JP2003212990A - Oligomer of thermosetting PPE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin which has excellent electrical properties and toughness of PPE and has improved compatibility with other resins and fabricability, and to render it in a form capable of being broadly utilized in a variety of applications including the field of electronics. <P>SOLUTION: By converting both terminal groups of a difunctional PPE oligomer having a bisphenol structure having substituents at least at 2,6-positions as the nucleus into thermosetting functional groups, a highly active thermosetting resin which inherits excellent electrical properties and toughness of PPE could have been made. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bifunctional phenylene ether oligomer having thermosetting functional groups at both ends, and is applicable to an electronic field requiring low dielectric constant, low dielectric loss tangent and high toughness. The present invention relates to a thermosetting resin used for various purposes such as painting, adhesion and molding.

[0002]

2. Description of the Related Art As materials for electrical and electronic applications, due to the use of high frequency (gigahertz band) along with the speeding up of transmission signals, a low dielectric constant that reduces the time delay and a low dielectric loss tangent that reduces the loss are used. Is desired. Further, high toughness is also desired in order to suppress microcracks which are considered to occur due to thermal shock and to obtain high reliability. In response to these demands, attempts have been made to blend engineering plastics such as polyphenylene ether (PPE) as a modified polymer having various properties. However, due to the fact that the thermoplastic resin is directly blended with the thermosetting resin, problems remain in the compatibility between the resins and the moldability.

In order to improve the compatibility, a method of improving the compatibility by blending with another resin as a compatibilizing agent, and a study of structuring a pseudo-IPN of PPE and a cyanate resin (JP-A-11-21452 etc.)
However, molding processability and heat resistance have not been solved. Further, in order to improve the moldability, studies have been conducted on a method of converting a high molecular weight PPE into a low molecular weight. For example, a method of redistributing polymer PPE and polyphenols under a radical catalyst (Japanese Patent Laid-Open No. 9-291148 etc.) is known. Further, in order to obtain toughness, a method is known in which a divalent phenol and a monovalent phenol are oxidatively polymerized to form a thermosetting resin having a cyanate ester group (Japanese Patent Publication No. 8-011747).

[0004]

SUMMARY OF THE INVENTION The present invention is to provide a thermosetting resin having excellent electrical properties and toughness of PPE, improved compatibility with other resins, and improved moldability. .
Furthermore, it is to be in a form that can be widely used in various applications including the electronics field.

[0005]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies on a thermosetting resin that inherits the excellent toughness of PPE and further has a low dielectric property. Bifunctional PPE represented by structural formula (6) obtained by oxidative copolymerization with phenol is obtained by dehydrohalogenation reaction with halogenated glycidyl such as epichlorohydrin in the presence of a base. Epoxy resin and bifunctional PPE represented by the above structural formula (6), with an allyl halide such as allyl bromide, under an alkaline condition in the presence of a phase transfer catalyst, an allyl resin obtained by a dehydrohalogenation reaction, The inventors have found that the above object is satisfied, and have completed the present invention. The present invention will be described in detail below.

According to the present invention, in the oxidative polymerization of phenols, a bifunctional PPE is efficiently synthesized by copolymerizing a divalent phenol and a monovalent phenol. It is characterized in that it is a thermosetting resin (epoxy body, allyl body) incorporated in the network. Here, at least 2,6-substituted bisphenols are used for the divalent phenol used as the raw material, and the monovalent phenol has a substituent at the 2,6-position required for the oxidative polymerization reaction. The present invention has been completed by using a compound having a substituent introduced at the 3-position as a raw material. The copolymerization of these compounds has led to the development of a resin that inherits the excellent electrical properties of PPE due to the effect of the phenylene ether structure and the effect of increasing the number of methyl groups. That is,
It has been found that a bifunctional PPE is very important for the present invention.

The bifunctional PPE oligomer which is an intermediate of the present invention has a structure represented by the following structural formula (6):
-XO)-is represented by structural formula (2),-(YO)-is one type of structure defined by structural formula (3) or 2 defined by structural formula (3)
It is a random arrangement of more than one type of structure. In the formula, R1, R2, R7, R8, R9 and R10 may be the same or different and each is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. R3, R4, R5, R6, R11 and R12 may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. A is
The straight-chain, branched, or cyclic hydrocarbons having 20 or less carbon atoms, a and b, represent an integer of 0 to 300, at least one of which is not 0. It is an oligomer of PPE in which it is essential that R1, R2, R7, R8, R9 and R10 are not hydrogen atoms.

[0008]

[Chemical 3]

The bifunctional PPE oligomer which is an intermediate of the present invention will be described. The oligomer of PPE represented by the structural formula (6) is obtained by diluting the divalent phenol represented by the structural formula (7) and the monovalent phenol defined by the structural formula (8) alone or in a mixture with toluene-alcohol. Alternatively, it can be efficiently produced by oxidative polymerization in a toluene-ketone or a ketone solvent.

[0010]

[Chemical 4]

Here, the divalent phenol of the structural formula (7) means that R1, R2, R7 and R8 may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. . R3, R4, R5 and R6 may be the same or different and each is a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group, and A is a linear or branched group having 20 or less carbon atoms. Alternatively, it is a cyclic hydrocarbon. R1, R2, R7, R8 is a divalent phenol which is essential not to be a hydrogen atom, and 4,4'-methylenebis (2,6-dimethylphenol), 4,4 '-(1-methylethylidene) bis [ 2,6-Dimethylphenol], 4,4'-methylenebis (2,3,6-trimethylphenol), 4,4'-cyclohexylidenebis [2,6-dimethylphenol], 4,4 '-(phenyl Methylene) bis-2,3,6
-Trimethylphenol, 4,4 '-[1,4-phenylenebis (1-
Methylethylidene)] bis [2,6-dimethylphenol], 4,
4'-methylenebis [2,6-bis (1,1-dimethylethyl) phenol], 4,4'-cyclopentylidenebis [2,6-dimethylphenol], 4,4 '-[2-furylmethylene] Bis (2,6-dimethylphenol), 4,4 '-[1,4-phenylenebismethylene] bis [2,6-dimethylphenol], 4,4'-(3,3,5-trimethylcyclohexidene) Bis [2,6-dimethylphenol], 4,
4 '-[4- (1-Methylethyl) cyclohexylidene] bis [2,6-
Dimethylphenol], 4,4 '-(4-methylphenylethylene) bis [2,3,6-trimethylphenol], 4,4'-[1,4-phenylenebismethylene] bis [2,3,6- Trimethylphenol], 4- [1- [4- (4-hydroxy-3,5-dimethylphenyl) -4
-Methylcyclohexyl] -1-methylethyl] -2,6-dimethylphenol, 4,4 '-(4-methoxyphenylmethylene) bis [2,3,6-trimethylphenol], 4,4'-[4- (1-Methylethyl) phenylmethylene] bis [2,3,6-trimethylphenol], 4,4 '-(9H-fluorene-9-ylidene) bis [2,6-
Dimethylphenol], 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bis [2,3,6-trimethylphenol],
4,4 '-(1,2-ethanediyl) bis [2,6-di- (1,1-dimethylethyl) phenol], 5,5'-(1-methylethylidene) bis [3-
(1,1-dimethylethyl) -1,1-biphenyl-2-ol] and the like, but are not limited thereto.

Next, the monovalent phenol of the structural formula (8) is
R9 and R10 may be the same or different and each is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. R
11, R12 may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. In particular, it is preferable to use one having a substituent at the 2,6 position alone or a combination thereof with one having a substituent at the 3 position or the 3,5 position. More preferably, alone
2,6-dimethylphenol or 2,3,6-trimethylphenol is good, and when used in combination, 2,6-dimethylphenol and 2,3,6-
6-trimethylphenol is good.

As a method of oxidation, there is a method of directly using oxygen gas or air. There is also a method of electrode oxidation. Either method may be used and is not particularly limited. Air oxidation is preferable because of safety and inexpensive capital investment. As a catalyst for oxidative polymerization using oxygen gas or air, CuCl, CuBr, Cu2SO4, CuCl2, CuB can be used.
r2, CuSO4, one or more of copper salts such as CuI is used, in addition to the above catalyst, mono- and dimethylamine,
Mono- and diethylamine, mono- and dipropylamine, mono- and di-n-butylamine, mono- and di-sec-
Dipropylamine, mono- and dibenzylamine, mono-
And dicyclohexylamine, mono- and diethanolamine, ethylmethylamine, methylpropylamine,
Butyldimethylamine, allylethylamine, methylcyclohexylamine, morpholine, methyl-n-butylamine, ethylisopropylamine, benzylmethylamine, octylbenzylamine, octyl-chlorobenzylamine, methyl (phenylethyl) amine, benzylethylamine, Nn-butyl Dimethylamine, N, N'-di-te
One or more amines such as rt-butylethylenediamine, di (chlorophenylethyl) amine, 1-methylamino-4-pentene, pyridine, methylpyridine, 4-dimethylaminopyridine and piperidine are used in combination.
If it is a copper salt and an amine, it will not be limited to these.

As the reaction solvent, toluene, benzene,
In addition to an aromatic hydrocarbon solvent such as xylene, a halogenated hydrocarbon solvent such as methylene chloride, chloroform and carbon tetrachloride, etc., it can be used in combination with an alcohol solvent or a ketone solvent. Examples of the alcohol solvent include methanol, ethanol, butanol, propanol, methyl propylene diglycol, diethylene glycol ethyl ether, butyl propylene glycol and propyl propylene glycol, and examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone and methyl butyl. Ketone, methyl isobutyl ketone and the like, and others, tetrahydrofuran,
Examples include, but are not limited to, dioxane and the like.

The reaction temperature is not particularly limited, but is preferably 25 to 50 ° C. Because oxidative polymerization is an exothermic reaction,
Above 50 ° C, temperature control is difficult and molecular weight control becomes difficult. At 25 ° C or lower, the reaction rate becomes extremely slow, and efficient production cannot be performed.

The thermosetting PPE oligomer of the present invention comprises:
It is shown in Structural Formula (1). That is,-(OXO)-is the structural formula
In the formula (2), R1, R2, R7 and R8 may be the same or different and each is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. R3, R4, R5, and R6, which may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A has 2 carbon atoms
It is a straight-chain, branched or cyclic hydrocarbon having a number of 0 or less. -(YO)-is represented by structural formula (3), and R9 and R10 are
May be the same or different, halogen atom or carbon number
An alkyl group of 6 or less or a phenyl group. R11, R12
May be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -(YO)-is one type of structure defined by structural formula (3),
Alternatively, two or more kinds of structures defined by the structural formula (3) are randomly arranged. Z is an organic group having 1 or more carbon atoms and may include an oxygen atom. a and b show the integer of 0-300 in which at least one is not 0. i independently represents an integer of 0 or 1.

[0017]

[Chemical 5]

In the Z portion, an organic group having 1 or more carbon atoms and optionally containing oxygen atom can be placed. For example,-(-CH2
-)-,-(CH2-CH2-)-,-(-CH2-Ar-O-)-and the like, but are not limited thereto. How to add is structural formula
There is a method of directly adding the intermediate represented by (6) to the bifunctional PPE, and a method of using a halide having a long carbon chain during the synthesis of the derivative, but the method is not limited thereto.

For the sake of convenience, the following description will be made on the derivative from the intermediate represented by the structural formula (6), which is the simplest structure.
explain. As the intermediate for producing the thermosetting PPE oligomer, the bifunctional PPE oligomer represented by the above structural formula (6) is used, but it is in the form of powder separated from the reaction solution or dissolved in the reaction solution. Either can be used.

A method for producing the epoxy body of the present invention will be illustrated. A compound having a bifunctional type and a phenolic hydroxyl group at the terminal represented by the above structural formula (6) as an intermediate is subjected to dehydrohalogenation reaction with a halogenated glycidyl such as epichlorohydrin in the presence of a base. Can be synthesized.

Representative examples of the base include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and the like, but are not limited thereto. Not a thing.

The reaction temperature is preferably between -10 ° C and 110 ° C.

Next, the method for producing the allyl compound of the present invention will be illustrated. 2 represented by the above structural formula (6) as an intermediate
A functional type compound having a phenolic hydroxyl group at the terminal can be synthesized by a dehydrohalogenation reaction under basic conditions with an allyl halide such as allyl bromide or allyl chloride in the presence of a phase transfer catalyst.

Examples of the phase transfer catalyst include tertiary amines such as triethylamine and tetramethylethylenediamine, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltri-n-butylammonium chloride and benzyltrin-butylammonium. Typical examples are quaternary ammonium salts such as bromide and benzyl-n-butylammonium iodide, or quaternary phosphonium salts, but not limited thereto.

Representative examples of the base include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and the like, but are not limited thereto. Not a thing.

The reaction temperature is preferably between -10 ° C and 60 ° C.

The thermosetting PPE oligomer of the present invention comprises:
Alone or other cyanate compound, epoxy compound,
It can be cured as a resin composition containing another polymerizable compound or catalyst.

As a curing method, all known methods can be applied. Exemplifying the above-mentioned other cyanate compounds,
m- or p-phenylenebiscyanate, 1,3,5-tricyanatebenzene, 4,4'-dicyanatobiphenyl, 3,
3 ', 5,5'-tetramethyl-4,4'-dicyanatobiphenyl,
2,3,3 ', 5,5'-pentamethyl-4,4'-dicyanatobiphenyl, 2,2'3,3', 5,5'-hexamethyl-4,4'-dicyanatobiphenyl, Bis (4-cyanatophenyl) methane, 1- (2,
3,5-trimethyl-4-cyanatophenyl) -1- (3,5-dimethyl-4-cyanatophenyl) methane, bis (2,3,5-trimethyl-4-dicyanatophenyl) methane, 1 , 1-bis (4-cyanatophenyl) ethane, 1- (2,3,5-trimethyl-4-cyanatophenyl) -1- (3,5-dimethyl-4-cyanatophenyl) ethane, 1, 1-bis (2,3,5-trimethyl-4-dicyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2- (2,3,5-trimethyl-4-cyanate Phenyl) -2- (3,5-dimethyl-4-cyanatophenyl) propane, 2,2-bis (2,3,5-trimethyl-4-dicyanatophenyl) propane, bis (4-cyanatophenyl) )ether,
Such as bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) sulfide, 4,4′-dicyanatobenzophenone, tris (4-cyanatophenyl) methane,
Biphenol or bis or polycyanate compounds in which an aromatic ring having a cyanate group is directly bonded by a bridge portion, and prepolymers of these cyanate compounds, prepolymers of these cyanate compounds and diamines, and phenol, One or more of cyanate group-containing novolac-type phenolic resins derived from novolac resins, which are reaction products of phenols such as o-cresol and formaldehyde, can be used.

Other polymerizable compounds include bismaleimide and epoxy resin, and these can be used as a mixed system. As an example of the above bismaleimide, N, N'-diphenylmethane bismaleimide, N,
N'-phenylene bismaleimide, N, N'-diphenyl ether bismaleimide, N, N'-dicyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'-diphenylsulfone bismaleimide, N, N'- Tolylene bimaleimide, N, N'-xylylene bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N'-dichloro-diphenylmethane bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N ' -Diphenylmethane bismethylmaleimide, N, N'-diphenylether bismethylmaleimide, N, N'-diphenylsulfone bismethylmaleimide, N, N'-ethylene bismaleimide, N, N'-hexamethylenebismethylmaleimide, and these N , N'-
Examples thereof include prepolymers of bismaleimide compounds, prepolymers of these bismaleimide compounds and diamines, and maleimides or methylmaleimides of aniline / formalin polycondensates.

When the above epoxy resin is exemplified,
Biphenol and its 2,2 ', 3,3', 5,5 'one or more positions substituted with a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group, bisphenol A and its 2 Substituted with a halogen atom or an alkyl group having a carbon number of 6 or less or a phenyl group at any one of the 3,3 and 5 positions, bisphenol F and its 2,3,5
At least one of the positions is a halogen atom or has 6 carbon atoms.
Substituted with the following alkyl groups or phenyl groups, hydroquinone, resorcin, tris-4- (hydroxyphenyl) methane, divalent or trivalent 1,1,2,2-telorakis (4-hydroxyphenyl) ethane, etc. Glycidyl ether compounds derived from phenols of higher valency or higher, phenol, novolac type epoxy resins derived from novolac resins which are reaction products of phenols such as o-cresol and formaldehyde, aniline, p-aminophenol, m- Aminophenol, 4-amino-m-cresol, 6-
Amino-m-cresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene , 1,4-bis
(3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p- Phenylenediamine, m-phenylenediamine, 2,
4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexane-bis (methylamine), 5-amino-1- (4'-aminophenyl)- Amine-based epoxy resin derived from 1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, p-oxybenzoic acid, m-oxy Glycidyl ester compounds derived from aromatic carboxylic acids such as benzoic acid, terephthalic acid and isophthalic acid,
Hydantoin-based epoxy resin derived from 5,5-dimethylhydantoin, etc., 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl)
Cyclohexyl] propane, vinylcyclohexenedioxide, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and others, triglycidyl isocyanurate,
One or more kinds of 2,4,6-triglycidoxy-S-triazine and the like can be mentioned.

Further, a curing agent corresponding to each component may be combined with the above resin composition. The curing agent in the case of containing an epoxy resin in the epoxy body or composition of the present invention includes dicyandiamide, tetramethylguanidine, aromatic amine, phenol novolac resin, cresol novolac resin, acid anhydride, other aliphatic and alicyclic compounds. One kind or two or more kinds of various amines are used. As the aromatic amine, the above-mentioned aromatic diamine is typical. As the curing agent when the composition contains a cyanate compound and bismaleimide, the above aromatic diamine and alicyclic diamine are typical. These hardeners may be blended in the resin composition alone, or may be blended in the composition in the form of prepolymers of the corresponding components.

The above resin composition can be thermoset in a relatively short time without containing a catalyst, but by using a catalyst, the molding temperature can be lowered and the time can be further shortened. it can. As such a catalyst, N, N-
Dimethylaniline, triethylenediamine, amines such as tri-n-butylamine, 2-methylimidazole, imidazoles such as 2-ethyl-4-methylimidazole, phenol, phenols such as resorcin, cobalt naphthenate, lead stearate, Tin oleate, tin octylate,
Examples thereof include organic metal salts such as zinc octylate and titanium butyrate, chlorides such as aluminum chloride, tin chloride and zinc chloride, and metal chelates. These catalysts can be used alone or in combination of two or more kinds. can do.

In the above composition, a filler, a filler (including an organic / inorganic filler), a reinforcing agent, a pigment and the like are used in combination, if necessary. For example, silica, calcium carbonate, antimony trioxide, kaolin, titanium dioxide, zinc oxide, mica, barite, carbon black, polyethylene powder, polypropylene powder, glass powder, aluminum powder,
One or more of iron powder, copper powder, glass fiber, carbonic acid fiber, alumina fiber, asbestos fiber, aramid fiber, glass woven fabric, glass non-woven fabric, aramid non-woven fabric, liquid crystal polyester non-woven fabric and the like can be mentioned.

Further, a composition using these is molded,
It is used for applications such as laminates, adhesives, and composite materials such as copper-clad laminates. In particular, when a cyanate body or an epoxy body is used alone or in combination, a prepreg in which a resin is semi-cured and a laminated plate in which this prepreg is cured are typically used. Further, when an epoxy body is used, a typical application example is a semiconductor encapsulating material.

[0035]

EXAMPLES Next, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples. The number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography (GPC) method. The dielectric constant and the dielectric loss tangent were obtained by the cavity resonance perturbation method.

(Example 1) Method for producing bifunctional PPE oligomer body 2 L equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate
To the vertical reactor of CuBr2, 2.7g (0.012 mol) of CuBr2, 70.7g (0.55 mol) of di-n-butylamine and 600g of toluene were charged.
The mixture was stirred at a reaction temperature of 40 ° C, and divalent phenol 4,4 '-(1-methylethylidene) bis (2,6-dimethylphenol) 59.6 g (0.21 m) was dissolved in 600 g of methanol in advance.
ol) and 5,6-dimethylphenol 50.4 g (0.41 mol) mixed solution (divalent phenol represented by structural formula (7) and structural formula
The molar ratio of monohydric phenol shown in (8) 1: 2) is 2 L / mi.
While bubbling n air, drop over 120 minutes,
Further, stirring was carried out for 30 minutes after completion of dropping while continuing bubbling of air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, after washing 3 times with a 1 M hydrochloric acid aqueous solution,
It was washed with ion-exchanged water. The obtained solution was concentrated with an evaporator to remove methanol, and then toluene was added to give a 70% toluene solution (hereinafter, this solution is referred to as "a"). A part of this was further concentrated and dried under reduced pressure to obtain a powder. The number average molecular weight of this product is 690,
The weight average molecular weight was 970 and the hydroxyl group equivalent was 360.

Method for Manufacturing Epoxy Body A reactor equipped with a stirrer, a thermometer and a dropping funnel was heated to 100 ° C., and 57.1 g of a solution of “a” (0.11 mol of hydroxyl group) and 308.4 g of epichlorohydrin were charged. Then, a solution prepared by dissolving 9.1 g (0.13 mol) of sodium ethoxide in 32.0 g of ethanol was added dropwise from a dropping funnel over 60 minutes, and stirring was continued for 5 hours after the addition was completed. After that, washing with a 0.1 N hydrochloric acid aqueous solution three times, washing with ion-exchanged water, and filtration were performed to remove the produced salt and impurities. Excessive epichlorohydrin was distilled off from the resulting solution, and further dried under reduced pressure to obtain 44.0 g of an epoxy compound. The result is I
The absorption peak of the phenolic hydroxyl group (3600 cm
-1) disappeared and the peak of glycidyl ether was expressed by NMR analysis to confirm 100% functional group conversion.

To 100 parts of the thus obtained epoxy compound, 3 parts of 1-benzyl-2-methylimidazole was added to give 15 parts.
Melt, degas, and mold at 0 ℃, cure at 180 ℃ for 10 hours,
A cured product was obtained. This cured product is measured for dynamic viscoelasticity (DMA)
As a result, the glass transition temperature was 193 ° C. Moreover, the dielectric constant at 1 GHz was 2.82 and the dielectric loss tangent was 0.0177.

(Example 2) Method for producing bifunctional PPE oligomer body Stirrer, thermometer, air inlet tube, 2 L equipped with baffle plate
To the vertical reactor of CuBr2, 2.7g (0.012 mol) of CuBr2, 70.7g (0.55 mol) of di-n-butylamine and 600g of toluene were charged.
Divalent phenol 4,4'-cyclohexylidenebis [2,6-dimethylphenol] 68.0 g dissolved in 600 g of methyl ethyl ketone in advance with stirring at a reaction temperature of 40 ° C.
(0.21mol) and 2,6-dimethylphenol 25.6g (0.21mo
l) and 2,3,6-trimethylphenol 28.6 (0.21 mol) mixed solution (divalent phenol represented by structural formula (7) and structural formula
The molar ratio of monohydric phenol shown in (8) 1: 2) is 2 L / mi.
While bubbling n air, drop over 120 minutes,
Further, stirring was carried out for 30 minutes after completion of dropping while continuing bubbling of air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, after washing 3 times with a 1 M hydrochloric acid aqueous solution,
It was washed with ion-exchanged water. The obtained solution was concentrated with an evaporator to remove methyl ethyl ketone, and then toluene was added to give a 70% toluene solution (hereinafter, this solution is referred to as "b"). A part of this was further concentrated and dried under reduced pressure to obtain a powder. The number average molecular weight of this product is
The weight average molecular weight was 610, and the hydroxyl group equivalent was 320.

Method for Producing Epoxy Body A reactor equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 57.1 g of a solution of “b” (0.13 mol of hydroxyl group) and 347.0 g of epichlorohydrin were charged. After that, sodium ethoxide 10.2 g (0.15 mol) in ethanol 35.8 g in advance.
The solution in which was dissolved was added dropwise from the addition funnel over 60 minutes, and after the completion of the addition, stirring was carried out for 5 hours. After that, washing with a 0.1 N hydrochloric acid aqueous solution three times, washing with ion-exchanged water, and filtration were performed to remove the produced salt and impurities. Excessive epichlorohydrin was distilled off from the resulting solution, and further dried under reduced pressure to obtain 45.2 g of an epoxy compound. The obtained product was analyzed by IR and the absorption peak (3
It was confirmed that 100% conversion of the functional group was confirmed by the disappearance of (600 cm −1) and the expression of a peak derived from glycidyl ether by NMR analysis.

To 100 parts of the thus obtained epoxy compound, 3 parts of 1-benzyl-2-methylimidazole was added to obtain 15 parts.
Melt, degas, and mold at 0 ℃, cure at 180 ℃ for 10 hours,
A cured product was obtained. This cured product is measured for dynamic viscoelasticity (DMA)
As a result, the glass transition temperature was 192 ° C. Moreover, the dielectric constant at 1 GHz was 2.80 and the dielectric loss tangent was 0.0175.

(Example 3) Method for producing bifunctional PPE oligomer body 2 L equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate
CuCl 1.3g (0.013 mol), di-n-butylamine 79.5g (0.62 mol), and methyl ethyl ketone 400g were charged in the vertical reactor of and the mixture was stirred at a reaction temperature of 40 ° C.
divalent phenol 4,4'-methylenebis (2,3,6-dissolved in 400 g of methyl ethyl ketone and 400 g of tetrahydrofuran
(Trimethylphenol) 42.6 g (0.15 mol) and 2,6-dimethylphenol 56.7 g (0.46 mol) and 2,3,6-trimethylphenol 21.1 g (0.16 mol) mixed solution (2 represented by structural formula (7) The molar ratio of monohydric phenol and monohydric phenol represented by the structural formula (8) 1: 4) is added dropwise over 120 minutes while bubbling 2 L / min of air, and 60 minutes after the addition, 2 Stirring was performed while continuing to bubble air at L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, it was washed three times with a 1 M aqueous hydrochloric acid solution and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 113.2 g. This product had a number average molecular weight of 1050, a weight average molecular weight of 1490 and a hydroxyl group equivalent of 550. (Hereinafter, this resin is referred to as "C")

Method for Manufacturing Epoxy Body A reactor equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 40 g of “ha” (hydroxyl group 0.07 mol) and 336.5 g of epichlorohydrin were charged. Then ethanol beforehand
A solution prepared by dissolving 5.9 g (0.09 mol) of sodium ethoxide in 20.8 g was added dropwise from a dropping funnel over 60 minutes, and stirring was continued for 5 hours after completion of the addition. After that, washing with a 0.1 N hydrochloric acid aqueous solution three times, washing with ion-exchanged water, and filtration were performed to remove the produced salt and impurities. Excessive epichlorohydrin was distilled off from the resulting solution, and further dried under reduced pressure to obtain 42.8 g of epoxy compound. For the obtained product, 100% conversion of the functional group was confirmed by the disappearance of the absorption peak (3600 cm -1) of the phenolic hydroxyl group by IR analysis and the expression of the peak derived from glycidyl ether by NMR analysis.
To 100 parts of the thus obtained epoxy body, 3 parts of 1-benzyl-2-methylimidazole was added and melted at 150 ° C.
It was degassed and molded, and cured at 180 ° C for 10 hours to obtain a cured product. This cured product had a glass transition temperature of 198 ° C. according to measurement of dynamic viscoelasticity (DMA). Also, the dielectric constant at 1 GHz is
2.79 and dielectric loss tangent of 0.0173 were obtained.

(Example 4) Method for producing bifunctional PPE oligomer body Stirrer, thermometer, air inlet tube, 2 L with baffle plate
CuCl 1.1g (0.011mol), di-n-butylamine 66.3g (0.51mol) and toluene 400g were charged in the vertical reactor of the above and stirred at a reaction temperature of 40 ° C and dissolved in 400g of methyl ethyl ketone and 400g of tetrahydrofuran in advance. Let 2
Value phenol 4,4 '-[1,4-phenylene bis (1-methylethylidene)] bis (2,3,6-trimethylphenol) 33.1 g
(0.077mol) and 2,6-dimethylphenol 75.6g (0.62mo
l) mixed solution (molar ratio of divalent phenol represented by structural formula (7) to monovalent phenol represented by structural formula (8) 1: 8).
Dropping was performed over 120 minutes while bubbling 2 L / min of air, and stirring was continued for 30 minutes after the dropping was completed while continuing bubbling of 2 L / min of air. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, it was washed three times with a 1 M aqueous hydrochloric acid solution and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 102.2 g.
Got This product had a number average molecular weight of 1820, a weight average molecular weight of 2510 and a hydroxyl group equivalent of 970. (Hereinafter, this resin will be referred to as "D")

Method for Manufacturing Epoxy Body A reactor equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 40 g of “d” (hydroxyl group 0.04 mol) and 267.1 g of epichlorohydrin were charged. Then ethanol beforehand
A solution prepared by dissolving 3.4 g (0.05 mol) of sodium ethoxide in 11.8 g was added dropwise from a dropping funnel over 60 minutes, and after the addition was completed, stirring was performed for 5 hours. After that, washing with a 0.1 N hydrochloric acid aqueous solution three times, washing with ion-exchanged water, and filtration were performed to remove the produced salt and impurities. Excessive epichlorohydrin was distilled off from the resulting solution, and further dried under reduced pressure to obtain 41.1 g of an epoxy compound. For the obtained product, 100% conversion of the functional group was confirmed by the disappearance of the absorption peak (3600 cm -1) of the phenolic hydroxyl group by IR analysis and the expression of the peak derived from glycidyl ether by NMR analysis.
To 100 parts of the thus obtained epoxy body, 3 parts of 1-benzyl-2-methylimidazole was added and melted at 150 ° C.
It was degassed and molded, and cured at 180 ° C for 10 hours to obtain a cured product. This cured product had a glass transition temperature of 197 ° C. according to measurement of dynamic viscoelasticity (DMA). Also, the dielectric constant at 1 GHz is
2.81 and dielectric loss tangent of 0.0168 were obtained.

(Example 5) Method for producing bifunctional PPE oligomer body 2 L equipped with a stirrer, a thermometer, an air introduction tube, and a baffle plate
CuBr2 2.7g (0.012mol), di-n-butylamine 70.7g (0.55mol) and toluene 600g were charged into the vertical reactor of the above and stirred at a reaction temperature of 40 ° C. Phenol 4,4'-methylenebis (2,6
-Dimethylphenol) 53.8 g (0.21 mol) and 2,6-dimethylphenol 50.4 g (0.41 mol) mixed solution (Structural formula (7)
The molar ratio of the divalent phenol represented by the formula (1) and the monovalent phenol represented by the structural formula (8) 1: 2) was added dropwise over 120 minutes while bubbling air at 2 L / min. Stirring was performed for 30 minutes while continuing to bubble air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, it was washed three times with a 1 M aqueous hydrochloric acid solution and then washed with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 97.9 g. This product had a number average molecular weight of 620, a weight average molecular weight of 860 and a hydroxyl group equivalent of 320. (Hereafter, this resin will be referred to as "e")

Method for producing allyl compound In a reactor equipped with a stirrer and a thermometer, a solution prepared by dissolving 50.0 g of "e" (hydroxyl group 0.16 mol) and allyl bromide 37.8 g (0.31 mol) in 150 g of methylene chloride at room temperature. , 120 ml of 1N sodium hydroxide solution was charged, and 5.6 g of benzyltri-n-butylammonium bromide (0.
02 mol) was added and stirring was carried out for 5 hours. Then 0.1N
The resulting salt and impurities were removed by washing three times with the hydrochloric acid aqueous solution of No. 3, washing with ion-exchanged water, and filtration. Methylene chloride was distilled off from the obtained solution, and further dried under reduced pressure to obtain 54.15 g of an allyl derivative. In the obtained product, 100% conversion of the functional group was confirmed by the disappearance of the absorption peak (3600 cm-1) of the phenolic hydroxyl group by IR analysis and the expression of the peak derived from the allyl group by NMR analysis.

The allyl compound thus obtained was melted, degassed and molded at 150 ° C. and cured at 230 ° C. for 3 hours to obtain a cured product. This cured product had a glass transition temperature of 208 ° C. according to measurement of dynamic viscoelasticity (DMA). Moreover, the dielectric constant at 1 GHz was 2.76 and the dielectric loss tangent was 0.0046.

Comparative Example 1 3,3 ′, 5,5′-Tetramethyl- [1,1′-biphenyl] -4,4′-glycidyl ether 100, which is a biphenyl type epoxy resin for semiconductor encapsulant To 1 part, 3 parts of 1-benzyl-2-methylimidazole was added, melted, degassed and molded at 150 ° C, and cured at 180 ° C for 10 hours to obtain a cured product. This cured product, from the measurement of dynamic viscoelasticity (DMA),
The glass transition temperature was 133 ° C. Moreover, the dielectric constant at 1 GHz was 3.06 and the dielectric loss tangent was 0.030.

Comparative Example 2 3 parts of 1-benzyl-2-methylimidazole was added to 100 parts of dicyclopentadiene type epoxy for semiconductor encapsulating material, and the mixture was melted, degassed and molded at 150 ° C. Curing was performed at 10 ° C. for 10 hours to obtain a cured product. This cured product had a glass transition temperature of 182 ° C. according to measurement of dynamic viscoelasticity (DMA). Moreover, the dielectric constant at 1 GHz was 2.90 and the dielectric loss tangent was 0.020.

The above results are summarized in Table 1.

[Table 1]

[0052]

EFFECT OF THE INVENTION The thermosetting PPE oligomer of the present invention has excellent compatibility with other thermosetting resins while maintaining the excellent properties of PPE (low dielectric property, toughness), Was confirmed to be incorporated into the network. Therefore, for example, the varnish of the laminate can be easily adjusted, and a laminate material having excellent moldability can be manufactured. In addition, a low dielectric property is achieved even in a cured product alone or in a mixture with another resin, and it becomes an electric / electronic material that inherits the excellent properties of PPE polymer. It was found that the compound of the present invention having a phenolene ether structure was extremely useful as compared with a special epoxy for semiconductor encapsulation, and was confirmed to have superiority in dielectric properties and heat resistance.

Continued front page    (72) Inventor Seisei Hiramatsu             6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi tile             The Chemical Research Institute Tokyo Research Center (72) Inventor Makoto Miyamoto             6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi tile             The Chemical Research Institute Tokyo Research Center F-term (reference) 4J005 AA23 BD00

Claims (5)

[Claims] 1. A thermosetting resin represented by the following structural formula (1). [Chemical 1] (In the formula,-(OXO)-is represented by the structural formula (2), and R1, R2, R7, R8
May be the same or different and each is a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R3, R
4, R5 and R6, which may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A is a straight chain having 20 or less carbon atoms, or
It is a branched or cyclic hydrocarbon. -(YO)-is represented by Structural Formula (3), and R9 and R10 may be the same or different and each is a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R11 and R12, which may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -(YO)-is one kind of structure defined by the structural formula (3) or two or more kinds of structures defined by the structural formula (3) randomly arranged. Z is an organic group having 1 or more carbon atoms and may include an oxygen atom. a and b show the integer of 0-300 in which at least one is not 0. i is 0 or
Indicates an integer of 1. ) 2. The thermosetting resin according to claim 1, wherein in the structural formula (1), R is a glycidyl group. 3. The thermosetting resin according to claim 1, wherein in the structural formula (1), R is an allyl group. 4.-(YO)-is structural formula (4) or structural formula (5)
Alternatively, the thermosetting resin according to claim 1, having a structure in which the structural formulas (4) and (5) are randomly arranged. [Chemical 2] 5. The thermosetting resin according to claim 1, wherein-(YO)-has a structure represented by structural formula (5).