JP2012067253A - Method of manufacturing allyl etherification novolak type phenol resin, and allyl etherification novolak type phenol resin obtained by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method which can obtain a novolak type phenol resin which makes the dimer of allyl etherification phenols a principal component by high yield, and to provide the allyl etherification novolak type phenol resin obtained by the manufacturing method.SOLUTION: The method of manufacturing an allyl etherification novolak type phenol resin is characterized in that allyl etherification phenols shown by general formula (I) are reacted with aldehydes under the presence of an acid catalyst. In the formula, Rdenotes an alkyl group, an alkenyl group, an aryl group or a halogen, or may form a condensed ring together with Rand the benzene ring of the phenol, Rand Reach independently denote an alkyl group, an alkenyl group, an aryl group or a hydrogen atom, provided that Rmay form a condensed ring together with Rand the benzene ring of the phenol.

Description

  The present invention relates to a production method capable of obtaining an allyl etherified novolak type phenol resin mainly composed of a dimer of allyl etherified phenols in a high yield, and an allyl etherified novolac type phenol obtained by the production method. It relates to resin. Specifically, by using allyl etherified phenols having a substituent at the ortho position, the allyl etherified phenols are efficiently dimerized.

  Allyl etherified phenol resins are used as raw materials for epoxy resin synthesis by oxidation of allyl groups, epoxy resin curing agents utilizing Claisen transition, and the like.

Epoxy resins have excellent electrical properties and adhesive strength, and are therefore used in various applications in the electric / electronic field.
In recent years, electronic devices have become increasingly lighter, shorter, more multifunctional, and more highly integrated with semiconductors. The mounting method for mounting a package on a printed wiring board has been changed from a conventional pin insertion method to a surface mounting method. The epoxy resins used are liquid and low-viscosity epoxy resins such as bisphenol A type and bisphenol F type.

Epoxy resins are generally synthesized by synthesizing halohydrin ethers from novolak resins and epihalohydrins and dehydrohalogenating to obtain epoxy resins. By-products in the resulting epoxy resins, dehydrohalogenation process There are a lot of halogen components such as unreacted parts, and the halogen causes the reliability of electric / electronic parts and the like to be lowered.
In order to reduce the halogen content and improve the reliability of electrical and electronic parts, the epoxy resin with less halogen content is obtained by converting the allyl etherified phenol resin described in Patent Document 1 into an epoxy resin with an organic peracid. Can be synthesized.

Epoxy resin curing agents include phenol-based, amine-based, and acid anhydride-based ones, and the performance of the cured product varies depending on the curing agent.
Liquid epoxy resin composition for sealing materials for electrical and electronic parts. Phenolic curing agents have a good balance of physical properties such as adhesion, water resistance and electrical performance. In addition, the epoxy resin composition has a high viscosity and poor fluidity.
In recent years, electronic devices have become increasingly lighter, shorter, more multifunctional, and more highly integrated with semiconductors. The mounting method for mounting a package on a printed wiring board has been changed from a conventional pin insertion method to a surface mounting method. It has become the mainstream, various proposals have been made as curing agents for low-viscosity epoxy resins, and it has been proposed to use resins obtained by transitioning the allyl etherified novolak described in Patent Documents 2 and 3 to Claisen. . Patent Document 4 proposes an epoxy resin composition in which a phenolic hydroxyl group is compounded with an allyl ether compound and an epoxy resin.

  Dimers of allyl etherified phenols are dimers of phenols produced by addition condensation of a large excess of phenols and aldehydes in the presence of an acid catalyst, allyl halides such as allyl chloride, and Reaction of allylated carboxylic acids such as allyl acetate, or phenols with allyl halides and allylated carboxylic acids such as allyl acetate, and the resulting allyl etherified phenols and aldehydes in the presence of an acid catalyst It can be obtained by addition condensation.

Dimers of phenols can be obtained by reacting a large excess of phenols with aldehydes, but unreacted phenols are removed by distillation under reduced pressure, so a decrease in yield is inevitable. .
Patent Document 5 discloses a method in which 0.33 mol or more and less than 0.40 mol of aldehyde is reacted in the presence of phosphoric acid with respect to 1 mol of phenols.
There is a description that a phenol resin mainly composed of a dimer of phenols is obtained by reacting in a two-layer separated state formed from phenols, aldehydes, and phosphoric acid. In the example, the dimer of orthocresol is 80% and the dimer is the main component, but the yield is as low as 60% with respect to the orthocresol used, and the resin is not efficiently obtained.
A phenol resin mainly composed of such a dimer of phenols has a low yield, and further, the phenol resin is allylated, so that the efficiency is poor.

  In addition, 2,6-substituted phenols and 2,4-substituted phenols can obtain dimers in high yield, but allyl etherified phenols do not undergo Claisen transition and can be used as epoxy resin curing agents. Can not.

  In Patent Document 6, polyallyl ether can be obtained in high yield by reacting an allyl etherified phenol in the presence of an acid catalyst and using an organic acid as a solvent. It is not a resin.

JP 59-66414 A Japanese Patent No. 3633684 Japanese Patent No. 2985700 Japanese Patent No. 3350975 Japanese Patent No. 3950079 JP 59-168019 A

  In order to obtain a novolak type phenol resin whose main component is a dimer of allyl etherified phenols, after reacting excess phenols with aldehydes, removing unreacted phenols, allyl etherification is performed. It is necessary to remove a large amount of unreacted phenols or allyl etherified phenols such as removing unreacted allyl etherified phenols after reacting excess allyl etherified phenols with aldehydes. There is poor efficiency.

  The present invention has been made on the basis of the circumstances as described above, and a production method capable of obtaining a novolak type phenol resin mainly composed of a dimer of allyl etherified phenols in a high yield, and the production An object of the present invention is to provide an allyl etherified novolak type phenolic resin obtained by the method.

  The present inventors have found that the above problem can be solved by making allyl ethers of phenols having a specific structure and reacting them with aldehydes in the presence of an acid catalyst, and have completed the present invention. .

That is, the gist of the present invention is as follows.
This is a method for producing an allyl etherified novolak type phenol resin in which an allyl etherified phenol represented by the general formula (I) and an aldehyde are reacted in the presence of an acid catalyst.

(In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, a halogen, or a condensed ring together with R ₂ and a benzene ring of phenol. R ₂ and R _{3 each} independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, or a hydrogen element, provided that R ₂ represents R ₁ and the benzene ring of phenol may form a condensed ring.)

  According to the present invention, the monomer content of the unreacted allyl etherified phenols is small, and the dimer of allyl etherified phenol is a high proportion, that is, allyl in the area ratio of the chart by gel permeation chromatography (GPC) An allyl etherified novolak type phenol resin containing 70% or more of a dimer of etherified phenols can be obtained. In addition, the allyl etherified novolak type phenolic resin obtained in the present invention has high work efficiency and productivity due to the low monomer content of phenols, and further has a low halogen content, and is an epoxy resin material and an epoxy resin curing agent. As extremely useful.

2 is a GPC chart of allyl etherified novolak type phenol resin A in Example 1. FIG. 2 is a GPC chart of an allyl etherified novolac type phenol resin G in Comparative Example 1.

The present invention will be described in detail below.
The allyl etherified phenols used in the present invention can be obtained by reacting a phenol substituted with one of the ortho positions represented by the general formula (II) with an allyl halide in the presence of an alkali. Further, as described in Japanese Patent No. 3819426, allyl etherified phenols can be obtained by reacting phenols with allyl carboxylate or allyl carbonate in the presence of a complexing agent, a transition metal catalyst and an alkali. . A resin having a dimer of allylated phenols as a main component is obtained by reacting the obtained allyl etherified phenols with aldehydes.

(In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, a halogen, or a condensed ring together with R ₂ and a benzene ring of phenol. R ₂ and R _{3 each} independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, or a hydrogen element, provided that R ₂ represents R ₁ and the benzene ring of phenol may form a condensed ring.)

R ₁ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, a halogen, or forms a condensed ring together with R ₂ and the benzene ring of phenol. Also good. Specifically, the alkyl group having 1 to 10 carbon atoms is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, s- Examples include a pentyl group, a t-pentyl group, a hexyl group, an s-hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, isopentenyl group, hexenyl group, heptenyl group, octenyl and the like. Examples of the aryl group include phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group and the like. Examples of the halogen include fluorine, chlorine, bromine and iodine. Examples of the condensed ring formed together with R ₁ , R ₂ and the benzene ring of phenol include bicyclic condensed rings. R ₁ is preferably a bicyclic condensation formed with an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group, R ₂ and a benzene ring of phenol, from the viewpoint of obtaining raw materials. It is a ring. More preferably, it is a bicyclic condensed ring formed with a methyl group, an ethyl group, an allyl group, a phenyl group, R ₂ and a benzene ring of phenol.

R ₂ and R ₃ independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, or a hydrogen element. Specific examples of the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the aryl group of R ₂ and R ₃ are the same as those in the above R ₁ . Preferably, they are a C1-C5 alkyl group or a hydrogen atom, Most preferably, they are a methyl group or a hydrogen atom. R ₂ may form a bicyclic condensed ring with R ₁ and the benzene ring of phenol.

  Specific examples of the ortho-substituted phenols represented by the general formula (II) include orthocresol, 2,3-xylenol, 2,5-xylenol, 2,3,5-trimethylphenol, orthoethylphenol, orthopropylphenol. , Orthobutylphenol, orthooctylphenol, orthononylphenol, orthophenylphenol, orthocyclohexylphenol, orthochlorophenol, 1-naphthol and the like. These ortho-substituted phenols can be used alone or in admixture of two or more. Of these, orthocresol, 2,3-xylenol, 2,5-xylenol, and 1-naphthol are practically preferable.

A method for producing allyl etherified phenols using ortho-substituted phenols and allyl halides will be described.
Specific examples of allyl halides to be reacted with ortho-substituted phenols include, but are not limited to, allyl chloride, allyl bromide, allyl iodide, and the like. These allyl halides can be used alone or in admixture of two or more.
The allyl halide is preferably 0.8 to 1.2 moles per mole of ortho-substituted phenols, but is not limited thereto.

Examples of basic compounds used in the reaction of ortho-substituted phenols with allyl halides include, but are not limited to, sodium hydroxide and potassium hydroxide aqueous solutions.
It is of course possible to use a solvent during the reaction. As the solvent, alcohol, ketone, aprotic polar solvent and the like can be used. Specifically, propanol, butanol, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like can be used. Examples include but are not limited to these.

  A flask equipped with a condenser and a stirrer is charged with an ortho-substituted phenol, a basic compound, and, if necessary, a solvent, and charged with an allyl halide. The reaction temperature is in the range of room temperature to 150 ° C. Is good. A temperature exceeding 150 ° C. is not preferable because a Claisen transition may occur partially. There is no restriction | limiting in particular in reaction time, What is necessary is just to adjust with the quantity of a basic compound, an allyl halide, a solvent, and reaction temperature.

A method for producing allyl etherified phenols using ortho-substituted phenol and allyl carboxylate or allyl carbonate will be described.
Examples of allyl carboxylates and allyl carbonates to be reacted with ortho-substituted phenols include, but are not limited to, allyl formate, allyl acetate, allyl propionate, diallyl carbonate, and the like. These allyl carboxylates and allyl carbonates can be used alone or in admixture of two or more. The allyl carboxylate is preferably in a ratio of 0.5 to 5 moles per mole of allyl etherified phenols, but is not limited thereto.

  Alkali metal or alkaline earth metal bicarbonates, carbonates, phosphates, acetates, hydroxides, etc. may be used as base compounds for the reaction of ortho-substituted phenols with allyl carboxylates and allyl carbonates. Specific examples include, but are not limited to, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate and the like. These basic compounds can be used alone or in admixture of two or more.

Rhodium, ruthenium, rhenium, palladium, iridium, tungsten, molybdenum, chromium, cobalt, platinum, nickel, copper, iron are free metals as transition metals for the catalyst used in the reaction of ortho-substituted phenol with allyl carboxylate and allyl carbonate Or in a non-oxidized state as a complex or in the oxidized state as a salt thereof, for example, a carboxylate, halide, oxide, nitrate or sulfate. Preferable catalysts are palladium, platinum, molybdenum, and nickel. In the case of a free metal, it is preferably supported on carbon, charcoal, activated carbon, silica, alumina, zeolite, clay, or the like.
Examples of the complexing agent used in the reaction of the ortho-substituted phenol with allyl carboxylate and allyl carbonate include, but are not limited to, triphenylphosphine, tris-tolylphosphine, diphenylmethylphosphine, diphenylphosphinoethane, and the like.

  It is of course possible to use a solvent during the reaction. As the solvent, water, excess amount of allyl carboxylate, alcohol, ether, glycol, glycol ether, ketone, ester, aprotic polar solvent, aromatic and aliphatic hydrocarbon, etc. can be used, specifically Examples include, but are not limited to, water, allyl acetate, toluene, xylene, tetrahydrofuran, isopropanol, t-butanol, acetonitrile, methyl ethyl ketone, ethyl acetate, dimethylformamide, dimethyl sulfoxide, nitromethane, and the like.

  A flask equipped with a condenser and a stirrer is charged with an ortho-substituted phenol, an allyl carboxylate, a transition metal catalyst, a complexing agent, a basic compound, and a solvent as required, and the reaction temperature is 50 to 150 at this time. It is good to carry out in the range of ° C. If the temperature is less than 50 ° C., the progress of the reaction is slow, and if it exceeds 150 ° C., the Claisen transition may partially occur, which is not preferable. There is no restriction | limiting in particular in reaction time, What is necessary is just to adjust with carboxylate allyls, the quantity of a catalyst, and reaction temperature.

As the aldehyde to be reacted with the allyl etherified phenol of the present invention, any aldehyde that can be used for producing a novolak type phenol resin can be used. Examples include, but are not limited to, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, benzaldehyde, propylaldehyde, butyraldehyde, isovaleraldehyde, hexylaldehyde, glyoxal, crotonaldehyde, and glutaraldehyde. These aldehydes can be used alone or in admixture of two or more. From the viewpoint of reaction efficiency, formaldehyde, paraformaldehyde and trioxane are preferred.
The aldehydes are used in an amount of 0.3 to 0.6 mol, preferably 0.4 to 0.5 mol, per 1 mol of the total amount of allyl etherified phenols. If the amount of aldehyde used is less than 0.3 mol, the remaining allyl etherified phenol monomer increases, which is not efficient. On the other hand, when the amount of the aldehyde used exceeds 0.6 mol, the amount of unreacted aldehyde increases, which is not preferable because of poor efficiency. In addition, when using paraformaldehyde or olioxane, it is made to correspond to the said usage-amount in terms of the amount of formaldehyde produced | generated from these.

The acid of the catalyst used in the method of the present invention may be any acid used in the production of general novolak resins, such as oxalic acid, phosphoric acid, paratoluenesulfonic acid, boric acid, sulfuric acid, and hydrochloric acid. Can be used alone or in admixture of two or more.
The catalyst acid is used in an amount of 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of allyl etherified phenols.

  The method for reacting allyl etherified phenols with aldehydes is not particularly limited. For example, allyl etherified phenols, aldehydes, a method in which an acid of a catalyst is charged and reacted, or allyl etherified phenols, Examples include a method of adding a catalyst acid and adding aldehydes at a predetermined reaction temperature. At this time, the reaction temperature is preferably 30 to 150 ° C. When the temperature is lower than 30 ° C., the reaction proceeds slowly and unreacted phenols remain, which is not preferable, and when the temperature exceeds 150 ° C., Claisen transition may partially occur, which is not preferable. There is no restriction | limiting in particular in reaction time, What is necessary is just to adjust with the amount of aldehydes, the acid of a catalyst, and reaction temperature.

It is of course possible to use an organic solvent during the reaction. Organic solvents include alcohols such as propyl alcohol and butanol, glycols such as ethylene glycol and propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether Glycol ethers such as butylene glycol monoethyl ether and butylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, propyl acetate, butyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. Esters, ethers such as 1,4-dioxane, Can aromatics such as xylene is used alone or in combination of two or more.
The said organic solvent can be used so that it may become 0-1,000 mass parts with respect to 100 mass parts of allyl etherified phenols, Preferably it is about 10-100 mass parts. After the reaction, the condensed water may be removed by distillation, or, if necessary, the remaining catalyst acid may be removed by washing with water. Furthermore, unreacted allyl etherified phenols and unreacted aldehydes may be removed by distillation under reduced pressure or steam distillation.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples of novolak type phenol resins mainly composed of a dimer of allyl etherified phenols by the production method of the present invention. Is not limited to the following examples.

About the obtained resin, the value measured by the following analysis method is shown below. First, analysis items and analysis methods of the obtained resin are as follows.
Number average molecular weight, weight average molecular weight, dispersity, dimer content rate Measured by gel permeation chromatography (GPC).
The column configuration was measured using a differential refractometer as a detector using two KF-804s manufactured by Showa Denko KK, using tetrahydrofuran as a solvent, a flow rate of 1 ml / min, a column temperature of 40 ° C., and a detector.
The molecular weight was calculated in terms of polystyrene, and the dimer content was calculated as a percentage of the total peak area.
The degree of dispersion was calculated by weight average molecular weight / number average molecular weight.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 324 g of orthocresol, 330 g of allyl acetate, 150 g of isopropyl alcohol, 9 g of 5% Pd carbon powder (hydrated product), 9 g of STD type, 3 g of triphenylphosphine, and 870 g of 50% potassium carbonate aqueous solution. The mixture was reacted at 0 ° C. for 7 hours, and the resulting reaction solution was filtered, washed 5 times with distilled water, and concentrated to obtain 420 g of allyl etherified orthocresol.

Synthesis example 2
The reaction was conducted in the same manner as in Synthesis Example 1 except that 282 g of phenol was used as the phenol, to obtain 381 g of allyl etherified phenol.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 366 g of 2,3-xylenol, 230 g of allyl chloride and 450 g of dimethyl sulfoxide, and 285 g of 48% aqueous sodium hydroxide solution was charged with attention to heat generation and reacted at 65 ° C. for 10 hours. The resulting reaction solution was washed 5 times with distilled water and concentrated to obtain 423 g of allyl etherified 2,3-xylenol.

Synthesis example 4
The reaction was conducted in the same manner as in Synthesis Example 3 except that 510 g of orthophenylphenol was used as the phenol, to obtain 567 g of allyl etherified orthophenylphenol.

Synthesis example 5
The reaction was conducted in the same manner as in Synthesis Example 3 except that 477 g of 2-allylphenol was used as a phenol, to obtain 563 g of allyl etherified 2-allylphenol.

Synthesis Example 6
A reaction was carried out in the same manner as in Synthesis Example 3 except that 432 g of 1-naphthol was used as a phenol to obtain 478 g of allyl etherified 1-naphthol.

Example 1
A flask equipped with a condenser and a stirrer was charged with 148 g of allyl etherified orthocresol obtained in Synthesis Example 1, 18 g of 85% paraform, 1 g of boric acid and 1 g of oxalic acid, and reacted at 120 ° C. for 13 hours. Subsequently, washing was performed 5 times with 100 g of pure water to remove boric acid and oxalic acid. Next, the distillate was removed under reduced pressure at 140 ° C. and 50 mmHg to obtain 140 g of resin A (yield 95% by mass) mainly composed of a dimer of liquid allyl etherified phenols. In addition, the yield showed the quantity of resin obtained with respect to the preparation amount of allyl etherified phenols in percentage.
The number average molecular weight of the obtained resin was 205, the weight average molecular weight was 229, the degree of dispersion was 1.12, and the dimer content was 88.4%.
In FIG. 1, the gel permeation chromatography (GPC) chart of resin A is shown. The horizontal axis indicates the elution time (minutes). It can be seen from FIG. 1 that the resin A has a low molecular weight dimer as the main product.

Example 2
The reaction was conducted in the same manner as in Example 1 except that 162 g of allyl etherified 2,3-xylenol obtained in Synthesis Example 3 was used as the allyl etherified phenol, and 165 g of a crystalline allyl etherified phenol resin B (yield: 102 mass). %).
The number average molecular weight of the obtained resin was 215, the weight average molecular weight was 226, the degree of dispersion was 1.05, and the dimer content was 93.3%.

Example 3
The reaction was carried out in the same manner as in Example 1 except that 210 g of the allyl etherified orthophenylphenol obtained in Synthesis Example 4 was used as the allyl etherified phenol, and 194 g of a liquid allyl etherified phenol resin C (yield 92% by mass) was obtained. Obtained.
The number average molecular weight of the obtained resin was 312, the weight average molecular weight was 333, the degree of dispersion was 1.07, and the dimer content was 86.3%.

Example 4
A liquid allyl etherified phenol resin D168 (yield 97% by mass) was reacted in the same manner as in Example 1 except that 174 g of allyl etherified 2-allylphenol obtained in Synthesis Example 5 was used as the allyl etherified phenol. Got.
The number average molecular weight of the obtained resin was 318, the weight average molecular weight was 365, the degree of dispersion was 1.15, and the dimer content was 81.9%.

Example 5
A reaction was carried out in the same manner as in Example 1 except that 0.3 g of p-toluenesulfonic acid was used as a catalyst to obtain 135 g (yield 91% by mass) of a liquid allyl etherified phenol resin.
The number average molecular weight of the obtained resin was 221, the weight average molecular weight was 246, the degree of dispersion was 1.11, and the dimer content was 87.5%.

Example 6
A flask equipped with a condenser and a stirrer was charged with 184 g of allyl etherified 1-naphthol obtained in Synthesis Example 6, 18 g of 85% paraform, 1 g of boric acid and 1 g of oxalic acid, and reacted at 80 ° C. for 20 hours. Subsequently, washing was performed 5 times with 100 g of pure water to remove boric acid and oxalic acid. Subsequently, the distillate was removed under reduced pressure at 80 ° C. and 50 mmHg to obtain 180 g of resin F (yield 98 mass%) mainly composed of a dimer of liquid allyl etherified phenols.
The number average molecular weight of the obtained resin was 200, the weight average molecular weight was 221, the degree of dispersion was 1.11 and the dimer content was 75.7%.

Example 7
A reaction was carried out in the same manner as in Example 6 except that 1 g of p-toluenesulfonic acid was used as a catalyst to obtain 190 g (yield 103 mass%) of a liquid allyl etherified phenol resin G.
The number average molecular weight of the obtained resin was 201, the weight average molecular weight was 226, the degree of dispersion was 1.12, and the dimer content was 75.3%.

Comparative Example 1
A reaction was carried out in the same manner as in Example 1 except that 134 g of the allyl etherified phenol obtained in Synthesis Example 2 was used as the allyl etherified phenol, to obtain a liquid allyl etherified phenol resin G93 g (yield 69% by mass). .
The number average molecular weight of the obtained resin was 351, the weight average molecular weight was 485, the degree of dispersion was 1.38, and the dimer content was 41.4%.
In FIG. 2, the gel permeation chromatography (GPC) chart of resin G is shown. It can be seen from FIG. 2 that resin G is not a main product of dimer.

INDUSTRIAL APPLICABILITY The present invention is industrially useful because it can efficiently synthesize an allyl etherified novolak type phenol resin mainly composed of a dimer of allyl etherified phenols, and has a low burden on the environment.
Furthermore, since phenol monomers are allyl etherified, unlike allyl etherification of phenol resins, allyl etherification in a process that does not use halogen, as well as distillation, recrystallization, column even when allyl halide and phenols are reacted. Since it can be easily purified by ordinary methods such as purification, it becomes a curing agent for epoxy resins and epoxy resins with a low halogen content that causes deterioration of electrical characteristics. Very useful for electronics industry applications.

Claims (8)

A method for producing an allyl etherified novolac type phenol resin, comprising reacting an allyl etherified phenol represented by the general formula (I) with an aldehyde in the presence of an acid catalyst.

(In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, a halogen, or a condensed ring together with R ₂ and a benzene ring of phenol. R ₂ and R _{3 each} independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, or a hydrogen element, provided that R ₂ represents R ₁ and the benzene ring of phenol may form a condensed ring.)   The manufacturing method of Claim 1 which mix | blends aldehydes in the ratio of 0.3-0.6 mol with respect to 1 mol of allyl etherified phenols represented with the said general formula (I). The allyl etherified phenol represented by the general formula (I) can be obtained by reacting an ortho-substituted phenol of the general formula (II) with an allyl halide in the presence of an alkali, or the general formula (II) The production method according to claim 1, which is obtained by reacting an ortho-substituted phenol of the above and allyl carboxylate in the presence of a transition metal.

(In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, a halogen, or a condensed ring together with R ₂ and a benzene ring of phenol. R ₂ and R _{3 each} independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group, or a hydrogen element, provided that R ₂ represents R ₁ and the benzene ring of phenol may form a condensed ring.)   The manufacturing method according to any one of claims 1 to 3, wherein the aldehyde is one or more selected from formaldehyde, paraformaldehyde, or trioxane. R ₁ is a bicyclic condensed ring formed with an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group, R ₂ and a benzene ring of phenol, and R ₂ and R ₃ Is independently an alkyl having 1 to 5 carbon atoms or a hydrogen atom, provided that R ₂ together with R ₁ and the benzene ring of phenol may form a condensed ring. The manufacturing method in any one of -4.   The compound represented by the general formula (I) is one or more selected from orthocresol, 2,3-xylenol, orthophenylphenol, 2-allylphenol and 1-naphthol. The manufacturing method in any one of -5.   An allyl etherified novolak-type phenol resin obtained by the production method according to claim 1.   The allyl etherified novolak type phenol resin is an allyl etherified novolak according to claim 7, wherein a dimer of allyl etherified phenols occupies 70% or more of a peak area obtained by gel permeation chromatography (GPC) analysis. Type phenolic resin.

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