition, when becoming phenolic hydroxyl group end, epoxy Base concentration will become 0, therefore epoxide equivalent can become unlimited value.Therefore, the upper limit of epoxide equivalent defines substantially without critical Meaning.However, from make it is operational good from the viewpoint of, preferably 100,000 hereinafter, more preferable 50, and 000 hereinafter, even more preferably 30,000 hereinafter, particularly preferably 20,000 or less.

For the manufacturing method of phosphorous phenoxy resin of the invention, though have it is following shown in a terrace work (directly Method) and two phase method (indirect method), but not limited to this etc..

One terrace work is to make the epoxyhalopropane such as epoxychloropropane or epoxy bromopropane and comprising shown in following formula (6a) What the phenolic compounds of 2 phosphorous function phenolic compounds reacted in the presence of the alkali metal hydroxides such as sodium hydroxide or potassium hydroxide Method.The phenolic compounds of raw material also may include shown in following formula (6b) other than comprising the 2 phosphorous function phenolic compounds 2 phosphorous function phenolic compounds of others shown in not phosphorous 2 function phenolic compounds, following formula (6c).

H-X¹-H(6a)

H-X²-H(6b)

H-X³-H(6c)

Here, X¹、X²、X³It is synonymous with the base (X1), base (X2), base (X3) respectively.

Two phase method is the method for reacting 2 function phenolic compounds usually in the presence of a catalyst with 2 functional epoxy resins.

For 2 function phenolic compounds and 2 functional epoxy resins, can be used it is one kind or two or more have the base (X1), The phenolic compounds or epoxy resin of base (X2) or base (X3).At this point, 2 function phenolic compounds or 2 functional epoxy resins' is at least one kind of Contain the base (X1).

The example of 2 function phenolic compounds can enumerate phenolic compounds shown in the formula (6a) to (6c).With regard to 2 functional epoxy resins For, can enumerate makes phenolic compounds shown in the formula (6a) to (6c) carry out epoxy resin obtained by epoxidation.2 function Epoxy resin, phenolic compounds can also contain two or more of base (X1), base (X2) or base (X3) simultaneously in the molecule.

The base in phenoxy resin (X1), base (X2) or base (X3) can be regulated and controled by changing the use ratio of these raw materials Ratio.

Mw, the epoxide equivalent of phosphorous phenoxy resin can be by adjusting epoxyhalopropane and 2 functions in a terrace work The raw materials components mole ratio of phenolic compounds and manufacturing objective range, two phase method can be by adjusting 2 functional epoxy resins and 2 function phenol The raw materials components mole ratio of compound and manufacturing objective range.Though phosphorous phenoxy resin of the invention can by any manufacturing method and It obtains, but in general, two phase method is easier to obtain phenoxy resin, therefore it is preferable to use the two-stages compared to a terrace work Method.

For the manufacturing method of 2 phosphorous function phenolic compounds shown in the formula (6a), though it is not particularly limited, it is excellent Phase selection is for 1 mole of organic phosphorus compound shown in following formula (7), with 0.5 mole or more and not up to 1.0 moles of range use Naphtoquinone compounds, and there are the organic solvents of 0.05 to 0.5 mole of moisture for 1 mole of organic phosphorus compound In, 100 to 200 DEG C of reaction temperature, preferably at reflux, the manufacturing method reacted.

In formula (7), R¹、R², k1 and the k2 R with formula (3) respectively¹、R², k1 and k2 it is synonymous.

It, can the by-produced phosphorus compound with structure shown in the formula (5) in the reaction.In order to separate containing for target 2 function phenolic compounds of phosphorus can after the completion of reaction mix reaction product with good solvent, in the 2 phosphorous officials for making target While energy phenolic compounds dissolution, by-produced phosphorus compound is removed as insoluble composition.After solid separation It is mostly to belong to the 2 phosphorous function phenolic compounds of target product, but remain slight amount sometimes present in solution By-produced phosphorus compound preferably further refine therefore for high-purity.For refining methd, by the solution and not Good solvent mixes and the crystallization for the 2 phosphorous function phenolic compounds for belonging to target product is precipitated.Also, by-product etc. can be molten Solution is in poor solvent solution.In addition, for refining methd in addition to this, it the essences such as can also be extracted, clean, distill System operation etc..Furthermore since the phosphorus compound with structure shown in the formula (5) can give base (X3), therefore can also be by it As the useful component that can play anti-flammability, part or all is not separated, and directly uses mixture.

For organic solvent workable for the reaction, though it can enumerate: the alcohols such as 1- methoxy-2-propanol, diethyl two The Sai Lusu such as the benzoates such as acetate esters, the methyl benzoates such as alcohol list monoethyl ether acetate, methyl Sai Lusu (cellosolve) ethers, toluene such as the carbitols such as class, butyl carbitol class, diethylene glycol diethyl ether etc. it is aromatic hydrocarbon, The amides such as n,N-Dimethylformamide (DMF), dimethyl sulfoxide, acetonitrile, N- methylpyrrole pyridine ketone etc., but not limited to this etc..This Equal organic solvents can be used alone or mix two or more and use.

Naphtoquinone compounds workable for the reaction, if purity can make without problems for industrial product for 90% or more With.

When A in formula (2) can become phenyl ring, used naphtoquinone compounds can illustrate such as: benzoquinones, methylbenzoquinone, ethylo benzene Quinone, butyl benzoquinones, phlorone, diethyl benzoquinones, dibutyl benzoquinones, isopropyl methyl benzoquinones, diethoxy benzoquinones, methyl Methoxyl group benzoquinones, Phenylbenzoquinone, tolyl benzoquinones, ethoxyl phenenyl benzoquinones, diphenyl-benzoquinone etc..

When A in formula (2) can become naphthalene nucleus, used naphtoquinone compounds can illustrate such as: naphthoquinones, methylnaphthoquinone, cyclohexyl Naphthoquinones, methoxynaphthoquinone, ethoxynaphthoquinone, dimethyl naphthoquinones, dimethylisopropyl naphthoquinones, methyl methoxy base naphthoquinones etc..

When A in formula (2) can become anthracene nucleus, used naphtoquinone compounds can illustrate such as: anthraquinone, tectoquinone, ethyl anthracene Quinone, methoxy anthraquinone, dimethoxy anthraquinone, two phenoxy group anthraquinones etc..

When A in formula (2) can become phenanthrene ring, used naphtoquinone compounds can illustrate such as: phenanthrenequione, methyl phenanthrenequione, isopropyl Phenanthrenequione, methoxyl group phenanthrenequione, butoxy phenanthrenequione, dimethoxy phenanthrenequione etc..

These naphtoquinone compounds can be used alone or be used in combination of two or more.

For the organic phosphorus compound shown in the formula (7), it can illustrate such as: dimethyl phosphine oxide, diethyl phosphine oxygen Compound, dibutyl phosphine oxide, diphenyl phosphine oxide, benzhydryl phosphine oxide, cyclooctylene phosphine oxide, tolylphosphine Oxide, bis- (methoxyphenyl) phosphine oxides etc.；Phenyl-phosphonite phenyl ester, phenyl-phosphonite ethyl ester, tolyl phosphonous acid first Phenyl ester, benzyl phosphonous acid benzene methyl etc.；Miscellaneous -10- phospho hetero phenanthrene -10- the oxide (DOPO) of 9,10- dihydro-9-oxy, 8- methyl - Miscellaneous -10- phospho hetero phenanthrene -10- the oxide of 9,10- dihydro-9-oxy, the miscellaneous -10- phospho hetero phenanthrene -10- of 8- benzyl -9,10- dihydro-9-oxy Oxide, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 8- phenyl -9,10- dihydro-9-oxy, 2,6,8- tri-tert -9,10- dihydro - 9- oxa- -10- phospho hetero phenanthrene -10- oxide, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 6,8- dicyclohexyl -9,10- dihydro-9-oxy Deng；Diphenyl phosphite, phosphorous acid diformazan phenyl ester, phosphorous acid benzhydryl ester, 5,5- dimethyl -1,3,2- dioxaphosphepin hexamethylene Alkane etc..These organic phosphorus compounds can be used alone or be used in combination of two or more.

For the good solvent, can enumerate ethylene glycol, propylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, acetic acid esters and Benzoic ether etc..This equal solvent can be used alone or mix two or more and use.In this equal solvent, preferred acetic acid esters, more preferably Phenylmethyl acetate.

For the poor solvent, methanol, ethyl alcohol, butanol and acetone etc. can be enumerated.This equal solvent can be used alone or It mixes two or more and uses.In this equal solvent, preferably methanol, ethyl alcohol, acetone, more preferable methanol, ethyl alcohol.This equal solvent can be Aqueous solvent, at this point, relative to 100 mass parts of solvent, it can be containing until water to 100 mass parts.

For the 2 function phenolic compounds used in the manufacture of a terrace work and two phase method, although must have formula 2 phosphorous function phenolic compounds shown in (6a), but other 2 function phenolic compounds also can be used together.

For example, can and shown in the formula (6b) as described in phenolic compounds with divalent base shown in formula (4a) to (4c) etc. 2 not phosphorous function phenolic compounds contain as shown in the phenolic compounds equation (6c) with phosphorous-containigroups groups shown in 1 formula (3) 2 function phenolic compounds of phosphorus.

2 phosphorous function phenolic compounds with phosphorous-containigroups groups shown in 1 formula (3) can be by will be organic shown in formula (7) Phosphorus compound is reacted using known synthetic method with naphtoquinone compounds and is obtained.For synthetic method, though there is such as Japan special Open clear 60-126293 bulletin, Japanese Unexamined Patent Application 61-236787 bulletin, zh.Obshch.Khim, 42 (11), 2415- The methods of method shown in page 2418 (1972) etc., but not limited to this.

With regard to it is described can 2 not phosphorous function phenolic compounds for, can illustrate such as: bisphenol-A, Bisphenol F, bisphenol S, double The bisphenols such as phenol B, bis-phenol E, bisphenol-c, bisphenol Z, bis-phenol acetophenone, bis-phenol Fluorenone；With norcamphane structure, two ring penta 2 of tetrahydro The dihydroxy compounds of alkene structure, three cyclopentadiene structure of tetrahydro or adamantane structure；Biphenyl phenols；Catechol, isophthalic two 2 function phenols of the monocycles such as phenol, hydroquinone；Dihydroxy naphthalenes etc..

Can 2 phosphorous function phenolic compounds for, can illustrate such as: 10- (2,5- dihydroxy phenyl) -10H-9- Oxa- -10- phospho hetero phenanthrene -10- oxide (hreinafter referred to as DOPO-HQ), 10- (2,7- dihydroxy naphthalene) -10H-9- oxa- - 10- phospho hetero phenanthrene -10- oxide (hreinafter referred to as DOPO-NQ), diphenylphosphino hydroquinone, diphenyl benzene phosphino- -1, Bis- oxygroup naphthalene of 4-, 1,4- cyclooctylene phosphono -1,4- phenyl glycol, 1,5- cyclooctylene phosphono -1,4- phenyl glycol etc..

In addition, these substituent groups that can be had no adverse effects through alkyl, aryl etc. replace.These 2 function phenolic compounds can be simultaneously With a variety of.

Firstly, one terrace work of explanation.

The situation of one terrace work makes 0.985 to 1.015 mole of epoxyhalopropane relative to 1 mole of 2 function phenolic compounds (preferably 0.99 to 1.012 mole, more preferable 0.995 to 1.01 mole) is in the presence of alkali metal hydroxide non-reacted molten It is reacted in agent, epoxyhalopropane is consumed, so that Mw carries out condensation reaction as 10,000 or more mode, can be contained whereby The phenoxy resin of phosphorus.Furthermore after reaction, it is necessary to remove by-produced salt by filtering or washing.

Be used as 2 function phenolic compounds shown in the formula (6a) of raw material preferably in 2 function phenolic compounds of raw material for 1 to 100 moles of %, more preferable 2 to 75 moles of %, even more preferably 5 to 50 moles of %, particularly preferably 10 to 40 moles of %, most preferably 15 to 35 moles of %.

Though using 2 function phenolic compounds, preferably 0 to 75 shown in formula (6b) to assign the characteristic other than anti-flammability Mole %, more preferable 25 to 75 moles of %, even more preferably 45 to 55 moles of %.

Though in order to assign the characteristic of anti-flammability and and the 2 function phenolic compounds shown in formula (6c), preferably 0 to 50 rubs You are %, more preferable 10 to 40 moles of %.When 2 function phenolic compounds shown in formula (6c), usually with not separate type (6a) Shown in 2 function phenolic compounds and to use as mixture be advantageous.

The reaction can carry out under normal pressure or under reduced pressure.When usually reacting under normal pressure, reaction temperature preferably 20 to 200 DEG C, more preferable 30 to 170 DEG C, even more preferably 40 to 150 DEG C, particularly preferably 50 to 100 DEG C.When reacting under reduced pressure, preferably 20 to 100 DEG C, more preferable 30 to 90 DEG C, even more preferably 35 to 80 DEG C.If reaction temperature within this range, be not susceptible to side reaction and Easily carry out reaction.Reaction pressure is usually normal pressure.In addition, usually being led by because of reaction heat when needing to remove reaction heat Cause with vaporization/condensation/circumfluence method of solvent, indirect cooling method or this methods of and be used to carry out.

For non-reactive solvent, can illustrate such as: toluene, dimethylbenzene are aromatic hydrocarbon；Methyl ethyl ketone, methyl are different The ketones such as butyl ketone, cyclohexanone；The ethers such as dibutyl ethers, dioxane, tetrahydrofuran；The alcohols such as ethyl alcohol, isopropanol, butanol； The Sai Lusu classes such as methyl Sai Lusu, ethyl Sai Lusu；Glycol ethers such as ethylene glycol dimethyl ether etc., but these are not particularly limited to, This equal solvent can be used alone or mix two or more and use.

In addition, catalyst can be used.It for workable catalyst, can illustrate such as: tetramethyl ammonium chloride, bromination tetrem The quarternary ammonium salts such as base ammonium；The tertiary amines such as benzyl dimethyl amine, 2,4,6- three (dimethylaminomethyl) phenol；2- ethyl -4- first The imidazoles such as base imidazoles, 2- phenylimidazole；Iodate Yi base triphenyl phosphonium Deng phosphonium salts；Phosphines such as triphenylphosphine etc..These catalyst Can be used alone or and in 2 kind more than.

Secondly, illustrating two phase method.

For the meeting of two phase method becomes 2 functional epoxy resins of raw material epoxy resin, preferably make the formula (6b) institute The 2 not phosphorous function phenolic compounds shown react 2 functional epoxy resins shown in resulting following formula (8) with epoxyhalopropane. Furthermore in the situation of 2 phosphorous functional epoxy resins, it can become the X of formula (8)²It is substituted by X¹Or X³Structure.

In formula (8), X²With the X of formula (6b)²It is synonymous, and preferably divalent base shown in the formula (4a) to (4c).G is epoxy third Base.J is number of repetition and its average value is 0 to 6, preferably 0 to 3, more preferable 0 to 1.

Two phase method to obtain in the reacting of 2 function phenolic compounds of raw material epoxy resin and epoxyhalopropane, phase For the functional group in 2 function phenolic compounds, the hydroxide of 0.8 to 1.2 times mole of use (preferably 0.85 to 1.05 times mole) The alkali metal hydroxides such as sodium, potassium hydroxide.It can become mostly if the amount less than remaining water-disintegrable chlorine if this range without preferred.Gold Belonging to hydroxide is used with the state of aqueous solution, alcoholic solution or solid.

When epoxidation reaction, relative to 2 function phenolic compounds, excessive epoxyhalopropane is used.Relative to 2 function phenolate 1 mole of functional group in conjunction object, usually used 1.5 to 15 times moles of epoxyhalopropane, but preferably 2 to 10 times moles, it is more excellent Select 5 to 8 times moles.It is reduced if more than production efficiency if this range, if be less than the high molecular weight body of this range epoxy resin Production quantity increases and becomes unsuitable for the raw material of phosphorous phenoxy resin.

Epoxidation reaction is usually carried out in 120 DEG C of temperature below.When reaction, the so-called water-disintegrable chlorine of hardly possible if temperature height Amount can become more and become difficult to high purity.It is preferred that 100 DEG C hereinafter, even more preferably 85 DEG C of temperature below.

For the meeting of two phase method becomes 2 functional epoxy resins of raw material, 2 functional epoxy trees shown in preferred formula (8) Rouge, the more preferably epoxy resin of the divalent base with the formula (4a) to (4c).In addition, these epoxy resin can be through alkyl, aryl Replace etc. the substituent group having no adverse effects.Furthermore in the range of not undermining the purpose of the present invention, alkylene glycols type ring can be used 2 functional epoxy resins such as oxygen resin, aliphatic cyclic epoxy resin.

The use ratio (molar ratio) of raw material in the form of 2 functional epoxy resins/2 function phenolic compounds for preferably 0.95 To 1.10, more preferable 1.00 to 1.05.

When two phase method, catalyst can be used, the catalyst that reacts of the epoxy group with phenolic hydroxyl group can be promoted if having The compound of ability then all may be used by any compound.Can illustrate as alkali metal compound, organic phosphorus compound, tertiary amine, quarternary ammonium salt, Cyclic amine, imidazoles etc..These catalyst can be used alone or be used in combination of two or more.

It for alkali metal compound, can illustrate such as: sodium hydroxide, lithium hydroxide, potassium hydroxide alkali metal hydroxide The alkali metal alkoxylates such as the alkali metal salts such as object, sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, potassium chloride, sodium methoxide, sodium ethoxide The alkali metal salt of the organic acids such as object, alkali metal phenoxide, sodium hydride, lithium hydride etc., sodium acetate, odium stearate.

For organic phosphorus compound, it can illustrate such as: three n-propyl phosphines, tri-n-butyl phosphine, tri-tert-butylphosphine, triphenyl Phosphine, trimethylphenyl phosphine, trimethoxyphenyl phosphine, tricyclohexyl phosphine, bromination tetramethyl phosphonium, iodate tetramethyl phosphonium, tetramethylphosphonihydroxide hydroxide Base Phosphonium, chlorination 3-methyl cyclohexanol base Phosphonium, bromination 3-methyl cyclohexanol base Phosphonium, chlorination trimethyl benzyl Phosphonium, bromination trimethylbenzene first Ji Phosphonium, Xiuization tetraphenylphosphoniphenolate, bromination triphenyl methylphosphonium, iodate triphenyl methylphosphonium, chlorinated triphenyl base Yi Ji Phosphonium, bromination triphen Base second base Phosphonium, three phenylethyl Phosphonium of iodate, chlorinated triphenyl base benzene first base Phosphonium, bromination triphenyl benzyl Phosphonium etc..

It for tertiary amine, can illustrate such as: triethylamine, three n-propyl amine, tri-n-butyl amine, triethanolamine, benzyl two Methyl amine etc..For quarternary ammonium salt, it can illustrate such as: tetramethyl ammonium chloride, tetramethylammonium bromide, tetramethyl ammonium hydroxide, chlorine Change triethylmethylammonium, etamon chloride, tetraethylammonium bromide, iodate tetraethyl ammonium, bromination tetrapropyl ammonium, hydroxide 4 third Base ammonium, tetrabutylammonium chloride, Tetrabutylammonium bromide, tetrabutylammonium iodide, Benzene Chloride methyl trimethoxy base ammonium, benzyl bromide front three Base ammonium, hydroxide benzyl trimethyl ammonium, Benzene Chloride methyltributylammoni,m, chlorination phenyltrimethyammonium etc..

It for imidazoles, can illustrate such as: 2-methylimidazole, 2- phenylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl- 4-methylimidazole, 1- benzyl -2-methylimidazole, 1- benzyl -2- phenylimidazole etc..

For cyclic amine, can illustrate such as: Isosorbide-5-Nitrae-diazabicyclo [2,2,2] octane (DABCO), 1,8- diaza are double Ring [5,4,0] -7- hendecene (DBU), 1,5- diazabicyclo [4,3,0] -5- nonene (DBN), tetrahydro -1,4- oxazines ( Quinoline), N-methylmorpholine, N, N- dimethylaminopyridine (DMAP) etc..

Relative to reaction solid, the usage amount of catalyst is usually 0.001 to 1 quality %.Use alkali metal compound When as catalyst, alkali metal component can be remained in phosphorous phenoxy resin, and can allow the electronic/electrical for having used this catalyst Property part, printed circuit board insulation characterisitic deteriorate, therefore alkali metal contents such as lithium, sodium, potassium in phosphorous phenoxy resin Add up to preferred 100ppm hereinafter, more preferably 60ppm is hereinafter, even more preferably 50ppm or less.

In addition, when using organic phosphorus compound, tertiary amine, quarternary ammonium salt, cyclic amine, imidazoles etc. as catalyst, It can be remained in phosphorous phenoxy resin in the form of catalyst residue, and can allow electricity in the same manner as the residual of alkali metal component Son/electrical part, printed circuit board insulation characterisitic deteriorate, therefore the phosphorus atoms or nitrogen-atoms in phosphorous phenoxy resin contain Preferred 300ppm is measured hereinafter, more preferably 200ppm is hereinafter, even more preferably 100ppm or less.

When two phase method, solvent can be used, for the solvent, if phosphorous phenoxy resin can be dissolved and for anti- Dysgenic solvent would not be caused, then any solvent all may be used.It can illustrate such as aromatic system hydro carbons, ketone, ester series solvent, ether Series solvent, acid amides series solvent, glycol ether series solvent etc..This equal solvent can be used alone or mix two or more and use.

For aromatic system hydro carbons, can illustrate such as benzene,toluene,xylene.

For ketone, can illustrate such as: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), 2-HEPTANONE, 4- heptanone, 2- are pungent Ketone, cyclopentanone, cyclohexanone, pentanedione etc..

For ester series solvent, can illustrate such as: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, Ethyl butyrate, butyl butyrate, valerolactone, butyrolactone etc..

For ether series solvent, it can illustrate such as: Anaesthetie Ether, dibutyl ethers, t-butyl methyl ether, tetrahydrofuran, dioxy Six rings etc..

It for acid amides series solvent, can illustrate such as: formamide, N-METHYLFORMAMIDE, DMF, acetamide, N- methyl vinyl Amine, DMAC N,N' dimethyl acetamide, 2- Pyrrolizidine ketone, N- methylpyrrole pyridine ketone etc..

For glycol ether series solvent, can illustrate such as: ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list are just Butyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol list n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetic acid esters, propylene glycol monomethyl ether, third Glycol list n-butyl ether, propylene glycol monomethyl ether etc..

Though the amount of the solvent used can be properly selected in response to reaction condition, such as the feelings when two phase method manufactures Condition, solid concentration preferably 35 to 95 quality %.In addition, when generating high viscosity product in the reaction, it can be in reaction Simultaneously the reaction was continued for way addition solvent.After reaction, solvent optionally and by distillation etc. can be removed, can also further chased after Solubilizer.

Reaction when two phase method is the temperature range progress in the not resolvent degree of the catalyst used.Reaction temperature When excessively high, there is the anxiety of the phosphorous phenoxy resin deterioration of generation, when too low, there is reaction to get nowhere and be unable to reach target molecule The anxiety of amount.Therefore, preferably 50 to 230 DEG C of reaction temperature, more preferable 120 to 200 DEG C.In addition, the reaction time is usually 1 to 12 small When, preferably 3 to 10 hours.It, can be by using autoclave under high pressure when using the low boiling point solvents such as such as acetone, methyl ethyl ketone It is reacted to ensure reaction temperature.In addition, when needing to remove reaction heat, usually by using solvent caused by because of reaction heat Vaporization/condensation/circumfluence method, indirect cooling method or this methods of and be used to carry out.

Phosphorous phenoxy resin of the invention inherently has anti-flammability and belongs to the thermoplastic resin for having pliability And it can be used alone.Phosphorus containing ratio can be got higher when the X of formula (1) is largely base (X1), therefore can be used as polycarbonate resin The fire retardant of the thermoplastic resins such as rouge.

Thermosetting resin composition is made as alternatively, it is also possible to deploy hardening resin ingredient.At this point, can by A part of X imports not phosphorous-containigroups groups (X2), and is made as the anti-flammability phenoxy group tree in advance with characteristic needed for resin combination Rouge.

Secondly, illustrating resin combination of the invention.

Resin combination of the invention is formed by deploying hardening resin ingredient in the phosphorous phenoxy resin.

It for hardening resin ingredient, can illustrate such as: epoxy resin, acrylate, phenol resin, melamine tree Rouge, urea resin, unsaturated polyester resin, isocyanate resin, alkyd resin, thermosetting polyimide resin etc..These Among, preferred epoxy, phenol resin, melamine resin, isocyanate resin, more preferable epoxy resin.These hardenability Resin component can be used alone or be used in combination of two or more.

Hardening resin ingredient can illustrate such as: the resin combination that hardens epoxy resin by curing agent makes propylene Resin combination that acid ester resin is hardened by radical polymerization initiator makes phenol resin, melamine resin, isocyanates The resin component etc. that resin etc. passes through hot auto polymerization.It is appreciated that and needs curing agent when in order to harden hardening resin, urges Whens agent, promotor etc., hardening resin contains these at branch.

The blending amount of hardening resin ingredient is in phosphorous phenoxy resin/hardening resin ingredient (mass ratio) form For preferably 1/99 to 99/1, more preferable 10/90 to 90/10, even more preferably 25/75 to 75/25.By deploying hardening resin The superior material of heat resistance can be obtained in ingredient.

When hardening resin ingredient is epoxy resin, previous known epoxy resin can be used.Furthermore epoxy resin refers to At least with the epoxy resin of 1 epoxy group, but preferably there is the epoxy resin of 2 or more epoxy groups, more preferably there are 3 The epoxy resin of above epoxy group.Can particularly enumerate: polycyclic oxygen propyl group ether compound, gathers polycyclic oxygen propyl group amine compounds Glycidyl ester compounds, cycloaliphatic epoxy, other modification epoxy resin etc..These epoxy resin can be used alone, Also the epoxy resin of two or more kinds may be used same system, and the epoxy composite of not homology can also be used.

It for polycyclic oxygen propyl group ether compound, can particularly enumerate: bisphenol A type epoxy resin, bisphenol F type epoxy tree Rouge, tetramethyl bisphenol f type epoxy resin, united phenol-type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type asphalt mixtures modified by epoxy resin Rouge, naphthalenediol type epoxy resin, bisphenol-s epoxy resin, diphenylsulfide type epoxy resin, diphenyl ether type epoxy, Resorcinol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alkyl phenolic varnish Type epoxy resin, styrenated phenol phenolic resin varnish 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 Rouge, biphenyl aralkylphenol type epoxy resin, trihydroxy benzene methylmethane type epoxy resin, tetrahydroxy diphenylphosphino ethane type asphalt mixtures modified by epoxy resin Rouge, dicyclopentadiene-type epoxy resin, alkylene glycols type epoxy resin, aliphatic cyclic epoxy resin etc..

It for polycyclic oxygen propyl group amine compounds, can particularly enumerate: two aminodiphenylmethane type epoxy resin, isophthalic Dimethylamine type epoxy resin, 1,3- diamine ylmethyl hexamethylene type epoxy resin, isocyanuric acid ester type epoxy resin, aniline type Epoxy resin, hydantoins type epoxy resin, amino-phenol type epoxy resin etc..

It for polycyclic oxygen propyl group ester compounds, can particularly enumerate: dimer acid type epoxy resin, hexahydro O-phthalic Acid type epoxy resin, trimellitic acid type epoxy resin etc..

For cycloaliphatic epoxy, (the limited public affairs of Daicel chemical industry share of CELLOXIDE 2021 can be enumerated Department's system) etc. aliphatic cyclic epoxy resins etc..

For other modification epoxy resin, can particularly enumerate: amine formic acid esters modifies epoxy resin, the ketone ring of pyridine containing oxazole Epoxy resin, epoxy modification polybutadiene rubber derivative, carboxyl terminal butadiene- nitrile rubber (CTBN) modification epoxy resin, Polyvinyl arene polyoxide (for example, divinylbenzene dioxide, trivinyl naphthalene trioxide etc.), phosphorous epoxy Resin etc..

In the situation of allotment epoxy resin, curing agent can be contained.Curing agent, which refers to, to be facilitated between the epoxy group of epoxy resin Cross-linking reaction and/or chain length extend reaction substance.

Relative to 100 mass parts of epoxy resin, the blending amount of curing agent optionally uses 0.1 to 100 mass parts, preferably 1 to 80 mass parts, more preferable 5 to 60 mass parts, even more preferably 10 to 60 mass parts.

It for curing agent, is not particularly limited, the curing agent known usually as epoxy resin hardener all may be used It uses.From the viewpoint of improving heat resistance, phenol system curing agent, amide system curing agent and imidazoles can be preferably enumerated.In addition, from From the viewpoint of reducing water imbibition, active ester system curing agent can be preferably enumerated.In addition, can also enumerate: amine system curing agent, acid anhydrides system Curing agent, organic phosphine class, phosphonium salt, benzoxazine compound, tetraphenyl borate salts, organic acid dihydrazide, halogenation Boron Amine Complex, Polymercaptan system curing agent, isocyanates system curing agent, blocked isocyanate system curing agent etc..These curing agents can be used alone, Also two or more kinds may be used congener curing agent, can also combine other types and use.

It for phenol system curing agent, can illustrate such as: bisphenol-A, Bisphenol F, dihydroxydiphenyl methane, dihydroxydiphenyl It is ether, bis- (hydroxyphenoxy) benzene, dihydroxydiphenyl thioether, dihydroxydiphenyl ketone, dihydroxy-diphenyl sulfone, fluorenes bis-phenol, right Benzenediol, resorcinol, catechol, tert-butyl catechol, tert-butyl hydroquinone, dihydroxy naphthlene, bishydroxymethyl naphthalene Etc. dihydric phenolic compounds；Phenol novolacs, bisphenol A novolac, cresol novolak, dimethlbenzene novolaks, three hydroxyl Base phenylmethane novolaks, dicyclopentadiene phenol, naphthol novolac varnish, styrenated phenol novolaks, terpene phenolic, again Matter oil modifies phenol, phenol aralkyl, naphthols aralkyl, polycarboxylated styrene, phloroglucin, pyrogallol, tert-butyl o benzene The phenolic compounds of 3 yuan or more of triphenol, benzenetriol, trihydroxynaphthalene, trihydroxy diphenylketone, trihydroxy-acetophenone etc.；10-(2,5- Dihydroxy phenyl) the phosphorous phenolic compounds such as -10H-9- oxa- -10- phospho hetero phenanthrene -10- oxide.It can also will make these phenolate It closes the aromatic compounds such as object and indenes, styrene and is used in curing agent through the obtained compound of addition reaction.Phenol system curing agent It is preferred that being used with the range that molar ratio of the activity hydroxy in curing agent to the epoxy group in epoxy resin is 0.8 to 1.5.

For amide system curing agent, it can illustrate such as dicyanodiamine (dicyandiamide) and its derivative, polyamide resin Rouge etc..Relative to whole 100 mass parts of epoxy resin ingredient, amide system curing agent is preferably made with the range of 0.1 to 25 mass parts With.

For imidazoles, can illustrate such as: 2- phenylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl -4-methylimidazole, 1- benzyl -2-methylimidazole, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2- undecylimidazole, 1- cyano -2- phenyl Imidazoles, trimellitic acid 1- cyano ethyl -2- undecylimidazole, trimellitic acid 1- cyano ethyl -2- phenylimidazole, 2,4- Two amido -6- [2 '-methylimidazolyls-(1 ')]-ethyl-symmetrical triazine, bis- amido -6- [2 '-ethyls -4 '-methylimidazole of 2,4- Base-(1 ')] symmetrically the symmetrical triazine trimerization of triazine, 2,4- bis- amido -6- [2 '-methylimidazolyls-(1 ')]-ethyl-is different for-ethyl - Cyanic acid addition product, 2- phenylimidazole cyamelide addition product, 2- phenyl -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- first The addition product etc. of base -5- hydroxymethylimidazole and epoxy resin and the imidazoles.Relative to whole epoxy resin ingredients 100 Mass parts, imidazoles are preferably used with the range of 0.1 to 25 mass parts.Furthermore imidazoles have catalyst ability, therefore generally also It is classified as aftermentioned hardening accelerator, but is classified as curing agent in the present invention.

For active ester system curing agent, preferably phenolic ester class, thiophenol esters, N- hydroxylamine esters, heterocycle hydroxyl compound 1 molecule such as esters in the compound with the high ester group of 2 or more reactivities, wherein more preferably such as Japan Patent Phenolic ester class made of reacting multifunctional phenolic compounds with aromatic carboxylic acid documented by No. 5152445 bulletins.With regard to Carboxylation Close object for, can illustrate such as: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, Terephthalic acid (TPA), Pyromellitic Acid etc..For the aromatic compound with phenolic hydroxyl group, it can illustrate such as: catechol, two Hydroxyl naphthalene, dihydroxydiphenyl ketone, trihydroxy diphenylketone, tetrahydroxy diphenylketone, phloroglucin, benzenetriol, two rings penta 2 Alkenyl diphenol, phenol novolacs etc..Commercially available product has EPICLON HPC-8000-65T (DIC limited liability company system) etc., but It is not limited to these.Active ester system curing agent is preferably with the active ester groups in curing agent to mole of the epoxy group in resin combination Than the range use for 0.2 to 2.0.

It for amine system curing agent, can illustrate such as: two sub- second triamines, tetramine, m-xylene diamine, isophorone two Amine, two aminodiphenylmethane, two amido diphenyl sulfones, two amido diphenyl ethers, benzyl dimethyl amine, 2,4,6- three (two Methylamino methyl) acids such as phenol, dicyanodiamine, dimer acid and polyamines class the amine systems chemical combination such as the daiamid of condensation product Object etc..Amine system curing agent preferably with the active hydrogen-based in curing agent to the molar ratio of the epoxy group in resin combination be 0.5 to 1.5 range uses.

For acid anhydrides system curing agent, it can illustrate such as: methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, six Hydrogen phthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic dianhydride, phthalic anhydride, trimellitic anhydride, first Base carbic anhydride, maleic anhydride etc..Acid anhydrides system curing agent is preferably with the anhydride group in curing agent in resin combination Epoxy group molar ratio be 0.5 to 1.5 range use.

Furthermore active hydrogen-based refers to (can be because of water comprising having with the functional group for having reactive reactive hydrogen to epoxy group Solution etc. and the functional group for generating the functional group of the potentiality reactive hydrogen of reactive hydrogen, the same induration of display), it can particularly arrange Lift anhydride group, carboxyl, amido, phenolic hydroxyl group etc..Furthermore active hydrogen-based, carboxyl (- COOH) and phenolic hydroxyl group (- OH) are rubbed with 1 You, amido (- NH₂) calculated with 2 moles.In addition, when activity hydrogen-based is indefinite Ahew can be acquired by measuring. For example, can be by making monoepoxy resin and Ahew known to the epoxide equivalents such as phenyl glycidyl ether be unknown hard Agent reaction, and the amount for the monoepoxy resin consumed is measured to acquire the Ahew of used curing agent.

In addition, optionally hardening accelerator can be used when allotment epoxy resin.For hardening accelerator, it can illustrate Such as: imdazole derivatives, tertiary amines, phosphine phosphorus compound, metallic compound, lewis acid, amine complex salt etc..These hardening promote Agent can be used alone or be used in combination of two or more.

For imdazole derivatives, if the compound with imidazole skeleton, it is not particularly limited.It can illustrate such as: 2- Methylimidazole, 2- ethyl imidazol(e), 2-ethyl-4-methylimidazole, double -2-ethyl-4-methylimidazole, 1- methyl -2- ethyl imidazol(e), 2 isopropyl imidazole, 2,4- methylimidazole, 2- heptadecylimidazole etc. are through alkyl-substituted imidazolium compounds；2- phenylimidazole, 2- phenyl -4-methylimidazole, 1- benzyl -2-methylimidazole, 1- benzyl -2- ethyl imidazol(e), 1- benzyl -2- phenyl miaow Azoles, benzimidazole, 2- ethyl-4- methyl-1-(2 '-cyano ethyl) imidazoles, 2,3- dihydro-1H- pyrrolo- [1,2-a] benzo miaow The imidazolium compounds etc. that the alkyl through aryl or aralkyl etc. containing circular structure such as azoles replaces.

It for tertiary amines, can illustrate such as: 2- dimethylaminopyridine, 4- dimethylaminopyridine, 2- (dimethyl amido Methyl) phenol, 1,8- diaza-bicyclic [5.4.0] -7- hendecene (DBU) etc..

It for phosphine, can illustrate such as: triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine triphenylborane.

For metallic compound, can illustrate such as tin octoate.

For amine complex salt, can illustrate such as: boron trifluoride monoethylamine complex compound, boron trifluoride diethylamide complex compound, Boron trifluoride isopropylamine complex compound, boron trifluoride chlorphenyl amine complex, boron trifluoride benzyl amine complex, boron trifluoride Boron trifluoride complexes class such as aniline complex compound or these mixture etc..

In these hardening accelerators, with increasing layer (build up) material applications, circuit substrate purposes in use, from heat-resisting From the viewpoint of property, dielectric property, soldering resistance etc. are excellent, preferably 2- dimethylaminopyridine, 4- dimethylaminopyridine, imidazoles Class.In addition, with semiconductor sealing material use way and in use, excellent from hardenability, heat resistance, electrical characteristics, moisture-proof reliability etc. From the viewpoint of, triphenylphosphine, DBU.

The blending amount of hardening accelerator is properly selected according to purpose is used, but relative to the ring in resin combination 100 mass parts of oxygen resin component, optionally and use 0.01 to 15 mass parts, preferably 0.01 to 10 mass parts, more preferable 0.05 To 8 mass parts, even more preferably 0.1 to 5 mass parts.By using hardening accelerator, when can reduce hardening temperature or shorten hardening Between.

Make the resin that the acrylate as hardening resin group ingredient is hardened by radical polymerization initiator Composition can enumerate the thermosetting resin composition and photocurable resin composition of (methyl) acrylate based compound. (methyl) acrylate based compound adjusts as viscosity, hardener and at least with 1 or more (first in the molecule that uses Base) acryloyl group acrylate.A part of (methyl) acrylate based compound is with (methyl) propylene with 2 or more Acyl group is advisable.Resin combination at this time is caused with (methyl) acrylate based compound and thermal polymerization, photopolymerization Agent or both be essential component.

It for these (methyl) acrylate based compounds, can illustrate such as: the different camphane ester of (methyl) acrylic acid, (methyl) third Olefin(e) acid cyclohexyl, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester, (methyl) acrylic acid Two ring pentyl esters, acryloyl morpholine, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) third Olefin(e) acid 4- hydroxybutyl, polyethyleneglycol (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, hexamethylene -1,4- Dimethanol list (methyl) acrylate, (methyl) acrylic acid tetrahydrofuran methyl esters, (methyl) phenoxyethyl acrylate, phenyl are poly- Ethyoxyl (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- phenyl oxygroup propyl ester, o-phenyl phenol monosubstituted ethoxy (first Base) acrylate, o-phenyl phenol polyethoxy (methyl) acrylate, (methyl) acrylic acid is to cumenyl phenoxy group second Ester, the different camphane ester of (methyl) acrylic acid, (methyl) acrylic acid tribromo phenyl oxygroup ethyl ester, (methyl) dicyclopentanyl acrylate, (first Base) simple functions (methyl) acrylate, 1,4- such as acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester Butanediol two (methyl) acrylate, 1,6- hexane diol two (methyl) acrylate, two (methyl) third of 1,9- nonane glycol Olefin(e) acid ester, bisphenol-A polyethoxy two (methyl) acrylate, polymer with bis phenol A propoxyl group two (methyl) acrylate, the poly- second of Bisphenol F Oxygroup two (methyl) acrylate, ethylene glycol two (methyl) acrylate, (methyl) acrylic acid trimethylolpropane tris oxygroup second Ester, three (2- hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, pentaerythrite three (methyl) acrylate, Ji Wusi Alcohol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, polyethylene glycol two (methyl) acrylate, three (third Alkene trimethylammonium) isocyanuric acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid Ester, tripentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, hydroxyl trimethylace tonitric season penta 2 Alcohol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane polyethoxy three (methyl) Acrylate, two-trimethylolpropane four (methyl) acrylate, (methyl) acrylate of cyclohexanedimethanol two and dihydroxy first The multifunctional (methyl) acrylates such as base tristane two (methyl) acrylate make polyol compound and polyisocyanate chemical combination Object reaction and with resulting amine formic acid esters (methyl) acrylate of (methyl) acrylate reactions, epoxide and (methyl) third Olefin(e) acid ester reacts resulting epoxy acrylate etc..These (methyl) acrylate based compounds can be used alone or and with 2 Kind or more.

In addition, for the compound that the polymerization initiator that can be used as (methyl) acrylate based compound uses, if It can be generated free radicals, can be used without particular limitation by the methods of heating, the irradiation of active-energy linear light.Polymerization is drawn For sending out agent, such as when being hardened by heating, if the azos such as azobis isobutyronitrile, benzoyl peroxide system, peroxide The initiator that series initiators etc. may be used at common free radical thermal polymerization then all can be used.In addition, being polymerize by optical free radical When carrying out free radical polymerization, if benzoin class, acetophenones, Anthraquinones, thioxanthones, ketal class, diphenyl ketone, oxygen The initiator that change phosphine etc. may be used at common optical free radical polymerization then all can be used.These polymerization photoinitiators can individually make With or by the form of mixture of more than two kinds come using.Furthermore it, can also be with tertiary amines for optical free radical polymerization initiator Compound, N, promotors such as N- dimethyl amido ethyl benzoate etc. are combined and are used.

It is used in addition, organic solvent or reactive diluent can be used to adjust as viscosity for resin combination of the invention.This Equal organic solvents or reactive diluent can be used alone or mix two or more.

It for organic solvent, can illustrate such as: DMF, n,N-dimethylacetamide amides；Dioxane, tetrahydro furan It mutters, ethylene glycol single methyl ether, dimethoxy diethylene glycol, ethylene glycol Anaesthetie Ether, diethylene glycol diethyl ether, triethylene glycol two The ethers such as methyl ether；The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Methanol, ethyl alcohol, 1- methoxyl group -2- The alcohols such as propyl alcohol, 2- ethyl -1- hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl glycol, pine tar；Ethyl acetate, acetic acid fourth Ester, methoxy butyl acetate, methyl Sai Lusu acetic acid esters, Sai Lusu acetic acid esters, glycol acetic acid esters, propylene glycol monomethyl ether The acetate esters such as acetic acid esters, carbitol acetate, benzyl alcohol acetic acid esters；The benzoates such as methyl benzoate, ethyl benzoate； The Sai Lusu classes such as methyl Sai Lusu, Sai Lusu, butyl Sai Lusu；The carbitols such as methyl carbitol, carbitol, butyl carbitol Class；Benzene,toluene,xylene etc. is aromatic hydrocarbon；The sulfoxide types such as dimethyl sulfoxide；The alkanes such as hexane, hexamethylene；Acetonitrile, N- first Base Pyrrolizidine ketone etc., but not limited to this etc..

It for reactive diluent, can illustrate such as: allyl glycidyl ethers, butyl glycidyl ethers, 2- ethyl hexyl The monofunctional epoxies propyl ethers such as base glycidyl ethers, phenyl glycidyl ether, cresyl glycidyl ether；Two ring of resorcinol Oxygen propyl group ether, season pentanediol bisglycidyl ethers, 1,4- butanediol bisglycidyl ethers, 1,6- hexane diol diepoxy propyl Two functional epoxy's propyl ethers such as ether, cyclohexanedimethanol bisglycidyl ethers, propylene glycol bisglycidyl ethers；Glycerol polycyclic oxygen The poly- glycidyl ethers of propyl ether, trimethylolpropane, the poly- glycidyl ethers of trimethylolethane, the poly- glycidyl ethers of pentaerythrite Equal multi-functional epoxies' propyl ethers；The glycidyl esters such as neodecanoic acid glycidyl ester；Phenyl diepoxy propyl amine, tolyl two The glycidyl amine such as glycidyl amine, but not limited to this etc..

Organic solvent preferably by when non-volatile content calculates for 20 to 90 quality % in a manner of be used alone or using mix it is more It kind forms, type appropriate, usage amount are properly selected according to purposes.For example, printed circuit board is on the way, preferred methyl second The boiling points such as base ketone, acetone, 1- methoxy-2-propanol are 160 DEG C of polar solvents below, and usage amount is preferably in terms of non-volatile content It is 40 to 80 quality % when calculation.In addition, bonding film is on the way, it is preferable to use such as ketone, acetate esters, carbitol class, fragrance Race's hydro carbons, dimethylformamide, dimethyl acetamide, N- methylpyrrole pyridine ketone etc., usage amount is preferably calculated with non-volatile content When be 30 to 60 quality %.

Reactive diluent mainly uses when viscosity reduction, adjustment gel time in solvent-free system.This usage amount is more When, the insufficient progress of sclerous reaction and there is unreacted component the anxiety of exudation or to have from hardening thing and make the hardening things such as mechanical strength The anxiety of physical property reduction, thus it is preferred that it is not used above must measure.Therefore, in epoxy resin preferably 30 mass % hereinafter, more excellent 20 mass % are selected hereinafter, even more preferably 10 mass % or less.

Resin combination of the invention can will not allow reliability to drop for the purpose of the anti-flammability for promoting resulting hardening thing Low range and with the various non-halogen fire retardants for being substantially free of halogen atom.With regard to workable non-halogen fire retardant Speech, can illustrate as phosphorus flame retardant, nitrogenated flame retardant, poly- silicon oxygen flame retardant, inorganic flame retardant, organic metal salt system are fire-retardant Agent etc..These non-halogen fire retardants are limited without any system when in use, can be used alone, also two or more kinds may be used same system Fire retardant, also, the not fire retardant of homology can also be combined and used.

Phosphorous phenoxy resin of the invention can be not necessary to allotment fire retardant or allotment is greatly decreased because of excellent in flame retardance Fire retardant.

For phosphorus flame retardant, any one of inorganic phosphorus series compound, organophosphorus compound all be can be used.With regard to nothing For machine phosphorus series compound, can illustrate such as red phosphorus, monoammonium phosphate, Diammonium phosphate (DAP), triammonium phosphate, ammonium polyphosphate ammonium phosphate type, The nitrogenous inorganic phosphorus series compound such as phosphoamide.

In addition, red phosphorus has preferably applied surface treatment for the purpose of preventing water solution etc., for surface treatment method, can lift Such as: (1) with magnesium hydroxide, aluminium hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or these The method that the inorganic compounds such as mixture carry out cladding processing；(2) with magnesium hydroxide, aluminium hydroxide, zinc hydroxide, titanium hydroxide The method that the mixture of the equal thermosetting resins such as inorganic compounds and phenol resin carries out cladding processing；(3) magnesium hydroxide, It is carried out on the envelope of the inorganic compounds such as aluminium hydroxide, zinc hydroxide, titanium hydroxide with the thermosetting resins such as phenol resin two degrees The method etc. for coating processing.

It for organophosphorus compound, can illustrate such as: phosphate compound, condensed phosphoric acid esters, phosphinic acid compounds, secondary Phosphate cpd, phosphine oxide compound, phosphine hydride compounds etc. it is general with organophosphorus compound, nitrogenous organophosphorus compound, Hypophosphorous acid metal salt etc., there are also have directly to be bonded the phosphorus compound in the active hydrogen-based of phosphorus atoms (for example, DOPO, diphenyl Phosphine oxide etc.) or phosphorous phenolic compounds (for example, DOPO-HQ, DOPONQ, diphenylphosphino hydroquinone, diphenyl benzene Two oxygroup naphthalene of phosphino- -1,4-, 1,4- cyclooctylene phosphono -1,4- phenyl glycol, 1,5- cyclooctylene phosphono -1,4- phenyl Glycol etc.) etc. organophosphorus compounds, make the compounds such as these organophosphorus compounds and epoxy resin or phenol resin react and At derivative etc..

In addition, for the reactive phosphorus compound used in workable phosphorous epoxy resin, the phosphorous curing agent, It is preferred that organic phosphorus chemical combination shown in 2 phosphorous function phenolic compounds, formula (7) with phosphorous-containigroups groups shown in 1 or 2 formulas (3) Object.

For phosphorous epoxy resin, it is disclosed in Japanese Unexamined Patent Publication 04-11662 bulletin, Japanese Unexamined Patent Publication 05- No. 214070 bulletins, Japanese Unexamined Patent Publication 2000-309624 bulletin and Japanese Unexamined Patent Publication 2002-265562 bulletin etc..With regard to phosphorous It for the concrete example of epoxy resin, can illustrate such as: Epotohto FX-305, Epotohto FX-289B, Epotohto FX- 1225, YDFR-1320, TX-1328 (more than, aurification limited liability company system is lived by Nippon Steel) etc., but not limited to this etc..

The epoxide equivalent (g/eq.) preferably 200 to 800 of these phosphorous epoxy resin, more preferable 300 to 780, then it is more excellent Select 400 to 760.Phosphorus containing ratio preferably 0.5 to 7 quality %, more preferable 1 to 6 quality %, even more preferably 2 to 5.5 quality %, special It is preferred that 3 to 5 quality %.

It, can also be by Japanese Unexamined Patent Application Publication 3008- other than the 2 phosphorous function phenolic compounds for phosphorous curing agent No. 4548547 No. 501063 bulletins, Japanese Patent No. revealed manufacturing methods of bulletin, make with structural portion shown in formula (3) Phosphorus compound reacted with aldehydes and phenolic compounds and obtain phosphorous phenolic compounds.At this point, having structural portion shown in formula (3) Phosphorus compound be to carry out condensation in the aromatic ring of phenolic compounds via aldehydes and addition and intramolecular is entered by group.In addition, Japanese It, can be from having by further being reacted with aromatic carboxylic acid in the revealed manufacturing method of special open 2013-185002 bulletin The phosphorus compound phenolic compounds of structural portion shown in formula (3) obtains phosphorous active ester compound.In addition, the special table public again of Japan In the revealed manufacturing method of WO2008/010429 bulletin, the phosphorous benzo with structural portion shown in formula (3) can be obtained Oxazines compound.

Phosphorus compound blending amount according to the type and phosphorus containing ratio of phosphorus compound, the ingredient of resin combination, institute The degree of desired anti-flammability and properly select.Phosphorus compound is that reactive phosphorus compound is (i.e. phosphorous epoxy resin, phosphorous Curing agent) when, relative to phosphorous phenoxy resin, hardening resin ingredient, fire retardant and other filling materials or addition The full solid in resin combination that agent etc. has all been deployed is (in general, the full solid in resin combination refers to resin Ingredient in addition to solvents in composition it is total), phosphorus containing ratio preferably 0.2 to 6 quality %, more preferable 0.4 to 4 matter % is measured, even more preferably 0.5 to 3.5 quality %, particularly preferably 0.6 to 3.0 quality %.Phosphorus containing ratio had when few be difficult to ensure it is fire-retardant The anxiety of property, has the anxiety that adverse effect is caused to heat resistance, solvent solubility when excessive.Accordingly, with respect in resin combination Full solid, when using red phosphorus, the practical blending amount preferably range of 0.1 to 2 quality %, when using organophosphorus compound, The practical blending amount preferably range of 0.1 to 10 quality %, the range of more preferable 0.5 to 6 quality %.

In addition, in resin combination of the invention can and with such as hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, carbon Sour calcium, zinc molybdate etc. are used as flame retardant.

In the present invention, and with when fire retardant, it is preferable to use phosphorus flame retardant, but also can be used together it is following documented by it is fire-retardant Agent.

For nitrogenated flame retardant, can illustrate as triaizine compounds, cyanuric acid compound, cyamelide compound, Coffee thiazine etc., preferably triaizine compounds, cyanuric acid compound, cyamelide compound.Though the blending amount of nitrogenated flame retardant According to nitrogenated flame retardant type, other ingredients of resin combination, desired anti-flammability degree and properly select, but for example Preferably with respect to the full solid in resin combination, deployed with the range of 0.05 to 10 quality %, particularly preferably with 0.1 to 5 matter Measure the range allotment of %.In addition, when using nitrogenated flame retardant, can and with metal hydroxides, molybdenum compound etc..

For poly- silicon oxygen flame retardant, it can then be used with no particular limitation if the organic compound containing silicon atom, Can illustrate such as silicone, poly- silicone rubber, polysilicone.Though the blending amount of poly- silicon oxygen flame retardant is hindered according to poly- silicon oxygen system Combustion agent type, other ingredients of resin combination, desired anti-flammability degree and properly select, but it is for example preferably opposite Full solid in resin combination is deployed with the range of 0.05 to 20 quality %.In addition, using poly- silicon oxygen flame retardant When, can and with molybdenum compound, aluminium oxide etc..

For inorganic flame retardant, can illustrate such as: metal hydroxides, metal oxide, metal carbonate compounds, Metal powder, boron compound, low-melting glass etc..Though the blending amount of inorganic flame retardant is according to inorganic flame retardant type, resin group Close other ingredients of object, desired anti-flammability degree and properly select, but for example preferably with respect to phenoxy resin, hard The full solid in resin combination that the property changed resin component, fire retardant and other filling materials or additive etc. have all been deployed Part, it is deployed with the range of 0.05 to 20 quality %, is particularly preferably deployed with the range of 0.5 to 15 mass parts.

For organic metal salt flame retardant, it can illustrate such as: ferrocene, acetylacetone metal complex, organic metal Carbonyls, organic cobalt salt compound, metal organic sulfonate, metallic atom and aromatic compound or heterocyclic compound warp Compound made of ion bond or coordination bond etc..Though the blending amount of organic metal salt flame retardant is hindered according to organic metal salt system Combustion agent type, other ingredients of resin combination, desired anti-flammability degree and properly select, but it is for example preferably opposite In the resin group that phenoxy resin, hardening resin ingredient, fire retardant and other filling materials or additive etc. have all been deployed The full solid of object is closed, is deployed with the range of 0.005 to 10 quality %.

In addition, resin combination can deploy filling material, thermoplastic resin, ring optionally and in the range of not undermining characteristic It is thermosetting resin, coupling agent, antioxidant, mould release, defoaming agent, emulsifier, thixotropy imparting agent other than oxygen resin, flat Other additives such as lubrication prescription, pigment.

It is filled with for material, can illustrate such as: fused silica, crystalline silica, aluminium oxide, silicon nitride, boron nitride, nitridation Aluminium, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, diaspore, talcum, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, oxidation The inorganic fillers such as zinc, titanium oxide, magnesia, magnesium silicate, calcium silicates, zirconium silicate, barium sulfate, carbon；Carbon fiber, glass fibre, Alumina fibre, silica alumina fiber, silicon carbide fibre, polyester fiber, cellulose fibre, aramid fiber, ceramic fibre Equal fibrous fillers；Particulate rubber etc..

Among these, preferably will not permanganate used in the surface roughening treatment because of hardening thing the oxidation such as aqueous solution Property compound and the filling material that decomposes or dissolve, fused silica, crystalline silica are special due to being easy to get minuteness particle Not not preferably.In addition, especially when keeping the blending amount for filling material big, it is preferable to use fused silica.Although fused silica is broken Any one of shape, spherical all can be used, but in order to improve the blending amount of fused silica and inhibit the molten of moulding material simultaneously Melt viscosity rising, more preferably mainly uses spherical fused silica.It is excellent in order to further increase the blending amount of spherical silica Choosing suitably adjusts the size distribution of spherical silica.Furthermore filler can also carry out silane coupling agent processing, stearic acid etc. Organic acid processing.In general, the promotion effect of impact resistance of hardening thing, hardening thing can be enumerated using the reasons why filling material Low linear expansion.In addition, can be helped as fire-retardant when having used the metal hydroxides such as aluminium hydroxide, diaspore, magnesium hydroxide Agent and play a role and have promoted anti-flammability effect.When thermal conductivity to be promoted, preferably aluminium oxide, silicon nitride, boron nitride, nitridation Aluminium, fused silica, crystalline silica, more preferable aluminium oxide, boron nitride, fused silica, crystalline silica.It is used in conduction When the purposes such as cream, the conductive fillers agent such as silver powder, copper powder can be used.

When low linear expansion, the anti-flammability of hardening thing is contemplated, the blending amount of material is filled with a height of preferred.Relative to tree Full solid in oil/fat composition, preferably 1 to 98 quality %, more preferable 3 to 90 quality %, even more preferably 5 to 80 quality %, special It is preferred that 10 to 60 quality %.When blending amount is more, the anxiety of adhesiveness reduction needed for having plywood purposes, and hardening thing is fragile And there is the anxiety for being unable to get sufficient mechanical properties.In addition, having the impact resistance that can not show hardening thing when blending amount is few The coordination effect of fillers such as promotion anxiety.

In addition, be easy the residual clearance in hardening thing when the partial size of inorganic filler is excessive, when too small, be easy agglutination and Dispersibility is deteriorated.Preferably 0.01 to 5 μm of average grain diameter, more preferable 0.05 to 1.5 μm, even more preferably 0.1 to 1 μm.Inorganic fill The average grain diameter of agent can then keep the mobility of good resin combination if range.Furthermore average grain diameter can pass through granularity Distribution measurement device measures.

In resin combination of the invention can and with the thermoplastic resin other than phosphorous phenoxy resin of the invention.Just It for thermoplastic resin, can illustrate such as: phenoxy resin, polyamine formate resin, polyester resin, polyvinyl resin, polypropylene Resin, polystyrene resin, ABS resin, AS resin, vinyl chloride resin, vinylite, polymethyl methacrylate Resin, polyacetal resin, cyclic polyolefin resin, polyamide, thermoplastic polyimide resin, gathers polycarbonate resin Amide imide resin, polyflon, polyetherimide resin, polyphenylene oxide resin, modification polyphenylene oxide resin, polyether sulfone Resin, polysulfone resin, polyether-ether-ketone resin, polyphenylene sulfide, vinyl-formal resin etc..Come from the level of intermiscibility See, preferably phenoxy resin, from the point of view of the level of low dielectric property, preferably polyphenylene oxide resin, modification polyphenylene oxide resin.

The adjustable coupling agent of resin combination of the invention.By deploying coupling agent, can be promoted and the adhesiveness of substrate, base The adhesiveness of matter resin and inorganic filler.For coupling agent, silane coupling agent, titanate esters coupling agent etc. can be enumerated.These idols Mixture can be used alone or be used in combination of two or more.Furthermore relative to the full solid in resin combination, the blending amount of coupling agent It is preferably set to 0.1 to 2.0 quality % or so.When the blending amount of coupling agent is very few, it is unable to fully caused by obtaining allotment coupling agent The promotion effect of matrix resin and the adhesion of inorganic filler, on the other hand, when the blending amount of coupling agent is excessive, coupling agent can be from The anxiety of exudation in resulting hardening thing.

It for silane coupling agent, can illustrate such as: γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy The epoxy radicals silicone hydrides, γ-aminocarbonyl propyl such as propyl-triethoxysilicane, β-(3,4- expoxycyclohexyl) ethyl trimethoxy silane Triethoxysilane, N- β (amido ethyl) γ-aminocarbonyl propyl trimethoxy silane, N- β (amido ethyl) γ-aminocarbonyl propyl first The amino containing silanes such as base dimethoxysilane, γ-aminocarbonyl propyl trimethoxy silane, γ-ureidopropyltriethoxysilane, 3- mercapto The hydrosulphonyl silanes such as base propyl trimethoxy silicane, to styryltrimethoxysilane, vinyl trichlorosilane, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxy The vinyl silanes such as propyl trimethoxy silicane, there are also epoxy, amido system, polymer electrolyte silane of ethylene base system etc..

It for titanate esters coupling agent, can illustrate such as: three isostearoyl base titanate esters of isopropyl, (the N- amido of isopropyl three Ethyl/amido ethyl) titanate esters, bis- (dioctylphosphoric acid ester) titanate esters of diisopropyl, bis- (dioctyl phosphite) titaniums of tetra isopropyl Bis- (two-tritriacontyl of the phosphorous acid ester) titanate esters of acid esters, four octyls, four (2,2- diallyloxymethyl -1- butyl) bis- (phosphorous Sour two-tritriacontyl esters) titanate esters, bis- (dioctyl pyrophosphate) ethoxyacetic acid ester titanate esters, bis- (dioctyl pyrophosphate) ethylidene Titanate esters etc..

It for other additives, can enumerate: the organic pigments such as quinacridone, azo system, phthalein blueness system；Titanium oxide, gold Belong to the inorganic pigments such as foil-like pigment, rust resisting pigment；Be obstructed the ultraviolet absorbing agents such as amine system, enumerate BTA system, diphenylketone system；By Hinder the antioxidants such as phenol system, phosphorus system, sulphur system, hydrazides system；The mould releases such as stearic acid, palmitinic acid, zinc stearate, calcium stearate；Stream Flat agent, pigment dispersing agent, prevents the additives such as contracting agent, defoaming agent etc. at rheology adjusting control agent.Relative to complete in resin combination Solid, the blending amount of these the other additives preferably range of 0.01 to 20 quality %.

Resin combination of the invention can be by the way that each ingredient to be uniformly obtained by mixing.Allotment has phosphorous phenoxy group tree The resin combination of rouge, hardening resin ingredient and various additives optionally can be by identical with previously known method Method and be easily made hardening thing.For hardening thing, can enumerate sandwich, injection molding object, molding, adhesive layer, insulating layer, Film etc. shapes hardening thing.For the method to obtain hardening thing, method identical with known resin combination can be used, it can It is suitble to use: injection molding, injection, encapsulation (potting), dipping, drop coating (drip coating), metaideophone forming, compression molding etc. The methods of or be laminated in the form of resin sheet, the copper foil with resin, prepreg etc. and heat press quenching and plywood is made.Tree Though the method for curing of oil/fat composition is different because of the allotment ingredient and blending amount in resin combination, usual hardening temperature be 80 to 300 DEG C, firm time is 10 to 360 minutes.This heating preferably in 80 to 180 DEG C and 10 to 90 minutes of primary heating and It handles and carries out in the two-stage of 120 to 200 DEG C and 60 to 150 minutes of reheatings, in addition, super at glass transition temperature (Tg) It crosses in the allotment system of the temperature of reheating, is preferably further carried out at 150 to 280 DEG C and 60 to 120 minutes of heating three times. By carrying out reheating so, heating three times, it is bad that hardening can be reduced.Make resin sheet, the copper foil with resin, preimpregnation When the resins semihard compound such as body, usually by heating etc. and to keep the degree of shape to carry out the sclerous reaction of resin combination. When resin combination contains solvent, most solvent usually is removed by the gimmicks such as heating, decompression, air-dried, but in resin 5 mass % solvents below can be remained in semihard compound.

For using the purposes of resin combination of the invention, circuit board use material, sealing material, note can be applied to The miscellaneous field such as mold materials, conductive paste, adhesive, insulating materials, is used especially for as in electrical property/electronic field Insulate injection molding, stacking material, sealing material etc..For an example of purposes, though printed wiring board, flexible wiring base can be enumerated The bonding such as the electrical property/electronic circuit such as plate, capacitor plywood, the metal foil with resin, film adhesive, aqueous binder Filler, circuit board use insulating materials, insulating trip, preimpregnation between agent, semiconductor-encapsulating material, underfill material, 3D-LSI chip Body, heat-radiating substrate, resist printing ink, but not limited to this etc..

Printed circuit board material, circuit board use insulating materials, increasing layer bonding film purposes in these various uses In, it can be used as by the so-called electronics zero in the active parts insertion substrate such as passive part, the IC chip such as capacitor Part is built-in with the insulating materials of substrate.Among these, from the point of view of the characteristics such as high flame retardant, high-fire resistance and solvent solubility, It is preferable to use in printed circuit board material, flexible wiring substrate resin combination, increasing layer substrate interlayer dielectic etc. Circuit substrate (plywood) material and semiconductor-encapsulating material.

When the plates such as plywood are made in resin combination, for the viewpoint of its dimensional stability, bending strength etc., make Filling material is preferably fibrous, more preferable glass cloth, glass felt (glass mat), glass roving cloth.

Resin combination can be fabricated to preimpregnation used in printed circuit board etc. by being impregnated in fibrous reinforcement substrate Body.For fibrous reinforcement substrate, it can be used for example: the inorfils such as glass or polyester resin etc., polyamino resin, poly- third The woven fabric or nonwoven fabric of the organic matters fiber such as olefin(e) acid resin, polyimide resin, aromatic polyamide resin, but not limited to this.

For the method from resin combination manufacture prepreg, it is not particularly limited, such as can be described organic by that will contain The resin combination of the varnish shape of solvent further deploys organic solvent and is fabricated to the resin varnish for being adjusted to appropriate viscosity, and After the resin varnish is impregnated in the fibrous substrate, heat drying and make resin component semi-harden (B-stage) to obtain. For heating up temperature, in response to the type of used organic solvent, preferably 50 to 200 DEG C, more preferable 100 to 170 DEG C.Heating Time is adjusted according to the type of used organic solvent and the hardenability of prepreg, and preferably 1 to 40 minute, more preferable 3 To 20 minutes.At this point, being not particularly limited for the quality ratio of the resin combination and reinforcement substrate that use, but usually excellent Choosing is adjusted in a manner of making the resin in prepreg be divided into 20 to 80 quality %.

Resin combination of the invention can shape as sheet or membranaceous and use.At this point, previous known method can be used And give piece or membranization.For manufacturing the method for resin sheet, though being not particularly limited, can illustrate such as: (A) is by resin combination Object squeezes out after being kneaded with extruding machine, and the extrusion molding of sheet is configured to using T mould, circle mould etc.；(B) by resin combination After being dissolved or dispersed in organic solvent equal solvent, the casting forming method of sheet is cast and is configured to；And (C) is previous known other Piece forming process etc..Though for example, 10 to 300 μm, preferably 25 to 200 μm are more excellent in addition, the film thickness of resin sheet is not particularly limited Select 40 to 180 μm.In Layer increasing method in use, most preferably 40 to 90 μm.Insulating properties then can be obtained if 10 μm or more in film thickness, if 300 μm or less then interelectrode circuit distance will not grow to must distance more than.Furthermore though the solvent content of resin sheet is without special It limits, but relative to resin combination entirety, preferably 0.01 to 5 quality %.It is whole relative to resin combination, the solvent in film Content is easy to get when being then laminated to circuit substrate if 0.01 mass % or more to adhesion, adhesiveness, if 5 mass % hereinafter, Then be easy to get the flatness to after heat hardening.

It, can be by the resin combination of the varnish shape containing the organic solvent for the manufacturing method of more specific bonding sheet Being coated on using coating machines such as reverse roll coaters, scraper funny formula coating machine (comma coater), die coaters will not After being dissolved on the support basement membrane of organic solvent, heat drying and make resin component B-stage to obtain.In addition, can be optionally And other support basement membrane is overlapped as protective film at coated face (adhesive phase), and drying is obtained in two mask of adhesive phase There is the bonding sheet of peeling layer.

For supporting basement membrane, the polyolefin films such as the metal foils such as copper foil, polyethylene film, polypropylene screen can be enumerated, is poly- to benzene Polyester films, polycarbonate membrane, silicon fiml, the polyimide films such as dioctyl phthalate second diester film etc. among these, are lacked preferably without particle etc. It falls into, dimensional accuracy is excellent and the also excellent polyethylene terephthalate film for cost.Additionally, it is preferred that the multilayer of plywood Change easy metal foil, particularly preferably copper foil.Though the thickness of support basement membrane is not particularly limited, from the intensity having as supporter And be difficult to cause it is laminated it is bad from the point of view of, preferably 10 to 150 μm, more preferable 25 to 50 μm.

Though the thickness of protective film is not particularly limited, and usually 5 to 50 μm.Furthermore in order to be easily peeled off through molding viscous Piece is closed, preferably imposes surface treatment using mould release in advance.In addition, after the thickness of coating resin varnish is preferably dry with a thickness of 5 to 200 μm, more preferable 5 to 100 μm.

For heating up temperature, in response to the type of used organic solvent, preferably 50 to 200 DEG C, more preferable 100 to 170℃.Heating time is adjusted, preferably 1 to 40 point according to the type of used organic solvent and the hardenability of prepreg Clock, more preferable 3 to 20 minutes.

Such resulting resin sheet would generally become the insulation bonding sheet with insulating properties, but can also be by resin combination The particulate for mixing conductive metal in object or being coated with through metal, to obtain electroconductive adhesive sheet.Furthermore the support Basement membrane is removed after being laminated at circuit substrate or after heat hardening forms insulating layer.If hard heating bonding sheet Support basement membrane is removed after change, then can prevent the attachment of dust in cure step etc..Here, the insulation bonding sheet is also exhausted Embolium.

Illustrate with the metal foil by the resulting resin of resin combination of the invention.For metal foil, usable copper, Aluminium, brass, nickel etc. individually, alloy, compound metal foil.It is preferable to use 9 to 70 μm of thickness of metal foils.Just from containing phosphorous For the method for the metal foil of fire retardant resin composition made of epoxy resin and metal foil manufacture with resin, without especially limit It is fixed, such as can will be clear as adjusting resin made of the phosphorous resin combination viscosity with solvent by using roll-coater etc. Paint be coated on after the one side of the metal foil, heat drying and make resin component semi-harden (B-stage) and form resin layer To obtain.When keeping resin component semi-harden, for example, can in 100 to 200 DEG C heat drying 1 to 40 minute.Here, with resin The thickness of the resin portion of metal foil is preferably formed as 5 to 110 μm.

In addition, prepreg to be made, insulation bonding sheet hardening, can be used the hard of plywood when usually manufacturing printed circuit board Change method, but not limited to this.

For example, one or more pieces prepregs can be laminated using prepreg and when forming plywood, match in unilateral or two sides It sets metal foil and constitutes sandwich, harden prepreg the sandwich pressurized, heated, and make its integration, and be laminated Plate.Here, for metal foil, independent, the alloy, compound metal foil such as usable copper, aluminium, brass, nickel.

For by the condition of sandwich heating pressurization, suitably adjusts and heat with the condition that resin combination can harden Pressurization, but when the pressure amount pressurizeed is too low, can rewarding plywood internal residual bubble and the situation that reduces of electrical characteristics, Therefore the condition pressurization preferably to meet mouldability.Preferably 160 to 250 DEG C of heating temperature, more preferable 170 to 220 DEG C.Moulding pressure is excellent Select 0.5 to 10MPa, more preferable 1 to 5MPa.Heating pressing time preferably 10 minutes to 4 hours, more preferable 40 minutes to 3 hours. When heating temperature is low, have the anxiety that sclerous reaction does not carry out sufficiently, when heating temperature is high, have cause hardening thing thermal decomposition it Anxiety.When moulding pressure is low, the situation that the internal residual bubble and electrical characteristics of the rewarding plywood of meeting reduce, moulding pressure height When, have the anxiety that resin before hardening pours off and be unable to get the plywood of desired thickness.In addition, heating pressing time is short When, it has the anxiety that sclerous reaction does not carry out sufficiently and has the anxiety for causing the thermal decomposition of hardening thing when heating pressing time is long.

Also, can be using the plywood of such resulting single layer as internal layer material, and it is fabricated to multi-layer board.At this point, first with Addition process or subraction etc. and circuit is imposed to plywood and is formed, circuit surface will be formed by and handled and imposed black with acid solution Change processing, and obtain internal layer material.In the single side of the internal layer material or the circuit forming face of two sides, with prepreg or resin sheet, insulation Bonding sheet or metal foil with resin form insulating layer and form conductor layer in surface of insulating layer, and form multi-layer board.

In addition, configuring a piece of prepreg or stacking in the circuit forming face of internal layer material when forming insulating layer using prepreg There is multi-disc prepreg, further forms laminated body in its outside configuration metal foil.Then, by the laminated body heat pressurization and one It is body formed, the hardening thing of prepreg is formed as insulating layer whereby and forms the metal foil on the outside of it as conductor layer. Here, metal foil identical with metal foil used in the plywood for being used as inner plating can be used for metal foil. In addition, heating press molding can carry out under the same conditions with the molding of internal layer material.It can be in so shaped multilayer laminate Surface imposes through-hole formation further with addition process or subraction, circuit is formed, and makes printed circuit board forming.In addition, can By the way that printed circuit board as internal layer material and is repeated the engineering method, and it is further formed the multi-layer board of multilayer.

For example, when forming insulating layer with the bonding sheet that insulate, in the circuit forming face configuration insulation bonding of the internal layer material of multi-disc Piece and form sandwich.Or insulation bonding sheet is configured between the circuit forming face and metal foil of internal layer material and forms stacking Object.Then, which is heated into pressurization and be integrally formed, whereby form the hardening thing for the bonding sheet that insulate as insulating layer simultaneously And form the multiple stratification of internal layer material.Or form internal layer material and the metal foil for conductor layer and the hardening thing shape by the bonding sheet that insulate At as insulating layer.Here, can be used for metal foil and be used as metal foil used in the plywood of internal layer material Identical metal foil.In addition, heating press molding can carry out under the same conditions in the molding with internal layer material.

In addition, in plywood be coated with resin combination and when forming insulating layer, preferably by resin combination coating for 5 to After 100 μm of thickness, in 100 to 200 DEG C of (preferably 150 to 200 DEG C) heat dryings 1 to 120 minute (preferably 30 to 90 minutes) And be formed as sheet.Belong to and is formed in the method for being commonly referred to as casting method.Thickness after drying is preferably formed as 5 to 150 μm, preferably 5 to 80 μm.Furthermore from sufficiently obtaining film thickness and be not likely to produce from the point of view of coating is uneven or striped, the viscosity of resin combination is excellent It is 10 to 40000mPas when being selected in 25 DEG C, even more preferably 200 to 30000mPas.It can be in the multilayer laminate being thusly-formed Surface, further with addition process or subraction impose through-hole formed, circuit formed and form printed circuit board.In addition, can lead to It crosses using the printed circuit board as internal layer material and repeats the engineering method, and be further formed the plywood of multilayer.

For using the resulting sealing material of resin combination of the invention, there is the semiconductor wafer of band (tape) shape to use, Encapsulation type liquid sealing use, bottom fill out use, semiconductor interlayer dielectric use etc., can be suitble to be used in these.For example, with regard to semiconductor For in package shape, it can enumerate using injection molding or metaideophone forming machine, emission forming machine etc. and shape resin combination, and in 50 to 200 DEG C of methods for heating 2 to 10 hours and obtaining molding.

In order to which resin combination is modulated to semiconductor sealing material use, it can enumerate and mix view in resin combination in advance Need and after the additives such as blenders and coupling agent, mould release such as the inorganic fill material deployed, using extruder, kneader, Roller etc. be sufficiently melted and mixed to uniformly until gimmick.At this point, for inorganic filler, usually using silica, but herein In the case of, it is preferable in resin combination, so that inanimate matter filler is deployed as the ratio of 70 to 95 quality %.

When using such resulting resin combination as band-like sealing material, it can enumerate and resin combination is heated and made Semi-harden, and after sealing material band is made, this sealing material band is set to semiconductor die on piece, it is soft with 100 to 150 DEG C of heating It is melted into shape, and in 170 to 250 DEG C of fully hardened methods.In addition, when using as encapsulation type liquid sealing material, by gained Resin combination optionally and after being dissolved in solvent, be coated on semiconductor wafer, on electronic component, directly harden.

In addition, resin combination of the invention can also be used as resist printing ink.At this point, can enumerate: in resin combination Allotment has the vinyl monomer of ethylene unsaturated double-bond, the cationic polymerization catalyst as curing agent in object, and adds After adding pigment, talcum and filler and resist printing ink composition being made, after being coated on printed base plate in a manner of screen painting, The method that resist printing ink hardening thing is made.Preferably 20 to 250 DEG C or so of the temperature range of hardening temperature at this time.

By the resulting hardening thing of resin combination of the invention due to heat resistance, excellent in flame retardance, thus be easily guided into The skeleton of various characteristics is assigned to phosphorous phenoxy resin.Therefore, be used especially for as must have simultaneously anti-flammability and be situated between The multilayer printed wiring boards of the specific features such as electrical characteristics, low water absorbable, solvent solubility, film adhesive, underfill material, absolutely Embolium, prepreg etc..

[embodiment]

Though enumerating Examples and Comparative Examples below to illustrate the present invention, the present invention is in the range without departing from its purport It is interior, then it is not limited to these.When without especially indicating, " part " indicates mass parts, and " % " indicates quality %.

Following presentation analysis method, measuring method.

(1) epoxide equivalent:

It is measured according to JIS K7236 specification, unit g/eq..

From non-volatile content, it is calculated as the numerical value of solid scaled value.

(2) weight average molecular weight (Mw):

It is found out by GPC measurement.Specifically, be used in ontology (TOSOH limited liability company system, HLC-8320GPC) with Series system has chromatographic column (TOSOH limited liability company system, TSKgel SuperH-H, SuperH2000, SuperHM- H, SuperHM-H) chromatograph, column temperature is set as 40 DEG C.In addition, dissolved liquid uses DMF (containing 20mM lithium bromide), it is set as 0.3mL/ minutes flow velocitys, detector use RI detector.Measurement sample " is dissolved in solid 0.1g using 20 μ L's The DMF of 10mL and the sample filtered through 0.45 μm of microstrainer ".By from standard polyethylene oxide (TOSOH limited liability company System, SE-2, SE-5, SE-8, SE-15, SE-30, SE-70, SE-150) obtained calibration curve converts and finds out Mw.Again Person, data processing use the GPC-8020 mode II version 6.00 of TOSOH limited liability company.

(3) phosphorus containing ratio:

Sulfuric acid is added in sample, hydrochloric acid, crosses chloric acid, is heated and wet type ashing, using all phosphorus atoms as orthophosphoric acid.In sulphur Make metavanadate and molybdic acid reactant salt in sour acid solution, measures the extinction in 420nm of generated phosphovanadomolybdic acid complex compound Degree, the phosphorus containing ratio found out by the calibration curve made in advance is indicated with %.

(4) glass transition temperature (Tg):

It is measured according to IPC-TM-650 2.4.25.c.Specifically, with obtained by second of circulation of differential scanning calorimetry DSC chart extrapolation gamma transition start temperature (Tig) indicate.Differential scanning calorimetry measurement device uses SII " EXSTAR6000DSC6200 " of NanoTechnology limited liability company.Sample use is measured by resin film punching press (punching), the sample for being laminated and being packaged in aluminum capsule.Measurement is with 10 DEG C/min of heating rate from room temperature to 240 It DEG C is recycled twice.

(5) anti-flammability:

According to UL94VTM (the safety certification specification of Underwriters Laboratories Inc.), commented with normal beam technique Estimate.Assessment is recorded as VTM-0, VTM-1, VTM-2.Anti-flammability is most excellent with VTM-0, and with the sequence of VTM-1, VTM-2 variation. But completely burned is to be recorded as X.

(6) water absorption rate:

The test film that resin film is cut into 50mm × 50mm square is measured using 5.Use heated air circulation type baking oven Test film is dried into after ten minutes quality measurement immediately with 100 DEG C under air environment, which is dipped in 50 DEG C of warm water, Water absorption rate is found out by the mass incremental after 48 hours.

Synthesis example 1

In the reaction unit for having agitating device, thermometer, nitrogen gatherer, cooling tube and separator, in room Under temperature, charging 200 parts of propylene glycol monomethyl ether, 108 parts of DOPO, 4.2 parts of water (water/DOPO molar ratio= 0.47) it, is warming up to 70 DEG C under nitrogen environment and makes it completely dissolved.In wherein, spending the NQ78.9 parts of (NQ/ of charging in 30 minutes Molar ratio=0.999 of DOPO).After charging, until being warming up to 145 DEG C that reflux starts, the same of temperature is being maintained the reflux for When sustained response 5 hours.

Resulting product is cooled to room temperature and is filtered with attracting filtering.2500 parts of acetic acid benzene first is added in filter residue It after ester and heating make it completely dissolved, is cooled to room temperature and stands 1 day, the sediment of generation is filtered with attracting filtering.It will Filtrate puts into 39% aqueous methanol, and the sediment of generation is filtered with attracting filtering, following formula is obtained in the form of filter residue (9) 2 phosphorous function phenolic compounds (99% or more purity) shown in.

Synthesis example 2

In device identical with synthesis example 1, at room temperature, 108 parts of DOPO of charging, (BQ/DOPO's rubs 53 parts of BQ Your ratio=0.98), 1.8 parts of water (molar ratio=0.20 water/DOPO), 200 parts of PMA, reflux is warming up under nitrogen environment Until 145 DEG C started, sustained response 3 hours while maintaining the reflux for state.

Resulting product is cooled to room temperature and is filtered with attracting filtering.2500 parts of acetic acid benzene first is added in filter residue It after ester and heating make it completely dissolved, is cooled to room temperature and stands 1 day, the sediment of generation is filtered with attracting filtering.It will Filtrate puts into 39% aqueous methanol, and the sediment of generation is filtered with attracting filtering, following formula is obtained in the form of filter residue (10) 2 phosphorous function phenolic compounds (99% or more purity) shown in.

Abbreviation used in Examples and Comparative Examples is described as follows.

[2 functional epoxy resins]

(A-1): (aurification limited liability company system, product name: YD- are lived to bisphenol A-type liquid epoxy resin by Nippon Steel 8125, epoxide equivalent: 172, the number of repetition j ≒ 0.01 of formula (8))

(A-2): 3,3 ', 5,5 '-tetramethyls -4,4 '-xenol epoxy resin (Chemical limited liability company, Mitsubishi System, product name: YX-4000, epoxide equivalent: 186, j ≒ 0.06)

(A-3): (aurification share is lived by Nippon Steel to be had the epoxy resin of 4,4 '-(3,3,5- trimethylcyclohexylene) bis-phenols Limit corporation, product name: TX-1468, epoxide equivalent: 218, j ≒ 0.04)

(A-4): (aurification limited liability company system, product name: YDF- are lived to bisphenol-f type liquid epoxy resin by Nippon Steel 170, epoxide equivalent: 169)

(A-5): phenol novolak type epoxy resin (aurification limited liability company system is lived by Nippon Steel, product name: YDPN-638, epoxide equivalent: 177)

[2 function phenolic compounds]

(B-1): the resulting phosphorous 2 function phenolic compounds of synthesis example 1 (hydroxyl equivalent: 294, phosphorus containing ratio 10.5%)

(B-2): the resulting phosphorous 2 function phenolic compounds of synthesis example 2 (hydroxyl equivalent: 269, phosphorus containing ratio 11.5%)

(B-3): (three photochemistry limited liability company systems, product name: HCA-HQ, hydroxyl are worked as by phosphorus-containing compound, DOPO-HQ Amount: 162, phosphorus containing ratio 9.5%)

(B-4): (three photochemistry limited liability company systems, product name: HCA-NQ, hydroxyl are worked as by phosphorus-containing compound, DOPO-NQ Amount: 187, phosphorus containing ratio 8.3%)

(B-5): (aurification limited liability company system, hydroxyl equivalent: 114) are lived to bisphenol-A by Nippon Steel

[catalyst]

(C-1): 2-ethyl-4-methylimidazole (chemical conversion industry limited liability company, four countries system, product name: CUREZOL2E4MZ)

(C-2): triphenylphosphine (reagent)

(C-3): three (2,6- Dimethoxyphenyl) phosphine (reagent)

[curing agent]

DICY: dicyanodiamine (Japanese CARBIDE Industries, Inc system, product name: DIHARD, Ahew 21)

Embodiment 1

In the reaction unit for having agitating device, thermometer, nitrogen gatherer and cooling tube, at room temperature, charging (A-1) 561 parts, 130 parts of (B-2), 309 parts of (B-5), 430 parts of diethylene glycol dimethyl ether, make nitrogen flow, rise while stirring Temperature after 0.1 part of addition (C-1), is warming up to 165 DEG C to 145 DEG C, carries out reaction 10 hours in synthermal.With methyl match road Soviet Union 800 800 parts of part, cyclopentanone dilutions mixing, obtain the resin varnish 1 of the phosphorous phenoxy resin of non-volatile content 33%.Use roller coating This resin varnish is coated on release film (polyimide film in a manner of making the film thickness after solvent seasoning become 60 μm by cloth machine System), after ten minutes in 150 DEG C of dryings, desciccator diaphragm is peeled from fractal film.2 desciccator diaphragms are overlapped, using vacuum molding machine, with Vacuum degree 0.5kPa, 180 DEG C of drying temperature, pressing pressure 2MPa condition suppress 60 minutes, obtain 100 μm of thickness of resin Film.Furthermore in order to adjust the spacer of 100 μm of thickness of thickness and use.

Epoxide equivalent and Mw are measured using resin varnish, uses resin film measurement phosphorus containing ratio, Tg, combustibility and water suction Rate the results are shown in table 1.Furthermore the molar ratio in table indicates (epoxy group of raw material epoxy resin)/(2 function phenol of raw material The hydroxyl of compound) molar ratio.X1 (mole %) carrys out the base (X1) in the X entirety molal quantity of expression (1) with mole % Ratio.

Embodiment 2 to 7

Ratio (part) is deployed according to documented by table 1, using device same as Example 1, is set with identical operation Rouge varnish 2 to 7 and resin film.The measurement result of epoxide equivalent, Mw, phosphorus containing ratio, Tg, combustibility and water absorption rate is shown in Table 1.

Comparative example 1 to 6

Ratio (part) is deployed according to documented by table 2, using device same as Example 1, is set with identical operation Rouge varnish H1 to H6 and resin film.The measurement result of epoxide equivalent, Mw, phosphorus containing ratio, Tg, combustibility and water absorption rate is shown in Table 2.

Table 1

Table 2

Embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, embodiment 5 and comparative example 4, embodiment 6 and comparative example 5 with And embodiment 7 and comparative example 6, just all containing phosphorous-containigroups groups shown in formula (3) and phosphorus containing ratio, epoxide equivalent and Mw it is almost same Situation is compared, although not having base (X1) in this point to be different with comparative example, know in all cases, compared to Comparative example, anti-flammability, the heat resistance of embodiment are more excellent.Even if in addition, changing known to embodiment 5, embodiment 6 and embodiment 7 Become the type of base (X2), anti-flammability is still excellent.

Embodiment 3 with comparative example 3 is compared with regard to improving the case where phosphorus containing ratio is until anti-flammability meets VTM-0 Compared with, it is known that heat resistance, the water resistance of the embodiment with base (X1) are more excellent.

Embodiment 4 with comparative example 3 is compared with regard to the identical situation of water absorption rate, it is known that the embodiment with base (X1) Heat resistance, water resistance are more excellent, and phosphorus containing ratio can be improved.

By described it is found that the range to import change of base (X2) extensively, can assign miscellaneous characteristic.

Embodiment 8

Addition 303 parts the resulting resin varnish 1 of embodiment 1, as 100 parts of (A-4) of epoxy resin, as hardening 6.2 parts of DICY of agent, as 0.2 part of (C-1) of hardening accelerator, as 50 parts of methyl Sai Lusu of solvent and 50 parts DMF and uniform stirring mixing, obtain composition varnish.Using roll-coater by this composition varnish so that after solvent seasoning The thickness of desciccator diaphragm is coated on release film as 60 μm of mode, after ten minutes in 150 DEG C of dryings, peels drying from fractal film Film.2 desciccator diaphragms are overlapped, using vacuum molding machine, with vacuum degree 0.5kPa, 200 DEG C of heating temperature, pressing pressure 2MPa Condition is suppressed 60 minutes, and 100 μm of thickness of cured film is obtained.Furthermore in order to adjust the interval of 100 μm of thickness of thickness and use Part.

9 to 11 comparative example 7 to 8 of embodiment

Ratio (part) is deployed according to documented by table 3, composition epoxy resin varnish is obtained with operation same as Example 8 And cured film.For cured film measurement Tg, combustibility and water absorption rate, table 3 the results are shown in.

Table 3

Though embodiment 8 known to is deployed in the same manner as comparative example 8 with comparative example 7, embodiment 9, and the heat resistance of embodiment is inhaled It is aqueous more excellent.

Claims

1. a kind of phosphorous phenoxy resin, by shown in following formula (1), weight average molecular weight 10,000 to 200,000；

In formula, X is divalent base, but at least part in X is that group X1, Y shown in following formula (2) are each independently hydrogen atom Or glycidyl, n is number of repetition and its average value is 25 to 500；

Wherein, A is the aromatic series ring group selected from phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring, these aromatic series ring groups can have carbon number 1 to 8 Alkyl, the alkoxy of carbon number 1 to 8, the naphthenic base of carbon number 5 to 8, the aryl of carbon number 6 to 10, the aralkyl of carbon number 7 to 11, carbon Any of aryloxy group or the aralkyl oxy of carbon number 7 to 11 of number 6 to 10 are used as substituent group, and Z is shown in following formula (3) Phosphorous-containigroups groups；

Wherein, R¹And R²For that can have the alkyl of heteroatomic carbon number 1 to 20, and it is identical to distinguish phase exclusive or, can for straight-chain, Branched, ring-type, R¹With R²It can also be bonded and become cyclic structure position, k1 and k2 independently are 0 or 1.

2. phosphorous phenoxy resin according to claim 1, wherein phosphorous-containigroups groups shown in the formula (3) are following formula Phosphorous-containigroups groups shown in (3a) and/or (3b)；

Wherein, R³And R⁴It is separately the alkyl of carbon number 1 to 11, m1 is separately 0 to 4 integer, and m2 is independently The integer that ground is 0 to 5.

3. phosphorous phenoxy resin according to claim 1 or 2, wherein the X contains the base X1, and opposite In the molal quantity of X entirety, the not phosphorous-containigroups groups X2 not containing phosphorus is contained with the range of 25 to 75 moles of %.

4. phosphorous phenoxy resin according to any one of claim 1 to 3, wherein the not phosphorous-containigroups groups X2 is at least Contain any group in divalent base shown in 1 following formula (4a) to (4c)；

Wherein, R⁵To be directly bonded or alkyl ,-CO- ,-O- ,-S- ,-SO selected from carbon number 1 to 20₂And-C (CF₃)₂Divalent Base, R⁶、R⁷And R⁸It is separately the alkyl of carbon number 1 to 11, m3 and m4 are separately 0 to 4 integer, and m5 is 0 to 6 Integer.

5. phosphorous phenoxy resin according to any one of claim 1 to 4, wherein phosphorus containing ratio is 1 to 10 matter Measure %.

6. a kind of resin combination is deployed phosphorous described in any one of claims 1 to 5 in hardening resin ingredient Phenoxy resin forms.

7. resin combination according to claim 6, wherein the hardening resin ingredient is selected from epoxy resin, third Alkene acid ester resin, melamine resin, isocyanate resin and phenol resin at least one kind of resin.

8. a kind of circuit board use material is obtained using resin combination described in claim 6 or 7.

9. a kind of hardening thing hardens resin combination described in claim 6 or 7.