Modified naphthol resin and method for producing the same

Abstract

To provide a method for producing a modified naphthol resin having a comparatively high hydrogenation rate, and a modified naphthol resin.SOLUTION: A method for producing a modified naphthol resin includes the following steps. In order to form a modified naphthol resin having an amino group in a structure, a nitration reaction and a hydrogenation reaction are performed on the naphthol resin in order. A solvent used in the hydrogenation reaction includes tetrahydrofuran, toluene, isopropanol, an amide solvent or a cosolvent of them.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a resin and a method for producing the same, and more particularly to a modified naphthol resin and a method for producing the same. [Background technology]

[0002] In the field of electronic products or their manufacturing methods, there is often a demand for resin materials such as insulating materials, adhesives, and film raw materials. At present, epoxy resin or polyphenylene ether (PPE) resin is widely used. However, epoxy resin or polyphenylene ether has poor dielectric properties or heat resistance, which may bring about corresponding limitations in the application of electronic products. Summary of the Invention [Problem to be solved by the invention]

[0003] Therefore, the present invention provides a modified naphthol resin and a method for producing the same. The method for producing the modified naphthol resin in the present invention has a relatively high hydrogenation rate.

[0004] In one embodiment, the present invention provides a method for preparing a modified naphthol resin, comprising: sequentially carrying out a nitration reaction and a hydrogenation reaction on the naphthol resin to form a modified naphthol resin having an amino group in its structure; the solvent used in the hydrogenation reaction comprises tetrahydrofuran, toluene, isopropanol, an amide solvent, or a co-solvent as mentioned above.

[0005] In one embodiment, the present invention provides a modified naphthol resin produced by the above-mentioned method for producing a modified naphthol resin. The modified naphthol resin has a structure represented by the formula (4) described below. Effect of the Invention

[0006] Based on the above, since the solvent used in the hydrogenation reaction includes tetrahydrofuran, toluene, isopropanol, amide solvent, or the above co-solvent, the preparation method of the modified naphthol resin can have a relatively high hydrogenation rate. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a flow diagram of a method for producing a modified naphthol resin according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In the following detailed description, exemplary embodiments disclosing specific details are set forth for purposes of explanation and not limitation in order to provide a thorough understanding of the various principles of the present invention. However, it will be apparent to one of ordinary skill in the art having the benefit of the present invention that the present invention may be practiced in other embodiments that depart from the specific details described herein. In addition, descriptions of well-known devices, methods and materials may be omitted so as not to obscure the description of the various principles of the present invention.

[0009] A range may be expressed herein as from "about" one particular value to "about" another particular value, or may be linearly expressed as one particular value and / or another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when a value is expressed as an approximation, by using "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are expressly related to, or independent of, the other endpoint.

[0010] As used herein, non-limiting terms (eg, may, can, or other similar terms) refer to non-required or optional implementations, inclusions, additions, or presence.

[0011] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as the meaning in the common knowledge or commonly understood meaning in the technical field to which the present invention belongs. It should be understood that terms (such as terms defined in commonly used dictionaries) should be interpreted as having a meaning consistent with the meaning in the relevant technical context, and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0012] Referring to FIG. 1, the method for preparing modified naphthol resin may include the following steps: in step S10, an unmodified naphthol resin is provided; in step S20, the unmodified naphthol resin is subjected to a nitration reaction; in step S30, the product of the nitration reaction is subjected to a hydrogenation reaction in a specific solvent to produce a modified naphthol resin. [Unmodified naphthol resin]

[0013] In one embodiment, the unmodified naphthol resin may have only hydrogen in the corresponding naphthol group (formula (1-1)) or hydrogen of 1 to 5 carbon atoms (counted as C1 to C5) replaced with an alkyl group. The naphthol resin may be a 1-naphthol group (formula (1-2)) or a 2-naphthol group (formula (1-3)). [ka]

[0014] In one embodiment, the unmodified naphthol resin does not have any nitro, nitroso, or amino groups on the corresponding naphthol group. In one embodiment, the unmodified naphthol resin does not have any nitro, nitroso, or amino groups on the corresponding naphthol group.

[0015] In one embodiment, the chemical formula of the unmodified naphthol resin can be represented by the following formula (1): [ka]

[0016] In the formula (1), n ​​may be a positive integer of 2 to 40.

[0017] In one embodiment, the chemical formula of the unmodified naphthol resin may be similar to formula (1). For example, the hydrogen atoms connected to the carbon atoms may be replaced with alkyl groups having 1 to 5 carbon atoms (counted as C1 to C5). As another example, the hydroxyl in the naphthol group may be located at other substitution positions.

[0018] In one embodiment, the number average molecular weight (Mn) or weight average molecular weight (Mw) of a polymer may be measured by gel permeation chromatography (GPC).

[0019] In one embodiment, the number average molecular weight or the weight average molecular weight is used for the estimation, and the average value of n may be between 4-31.

[0020] In one embodiment, the unmodified naphthol resin may be a commercially available product (e.g., product name ResiCare® 4000, manufactured by Shanghai Hengfeng New Material Technology Co., Ltd.).

[0021] <Nitration reaction>

[0022] The nitration reaction may be carried out on the unmodified naphthol resin with a nitrating agent.

[0023] In one embodiment, the nitration reaction may be carried out in a conventional nitration reactor.

[0024] In one embodiment, the nitrating agent used in the nitration reaction is a halonitrobenzene.

[0025] In one embodiment, taking into consideration the steric hindrance of the corresponding reaction and / or chemical reaction, the halonitrobenzene in the nitration reaction is 4-halonitrobenzene. For example, the nitration reaction may be carried out by adding 4-halonitrobenzene to a solvent in which the unmodified naphthol resin is dissolved.

[0026] The chemical formula of 4-halonitrobenzene may be represented by the following formula (2): [ka]

[0027] In formula (2), X can be fluoro, chloro, bromo, or iodo.

[0028] In one embodiment, taking into consideration the reactivity of the reactants, it is preferred that X is fluorine (ie, 4-fluoronitrobenzene).

[0029] In one embodiment, the ratio of the total moles of hydroxyl in the unmodified naphthol resin to the moles of 4-halonitrobenzene may be from 1:1 to 1:2.5, preferably from 1:1.01 to 1:1.05.

[0030] In one embodiment, the total moles of hydroxyl in the unmodified naphthol resin may be estimated from the moles of reactants that produce hydroxyl in the unmodified naphthol resin.

[0031] In one embodiment, the total moles of hydroxyl in the unmodified naphthol resin may be estimated by commonly used standards (e.g., but not limited to, ISO 4629-2:2016, ASTM E222-10, GB / T 12008.3, CNS 6681).

[0032] In one embodiment, taking into consideration the corresponding reactivity, the nitration reaction is preferably carried out in an alkaline environment.

[0033] In one embodiment, considering the corresponding reactivity and the corresponding solubility of the unmodified naphthol resin, the solvent used in the nitration reaction may be a co-solvent containing an amide solvent, or an amide solvent, which may include, but is not limited to, N-methylpyrrolidone (NMP), dimethylacetamide (DMAC), dimethylformamide (DMF), or tetramethylurea (TMU).

[0034] In one embodiment, the corresponding pH value may be adjusted by adding an alkaline agent (eg, sodium carbonate, potassium carbonate, etc.).

[0035] In one embodiment, the number of moles of corresponding hydroxyl ions in the alkaline agent is about 1 to 2 times the total number of moles of hydroxyls in the unmodified naphthol resin.

[0036] In one embodiment, the solvent for the nitration reaction may be, for example, potassium carbonate in an amount of 5 moles to 7 moles dissolved in 6 moles of dimethylacetamide, or dimethylacetamide with the same alkali equivalent.

[0037] After the unmodified naphthol resin of formula (1) and the halonitrobenzene of formula (2) are subjected to a nitration reaction, a naphthol resin having a nitro structure as shown in the following formula (3) can be obtained. [ka]

[0038] The definition of n in formula (3) is essentially the same as the corresponding definition of n in formula (1). The reason that "the definition of n is essentially the same" is that in a chemical reaction, there may be unintended, unpredictable and / or unavoidable side reactions.

[0039] <Hydrogenation reaction>

[0040] After the naphthol resin having the nitro structure of formula (3) is subjected to a hydrogenation reaction, a modified naphthol resin as shown in the following formula (4) can be produced. [ka]

[0041] The definition of n in formula (4) is basically the same as the definition of n in the corresponding formula (1) and / or formula (3).

[0042] In one embodiment, the hydrogenation reaction may be carried out in a general hydrogenation reaction vessel. For example, an inlet gas mixer is provided in the hydrogenation reaction vessel. In addition, after the reaction solution is placed in the hydrogenation reaction vessel, hydrogen gas is injected into the hydrogenation reaction vessel to carry out the hydrogenation reaction. The amount and / or flow rate of hydrogen gas may be adjusted according to the set gas pressure (about 5 bar to about 100 bar).

[0043] In one embodiment, the temperature of the hydrogenation reaction does not substantially exceed the boiling or azeotropic point of the solvent used.

[0044] In one embodiment, the hydrogenation reaction is carried out at a temperature of about 50°C to 120°C, and preferably at about 80°C to 110°C.

[0045] In one embodiment, the hydrogenation reaction may be carried out in tetrahydrofuran (THF), toluene, isopropanol (IPA), an amide solvent (e.g., dimethylacetamide (DMAC)), or a co-solvent thereof. The solvent used in the hydrogenation reaction may have a direct effect on the hydrogenation rate and / or side reactions.

[0046] In one embodiment, the solvent for the hydrogenation reaction may be a co-solvent of toluene and isopropanol. The volume ratio of toluene to isopropanol may be about 80:20 to 100:0, preferably about 80:20 to 75:25.

[0047] In one embodiment, the hydrogenation reaction may be carried out in a co-solvent formed from dimethylacetamide and toluene, or dimethylacetamide. The volume ratio of dimethylacetamide to toluene may be about 75:25 to 100:0, and preferably about 90:10 to 100:0.

[0048] In one embodiment, taking into account the previously performed nitration reaction, the solvent used in the hydrogenation reaction may be similar to the solvent used in the previously performed nitration reaction, hi one embodiment, the solvent used in the hydrogenation reaction may be a co-solvent including an amide solvent, or an amide solvent.

[0049] In one embodiment, the solvent used in the hydrogenation reaction may be only an amide solvent and may not contain other non-amide solvents. In one embodiment, when the solvent used in the hydrogenation reaction is only an amide solvent, it is possible to have a higher hydrogenation rate.

[0050] In one embodiment, the pressure of the reaction gas (eg, hydrogen gas) in the hydrogenation reaction may be about 5 bar to about 100 bar, and preferably about 15 bar to about 30 bar.

[0051] In one embodiment, the reaction time of the hydrogenation reaction is about 4 hours to 12 hours, and preferably about 8 hours to 12 hours.

[0052] In one embodiment, the hydrogenation reaction may be carried out at a pressure of about 5 bar to about 100 bar for about 4 hours to about 12 hours, preferably at about 15 bar to about 30 bar, and more preferably at about 8 hours to about 12 hours, and more preferably at a pressure of about 5 bar to about 30 bar for about 8 hours to about 12 hours.

[0053] In one embodiment, the hydrogenation reaction may be suitably heated in a corresponding pressure atmosphere.

[0054] In one embodiment, the hydrogenation reaction may include a suitable catalyst. For example, the reaction liquid and the hydrogenation catalyst may be placed in a hydrogenation reactor so as to be mixed. In addition, after the reaction liquid is placed in the hydrogenation reactor, hydrogen gas may be injected into the hydrogenation reactor to carry out the hydrogenation reaction. After the hydrogenation reaction, the hydrogenation catalyst may be removed by filtration.

[0055] In one embodiment, a hydrogenation catalyst may be used to promote the hydrogenation reaction of the terminal nitro group. The hydrogenation catalyst may be a ruthenium (Ru) catalyst, a palladium (Pd) catalyst, a rhodium (Rh) catalyst, a platinum (Pt) catalyst, a nickel (Ni) catalyst, or a combination thereof.

[0056] In one embodiment, the hydrogenation catalyst is a solid heterogeneous catalyst, for example, a metal, metal alloy, or metal containing catalyst having a porous structure, which may include, but is not limited to, ruthenium metal oxide (e.g., ruthenium-magnesium oxide (Ru-MgO) or ruthenium-titanium dioxide (Ru-TiO2)), palladium on carbon or similar palladium on carbon (Pd / C), platinum black, Raney nickel, or a porous alumina (e.g., γ-Al2O3) support containing platinum, rhodium, and / or palladium.

[0057] In one embodiment, the amount of the hydrogenation catalyst used is about 0.5 to 2 parts by weight, preferably about 1.0 to 1.4 parts by weight, and more preferably about 1.2 parts by weight (i.e., 1.2±10% by weight), based on 100 parts by weight of the total amount of reactants used.

[0058] In one embodiment, the hydrogenation rate of the hydrogenation reaction by the above method may be about 90% or more, preferably about 94% or more, and more preferably about 98% or more.

[0059] In one embodiment, the hydrogenation rate may be estimated by comparing characteristic spectra. For example, the hydrogenation rate may be estimated by the decrease and / or increase of the corresponding infrared characteristic spectra of the terminal nitro group and / or the terminal amino group.

[0060] In one embodiment, the hydrogenation reaction may include the following reaction conditions: the solvent is a co-solvent of toluene and isopropanol; the volume ratio of toluene to isopropanol is about 80:20 to 75:25; the total amount of reactants used is 100 parts by weight, the amount of hydrogenation catalyst used is 1.2 parts by weight (i.e., 1.2±10% by weight, 1.08% by weight to 1.32% by weight), the reaction pressure is about 5 bar (i.e., 5±10% bar, 4.5 bar to 5.5 bar), the reaction temperature is about 110°C (i.e., 110±10°C, 100°C to 120°C), and the reaction time is about 5 hours (i.e., 5±0.5 hours, 4.5 hours to 5.5 hours). In addition, the hydrogenation rate corresponding to the above reaction conditions is about 94%. In addition, the polydispersity index (PDI) corresponding to the above reaction conditions is about 3.03.

[0061] In one embodiment, the hydrogenation reaction may include the following reaction conditions: The solvent is an amide solvent and other non-amide solvents (e.g., dimethylacetamide and toluene). The total amount of reactants used is 100 parts by weight, the amount of hydrogenation catalyst used is 1.2 parts by weight (i.e., 1.2±10% by weight, 1.08% to 1.32% by weight), the reaction pressure is about 20 bar (i.e., 20±10% bar, 18 bar to 22 bar), the reaction temperature is about 90°C (i.e., 90±10°C, 80°C to 100°C), and the reaction time is about 10 hours (i.e., 10±1 hour, 9 hours to 11 hours). In addition, the hydrogenation rate corresponding to the above reaction conditions is about 98% or more. In addition, the polydispersity index corresponding to the above reaction conditions is about 1.63, which may be due to the use of an amide solvent to reduce the possibility of side reactions.

[0062] In one embodiment, the hydrogenation reaction may include the following reaction conditions: The solvent is only an amide solvent (e.g., dimethylacetamide). The total amount of reactants used is 100 parts by weight, the amount of hydrogenation catalyst used is 1.2 parts by weight (i.e., 1.2±10% by weight, 1.08% to 1.32% by weight), the reaction pressure is about 20 bar (i.e., 20±10% bar, 18 bar to 22 bar), the reaction temperature is about 90°C (i.e., 90±10°C, 80°C to 100°C), and the reaction time is about 10 hours (i.e., 10±1 hour, 9 hours to 11 hours). In addition, the hydrogenation rate corresponding to the above reaction conditions is about 99% or more. In addition, the polydispersity index corresponding to the above reaction conditions is about 1.53, which may be due to the use of an amide solvent to reduce the possibility of side reactions.

[0063] <Applications of modified naphthol resin>

[0064] The modified naphthol resin represented by formula (4) has more favorable qualities (eg, relatively uniform functional groups, morphology, and / or structure), making it suitable for application in electronic products.

[0065] For example, the modified naphthol resin represented by formula (4) is suitable for synthesis of maleimide resin, benzoxazine resin, and / or polyimide resin (PI resin). The corresponding maleimide resin, benzoxazine resin, and / or polyimide resin is suitable for manufacturing electronic products, such as copper clad circuit boards (CCL) for manufacturing circuit boards.

[0066] In one embodiment, in the application of the modified naphthol resin represented by formula (4) to electronic products, the modified naphthol resin used has better quality, so that the electronic products can also have better quality or better yield.

[0067] <Example of modified naphthol resin production>

[0068] A commercially available unmodified naphthol resin containing 1 mole of hydroxyl (product name ResiCare® 4000, manufactured by Shanghai Hengfeng New Material Technology Co., Ltd. and distributed by Prior Company Limited, containing an unmodified naphthol resin represented by formula (1)) was added to about 6 moles of dimethylacetamide (DMAC) and dissolved. Next, about 1.25 moles of potassium carbonate and about 1.25 moles of 4-fluoronitrobenzene were added and reacted at a temperature of about 120° C. for about 5 hours, and then cooled to room temperature. Then, the mixture was filtered to remove solids, and precipitated in a mixed solution of methanol and water to obtain a precipitate of nitrated naphthol resin (e.g., formula (3)). Next, the precipitate was added to a mixed solution formed by toluene and isopropanol (volume ratio of about 80:20), and about 1.2 parts by weight (precipitate is taken as 100 parts by weight) of palladium carbon was added, and the reaction was carried out for about 8 hours at a temperature of about 110°C and a pressure of about 5 bar to perform a hydrogenation reaction to obtain the modified naphthol resin of Example 1 (for example, formula (4)). The modified naphthol resin thus prepared was evaluated by the following evaluation methods, and the results are shown in Table 1.

[0069] Modified naphthol resins of Examples 2 and 3 were prepared using the same or similar steps as in Example 1. The difference was that the solvent, reaction time, reaction temperature, and / or reaction pressure used in the hydrogenation reaction were changed (as shown in Table 1). The prepared modified naphthol resins were evaluated by the following evaluation methods, and the results are shown in Table 1.

[0070] [Table 1]

[0071] <Evaluation method>

[0072] Number average molecular weight (Mn): The modified naphthol resin prepared was dissolved in tetrahydrofuran (THF) to prepare a solution to be tested with a concentration of 1% by weight.Then, the number average molecular weight of the solution to be tested was measured by gel permeation chromatography (GPC).

[0073] Weight average molecular weight (Mw): The modified naphthol resin prepared was dissolved in tetrahydrofuran (THF) to prepare a solution to be tested with a concentration of 1% by weight.Then, the weight average molecular weight of the solution to be tested was measured by gel permeation chromatography (GPC).

[0074] Polydispersity Index (PDI): To obtain the polydispersity index (PDI), the measured weight average molecular weight was divided by the number average molecular weight (e.g., Mw / Mn). A relatively low PDI indicates a relatively concentrated molecular weight distribution. Under the same or similar conditions of initial reactants, catalysts, and their corresponding amounts, the lower the PDI, the lower the corresponding side reaction possibility, and the more concentrated the molecular weight distribution. Therefore, when the molecular weight distribution is more concentrated (i.e., PDI is low), it can be said that the functional groups, morphology, and / or structure are more uniform, and it can be called a more uniform reaction / synthesis. In addition, when the molecular weight distribution is relatively concentrated (i.e., PDI is low), the proportion of the products of side reactions (e.g., relatively large polymer molecules formed by repolymerization) is correspondingly lower. Therefore, in terms of product application, it is more stable for subsequent processing or application, and the subsequent processed products can have better quality or better yield.

[0075] Solubility in toluene: 1 g of the modified naphthol resin was placed in a container, and toluene was added to make a solution weighing 2 g. The solution was shaken and then left to stand at room temperature for about 30 minutes. After the solution became clear, its solubility was measured.

[0076] Solubility in butanone: 1 g of the modified naphthol resin prepared was placed in a container, and butanone was added to make a solution weighing 2 g. The solution was shaken and then left to stand at room temperature for about 30 minutes. After the solution became clear, its solubility was measured.

[0077] Dielectric constant (Dk): The modified naphthol resin prepared was applied to a substrate, baked at 120°C for 2 minutes, and then hot pressed at 210°C for 3 hours to form a film with a thickness of 100 μm. The dielectric constant (Dk) at a frequency of 10 GHz was then measured using a dielectric analyzer (model E4991A, manufactured by Agilent Technologies, Inc.). A small dielectric constant indicates that the modified naphthol resin has good dielectric properties.

[0078] Dielectric loss tangent (Df): The modified naphthol resin prepared was applied to a substrate, baked at 120°C for 2 minutes, and then hot pressed at 210°C for 3 hours to form a film with a thickness of 100 μm. The dielectric loss tangent (Df) at a frequency of 10 GHz was then measured using a dielectric analyzer (model E4991A, manufactured by Agilent Technologies, Inc.). A small dielectric loss tangent indicates that the modified naphthol resin has good dielectric properties.

[0079] Glass transition temperature (Tg): The glass transition temperature of the prepared modified naphthol resin was measured using a dynamic mechanical analyzer (DMA). A high Tg indicates that the modified naphthol resin has a good ability to resist phase change, i.e., good heat resistance. The temperature increase rate during the measurement is 10°C per minute. The temperature range during the measurement is 30°C to 300°C (heating, cooling, heating).

[0080] Peel strength: The modified naphthol resin prepared was applied to a substrate and baked at 120°C for 2 minutes to form a resin film. Then, copper foil was laminated on the top and bottom of the resin film, and hot pressed at 210°C for 3 hours to form a film with a thickness of 200 μm. The peel strength was then measured by a universal tensile machine. A high peel strength indicates that the modified naphthol resin has good resistance ability to peeling from the substrate, i.e., good peel strength.

[0081] <Evaluation Results>

[0082] From Table 1, the method for preparing the modified naphthol resin includes the following: carrying out nitration reaction and hydrogenation reaction on the unmodified naphthol resin in sequence to form a modified naphthol resin having an aminobenzene group in the structure. Furthermore, the hydrogenation reaction is carried out in at least a specific solvent, which can have a more favorable hydrogenation rate. In addition, the prepared modified naphthol resin also has a more favorable molecular weight distribution.

[0083] In addition, compared to the modified naphthol resin made by using a mixed solvent formed by toluene and isopropanol as a solvent for the hydrogenation reaction (Example 1), the modified naphthol resin made by using a solvent containing dimethylacetamide as a solvent for the hydrogenation reaction (Example 2 or Example 3) has a higher hydrogenation rate and a lower polydispersity index (i.e., a more uniform distribution of molecular weights).

[0084] In addition, compared with the modified naphthol resins prepared by using a mixed solvent as a solvent for the hydrogenation reaction (Example 1 or Example 2), the modified naphthol resins prepared by using only an amino solvent (e.g., dimethylacetamide) as a solvent for the hydrogenation reaction (Example 3) have a higher hydrogenation rate and a lower polydispersity index (i.e., a more uniform distribution of molecular weights).

[0085] In addition, compared with the modified naphthol resin (Example 1) prepared by the hydrogenation reaction at a temperature of 50°C to 90°C and a pressure of 15 bar to 50 bar, the modified naphthol resin (Example 2 or Example 3) prepared by the hydrogenation reaction at a temperature of 50°C to 90°C and a pressure of 15 bar to 50 bar has a higher hydrogenation rate and a lower polydispersity index (i.e., a more uniform distribution of molecular weights).

[0086] Based on the above, the preparation method of modified naphthol resin in the present invention can have a relatively high hydrogenation rate.In addition, the modified naphthol resin can have good distribution uniformity of molecular weight, and is suitable for use as a curing agent or for forming naphthol resin with other reactive groups, and has good applicability.

[0087] Although the present invention has been described with reference to the above embodiments, they are not intended to limit the present invention. It will be apparent to those skilled in the art that modifications can be made to the described embodiments without departing from the scope or spirit of the present invention. Therefore, the scope of the present invention is defined by the appended claims and their equivalents, rather than the above detailed description. [Industrial Applicability]

[0088] The modified naphthol resin of the above embodiment of the present invention can be directly or indirectly applied to copper-clad substrates and further processed into electronic components or products (e.g., circuit boards or copper-clad substrates) for consumer, industrial, or suitable applications. [Explanation of symbols]

[0089] S10, S20, S30: Step

Claims

1. carrying out a nitration reaction and a hydrogenation reaction on the naphthol resin in order to form a modified naphthol resin having an amino group in the structure; Including, The solvent used in the hydrogenation reaction includes tetrahydrofuran, toluene, isopropanol, an amide solvent, or a co-solvent thereof. Method for preparing modified naphthol resin.

2. The solvent used in the hydrogenation reaction contains at least the amide solvent. A method for producing the modified naphthol resin according to claim 1.

3. The amide solvent is N-methylpyrrolidone, dimethylacetamide, dimethylformamide, tetramethylurea, or a cosolvent thereof; A method for producing the modified naphthol resin according to claim 1.

4. The amide solvent includes at least dimethylacetamide. A method for producing the modified naphthol resin according to claim 3.

5. The hydrogenation reaction is A reaction gas pressure of 5 bar to 100 bar; A reaction time of 4 to 12 hours; Reaction temperature: 50°C to 120°C It is executed under the condition that A method for producing the modified naphthol resin according to claim 1.

6. The hydrogenation reaction further includes the use of a hydrogenation catalyst, and the amount of the hydrogenation catalyst is 0.5 to 2 parts by weight per 100 parts by weight of the total amount of reactants. A method for producing the modified naphthol resin according to claim 1.

7. The nitration reaction is carried out in an alkaline environment. A method for producing the modified naphthol resin according to claim 1.

8. The nitrating agent used in the nitration reaction is a halonitrobenzene. A method for producing the modified naphthol resin according to claim 1.

9. The naphthol resin has a structure represented by the following formula (1): 【Chemistry 6】 In the formula (1), n ​​represents a positive integer of 2 to 40. A method for producing the modified naphthol resin according to claim 1.

10. The modified naphthol resin according to claim 1 has a structure represented by the following formula (4): 【Chemistry 7】 In the formula (4), n represents a positive integer of 2 to 40. Modified naphthol resin.

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