Novolak-type phenol resin and method for producing the same

Abstract

A method for producing a novolac phenolic resin according to one embodiment of the present invention includes the steps of preparing a mixed solution by adding 4,4'-bis(chloromethyl)-1,1-biphenyl and a phenolic compound in the absence of an acid catalyst, reacting the mixed solution at 40 to 180°C for 1 to 10 hours, and evaporating and removing the reaction solvent and residual substances to solidify the reaction product.

Description

Technical Field

[0001] The present invention relates to a novolac-type phenolic resin and a method for producing the same, and more particularly, to a novolac-type phenolic resin that suppresses the reaction of by-products such as ether-based or alkyl halides and minimizes the disappearance of hydroxyl groups during the reaction process, and a method for producing the same.

Background Art

[0002] Novolac-type phenolic resin (Phenolic Novolac Resin) is widely used in adhesives, molding materials, paints, photoresist materials, epoxy resin raw materials, etc. due to its excellent heat resistance and moisture resistance.

[0003] In particular, as a curing agent for epoxy resins and the like, it is widely used in the electrical and electronic fields such as semiconductor encapsulants and insulating materials for printed wiring boards.

[0004] Conventional novolac-type phenolic resins have been synthesized by adding 4,4'-bis(chloromethyl)-1,1-biphenyl and phenol to an organic solvent or an alcohol-based solvent and then reacting them in the presence of an acid catalyst.

[0005] However, when an organic solvent is used in the reaction process, there is a problem that a side reaction occurs in which an ether-based by-product is generated, and the hydroxyl g-equivalent (the reciprocal of the number of OH per unit g) value appears high.

[0006] When the hydroxyl g-equivalent (hydroxyl equivalent weight) increases, it means that the number of hydroxyl groups per unit molecule decreases. In this case, the part that can be epoxidized decreases, and as a result, after the product is cured, due to the decrease in the crosslink density of the polymer, there is a problem that the physicochemical properties of the product may deteriorate.

[0007] Also, when using alcohol solvents such as methanol, ethanol, and isopropyl alcohol, alkyl halides are produced by the reaction of an acid catalyst and alcohol, and the alkyl halides react with the reactant phenol to form various by-products such as alkylphenols. The formation of by-products not only reduces the yield of the final product but also causes further problems in the process of recovering and reusing the reactant phenol.

[0008] Therefore, there has emerged a need for a new manufacturing method capable of producing novolak-type phenol resins of excellent quality while suppressing side reactions that form various forms of by-products.

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present invention has been devised to solve the above problems, and an object of the present invention is to provide a high-quality novolak-type phenol resin produced by suppressing side reactions that cause by-products and a manufacturing method thereof.

[0010] The problems of the present invention are not limited to the above problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

Means for Solving the Problems

[0011] A method for producing a novolak-type phenol resin according to an embodiment of the present invention for achieving the above object includes a step of adding 4,4'-bis(chloromethyl)-1,1-biphenyl and a phenolic compound to water as a reaction solvent in the absence of an acid catalyst to produce a mixed solution, a step of reacting the mixed solution at 40 to 180 °C for 1 to 10 hours, and a step of evaporating and removing the reaction solvent and the residual substances to solidify the reactants.

[0012] According to one embodiment of the present invention, it may further include a step of discharging all or part of the hydrogen chloride generated in the reaction process in a state where it is dissolved in water which is the reaction solvent.

[0013] According to one embodiment of the present invention, the step of manufacturing the mixed solution may include a step of adding 10 wt% to 500 wt% of water based on the weight of the 4,4'-bis(chloromethyl)-1,1-biphenyl.

[0014] According to one embodiment of the present invention, it may further include a step of adding 1.5 to 5 mol-equivalent of a phenolic compound to the 4,4'-bis(chloromethyl)-1,1-biphenyl.

[0015] According to one embodiment of the present invention, the novolak-type phenolic resin is represented by the following chemical formula (I). JPEG0007693803000001.jpg37170

[0016] The novolak-type phenolic resin composition according to still another embodiment of the present invention contains a compound represented by the following chemical formula (I) having a hydroxyl equivalent of 200 to 235 g / eq and a softening point of 86 to 92°C. JPEG0007693803000002.jpg37170

[0017] According to one embodiment of the present invention, the content of the compound represented by the following chemical formula (II) or the compound represented by the chemical formula (III) may be less than 0.5 wt% based on the weight of the novolak-type phenolic resin composition. JPEG0007693803000003.jpg29170JPEG0007693803000004.jpg37170

[0018] According to one embodiment of the present invention, it may not contain the compound represented by the chemical formula (II) or the compound represented by the chemical formula (III).

Advantages of the Invention

[0019] According to the above novolak-type phenol resin and its manufacturing method, it is possible to achieve the effect of suppressing the generation of by-products such as ether-based or alkylphenols and manufacturing a high-purity novolak-type phenol resin.

[0020] Also, it is possible to achieve the effect of manufacturing a novolak-type phenol resin in which the g-equivalent of hydroxyl groups matches the target level.

[0021] The effects of the present invention are not limited to the above effects, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

Embodiments for Carrying Out the Invention

[0022] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. However, it will be easily understood by those having ordinary knowledge in this technical field that the attached drawings are only described to more easily disclose the content of the present invention, and the scope of the present invention is not limited to the scope of the attached drawings.

[0023] And when describing the embodiments of the present invention, only the same names and the same reference numerals are used for components having the same functions, and it is clarified in advance that they are not completely the same as the components of the prior art in essence.

[0024] Furthermore, the terms used in the present application are only used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. Terms such as "including" or "having" in the present application are intended to indicate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and it should be understood that the presence or addition possibility of one or more other features, numbers, steps, operations, components, parts, or combinations thereof is not precluded in advance.

[0025] The compound represented by Chemical Formula 1 can be obtained by subjecting 4,4'-bis(chloromethyl)-1,1-biphenyl and a phenolic compound to a condensation reaction.

Chemical formula

[0026] Here, the phenolic compound can be any one of phenol, o-cresol, m-cresol, p-cresol, catechol, hydroquinone, resorcinol, pyrogallol, and α-naphthol. Desirably, the phenolic compound is phenol.

[0027] When phenol is used as the phenolic compound, the amount of phenol used is 1.5 to 5 mol-equivalents based on 4,4'-bis(chloromethyl)-1,1-biphenyl. Desirably, 2 to 4.5 mol-equivalents are used.

[0028] On the other hand, water is used as the reaction solvent in the production method according to one embodiment of the present invention. Specifically, water as the reaction solvent is added to the reactor simultaneously with 4,4'-bis(chloromethyl)-1,1-biphenyl and the phenolic compound or sequentially added.

[0029] Water as the reaction solvent is used in an amount of 10 wt% to 300 wt%, desirably 30 wt% to 200 wt%, more desirably 50 wt% to 100 wt% based on the weight of 4,4'-bis(chloromethyl)-1,1-biphenyl.

[0030] When water is used as the reaction solvent, the effect of suppressing the formation of by-products of ether-based, alkyl halide compounds, or dialkyl ether compounds without the disappearance of hydroxyl groups and increasing the product yield can be achieved.

[0031] Moreover, even without a large-capacity scrubber device for collecting gaseous HCl that is inevitably generated during the reaction process, it is possible to achieve the effect of dissolving all or part of the HCl in water, which is the reaction solvent, and discharging it.

[0032] In addition, since it becomes possible to suppress the reaction of the phenolic compound added as a reactant with other compounds during the reaction process, the effect of facilitating the recovery and reuse of the phenolic compound can be achieved.

[0033] After charging the above-mentioned reactants and reaction solvent into the reactor, the reaction temperature is set to 40 - 180°C under normal pressure conditions. Desirably, the reaction temperature is 90 - 110°C. Also, the reaction time is 1 - 10 hours.

[0034] When the temperature inside the reactor reaches 90 - 110°C under the above conditions, hydrogen chloride gas is generated. The hydrogen chloride gas can be dissolved in water, which is the reaction solvent, and discharged to the outside.

[0035] After the reaction is completed, an organic solvent is added to the reactor to extract the organic matter. As the organic solvent for extracting the organic matter, methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, etc. can be used. Desirably, toluene is used.

[0036] Furthermore, water, which is the reaction solvent, and phenol, etc. are removed by evaporation using a fractionating column, and various foreign substances are removed by filtration. After all the distillation is completed, the product is cooled and solidified.

[0037] The hydroxyl equivalent (the reciprocal of the number of OH per gram) of the novolak-type phenol resin represented by Chemical Formula 1 obtained by the above process is 200 - 235 g / eq. Desirably, it is 225 - 235 g / eq.

[0038] The method for measuring the hydroxyl equivalent is as follows. Potentiometer: Metrohm 888titrando Electrode: Metrohm 6.0229.100 Solvotrode

[0039] First, 7.8 ml of acetic anhydride and 35 ml of pyridine were mixed to prepare a solution. 5 ml of the mixed solution was mixed with 1 g of the sample and reacted at 160 °C for 1 hour. Next, after adding 1 - 1.5 ml of distilled water, the reaction was further carried out for more than 15 minutes and then cooled.

[0040] Next, THF and acetone were added for dilution, and potentiometric titration was performed on the sample solution and the Blank using 0.5N - KOH(EtOH) solution respectively.

[0041] The measured values of the Blank and the sample solution were substituted into the following formula to calculate the hydroxyl equivalent. 28.05×(B - V)×F / sample amount [g] = OH value [KOH mg / g]

[0042] Here, B is the measured value of the Blank solution, and V is the measured value of the sample solution.

[0043] Hydroxyl equivalent [g / eq] = 26110 / OH value [KOH mg / g]

[0044] On the other hand, the softening point of the novolak - type phenol resin represented by Chemical Formula 1 is 86 - 92 °C.

[0045] The softening point was measured using the model name DP70 of Mettler Toledo. First, the sample to be measured was melted at 140 °C - 160 °C, then filled into the cup provided in the measuring device and the surface was flattened. The upper part of the cup was covered with a cover, and the lower part was fixed to the carrier by inserting a glass tube. After that, the measurement was started with the carrier placed in the measuring device.

[0046] After putting the sample into the measuring device, the initial temperature was set to 60 °C and maintained for 10 seconds, then heated at a rate of 2 °C / min. The temperature when the sample in the cup softened, flowed down and reached the final point by gravity was determined as the softening point.

[0047] In addition, the content of the compound represented by Chemical Formula 2 or Chemical Formula 3 contained in the novolak-type phenol resin composition synthesized by the above process is less than 0.5 wt% based on the weight of the entire novolak-type phenol resin composition. Desirably, it is less than 0.3 wt%. More desirably, the novolak-type phenol resin composition substantially does not contain the compound represented by the following Chemical Formula 2 or Chemical Formula 3.

Chemical Formula

Chemical Formula

[0048] The content of the by-products represented by Chemical Formula 2 and Chemical Formula 3 was measured by GPC (Gel Permeation Chromatograph) analysis.

[0049] Column: Shoedex KF-801, 802, 803 Detector: water 2414RI Pump: water 1515 Autosampler: water 2707 Mobile phase: THF (GPC grade) 1 ml / min The mobile phase THF (GPC grade) was set to 1 ml / min. After starting the operation of GPC, THF was sufficiently flowed to stabilize it. Next, 0.05 g of the sample was dissolved in THF to prepare a sample solution.

[0050] 50 μl each of Blank THF and the sample solution were injected for analysis. After integrating so that the baseline became horizontal for all peaks, it was vertically divided based on the valley of each peak. The common peaks were excluded by comparing with the Blank in the measured sample analysis results, and the Area% of each peak was filled in.

[0051] Hereinafter, the present invention will be described more specifically, but the present invention is not limited to the following examples.

[0052] [Example 1] Based on 4,4'-bis(chloromethyl)-1,1-biphenyl, 2.3 molar equivalents of phenol were charged into the reactor. As the reaction solvent, water was used. Water was used at 50 wt% based on 4,4'-bis(chloromethyl)-1,1-biphenyl.

[0053] Next, after raising the temperature of the reactor to 80 - 110°C, the hydrochloric acid gas generated as the reaction proceeded was discharged outside the reactor and collected in water or a sodium hydroxide solution.

[0054] After continuing the reaction for 3 hours and when the reaction was completed, toluene, an organic solvent, was added to remove the acidic wastewater by oil-water layer separation. Then, water as the reaction solvent, hydrochloric acid as a by-product, toluene as the extraction solvent, and residual phenol were removed by distillation. After the distillation was completed, the final product was cooled to obtain a novolak-type phenol resin composition containing the compound represented by Chemical Formula 1.

[0055] The compounds represented by Chemical Formula 2 or Chemical Formula 3 contained in the novolak-type phenol resin composition obtained by the above process were not detected.

[0056] Also, the hydroxyl equivalent of the novolak-type phenol resin represented by Chemical Formula 1 was measured to be 227 g / eq, and the softening point was 91.6°C.

[0057] [Example 2] Based on 4,4'-bis(chloromethyl)-1,1-biphenyl, 2.5 molar equivalents of phenol were charged into the reactor. As the reaction solvent, water was used. Water was used at 100 wt% based on 4,4'-bis(chloromethyl)-1,1-biphenyl.

[0058] Next, after raising the temperature of the reactor to 80 - 110 °C, hydrochloric acid gas generated as the reaction proceeded was discharged outside the reactor and collected in water or a sodium hydroxide solution.

[0059] After continuing the reaction for 3 hours and when the reaction was completed, toluene, an organic solvent, was added to remove the acidic wastewater by oil - water layer separation. Then, water as the reaction solvent, hydrochloric acid as a by - product, toluene as the extraction solvent, and residual phenol were removed by distillation. After the distillation was completed, the final product was cooled to obtain a novolak - type phenol resin composition containing the compound represented by Chemical Formula 1.

[0060] It was confirmed that the compound represented by Chemical Formula 2 or Chemical Formula 3 contained in the novolak - type phenol resin composition obtained by the above process was 0.06 wt%.

[0061] Also, the hydroxyl equivalent of the novolak - type phenol resin was measured to be 227 g / eq, and the softening point was 89.1 °C.

[0062] [Comparative Example 1] 2.1 molar - equivalents of phenol based on 4,4’ - bis(chloromethyl)-1,1 - biphenyl and hydrochloric acid diluted to a concentration of 35% were charged into the reactor. Toluene was used as the reaction solvent. Water was used at 100 wt% based on 4,4’ - bis(chloromethyl)-1,1 - biphenyl, and hydrochloric acid was used at 0.8 wt%.

[0063] Next, the temperature of the reactor was raised to 110 - 115 °C to reflux toluene, and hydrochloric acid gas generated as the reaction proceeded was discharged outside the reactor and collected in water or a sodium hydroxide solution.

[0064] After continuing the reaction for 8 hours and when the reaction was completed, toluene as the reaction solvent, the catalyst, hydrochloric acid as a by - product, and residual phenol were removed by distillation. After the distillation was completed, the final product was cooled to obtain a novolak - type phenol resin composition represented by Chemical Formula 1.

[0065] It was confirmed that the compound represented by Chemical Formula 2 or Chemical Formula 3 contained in the novolak-type phenol resin composition obtained by the above process was 4.55 wt%.

[0066] Also, the hydroxyl equivalent of the novolak-type phenol resin represented by Chemical Formula 1 was measured to be 244 g / eq, and the softening point was 85.9 °C.

[0067] As described above, although the preferred embodiments according to the present invention have been described, in addition to the above-described embodiments, it is obvious to those having ordinary knowledge in the art that the present invention can be embodied in other specific forms without departing from its spirit and scope. Therefore, the above embodiments should not be construed as restrictive, but should be regarded as exemplary, whereby the present invention is not limited to the above description, and can also be modified within the scope of the appended claims and their equivalents.

Claims

1. A step of adding 4,4'-bis(chloromethyl)-1,1-biphenyl and a phenolic compound to water as a reaction solvent in the absence of an acid catalyst to produce a mixed solution; A step of reacting the mixed solution at 40 to 180 °C for 1 to 10 hours; A step of discharging all or part of the hydrogen chloride generated during the reaction in a state dissolved in water as the reaction solvent; A step of evaporating and removing the reaction solvent and the residual substances and solidifying the reaction product; A method for producing a novolak-type phenolic resin comprising the above steps.

2. The step of producing the mixed solution is: The method for producing a novolak-type phenolic resin according to claim 1, wherein the method is to add the phenolic resin to water as the reaction solvent in an amount of 10 wt% to 500 wt% based on the weight of 4,4'-bis(chloromethyl)-1,1-biphenyl.

3. The step of producing the mixed solution is: The method for producing a novolak-type phenolic resin according to claim 2, wherein 1.5 to 5 mol-equivalents of the phenolic compound are added to 4,4'-bis(chloromethyl)-1,1-biphenyl.

4. The novolak-type phenolic resin is the novolak-type phenolic resin according to any one of claims 1 to 3, which is represented by the following chemical formula (I). [In the formula, n is an integer of 0 or 1 or more]

5. The novolak-type phenolic resin represented by the following chemical formula (I) has a hydroxyl equivalent of 200 to 235 g / eq and a softening point of 86 to 92 °C. The method for producing a novolak-type phenolic resin according to claim 4. [In the formula, n is an integer of 0 or 1 or more]

6. The manufacturing method of the novolak type phenol resin according to any one of claims 1 to 5, wherein the content of the compound represented by the following chemical formula (II) or the compound represented by chemical formula (III) in the novolak type phenol resin is less than 0.5 wt% based on the weight of the novolak type phenol resin.

7. The manufacturing method of the novolak type phenol resin according to claim 6, wherein the novolak type phenol resin does not contain the compound represented by the chemical formula (II) or the compound represented by the chemical formula (III).

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