JPH09263641A - Production of resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a producing method of a phenol resin giving excellent physical properties without industrially affecting any effect to the environment by almost completely and readily removing unreacted phenolic OH-containing compound from a reaction product in a production of a phenol resin obtained by a reaction of an unsaturated hydrocarbon compound having more than two C=C bonds with a phenolic OH-containing compound, and to readily produce an epoxy resin having excellent resistances, to heat, solvent, acid and humidity and electric properties, etc. SOLUTION: The objective phenol resin is produced by reacting an unsaturated hydrocarbon compound having more than two C=C bonds with a phenolic OH-containing compound in the presence of an acid catalyst, neutralizing the resultant reacted solution with inorganic bases, and removing an unreacted phenolic OH-containing compound by distillation in the presence of an acid and as necessary, washing. The second objective epoxy resin is produced by reacting the phenol resin with an epihalohydrin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for easily producing a specific phenol resin and epoxy resin, which are optimal as raw materials for semiconductor encapsulants and printed wiring boards, in high purity and without polluting the environment. . More specifically, the present invention relates to a phenolic hydroxyl group-containing compound and carbon-
By reacting with an unsaturated hydrocarbon compound having two or more carbon double bonds and then performing a specific treatment, a phenol resin and an epoxy resin having an extremely low residual amount of unreacted phenolic hydroxyl group-containing compound can be obtained. It relates to a manufacturing method.

[0002]

2. Description of the Related Art In recent years, with the rapid progress of science and technology centered on the electronics industry, requirements for each product and its raw material have become more and more strict. Above all, semiconductor-related technologies have made remarkable progress, and the degree of integration of semiconductor memory has improved more and more, and along with this, the miniaturization of wiring and the increase in chip size have progressed. Furthermore, the mounting method has changed from through-hole mounting to surface mounting. The transition is progressing. However, in the surface mounting automation line, the semiconductor package undergoes a rapid temperature change during soldering of the lead wire, cracks occur in the resin molding part for the semiconductor encapsulant, and the interface between the lead wire resins deteriorates. Then, there is a problem that the moisture resistance is lowered.

For the purpose of improving the deterioration of moisture resistance, a method has been proposed in which the filler is highly filled by changing the shape of the filler. In this method, however, the elastic modulus of the resin is increased and the filler is resistant to thermal shock. There is a problem that cracks are likely to occur. Therefore, in order to mitigate the thermal shock when the semiconductor package is immersed in a solder bath, a method of modifying a resin composition such as addition of a silicone compound to a resin, addition of a thermoplastic oligomer, or silicone modification has been proposed. None of these methods has resulted in cracks in the molded product after immersion in the solder bath, and it has not been possible to obtain a reliable resin composition for semiconductor encapsulating material.

In the resin composition for semiconductor encapsulant, phenol resin is used as a curing agent for epoxy resin, and novolac phenol resin or novolac cresol resin is used as phenol resin. However, when such a phenol resin is used, the semiconductor package has a strong hygroscopic property, and as a result, there is a problem in that the generation of cracks when the solder bath is immersed as described above cannot be avoided.

Therefore, in recent years, in order to improve the heat resistance of the resin composition for semiconductor encapsulant, studies have been made to improve the phenol resin which is a curing agent for the epoxy resin. The inventors of the present invention have proposed, in JP-A-3-66919, a phenol resin obtained by reacting a phenol with an unsaturated polycyclic hydrocarbon compound having two or more carbon-carbon double bonds. , And reported that the above-mentioned problems can be solved by using such a phenol resin as a curing agent.

However, such a phenolic resin cannot be obtained by completely removing the acid catalyst or the catalyst residue used in the synthesis after the reaction, and the resulting phenolic resin is used as a resin composition for semiconductor encapsulant or a resin composition for laminates. When it is used for such as, it causes the properties of the resin composition for semiconductor encapsulant and the resin composition for laminated plate to be remarkably deteriorated, so that it must be completely removed.

As a method for completely removing the acid catalyst or the catalyst residue, Japanese Patent Application Laid-Open No. 5-214051 proposes a method in which a reaction solution containing a resin is treated with hydrotalcites. In order to recover unreacted phenols and reaction products from the liquid, it is necessary to filter the reaction liquid after the treatment, which causes a problem that the manufacturing process becomes complicated.

Further, JP-A-2-182721 discloses a method of treating a reaction solution with an inorganic base. This method has the advantage of being able to simplify the manufacturing process because it is easy to neutralize the acid catalyst with inorganic bases and to easily remove these salts, but on the other hand, a large amount of catalyst residue and unreacted phenols in the resin There is a problem that will remain.

Such catalyst residue and unreacted phenols can be easily removed by diluting the concentrate of the above reaction solution with a solvent and then washing with water, but unreacted phenol is mixed during the washing with recovered water, There is a serious problem that unreacted phenol is discharged with the disposal of recovered water and pollutes the environment.

Further, using such a phenol resin in which a large amount of unreacted phenol remains in the resin as a raw material,
When producing an epoxy resin by glycidylating this,
There is a problem that unnecessary monofunctional compounds are produced as by-products, the physical properties of the resin, particularly the curability are deteriorated, and the properties of the cured product are significantly deteriorated.

Therefore, there is an urgent need to develop a method for producing a phenolic resin that efficiently removes unreacted phenols and reduces the amount of residual unreacted phenols in the resin.

[0012]

That is, the object of the present invention is to produce a phenol resin obtained by reacting an unsaturated hydrocarbon compound having two or more carbon-carbon double bonds with a phenolic hydroxyl group-containing compound. , A phenolic resin that has a method for removing unreacted phenolic hydroxyl group-containing compound from the reaction product almost completely and easily, and that does not affect the environment industrially and has good physical properties It is to provide a manufacturing method of.

A further object of the present invention is to provide a method for easily producing an epoxy resin having excellent heat resistance, solvent resistance, acid resistance, moisture resistance, electrical characteristics, etc., using the phenol resin obtained by the above-mentioned production method. To provide.

[0014]

According to the present invention, a reaction obtained by reacting an unsaturated hydrocarbon compound having two or more carbon-carbon double bonds with a phenolic hydroxyl group-containing compound in the presence of an acid catalyst. After neutralizing the liquid with inorganic bases,
Provided is a method for producing a phenol resin, which comprises removing an unreacted phenolic hydroxyl group-containing compound by distillation in the presence of an acid.

According to the present invention, the reaction solution obtained by reacting an unsaturated hydrocarbon compound having two or more carbon-carbon double bonds with a phenolic hydroxyl group-containing compound in the presence of an acid catalyst is used as an inorganic base. The method for producing a phenol resin is characterized in that the phenolic hydroxyl group-containing compound that has not reacted is distilled off in the presence of an acid, followed by washing with water after neutralization with.

Further, according to the present invention, there is provided a method for producing an epoxy resin, which comprises reacting the phenol resin obtained by the above method with epihalohydrin.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a phenol resin of the present invention includes the following steps 1 to 3. That is, step 1: reaction step. In the presence of an acid catalyst, an unsaturated hydrocarbon compound having two or more carbon-carbon double bonds is reacted with a phenolic hydroxyl group-containing compound. Step 2: Catalyst neutralization step. Step 1
The step of neutralizing the reaction liquid obtained after the reaction of (1) with inorganic bases. Step 3: Step of removing unreacted phenolic hydroxyl group-containing compound. The reaction solution neutralized in step 2
Further, it is distilled in the presence of an acid to remove the unreacted phenolic hydroxyl group-containing compound.

The method for producing the phenolic resin of the present invention will be described in detail below according to the above steps.

First, the reaction step of step 1 will be described.
In step 1, first, an unsaturated hydrocarbon compound having two or more carbon-carbon double bonds is reacted with a phenolic hydroxyl group-containing compound in the presence of an acid catalyst.

The unsaturated hydrocarbon compound having two or more carbon-carbon double bonds is a cyclic conjugated diene compound,
Diels-Alder reaction product of conjugated diene compound,
A butadiene polymer etc. are mentioned.

The cyclic conjugated diene compound has 5 to 5 carbon atoms.
It is preferably 16, and specific examples thereof include cyclopentadiene, vinylcyclohexene, methylcyclopentadiene, limonene, and a mixture thereof.

As the Diels-Alder reaction product of the conjugated diene compound, a chain conjugated diene compound such as butadiene, isoprene and piperylene, or various conjugated diene compounds such as the above-mentioned cyclic conjugated diene compound can be used as the Diels-Alder compound. The thing reacted by reaction can be mentioned. More specifically, a compound represented by the following chemical formula or a mixture thereof can be preferably mentioned.

[0023]

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[0024]

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The Diels-Alder reaction products of the conjugated diene compounds are all third components of EPDM (ethylene / propylene / diene / methylene rubber).
It is a raw material that can be industrially inexpensively obtained as an intermediate raw material or a by-product in the production plant of ethylidene norbornene.

Examples of the butadiene polymer include a polymer obtained by homopolymerizing butadiene and a copolymer obtained by copolymerizing with other copolymerizable comonomer. Other copolymerizable comonomers include isoprene, conjugated diolefins such as 1,3-pentadiene; styrene, α-methylstyrene, vinyltoluene,
Aromatic vinyl monomers such as vinylbenzene can be preferably mentioned, and a butadiene copolymer can be obtained by subjecting these to block copolymerization or random copolymerization with butadiene. The blending ratio of butadiene and other comonomer that can be copolymerized is 0.05 mol of other comonomer that is copolymerizable with 1 mol of butadiene.
It is desirable that the amount is ˜0.8 mol, preferably 0.1 to 0.7 mol. The number average molecular weight of the butadiene polymer is not particularly limited, but is preferably 300 to 4000, preferably 500 to 3000.

Examples of the phenolic hydroxyl group-containing compound include phenols represented by the following general formula (1), naphthols represented by the following general formula (2), biphenols, bisphenols, trisphenols, and the like. A mixture and the like are preferable.

[0028]

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In the general formula (1), R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms.
A cycloalkyl group having 0 or an aryl group having 1 to 10 carbon atoms is shown. Further, m and n each represent an integer of 1 to 3. When m or n is 4 or more, the production is difficult. Specific examples of the phenols represented by the general formula (1) include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol. , M-propylphenol, p-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, p-se
c-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol,
Examples include monohydric phenols such as p-bromophenol; dihydric phenols such as resorcin, catechol and hydroquinone.

In the general formula (2), R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms.
A cycloalkyl group having 0 or an aryl group having 1 to 11 carbon atoms is shown. Further, p and q each represent an integer of 1 to 3. When p and q are 4 or more, the production is difficult. Specific examples of the naphthol represented by the general formula (2) include 1,1′-bis (dihydroxynaphthyl) methane.

Specific examples of the biphenols include biphenol and tetramethylbiphenol.

Specific examples of the bisphenols include 2,2-bis (4'-hydroxyphenyl) propane,
1,1′-bis (dihydroxyphenyl) methane and the like can be mentioned.

Specific examples of the above-mentioned trisphenols include trishydroxyphenylmethane.

Of these phenolic hydroxyl group-containing compounds, phenol, o-cresol, m-cresol, and 2,2-bis (4'-hydroxyphenyl) propane are particularly desirable from the viewpoints of economy and ease of production.

The ratio of the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds to the compound containing a phenolic hydroxyl group is such that the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds is used. On the other hand, it is desirable to use the phenolic hydroxyl group-containing compound in an amount of usually 0.8 to 12 times molar equivalent, preferably 1 to 8 times molar equivalent. By setting the charging ratio of the phenolic hydroxyl group-containing compound to 0.8 times the molar equivalent or more, it is possible to prevent the homopolymerization of hydrocarbons from occurring simultaneously, and the contact ratio of the phenolic hydroxyl group-containing compound is 12 times the molar equivalent. By the following, it becomes easy to recover unreacted phenols.

The acid catalyst used in reacting the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds with the phenolic hydroxyl group-containing compound is boron trifluoride; boron trifluoride. Boron trifluoride complexes such as ether complex, boron trifluoride / water complex, boron trifluoride / amine complex, boron trifluoride / phenol complex, boron trifluoride / alcohol complex; aluminum trichloride, diethyl aluminum monochloride Aluminum compounds such as; iron chloride; titanium tetrachloride; sulfuric acid; hydrogen fluoride; trifluoromethanesulfonic acid and the like can be preferably used, and boron trifluoride and trifluoride are particularly preferable from the viewpoint of activity and easy removal of the catalyst. Boron fluoride complexes are preferred, with boron trifluoride and boron trifluoride-phenol complexes being most preferred. .

The amount of the acid catalyst used is not particularly limited and may be appropriately selected depending on the catalyst used. Usually, 100 parts by weight of an unsaturated hydrocarbon compound having two or more carbon-carbon double bonds. It is preferably 0.1 to 50 parts by weight. Especially when boron trifluoride / phenol complex is used as the acid catalyst, 0.1 to 20 parts by weight, preferably 0 to 100 parts by weight of the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds is used. .5-
It is desirable to use 10 parts by weight.

The reaction of the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds with the phenolic hydroxyl group-containing compound can be carried out with or without a solvent. When a solvent is not used, it is preferable to use the phenolic hydroxyl group-containing compound in an equimolar amount or more, particularly 3 to 12 times the molar equivalent amount with respect to the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds. preferable. When a solvent is used, the solvent is not particularly limited as long as it does not inhibit the reaction, and particularly preferable solvents include aromatic hydrocarbon compounds such as benzene, toluene and xylene.

The reaction temperature of the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds and the phenolic hydroxyl group-containing compound varies depending on the kind of the acid catalyst used, but is usually 20 to 300 ° C. Preferably. Especially when boron trifluoride / phenol complex is used as an acid catalyst, it is 20 to 170 ° C., preferably 50 to 150 ° C.
C. is desirable. When the reaction temperature is 170 ° C. or lower, decomposition or side reaction of the catalyst can be suppressed, and when it is 20 ° C. or higher, the reaction time is short and economically advantageous reaction operation can be performed.

In the reaction of the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds with the phenolic hydroxyl group-containing compound, the water content in the system should be reduced as much as possible in order to allow the reaction to proceed smoothly. Is preferred,
Particularly, it is preferable to keep it at 100 ppm by weight or less.

Further, in the reaction of the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds with the phenolic hydroxyl group-containing compound, two carbon-carbon double bonds are formed.
In order to prevent the homopolymerization of the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds and control the reaction heat, it is possible to carry out the polymerization while sequentially adding the unsaturated hydrocarbon compound having two or more carbon atoms. preferable.

Next, the step 2 of neutralizing the catalyst will be described. In step 2, after the reaction of the unsaturated hydrocarbon compound having two or more carbon-carbon double bonds with the phenolic hydroxyl group-containing compound is completed, the obtained reaction solution is neutralized with an inorganic base. By this step, the acid catalyst can be deactivated.

Specific examples of the inorganic bases include alkali metals; alkaline earth metals; alkali metal oxides; alkaline earth metal oxides; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Alkaline earth metal hydroxides such as calcium hydroxide; Alkali metal carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate; alkaline earth metal carbonates; ammonium hydroxide; ammonia gas; Urea; anionic compounds such as ammonium carbonate and the like can be mentioned. Among them, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide and hydroxides of alkaline earth metals such as calcium hydroxide are particularly preferable.

The amount of the inorganic bases added is not particularly limited, but it is 1: 1 to 20: 1, preferably 3: 1 to 10: 1 by mole with respect to the acid catalyst used in the step 1. It is desirable to add them in a ratio.

The temperature for neutralizing the acid catalyst or the catalyst residue with the inorganic bases is not particularly limited, but is usually 10 to 15
It is desirable that the temperature is 0 ° C, preferably 30 to 90 ° C.
The neutralization treatment time is not particularly limited, but usually 1
It is desired that the time is 0 minutes to 10 hours, preferably 20 minutes to 5 hours.

Next, the step 3 of removing the unreacted phenolic hydroxyl group-containing compound will be described. In step 3, the reaction solution neutralized in step 2 is further distilled in the presence of an acid to remove unreacted phenolic hydroxyl group-containing compound.

Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid, oxalic acid, lactic acid, succinic acid and benzoic acid. Organic acids are preferred, and oxalic acid is particularly preferred among the organic acids. preferable.

The amount of the acid to be coexisted is 0.01: 1 to 10: 1, preferably 0.1: 1 with respect to the inorganic bases.
It is desirable to add them in a molar ratio of ˜5: 1, more preferably 0.5: 1 to 3: 1.

In the above-mentioned distillation, the residual amount of the unreacted phenolic hydroxyl group-containing compound in the crude phenol resin after distillation was 2%.
It is desirable to carry out the treatment until the amount becomes 00 weight ppm or less, preferably 100 weight ppm or less, more preferably 50 weight ppm or less.

The distillation may be carried out under normal pressure, reduced pressure, increased pressure or a combination thereof.

The distillation is carried out at 100 ° C to 300 ° C, preferably 150 ° C to 270 ° C, more preferably 170 ° C to 2 ° C.
It is desirable to carry out in the temperature range of 50 ° C. Distillation temperature is 3
When the temperature is set to 00 ° C. or less, side reactions such as resin decomposition can be suppressed. Further, in order to carry out the distillation smoothly and quickly, nitrogen or steam may be blown into the distillation system. Further, thin film distillation or the like may be carried out if necessary.

After completion of the distillation, the desired phenol resin is usually obtained by cooling. Since this resin has a very small amount of unreacted phenolic hydroxyl group-containing compound remaining in the resin, it has good physical properties in the production of epoxy resin by reaction with epihalohydrin and the production of cyanate resin by reaction with cyanogen halide. Suitable for supplying various resins.

In the method for producing phenol of the present invention, the phenol resin obtained can be further washed with water after the completion of the above steps 1 to 3. By this washing with water, there is almost no catalyst residue such as boron-containing or fluorine-containing inorganic salt,
A high-purity phenol resin can be produced.

The method of washing with water is not particularly limited, but a method of diluting the phenol resin with a solvent and washing the diluted solution may be employed instead of washing the phenol resin as it is. Specifically, first, the phenol resin is diluted with a solvent to be dissolved, the diluted solution is washed with water, and then the solvent can be distilled off. As a method for washing the diluted solution with water, a method is generally used in which water is added to the diluted solution, the mixture is left standing after stirring, and the separated aqueous layer is removed. It is desirable to wash the diluted solution with water twice or more, preferably three times or more.

The solvent used for the dilution is preferably a hydrocarbon solvent having 3 to 10 carbon atoms or a derivative thereof, specifically, benzene, toluene, o-xylene, p-xylene, m-xylene, mesitylene, acetone, cyclohexanone. , Methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, normal propyl alcohol, isopropyl alcohol, butanol, isobutyl alcohol, diethyl ether, dibutyl ether,
Diisobutyl ether, tetrahydrofuran, ethyl cellosolve, butyl cellosolve, dimethyldiglycol,
Dimethyl triglycol, methyl propylene glycol and the like are preferable, but among them, benzene, toluene, o
-Xylene, p-xylene and m-xylene are particularly preferred.

The concentration of the dilution is not particularly limited,
The concentration of the phenol resin in the diluted solution is 1 to 80% by weight, preferably 5 to 60% by weight, more preferably 10
It is desirable to dilute in the range of ˜40% by weight.

The distillation may be carried out under normal pressure, reduced pressure, increased pressure or a combination thereof. The distillation is usually 100 to 300 ° C, preferably 150 to 270.
C., more preferably 170 to 250.degree. C., in the temperature range. By setting the distillation temperature to 300 ° C. or less, it is possible to suppress the occurrence of side reactions such as resin decomposition. Further, in order to carry out the distillation smoothly and quickly, nitrogen or steam may be blown into the distillation system. Further, thin film distillation or the like may be carried out if necessary.

Next, the method for producing the epoxy resin of the present invention will be described.

In the method for producing an epoxy resin of the present invention, epihalohydrin is reacted with the phenol resin obtained by the method for producing a phenol resin of the present invention. An epoxy resin can be produced by glycidylating a phenol resin in this reaction. The reaction method for reacting the epihalohydrin is not particularly limited,
For example, the phenol resin obtained by the method for producing a phenol resin of the present invention is reacted with epihalohydrin at a temperature of usually 10 to 80 ° C. in the presence of a base such as sodium hydroxide or potassium hydroxide, and then washed with water if necessary, An epoxy resin can be obtained by drying.

Specific examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorhydrin, and the like, and epichlorohydrin, which is easily available, is preferable.

The amount of the epihalohydrin used is usually 2 to 20 times, and preferably 3 to 7 times the molar equivalent of the phenolic hydroxyl group-containing compound. Further, during the reaction, the glycidylation reaction can be made to proceed faster by distilling off water by azeotropic distillation with epihalohydrin under reduced pressure.

When an epoxy resin for use as a component of an electronic material is produced by the production method of the present invention, sodium chloride, which is a by-product after the reaction with epihalohydrin, is removed by the above washing operation. Is particularly desirable, but at this time, the catalyst residue mixed during the production of the phenol resin can also be removed at the same time. Therefore,
When the phenol resin obtained by the above-mentioned production method is used in the production method of the epoxy resin of the present invention, the steps 1 to 3 above are used.
If the method is applied to the production of the epoxy resin of the present invention without performing the subsequent washing operation, it is possible to efficiently produce a high-purity epoxy resin.

After completion of the reaction with epihalohydrin, the reaction solution may be concentrated by distillation to remove epihalohydrin, and the concentrate may be diluted with a solvent and washed with water. The solvent used here is preferably a hydrocarbon solvent having 3 to 10 carbon atoms or a derivative thereof, specifically, benzene, toluene, o-xylene, p-xylene, m-xylene, mesitylene, acetone, cyclohexanone, methyl ethyl ketone, methyl. Isobutyl ketone, methanol, ethanol, normal propyl alcohol, isopropyl alcohol, butanol, isobutyl alcohol, diethyl ether, dibutyl ether, diisobutyl ether, tetrahydrofuran, ethyl cellosolve,
Examples thereof include butyl cellosolve, dimethyldiglycol, dimethyltriglycol, and methylpropylene glycol. Among them, benzene, methyl isobutyl ketone, cyclohexanone, and butyl cellosolve are particularly preferable. The distillation concentration may be carried out under normal pressure, reduced pressure, increased pressure, or a combination thereof. The distillation is usually 100 to 300 ° C, preferably 120 to 250.
C., more preferably 140 to 200.degree. C. in the temperature range. By setting the distillation temperature to 300 ° C. or less, it is possible to suppress the occurrence of side reactions such as resin decomposition. Further, in order to carry out the distillation smoothly and quickly, nitrogen or steam may be blown into the distillation system. Further, thin film distillation or the like may be carried out if necessary.

When the concentrate is diluted with a solvent and then washed with water, the solvent is heated and concentrated after the washing with water,
An epoxy resin can be obtained.

[0065]

EFFECTS OF THE INVENTION According to the method for producing a phenol resin of the present invention, a phenol resin having an extremely low residual amount of unreacted phenolic hydroxyl group-containing compound can be obtained. Further, not only the residual amount of the unreacted phenolic hydroxyl group-containing compound is extremely low, but also a phenol resin containing almost no halogen atom ions and catalyst residues can be obtained. That is, it is possible to simply and easily produce a high-purity phenol resin by the method for producing a phenol resin of the present invention. Moreover, according to the method for producing a phenolic resin of the present invention, a resin can be produced without damaging the environment without containing a toxic unreacted phenolic hydroxyl group-containing compound during the washing with recovered water. The phenol resin obtained by the method for producing a phenol resin of the present invention has a very low water absorption. Furthermore, according to the method for producing an epoxy resin of the present invention, it is possible to obtain an epoxy resin having excellent moisture resistance, moisture absorption resistance, curability and electrical characteristics. Therefore, the cured product obtained by using the epoxy resin obtained by the method of the present invention has excellent electrical properties and moisture resistance, and is useful for semiconductor resins, printed wiring board laminates, powder coatings, brake shoes, and the like. .

[0066]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

[0067]

Example 1 (Synthesis of Phenolic Resin-1) 2000 g of phenol and 400 g of toluene were charged into a reactor having a capacity of 5 liters equipped with a reflux condenser and a Liebig condenser, heated to 170 ° C., and toluene 3 was added.
50 g was distilled off to adjust the water content in the reaction system to 70 ppm. Then, the reaction system was cooled to 70 ° C., 10 g of boron trifluoride / phenol complex was added, and 400 g of dicyclopentadiene having a water content of 20 ppm was taken for 1.5 hours while controlling the reaction temperature at 70 ° C. Was gradually added dropwise, and after completion of the addition, the reaction was carried out at 140 ° C. for 3 hours. After the completion of the reaction, 22.5 g of a 40 wt% caustic soda aqueous solution was added to the obtained reaction product and stirred for 30 minutes to deactivate the catalyst. Subsequently, 40 g of a 10 wt% oxalic acid aqueous solution was added to the system, and the reaction solution was distilled under reduced pressure at 210 ° C.
60 g of crude phenolic resin was obtained. When the residual amount of phenol in this crude resin was measured, it was 10 ppm by weight.

[0068]

Example 2 (Synthesis of Phenolic Resin-2) 1 liter of toluene was added to 280 g of the crude phenol resin obtained in Example 1 and dissolved by stirring at room temperature for 1 hour. After this solution was washed with water three times, the organic layer was separated and distilled under reduced pressure at 210 ° C. to obtain 260 g of a phenol resin (A) represented by the following chemical formula (3). The results of various analyzes are shown below.

[0069]

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The obtained phenol resin (A) had a softening point of 96 ° C., Gardner hue 7, residual boron of 5 ppm, and fluorine of 1 ppm or less.

The content of phenolic hydroxyl group was determined by back titration after acetylation with acetic anhydride.
The phenolic hydroxyl group equivalent was 170.

In ¹ H-NMR analysis, δ 6.5-7.5.
Protons bound to the aromatic ring at ppm are also δ 0.8
Protons of the naphthene ring were observed at ˜2.5 ppm, and absorption of protons due to carbon-carbon double bonds was not observed. Further, δ 6.5 to 8 ppm and δ 0.8 to 2.
When the content of the phenolic hydroxyl group was determined from the peak area ratio with 5 ppm, the phenolic hydroxyl group equivalent was 170 as in the case of the titration result.

In the ¹³ C-NMR analysis, 158 pp produced when phenol was ether-added to the double bond.
Since no carbon signal of m was observed, it was found that all the phenols were added by alkylation. Further, the number average molecular weight of the phenol resin (A) was determined by GPC analysis and found to be 430.

[0074]

Example 3 (Synthesis of Epoxy Resin-1) The crude phenol resin obtained in Example 1 was glycidylated by the following method.

3 with stirrer, reflux condenser and thermometer
In a liter 4-neck flask, the crude phenol resin 17
After charging 0 g and 400 g of epichlorohydrin, the mixture was dissolved and stirred, the inside of the reaction system was adjusted to a pressure of 150 mmHg, and the temperature was raised to 68 ° C. While continuously adding 100 g of a 48 wt% concentration aqueous sodium hydroxide solution to this system, the reaction was carried out for 3.5 hours. The water generated by the reaction and the water of the sodium hydroxide aqueous solution were decomposed by refluxing the water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After completion of the reaction, the reaction system was returned to normal pressure and heated to a temperature of 110 ° C. to completely remove water in the reaction system. Excessive epichlorohydrin was distilled off under atmospheric pressure for a further 15
Distillation was performed at 140 ° C. under reduced pressure of mmHg.

Then, in order to completely react the unreacted raw materials, the resulting resin and sodium chloride were added to the mixture.
300 g of methyl isobutyl ketone and 36 g of a 10 wt% sodium hydroxide aqueous solution were added, and the reaction was carried out at a temperature of 85 ° C. for 1.5 hours. After completion of the reaction, 750 g of methyl isobutyl ketone and 300 g of water were added, and the lower layer sodium chloride aqueous solution was separated and removed. Next, 150 g of water was added to the methyl isobutyl ketone liquid layer to wash it, and the mixture was neutralized with phosphoric acid. The aqueous layer was separated and then washed with 800 g of water to separate the aqueous layer. The oil layer and the water layer have good separability, and after quantitatively recovering the inorganic salt, the methyl isobutyl ketone liquid layer is distilled under normal pressure, followed by vacuum distillation at 5 mmHg and 140 ° C. to obtain 180 g of epoxy resin (B ) Got. The epoxy equivalent of this epoxy resin was 262. Moreover, the content of the monofunctional compound by liquid chromatography is 0.1 w.
It was t% or less.

[0077]

Example 4 (Synthesis of Epoxy Resin-2) The same as Example 3 except that 170 g of the phenol resin (A) obtained in Example 2 was used in place of the crude phenol resin obtained in Example 1. The reaction was carried out by the method of 1. to obtain 185 g of an epoxy resin (C). The epoxy equivalent of this epoxy resin was 261. The content of the monofunctional compound by liquid chromatography was 0.1 wt% or less.

[0078]

Example 5 (Synthesis of Phenolic Resin-3) Phenol represented by the following chemical formula (4) was reacted and purified in the same manner as in Examples 1 and 2 except that 2300 g of o-cresol was used instead of phenol. Resin (D) 60
0 g was obtained.

[0079]

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The obtained phenol resin (D) has a softening point of 92 ° C., a Gardner hue of 7, and a residual boron content of 5 pp.
m and fluorine were 1 ppm or less. The phenolic hydroxyl group equivalent was 180. ^{In 1} H-NMR analysis, absorption of a proton due to a carbon-carbon double bond was not recognized. Further, when the content of the phenolic hydroxyl group was determined from the peak area ratio, the phenolic hydroxyl group equivalent was 180 as in the case of the titration result. Further, the number average molecular weight of the phenol resin (D) was determined by GPC analysis and found to be 470.

[0081]

Example 6 (Synthesis of Epoxy Resin-3) An epoxy resin was synthesized in the same manner as in Example 3 except that 180 g of the phenol resin (D) obtained in Example 5 was used, and 200 g of the epoxy resin was used. (E) was obtained. The epoxy equivalent of this epoxy resin was 272. The content of monofunctional compound by liquid chromatography is 0.1 wt%
It was below.

[0082]

Example 7 (Synthesis of Phenol Resin-4) 2000 g of phenol and 400 g of toluene were charged into a reactor having a capacity of 5 liters equipped with a reflux condenser and a Liebig condenser, heated to 170 ° C., and toluene 3 was added.
50 g was distilled off to adjust the water content in the reaction system to 70 ppm. Then, the reaction system was cooled to 70 ° C., 10 g of boron trifluoride / phenol complex was added, and 400 g of tetrahydroindene having a water content of 20 ppm was added over 1.5 hours while controlling the reaction temperature at 70 ° C. The mixture was gradually added dropwise, and after the completion of the addition, the reaction was carried out at 140 ° C. for 3 hours. After completion of the reaction, 25 g of a 40 wt% aqueous sodium hydroxide solution was added to the obtained reaction product, and the mixture was stirred for 30 minutes to deactivate the catalyst. Subsequently, 45 g of a 10% by weight aqueous oxalic acid solution was added to the system, and the reaction solution was subjected to vacuum distillation at 210 ° C. to give 450
g of crude phenolic resin was obtained. When the residual amount of phenol in this crude resin was measured, it was 15 ppm by weight.

[0083]

[Example 8] (Synthesis of phenol resin-5) To 225 g of the crude phenol resin obtained in Example 7, 1 liter of toluene was added, and the mixture was stirred and dissolved at room temperature for 1 hour. After this solution was washed with water three times, the organic layer was separated and distilled under reduced pressure at 210 ° C. to obtain 210 g of a phenol resin (F) represented by the following chemical formula (5). The results of various analyzes are shown below.

[0084]

[Chemical 6]

The phenol resin (F) thus obtained had a softening point of 105 ° C. The hydroxyl equivalent of the phenol resin (F) is 195, the Gardner hue is 8, and the residual boron is 7 p.
pm and fluorine were 1 ppm or less.

[0086]

Example 9 (Synthesis of Phenolic Resin-6) Instead of dicyclopentadiene, Diels-Alder reaction product 300 of butadiene and dicyclopentadiene
The reaction was performed in the same manner as in Example 7 except that g was used.
60 g of crude phenolic resin was obtained.

[0087]

Example 10 (Synthesis of Phenol Resin-7) To 280 g of the crude phenol resin obtained in Example 9 was added 1 liter of toluene, and the mixture was stirred and dissolved at room temperature for 1 hour. After this solution was washed with water three times, the organic layer was separated and distilled under reduced pressure at 210 ° C. to obtain 560 g of a mixture (G) of two kinds of compounds represented by the following chemical formulas (6) and (7). .

[0088]

Embedded image

The resulting mixture (G) has a softening point of 115 ° C.
The Gardner hue was 8, residual boron was 9 ppm, and fluorine was 1 ppm or less. The phenolic hydroxyl group equivalent was 205.

[0090]

Comparative Example 1 (Synthesis of Phenolic Resin-8) Instead of the caustic soda aqueous solution in Example 1, Mg _0.7 Al _0.3 (O 2
H) ₂ (CO ₃ ) _0.15 · mH ₂ 0 (m is 0.46 ≦ m ≦ 0.56) The reaction was performed in the same manner as in Example 1 except that 25 g of hydrotalcites was added to deactivate the catalyst. After the completion of the reaction, hydrotalcites were filtered off and concentrated by distillation to obtain 550 g of phenol resin (H).

The obtained phenol resin (H) has a softening point of 96 ° C., a Gardner hue of 7 and a residual boron content of 4 pp.
m and fluorine were 1 ppm. The phenolic hydroxyl group equivalent was 170 and had substantially the same physical properties as the phenolic resin (A) obtained in Example 2.

[0092]

Comparative Example 2 (Synthesis of Epoxy Resin-4) An epoxy resin was synthesized in the same manner as in Example 3 except that the phenol resin (H) obtained in Comparative Example 1 was used.

The epoxy equivalent of the obtained epoxy resin is 2
72, the content of the monofunctional compound by liquid chromatography was 0.1 wt% or less, and it had substantially the same physical properties as the epoxy resin obtained in Example 3.

[0094]

Comparative Example 3 (Synthesis of Phenolic Resin-9) After completion of the reaction in Example 1, the crude phenol resin obtained in Example 1 was reacted and treated in the same manner except that oxalic acid was not added during concentration. 545 g of crude phenol resin (I) similar to the above was obtained. However, since the separation of the organic layer and the aqueous layer was difficult at the stage of recovering the organic layer at the time of washing, the loss amount of the crude phenol resin (I) as the target substance was large, and only 450 g was obtained. . Moreover, the crude phenol resin (I) had a high hue (Gardner hue 11). When the residual amount of phenol of this resin was measured, it was 220 ppm by weight.

The crude phenol resin (I) had a sodium content of 30 ppm, a boron content of 200 pm and a fluorine content of 40 ppm.

[0096]

[Comparative Example 4] (Synthesis of phenol resin-10) To 200 g of the crude phenol resin (I) obtained in Comparative Example 3 was added 750 ml of toluene, and the mixture was stirred and dissolved at room temperature for 1 hour to give 3
It was washed with water twice to obtain a phenol resin (J). However, since it was difficult to separate the organic layer and the aqueous layer at the stage of recovering the organic layer at the time of washing, the amount of the phenol resin (J) as the target substance was large, and the recovery amount was 160 g. . Moreover, the hue of the phenol resin (J) was high (Gardner hue 11). When the residual amount of phenol of this resin was measured, it was 220 ppm by weight.

The phenol resin (J) thus obtained had a softening point of 92 ° C. and a Gardner hue of 11, which was high. Residual boron was 10 ppm and fluorine was 2 ppm. The phenolic hydroxyl group equivalent was 171.

[0098]

Comparative Example 5 (Synthesis of Epoxy Resin-5) An epoxy resin was synthesized in the same manner as in Example 3 except that the crude phenol resin (I) obtained in Comparative Example 3 was used.

The epoxy equivalent of the obtained epoxy resin is 2
In 74, the content of the monofunctional compound by liquid chromatography was as high as 0.5 wt%, and the resin physical properties were different from those of the epoxy resin obtained in Example 3.

Continuation of the front page (72) Inventor Yu Otsuki 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Nippon Petroleum Co., Ltd. Central Research Laboratory

Claims (3)

[Claims] 1. A carbon-carbon double bond is converted into a carbon-carbon double bond in the presence of an acid catalyst.
After neutralizing the reaction solution obtained by reacting an unsaturated hydrocarbon compound having 1 or more with a phenolic hydroxyl group-containing compound with an inorganic base, the unreacted phenolic hydroxyl group-containing compound is distilled off in the presence of an acid. A method for producing a phenolic resin, comprising: 2. A carbon-carbon double bond is converted into a carbon-carbon double bond in the presence of an acid catalyst.
After neutralizing the reaction solution obtained by reacting an unsaturated hydrocarbon compound having one or more with a phenolic hydroxyl group-containing compound with an inorganic base, the unreacted phenolic hydroxyl group-containing compound is distilled off in the presence of an acid. And then washing with water, the method for producing a phenol resin. 3. A method for producing an epoxy resin, which comprises reacting the phenol resin obtained by the method according to claim 1 or 2 with epihalohydrin.