JP2012251106A - Process for producing phenolic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a phenolic resin having a high weight average molecular weight with the use of two or more phenolic compounds while inhibiting gel formation.SOLUTION: The process for producing a phenolic resin includes allowing a phenolic compound component composed of at least two types of phenolic compounds having different reaction activities to react with a specific polymerization component, and the at least two types of the phenolic compounds are stepwise introduced into the reaction system one by one in order of lower reaction activity and simultaneously the polymerization component is introduced into the reaction system to react with the phenolic compound in such an amount that the molar ratio of the phenolic compound to be introduced to the polymerization component to be introduced is 1:1 to 2.5:1 in introducing each phenolic compound into the reaction system to thereby consecutively react the at least two phenolic compounds one by one.

Description

  The present invention relates to a method for producing a phenol resin.

  Phenol resins usually use phenols and aldehydes as catalysts for known organic acids and / or inorganic acids such as oxalic acid, paratoluenesulfonic acid, hydrochloric acid, and sulfuric acid, and at normal pressure and at reflux temperature. It is obtained by a method in which a time addition condensation reaction is performed, followed by dehydration and removal of unreacted monomers.

  On the other hand, in order to improve the performance of a phenol resin, a method of copolymerizing two types of phenol compounds when synthesizing a phenol resin has been reported. Patent Document 1 discloses biphenyl containing both a phenolic compound having one phenolic hydroxyl group in the molecule and a phenolic compound having two phenolic hydroxyl groups in the molecule in order to improve the flow performance when the phenol resin is used. A method for reducing the melt viscosity of the obtained phenolic resin by copolymerizing a diyl crosslinkable polymer unit and a methylene crosslinkable polymer unit and setting the ratio of the degree of polymerization of both to a specific range. is suggesting. As a method for synthesizing a copolymerized phenol resin, a raw material two-stage charging method is mentioned, but in the examples, only an addition example of a biphenyldiyl crosslinking group type polymer is disclosed as the second raw material. Furthermore, in the above-mentioned Patent Document 1, the total amount of phenolic compound used is at least 2.5 times the total amount of the mixed crosslinking group-type polymer. In the method described in Patent Document 1, the weight average molecular weight is Only a phenolic resin having an A of 1,000 or less can be obtained.

JP 2008-156553 A

  For example, it is required to stably produce a high molecular weight copolymer phenolic resin from two or more types of phenolic compounds in order to be suitably used as a surface protective film and an interlayer insulating film for semiconductor devices and light emitting devices. When producing a high molecular weight copolymerized phenolic resin, gel formation during the reaction becomes a problem. If a high molecular weight copolymerized phenolic resin can be synthesized while suppressing gel formation, it is possible to provide a copolymerized phenolic resin with excellent mechanical properties. We have found that this is possible. In view of the current situation, the problem to be solved by the present invention is that, when a phenol resin is synthesized using two or more types of phenol compounds, gel formation during the reaction can be easily suppressed, and a high weight average molecular weight can be obtained. It is providing the manufacturing method of a phenol resin which can obtain the phenol resin which has this.

  As a result of intensive studies to solve such problems and repeated experiments, the inventors of the present invention use two or more types of phenol compounds, and phenol compounds and aldehydes that are polymerization components for polymerizing with the phenol compounds. One selected from the group consisting of a compound, a ketone compound, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, a diene compound, and a compound having two haloalkyl groups in the molecule While controlling the molar ratio with the above compounds within a certain range and polymerizing the phenol compound used with the polymerization component step by step in order of low reaction activity, it prevents gelation during the reaction process. The present inventors have unexpectedly found that a phenol resin having a high weight average molecular weight can be produced, thereby completing the present invention. That is, the present invention is as follows.

[1] A phenol compound component comprising at least two types of phenol compounds having different reaction activities, an aldehyde compound, a ketone compound, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a diene A method for producing a phenol resin by reacting a compound and one or more polymerization components selected from the group consisting of compounds having two haloalkyl groups in the molecule, the following steps:
The at least two types of phenol compounds are introduced stepwise into the reaction system one by one in the order of the low reaction activity, and at each introduction, the molar ratio of the phenol compound to be introduced and the polymerization component to be introduced is 1: Introducing the polymerization component into the reaction system in an amount of 1 to 2.5: 1 and reacting with the phenol compound, thereby sequentially reacting the at least two types of phenol compounds with the polymerization component one by one;
Including
The method for producing a phenol resin, wherein the reaction activity is relatively defined between the phenol compounds based on an index that the lower the minimum reaction temperature for polymerization with the same polymerization component, the higher the reaction activity.
[2] The method for producing a phenol resin according to [1], wherein at least one of the at least two phenol compounds is pyrogallol, and the polymerization component is a compound having a biphenyldiyl skeleton.

  According to the present invention, it is possible to prevent gelation during synthesis when synthesizing a phenol resin using two or more kinds of phenol compounds, and the obtained phenol resin can have a high weight average molecular weight. . Therefore, according to the present invention, a copolymerized phenol resin having excellent mechanical properties can be obtained.

Hereinafter, a method for producing a phenol resin of the present invention (hereinafter, also simply referred to as “manufacturing method”) will be described in detail.
The present invention includes a phenol compound component composed of at least two types of phenol compounds having different reaction activities, an aldehyde compound, a ketone compound, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, A method for producing a phenol resin by reacting a diene compound and a polymerization component which is one or more compounds selected from the group consisting of compounds having two haloalkyl groups in the molecule, comprising the following steps: Two types of phenol compounds are introduced step by step into the reaction system one by one in the order of the low reaction activity, and at each introduction, the molar ratio of the phenol compound to be introduced and the polymerization component to be introduced is 1: 1 to 1. By introducing the polymerization component into the reaction system in an amount of 2.5: 1 and reacting with the phenol compound, Sequentially reacting at least two phenolic compounds one by one with the polymerization component, and the reaction activity is based on an index that the lower the minimum reaction temperature for polymerization with the same polymerization component, the higher the reaction activity. Provided is a method for producing a phenolic resin, which is relatively defined among phenolic compounds. In the present invention, one type of phenol compound is gradually introduced into the reaction system, and this is given in a predetermined amount (that is, an amount in which the molar ratio of the phenol compound to the polymerization component is 1: 1 to 2.5: 1). The process of reacting with the polymerization component introduced in step 1 is repeated. Thereby, in this invention, the molar ratio of the total number of moles (P) of the phenolic compound in a reaction system and the total number of moles (M) of a polymerization component is 1: 1-2.5: It can be in the range of 1.

<Phenol compound component>
The phenol compound component is composed of at least two types of phenol compounds having different reaction activities. In the present specification, the phenol compound means all compounds having a phenolic hydroxyl group. The reaction activity of the phenol compound defined in the present invention is relatively defined between the two or more types of phenol compounds based on an index that the lower the minimum reaction temperature for polymerization with the same polymerization component, the higher the reaction activity. Is done. The reaction activity is specifically determined by the following model experiment. That is, each reaction of each phenol compound and any identical polymerization component (specified in the present invention) is carried out under heating, and the reaction solution is analyzed by gel permeation chromatography (GPC). A phenol compound in which the disappearance of the polymerization component is confirmed at the heating temperature is determined as a phenol compound having a higher reaction activity. The reaction activity tends to increase as the electron density of the benzene ring of the phenol compound increases. Therefore, examples of combinations of two or more types of phenolic compounds having different reaction activities include combinations of compounds such as pyrogallol, phloroglucinol, and resorcinol with high electron density with compounds such as hydroxybenzoic acid and fluorophenol with low electron density. it can.

  Phenol compounds include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, nitrobenzylphenol, cyanobenzylphenol, adamantanephenol, xylenol, nitrophenol, fluorophenol, chlorophenol , Bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (hydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboximide , Trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, hydroxybenzoic acid Benzyl, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol, resorcinol, methylresorcinol, ethylresorcinol, hexylresorcinol, benzylresorcinol, Nitrobenzylresorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitri N- (dihydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (dihydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboximide, nitrocatechol, fluorocatechol, chloro Catechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, trihydroxy Methyl benzoate, ethyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetopheno , Trihydroxybenzophenone, trihydroxybenzonitrile and the like. From the viewpoint of solubility in an alkaline developer when a phenol resin is used as an alkali development type photosensitive composition, at least one of the at least two phenol compounds is preferably pyrogallol or phloroglucinol.

  Usually, from the viewpoint of the balance of physical properties of the obtained phenolic resin, it is preferable to use at least two types of phenolic compounds having different phenolic hydroxyl values, and in particular, a phenolic compound having a monovalent hydroxyl value and a phenol having a trivalent hydroxyl value. A combination with a compound is more preferred. Preferable examples of the phenol compound having a monovalent hydroxyl value include, for example, phenol, cresol, fluorophenol and the like. Moreover, as a preferable example of a phenolic compound whose hydroxyl value is trivalent, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, etc. are mentioned, for example, pyrogallol or phloroglucinol is particularly preferable.

<Polymerization component>
The polymerization component for polymerizing with the phenol compound component is an aldehyde compound, a ketone compound, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, a diene compound, and a haloalkyl group in the molecule. And one or more compounds selected from the group consisting of two compounds.

  Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornenecarboxyl Examples include aldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, and the like.

  Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, butynone, norbornanone, adamantanone, and bis (oxocyclohexyl) propane. Is mentioned.

  Compounds having two methylol groups in the molecule include bis (hydroxymethyl) urea, ribitol, arabitol, allitol, bis (hydroxymethyl) butyric acid, benzyloxypropanediol, dimethylpropanediol, diethylpropanediol, monoacetin, methyl Nitropropanediol, norbornene dimethanol, pentaerythritol, phenylpropanediol, trimethylolethane, trimethylolpropane, bis (hydroxymethyl) durene, nitroxylylene glycol, dihydroxydecane, dihydroxydodecane, bis (hydroxymethyl) cyclohexane, bis ( Hydroxymethyl) cyclohexene, bis (hydroxymethyl) adamantane, benzenedimethanol, benzenedimethanol, (Hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) naphthalene, bis (hydroxymethyl) anthracene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) diphenylthioether, bis (hydroxymethyl) benzophenone, Hydroxymethylphenyl hydroxymethylbenzoate, hydroxymethylanilide hydroxymethylbenzoate, bis (hydroxymethyl) phenylurea, bis (hydroxymethyl) phenylurethane, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (hydroxy Methylphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene Glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and the like. From the viewpoint of reactivity and mechanical properties of the obtained phenol resin, a compound having a benzene ring in the molecular skeleton is preferable, a compound having a biphenyldiyl skeleton is more preferable, and 4,4′-bis (hydroxymethyl) biphenyl is particularly preferable. .

  Examples of the compound having two alkoxymethyl groups in the molecule include bis (methoxymethyl) urea, bis (methoxymethyl) butyric acid, bis (methoxymethyl) norbornene, bis (methoxymethyl) cyclohexane, bis (methoxymethyl) cyclohexene, Bis (methoxymethyl) adamantane, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) naphthalene, bis (methoxymethyl) anthracene, bis (methoxymethyl) diphenyl ether, Bis (methoxymethyl) diphenylthioether, bis (methoxymethyl) benzophenone, methoxymethylphenyl methoxymethylbenzoate, methoxymethylanilide methoxymethylbenzoate, bis (meth Xymethyl) phenylurea, bis (methoxymethyl) phenylurethane, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, bis (methoxymethylphenyl) propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene Examples include glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether. The number of carbon atoms of the alkoxymethyl group is preferably 1 to 10 from the viewpoint of reaction activity. The number of carbon atoms is more preferably 1 to 2, and most preferably 1. From the viewpoint of reactivity and mechanical properties of the obtained phenol resin, those having a benzene ring in the molecular skeleton are preferred, compounds having a biphenyldiyl skeleton are more preferred, and 4,4′-bis (methoxymethyl) biphenyl is particularly preferred. It is.

  Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, decadiene, methylbutadiene, butanediol dimethacrylate, hexadieneol, methylcyclohexadiene, cyclopentadiene, cyclohexadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene. , Hydroxydicyclopentadiene, methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, norbornadiene, tetrahydroindene, ethylidene norbornene, vinyl norbornene, diallyl oxalate, diallyl glutarate, diallyl adipate, cyanuric acid Triallyl, diallyl cyanurate, diallylpropyl cyanurate, Null triallyl isocyanuric acid, diallyl propyl etc. isocyanuric acid.

  Examples of the compound having two haloalkyl groups in the molecule include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, and bischloromethyl-biphenyldicarboxylic acid. Bischloromethyl-methylbiphenyl, bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis (chloroethyl) ether, diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, tetraethylene glycol bis (chloroethyl) ) Ether and the like.

  Particularly preferable examples are at least from the viewpoint of reactivity and mechanical properties of the obtained phenolic resin, and from the viewpoint of solubility in an alkaline developer when the phenolic resin is used as an alkali development type photosensitive composition. At least one of the two phenol compounds is pyrogallol or phloroglucinol, and the polymerization component has a biphenyldiyl skeleton as a compound having two alkoxymethyl groups having 1 to 10 carbon atoms in the molecule. The combination which is a compound is mentioned. Among them, it is particularly preferable that at least one of at least two phenol compounds is pyrogallol and the polymerization component is a compound having a biphenyldiyl skeleton.

  In the present invention, the same number of raw material preparations as the number of types of phenolic compounds to be used is adopted, and at least two types of phenolic compounds are introduced step by step into the reaction system one by one in order of decreasing reaction activity. At this time, the polymerization component is introduced into the reaction system in an amount such that the molar ratio of the phenol compound to be introduced and the polymerization component to be introduced is 1: 1 to 2.5: 1, and reacted with the phenol compound. The polymerization component may be introduced into the reaction system in the form of a mixture with one type of phenol compound, or one type of phenol compound and the polymerization component may be separately introduced into the reaction system. In this manner, at least two types of phenol compounds are sequentially reacted with the polymerization component one by one. Here, the reaction at each stage is mainly intended to cause the phenol compound to react substantially one by one, but for example, it hinders the possibility that the unreacted phenol compound derived from the previous process reacts in the subsequent process. is not. When producing a phenol resin by reacting two or more types of phenolic compounds with a polymerization component (a compound having two alkoxymethyl groups or methylol groups having 1 to 10 carbon atoms in the molecule), the above stepwise process By adopting the procedure, the molar ratio of the total number of moles of the phenolic compound to the total number of moles of the polymerization components is kept in the range of 1: 1 to 2.5: 1 in the reaction system throughout the reaction. Can do. Therefore, according to the present invention, gelation during the synthesis of the phenol resin can be prevented, and the obtained phenol resin can have a high weight average molecular weight.

For example, when the phenol compound component used in the present invention comprises two types of phenol compounds, the reaction can be carried out in the order of the following steps (i) and (ii).
(I) Of the two types of phenol compounds, a phenol compound having a lower reaction activity and a polymerization component (a compound having two alkoxymethyl groups or methylol groups having 1 to 10 carbon atoms in the molecule) for the polymerization component After mixing so that the molar ratio of the phenol compound is 1 to 2.5, the mixture is introduced into the reaction system, and the phenol compound and the polymerization component are reacted.
(Ii) After the step (i), among the phenol compounds, a phenol compound having a higher reaction activity and a polymerization component (a compound having two alkoxymethyl groups or methylol groups having 1 to 10 carbon atoms in the molecule) Are mixed so that the molar ratio of the phenol compound to the polymerization component is 1 to 2.5, and then introduced into the reaction system to react the phenol compound and the polymerization component.

  By synthesizing a copolymerized phenol resin by the reaction in the order of the step (i) and the step (ii), a polymerization component (alkoxymethyl having 1 to 10 carbon atoms) present in the reaction system throughout the entire reaction. The amount of the phenol compound is 1 time mole or more relative to the amount of the compound having two groups or methylol groups in the molecule). Therefore, it is possible to prevent the occurrence of gelation due to the reaction between an excessive alkoxymethyl group or methylol group and a phenolic hydroxyl group.

  In the reaction at each stage of the present invention, the amount of the phenol compound used is 1 to 2.5 times the mole, preferably 1.1 to 2 times the total moles of the polymerization components. It is 3 times mol or less, Most preferably, it is 1.2 times mol or more and 2.0 times mol or less. If the amount of the phenolic compound used is at least 1 mol per mol of the total number of moles of polymerization components, gelation due to the reaction between excess alkoxymethyl group or methylol group and phenolic hydroxyl group can be prevented, If it is 2.5 times mol or less, a high weight average molecular weight phenol resin can be obtained.

  The reaction between the phenol compound component and the polymerization component is usually performed in the presence of a catalyst. The catalyst is not particularly limited, but an acid catalyst is preferable. Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, oxalic acid and diethyl sulfate, Lewis such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. Acid, and the like. These can be used alone or in combination of two or more. The amount of the catalyst used is preferably in the range of 0.01 to 2 moles per mole of the polymerization components. More preferably, it is the range of 0.02-1 times mole.

  The reaction between the phenol compound component and the polymerization component can be performed in an organic solvent as necessary. Specific examples of organic solvents that can be used include diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl cellosolve, ethyl cellosolve, toluene, xylene, γ-butyrolactone, and N-methyl-2-pyrrolidone. However, it is not limited to these. The amount of the organic solvent used is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass with respect to 100 parts by mass of the total mass of the charged raw materials. The reaction temperature in each stage of the present invention is usually from 40 to 250 ° C, more preferably from 100 to 200 ° C. In the present invention, phenol compounds are sequentially reacted in ascending order of reaction activity. Therefore, the reaction temperature may be changed throughout the reaction process, for example, the reaction temperature is lowered stepwise for each phenol compound to be reacted. Further, at the time of introducing the phenol compound at each stage, the temperature of the reaction system may be once lowered (for example, to room temperature) and then the reaction system may be heated again to a desired reaction temperature. The reaction time is usually 1 to 10 hours.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

In the following examples, two types of gel permeation chromatography (GPC) having different column configurations are used as follows.
GPC-1:
Column: Two Shodex KF-801 and one KF-802 in series Mobile phase: THF
GPC-2:
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l EtBr / NMP
GPC-1 and 2 common:
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Flow rate: 1 ml / min.
Moreover, when measuring the average molecular weight of a polymer by GPC-2, it calculated in conversion of standard polystyrene (The organic solvent type | system | group standard sample STANDARD SM-105 by Showa Denko KK).

<Reaction activity evaluation of phenolic compounds>
The reaction activity was evaluated by the following model experiment.
[Reaction activity of m-cresol]
While purging with nitrogen, m-cresol 9.73 g (hereinafter also referred to as “mC”) (0.09 mol), 4,4′-bis (in a separable flask with 0.5 L Dean-Stark apparatus) Methoxymethyl) biphenyl (hereinafter also referred to as “BPDM”) 10.90 g (0.045 mol), diethyl sulfate (hereinafter also referred to as “DES”) 1.05 g (0.00675 mol), diethylene glycol dimethyl ether (hereinafter “DMDG”) 30 g) was mixed and stirred at 50 ° C. to dissolve the solid matter.

  While stirring the mixed solution for 1 hour at an oil bath temperature of 80 ° C. and analyzing the reaction solution by GPC-1, the polymerization component BPDM did not disappear, so the temperature was raised to an oil bath temperature of 90 ° C., The reaction was further stirred for 1 hour, and disappearance of BPDM could not be confirmed. The above operation was repeated to increase the oil bath temperature setting by 10 ° C., and the reaction was performed for 1 hour at each temperature. After heating at an oil bath temperature of 140 ° C. for 30 minutes, disappearance of BPDM was confirmed.

[Reaction activity of 2-fluorophenol]
The reaction was performed in the same manner as in the mC reaction activity confirmation experiment, except that 10.09 g of 2-fluorophenol (hereinafter also referred to as “2FP”) (0.09 mol) was used instead of mC in the mC reaction activity confirmation experiment. Went. The disappearance of BPDM was confirmed after heating at an oil bath temperature of 140 ° C. for 30 minutes.

[Reactivity of pyrogallol]
The reaction was performed in the same manner as in the mC reaction activity confirmation experiment, except that 11.35 g of pyrogallol (hereinafter also referred to as “PyG”) (0.09 mol) was used instead of mC in the mC reaction activity confirmation experiment. . The disappearance of BPDM was confirmed after heating at an oil bath temperature of 110 ° C. for 35 minutes.

The relationship of the reaction activity of the phenol compound, which is derived from the above results on the reaction activity of each phenol compound and BPDM, is as follows:
PyG> mC = 2FP

<Example 1>
While purging with nitrogen, mC 9.73 g (0.09 mol), BPDM 10.90 g (0.045 mol), DES 1.05 g (0.00675 mol), DMDG 30 g in a separable flask with 0.5 L Dean-Stark apparatus Were mixed and stirred at 50 ° C. to dissolve the solid matter.

  The mixed solution was heated to 140 ° C. with an oil bath and reacted for 1 hour, and then generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 140 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, 26.48 g (0.21 mol) of PyG, 32.71 g (0.135 mol) of BPDM, 50 g of DMDG, and 0.35 g (0.00225 mol) of DES were added to the reaction solution, and the reaction solution was added again. The mixture was heated to 120 ° C. with an oil bath and further stirred for 1.5 hours.

  Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added to the reaction vessel and stirred to dilute. The reaction diluted solution was dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, and this was recovered, appropriately washed with water and dehydrated, followed by vacuum drying to obtain a phenol resin in a yield of 78%. The obtained phenol resin was not gelled, and the weight average molecular weight by GPC-2 was 22,698 in terms of polystyrene.

<Example 2>
While purging with nitrogen, mC 16.55 g (0.15 mol), BPDM 18.17 g (0.075 mol), DES 1.15 g (0.0075 mol), DMDG 40 g in a separable flask with 0.5 L Dean-Stark apparatus Were mixed and stirred at 50 ° C. to dissolve the solid matter. Similar to Synthesis Example 1, the reaction solution was reacted at 140 ° C. for 4 hours, and then PyG 18.92 g (0.15 mol), BPDM 30.29 g (0.125 mol), DMDG 43.6 g, DES 0.39 g (0. 0025 mol) was added, and the reaction solution was heated again to 120 ° C. with an oil bath, and further stirred and reacted for 1.5 hours.

  Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added to the reaction vessel and stirred to dilute. The reaction diluted solution was dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, and this was recovered, appropriately washed with water and dehydrated, followed by vacuum drying to obtain a phenol resin in a yield of 76%. The obtained phenol resin was not gelled, and the weight average molecular weight by GPC-2 was 18,800 in terms of polystyrene.

<Example 3>
Synthesis was performed in the same manner as in Example 2 except that 2FP 16.82 g (0.15 mol) was used instead of m-cresol in Example 2, and a phenol resin was obtained in a yield of 73%. The obtained phenol resin was not gelled, and the weight average molecular weight by GPC-2 was 16,253 in terms of polystyrene.

<Comparative Example 1>
Instead of the raw material two-stage charging method in which mC and BPDM are first condensed and polymerized in Example 1 and then charged with PyG and BPDM are added, all the raw materials are charged all at once, and then an oil bath is added to 140 Heating was started at a temperature set to ° C. When the oil bath reached 133 ° C., generation of methanol was confirmed. When the heating was further continued for 10 minutes, the reaction system gelled at once.

<Comparative example 2>
Instead of the raw material two-stage charging method in which 2FP and BPDM are first condensation polymerized in Example 3 and PyG and BPDM are added, all the raw materials are charged in a lump, and then the oil bath is added to 140 Heating was started at a temperature set to ° C. When the oil bath reached 140 ° C., generation of methanol was confirmed. When heating was continued for another 16 minutes, the reaction system gelled at once.

<Comparative Example 3>
The reaction was carried out in the order of PyG and mC instead of the order of mC and PyG in Example 2. First, 18.92 g (0.15 mol) of PyG, 30.29 g (0.125 mol) of BPDM, 43.6 g of DMDG, and 0.39 g (0.0025 mol) of DES were heated to 120 ° C. with an oil bath and stirred for 1.5 hours. After cooling the reaction solution to room temperature, mC 16.55 g (0.15 mol), BPDM 18.17 g (0.075 mol), DES 1.15 g (0.0075 mol), DMDG 40 g were added, and the oil bath was heated to 140 ° C. I started. When the oil bath temperature reached 130 ° C., the viscosity of the reaction system suddenly increased and gelled in 2 minutes.

The results of Examples 1 to 3 and Comparative Examples 1 to 3 are summarized in Table 1. In addition, about the reaction activity of the phenolic compound in a table | surface, it is as having been confirmed by the said model experiment, and is represented as follows.
PyG> mC = 2FP

  In the above table, the P / M molar ratio is the ratio of the total number of moles of phenolic compounds used in the synthesis to the total number of moles of BPDM used in the synthesis.

  From Table 1 above, in Examples 1 to 3, the molar ratio of the phenolic compound to the polymerization component in each stage charge amount was in the range of 1 to 2.5, so the total moles of phenolic compound throughout the entire reaction process. The ratio of the number of BPDM to the total number of moles of BPDM is in the range of 1 to 2.5, and the phenol compound having a low reaction activity with BPDM was reacted with BPDM first, so that no gelation occurred during the reaction, and A high weight average molecular weight phenolic resin was obtained. On the other hand, in Comparative Examples 1 and 2, two types of phenolic compounds having different reaction activities and BPDM were charged together. Further, in Comparative Example 3, a split preparation method of two types of phenol compounds was adopted, but a phenol compound having a high reaction activity was reacted with BPDM first. Therefore, in any of Comparative Examples 1 to 3, gelation occurred during the reaction.

  The phenol resin obtained by the production method of the present invention is a photosensitive resin composition for forming a surface protective film of a semiconductor device and a light emitting device, a protective film for a flip chip device, a protective film of a device having a bump structure, and the like. Moreover, as an interlayer insulating film, it can be suitably used for a photosensitive resin composition for forming a rewiring insulating film, an interlayer insulating film of a multilayer circuit, and the like.

Claims (2)

A phenol compound component comprising at least two types of phenol compounds having different reaction activities, an aldehyde compound, a ketone compound, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, a diene compound, and A method for producing a phenol resin by reacting with one or more polymerization components selected from the group consisting of compounds having two haloalkyl groups in the molecule, comprising the following steps:
The at least two types of phenol compounds are introduced stepwise into the reaction system one by one in the order of the low reaction activity, and at each introduction, the molar ratio of the phenol compound to be introduced and the polymerization component to be introduced is 1: Introducing the polymerization component into the reaction system in an amount of 1 to 2.5: 1 and reacting with the phenol compound, thereby sequentially reacting the at least two types of phenol compounds with the polymerization component one by one;
Including
The method for producing a phenol resin, wherein the reaction activity is relatively defined between the phenol compounds based on an index that the lower the minimum reaction temperature for polymerization with the same polymerization component, the higher the reaction activity.   The method for producing a phenol resin according to claim 1, wherein at least one of the at least two phenolic compounds is pyrogallol and the polymerization component is a compound having a biphenyldiyl skeleton.