JP3122834B2 - New phenol novolak condensate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel phenol novolak condensate obtained by reacting a mixture of a bis (methoxymethyl) biphenyl with a phenol compound. The condensate can be used as a thermosetting resin using a cross-linking agent such as hexamethylenetetramine, as well as a curing agent for an epoxy resin and a raw material for an epoxidized novolak resin.

[0002]

2. Description of the Related Art Phenol novolak resin is used in a brake pad when mixed with a fibrous filler such as asbestos fiber because of its low abrasion, good dimensional stability at high temperatures, and good adhesion. Although it has been used as a material, it has not always been satisfactory in heat resistance and the like. In addition, novolak type epoxy resins obtained by reacting an epoxy compound with a phenol novolak resin, particularly cresol novolak type epoxy resins, are widely used in semiconductor packages because of their low cost and good productivity. Cracks called popcorn phenomena were sometimes generated due to rapid vaporization and expansion. Therefore, a material having low hygroscopicity and excellent heat resistance has been required. These improvements in moisture absorption and heat resistance are also desired for phenol novolak resins used as curing agents for epoxy resins.

As a method for solving the problem of heat resistance, Japanese Patent Publication No. 47-13772, Japanese Patent Publication No. 47-15111 and Japanese Patent Publication No. 48-10960 discloses a method in which a part or all of formaldehyde is converted to 1,4-bis (methoxymethyl). )
It has been proposed to react an epoxy compound with a phenol condensate obtained in place of benzene. JP-A-4-110317 describes a condensate of bis (hydroxymethyl) benzene and phenol. However, the epoxidized phenolic resin obtained by this method is
Heat resistance is not sufficient, and improvement in hygroscopicity is also insufficient. Further, in order to reduce water absorption, a method is known in which divinylbenzene is subjected to an addition reaction with phenol instead of formaldehyde, and then an epoxy compound is reacted.
Although it is disclosed in -78457, it is not sufficient in strength and water resistance. By the way, Tokiko 47-13782
No. 47-15111 and JP-A-4-110.
No. 317 also describes that bis (methoxymethyl) biphenyl or bis (hydroxymethyl) biphenyl can be used to obtain a phenol condensate, but there is no specific disclosure of the present invention. Japanese Patent Application Laid-Open No. 5-117350 describes a specific example of a condensate of phenol and 4,4'-di (2-hydroxy-2-propyl) biphenyl having two molecules and one molecule. However, this low-molecular phenolic compound has a problem in that it is crystalline and has a low melt viscosity, so that the fluidity during molding is too large to be easily handled. On the other hand, there is a description that bis (methoxymethyl) biphenyl can be used, but there is no specific disclosure of the present invention.

[0004]

SUMMARY OF THE INVENTION The present invention provides a novel phenol novolak condensate and a new use utilizing the same. That is, an epoxy resin cured product obtained by reacting this condensate with an epoxy resin using the epoxy resin as a curing agent, and a curing agent for epoxy resin reacting with an epoxidized novolak resin obtained by epoxidizing this condensate. The epoxy resin cured product thus obtained exhibits very excellent properties in terms of moisture absorption, heat resistance and flexibility. Further, the phenol novolak condensate of the present invention and the epoxidized novolak resin obtained by epoxidizing the phenol novolak condensate have favorable molecular weight distributions and have advantages such as less occurrence of burrs during molding, so that productivity can be improved. . In addition, the phenol resin cured product obtained by curing this condensate using a phenol resin curing agent such as hexamethylenetetramine is extremely excellent in terms of abrasion resistance, dimensional stability at high temperatures, and adhesion. Shows the characteristics.

[0005]

The present invention provides a compound represented by the general formula (I):
And a phenol novolak condensate obtained by reacting each isomer of bis (methoxymethyl) biphenyl or a mixture thereof with a phenol compound.

[0006]

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This phenol novolak condensate can be used as a curing agent for epoxy resins.

The present invention also relates to an epoxy resin composition containing the phenol novolak condensate and an epoxy resin, and a cured product thereof.

[0009] The present invention also relates to an epoxidized novolak resin obtained by epoxidizing the phenol novolak condensate.

[0010] The present invention also relates to an epoxy resin composition containing an epoxidized novolak resin obtained by epoxidizing the phenol novolak condensate and a curing agent for an epoxy resin, and a cured product thereof.

The epoxy resin composition and the cured product thereof include an epoxy resin composition comprising an epoxidized novolak resin obtained by epoxidizing the phenol novolak condensate and a curing agent for an epoxy resin comprising the phenol novolak condensate. And cured products thereof are preferred.

Further, the present invention relates to a phenol resin composition containing the phenol novolak condensate and a curing agent for phenol resin, and a cured product thereof.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The phenol compound of the present invention and the general formula (I)
The phenol novolak condensate obtained by reacting each isomer of bis (methoxymethyl) biphenyl or a mixture thereof represented by the formula (1) will be described.

The phenol compound used in the present invention is a compound having at least one phenolic hydroxyl group on an aromatic ring. Specific examples include unsubstituted phenols such as phenol, resorcinol, and hydroquinone;
Mono-substituted phenols such as cresol, ethyl phenol, n-propyl phenol, iso-propyl phenol, t-butyl phenol, octyl phenol, nonyl phenol, phenyl phenol; xylenol;
Methylpropylphenol, methylbutylphenol,
Disubstituted phenols such as methylhexylphenol, dipropylphenol, dibutylphenol, guaiacol and guetol; trisubstituted phenols represented by trimethylphenol; naphthol, methylnaphthol and the like naphthols; biphenol, bisphenol-
A and bisphenols such as bisphenol-F.

The respective isomers of bis (methoxymethyl) biphenyl represented by the general formula (I) are specifically compounds represented by the following structural formulas (Ia) to (If). These isomers can be used as a mixture of two or more kinds.

[0016]

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Of these, preferred are 2,4'-forms represented by (Ic), 4,4'-forms represented by formula (If),
And a mixture of isomers containing at least 5% or more of the 2,4'-isomer and at least 40% or more of the 4,4'-isomer.
Particularly preferred is a mixture of isomers containing at least 5% or more of the 2,4'-isomer and at least 40% or more of the 4,4'-isomer. More preferably, it is a mixture of isomers containing at least 10% or more of the 2,4'-isomer and at least 40% or more of the 4,4'-isomer. Here, since the 2,4′-form is effective in increasing the breaking energy of the epoxy cured product, the use of a phenol novolak condensate obtained from a mixture containing the 2,4′-form as a raw material results in poor mechanical properties. Excellent cured epoxy resin is obtained.

Each of these isomers of bis (methoxymethyl) biphenyl or a mixture thereof can be obtained by subjecting methoxymethylhalogenated benzene to a dehalogenation coupling reaction. The ratio of isomers in the reaction product is generally Ia: Ib: Ic: Id:
Ie: If = (1): (0.2 to 0.6): (4 to
7): (0.01-0.2): (0.5-2.0):
(5 to 15), but a specific isomer or a mixture of specific isomers can be obtained by selecting raw materials and reaction conditions. Also, 4,4'-bis (methoxymethyl) biphenyl is obtained by chloromethylating biphenyl,
It can also be obtained by reacting with sodium methoxide.

The phenol novolak condensate of the present invention comprises
Each of the isomers of bis (methoxymethyl) biphenyl or a mixture thereof and a phenol compound are reacted with a phenol compound in the presence of an acid catalyst.
It is obtained by reacting while removing methanol for ~ 7 hours. At that time, the use ratio of the phenol compound and the bis (methoxymethyl) biphenyl mixture is 1: 0.1 to 1: 1.
Is preferable. If it is less than 0.1, a large amount of unreacted phenol must be removed, which is not economical. In the case of one or more, gelation occurs, which is not preferable as a practical resin. At that time, as the acid catalyst used,
Examples thereof include p-toluenesulfonic acid, sulfuric acid, dimethyl sulfate, and diethyl sulfate. The use amount thereof is preferably 1/10 to 1/100 times mol of phenol. If the amount is too small, the reaction speed is slow. If the amount is too large, the reaction proceeds rapidly and the reaction cannot be controlled. The reaction temperature is preferably from 120 to 190C.
If the temperature is low, the reaction rate is low, and if the temperature is high, there are problems such as gelation.

The thus obtained phenol novolak condensate has, for example, a structure represented by the general formula (II), and depending on the type of phenol compound used,
The phenol has a substituent on the ring.

[0021]

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In the present invention, it is usually obtained as a mixture in which n in formula (I) is 0 to 9. Since the compound in which n is 0 has a low melt viscosity and easily flows during use, a mixture of condensates containing 50% by weight or more (preferably 60% by weight or more) of a condensate in which n is 1 or more is practically preferable.

Next, the use of this phenol novolak condensate as a curing agent for an epoxy resin will be described.
Since this phenol novolak condensate has a phenolic hydroxyl group, it can be used as a curing agent for an epoxy resin, like a normal phenol novolak resin. A cured product of an epoxy resin using this phenol novolak condensate as a curing agent is excellent in hygroscopicity, heat resistance, adhesiveness and flexibility. The epoxy resin used at this time includes, for example, bisphenol diglycidyl ether type epoxy resin obtained by adding an epoxy group to bisphenols such as bisphenol A and bisphenol F; ordinary phenol novolak resin, orthocresol novolak resin, and brominated phenol novolak resin Novolak-type epoxy resins obtained by adding an epoxy group to a phenol novolak-based resin; glycidylamine-type epoxy resins such as diphenylmethanediaminetetraglycidylether and cyclohexanediaminetetraglycidylether; polyethylene glycol diglycidylether;
Aliphatic epoxy resins such as epoxidized SBR and epoxidized soybean oil; 4,4′-dihydroxybiphenyl and 3,
Dihydroxybiphenyl diglycidyl ether type epoxy resin obtained by adding an epoxy group to dihydroxybiphenyls such as 3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl; and various resins such as 1,6-dihydroxynaphthalenediglycidyl ether. Ring aromatic epoxy resins and the like can be mentioned. Among these, a novolak type epoxy resin, a dihydroxybifevir diglycidyl ether type epoxy resin and a polycyclic aromatic type epoxy resin are preferable, and a novolak type epoxy resin is particularly preferable.

In order to obtain a cured epoxy resin using the phenol novolak condensate of the present application as a curing agent, the ratio of the hydroxyl group of the phenol novolak condensate of the present application to the epoxy group of the epoxy resin is substantially equivalent. The phenol novolak condensate of the present application and the above-mentioned epoxy resin are mixed to form an epoxy resin composition, which is prepared at 100 to 250 ° C.
Heat to about. At this time, it is preferable that a curing accelerator generally used for accelerating the curing, for example, N-methylimidazole, triethylamine, triphenylphosphine, or the like is added to the epoxy resin composition. If necessary, various additives such as a filler, a coupling agent, a flame retardant, a lubricant, a release agent, a plasticizer, a colorant, and a thickener may be added.

Next, the use of the phenol novolak condensate of the present invention as a raw material for an epoxy resin will be described. The phenol novolak condensate of the present invention can be epoxidized into an epoxidized novolak resin. The epoxidized novolak resin is, for example, a novolak type epoxy resin having a glycidyl group represented by the formula (III) obtained by reacting the phenol novolak condensate of the present invention with an epihalohydrin such as epichlorohydrin in the presence of an alkali. is there.

[0026]

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(In the formula, n is an integer of 0 to 9. In addition, depending on the type of the phenol compound used as a raw material of the phenol novolak condensate, a substituent may be present on the phenol ring.)

The epoxidized novolak resin of the present invention can be cured by using various epoxy resin curing agents. The obtained cured product of the epoxy resin has excellent hygroscopicity, heat resistance, adhesiveness and flexibility similarly to the above-mentioned epoxy resin. As the curing agent for the epoxy resin at this time, various amines, polycarboxylic acids and their anhydrides, phenol novolak resins (including the phenol novolak condensates of the present invention), urea resins, melamine resins and the like can be mentioned. . Among them, phenol novolak resins (including the phenol novolak condensate of the present invention) such as ordinary phenol novolak resins, ortho-cresol novolak resins, and brominated phenol novolak resins are preferred.

Among the above combinations of the epoxy resin and the curing agent for the epoxy resin, the best results are obtained by the combination of the epoxidized novolak resin of the present invention and the phenol novolak resin of the present invention.

In order to obtain a cured product of the epoxidized novolak resin of the present invention, an epoxy resin composition can be obtained in the same manner as in the above-mentioned curing method, and then heated. The same applies to the point that a curing accelerator and other additives can be added.

Next, the use of the phenol novolak condensate of the present invention as a raw material for a phenol resin (cured product) will be described. In order to obtain a cured product of a phenol resin using the phenol novolak condensate of the present invention, a phenol resin composition is obtained by mixing the phenol novolak condensate of the present invention with a curing agent for phenol resin such as hexamethylenetetramine and formaldehyde, 80 to 200
The composition is cured by heating at about 150C, preferably 150-180C.

The phenolic resin composition and the phenolic resin (cured product) may contain, if necessary, a filler, a coupling agent, a flame retardant, a lubricant, a release agent, a plasticizer, a colorant, a thickener, and the like. May be added. The phenolic resin (cured product) thus obtained is excellent in abrasion, dimensional stability at high temperature, and adhesion.

As described above, the resin obtained by using the phenol novolak condensate of the present invention as a curing agent for an epoxy resin can be used for adhesives, paints, sealing materials, friction materials, grinding wheels and the like. It has excellent heat resistance, adhesiveness, water absorption and mechanical properties. In addition, a resin obtained by curing a phenol novolak condensate using hexamethylenetetramine or aldehydes is also used as an adhesive, a paint, a sealing material,
Can be used for friction materials and grinding stones, heat resistance,
Shows excellent properties of adhesion, water absorption and mechanical properties. Further, pigments such as carbon black, asbestos, silica, fillers such as talc in the phenol novolak resin and epoxidized novolak resin obtained in the present invention,
Even if a reinforcing material such as glass fiber, rock wool or cotton cloth is added, a resin having excellent properties can be obtained.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail based on embodiments. Example 1 Synthesis of phenol novolak condensate (resin A) 564 g of phenol in a flask equipped with a stirrer and a condenser
(6 mol), a mixture of the general formula (I) (Ia: Ib: I
c: Id: Ie: If = 1: 0.2: 6: 0.01:
0.5: 8.5) 484 g (2 mol) was charged, and diethyl sulfate 15.4 g (0.1 mol) was added dropwise. The reaction was performed for 3 hours while maintaining the reaction temperature at 160 ° C. in the meantime,
The alcohol formed was distilled off. After completion of the reaction, the reaction mixture was cooled and washed three times with water. The oil layer was separated, and unreacted phenol was distilled off under reduced pressure to obtain 700 g of the resin (A).
Obtained. The obtained resin (A) had a softening point of 74 ° C. and a hydroxyl equivalent of 175 g / eq. GPC (gel perm
Eation chromatography data is shown in FIG. The weight ratio of the condensate where n was 1 or more was 63.8%. The average (weight average) of n was 0.6.

Example 2 Synthesis of phenol novolak condensate (resin B) In Example 1, 470 g (5 mol) of phenol was used.
The same reaction was carried out except that the resin (B) was used,
g was obtained. The softening point of this resin is 78 ° C. and the hydroxyl equivalent is 17
It was 5 g / eq. FIG. 2 shows GPC data. The weight ratio of the condensate where n was 1 or more was 71.0%. The average (weight average) of n was 0.9.

Example 3 Synthesis of Epoxidized Novolak Resin (Resin C) 175 g of the resin (A) obtained in Example 1, 555 g (6 mol) of epichlorohydrin and 50 g of methanol were mixed and dissolved. While maintaining the reaction temperature at 50 ° C., 40 g (1 mol) of solid NaOH was added little by little.
After completion of the addition, the reaction was continued for 2 hours, and the temperature was raised to 70 ° C., and the reaction was further continued for 2 hours. After the completion of the reaction, by-product salt was removed by washing with water, and unreacted epichlorohydrin was removed by distillation under heating under reduced pressure. 400 g of methyl isobutyl ketone was added to the residue to make a homogeneous solution, 20 g of a 20% aqueous NaOH solution was added to this mixture, and the mixture was heated to 70 ° C. and reacted for 1 hour. After the completion of the reaction, washing was performed five times in total until the washing solution became neutral. The organic layer was separated, and methyl isobutyl ketone was distilled off to obtain 228 g of an epoxy resin (C). The softening point of this resin is 60 ° C. and the epoxy equivalent is 23
It was 9 g / eq.

Example 4 Synthesis of Epoxidized Novolak Resin (Resin D) The same reaction was carried out as in Example 3, except that 175 g of resin (B) was used, to obtain 225 g of epoxy resin (D). This resin has a softening point of 64 ° C. and an epoxy equivalent of 239.
g / eq.

Example 5 Synthesis of phenol novolak condensate (resin E) In the same manner as in Example 1, 117.5 g of phenol (1.
25 mol), using 121.0 g (0.50 mol) of 4,4′-bis (methoxymethyl) biphenyl, and dropwise adding 0.11 ml of 48% sulfuric acid instead of diethyl sulfate.
The reaction was conducted for 3 hours while maintaining the reaction temperature at 150 ° C.
8 g of resin E was obtained. The softening point of the obtained resin (E) is 8
At 2.6 ° C., the hydroxyl group equivalent was 199 g / eq. FIG. 3 shows GPC data. The weight ratio of the condensate where n was 1 or more was 64.9%. The average (weight average) of n was 0.6.

Example 6 Synthesis of phenol novolak condensate (resin F) In Example 5, 50% of 2,4′-form and 50% of 4,4′-form
% Of bis (methoxymethyl) biphenyl, and 156 g of resin F
I got The obtained resin (F) has a softening point of 82.0 ° C.
The hydroxyl group equivalent was 199 g / eq. FIG. 4 shows GPC data. The weight ratio of the condensate where n was 1 or more was 68.5%. The average (weight average) of n was 0.8.

The resin (A) obtained in the above examples,
When (B), (E), and (F) are used as a curing agent for an epoxy resin, the mixing ratio of the epoxy resin composition and the properties of the cured product, and the resin (C), (D), and the epoxy curing agent Tables 1 and 2 show the results of measuring the mixing ratio of the epoxy resin composition and the properties of the cured product thereof, and the mixing ratio of the epoxy resin composition composed of the resin (A) and the resin (C) and the properties of the cured product thereof. Show.

[0041]

[Table 1]

[0042]

[Table 2]

The phenol novolak resins in Tables 1 and 2 are H-1 (softening point: 86 ° C., hydroxyl equivalent: 104 g / eq) manufactured by Meiwa Kasei Co., Ltd. Epoxy-o-cresol novolak resins are Nippon Kayaku EOCN-1020
(Softening point: 70 ° C., epoxy equivalent: 200 g / eq). As a filler, RD-8 manufactured by Tatsumori Chemical Co., Ltd. was used, and triphenylphosphine was used as a curing accelerator.

Preparation of Test Pieces for Measurement of Physical Properties in Table 1 and Test Method The components shown in Table 1 were blended, heated to 150 ° C., melt-mixed, deaerated in a vacuum, and placed in a 150 ° C. mold (4 mm thick). Cast and cure (150 ° C, 3hr curing, 180 ° C, 5hr
Post-curing).

Test method Water absorption: Specimen dimensions 25 × 70 × 4 mm, 24 h
r, boiling method Breaking energy, flexural modulus, flexural strength: 3-point bending test, specimen size 4 × 6 × 70 mm Tg: TMA (Thermal Mechanical Analysis) method.

Preparation of Test Pieces for Measurement of Physical Properties shown in Table 2 and Test Method Adhesives shown in Table 2 were mixed, melted at 150 ° C., and degreased beforehand (aluminum foil 0.1 × 20 × 100 mm)
A melted adhesive is applied to one end of 10 mm, the adherends are overlapped, the thickness of the adhesive is adjusted to be 0.1 mm, and fixed after fixing with a clamp (after curing at 150 ° C. for 3 hours,
180 ° C. for 5 hours after curing). After curing, the T-peel strength (adhesive strength) was measured.

From the results in Tables 1 and 2, the phenol novolak condensate and the epoxidized phenol novolak resin using the compound of the general formula (I) are compared with the conventional products.
It can be seen that excellent values are shown in all items such as water absorption (hygroscopicity), mechanical properties, and adhesive properties. Also, no burrs were found.

Next, the formulation examples of the phenolic resin composition using the resin (A) obtained in Example 1 and the resin (B) obtained in Example 2 and the properties of the cured product of this composition are shown in Table 3.
Shown in

[0049]

[Table 3]

In Table 3, the phenol novolak resin used was H-1 (softening point: 86 ° C.) manufactured by Meiwa Kasei Co., Ltd., and the glass fiber used was 5 mm chopped strand manufactured by Nittobo. The test pieces for measuring physical properties shown in Table 3 were prepared by mixing and mixing the components shown in Table 3 and then putting the mixture into a bending test mold (test piece size: 10 × 10 × 100 mm) and forming pressure. Curing molding was performed at 200 kg / cm ² and 160 ° C. for 5 minutes. The heat resistance test was conducted at 250 ° C.
It heated at 60 degreeC and 270 degreeC for 500 hours, and measured the bending strength at normal temperature after cooling.

From the results shown in Table 3, the phenol resin using the phenol novolak condensate of the present invention shows superior values in heat resistance and mechanical properties as compared with conventional products.

Reference Example A synthesis example of bis (methoxymethyl) biphenyl used in the present invention will be described below.

Reference Example 1 Methoxymethylbenzene
146.5 g (1.20 mol) of iodized methoxymethylbenzene, acetic acid 300 m
l, 101.5 g (0.40 mol) of iodine in a solution of 80 ml of n-hexane,
Add 70.3 g (0.40 mol) of iodic acid and 4 ml of sulfuric acid, and add
Stir for 5 hours. N-hexane 600 ml and water 700 ml
After adding and shaking well, the n-hexane layer is separated, washed,
Dried. After distilling off the solvent, methoxymethy
A mixture of three isomers of luiodobenzene 216.5 g (0.8
7 mol). Boiling point: 93 ~ 96 ℃ / 4mmHg. Gas chromatography (Column: Apiezon grease
L 10% on Uniport 2m), two peaks (peak area
Ratio 1: 3). But,¹³As a result of C-NMR measurement, 0-
It was found that m-form was mixed in addition to body and p-form. This
Based on these results ¹Determination of isomers in the composition by H-NMR
0-form: m-form: p-form = 1: 0.25: 2.8
won.

Reference Example 2 Deiodine Coupling of Methoxymethyl Iodobenzene The methoxymethyl iodobenzene (3
174.3 g (0.70 mol) of a mixture of isomers of various species, 14.2 g (46.7 mmo) of bipyridyl nickel dichloride (Ni (bipy) Cl ₂ .H ₂ O)
l), zinc powder 50.4 g (0.77 g atom), pyridine 9.2 g (0.11 g
(7 mol) and 350 ml of DMI were stirred vigorously at 90 ° C. for 5.5 hours. After completion of the reaction, the solid matter was removed by suction filtration, and most of the solvent was removed by distillation under reduced pressure. After cooling
A 5% aqueous hydrochloric acid solution was added, mixed well, and separated. The oil layer was further washed with water, and a small amount of the remaining solvent was distilled off under reduced pressure.
The residue was subjected to gas chromatography analysis (SE-30, 5%, 2 m, 120-230 ° C), and as a result, 80.3 g (0.332 mol) of a mixture of six isomers of bis (methoxymethyl) biphenyl was obtained. The ratio of each isomer is 2,2 '-: 2,3'-: 2,4 '-: 3,3'-: 3,4 '-: 4,4'- = 1: 0.5: 5.5:
0.08: 0.3: 7.5.

Reference Example 3 p-methoxymethylchlorbe
4,4'-bis (meth)
Synthesis of Toximethyl) biphenyl 100ml 4-port equipped with cooling tube, gas inlet tube and stirrer
Ni (bipy) Cl in flask _Two・ H_TwoO 1.43 g (5 mmol) and manga
4.62g (82.4 milligram atoms)
The mixture was heated under pressure at 100 ° C. for 1 hour. Then bring the mixture to room temperature
After cooling, 23.49 g of p-methoxymethylchlorobenzene (150 mm
ol) and 52 ml of DMAc.
And react for 3 hours at 120 ° C with vigorous stirring.
Was. After cooling to room temperature, the solid is filtered off and the filtrate is distilled under reduced pressure.
As a result, DMAc was distilled off. 3% hydrochloric acid aqueous solution in the pot residue
After adding 20 ml of the liquid and sufficiently stirring, the precipitate is separated by filtration. Filtrate
Is washed successively with 3% aqueous sodium carbonate solution (20 ml) and water (20 ml)
Was cleaned. The oil layer was distilled under reduced pressure at 200 ° C and 3 torr.
By taking 17.82 g (73.6 mmol) of the fraction at 174 ° C, 4,
4'-Bis (methoxymethyl) biphenyl was obtained. this
Things become solid at room temperature, and gas chromatographic analysis
The purity was 98.7%, and the yield of the target product was 96.8%. Former
The result of elementary analysis was H: C = 7.52: 79.34. Mass spectrometry (EI) was as shown in FIG. Red
The external absorption spectrum was as shown in FIG.¹H-NMR
(Solvent: CDCl_Three7) are as shown in FIG.

Reference Example 4 Dechlorination Coupling of Methoxymethyl Chlorobenzene 30.4 g (0.1 g of Ni (bipy) Cl ₂ .H ₂ O was placed in a 3 l four-necked flask equipped with a cooling tube, a gas introduction tube, and a stirrer. mol) and 90.5 g (1.65 g atom) of manganese powder in a stream of nitrogen gas.
Heated at 100 ° C. for 1 hour. Next, a mixed solution of 352.1 g (2.25 mol) of p-methoxymethyl chlorobenzene, 117.4 g (0.75 mol) of o-methoxymethyl chlorobenzene and 1.5 l of DMAc was added to the four-necked flask and stirred vigorously at 120 ° C. While reacting for 3 hours. After cooling to room temperature, the solid was filtered off, and the filtrate was distilled under reduced pressure to remove DMAc. 400 ml of a 3% aqueous hydrochloric acid solution is added to the still residue, and the mixture is sufficiently stirred, and the precipitate is filtered off. The filtrate was successively washed with a 3% aqueous solution of sodium carbonate (250 ml) and water (250 ml).
Distilled under reduced pressure at 3 ° C and 3 torr, 328.4g of distillate of 154 ~ 174 ° C
(1.36 mol) was obtained. When this liquid was measured by gas chromatography,
The purity was 99.6%, and the yield of the target product was 90.0%.
The ratio of each isomer was 2,2'-: 2,4 '-: 4,4'- = 0.2: 42.6: 55.8.

Reference Example 5 Synthesis of 2,4'-bis (methoxymethyl) biphenyl The mixture of the bis (methoxymethyl) biphenyl isomers obtained in Reference Example 4 was cooled to 0 ° C. Was quickly filtered to obtain a filtrate containing about 75% of 2,4′-isomer. The filtrate was distilled under reduced pressure at 180 ° C. and 3.5 torr, and a fraction at 155 ° C. was collected to obtain 2,4′-bis (methoxymethyl) biphenyl. Purity was 92%. ^{As a result of 1} H-NMR (solvent: CDCl ₃ ), as shown in FIG. 8, it was found that there were eight kinds of H as benzene ring. The infrared absorption spectrum was as shown in FIG.

[0058]

According to the present invention, it is possible to provide a novel phenol novolak condensate which can be used as a thermosetting resin, a curing agent for an epoxy resin, a raw material for an epoxidized novolak resin, and the like. The cured product using the phenol novolak condensate of the present invention and the epoxidized phenol novolak resin is superior to conventional products in water absorption (hygroscopicity), heat resistance, mechanical properties, adhesive properties, and the like. Further, bis (methoxymethyl) biphenyl, which is a raw material for producing the phenol novolak condensate of the present invention, can be used as it is obtained by a simple separation operation, and therefore does not need to be particularly purified. Further, since the condensation reaction at the time of production is a methanol removal reaction, it is technically and economically advantageous in the step of removing by-products as compared with the conventional technique which is a dehydration reaction.

[Brief description of the drawings]

FIG. 1 is a GPC chart of a resin (A) obtained in Example 1.

FIG. 2 is a GPC chart of a resin (B) obtained in Example 2.

FIG. 3 is a GPC chart of a resin (E) obtained in Example 3.

FIG. 4 is a GPC chart of a resin (F) obtained in Example 4.

FIG. 5 is a mass spectrometry spectrum of 4,4′-bis (methoxymethyl) biphenyl obtained in Reference Example 3.

FIG. 6 is an infrared absorption spectrum of 4,4′-bis (methoxymethyl) biphenyl obtained in Reference Example 3.

FIG. 7 is a ¹ H-NMR spectrum of 4,4′-bis (methoxymethyl) biphenyl obtained in Reference Example 3.

8 is a ¹ H-NMR spectrum of 2,4′-bis (methoxymethyl) biphenyl obtained in Reference Example 5. FIG.

FIG. 9 is an infrared absorption spectrum of 2,4′-bis (methoxymethyl) biphenyl obtained in Reference Example 5.

Continuation of the front page (72) Inventor Yumiki Noda 5 in 1978 Kogushi, Oji, Ube City, Yamaguchi Prefecture Inside Ube Research Institute (72) Inventor Hiroshi Jiki Hiki 5 in 1978 Kogushi, Oji in Ube City, Yamaguchi Prefecture 5 Ube Industries Ube Research Institute, Inc. (72) Inventor Takashi Homma 5 Ube Kogyo Co., Ltd., Ube Laboratory, 1978 Kogushi, Ube City, Ube City, Yamaguchi Prefecture (56) References JP-A-6-271654 (JP, A) (58) Survey Field (Int. Cl. ⁷ , DB name) C08G 61/00-61/12 CA (STN) REGISTRY (STN)

Claims (11)

(57) [Claims] 1. A phenol novolak condensate obtained by reacting a bis (methoxymethyl) biphenyl isomer represented by the general formula (I) or a mixture thereof with a phenol compound. Embedded image 2. A curing agent for an epoxy resin comprising the phenol novolak condensate of claim 1. 3. A phenol novolak condensate according to claim 1,
An epoxy resin composition containing an epoxy resin. 4. A phenol novolak condensate according to claim 1,
Curing composed of epoxy resin composition containing epoxy resin
object. 5. The phenol novolak condensate of claim 1
Epoxidized novolak resin. 6. The phenol novolak condensate of claim 1
Epoxidized novolak resin and epoxy
An epoxy resin composition comprising a resin curing agent. 7. The phenol novolak condensate of claim 1
Epoxidized novolak resin and epoxy
Curing composed of epoxy resin composition containing curing agent for resin
object. 8. The phenol novolak condensate of claim 1
An epoxidized novolak resin which has been epoxidized, and an epoxidized novolak resin.
Of phenol novolak condensates of epoxy resin
An epoxy resin composition containing a curing agent. 9. The phenol novolak condensate of claim 1
An epoxidized novolak resin which has been epoxidized, and an epoxidized novolak resin.
Of phenol novolak condensates of epoxy resin
A cured product comprising an epoxy resin composition containing a curing agent. 10. The phenol novolak condensate according to claim 1.
Resin composition containing phenol and a curing agent for phenol resin
object. 11. The phenol novolak condensate according to claim 1.
Resin composition containing phenol and a curing agent for phenol resin
Cured product consisting of