CN102206326A - Multielement hydroxyl resin, epoxy resin, methods of manufacturing multielement hydroxyl resin and epoxy resin, epoxy resin composition and cured resin comprising multielement hydroxyl resin and epoxy resin - Google Patents

Multielement hydroxyl resin, epoxy resin, methods of manufacturing multielement hydroxyl resin and epoxy resin, epoxy resin composition and cured resin comprising multielement hydroxyl resin and epoxy resin Download PDF

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CN102206326A
CN102206326A CN2011100762514A CN201110076251A CN102206326A CN 102206326 A CN102206326 A CN 102206326A CN 2011100762514 A CN2011100762514 A CN 2011100762514A CN 201110076251 A CN201110076251 A CN 201110076251A CN 102206326 A CN102206326 A CN 102206326A
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resin
epoxy
epoxy resin
resins
hydroxyl
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CN102206326B (en
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中原和彦
梶正史
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Nippon Steel Chemical and Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/26—Polyhydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/14—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with at least one hydroxy group on a condensed ring system containing two rings
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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    • H01L33/56—Materials, e.g. epoxy or silicone resin

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Abstract

The invention provides an epoxy resin composition having good wet resistance and high heat resistance as well as excellent mechanical performances such as impact resistance and suitably applied for lamination, moulding, casting and bonding, etc. The invention further provides epoxy resin and an intermediate compound applied in the above-mentioned epoxy resin composition. The invention relates to a multielement hydroxyl resin shown in the general formula (1), the epoxy resin shown in the general formula (3), or the epoxy resin composition selecting one or two of the multielement hydroxyl resin and the epoxy resin as necessary components. In the formulas, A represents a phenyl ring or a naphthalene ring which can be replaced by alkyl with 1 to 6 usable carbon numbers. G represents a glycidol base. Furthermore, n represents an integer ranging between 1 and 15.

Description

Multi-hydroxy resin, Resins, epoxy, their manufacturing process, the composition epoxy resin that has used them and cured article
Technical field
The present invention relates to give excellent in flame retardance, simultaneously wet fastness, thermotolerance, with cementability of metal base etc. also Resins, epoxy, its intermediate, the solidifying agent of excellent cured article and composition epoxy resin and the cured article thereof that has used them.
Background technology
In recent years, particularly along with the development in tip materials field, require the more high performance base resin of exploitation.For example, in the field of encapsulating semiconductor, because popularizing of thin typeization, big areaization and the surface mounting mode of the encapsulation of corresponding high-density installationization in recent years, encapsulation rimose problem becomes serious, as their base resin, strong request wet fastness, thermotolerance, with the improvement of the cementability of metal base etc.In addition, recently,, there is the trend that the halogen flame retardant is got rid of, requires the more excellent base resin of flame retardant resistance from alleviating the viewpoint of carrying capacity of environment.
But, in the known so far Resins, epoxy, do not know the Resins, epoxy that satisfies these requirements as yet.For example, known bisphenol-type epoxy resin, normal temperature are liquid down, and the operation excellence is easy with mixing of solidifying agent, additive etc., and is therefore widely-used, but has problems aspect thermotolerance, wet fastness.In addition, as thermotolerance has been carried out improved product, known phenolic resin varnish type epoxy resin has problems on wet fastness, shock resistance.In addition, in the patent documentation 1,, the epoxy compounds of phenol (phenol) aralkyl resin has been proposed in order to improve wet fastness, shock resistance, but aspect thermotolerance, flame retardant resistance deficiency.
In addition, proposed to have the naphthols aralkyl-type epoxy resin of the structure that naphthols is connected with terephthalylidene in the patent documentation 2, but deficiency aspect thermotolerance, flame retardant resistance still.In addition, proposed to have the naphthols aralkyl-type epoxy resin of the structure that naphthols is connected with naphthylidene in the patent documentation 3, but whole aromatic structures is a naphthalene nucleus, so viscosity, softening temperature raises, have the problem that property handled and formability are reduced.
The prior art document
Patent documentation
Patent documentation 1: the spy opens clear 63-238122 communique
Patent documentation 2: the spy opens flat 3-90075 communique
Patent documentation 3: the spy opens the 2004-59792 communique
Summary of the invention
The problem that invention will solve
Therefore, the object of the present invention is to provide and have the formability excellence, also excellent performances such as while wet fastness, thermotolerance, flame retardant resistance, can be used for the Resins, epoxy of laminated, moulding, casting, purposes such as bonding and as the useful multi-hydroxy resin (polyhydroxy resin) of epoxy curing agent, the composition epoxy resin that their manufacturing process also is provided and has used them also provides its cured article.
The means that are used to deal with problems
That is, the present invention relates to the multi-hydroxy resin, it is by following general formula (1)
[changing 1]
Figure BDA0000052529070000021
(wherein, A represents naphthalene nucleus (N) or phenyl ring (B), and n represents 1～15 number.) shown in, and N/ (N+B) is 0.2～0.7 (mol ratio), and softening temperature is 70～120 ℃ simultaneously, and the melt viscosity under 150 ℃ is 2～10Pas.
In addition, the invention still further relates to the manufacture method of multi-hydroxy resin, it is characterized in that: with respect to 1 mole of the total amount of phenol and aphthols, use 0.10～0.40 mole aphthols, make following general formula (2)
[changing 2]
Naphthalene shown in (wherein, X represents the alkoxyl group of hydroxyl, halogen atom or carbon number 1～6) is condensing agent 0.05～0.35 molar reactive.
In addition, the invention still further relates to Resins, epoxy, it is by following general formula (3)
[changing 3]
Figure BDA0000052529070000031
(wherein, A represents naphthalene nucleus (N) or phenyl ring (B), and G represents glycidyl, and n represents 1～15 number.) shown in, and N/ (N+B) is 0.2～0.7, and softening temperature is 60～100 ℃ simultaneously, and the melt viscosity under 150 ℃ is 0.2～1.0Pas.
In addition, the invention still further relates to the manufacturing process of the Resins, epoxy shown in the above-mentioned general formula (3), it is characterized in that: make the reaction of multi-hydroxy resin shown in the above-mentioned general formula (1) and Epicholorohydrin.
In addition, the invention still further relates to composition epoxy resin, it forms for cooperating above-mentioned Resins, epoxy or any one neccessary composition as Resins, epoxy composition or curing agent component at least in the multi-hydroxy resin, in addition, also relates to the cured article that this composition epoxy resin curing is formed.
The effect of invention
The cured article that will solidify by the composition epoxy resin that Resins, epoxy of the present invention or multi-hydroxy resin obtain and obtain, have wet fastness, excellent heat resistance, and the performance that mechanical characteristicies such as shock resistance are also excellent can be adapted at using in laminated, moulding, casting, the purposes such as bonding.
Description of drawings
Fig. 1 is the GPC figure of multi-hydroxy Resin A.
Fig. 2 is the GPC figure of multi-hydroxy resin B.
Fig. 3 is the GPC figure of multi-hydroxy resin C.
Fig. 4 is the GPC figure of multi-hydroxy resin D.
Fig. 5 is the GPC figure of multi-hydroxy resin E.
Fig. 6 is the GPC figure of multi-hydroxy resin F.
Fig. 7 is the GPC figure of multi-hydroxy resin G.
Fig. 8 is the GPC figure of multi-hydroxy resin H.
Fig. 9 is the GPC figure of Resins, epoxy A.
Figure 10 is the GPC figure of Resins, epoxy B.
Figure 11 is the GPC figure of Resins, epoxy C.
Figure 12 is the GPC figure of Resins, epoxy D.
Figure 13 is the GPC figure of Resins, epoxy E.
Embodiment
Below to the detailed description of the invention.
Multi-hydroxy resin of the present invention is by shown in the above-mentioned general formula (1).Wherein, A represents naphthalene nucleus or phenyl ring, has the structure of naphthalene nucleus (N) and phenyl ring (B) coexistence, and naphthalene nucleus (N) shared ratio (mol ratio) in A is represented with N/ (N+B), is 0.2～0.7 scope.If littler than it, based on the thermotolerance of naphthalene structure, wet fastness etc. to improve effect little, if more than it, softening temperature, viscosity raise, formability reduces.Wherein, above-mentioned mol ratio is the molar average ratio of naphthalene nucleus and phenyl ring in the multi-hydroxy resin.
Above-mentioned naphthalene nucleus and phenyl ring can be replaced by the alkyl of carbon number 1～6, do not replace or by methyl substituted but be preferably.N represents average repeat number (number is average), is 1～15, is preferably 1.1～5.N is littler than it, and is not preferred aspect thermotolerance.In addition, bigger than it, then softening temperature, viscosity raise, and formability reduces.The softening temperature of multi-hydroxy resin of the present invention is 75～125 ℃ a scope, is preferably 80～120 ℃ scope.In addition, the melt viscosity under 150 ℃ is the scope of 2～10Pas, is preferably the scope of 3～8Pas.
Such multi-hydroxy resin can obtain by making the condensing agent reaction shown in phenol and aphthols and the general formula (2).
Wherein, so-called phenol, the alkyl (alkyl) that is carbon number 1～6 replaces or unsubstituted phenol, particularly, can illustration phenol, ortho-cresol, meta-cresol, p-cresol, ethylbenzene phenols, isopropyl benzene phenols, tert-butyl phenol, orthoxenol, p-phenyl phenol, 2,2,6-diethyl phenol etc., viewpoint from the low viscosity of the resin that obtains and hyperergy etc. is preferably unsubstituted phenol.In addition, so-called aphthols, alkyl replacement or unsubstituted naphthols for carbon number 1～6 are preferably unsubstituted naphthols, are in particular 1-naphthols, beta naphthal.Above-mentioned phenol or aphthols can use separately, also can will also use more than 2 kinds.
Phenol during reaction and the usage ratio of aphthols with respect to both 1 mole of total amounts, in theoretical amount, can be used 0.2～0.7 mole aphthols, if but consider reactive difference etc., can use 0.10～0.40 mole aphthols.
In addition, the naphthalene of general formula (2) is in the condensing agent, and X is the alkoxyl group of hydroxyl, halogen atom or carbon number 1～6.From with reactive viewpoint of phenoloid, preferred hydroxyl or halogen atom.As halogen atom, preferred chlorine atom, as alkoxyl group, preferred methoxyl group.2 CH with respect to naphthalene nucleus 2The position of substitution of X base can be on the identical phenyl ring, also can be on each phenyl ring, and preferred the position of substitution is 1,4-position, 1,5-position, 1,6-position, 2,6-position, 2,7-position.From the viewpoint of rerum naturas such as thermotolerance, physical strength and toughness, more preferably 1,4-position and 1,5-position.Naphthalene is that condensing agent can be these mixture, but preferred naphthalene be in the condensing agent, 1,4-two replaces bodies and 1, the total containing ratio that 5-two replaces bodies is more than the 90 weight %.
Naphthalene shown in the general formula (2) is a condensing agent, is not particularly limited, usually can be via the chlorination reaction of the methyl of the chloromethylation of naphthalene or dimethylnaphthalene class and make.In the condensing agent, can contain and have only 1 CH on the naphthalene nucleus 2Single naphthalene class that replaces that the X base replaces, but single content that replaces body is below the 10wt%, is preferably below the 5wt%, more preferably below the 3wt%.If the content of single replacement body is more than it, the cross-linking density when making resin solidification sometimes reduces, and brings stable on heating reduction.
Phenoloid and naphthalene are in the reaction of condensing agent, are condensing agent with respect to naphthalene, use excessive phenol and aphthols.Naphthalene is the usage quantity of condensing agent, with respect to 1 mole of the total amount of phenol and aphthols, is 0.05～0.35 mole scope, is preferably 0.1～0.3 mole scope.If more than it, the softening temperature of resin raises, and brings obstacle for operations for forming.In addition, if lack than it, after reaction finished, the phenol of excessive use and the removal amount of aphthols increased, industrial not preferred.Naphthalene is a condensing agent, owing to compare use slightly with theoretical amount, can be the moment that condensing agent reacts to finish to react at the naphthalenes of all measuring basically.
This reaction can be carried out in the presence of acid catalyst, as this acid catalyst, can suitably select from known mineral acid, organic acid.As such acid catalyst, can enumerate for example mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, tosic acid, diethyl sulfuric acid, solid acid such as Lewis acid such as zinc chloride, aluminum chloride, iron(ic) chloride, boron trifluoride or atlapulgite, silica-alumina, zeolite etc.In addition,, use under the situation of dichloride methyl naphthalene, can under catalyst-free, react as the condensing agent shown in the general formula (2).
Usually, this is reflected at and carried out under 10～250 ℃ 1～20 hour.In addition, as reaction solvent, can use alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, methylcyclohexane, ethyl cellosolve, benzene, toluene, chlorobenzene, dichlorobenzene etc.
After reaction finishes, adopt methods such as neutralization, washing sometimes, catalyzer is removed, adopt method such as underpressure distillation that remaining solvent and unreacted phenoloid are removed to outside the system as required, obtain the multi-hydroxy resin.The unreacted phenoloid is generally below 3%, is preferably below 1%.If more than it, the thermotolerance when forming cured article reduces.But, use under the situation of the phenoloid more than 2 yuan in the reaction, can remaining phenoloid not removed after the reaction.
Among the present invention, can contain the multi-hydroxy resin of naphthyl methyl bonding in the multi-hydroxy resin shown in the above-mentioned general formula (1).For example, at the naphthalene with the phenoloid reaction is in the condensing agent, contain under the situation of monochloro methylnaphthalene, monohydroxy naphthalene or monoalkoxy methylnaphthalene the mixture of the multi-hydroxy resin that becomes general formula (1) and the compound of the naphthyl methyl addition more than 1 or 1 on the aromatic ring of the multi-hydroxy resin of general formula (1).Even their mixtures can not produce obstacle to bringing into play effect of the present invention yet, they can be used as epoxy curing agent, and can use as the raw material of Resins, epoxy of the present invention.
Resins, epoxy of the present invention is represented by above-mentioned general formula (3).Wherein, A is identical with the explanation of the multi-hydroxy resin of general formula (1) with n.The softening temperature of Resins, epoxy of the present invention is 60～100 ℃ a scope, more preferably 75～95 ℃ scope.In addition, the melt viscosity under 150 ℃ is the scope of 0.1～1.0Pas, more preferably the scope of 0.2～0.8Pas.
Resins, epoxy of the present invention can obtain by making the reaction of multi-hydroxy resin shown in the above-mentioned general formula (1) and Epicholorohydrin.This reaction can similarly be carried out with common epoxidation reaction.
For example, can enumerate the multi-hydroxy resin dissolves shown in the above-mentioned general formula (1) after the Epicholorohydrin of surplus, in the presence of alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, under 50～150 ℃, preferred 60～120 ℃ scope, react 1～10 hour method.At this moment, the usage quantity of alkali metal hydroxide with respect to 1 mole of the hydroxyl in the multi-hydroxy resin, is 0.8～2 mole, is preferably 0.9～1.2 mole scope.In addition, Epicholorohydrin can excessively use with respect to the hydroxyl in the multi-hydroxy resin, usually, with respect to 1 mole of the hydroxyl in the multi-hydroxy resin, is 1.5～15 moles, is preferably 2～8 moles scope.In addition, during reaction, can add quaternary ammonium salt etc.As quaternary ammonium salt, for example tetramethyl ammonium chloride, tetrabutylammonium chloride, benzyltriethylammoinium chloride etc. are arranged, as its addition, with respect to the multi-hydroxy resin, the scope of preferred 0.1～2.0wt%.If lack than it, the effect that quaternary ammonium salt adds is little, if more than it, the generation of difficult water-disintegrable chlorine increases, and it is difficult that high purityization becomes.In addition, can also use dimethyl sulfoxide (DMSO), diglyme isopolarity solvent, its addition, with respect to the multi-hydroxy resin, the scope of preferred 10～200wt%.If lack than it, the effect of interpolation is little, if more than it, volumetric efficiency reduces, and is not preferred economically.After reaction finishes, the Epicholorohydrin of surplus is distilled, residue is dissolved in toluene, methyl iso-butyl ketone (MIBK) equal solvent, after the filtration, wash inorganic salt are removed, then solvent is distilled, thereby can access the Resins, epoxy of target.This Resins, epoxy is principal constituent with the Resins, epoxy shown in the general formula (3), can contain on the aromatic ring of the multi-hydroxy resin of general formula (1) the glycidyl ether thing of the compound of 1 or the addition of 1 above naphthyl methyl.In addition, also can contain epoxy group(ing) in the Resins, epoxy of the present invention with the product of the oligomeric materialization of form of ehter bond.
Composition epoxy resin of the present invention comprises Resins, epoxy and solidifying agent, will as the Resins, epoxy shown in the general formula (3) of Resins, epoxy composition or as in the multi-hydroxy resin shown in the above-mentioned general formula (1) of curing agent component any one cooperates as neccessary composition and forms at least.Especially, cooperate the Resins, epoxy shown in the general formula (3), have high flame retardancy, rerum natura harmony as the composition of the multi-hydroxy resin shown in Resins, epoxy composition, the cooperation general formula (1) as curing agent component, therefore preferred.
As the solidifying agent during as neccessary composition, can use generally as known all solidifying agent of curing agent for epoxy resin with the Resins, epoxy shown in the general formula (3).For example Dyhard RU 100, polyatomic phenol, anhydrides, aromatic series and aliphatics amine etc. are arranged.If illustration particularly, as polyatomic phenol, for example dihydroxyphenyl propane is arranged, Bisphenol F, bisphenol S, the fluorenes bis-phenol, 4,4 '-xenol, 2,2 '-xenol, quinhydrones, Resorcinol, the phenols that naphthalenediol etc. are 2 yuan, perhaps, three-(4-hydroxy phenyl) methane, 1,1,2,2-four (4-hydroxy phenyl) ethane, the phenol novolak, the ortho-cresol novolak, the naphthols novolak, polyvinylphenol etc. are the phenols more than 3 yuan of representative, and phenol, aphthols or dihydroxyphenyl propane, Bisphenol F, bisphenol S, the fluorenes bis-phenol, 4,4 '-xenol, 2,2 '-xenol, quinhydrones, Resorcinol, 2 yuan of phenols such as naphthalenediol utilize formaldehyde, acetaldehyde, phenyl aldehyde, p-Hydroxybenzaldehyde, the polynary phenoloids of condensing agent synthetic such as terephthalyl alcohol etc., as acid anhydrides, Tetra hydro Phthalic anhydride is arranged, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl Ha イ ミ Star Network acid anhydrides, carbic anhydride, trimellitic acid 1,2-anhydride etc.In addition, as amine, have 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl propane, 4, aliphatics amines such as aromatic amines such as 4 '-diamino diphenyl sulfone, mphenylenediamine, p dimethylamine, quadrol, hexamethylene-diamine, diethylenetriamine, Triethylenetetramine (TETA), perhaps the multi-hydroxy resin shown in the general formula (1).In the resin combination of the present invention, can use a kind of these solidifying agent or will mix use more than 2 kinds, the use level of the Resins, epoxy that the present invention relates in Resins, epoxy is all, is 5～100% scope.
As the Resins, epoxy during as the neccessary composition of curing agent component with the multi-hydroxy resin shown in the general formula (1), the common Resins, epoxy that has 2 above epoxy group(ing) in the molecule can use entirely.If for example, have by dihydroxyphenyl propane, bisphenol S, fluorenes bis-phenol, 4,4 '-xenol, 2,2 yuan of phenols such as 2 '-xenol, quinhydrones, Resorcinol, perhaps, three-(4-hydroxy phenyl) methane, 1,1,2, phenols more than 3 yuan such as 2-four (4-hydroxy phenyl) ethane, phenol novolak, ortho-cresol novolak, perhaps, halogenated bisphenol class deutero-glycidyl ether things such as tetrabromo-bisphenol, the polyfunctional epoxy resin shown in the perhaps above-mentioned general formula (1) etc.These Resins, epoxy can use a kind or will be more than 2 kinds mix and use, and the use level of the multi-hydroxy resin that the present invention relates in Resins, epoxy is all, is 5～100% scope.
In addition, in with multi-hydroxy resin shown in Resins, epoxy shown in the general formula (3) or the general formula (1) or composition epoxy resin of the present invention that both are neccessary composition, oligopolymer or macromolecular compounds such as polyester, polymeric amide, polyimide, polyethers, urethane, petroleum resin, indene-coumarone resin ying, phenoxy resin can be suitably cooperated, additives such as inorganic filler, pigment, fire retardant, thixotropy imparting agent, coupling agent, fluidity improver can be cooperated.As inorganic filler, can enumerate SiO 2 powder, alumina powder, glass powder or mica, talcum, lime carbonate, aluminum oxide, the hydrated aluminum oxide etc. such as fused silica, crystalline silica of for example spherical or broken shape, as pigment, filler pigment, flakey pigment of organic system or inorganic system etc. are arranged.As the thixotropy imparting agent, can enumerate silicon system, Viscotrol C system, aliphatic amide wax, oxidized polyethlene wax, organobentonite system etc.In addition, can use known in the past curing catalyst as required.If for example, amine, imidazoles, organic phosphine class, Lewis acid etc. are arranged.As addition, usually,, be the scope of 0.2～5 weight part with respect to Resins, epoxy 100 weight parts.In addition, as required, also can in resin combination of the present invention, use lubricants such as low-stress agent, calcium stearate such as fire retardants such as tinting materials such as coupling agents such as releasing agent, γ-glycidoxypropyltrime,hoxysilane, carbon black, ANTIMONY TRIOXIDE SB 203 99.8 PCT, silicone oil such as carnauba wax, OP wax etc.
Cured article of the present invention can adopt methods such as casting, compressed moulding, transfer molding that above-mentioned composition epoxy resin forming process is obtained.Temperature during generation is generally 120～220 ℃ scope.
Embodiment
Below based on embodiment and comparative example, the present invention is specifically described.
Embodiment 1 (manufacturing of multi-hydroxy resin)
In 4 mouthfuls of removable flasks of 1L, measure 1-naphthols 96g, phenol 251g, dichloromethyl naphthalene (1,4-dichloromethane matrix 43.5%, 1,5-dichloromethane matrix 55.3%, other dichloromethane matrixes 1.2%) 150g and chlorobenzene 450g, rising temperature for dissolving slowly while stirring under nitrogen gas stream is in about 80 ℃ of reactions 2 hours so down.Then, the limit distills the limit with chlorobenzene and is warmed up to 180 ℃, reacts like this 1 hour.After the reaction, after by underpressure distillation solvent and unreacted monomer being removed, obtained the resin 235g (multi-hydroxy Resin A) of brown.The hydroxyl equivalent of the multi-hydroxy resin that obtains is 230g/eq., and softening temperature is 123 ℃, and the melt viscosity under 150 ℃ is 9.5Pas.By the analysis of the unreacted monomer that reclaims as can be known, entering the 1-naphthols (N) in the resin and the ratio (mol ratio) of phenol (B) is N/ (N+B)=0.57.GPC is illustrated in Fig. 1.Wherein melt viscosity uses the system CAP2000H of BROOKFIELD society, GPC measures using appts: MODEL151 (Waters (strain) system) and post: TSK-GEL2000H * 3 piece and TSK-GEL4000H * 1 piece (being eastern ソ one (strain) system), at solvent: tetrahydrofuran (THF), flow velocity: 1.0ml/ branch, temperature: carry out under 38 ℃, the condition of detector: RI.
Embodiment 2 (manufacturing of multi-hydroxy resin)
Replace the 1-naphthols and use beta naphthal, react similarly to Example 1, obtained the resin 237g (multi-hydroxy resin B) of brown.The hydroxyl equivalent of the multi-hydroxy resin that obtains is 217g/eq., and softening temperature is 121 ℃, and the melt viscosity under 150 ℃ is 6.2Pas.By the analysis of the unreacted monomer that reclaims as can be known, entering the 1-naphthols (N) in the resin and the ratio of phenol (B) is N/ (N+B)=0.50.GPC is illustrated in Fig. 2.
Embodiment 3 (manufacturing of multi-hydroxy resin)
In 4 mouthfuls of removable flasks of 1L, take by weighing 1-naphthols 100g, phenol 437g, dichloromethyl naphthalene (1,4-dichloromethane matrix 43.5%, 1,5-dichloromethane matrix 55.3%, other dichloromethane matrixes 1.2%) 180g and chlorobenzene 200g, under nitrogen gas stream, rising temperature for dissolving slowly while stirring is in about 80 ℃ of reactions 2 hours so down.Then, the limit distills the limit with chlorobenzene and is warmed up to 180 ℃, reacts like this 1 hour.After the reaction, after by underpressure distillation solvent and unreacted monomer being removed, obtained the resin 275g (multi-hydroxy resin C) of brown.The hydroxyl equivalent of the multi-hydroxy resin that obtains is 206g/eq., and softening temperature is 105 ℃, and the melt viscosity under 150 ℃ is 3.4Pas.By the analysis of the unreacted monomer that reclaims as can be known, entering the 1-naphthols (N) in the resin and the ratio of phenol (B) is N/ (N+B)=0.29.GPC is illustrated in Fig. 3.
Embodiment 4 (manufacturing of multi-hydroxy resin)
In 4 mouthfuls of removable flasks of 1L, take by weighing beta naphthal 46g, phenol 271g, dichloromethyl naphthalene (1,4-dichloromethane matrix 43.5%, 1,5-dichloromethane matrix 55.3%, other dichloromethane matrixes 1.2%) 215g and chlorobenzene 300g, under nitrogen gas stream, rising temperature for dissolving slowly while stirring is in about 80 ℃ of reactions 2 hours so down.Then, the limit distills the limit with chlorobenzene and is warmed up to 180 ℃, reacts like this 1 hour.After the reaction, after by underpressure distillation solvent and unreacted monomer being removed, obtained the resin 306g (multi-hydroxy resin D) of brown.The hydroxyl equivalent of the multi-hydroxy resin that obtains is 213g/eq., and softening temperature is 115 ℃, and the melt viscosity under 150 ℃ is 4.9Pas.By the analysis of the unreacted monomer that reclaims as can be known, entering the beta naphthal (N) in the resin and the ratio of phenol (B) is N/ (N+B)=0.23.GPC is illustrated in Fig. 4.
Embodiment 5 (manufacturing of multi-hydroxy resin)
In 4 mouthfuls of removable flasks of 1L, take by weighing beta naphthal 224g, phenol 272g, dichloromethyl naphthalene (1,4-dichloromethane matrix 43.5%, 1,5-dichloromethane matrix 55.3%, other dichloromethane matrixes 1.2%) 100g and chlorobenzene 300g, under nitrogen gas stream, rising temperature for dissolving at leisure while stirring is in about 80 ℃ of reactions 2 hours so down.Then, the limit distills the limit with chlorobenzene and is warmed up to 180 ℃, reacts like this 1 hour.After the reaction, after by underpressure distillation solvent and unreacted monomer being removed, obtained the resin 207g (multi-hydroxy resin E) of brown.The hydroxyl equivalent of the multi-hydroxy resin that obtains is 220g/eq., and softening temperature is 120 ℃, and the melt viscosity under 150 ℃ is 6.2Pas.By the analysis of the unreacted monomer that reclaims as can be known, entering the 1-naphthols (N) in the resin and the ratio of phenol (B) is N/ (N+B)=0.70.GPC is illustrated in Fig. 5.
Comparative example 1 (manufacturing of multi-hydroxy resin)
In 4 mouthfuls of removable flasks of 1L, take by weighing 1-naphthols 251g, phenol 200g, dichloromethyl naphthalene (1,4-dichloromethane matrix 43.5%, 1,5-dichloromethane matrix 55.3%, other dichloromethane matrixes 1.2%) 131g and chlorobenzene 300g, under nitrogen gas stream, rising temperature for dissolving at leisure while stirring is in about 80 ℃ of reactions 2 hours so down.Then, the limit distills the limit with chlorobenzene and is warmed up to 180 ℃, reacts like this 1 hour.After the reaction, after by underpressure distillation solvent and unreacted monomer being removed, obtained the resin 255g (multi-hydroxy resin F) of brown.The hydroxyl equivalent of the multi-hydroxy resin that obtains is 231g/eq., and softening temperature is 130 ℃, and the melt viscosity under 150 ℃ is 10.5Pas.By the analysis of the unreacted monomer that reclaims as can be known, entering the 1-naphthols (N) in the resin and the ratio of phenol (B) is N/ (N+B)=0.74.GPC is illustrated in Fig. 6.
Comparative example 2 (manufacturing of multi-hydroxy resin)
In 4 mouthfuls of removable flasks of 1L, take by weighing beta naphthal 57g, phenol 150g, dichloromethyl naphthalene (1,4-dichloromethane matrix 43.5%, 1,5-dichloromethane matrix 55.3%, other dichloromethane matrixes 1.2%) 180g and chlorobenzene 400g, under nitrogen gas stream, rising temperature for dissolving slowly while stirring is in about 80 ℃ of reactions 2 hours so down.Then, the limit distills the limit with chlorobenzene and is warmed up to 180 ℃, reacts like this 1 hour.After the reaction, after by underpressure distillation solvent and unreacted monomer being removed, obtained the resin 261g (multi-hydroxy resin G) of brown.The hydroxyl equivalent of the multi-hydroxy resin that obtains is 234g/eq., and softening temperature is 135 ℃, and the melt viscosity under 150 ℃ is 14.8Pas.By the analysis of the unreacted monomer that reclaims as can be known, entering the beta naphthal (N) in the resin and the ratio of phenol (B) is N/ (N+B)=0.29.GPC is illustrated in Fig. 7.
Comparative example 3 (manufacturing of multi-hydroxy resin)
In 4 mouthfuls of removable flasks of 1L, take by weighing beta naphthal 320g, dichloromethyl naphthalene (1,4-dichloromethane matrix 43.5%, 1,5-dichloromethane matrix 55.3%, other dichloromethane matrixes 1.2%) 100g and chlorobenzene 420g, under nitrogen gas stream, rising temperature for dissolving at leisure while stirring is in about 95 ℃ of reactions 2 hours so down.Then, the limit distills the limit with chlorobenzene and is warmed up to 180 ℃, reacts like this 1 hour.After the reaction, after by underpressure distillation solvent and unreacted monomer being removed, obtained the resin 171g (multi-hydroxy resin H) of brown.The hydroxyl equivalent of the multi-hydroxy resin that obtains is 253g/eq., and softening temperature is 174 ℃, and the melt viscosity under 150 ℃ is more than the 50Pas.Entering the 1-naphthols (N) in the resin and the ratio of phenol (B) is N/ (N+B)=1.00.GPC is illustrated in Fig. 8.
Embodiment 6
The multi-hydroxy resin B 100g that obtains among the embodiment 2 is dissolved among Epicholorohydrin 298g and the diglyme 45g, under reduced pressure (about 120mmHg), 60 ℃ down with 4 hours dropping 48% aqueous sodium hydroxide solution 38g.During this water that generates is removed to outside the system by the azeotropic with Epicholorohydrin, the Epicholorohydrin that distills out turns back in the system.After dripping end, continue reaction 1 hour again.Then, Epicholorohydrin and diglyme underpressure distillation are fallen, be dissolved in methyl iso-butyl ketone (MIBK) 295g after, by washing the salt that generates is removed.Then, add 48% aqueous sodium hydroxide solution 9g, reacted 2 hours down at 80 ℃.After the reaction, after washing, will fall, obtain the Resins, epoxy 121g (Resins, epoxy A) of brown as the methyl iso-butyl ketone (MIBK) underpressure distillation of solvent.The epoxy equivalent (weight) of the Resins, epoxy A that obtains is 268g/eq., and softening temperature is 87 ℃, and water-disintegrable chlorine is 120ppm, and the melt viscosity under 150 ℃ is 0.40Pas.GPC is illustrated in Fig. 9.Have, wherein water-disintegrable chlorine is by being dissolved in 1 with resin test portion 0.5g again, and 4-two
Figure BDA0000052529070000121
Alkane 30ml with 1N-KOH/ methanol solution 5ml boiling reflux 30 minutes, carries out the potential difference titration to product and obtains with silver nitrate solution.
Embodiment 7
The multi-hydroxy resin D 100g that obtains among the embodiment 4 is dissolved in Epicholorohydrin 307g and diglyme 48g, uses 48% aqueous sodium hydroxide solution 40g, react similarly to Example 6, obtained the Resins, epoxy 114g (Resins, epoxy B) of brown.The epoxy equivalent (weight) of the Resins, epoxy B that obtains is 261g/eq., and softening temperature is 84 ℃, and water-disintegrable chlorine is 200ppm, and the melt viscosity under 150 ℃ is 0.4Pas.GPC is illustrated in Figure 10.
Embodiment 8
The multi-hydroxy resin E 100g that obtains among the embodiment 5 is dissolved in Epicholorohydrin 300g and diglyme 45g, uses 48% aqueous sodium hydroxide solution 38.5g, react similarly to Example 4, obtained the Resins, epoxy 111g (Resins, epoxy C) of brown.The epoxy equivalent (weight) of the Resins, epoxy C that obtains is 262g/eq., and softening temperature is 93 ℃, and water-disintegrable chlorine is 180ppm, and the melt viscosity under 150 ℃ is 0.6Pas.GPC is illustrated in Figure 11.
Comparative example 4
The multi-hydroxy resin F 100g that obtains in the comparative example 1 is dissolved in Epicholorohydrin 280g and diglyme 42g, uses 48% aqueous sodium hydroxide solution 36.1g, react similarly to Example 3, obtained the Resins, epoxy 107g (Resins, epoxy D) of brown.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 282g/eq., and softening temperature is 102 ℃, and water-disintegrable chlorine is 320ppm, and the melt viscosity under 150 ℃ is 1.2Pas.GPC is illustrated in Figure 12.
Comparative example 5
The multi-hydroxy resin G 100g that obtains in the comparative example 2 is dissolved in Epicholorohydrin 277g and diglyme 42g, uses 48% aqueous sodium hydroxide solution 35.6g, react similarly to Example 3, obtained the Resins, epoxy 110g (Resins, epoxy E) of brown.The epoxy equivalent (weight) of the Resins, epoxy that obtains is 285g/eq., and softening temperature is 120 ℃, and water-disintegrable chlorine is 290ppm, and the melt viscosity under 150 ℃ is 2.5Pas.GPC is illustrated in Figure 13.
Embodiment 9～16 and comparative example 5～9
Use synthetic multi-hydroxy resin and Resins, epoxy in embodiment 1～8, the comparative example 1～5, beta naphthal aralkyl-type epoxy resin (the melt viscosity 0.38Pas under 84 ℃, 150 ℃ of the epoxy equivalent (weight)s 280, softening temperature; ESN-185, Nippon Steel's chemistry system; Resins, epoxy F), 3,3 ', 5,5 '-tetramethyl--4, the epoxide of 4 '-dihydroxybiphenyl (the melt viscosity 11mPas under 105 ℃, 150 ℃ of the epoxy equivalent (weight)s 195, water-disintegrable chlorine 450ppm, fusing point; YX-4000HK, ジ ヤ パ Application エ Port キ シ レ ジ Application system; Resins, epoxy G), phenol (phenol) aralkyl resin (the melt viscosity 30mPas under 50 ℃, 150 ℃ of the OH equivalents 162, softening temperature; MEH-7800-4L, bright and change into system; Phenol (phenol) Resin A), 1-naphthols aralkyl resin (the melt viscosity 35mPas under 74 ℃, 150 ℃ of the OH equivalents 208, softening temperature; SN-475, Nippon Steel's chemistry system; Multi-hydroxy resin I), as the triphenyl phosphine of curing catalyst, as the γ-glycidoxypropyltrime,hoxysilane of silane coupling agent, make resin combination by the cooperation shown in the table 1.
As the physical property measurement of resin combination, helicoidal flow is used according to the helicoidal flow mensuration of standard (EMMI-1-66) and is used mould, at the injection pressure (150kgf/cm of helicoidal flow 2), under 175 ℃ of the solidification values, the condition of 3 minutes set times with the composition epoxy resin moulding, investigate length of flow.Gelation time is the recess that composition epoxy resin is cast to the gelation trier (day new science (strain) system) that is heated to 175 ℃ in advance, use the stirring rod of PTFE system, the speed of changeing with a second 2 stirs, and investigates and solidifies needed gelation time until composition epoxy resin.The rerum natura of cured article is to use this composition epoxy resin at 175 ℃ of compacted unders, carries out 12 hours after fixing under 175 ℃, obtained the cured article test film after, in various physical property measurements.The mensuration of glass transformation temperature and thermal expansivity is to adopt hot mechanical determinator, tries to achieve under the condition of 7 ℃/minute of heat-up rates.Pliability test is to adopt 3 bending methods to carry out the high temperature bend strength under 240 ℃, the mensuration of modulus in flexure.Bonding strength is by adopting the forming composition of compacting shape machine at 175 ℃ of compacted under 25mm * 12.5mm * 0.5mm between 2 of 42 alloy sheets, carry out 175 ℃, 12 hours after fixing after, obtain tensile shear strength and estimate.Water-intake rate is to use this composition epoxy resin, and the disk of forming diameter 50mm, thick 3mm makes the value of its moisture absorption in the time of 100 hours behind the after fixing under 85 ℃, the condition of 85%RH.Flame retardant resistance is the thick 1/16 inch test film of moulding, estimates according to the UL94V-0 standard, represents combustion time with the total in the test of n=5.The result gathered be shown in table 2.
Figure BDA0000052529070000151
Figure BDA0000052529070000161

Claims (7)

1. multi-hydroxy resin, it is by following general formula (1) expression,
[changing 1]
Figure FDA0000052529060000011
Wherein, A represents naphthalene nucleus (N) or phenyl ring (B), and n represents 1～15 number,
The mol ratio of calculating with N/ (N+B) is 0.2～0.7, and softening temperature is 75～125 ℃, and the melt viscosity under 150 ℃ is 2～10Pas.
2. the manufacture method of the described multi-hydroxy resin of claim 1, it is characterized in that: with respect to 1 mole of the total amount of phenol and aphthols, use 0.10～0.40 mole aphthols, using the naphthalene shown in 0.05～0.35 mole the following general formula (2) is that condensing agent makes their reactions
[changing 2]
Figure FDA0000052529060000012
Wherein, X represents the alkoxyl group of hydroxyl, halogen atom or carbon number 1～6.
3. the manufacture method of the described multi-hydroxy resin of claim 2, wherein naphthalene be in the condensing agent, 1,4-two replaces bodies and 1, the total containing ratio that 5-two replaces bodies is more than the 90 weight %.
4. Resins, epoxy, it is by shown in the following general formula (3),
[changing 3]
Figure FDA0000052529060000013
Wherein, A represents naphthalene nucleus (N) or phenyl ring (B), and G represents glycidyl, and n represents 1～15 number,
The mol ratio of calculating with N/ (N+B) is 0.2～0.7, and softening temperature is 60～100 ℃, and the melt viscosity under 150 ℃ is 0.1～1.0Pas.
5. the manufacturing process of the described Resins, epoxy of claim 4 is characterized in that: make the reaction of described multi-hydroxy resin of claim 1 and Epicholorohydrin.
6. composition epoxy resin is the composition epoxy resin that comprises Resins, epoxy and solidifying agent, wherein cooperates in described multi-hydroxy resin of claim 1 or the described Resins, epoxy of claim 4 at least one as neccessary composition.
7. make the described composition epoxy resin of claim 6 solidify the cured article that forms.
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Cited By (5)

* Cited by examiner, † Cited by third party
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CN103724999A (en) * 2013-05-30 2014-04-16 广东生益科技股份有限公司 Cyanate resin composition and application thereof
CN103724998A (en) * 2013-05-30 2014-04-16 广东生益科技股份有限公司 Cyanate resin composition and application thereof
WO2014190526A1 (en) * 2013-05-30 2014-12-04 广东生益科技股份有限公司 Cyanate resin composition and application thereof
CN104334597A (en) * 2012-02-23 2015-02-04 新日铁住金化学株式会社 Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof
CN104945583B (en) * 2014-03-26 2018-09-11 新日铁住金化学株式会社 Modified multicomponent hydroxy resin, epoxy resin, composition epoxy resin and its hardening thing

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07206984A (en) * 1994-01-11 1995-08-08 Mitsui Toatsu Chem Inc Epoxy resin composition, its cured product and semiconductor apparatus
JP2004059792A (en) * 2002-07-30 2004-02-26 Nippon Steel Chem Co Ltd Polyhydroxy resin, epoxy resin, method for producing the same, epoxy resin composition and cured product using the same
JP2004123859A (en) * 2002-10-01 2004-04-22 Nippon Steel Chem Co Ltd Polyhydric hydroxy resin, epoxy resin, method for producing the same, epoxy resin composition using the same and cured product
CN1737055A (en) * 2004-08-19 2006-02-22 新日铁化学株式会社 Epoxy resin composition and its cured article
CN101027336A (en) * 2004-09-01 2007-08-29 大日本油墨化学工业株式会社 Epoxy resin composition, cured product thereof, semiconductor sealing material, new phenolic resin, new epoxy resin, method for producing the new phenolic resin, and method for producing the new epoxy
JP2009001812A (en) * 2008-08-04 2009-01-08 Nippon Steel Chem Co Ltd Polyvalent hydroxy resin, epoxy resin, their manufacturing method, epoxy resin composition using them, and cured product
CN101370870A (en) * 2006-01-23 2009-02-18 日立化成工业株式会社 Epoxy resin molding material for sealing and electronic component device
CN101522792A (en) * 2006-10-02 2009-09-02 日立化成工业株式会社 Epoxy resin molding material for sealing and electronic component device

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07206984A (en) * 1994-01-11 1995-08-08 Mitsui Toatsu Chem Inc Epoxy resin composition, its cured product and semiconductor apparatus
JP2004059792A (en) * 2002-07-30 2004-02-26 Nippon Steel Chem Co Ltd Polyhydroxy resin, epoxy resin, method for producing the same, epoxy resin composition and cured product using the same
JP2004123859A (en) * 2002-10-01 2004-04-22 Nippon Steel Chem Co Ltd Polyhydric hydroxy resin, epoxy resin, method for producing the same, epoxy resin composition using the same and cured product
CN1737055A (en) * 2004-08-19 2006-02-22 新日铁化学株式会社 Epoxy resin composition and its cured article
CN101027336A (en) * 2004-09-01 2007-08-29 大日本油墨化学工业株式会社 Epoxy resin composition, cured product thereof, semiconductor sealing material, new phenolic resin, new epoxy resin, method for producing the new phenolic resin, and method for producing the new epoxy
CN101370870A (en) * 2006-01-23 2009-02-18 日立化成工业株式会社 Epoxy resin molding material for sealing and electronic component device
CN101522792A (en) * 2006-10-02 2009-09-02 日立化成工业株式会社 Epoxy resin molding material for sealing and electronic component device
JP2009001812A (en) * 2008-08-04 2009-01-08 Nippon Steel Chem Co Ltd Polyvalent hydroxy resin, epoxy resin, their manufacturing method, epoxy resin composition using them, and cured product

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104334597A (en) * 2012-02-23 2015-02-04 新日铁住金化学株式会社 Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof
CN104334597B (en) * 2012-02-23 2016-06-22 新日铁住金化学株式会社 Multi-hydroxy resin, epoxy resin, their manufacture method, composition epoxy resin and solidfied material thereof
CN103724999A (en) * 2013-05-30 2014-04-16 广东生益科技股份有限公司 Cyanate resin composition and application thereof
CN103724998A (en) * 2013-05-30 2014-04-16 广东生益科技股份有限公司 Cyanate resin composition and application thereof
WO2014190526A1 (en) * 2013-05-30 2014-12-04 广东生益科技股份有限公司 Cyanate resin composition and application thereof
CN104945583B (en) * 2014-03-26 2018-09-11 新日铁住金化学株式会社 Modified multicomponent hydroxy resin, epoxy resin, composition epoxy resin and its hardening thing

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