CN102656204A

CN102656204A - Epoxy resin, process for production thereof, epoxy resin composition using same, and cured product

Info

Publication number: CN102656204A
Application number: CN2010800528652A
Authority: CN
Inventors: 梶正史; 大神浩一郎
Original assignee: Nippon Steel Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2009-12-14
Filing date: 2010-12-13
Publication date: 2012-09-05
Anticipated expiration: 2030-12-13
Also published as: TWI494338B; TW201144347A; JP5166610B2; MY156527A; KR20120115301A; SG181697A1; JPWO2011074517A1; WO2011074517A1; KR101752222B1; CN102656204B

Abstract

Provided is an epoxy resin which has a low viscosity and exhibits excellent handleability in a solid state and which has excellent performances such as heat resistance, moisture resistance and thermal conductivity. The epoxy resin is useful in various fields such as lamination, molding, casting, and adhesive bonding. Also provided are both an epoxy resin composition using the epoxy resin and a cured product. The epoxy resin is a crystalline epoxy resin that is represented by general formula (1) and exhibits an endothermic peak temperature of 100 to 150 DEG C assignable to the melting point in the differential scanning calorimetry. Further, the epoxy resin composition comprises the epoxy resin and a curing agent as the essential components. In general formula (1), n is 0.2 to 4.0 on average; and G is a glycidyl group.

Description

Epoxy resin, its method of manufacture, the composition epoxy resin that uses it and cured article

Technical field

The present invention relates to crystalline epoxy resin, its method of manufacture, the composition epoxy resin that uses it and cured article.

Background technology

In recent years, particularly follow the progress in tip materials field, seek the exploitation of more high performance matrix resin.For example, in the field of encapsulating semiconductor, seek the matrix resin of high heat resistance, thermolysis excellent in stability owing to the semi-conductive progress of vehicle mounted.On the other hand,, point to the high fill-ratio of inorganic filler, also seek the lowering viscousity of matrix resin strongly because the real dressization of high-density also gets along with.In addition, requirement is used for the raising of the high temperature reliability of corresponding harsh environment for use, considers from the viewpoint that thermal diffusivity improves, and also requires the raising of thermal conductivity.

But known in the past epoxy resin does not find to satisfy these requirements.For example motion has the resin of naphthols aralkyl-type epoxy resin as thermotolerance, excellent moisture resistance in patent documentation 1, but insufficient aspect thermotolerance, and viscosity is high, is inappropriate for the high fill-ratioization of inorganic filler.In addition,, in patent documentation 2, disclose and connected 4 with the p-Xylol base as the resin of excellent heat resistance, the epoxy resin of the aralkyl-type of 4 '-dihydroxybiphenyl, but aspect wet fastness, flame retardant resistance existing problems.In patent documentation 3, disclose and have the epoxy resin of biphenyl aralkyl-type that has connected the structure of bisphenol cpd with biphenylene, but for not having crystalline arborescens thing, viscosity and softening temperature uprise, existing problems aspect formability.

The prior art document

Patent documentation

Patent documentation 1: the spy opens flat 1-252624 communique

Patent documentation 2: the spy opens flat 4-255714 communique

Patent documentation 3: the spy opens flat 8-239454 communique

Summary of the invention

Therefore; The objective of the invention is to; LV property and excellent as the solid operability is provided; Have the also excellent performance of thermotolerance, wet fastness and heat conductivity simultaneously, in range upon range of, moulding, casting, bonding etc. purposes useful epoxy resin and the composition epoxy resin that uses it with and cured article.

That is, the present invention relates to have crystalline epoxy resin, it is by formula (1) expression, based on the endotherm peak temperature of the fusing point in the differential scanning calorimetric analysis scope at 100～150 ℃.

(wherein, n is in MV expression 0.2～4.0, and G representes glycidyl.)

In addition; The present invention relates to the following crystalline epoxy resin that has: with respect to 4,1 mole of 4 '-dihydroxybiphenyl make following biphenyl by general formula (2) expression be 0.1～0.4 mole of condensing agent react and after forming multi-hydroxy resin by formula (3) expression, itself and Epicholorohydrin are reacted and obtain based on the endotherm peak temperature of the fusing point in the differential scanning calorimetric analysis scope at 100～150 ℃.

(wherein, X representes the alkoxyl group of hydroxyl, halogen atom or carbonatoms 1～6.)

(wherein, n representes in MV expression 0.2～4.0.)

And then the cured article that the invention still further relates to composition epoxy resin and its curing is formed is characterized in that, in the composition epoxy resin that is made up of epoxy resin and solidifying agent, contains above-mentioned epoxy resin as the epoxy resin composition.

Description of drawings

Fig. 1 is the GPC chart of the resin that obtains in the reference example 1.

Fig. 2 is the GPC chart of the resin that obtains among the embodiment 1.

Fig. 3 is the DSC chart of the resin that obtains among the embodiment 1.

Embodiment

Below, specify the present invention.

Epoxy resin of the present invention, for by general formula (1) expression, and the different mixture of ingredients of the value of repeating unit n.At this, n is in MV expression 0.2～4.0.If strengthen than its little then crystallinity, fusing point uprises simultaneously, and operability reduces.If reduce than its big then crystallinity, viscosity uprises simultaneously, and formability reduces.Consider that from the viewpoint of LV property, operability and formability the content of n=0 body is preferably in 30～60% scope.The MV of so-called n refers to such an extent that be number MV among the present invention.

Epoxy resin of the present invention has crystallinity, crystallization under solid state.With this crystalline solid with 10 ℃/minute of heat-up rates measure based on the endotherm peak temperature of the fusing point in the differential scanning calorimetric analysis 100～150 ℃, preferably 120～150 ℃ scope.If than its height then when adjusting composition epoxy resin and the consistency of solidifying agent reduce, if lower then produce the problem of the caking etc. of composition epoxy resin, the operability reduction than it.Because of the crystalline state of epoxy resin, find the peak of a plurality of fusing points sometimes, but refer to the temperature of corresponding maximum peak at this so-called endotherm peak temperature.Think that the caloric receptivity at peak representes crystalline degree, but convert in the scope of 20～80J/g in resinous principle usually.If lower than its little then crystalline degree, operability reduces.

Epoxy resin of the present invention obtain through making multi-hydroxy resin and Epicholorohydrin reaction by general formula (3) expression, but in the invention of epoxy resin, method of manufacture is not limited thereto.But the invention through the explanation method of manufacture becomes easily the understanding of epoxy resin of the present invention, so from explaining as the multi-hydroxy resin of the raw material of epoxy resin and the method for manufacture of epoxy resin.

Multi-hydroxy resin by general formula (3) expression is the different mixture of ingredients of the value of n, and n counts 0.2～4.0 with MV.If the solvability to Epicholorohydrin during than its little then crystallinity grow, synthetic epoxy resin reduces, the fusing point of the epoxy resin that obtains simultaneously uprises, and operability reduces.If than its big then crystallinity reduce, viscosity uprises simultaneously, formability reduces.Consider that from the viewpoint of LV property, operability and formability the content of n=0 body is preferably in 30～60% scope.

Such multi-hydroxy resin is condensing agent and 4 through making the biphenyl by general formula (2) expression, and 4 '-dihydroxybiphenyl reacts and obtains.

In general formula (2), X representes the alkoxyl group of hydroxyl, halogen atom or carbonatoms 1～6.Particularly, can enumerate 4,4 '-two hydroxymethyl biphenyl, 4,4 '-dichloride methyl biphenyl, 4,4 '-two bromomethylbiphenyls, 4,4 '-bi-methoxy methyl diphenyl, 4,4 '-two ethoxyl methyl biphenyl.Consider from reactive viewpoint, preferred 4,4 '-two hydroxymethyl biphenyl, 4,4 '-dichloride methyl biphenyl is considered preferred 4,4 '-two hydroxymethyl biphenyl, 4,4 '-bi-methoxy methyl diphenyl from the viewpoint that ionic impurity reduces.

Make the mol ratio in its when reaction, with respect to 4,1 mole of 4 '-dihydroxybiphenyl, biphenyl are that condensing agent must be below 1 mole, generally speaking 0.1～0.5 mole scope, more preferably 0.2～0.4 mole scope.If than its at least when crystallinity grow, synthetic epoxy resin the solvability to Epicholorohydrin reduce, the fusing point of the epoxy resin that obtains simultaneously uprises, operability reduces.In addition, if the crystallinity of resin reduces at most, softening temperature and melt viscosity uprise simultaneously, and operation task property, formability are caused obstacle than it.

In addition, using 4,4 '-dichloride methyl biphenyl can under catalyst-free, make its reaction, but this condensation reaction is carried out in the presence of an acidic catalyst usually during as condensing agent.As this an acidic catalyst; Can from well-known mineral acid, organic acid, select, for example can enumerate Lewis acid or the solid acid etc. of organic acid or zinc chloride, ammonium chloride, iron(ic)chloride, the boron trifluoride etc. of mineral acid or formic acid, oxalic acid, trifluoracetic acid, tosic acid, methylsulfonic acid, the trifluoromethanesulfonic acid etc. of hydrochloric acid, sulfuric acid, phosphoric acid etc.

This is reflected at and carried out under 10～250 ℃ 1～20 hour.The aromatics etc. of alcohols or benzene, toluene, chlorobenzene, dichlorobenzene etc. that in addition, the time can use methyl alcohol, ethanol, propyl alcohol, butanols, terepthaloyl moietie, methylcyclohexane, ethyl cellosolve etc. in reaction is as solvent.After reaction finishes, can remove the water, the alcohol that desolvate or generate because of condensation reaction as required.

The multi-hydroxy resin that obtains like this can be used as the raw material of epoxy resin, in addition also can be used as epoxy curing agent and uses.In addition, also can be further through with the solidifying agent combination of hexamine etc., use as the resol formed material.

For utilizing method of manufacture to describe by the epoxy resin of the present invention of the reaction of the multi-hydroxy resin of general formula (3) expression and Epicholorohydrin.This reaction can likewise be carried out with well-known epoxidation reaction.

For example; Can enumerate following method: after will the Epicholorohydrin of multi-hydroxy resin dissolves in surplus by general formula (3) expression, in the presence of the alkali metal hydroxide of sodium hydroxide, Pottasium Hydroxide etc. 50～150 ℃, preferably make its reaction 1～10 hour 60～120 ℃ scope.The usage quantity of the Epicholorohydrin of this moment is 0.8～2 mole with respect to 1 mole of the hydroxyl in the multi-hydroxy resin, preferred 0.9～1.2 mole scope.Reaction finishes the back distillation and removes superfluous Epicholorohydrin, residue is dissolved in the solvent of toluene, MIBK etc., filters, washing and remove inorganic salt, and then distillation removes and desolvates, and can obtain the target epoxy resin by general formula (1) expression thus.When carrying out epoxidation reaction, also can use the catalyzer of quaternary ammonium salt etc.

The purity of epoxy resin of the present invention, particularly water-disintegrable chlorine dose consider that from the viewpoint that the safety of the electronic component used improves few person is advisable.Do not have special qualification, but be preferably below the 1000ppm, further be preferably below the 500ppm.Need to prove that so-called water-disintegrable chlorine is meant the value of measuring through following method among the present invention.Be among the: Zai diox 30ml behind the dissolved samples 0.5g, add 1N-KOH 10ml, carried out boiling reflux 30 minutes, be cooled to room temperature then, further add 80% acetone water 100ml, use 0.002N-AgNO ₃The aqueous solution carries out that potential difference drips and the value that obtains.

In composition epoxy resin of the present invention, contain epoxy resin and solidifying agent, as the epoxy resin composition, contain the epoxy resin of above-mentioned general formula (1).

In composition epoxy resin of the present invention, except epoxy resin, also can and be used in the epoxy resin of common other that has 2 above epoxy group(ing) in the molecule as the general formula (1) of must composition and using.If for example, dihydroxyphenyl propane, Bisphenol F, 3 are then arranged, 3 ', 5; 5 '-tetramethyl--4,4 '-dihydroxyl ditan, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxyl diphenyl sulfide, 4; 4 '-dihydroxyl diphenylketone, fluorenes bis-phenol, 4,4 '-xenol, 3,3 '; 5,5 '-tetramethyl--4,4 '-dihydroxybiphenyl, 2; 2 '-xenol, Resorcinol, catechol, tert-butyl catechol, Tert. Butyl Hydroquinone, 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1; 4-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 1; 7-dihydroxy naphthlene, 1,8-dihydroxy naphthlene, 2,3-dihydroxy naphthlene, 2; 4-dihydroxy naphthlene, 2,5-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, 2; 7-dihydroxy naphthlene, 2,2 yuan of phenols of the allylate of 8-dihydroxy naphthlene, above-mentioned dihydroxy naphthlene or poly-allylat thing, allylation dihydroxyphenyl propane, allylation Bisphenol F, allylation phenol phenolic varnish etc. or phenol phenolic varnish, bisphenol-A phenolic varnish, o-Hydroxytoluene Novolac, meta-cresol phenolic varnish, p-cresol phenolic varnish, xylenol phenolic varnish, poly(4-hydroxystyrene), three-(4-hydroxy phenyl) methane, 1,1; 2,2-four (4-hydroxy phenyl) ethane, fluorine glycinol, pyrogallol, tertiary butyl pyrogallol, allylation pyrogallol, poly-allylat pyrogallol, 1,2; 4-benzene triol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthols aralkyl resin, NSC 7352 be the phenols more than 3 yuan or tetrabromo-bisphenol of resin etc. etc. by halogenation bisphenols deutero-glycidyl ether thing etc.These epoxy resin can use a kind or mix more than 2 kinds to mix and use.

Composition epoxy resin of the present invention, expectation contain the epoxy resin of the above above-mentioned general formula (1) of the 50wt% of epoxy resin composition as epoxy resin.And then preferably, more than the 70wt% for total epoxy, more preferably more than the 80wt%.If usage ratio is littler then as the formability variation of composition epoxy resin, the raising effect of the thermotolerance when forming cured article simultaneously, wet fastness and heat conductivity and reflux-resisting welded connecing property etc. is little than it.

As the solidifying agent in the composition epoxy resin of the present invention, the solidifying agent of generally knowing as curing agent for epoxy resin all can use.Dyhard RU 100, polyatomic phenol, anhydrides, aromatic series and aliphatics amine etc. are for example arranged.In the field of sealing technology that requires wet fastness, stable on heating electrical/electronic part, preferably use polyatomic phenol.If concrete example these, then as shown in following.In resin combination of the present invention, can use a kind of these solidifying agent or mix use more than 2 kinds.

As polyatomic phenol, dihydroxyphenyl propane, Bisphenol F, bisphenol S, fluorenes bis-phenol, 4 are for example arranged, 4 '-xenol, 2,2 yuan of phenols of 2 '-xenol, Resorcinol, Resorcinol, naphthalene glycol etc.; Or three-(4-hydroxy phenyl) methane, 1; 1; 2; The phenols more than 3 yuan of representatives such as 2-four (4-hydroxy phenyl) ethane, phenol phenolic varnish, o-Hydroxytoluene Novolac, naphthol novolac varnish, polyvinylphenol and then phenols, aphthols or dihydroxyphenyl propane, Bisphenol F, bisphenol S, fluorenes bis-phenol, 4; 4 '-xenol, 2, the condensing agent that passes through formaldehyde, acetaldehyde, phenyl aldehyde, PARA HYDROXY BENZALDEHYDE, p-Xylol glycol etc. of 2 yuan of phenols of 2 '-xenol, Resorcinol, Resorcinol, naphthalene glycol etc. and the polynary phenoloid of synthetic etc.In addition, also can use the multi-hydroxy resin of representing by general formula (3).

As acid anhydrides, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, carbic anhydride, trimellitic acid 1,2-anhydride etc. are arranged.

As amine; Have 4; 4 '-diaminodiphenyl-methane, 4; 4 '-diamino-diphenyl propane, 4, the aromatic amine of 4 '-diamino diphenyl sulfone, mphenylenediamine, p-Xylol diamines etc., the aliphatics amine of quadrol, hexamethylene-diamine, NSC 446, Triethylenetetramine (TETA) etc.

In resin combination of the present invention, can use a kind of these solidifying agent or mix use more than 2 kinds.

In addition; In the composition epoxy resin of the present invention; Can suit to cooperate the oligopolymer or the macromolecular compound of polyester, polymeric amide, pi, polyethers, ppe, urethane, petroleum resin, indenes coumarone resin, phenoxy resin etc., also can cooperate the various additives of inorganic filler, pigment, fire retardant, thixotropy imparting agent, coupler, fluidity improver etc.

Further in composition epoxy resin of the present invention, can cooperate inorganic filler, for example can be separately or and with the powder of the SiO 2 powder of the fused silica of the spherical or broken shape more than 2 kinds, crystalline silica etc., aluminum oxide, zircon, Calucium Silicate powder, lime carbonate, silit, SP 1, beryllium oxide, zirconium white, forsterite, talcum, spinel, mullite, titanium oxide etc. or with these material spheroidizations the single crystal fiber, spun glass etc. of bead, potassium titanate, silit, silicon nitride, aluminum oxide etc.In above-mentioned inorganic filler, consider that from the viewpoint that linear expansivity reduces preferred molten silicon-dioxide is considered from the viewpoint of high thermal conductivity, preferred aluminum oxide.Flowability and the mould abradability of weighting agent shape during from moulding considered preferably to make 50% or more for sphere, especially preferably uses the spheroidal fused SiO 2 powder.

The addition of inorganic filling material usually, is more than the 50wt% with respect to composition epoxy resin, but is preferably more than the 70wt%, more preferably more than the 80wt%.If can't give full play to target effects of the present invention such as agent of low hygroscopicity, low heat expansion property, high heat resistance, high thermal conductivity at least than it.As far as these effects, the addition of inorganic filling material is The more the better, but can corresponding its volume fraction and improve, and is significantly improved by specific addition.On the other hand, if the addition of inorganic filling material than its at most viscosity uprise, so the formability variation is not preferred.

In composition epoxy resin of the present invention, can cooperate known curing catalyst.If for example; Amine, imidazoles, organic phosphine class, Lewis acid etc. are then arranged; Particularly; Can enumerate 1; 8-diazabicyclo (5; 4; 0) undecylene-7,1; 5-diazabicyclo (4,3,0) nonene, 5; 6-dibutylamino (ヂ Block チ Le アミノ)-1; The tetraphenyl borate salts (ester) of the organic phosphine class of the imidazoles of the verivate of the cyclic amidine compounds of 8-diazabicyclo (5,4,0) undecylene-7 grade and the compound with π key of addition maleic anhydride, benzoquinones, benzene diazonium methane etc. forms in these compounds tertiary amines and these materials, glyoxal ethyline, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazoles etc. and the verivate of these materials, tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, diphenylphosphine, Phenylphosphine etc. and four Qu Dai Phosphonium, the four substituted boracic acid esters that the compound with π key of addition maleic anhydride, benzoquinones, benzene diazonium methane etc. forms in these phosphine classes, 2-ethyl-4-methylimidazole tetraphenyl boric acid ester, N-methylmorpholine tetraphenyl boric acid ester etc. and the verivate of these materials etc. with intramolecularly polar compound, tetraphenylphosphoniphenolate tetraphenyl boric acid ester, tetraphenylphosphoniphenolate ethyl triphenyl boric acid ester, 4-butyl-phosphonium tetrabutyl boric acid ester etc. with intramolecularly polar compound, triethylenediamine, benzyl dimethyl amine, trolamine, dimethylaminoethanol, three (dimethylaminomethyl) phenol etc.As addition, usually, be the scope of 0.2～10 weight part with respect to epoxy resin 100 weight parts.These materials can use separately, also can and use.

In the composition epoxy resin of the present invention, can use fire retardant as required.As such fire retardant, for example can enumerate the nitrogen flame retardant of the phosphorus flame retardant, pyrrolotriazine derivatives etc. of red phosphorus, phosphate cpd etc.; The phosphorus-nitrogen containing flame retardant of phosphazene derivative etc.; The zn cpds of the organometallic complex of MOX, metal hydrate, metallocenes verivate etc., zinc borate, zinc, zinc molybdate etc. etc., wherein, the preferable alloy hydrate.As metal hydrate; For example can enumerate white lake, Marinco H, calcium hydroxide, nickel hydroxide, cobaltous hydroxide, ironic hydroxide, stannic hydroxide, zinc hydroxide, verditer, titanium hydroxide etc.; In addition, can use the composition metal hydrate of the MOX of these metal hydrates and nickel oxide, powder blue, red stone, White tin oxide, zinc oxide, cupric oxide, palladous oxide etc.The viewpoint of the influence that causes from the formability to security, flame retardant effect and formed material is considered, preferred Marinco H.

In composition epoxy resin of the present invention; Except that above-mentioned, can use higher fatty acid, higher fatty acid metal-salt, ester as required is the ion-trapping agent etc. of the stress negative catalyst, hydrotalcite, antimony-bismuth etc. of the flexible agent, organic silicone oil, organo-silicone rubber powder etc. of the coupling agent, organosilicon powder etc. of the tinting material, silane-based, titanic acid ester system, aluminic acid ester system etc. of the releasing agent, carbon black etc. of wax, polyolefin wax etc.

In addition in composition epoxy resin of the present invention, the flowability improvement during from moulding and consider with the aspect that the adaptation of the base material of lead frame etc. improves can be added thermoplastic oligopolymer class.As thermoplastic oligopolymer class, but the petroleum resin of illustration C5 system and C9 system, styron, indene resin, indenes styrene copolymerized resin, indenes vinylbenzene phenol copolymer resins, indenes coumarone copolymer resins, indenes thionaphthene copolymer resins etc.As addition, usually,, be the scope of 2～30 weight parts with respect to epoxy resin 100 weight parts.

The modulator approach of composition epoxy resin of the present invention; As long as can various starting material homodisperse be mixed; Can use any means; But as general method, can enumerate the starting material of the use level through thorough mixing such as mixing machine regulations after, the method for carrying out melting mixing, cooling, pulverizing through mixing roll, forcing machine etc.

Composition epoxy resin of the present invention is particularly suitable in semiconductor device, using as sealing.

Cured article of the present invention can obtain through making above-mentioned composition epoxy resin thermofixation.Obtain cured article in order to use composition epoxy resin of the present invention, but the method for application examples such as transfer molding, press compression molding, cast molding, injection molding, extrusion moulding etc., but consider preferred transfer molding from the viewpoint of the property produced in batches.

Embodiment

Below, through embodiment the present invention is described particularly further.

Synthetic example 1

In the 4 neck flasks of 2000ml, pack 4 into; 4 '-dihydroxybiphenyl 186.0g (1.0 moles), diglyme 600g; Under nitrogen gas stream, be warming up to 150 ℃ while stirring; Dropping is dissolved with 4 in diglyme 260g, behind the solution of 4 '-dichloride methyl biphenyl 75.3g (0.3 mole), be warming up to 170 ℃ and reacted 2 hours.After the reaction, drop in a large amount of pure water and reclaim, obtain faint yellow crystalline resin 220g through redeposition.The OH equivalent of the resin that obtains is 130.8.Peak temperature during DSC measures is 248.5 ℃, and the caloric receptivity of the fusion of accompanying crystallization is 95.5J/g.The GPC figure of the resin that obtains is shown in Fig. 1.As far as measure each composition ratio in the general formula of obtaining (3) through GPC, n=0 is 39.33%, and n=1 is 22.25%, and n=2 is 12.19%, and n=3 is 8.14%, and n=4 is 5.58%, and n >=5 are 11.88%.At this, the DSC peak temperature is meant and uses differential scanning calorimetric analysis device (セイコーイ Application ス Star Le system DSC220C type) with 5 ℃ of/minute values of measuring of heat-up rate.In addition; GPC is measured device: Japanese ウォーターズ (strain) system, 515A type, post: TSK-GEL2000 * 3 piece and TSK-GEL4000 * 1 piece (being Dong ソー (strain) makes), solvent: oxolane, flow: 1ml/min, temperature: 38 ℃, detector: according to the condition of RI.

Synthetic example 2

Use is with 4; 4 '-dihydroxybiphenyl 167.4g (0.9 mole), diglyme 540g, 4; 4 '-dichloride methyl biphenyl 90.4g (0.36 mole) is dissolved in the solution among the diglyme 320g; Likewise react with synthetic example 1 in addition, obtain faint yellow crystalline resin 205g.The OH equivalent of the resin that obtains is 139.2.The DSC peak temperature is 242.4 ℃, and as far as measure each composition ratio in the general formula of obtaining (3) through GPC, n=0 is 31.21%, and n=1 is 21.19%, and n=2 is 13.38%, and n=3 is 10.63%, and n=4 is 7.55%, and n >=5 are 15.35%.

Synthetic example 3

Use is with 4; 4 '-dihydroxybiphenyl 186.0g (1.0 moles), diglyme 540g, 4; 4 '-dichloride methyl biphenyl 50.2g (0.2 mole) is dissolved in the solution among the diglyme 320g; In addition, likewise react, obtain faint yellow crystalline resin 195g with synthetic example 1.The OH equivalent of the resin that obtains is 125.6.The DSC peak temperature is 255.4 ℃, and as far as measure each composition ratio in the general formula of obtaining (3) through GPC, n=0 is 50.87%, and n=1 is 20.67%, and n=2 is 11.54%, and n=3 is 7.11%, and n=4 is 3.78%, and n >=5 are 5.87%.

Synthetic example 4

Use is with 4; 4 '-dihydroxybiphenyl 152.5g (0.82 mole), diglyme 500g, 4; 4 '-dichloromethyl biphenyl 112.9g (0.45 mole) is dissolved in the solution among the diglyme 360g, likewise reacts with synthetic example 1 in addition, obtains light yellow resin 201g.The OH equivalent of the resin that obtains is 150.1.As far as measure each composition ratio in the general formula of obtaining (3) through GPC, n=0 is 22.03%, and n=1 is 14.65%, and n=2 is 11.89%, and n=3 is 9.46%, and n=4 is 7.36%, and n >=5 are 33.87%.

Synthetic example 5

Use is with 4; 4 '-dihydroxybiphenyl 186.0g (1.0 moles), diglyme 600g, 1; The two toluene(mono)chloride 52.5g (0.3 mole) of 4-are dissolved in the solution among the diglyme 260g, likewise react with synthetic example 1 in addition, obtain faint yellow crystalline resin 202g.The OH equivalent of the resin that obtains is 116.3.The DSC peak temperature is 241.7 ℃, measures through GPC in the general formula (3) obtain, as far as comparing with each corresponding composition of structure that biphenylene with cross-linking part is substituted by phenylene; N=0 is 40.33%, and n=1 is 23.31%, and n=2 is 11.22%; N=3 is 7.09%, and n=4 is 5.17%, and n >=5 are 12.35%.

Synthetic example 6

Use 4,4 '-dihydroxyl ditan 200.0g (1.0 moles) replaces 4, and 4 '-dihydroxybiphenyl (1.0 moles) likewise reacts with synthetic example 1 in addition, distills to remove through underpressure distillation then and desolvates, and obtains filbert resin 245g.The OH equivalent of the resin that obtains is 137.6.To measure through GPC in the general formula (3) obtain with 4,4 '-dihydroxybiphenyl skeleton is substituted by 4, each composition in 4 '-dihydroxyl diphenylmethyl alkyl structure than; N=0 is 36.89%, and n=1 is 20.36%, and n=2 is 12.30%; N=3 is 9.68%, and n=4 is 6.58%, and n >=5 are 13.56%.

Embodiment 1

The resin 120g that obtains in the synthetic example 1 is dissolved among Epicholorohydrin 509g, the diglyme 76.4g, and under reduced pressure (about 130Torr) dripped 48% aqueous sodium hydroxide solution 76.5g down at 62 ℃ through 4 hours.During this period, the water of generation is through removing to system with the azeotropic of Epicholorohydrin, and the Epicholorohydrin that distillation is removed turns back in the system.After dripping end, further continue reaction in 1 hour.Then, Epicholorohydrin is removed in distillation, behind the adding MIBK 971g, desalts through washing to remove.Then, add 24% aqueous sodium hydroxide solution 19.3g, under 85 ℃, carry out reaction in 2 hours.After after the reaction, filtering, washing, the MIBK as solvent is removed in underpressure distillation, obtains epoxy resin 148g (epoxy resin A).The epoxy resin equivalent is 183.7, and water-disintegrable chlorine is 1400ppm.The GPC figure of the resin that obtains is shown in Fig. 2.As far as measure each composition ratio in the general formula of obtaining (1) through GPC, n=0 is 42.49%, and n=1 is 19.41%, and n=2 is 12.23%, and n=3 is 8.50%, and n=4 is 4.56%, and n >=5 are 8.18%.DSC is measured the result be shown in Fig. 3.The peak temperature that DSC measures among the result is 140.0 ℃, and the caloric receptivity of the fusion of accompanying crystallization is 36.9J/g.In addition, capillary melting point is 111.5～143.8 ℃, and 150 ℃ melt viscosity is 51mPas.

Embodiment 2

The resin 122g that obtains in the synthetic example 2 is dissolved among Epicholorohydrin 486g, the diglyme 72.9g, and under reduced pressure (about 130Torr) dripped 48% aqueous sodium hydroxide solution 73.0g down at 62 ℃ through 4 hours.During this period, the water of generation is through removing to system with the azeotropic of Epicholorohydrin, and the Epicholorohydrin that distillation is removed turns back in the system.After dripping end, further continue reaction in 1 hour.Then, Epicholorohydrin is removed in distillation, behind the interpolation MIBK 970g, desalts through washing to remove.Then, add 24% aqueous sodium hydroxide solution 19.3g, under 85 ℃, carry out reaction in 2 hours.After after the reaction, filtering, washing, the MIBK as solvent is removed in underpressure distillation, obtains epoxy resin 146g (epoxy resin B).The epoxy resin equivalent is 195.1, and water-disintegrable chlorine is 715ppm.Peak temperature during DSC measures is 135.1 ℃, and the caloric receptivity of the fusion of accompanying crystallization is 29.8J/g.Capillary melting point is 107.8～140.1 ℃, and 150 ℃ melt viscosity is 95mPas.As far as measure each composition ratio in the general formula of obtaining (1) through GPC, n=0 is 32.25%, and n=1 is 18.42%, and n=2 is 12.85%, and n=3 is 9.42%, and n=4 is 6.01%, and n >=5 are 16.63%.

Embodiment 3

The resin 110g that obtains in the synthetic example 3 is dissolved among Epicholorohydrin 486g, the diglyme 71.5g, and under reduced pressure (about 130Torr) dripped 48% aqueous sodium hydroxide solution 70.8g down at 62 ℃ through 4 hours.During this period, the water of generation is through removing to system with the azeotropic of Epicholorohydrin, and the Epicholorohydrin that distillation is removed turns back in the system.After dripping end, further continue reaction in 1 hour.Then, Epicholorohydrin is removed in distillation, behind the interpolation MIBK 972g, desalts through washing to remove.Then, add 24% aqueous sodium hydroxide solution 15.5g, under 85 ℃, carry out reaction in 2 hours.After after the reaction, filtering, washing, the MIBK as solvent is removed in underpressure distillation, obtains epoxy resin 149g (epoxy resin C).The epoxy resin equivalent is 182.4, and water-disintegrable chlorine is 675ppm.The peak temperature that DSC measures is 146.1 ℃, and the caloric receptivity of the fusion of accompanying crystallization is 46.1J/g.Capillary melting point is 118.2～147.0 ℃, and 150 ℃ melt viscosity is 36mPas.As far as measure each composition ratio in the general formula of obtaining (1) through GPC, n=0 is 49.16%, and n=1 is 20.11%, and n=2 is 10.52%, and n=3 is 6.51%, and n=4 is 3.98%, and n >=5 are 6.65%.

Comparative example 1

The resin 125g that obtains in the synthetic example 4 is dissolved among Epicholorohydrin 462g, the diglyme 69.3g, and under reduced pressure (about 130Torr) dripped 48% aqueous sodium hydroxide solution 69.4g down at 62 ℃ through 4 hours.During this period, the water of generation is through removing to system with the azeotropic of Epicholorohydrin, and the Epicholorohydrin that distillation is removed turns back in the system.After dripping end, further continue reaction in 1 hour.Then, Epicholorohydrin is removed in distillation, behind the interpolation MIBK 972g, desalts through washing to remove.Then, add 24% aqueous sodium hydroxide solution 19.3g, under 85 ℃, carry out reaction in 2 hours.After after the reaction, filtering, washing, the MIBK as solvent is removed in underpressure distillation, obtains epoxy resin 148g (epoxy resin D).The epoxy resin equivalent is 209.2, and water-disintegrable chlorine is 621ppm.The crystallinity of the resin that obtains is low, in DSC, does not see clear and definite fusing point.150 ℃ melt viscosity is 0.52Pas.As far as measure each composition ratio in the general formula of obtaining (1) through GPC, n=0 is 20.75%, and n=1 is 12.48%, and n=2 is 10.59%, and n=3 is 8.57%, and n=4 is 5.99%, and n >=5 are 37.11%.

Comparative example 2

The resin 115g that obtains in the synthetic example 5 is dissolved among Epicholorohydrin 549g, the diglyme 82.4g, and under reduced pressure (about 130Torr) dripped 48% aqueous sodium hydroxide solution 82.4g down at 62 ℃ in 4 hours.During this period, the water of generation is through removing to system with the azeotropic of Epicholorohydrin, and the Epicholorohydrin that distillation is removed turns back in the system.After dripping end, further continue reaction in 1 hour.Then, Epicholorohydrin is removed in distillation, behind the interpolation MIBK 966g, desalts through washing to remove.Then, add 24% aqueous sodium hydroxide solution 19.2g, under 85 ℃, carry out reaction in 2 hours.After after the reaction, filtering, washing, the MIBK as solvent is removed in underpressure distillation, obtains epoxy resin 145g (epoxy resin E).The epoxy resin equivalent is 173.0, and water-disintegrable chlorine is 490ppm.Peak temperature during DSC measures is 133.6 ℃, and the caloric receptivity of the fusion of accompanying crystallization is 47.6J/g.Capillary melting point is 110.0～142.0 ℃, and 150 ℃ melt viscosity is 42mPas.As far as measure each composition ratio in the general formula of obtaining (1) through GPC, n=0 is 42.92%, and n=1 is 19.64%, and n=2 is 11.46%, and n=3 is 7.67%, and n=4 is 4.91%, and n >=5 are 10.64%.

Comparative example 3

The resin 120g that obtains in the synthetic example 6 is dissolved among Epicholorohydrin 484g, the diglyme 62.9g, and under reduced pressure (about 130Torr) dripped 48% aqueous sodium hydroxide solution 69.0g down at 62 ℃ in 4 hours.During this period, the water of generation is through removing to system with the azeotropic of Epicholorohydrin, and the Epicholorohydrin that distillation is removed turns back in the system.After dripping end, further continue reaction in 1 hour.Then, Epicholorohydrin is removed in distillation, behind the interpolation MIBK 956g, desalts through washing to remove.Then, add 24% aqueous sodium hydroxide solution 17.6g, under 85 ℃, carry out reaction in 2 hours.After after the reaction, filtering, washing, the MIBK as solvent is removed in underpressure distillation, obtains hazel amorphism epoxy resin 152.5g (epoxy resin F).The epoxy resin equivalent is 193.5, and water-disintegrable chlorine is 450ppm.Softening temperature is 82 ℃, and 150 ℃ melt viscosity is 68mPas.To measure through GPC in the general formula (1) obtain with 4,4 '-dihydroxybiphenyl skeleton is substituted by 4, each composition in 4 '-dihydroxyl diphenylmethyl alkyl structure than; N=0 is 34.54%, and n=1 is 18.65%, and n=2 is 12.34%; N=3 is 10.69%, and n=4 is 8.20%, and n >=5 are 15.22%.

Embodiment 4～6, comparative example 4～7

As the epoxy resin composition, use epoxy resin (epoxy resin (the epoxy resin D～F),, use phenol phenolic varnish (crowd's honorization length of schooling, PSM-4261 of epoxy resin A～C), comparative example 1～3 of embodiment 1～3 as solidifying agent; 82 ℃ of OH equivalent 103, softening temperatures).In addition,, use triphenylphosphine,, use spherical alumina (median size 12.2 μ m) as inorganic filling material as curing catalyst.Cooperate the composition shown in the table 1, behind the mixing machine thorough mixing, will cool off, pulverize, obtain the composition epoxy resin of embodiment 4～6, comparative example 4～7 respectively with the mixing about 5 minutes mixture of warming mill.Use this composition epoxy resin, behind 175 ℃, 5 minutes condition compacted under, under 180 ℃, carry out 12 hours after fixing, obtain the curing molding thing, estimate its rerum natura.

The result is shown in table 1 in the lump.Need to prove the numeral weight part of each title complex in the table 1.In addition, evaluation is carried out as follows.Therefore in addition, the flowability of comparative example 4 is significantly low, and difficult forming can not be estimated the rerum natura of forming composition.

(1) thermal conductivity: use NETZSCH system LFA447 type thermal conductivity meter to use the unstable state Hot Wire Technique for Measuring.

(2) linear expansivity, second-order transition temperature: use the mechanical determinator of セイコーイ Application ス Star Le (strain) system TMA120C type heat, measure for 10 ℃/minute with heat-up rate.

(3) water-intake rate: be shaped to the disk of diameter 50mm, thickness 3mm, behind the after fixing, under 85 ℃, the condition of relative humidity 85%, make it carry out 100 hours weight rates after the moisture absorption.

(4) gel time: be heated to 175 ℃ in advance the recess of gelation trier (day new science (strain) system) in flow into composition epoxy resin; The speed that the stirrer of use PTFE system changeed with 1 second time 2 stirs, needed gelation time till research composition epoxy resin to the curing.

(5) helical flow: use based on the helical flow of specification (EMMI-1-66) and measure with mould with the injection pressure (150kgf/cm of composition epoxy resin at helical flow ²), it is long that 175 ℃ of solidification values, the condition compacted under of 3 minutes set times and studying flows.

[table 1]

The possibility of the utilization on the industry

Epoxy resin of the present invention is crystallinity, have fusing point; Therefore excellent as the solid operability; And be LV, so formability is also excellent, is being applied under the situation of composition epoxy resin simultaneously; Excellent high heat resistance, thermolysis stability and high thermal conductivity excellent in curing thing can be produced, the purposes of the sealing, circuit base material etc. of electrical/electronic part class can be preferred for.In addition; The epoxy resin that obtains through the present invention; Can produce LV property and excellent as the solid operability; Also excellent in curing thing of thermotolerance, wet fastness and heat conductivity simultaneously can be preferred for the insulating material etc. in the electric and electronic field of printing distributing board, heat-radiating substrate, encapsulating semiconductor etc.

Claims

1. one kind has crystalline epoxy resin, and it is by formula (1) expression, based on the endotherm peak temperature of the fusing point in the differential scanning calorimetric analysis scope at 100～150 ℃,

Wherein, n is in MV expression 0.2～4.0, and G representes glycidyl.

2. one kind has crystalline epoxy resin; Wherein, With respect to 4; 1 mole of 4 '-dihydroxybiphenyl, to make biphenyl by formula (2) expression be that 0.1～0.4 mole of condensing agent reacts and after forming the multi-hydroxy resin by formula (3) expression, itself and Epicholorohydrin are reacted and obtain based on the endotherm peak temperature of the fusing point in the differential scanning calorimetric analysis scope at 100～150 ℃

Wherein, X representes the alkoxyl group of hydroxyl, halogen atom or carbonatoms 1～6;

Wherein, n is in MV expression 0.2～4.0.

3. epoxy resin as claimed in claim 1, wherein, the content of the n=0 body in the general formula (1) is 30～60% scope.

4. epoxy resin as claimed in claim 1, wherein, softening temperature is 100～150 ℃, and 150 ℃ melt viscosity is the scope of 0.02～0.2Pas.

5. a composition epoxy resin is characterized in that, in the composition epoxy resin that contains epoxy resin and solidifying agent, contains in the claim 1～4 each described epoxy resin as the epoxy resin composition.

6. cured article, it forms for the described composition epoxy resin of claim 5 solidified.