KR20130052495A - Flame-retardant epoxy resin, epoxy resin composition containing the epoxy resin as essential component and cured product thereof - Google Patents

Abstract

PURPOSE: A phosphate-containing epoxy resin is provided to control the molecular weight distribution of the phenol novolak type epoxy resin, to reduce use amount of phosphate compound with high costs, to improve flame retardancy, and to improve physical properties of cured material while increasing productivity. CONSTITUTION: A phosphate-containing epoxy resin is formed by conducting reaction of a novolak type epoxy resin and a phosphate compound represented by chemical formula 1. The novolak type epoxy resin, in a gel permeation chromatography, has a double nuclei content of 15 area% or less, a triple nuclei content of 15-60 area%, and a number average molecular weight of 350-700. In chemical formula 1, each of R1 and R2 is hydrogen or hydrocarbon group; can form a ring with phosphate atom; and n is 0 or 1.

Description

Flame-retardant epoxy resin and composition containing the epoxy resin as an essential component, cured product {FLAME-RETARDANT EPOXY RESIN, EPOXY RESIN COMPOSITION CONTAINING THE EPOXY RESIN AS ESSENTIAL COMPONENT AND CURED PRODUCT THEREOF}

Industrial Applicability The present invention is suitable for prepregs used in electronic circuit boards, film materials, sealing materials, molding materials, molding materials, adhesives, electrical insulating paints used in copper clad laminates and electronic components, composite materials requiring flame retardancy, powder coating materials, and the like. Phosphorus containing epoxy resin, a composition, and hardened | cured material.

Epoxy resins are widely used in electronic parts, electric devices, automobile parts, FRP, and sporting goods because of their excellent adhesiveness, heat resistance, and moldability, and among them, copper clad laminates and sealing materials used in electronic parts and electric devices are used for fire. Brominated epoxy resins have been used for safety reasons such as prevention and delay.

Flame-retardance was provided by introducing the halogen represented by bromine into an epoxy resin, and the hardened | cured material excellent in the high reactivity of an epoxy group was obtained. However, when it burns, it may generate harmful substances, such as a halogen compound, and the demand of the flame-retardant provision epoxy resin which does not use a halogen increased.

In contrast, Patent Document 1 discloses a method of imparting flame retardancy by introducing a phosphorus atom into an epoxy resin skeleton. However, in this method, since the epoxy group which contributes to hardening reaction is made to react with the phosphorus compound, the crosslinking density at the time of hardening falls, and hardened | cured material physical property was not satisfying. In view of this, Patent Document 2 discloses a method of making a phosphorus-containing compound having two phenol groups by reacting a phosphorus compound with a quinone compound and introducing the epoxy resin backbone by reaction with an epoxy resin. In this method, hardened | cured material physical properties improved remarkably and a high quality copper clad laminated board is obtained, but since the reaction process of a phosphorus compound and a quinone compound is required, reaction time became long and it fell in productivity. Although patent document 3 has description about the novolak-type epoxy resin which concerns on nuclide number 3-8, it is related with heat resistance and impregnation, and no indication or suggestion is made about flame retardance.

Japanese Patent Application Laid-Open No. 11-166035 Japanese Patent Laid-Open No. 11-279258 Japanese Laid-Open Patent Publication No. 62-064821 Japanese Laid-Open Patent Publication 2002-194041 Japanese Unexamined Patent Publication No. 2007-126683

As a result of intensive studies on phosphorus-containing epoxy resins, the present inventors have completed the present invention, and greatly improved flame retardancy by a phosphorus-containing epoxy resin in which a novolak-type epoxy resin having a specific molecular weight distribution reacts with a specific phosphorus compound. It succeeds in making it, and while reducing the quantity of an expensive phosphorus compound, while maintaining the productivity which is an advantage of patent document 1, the hardened | cured material physical property lacked in patent document 2 is realized. The bifunctional epoxy resin, which is a binuclear component constituting the novolak-type epoxy resin, generates a reaction component having no epoxy group when reacted with a phosphorus compound. The novolak-type epoxy resin used in the present invention contains a content of the binuclear component. It is thought that the reaction component which does not have an epoxy group can be reduced by reducing this, and the flame retardance and the physical property were improved. Moreover, it is thought that the novolak-type epoxy resin used by this invention can reduce content rate also about the high molecular weight component of 4 nucleus or more, and the flame retardance and physical property of the obtained phosphorus containing epoxy resin will further improve. When the phosphorus compound partially reacts with a high molecular weight component of at least four nucleolus contained in the novolak-type epoxy resin, this becomes a phosphorus-containing epoxy resin containing a structurally bulky portion, and in the reaction of the epoxy group and the curing agent, It is guessed that the cause of the remarkable deterioration of curing reactivity was caused by the obstacle. The present invention is suitable for prepregs used in electronic circuit boards, film materials, sealing materials, molding materials, molding materials, adhesives, electrical insulating paints, composite materials, powder paints, etc., which are used for copper clad laminates and electronic components. It is providing the flame-retardant phosphorus containing epoxy resin of high quality and its epoxy resin composition, reducing.

That is, the present invention,

(1) Novolak having a molecular weight distribution in which the nucleus content is 15 area% or less, the trinuclear content is 15 area% to 60 area%, and the number average molecular weight is 350 to 700 in the measurement in gel permeation chromatography. Phosphorus containing epoxy resin formed by making a type epoxy resin (A) and the phosphorus compound represented by General formula (1) react as an essential component,

(Gel permeation chromatography measurement conditions)

TSKgelG4000HXL, TSKgelG3000HXL, and TSKgelG2000HXL) manufactured by Tosoh Corporation were used in series, and the column temperature was 40 ° C. In addition, tetrahydrofuran was used for the eluent, the flow rate of 1 mL / min, and the detector used the RI (differential refractometer) detector. The number average molecular weight is measured by a calibration curve with standard polystyrene.

[Formula 1]

(In formula, R <1>, R <2> is a hydrogen atom or a hydrocarbon group, may be same or different, and a phosphorus atom and R <1>, R <2> may take a cyclic structure. N represents 0 or 1.)

(2) Phosphorus containing epoxy resin composition formed by mix | blending the phosphorus containing epoxy resin and hardening | curing agent as described in said (1) so that it may become the range of 0.3-1.5 active groups with respect to one epoxy group,

(3) a prepreg formed by impregnating a substrate with a phosphorus-containing epoxy resin composition according to (2);

(4) an epoxy resin cured product obtained by curing the phosphorus-containing epoxy resin composition according to the above (2),

(5) It is a laminated board formed by hardening | curing the phosphorus containing epoxy resin composition as described in said (2).

The phosphorus containing epoxy resin which made the novolak-type epoxy resin which has a specific molecular weight distribution of this invention, and the specific phosphorus compound react significantly improves flame retardance compared with what was obtained using the novolak-type epoxy resin which has a conventional molecular weight distribution. It is possible to reduce expensive phosphorus-containing compounds, and as a result, it is possible to improve the properties of the cured product, and to obtain a specific molecular weight distribution by controlling the molecular weight distribution of the novolak-type epoxy resin to be used. It is possible to achieve compatibility of cargo properties.

1 shows a GPC chart of a phenol novolac epoxy resin YDPN-638 having a molecular weight distribution of the conventional type. Elution time is shown on the horizontal axis and detection intensity is shown on the left vertical axis. The number average molecular weight M is represented by log (commercial log) on the right vertical axis. The measured value of the number average molecular weight of the used standard substance is plotted in a black circle, and it is set as the analytical curve. The peak represented by A is a nucleus, and the peak represented by B is a trinuclear body.
2 shows a GPC chart of Synthesis Example 4. FIG. The peak represented by A is a nucleus, and the peak represented by B is a trinuclear body.

The present invention will be described in detail.

A novolak-type epoxy resin is a polyfunctional novolak-type epoxy resin obtained by making the novolak resin and epihalohydrin which are reaction products of phenols and aldehydes react. Examples of the phenols used include phenol, cresol, ethyl phenol, butyl phenol, styrenated phenol, cumylphenol, naphthol, catechol, resorcinol, naphthalenediol, and bisphenol A. Examples of aldehydes include formalin and formaldehyde. , Hydroxybenzaldehyde, salicylic aldehyde and the like. Moreover, aralkyl phenol resin which used xylylene dimethanol, xylylene dichloride, bischloromethyl naphthalene, bischloromethyl biphenyl etc. instead of aldehyde is also included in novolak-type phenol resin in this invention. A novolak-type epoxy resin is obtained by epoxidizing these novolak-type phenol resins using epihalohydrin.

As a specific example of a novolak-type epoxy resin, Efototo YDPN-638 (phenol phenol novolak-type epoxy resin of Shin-Nitetsu Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (Mphenol phenol novolak-type epoxy of Mitsubishi Chemical Co., Ltd. make) Resin), Epiclone N-740, Epiclone N-770, Epiclone N-775 (phenolic novolac type epoxy resin manufactured by DIC Corporation), Efototo YDCN-700 series (Cresol novolac manufactured by Shinnitetsu Chemical Co., Ltd.) Type epoxy resin), epiclon N-660, epiclon N-665, epiclon N-670, epiclon N-673, epiclon N-695 (cresol novolac type epoxy resin manufactured by DIC Corporation), EOCN-1020 , EOCN-102S, EOCN-104S (cresol novolac type epoxy resin manufactured by Nippon Gunpowder Co., Ltd.), Efototo ZX-1071T, ZX-1270, ZX-1342 (alkyl novolac type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd.) , Efototo ZX-1247, GK-5855 (Shin Nitetsu Chemical Co., Ltd. Lenphenol phenol novolak-type epoxy resin), Efototo ZX-1142L (naphthol novolak-type epoxy resin from Shin-Nitetsu Chemical Co., Ltd.), ESN-155, ESN-185V, ESN-175 (β naphthol from Shin-Nitetsu Chemical Co., Ltd.) Aralkyl type epoxy resin), ESN-355 of ESN-300 series, ESN-375 (Dinaphthol aralkyl type epoxy resin of Shinnitetsu Chemical Co., Ltd.), ESN-475V of ESN-400 series, ESN-485 (Sinnittetsu) (Alpha) naphthol aralkyl-type epoxy resin) bisphenol novolak-type epoxy resin etc. made by the Chemicals Corporation are mentioned, These epoxy resins do not have specific molecular weight distribution in this invention.

To obtain a novolak type epoxy resin having a specific molecular weight distribution used in the present invention, a phenol novolak resin obtained by removing a low molecular weight component from a crude phenol novolak resin obtained by adjusting the molar ratio of phenols and aldehydes, Or you may epoxidize the phenol novolak resin obtained by the manufacturing method as shown in patent document 4 and patent document 5.

The molar ratio of phenols and aldehydes is represented by the molar ratio of phenols to 1 mole of aldehydes and is produced in a ratio of 1 or more. When the molar ratio is large, a large number of nuclei and trinuclear bodies are generated, and when the molar ratio is small, a high molecular weight is generated. 2 nuclei and 3 nuclei become smaller.

The novolak-type epoxy resin having a specific molecular weight distribution used in the present invention is a method for removing the binary nucleus component and / or quaternary nucleus component from the obtained crude phenol novolak resins by using the difference in solubility of various solvents. Although it can obtain by the method of melt | dissolving and removing a nuclide, you may obtain by other well-known separation methods.

The novolak-type epoxy resin which has a specific molecular weight distribution can be obtained using the well-known epoxidation method to the phenol resin which controlled molecular weight. Or the novolak-type epoxy resin which has a specific molecular weight distribution can also be obtained by removing the binary nucleus epoxy resin component from various commercially available novolak-type epoxy resins by various methods. In addition, you may obtain by a well-known separation method.

As for the novolak-type epoxy resin which has a specific molecular weight distribution of this invention, a binuclear body content rate is 15 area% or less, Preferably 5 area%-12 area% are preferable. By containing a small amount of binary nuclei, physical properties such as adhesive force can be improved. 3 Nuclear body content rate is 15 area%-60 area%, Preferably 20 area%-50 area% are preferable. As for a number average molecular weight, 350-700, Preferably 380-600 are preferable. The molecular weight dispersion degree (weight average molecular weight / number average molecular weight) can use 1.1-2.8, The preferable ranges are 1.2-2.5, More preferably, it is 1.2-2.3, and below 1.1, physical properties, such as adhesiveness, are inferior, 2.8 When exceeding, there exists a possibility that flame retardance, heat resistance, etc. may fall.

As a specific example of the phosphorus compound represented by General formula (1), a dimethyl phosphine, a diethyl phosphine, a diphenyl phosphine, 9,10- dihydro-9-oxa-10- phosphazanthanthene-10-oxide ( HCA Sanko Chemical Co., Ltd.), dimethyl phosphine oxide, diethyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide, 1, 4- cyclooctylene phosphine oxide, 1, 5- cyclooctylene phosphine Oxide (manufactured by CPHO Nippon Chemical Industry Co., Ltd.). These phosphorus compounds may be used independently or may be used in mixture of 2 or more types, and is not limited to these.

As a method of making the phosphorus compound represented by General formula (1), and the novolak-type epoxy resin which has a specific molecular weight distribution react, it can carry out by a well-known method. As reaction temperature, reaction is performed at 100 degreeC-200 degreeC, More preferably, stirring at 120 degreeC-180 degreeC. Active hydrogen directly connected to the phosphorus atom of the phosphorus compound represented by General formula (1), and the epoxy group of an epoxy resin react. The end point of the reaction was confirmed to be 99% or more of the theoretical epoxy equivalent by tracking the epoxy equivalent. Or the residual amount of the phosphorus compound represented by General formula (1) as an acid value of an epoxy resin is traced, and is represented by General formula (1) which remains by the apparatus analysis represented by the method of confirming a reaction end point, liquid chromatography, etc. Tracking of phosphorus compounds. Although either method may be taken, it is necessary to fully react the epoxy resin and the phosphorus compound represented by General formula (1). The catalyst is used as necessary in consideration of the reaction rate. Specifically, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphine such as triphenylphosphine, tris (2,6-dimethoxyphenyl) phosphine, and ethyltriphenyl Various catalysts, such as phosphonium salts, such as phosphonium bromide, imidazole, such as 2-methylimidazole and 2-ethyl 4 methylimidazole, can be used.

When reacting the phosphorus compound represented by General formula (1) with the novolak-type epoxy resin which has a specific molecular weight distribution, you may use together various epoxy resin modifiers so that the characteristic of this invention may not be impaired as needed. Modifiers include bisphenol A, bisphenol F, bisphenol AD, tetrabutylbisphenol A, hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, resorcinine, methylresorcin, biphenol, tetramethylbiphenol, dihydride Loxynaphthalene, dihydroxydiphenyl ether, dihydroxystilbenes, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadienephenol resin, phenol aralkyl resin, naphthol novolak resin, terpene Polyhydric phenol resin obtained by condensation reaction of various phenols, such as a phenol resin, heavy oil modified phenol resin, a brominated phenol novolak resin, and various phenols, such as hydroxy benzaldehyde, crotonaldehyde, glyoxal, aniline, phenylene Diamine, toluidine, xyldine, diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenyl Ethane, diaminodiphenylpropane, diaminodiphenylketone, diaminodiphenylsulfide, diaminodiphenylsulfone, bis (aminophenyl) fluorene, diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, Diaminobenzanilide, diaminobiphenyl, dimethyldiaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisaminophenoxybenzene, bisaminophenoxyphenyl ether, bisaminophenoxybiphenyl, bisaminophenoxyphenyl Amine compounds, such as sulfone, bisaminophenoxy phenyl propane, and diamino naphthalene, are mentioned, It is not limited to these, You may use together two or more types.

When reacting the phosphorus compound represented by General formula (1) with the novolak-type epoxy resin which has a specific molecular weight distribution, various epoxy resins can also be used to the extent which does not impair the characteristic of this invention as needed. Specifically, Efototo YDC-1312, ZX-1027 (hydroquinone type epoxy resin manufactured by Shin-Nitetsu Chemical Co., Ltd.), YX-4000 (manufactured by Mitsubishi Chemical Co., Ltd.), ZX-1251 (nonphenol type manufactured by Shin-Nitetsu Chemical Co., Ltd.) Epoxy resin), Efototo YD-127, Efototo YD-128, Efototo YD-8125, Efototo YD-825GS, Efototo YD-011, Efototo YD-900, Efototo YD -901 (BPA type epoxy resin manufactured by Shin-Nitetsu Chemical Co., Ltd.), Efototo YDF-170, Efototo YDF-8170, Efototo YDF-870GS, Efototo YDF-2001 (BPF by Shinnitetsu Chemical Co., Ltd.) Type epoxy resin), Efototo YDPN-638 (phenol phenol novolak type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd.), Efototo YDCN-701 (cresol novolak type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd.), ZX-1201 (Bisphenol Fluorene Type Epoxy Resin of Shin-Nitetsu Chemical Co., Ltd.), NC-3000 (Nippon Gunpowder Co., Ltd.) Biphenyl aralkyl phenol type epoxy resin of manufacture), EPPN-501H, EPPN-502H (polyfunctional epoxy resin of Nippon Kayaku Co., Ltd.), ZX-1355 (naphthalenediol type epoxy resin of Shin-Nitetsu Chemical Co., Ltd.), ESN- 155, ESN-185V, ESN-175 (β naphthol aralkyl type epoxy resin from Shinnitetsu Chemical Co., Ltd.), ESN-355, ESN-375 (Dinaphthol aralkyl type epoxy resin from Shinnitetsu Chemical Co., Ltd.), ESN- Phenolic compounds, such as polyhydric phenol resins, such as 475V and ESN-485 ((alpha) naphthol aralkyl type epoxy resin by Shin-Nitetsu Chemical Co., Ltd.), epoxy resin manufactured from epihalohydrin, epoto YH-434, e. Amine compounds such as Phototo YH-434GS (diaminodiphenylmethane tetraglycidyl ether manufactured by Shinnitetsu Chemical Co., Ltd.), epoxy resin produced from epihalohydrin, and YD-171 (manufactured by Shinnitetsu Chemical Co., Ltd.) Dimer Mountain And carboxylic acids, such as epoxy resin), there can be mentioned an epoxy resin prepared from Hi gave to be epitaxially, but are not limited to these may be used in combination of two or more.

The phosphorus containing epoxy resin composition of this invention makes a phosphorus containing epoxy resin using the novolak-type epoxy resin which has a specific molecular weight distribution an essential component, As a hardening | curing agent, various phenol resins, acid anhydrides, amines, hydrazides, The hardening | curing agent for epoxy resins normally used, such as acidic polyester, can be used, and these hardening | curing agents may use only one type, or may use two or more types.

As a specific example of the phenol resin as a hardening | curing agent mentioned above, bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, tetramethyl bisphenol Z Bisphenols such as dihydroxydiphenyl sulfide and 4,4'-thiobis (3-methyl-6-tert-butylphenol), catechol, resorcin, methylresorcin, hydroquinone and monomethyl hydro; Dihydroxybenzenes such as quinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, tri Phenols, such as hydroxy naphthalene, such as hydroxy naphthalene, a phenol novolak resin, DC-5 (cresol novolak resin by Shin-Nitetsu Chemical Co., Ltd.), a naphthol novolak resin, and / or Condensates of naphthols and aldehydes, phenols such as SN-160, SN-395, and SN-485 (manufactured by Shinnitetsu Chemical Co., Ltd.) and / or condensates of naphthols and xylylene glycol, phenols and / or naphthols; And phenol compounds such as condensates of isopropenyl acetophenone, phenols and / or naphthols and reactants of dicyclopentadiene, phenols and / or condensates of naphthols and biphenyl condensates.

Examples of the phenols include phenol, cresol, xylenol, butyl phenol, amyl phenol, nonyl phenol, butyl methyl phenol, trimethyl phenol and phenyl phenol. Examples of naphthols include 1-naphthol and 2-naphthol. Can be mentioned.

As aldehydes, formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromine aldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, aldehyde, aldehyde, aldehyde Melinaldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like. Bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, bis (chloromethyl) biphenyl etc. are illustrated as a biphenyl type condensing agent.

Specific examples of the acid anhydrides as the curing agent include acid anhydrides such as methyltetrahydro phthalic anhydride, hexahydro phthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and methylnadic acid.

Specific examples of the amines as the curing agent include diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, dicyandiamide, Amine type compounds, such as polyamideamine which is a condensate of acids, such as dimer acid, and polyamine, etc. are mentioned.

Moreover, you may mix | blend epoxy resins other than the phosphorus containing epoxy resin of this invention in the range which does not impair the characteristic of this invention, Specifically, Efototo YD-128 and Efototo YD-8125 (made by Shin-Nitetsu Chemical Co., Ltd.). BPA type epoxy resin), Efototo YDF-170, Efototo YDF-8170 (BPF type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd.), YSLV-80XY (Tetramethylbisphenol F type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd.) ), Efototo YDC-1312 (hydroquinone type epoxy resin), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), Efototo YDPN-638 (phenol phenol novolak type epoxy resin manufactured by Shinnitetsu Corporation) , Efototo YDCN-701 (cresol novolac type epoxy resin manufactured by Shin-Nitetsu Chemical Co., Ltd.), Efototo ZX-1201 (bisphenol fluorene type epoxy resin manufactured by Shin-Nitetsu Chemical Co., Ltd.), TX-0710 (Shin-Nitetsu Bisphenol S type epoxy resin manufactured by Chemical Co., Ltd., Epiclone EXA-1515 (Bisphenol S type epoxy resin manufactured by Dainippon Chemical Industry Co., Ltd.), NC-3000 (Biphenyl aralkyl phenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), Efototo ZX-1355, Efototo ZX-1711 (naphthalenediol type epoxy resin from Shin-Nitetsu Chemical Co., Ltd.), Efototo ESN-155 (β-naphthol aralkyl type epoxy resin from Shin-Nitetsu Chemical Co., Ltd.), Efototo ESN-355, Efototo ESN-375 (Dinaphthol aralkyl type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd.), Efototo ESN475V, Efototo ESN-485 (α-naphthol manufactured by Shinnitetsu Chemical Co., Ltd.) Polyhydric compounds such as aralkyl type epoxy resin), EPPN-501H (trisphenylmethane type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), Sumieepoxy TMH-574 (trisphenylmethane type epoxy resin manufactured by Sumitomo Chemical Co., Ltd.) Emine compounds and epihalohehe such as epoxy resin produced from phenolic compound of phenol resin and epihalohydrin, efototo YH-434 (diaminodiphenylmethane tetraglycidylamine manufactured by Shinnitetsu Chemical Co., Ltd.) Epoxy resin produced from Drin, jER 630 (aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation), Efototo FX-289B, Efototo FX-305, TX-0932A (Phosphorus-containing epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd.) Phosphorus-containing epoxy resin obtained by reacting epoxy resins, such as) with modifiers, such as a phosphorus containing phenolic compound, YSLV-120TE (bisthioether type epoxy resin by Shin-Nitetsu Chemical Co., Ltd.), Efototo ZX-1684 (Shin-Nitetsu Chemical Resorcinol type epoxy resin manufactured by Corporation, Denacol EX-201 (Resorcinol type epoxy resin manufactured by Nagase Chemtex, Inc.), Epiclone HP-7200H (DIC Corporation) Manufactured dicyclopentadiene type epoxy resin), urethane modified epoxy resin, oxazolidone ring containing epoxy resin, TX-0929, TX-0934 (The alkylene glycol type epoxy resin by Shin-Nitetsu Chemical Co., Ltd.), etc. are mentioned. .

The phosphorus content rate of the epoxy resin composition of this invention is 0.8%-7%, Preferably it is 1%-6%, More preferably, it is the range of 1.5%-4%. If it is less than 0.8%, flame retardancy is not obtained. If it is more than 7%, the heat resistance is lowered, the hygroscopicity is increased, and the physical properties are deteriorated.

As needed, well-known common epoxy resin hardening accelerators, such as a tertiary amine, a quaternary ammonium salt, phosphines, and imidazole, can be mix | blended with this composition. Specifically, phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2 Imidazoles such as undecylimidazole and 1-cyanoethyl-2-methylimidazole and imidazole salts such as trimellitic acid, isocyanuric acid and boron, benzyldimethylamine, 2,4 Amines such as, 6-tris (dimethylaminomethyl) phenol, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds and salts such as phenols and phenol novolak resins, boron trifluoride, amines and ether compounds Complex compounds, such as aromatic phosphonium or iodonium salt, etc. can be illustrated. These curing agents may be individual or may use two or more types together.

The organic solvent can also be used for the phosphorus containing epoxy resin composition of this invention for viscosity adjustment. Examples of the organic solvent that can be used include amides such as N and N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, benzene and toluene. Aromatic hydrocarbons, such as these, etc. are mentioned, The thing which mixed one or more types of these solvent can be mix | blended in 30 to 80 weight% as an epoxy resin concentration.

Moreover, if necessary, organic fillers such as inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, boehmite, titanium oxide, glass powder, and silica balloon, particulate rubber, and thermoplastic elastomers, glass fibers, and pulp Fibrous fillers such as fibers, synthetic fibers, ceramic fibers, reinforcing materials such as glass cross aramid cross, carbon fiber, pigments and the like can be used.

As a result of evaluating the laminated board of an epoxy resin composition, the phosphorus containing epoxy resin obtained by making the novolak-type epoxy resin which has a specific molecular weight distribution, and the phosphorus compound represented by General formula (1) as an epoxy resin react with phosphorus content rate, maintaining productivity. Even if it reduces, flame retardancy can be obtained and hardened | cured material properties can be improved, and not only the copper clad laminated board used for an electronic circuit board but also sealing materials, molding materials, molding materials, adhesives, electrical insulation paints, and composite materials which require flame retardance, etc. It can be used preferably.

Example

Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these. "Part" shows a weight part, and "%" shows the weight% unless there is particular notice. The measuring method was measured by the following method, respectively.

Epoxy equivalent: According to JIS K 7236.

Binary nucleus content, trinuclear content, number average molecular weight, weight average molecular weight: The molecular weight distribution was measured using gel permeation chromatography, and the dinuclear content and trinuclear content were the number average molecular weight and the weight average from the area% of the peak. Molecular weight is standard monodisperse polystyrene (A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F- by Tosoh Corporation It was converted from the calibration curve obtained from 40). Specifically, a column (TLSgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL, manufactured by Tosoh Corporation) was provided in series with the main body (HLC-8220GPC, manufactured by Tosoh Corporation), and the column temperature was 40 ° C. In addition, tetrahydrofuran was used for the eluent, the flow rate of 1 mL / min, and the detector used the RI (differential refractometer) detector.

Phosphorus content: The sulfuric acid, hydrochloric acid, and perchloric acid were added to the sample, and it heated and wet ignited and made all the phosphorus atoms into orthophosphoric acid. Metavanadate and molybdate are reacted in an acidic sulfuric acid solution, and the absorbance at 420 nm of the produced indiver molybdate complex is measured, and the phosphorus atom content determined by a calibration curve previously prepared using potassium dihydrogen phosphate is determined. It was shown by weight%. The phosphorus content of a laminated board was shown as content with respect to the resin component of a laminated board.

Copper foil peeling strength and interlayer adhesive force: It measured according to JIS C 6481, and the interlayer adhesive force peeled off between 7th layer and 8th layer, and measured.

Combustibility: According to UL94 (safety certification standard of Underwriters Laboratories Inc.). Five test pieces were tested and the sum total time of the flame burning duration after the 1st and 2nd inoculation (in total 10 times in total of 2 in 5 each) was shown by the second.

Glass transition temperature DSC: It represented by the temperature of the DSC extrapolation value when it measured on the temperature rising condition of 10 degree-C / min with the differential scanning calorimetry apparatus (EXSTAR6000 DSC6200 by SII Nanotechnology Co., Ltd.).

Glass transition temperature TMA: It was shown by the temperature of the TMA extrapolation value when it measured on the temperature rising conditions of 5 degree-C / min with the thermomechanical analyzer (EXSTAR6000 TMA / SS120U by SII Nanotechnology Co., Ltd.).

As the epoxy resin used:

YDF-170C (Bisphenol F type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd., measurement by gel permeation chromatography, binuclear content 81.9 area%, trinuclear content 5.3 area%, number average molecular weight 254, weight average molecular weight 285, dispersion Figure 1.12, Epoxy equivalent 169 g / eq)

YDPN-638 (Phenol novolak-type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd., measurement by gel permeation chromatography, 2 nucleus content 22.1 area%, 3 nucleus content 10.7 area%, number average molecular weight 463, weight average molecular weight 1003, Dispersion degree 2.17, epoxy equivalent weight 176 g / eq)

YDCN-700-2 (Cresol novolak-type epoxy resin manufactured by Shinnitetsu Chemical Co., Ltd., measurement by gel permeation chromatography, 2 nucleus content 10.5 area%, 3 nucleus content 10.9 area%, number average molecular weight 633, weight average molecular weight 1187, dispersion 1.88, epoxy equivalent 200 g / eq)

Synthesis Example 1

2500 parts of phenol and 7.5 parts of oxalic acid dihydrate were injected | poured into the four glass separable flasks equipped with the stirring apparatus, the thermometer, the cooling tube, and the nitrogen gas introduction apparatus, and it stirred while introducing nitrogen gas, heated and heated up. . 474.1 parts of 37.4% formalin were dripped at 80 degreeC, and dripping was complete | finished in 30 minutes. Furthermore, reaction was performed for 3 hours, maintaining reaction temperature at 92 degreeC. It heated up to 110 degreeC, heating up and removing reaction product water out of the system. Residual phenol was collect | recovered under reduced pressure at 160 degreeC, and the phenol novolak resin was obtained. The temperature was further raised to recover a portion of the two nuclei. The binary nucleus content rate of the obtained phenol novolak resin was 10 area% by the measurement by the gel permeation chromatography.

Synthesis Example 2

The phenol novolak resin obtained by the synthesis example 1 was melt | dissolved in MIBK, and water washing liquid separation was performed with the 5% sodium hydroxide aqueous solution. After the residual sodium hydroxide was removed by washing with water, MIBK was recovered under reduced pressure. The binary nucleus content rate of the obtained phenol novolak resin was 6 area% by the measurement by the gel permeation chromatography.

Synthesis Example 3

The same operation as in Synthesis Example 1 was performed except that 711.1 parts of 37.4% formalin of Synthesis Example 1 was used. The binary nucleus content rate of the obtained phenol novolak resin was 10 area% by the measurement by the gel permeation chromatography.

Synthesis Example 4

665.8 parts of phenol novolak resin, 2110.8 parts of epichlorohydrin and 17 parts of water were injected into the same apparatus as in Synthesis example 1, and it heated up to 50 degreeC, stirring. 14.2 parts of 49% sodium hydroxide aqueous solution were injected, and reaction was performed for 3 hours. It heated up to 64 degreeC, depressurized so that reflux of water might occur, and 457.7 parts of 49% sodium hydroxide aqueous solution were dripped over 3 hours, and reaction was performed. The temperature was raised to 70 ° C, dehydration was performed, and the remaining epichlorohydrin was recovered at a temperature of 135 ° C. The mixture was returned to normal pressure and dissolved by adding 1232 parts of MIBK. 1200 parts of ion-exchanged water was added, stirring was stopped and the by-product salt was dissolved in water and removed. Next, 37.4 parts of 49% sodium hydroxide aqueous solution were injected | poured, and it stirred for 90 minutes at 80 degreeC, and performed the purification reaction. MIBK was added and washed with water several times to remove ionic impurities. The solvent was recovered and a novolak-type epoxy resin was obtained. As a result of measurement by gel permeation chromatography, the content of dinuclear body was 9 area%, the content of trinuclear body 37.0 area%, the number average molecular weight 440, the weight average molecular weight 605, the dispersity 1.38, and the epoxy equivalent of 176 g / eq.

Synthesis Example 5

The same operation as in Synthesis Example 4 was carried out except that the phenol novolak resin of Synthesis Example 2 was used instead of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4 to obtain a novolak-type epoxy resin. As a result of measurement by gel permeation chromatography, the content of dinuclear body was 5.5 area%, the content of trinuclear body 34.6 area%, the number average molecular weight 485, the weight average molecular weight 684, the dispersity 1.41, and the epoxy equivalent of 176 g / eq.

Synthesis Example 6

A novolak-type epoxy resin was obtained in the same manner as in Synthesis Example 4 except that the phenol novolak resin of Synthesis Example 3 was used instead of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4. As a result of measurement by gel permeation chromatography, the content of dinuclear body was 9.1 area%, the content of trinuclear body 24.2 area%, number average molecular weight 593, weight average molecular weight 954, dispersion degree 1.61, and epoxy equivalent 177 g / eq.

Synthesis Example 7

Synthesis Example 4 except for using LV-70S (phenol phenol novolac resin, 2 nucleus component 2%, 3 nucleus component 75%) instead of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4. The same operation as the above was carried out to obtain a novolak-type epoxy resin. As a result of measurement by gel permeation chromatography, the content of dinuclear body was 1.4 area%, the content of trinuclear body was 56.1 area%, the number average molecular weight 486, the weight average molecular weight 617, the dispersity 1.27, and the epoxy equivalent of 176 g / eq.

Synthesis Example 8

Instead of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4, TRI6.5 (triphenylmethane type novolac resin manufactured by Showa Denko Co., Ltd., 4.6% of the nucleus component and 29.7% of the nucleus component) was 2326.5 parts, 4 A novolak-type epoxy resin was obtained in the same manner as in Synthesis example 4 except that 173.6 parts of, 4-methylene biscresol were used. As a result of measurement by gel permeation chromatography, the content of dinuclear body was 9.2 area%, the content of trinuclear body 21.8 area%, number average molecular weight 640, weight average molecular weight 1109, dispersion degree 1.80, and epoxy equivalent 177 g / eq.

Synthesis Example 9

Synthesis Example 4 and BRG-558 (phenol phenol novolak resin, 1 nucleus component 12.0%, trinuclear component 10.0%) used in place of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4 The same operation was performed and the novolak-type epoxy resin was obtained. As a result of measurement by gel permeation chromatography, the content of dinuclear body was 10.4 area%, the content of trinuclear body was 5.8 area%, the number average molecular weight 818, the weight average molecular weight 2436, the dispersity 2.98, and the epoxy equivalent of 177 g / eq.

Example 1

824 parts of the phenol novolak-type epoxy resin of the synthesis example 4, and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide phosphorus content of Sanco Corporation 14.2 in the same apparatus as the synthesis example 1 176 parts by weight) were injected, stirring was performed while introducing nitrogen gas, and heating was performed to raise the temperature. 0.18 part was added as a catalyst at 130 degreeC as a catalyst, and reaction was performed at 160 degreeC for 3 hours. The epoxy equivalent of the obtained epoxy resin was 266 g / eq, and phosphorus content rate was 2.5%. The results are summarized in Table 1.

Example 2

The same operation as in Example 1 was carried out except that 838 parts of the phenol novolac-type epoxy resin of Synthesis Example 4 and 162 parts of HCA were used. The epoxy equivalent of the obtained epoxy resin was 256 g / eq, and phosphorus content rate was 2.3%. The results are summarized in Table 1.

Example 3

The same operation as in Example 1 was carried out except that 880 parts of the phenol novolac-type epoxy resin of Synthesis Example 4 and 120 parts of HCA were used. The epoxy equivalent of the obtained epoxy resin was 226 g / eq, and phosphorus content rate was 1.7%. The results are summarized in Table 1.

Example 4

The same operation as in Example 1 was performed except that 824 parts of the phenol novolak type epoxy resin of Synthesis Example 5 and 176 parts of HCA were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 264 g / eq, and phosphorus content rate was 2.5%. The results are summarized in Table 1.

Example 5

The same operation as in Example 1 was performed except that 824 parts of the phenol novolak type epoxy resin of Synthesis Example 6 and 176 parts of HCA were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 256 g / eq, and phosphorus content rate was 2.5%. The results are summarized in Table 1.

Example 6

The same operation as in Example 1 was performed except that 711.9 parts of the phenol novolak type epoxy resin of Synthesis Example 7 and 112.1 parts of YDF-170C were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The binary nucleus content rate of the used epoxy resin was 11.9 area%, and the trinuclear content was 49.0 area%. The epoxy equivalent of the obtained epoxy resin was 257 g / eq, and phosphorus content rate was 2.5%. The results are summarized in Table 1.

Example 7

804 parts of phenol novolak type epoxy resins of Synthesis Example 4 and 55 parts of bisphenol F (manufactured by Honshu Chemical Co., Ltd.) were injected and heated to 120 ° C. 0.06 parts of triphenylphosphines were added and reacted at 150 degreeC for 2.5 hours. Further, 141 parts of HCA was added, and 0.14 part of triphenylphosphine was added to carry out the reaction at 160 ° C for 3 hours. The epoxy equivalent of the obtained epoxy resin was 301 g / eq, and phosphorus content rate was 2.0%. The results are summarized in Table 1.

Example 8

The same operation as in Example 7 was performed except that 799 parts of the phenol novolak-type epoxy resin of Synthesis Example 4 of Example 7 and 60 parts of bisphenol A were used instead of bisphenol F. The epoxy equivalent of the obtained epoxy resin was 295 g / eq, and phosphorus content rate was 2.0%. The results are summarized in Table 1.

Example 9

The same operation as in Example 1 was carried out except that 824 parts of the phenol novolak-type epoxy resin of Synthesis Example 8 were used instead of the phenol novolak-type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 260 g / eq, and phosphorus content rate was 2.5%. The results are summarized in Table 1.

Comparative Example 1

The same operation as in Example 1 was carried out except that 810 parts of YDPN-638 and 190 parts of HCA were used instead of the phenol novolac epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 271 g / eq, and phosphorus content rate was 2.7%. The results are summarized in Table 2.

Comparative Example 2

The same operation as in Example 1 was performed except that 824 parts of YDPN-638 was used instead of the phenol novolac epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 251 g / eq, and phosphorus content rate was 2.5%. The results are summarized in Table 2.

Comparative Example 3

The same operation as in Example 1 was carried out except that 838 parts of YDPN-638 and 162 parts of HCA were used instead of the phenol novolac epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 255 g / eq, and phosphorus content rate was 2.3%. The results are summarized in Table 2.

Comparative Example 4

The same operation as in Example 7 was carried out except that 804 parts of YDPN-638 was used instead of the phenol novolak-type epoxy resin of Synthesis Example 4 of Example 7. The epoxy equivalent of the obtained epoxy resin was 306 g / eq, and phosphorus content rate was 2.0%. The results are summarized in Table 2.

Comparative Example 5

The same operation as in Example 7 was carried out except that 799 parts of YDPN-638 was used instead of the phenol novolak-type epoxy resin of Synthesis Example 4 of Example 8. The epoxy equivalent of the obtained epoxy resin was 308 g / eq, and phosphorus content rate was 2.0%. The results are summarized in Table 2.

Comparative Example 6

The same operation as in Example 1 was carried out except that 824 parts of the phenol novolak-type epoxy resin of Synthesis Example 9 were used instead of the phenol novolak-type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 256 g / eq, and phosphorus content rate was 2.5%. The results are summarized in Table 2.

Comparative Example 7

The same operation as in Example 1 was performed except that 824 parts of YDCN-700-2 was used instead of the phenol novolak-type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 303 g / eq, and phosphorus content rate was 2.5%. The results are summarized in Table 2.

Comparative Example 8

141 parts of HCA and 330 parts of toluene were injected into the same apparatus as in Example 1, and heated to dissolve. Thereafter, 87.5 parts of 1,4-naphthoquinone was separately added while paying attention to the temperature increase by the heat of reaction. At this time, the molar ratio of 1,4-naphthoquinone and HCA was 1,4-naphthoquinone / HCA = 0.85. After hold | maintaining at 85 degreeC for 30 minutes, it heated up and reaction was continued at reflux temperature for 2 hours. The temperature was further increased to recover 200 parts of toluene, 771.5 parts of YDPN-638 was injected, stirred while introducing nitrogen gas, and heated to 120 ° C. 0.23 weight part of triphenylphosphines were added, and it reacted at 165 degreeC for 4 hours. The epoxy equivalent of the obtained epoxy resin was 327 g / eq, and phosphorus content rate was 2.0%. The results are summarized in Table 2.

Example 10- Example 18

The epoxy resin composition was manufactured using dicyandiamide (made by Nippon-Kabyte Co., Ltd.) as a phosphorus containing epoxy resin of Example 1-Example 9, and a hardening | curing agent. Table 3 shows the formulations for solids. At the time of blending, the epoxy resin was dissolved in methyl ethyl ketone and used. DICY was used by dissolving in methoxypropanol and DMF. 2E4MZ was used after being dissolved in methoxypropanol. After mix | blending, it adjusted so that it might become 50% of non volatile matters with methyl ethyl ketone and methoxy propanol, and it was set as the uniform solution.

The obtained resin varnish was impregnated into glass cross WEA 7628 XS13 (0.18 mm thickness manufactured by Nitto Spinning Co., Ltd.). The impregnated glass cross was dried for 8 minutes in a 150 degreeC hot air circulation path, and the prepreg was obtained. Eight obtained prepregs were superimposed, copper foil (3EC by Mitsui Metal Mining Co., Ltd. product) was piled up and down, and it heated and pressed for 130 degreeC x 15 minutes and 170 degreeC x 20 kg / cm <2> * 70 minutes, and obtained the laminated board. . Table 3 shows the physical properties of the obtained laminate.

Comparative Example 9- Comparative Example 16

The laminated board was manufactured using the phosphorus containing epoxy resin of Comparative Example 1- Comparative Example 8 similarly to Examples 10-18. Table 4 shows the physical properties of the formulation and the laminate.

The phosphorus containing epoxy resin obtained by making the phenol novolak epoxy resin which has a specific molecular weight distribution react with a specific phosphorus compound obtained the flame retardance even if the phosphorus content rate was 1.7% (Example 12), and raised phosphorus content rate to 2.3% and 2.5% (Examples 10 and 11) Flame retardancy is good in that the afterflaming time is shortened. On the other hand, the phosphorus containing epoxy resin obtained by making a conventional phenol novolak epoxy resin and a specific phosphorus compound react is not flame-retardant, and hardened | cured material physical property worsened unless the phosphorus content rate was 2.6% (comparative example 1). In Comparative Examples 2 and 3 in which the phosphorus content was 2.5% and 2.3%, the cured product properties were improved and the flame retardancy was not obtained. In Example 6, Example 7, and Example 8, although adhesiveness can be improved using another epoxy resin and an epoxy resin modifier, in the comparative example 4 and the comparative example 5 using the conventional phenol novolak epoxy resin, As a result of using an epoxy resin modifier, the flame retardancy was very bad.

Moreover, although reaction time of a phosphorus containing epoxy resin is 3 hours-5 hours, it is necessary for 9 hours in the comparative example 8 with favorable flame retardance and hardened | cured material physical property, and it is favorable also in productivity.

Phosphorus-containing epoxy resin of the present invention by controlling the molecular weight distribution of the phenol novolak-type epoxy resin as a raw material, it is possible to improve the flame retardancy while reducing the amount of expensive phosphorus compound, improve the physical properties of the cured product, It is useful for prepregs used in electronic circuit boards, film materials, sealing materials, molding materials, mold materials, adhesives, electrical insulating paints, composite paints and powder coating materials used for copper clad laminates and electronic components.

Claims (5)

Novolak-type epoxy resin which has molecular weight distribution whose binuclear content is 15 area% or less, trinuclear content is 15 area%-60 area%, and number average molecular weights are 350-700 in the measurement in gel permeation chromatography. The phosphorus containing epoxy resin formed by making (A) and the phosphorus compound represented by General formula (1) as an essential component and making it react.
(Gel permeation chromatography measurement conditions)
The column temperature was 40 degreeC using what was equipped with the TSKgelG4000HXL, TSKgelG3000HXL, and TSKgelG2000HXL by Toso Corporation made in series. In addition, tetrahydrofuran was used for the eluent, the flow rate of 1 mL / min, and the detector used the RI (differential refractometer) detector. 0.1 g of the sample was dissolved in 10 ml of THF. The number average molecular weight is measured by a calibration curve with standard polystyrene.
[Formula 1]

(In formula, R <1>, R <2> is a hydrogen atom or a hydrocarbon group, may be same or different, and a phosphorus atom and R <1>, R <2> may take a cyclic structure. N represents 0 or 1.) The phosphorus containing epoxy resin composition formed by making the phosphorus containing epoxy resin and hardening | curing agent of Claim 1 into an essential component, and mixing them into the range of 0.3-1.5 active groups of a hardening | curing agent with respect to one epoxy group of a phosphorus containing epoxy resin. The prepreg formed by impregnating a base material with the phosphorus containing epoxy resin composition of Claim 2. The epoxy resin hardened | cured material formed by hardening | curing the phosphorus containing epoxy resin composition of Claim 2. The laminated board formed by hardening | curing the phosphorus containing epoxy resin composition of Claim 2.

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