TW201144342A - Purifying method of alkylnaphthaleneformaldehyde polymer - Google Patents

Abstract

A purpose of the invention is to provide a method for purifying an alkylnaphthaleneformaldehyde polymer, in which the contents of metal have been decreased. The method is more beneficial to the industry. The method is characterized in that: a solution including the alkylnaphthaleneformaldehyde polymer and an organic solvent is used to contact an acidic aqueous solution, and the alkylnaphthaleneformaldehyde polymer is synthesized by reacting alkylnaphthalene and formaldehyde.

Description

201144342 VI. Description of the invention: [Technical field to which the invention pertains] Advantageous refining method [Prior art] There is a reduction in the metal content: upper = well-known fragrant chi _, which is a single f-naphthalene and/or dimethyl group The polycyclic aromatic hydrocarbon which is not a main component is obtained by reacting with furfural, and the obtained liquid phase epoxy resin has excellent solubility in phase = and 1-toluene (see Patent Document ^. A well-known method is: reacting a decyloxymethylene naphthalene compound, a compound having a heterogeneity with a benzene, m or a naphthalene material in the presence of diethyl sulphate, thereby obtaining a compound having naphthalene and a phenolic hydroxyl group via a sub- Age-dependent resin having a thiol-bonded structure (see Patent Document 2). These resins can be used as a coating agent for a semiconductor, a resin for a photoresist, and a semiconductor underlayer film forming resin. In these applications, in order to improve the yield In particular, the metal content is an important performance item. That is, when a resin having a large metal content is used, since the electrical properties of the semiconductor are lowered due to the residual metal in the semiconductor, it is required to lower the metal content. A method for producing an alkylnaphthylfurfural polymer having a reduced metal content is generally a method of bringing a solution containing a fluorenylnaphthaldehyde polymer and an organic solvent into contact with an ion exchange resin, or a method of filtering by a filter. However, in the method of using an ion exchange resin, it is difficult to select an ion exchange resin when various metal ions are contained, and there is a problem that the metal species 201144342 is removed, and it is difficult to remove the nonionic metal, and it is difficult to remove the nonionic metal. On the other hand, there is a problem that it is difficult to remove ionic metals by filtration, and it is difficult to remove ionic metals. [Pre-Technical Document] [Patent Document] Patent Document 1: Patent Publication No. Sho 54-86593 Patent Document 2: Japanese Patent Laid-Open No. Hei 2-9-9155 No. SUMMARY OF THE INVENTION The object of the present invention is to provide an industrially refined method for the alkylation of a formic acid polymer having a reduced metal content. In order to solve the above-mentioned problems, it is possible to dissolve the scorpion and the organic solvent: f-L-liquid is turned over, and the lining is low in various metals. The present invention is as follows. A method for purifying a silk naphthalene cap polymer, which comprises: contacting a solution containing a naphthylcarbamate polymer and an organic solvent with an acidic water content: the upper = naphthoquinone compound is obtained by reacting the silk. 2. The purification method according to Item 1, wherein the acidity is selected from the group consisting of hydrochloric acid, sulfuric acid, and phosphoric acid, and an aqueous solution of a mineral acid. The above acidic aqueous solution is 4 201144342, which is selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, sulfonic acid, phenolsulfonic acid, An aqueous solution of an organic acid or higher in the group consisting of p-toluenesulfonic acid and trifluoroacetic acid. 4. The purification method according to item 2, wherein the acidic aqueous solution is an aqueous solution of sulfuric acid. The purification method according to item 3, wherein the aqueous solution of the above acid oxalic acid is used. 4 Further, the method of purifying according to any one of the items 1 to 5, wherein the organic solvent is toluene, 2-g-g, cyclohexanone, cyclofine = butyl ketone, propylene glycol monoterpene ether acetate Or ethyl acetate. 7. The method of refining according to item 6, wherein the above is ketone or propylene glycol monomethyl ether acetate. The machine is a ring. The refined party according to any one of the items 1 to 7 above, wherein the stilbene naphthalene (tetra) compound comprises the following formula (1): wherein:

(In the formula (1), X is -(〇CH2)t_, tW~9. The refining as described in any one of items 1 to 7). 201144342 The above alkylnaphthalene aldehyde polymer comprises a unit represented by the following formula (2): [Chemical 2]

R R

R---R

(In the formula (2), 'X is the same as above; and R is each independently a hydrogen atom or a carbon number of 1 to a carbon number of 4). The purification method according to any one of the items 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (3): [Chemical 3] *

ZH

(In the formula (3), 'X is the same as the above; Ri each independently represents a hydrogen atom or an alkyl group selected from a carbon number of 1 to a carbon number 4, a thiol group, a cyclohexyl group, a triple 6 201144342 cyclodecyl group, an adamantyl group, More than one functional group in the group consisting of decahydronaphthyl, bicyclooctyl and ethanenaphthyl; in addition, 'the formula (3) indicates that -CO- or a single bond 'Ζ denotes an oxygen atom or a sulfur atom ; melon is 〇~3). The purification method according to any one of the items 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (4).

[化4] 疋. ZYR3

(In the formula (4), 'X, Υ, Ζ are the same as above; R2 each independently represents a hydrogen atom, or a hydrocarbon group having a carbon number of 1 to a carbon number of 'R3', respectively, independently derived from a thiol group, a cyclohexyl group, a tricyclic fluorene group. One or more functional groups in the group consisting of a group, an adamantyl group, a decahydronaphthyl group, and a bicyclooctyl group; and 1 is 〇~3). The purification method according to any one of the items 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (5): [Chemical 5] 201144342

(yr% (in the formula (5), X, Y, and Z are the same as the above; R4 each independently represents a hydrogen atom or an alkyl group selected from a carbon number of 1 to a carbon number of 3, a decyl group, a cyclohexyl group, a tricyclodecyl group. And one or more functional groups in the group consisting of adamantyl, decahydronaphthyl, bicyclooctyl and ethanenaphthyl; 〇 is 1 to 2, p is 0 4 ) 〇 13. as in item 1 to The purification method according to any one of the items 7, wherein the alkylnaphthalene formaldehyde polymer comprises a unit represented by the following formula (6): [Chem. 6]

(In the formula (6), X, Y, Z, and R3 are the same as defined above; and R5 each independently represents a hydrogen atom or a nicotine group having a carbon number of 1 to a carbon number of 3; q is 1 to 2, and r is 0. The purification method according to any one of item 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (7): 8 201144342 [Chem. 7]

(In the formula (7), X and R5 are the same as above; s is 0 to 4). The purification method according to any one of the items 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (8): [Chem. 8]

OH

(8) (In the formula (8), X, R5, and s are the same as described above). [Effect of the Invention] 201144342 According to the present invention, a method for purifying an alkylnaphthylfurfural polymer having a markedly reduced content of various metals can be provided. The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the invention. Ββ [Embodiment] Hereinafter, the present invention will be described in detail. In the present invention, the metal component contained in the solution containing the alkylnaphthalene formaldehyde polymer and the organic solvent is transferred to the aqueous phase by dissolving the alkylnaphthalene formaldehyde polymer in an organic solvent and bringing the solution into contact with the acidic aqueous solution. And an alkylnaphthalene formaldehyde polymer having a reduced refined metal content. The alkylnaphthylfurfural polymer used in the present invention is an alkylnaphthalene formaldehyde polymer obtained by reacting at least a naphthyl naphthalene with furfural, and a raw material other than alkyl naphthalene and furfural can be used for benzene and benzene. , naphthene, naphthalene derivatives, and the like. In addition, when the polymer is obtained, for example, an alkylene naphthalene and formaldehyde are reacted, and then phenol, a phenol derivative, a naphthol, a naphthol derivative or the like is modified to form a method of obtaining a target polymer or the like. The multi-stage reaction results in the final polymer obtained. The alkylnaphthalene which can be used in obtaining the polymer used in the present invention is selected from the group consisting of α-methylnaphthalene, β-mercaptophthalene, I2-didecylnaphthalene, I3·dimethylnaphthalene, and 1,4-dioxyl. Naphthalene, 1,5-didecylnaphthalene, 1,6-didecylnaphthalene, 1,7-dimethylnaphthalene, 1,8-didecylnaphthalene, 2,3-dimethylnaphthalene, 2,6 - dimethylnaphthalene, 2,7-dimethylnaphthalene, trimethylnaphthalene, tetramethylnaphthalene, ethane naphthalene, methylethane naphthalene, cyclohexylnaphthalene, decylnaphthalene, tricyclodecyl One type or a mixture of two or more kinds of naphthalene, adamantyl naphthalene, decyl naphthalene, and bicyclo 201144342 octyl naphthalene. It is preferable to use 1,5-dimethylnaphthalene, 2,6-di-f-naphthalene, 2,7-dimethylnaphthalene, j to improve the easiness and optical properties of the Wei and the tree. & Monomethyl naphthalene or ethyl dahne naphthalene, of which particularly preferred is hydrazine, 5-dimethylnaphthalene. Since dimethylnaphthalene is a structure in which two aromatic rings of a naphthalene ring each have a methyl group, a polyfunctional resin is formed by condensation with furfural in the presence of an acidic or basic catalyst. An unsubstituted naphthalene or a monomethyl phthalocyanine, a single aromatic ring of a naphthalene ring, which is dithiolated, 2 - dimethylnaphthalene, 2 L-nonylnaphthalene, 1,4-dioxylnaphthalene As a raw material, a polyfunctional resin cannot be obtained as long as a special reaction form such as an interfacial reaction is not employed. Further, when a tridecyl group is used in place of the above naphthalene compound, the reaction point becomes small, and a polyfunctional resin is obtained. The alkylnaphthalene aldehyde polymer used in the present invention preferably contains a structural unit which is not represented by the following formula (1).

(In the formula (1), 'X is -(〇CH2)t-, and t is 〇~2〇11 is 〇~4.)

11 201144342 [化 ίο]

(In the formula (2), X is the same as above. R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) The modified alkyl group of the present invention comprising the structural unit represented by the formula (2) A naphthylfurfural polymer which can be condensed under acidic or basic catalyst by a polymer comprising a structural unit represented by the formula (1) and a modifying agent comprising a compound represented by the following formula (9) The reaction comes. The compound represented by the formula (9) is particularly preferably a naphthalene. [化11]

R R

R---R 12 (9) 201144342 (R in the formula (9) is the same as the above.) The alkylnaphthylfurfural polymer used in the present invention may also have a group selected from the following formula (10) A structural unit in a group consisting of cells. [化 12]

(In the formula (10), hydrazine is the same as above.) The modified alkylnaphthylfurfural polymer containing the structural unit represented by the formula (10) of the present invention can be represented by the inclusion of the formula (1) The polymer of the structural unit and the modifier containing aryl, phenanthrene, anthracene, acenaphthylene, acenaphthene, anthracene, first, fullerene, etc. in acidic or alkaline touch The condensation reaction of the medium is obtained. The saxoquinone type of the alkylnaphthalene aldehyde polymer used in the present invention is preferably a structural unit represented by the formula (3). ^ 3 The following pass [Chemistry 13] 13 201144342

(In the formula (3), 'X is the same as above. R1 each independently represents a hydrogen atom or a group selected from a carbon number of 1 to a carbon number of 4, a thiol group, a cyclohexyl group, a tricyclodecanyl group, an adamantyl group, and a decahydrogen group. One or more functional groups in the group consisting of a naphthyl group, a bicyclooctyl group, and an ethionyl group; wherein, in the formula (3), Y represents -CO- or a single bond, and Z represents an oxygen atom or a sulfur atom. It is 0 to 3. The polymer containing the structural unit represented by the formula (3) of the present invention can be made acidic by modifying the above polymer with a modifying agent containing a compound represented by the following formula (11). Or a condensation reaction under a basic catalyst. [Chem. 14]

(Y'Z'R1, !!! in the formula (11) is the same as above.) The compound represented by the formula (11) is preferably a phenol or a phenol derivative. 201144342 Derivatives of benzene are obtained by alkylation of benzene with dentate or alcohol or dentate under acid catalyst. Further, after the exchange reaction of the ester compound is carried out, 'Fhes rearrangement is performed by a Lewis acid catalyst or the like to obtain a ketone compound having a number of partitions. The naphthylquinal aldehyde polymerization used in the present invention. The material preferably contains a structural unit represented by the following formula (4). [化15]

In the formula (4), X, Y, and Z are the same as above. R2 independently represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to a carbon number of 4, and R3 independently represents a selected group, a cyclohexyl group, and a tricyclic ring. The thiol, konjac, decandrein and bicyclooctyl group are functional groups of the group towel. ❻G~3.) The polymer of the present invention comprising the structural unit represented by the formula (4) is It is obtained by subjecting the above polymer to a condensation agent containing a compound represented by the following formula (12) under an acidic or basic catalyst. The compound which is not represented by the formula (1)) is preferably a phenol derivative. [化16] 201144342

(In the formula (12), γ, Z, R2, R3 and 1 are the same as above.) The alkylnaphthylfurfural polymer used in the present invention preferably contains a structural unit represented by the following formula (5). [Chem. 17]

(8) (In the formula (5), X, Y, and Z are the same as above. R4 each independently represents a hydrogen atom or an alkyl group selected from a carbon number of 1 to a carbon number of 3, a decyl group, a cyclohexyl group, a tricyclodecyl group, and a diamond. One or more functional groups in the group consisting of an alkyl group, a decahydronaphthyl group, a bicyclooctyl group, and an ethanenaphthyl group. 0 is 1 to 2, and ρ is 〇~4.) The inclusion formula of the present invention (5) The polymer of the structural unit shown is obtained by condensing the above polymer with a modifying agent containing a compound represented by the following formula (13) under an acidic or basic catalyst. 201144342 [Chemistry 18]

(In the formula (13), Y, Z, R4, ο, p are the same as above.) The compound represented by the formula (13) is preferably a naphthalene or naphthalene derivative. The naphthol derivative or the naphthalenediol derivative is obtained by subjecting a naphthol or a naphthalenediol to a halogenation reaction with a halogen or an alcohol or a halide under an acid catalyst. Further, after the esterification reaction is carried out using an esterified product, the ketone compound which blocks the carbonyl group is obtained by performing a Friedel rearrangement by a Lewis acid catalyst or the like. The alkylnaphthylfurfural polymer used in the present invention preferably contains a structural unit represented by the following formula (6). [Chem. 19]

(In the formula (6), X, Y, Z and R3 are the same as above. R5 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. q is 1 to 2, and r 17 201144342 is 0 to 4. The polymer containing the structural unit represented by the formula (6) of the present invention is a condensation reaction of the above polymer with a modifying agent comprising a compound represented by the following formula (14) under acidic or basic catalyst. And got it. The compound represented by the formula (14) is preferably a naphthalene derivative. [Chem. 20]

(14) In the formula (14), Y, Z, R3, R5, q, and r are the same as described above. The alkylnaphthylfurfural polymer of the present invention preferably contains the following formula (7). unit. [Chem. 21]

18 201144342 (In the formula (7), X and R5 are the same as above. s is 0 to 4.) The polymer of the present invention comprising the structural unit represented by the general formula (7) is such that the above polymer and the following are included The modifier of the compound represented by the formula (15) is obtained by a condensation reaction under an acidic or basic catalyst. [化22]

(In the formula (15), R5 and s are the same as above.) The alkylnaphthalene formaldehyde polymer of the present invention preferably contains a unit represented by the following formula (8). [Chem. 23]

19 201144342 (In the formula (8), X, R5, and s are the same as described above.) The polymer of the present invention comprising the structural unit represented by the formula (8) is such that the above polymer comprises the following formula (16) The modifier of the compound shown is obtained by condensation reaction under acidic or basic catalyst. [Chem. 24]

(In the formula (16), R5 and s are the same as above.) The alkylnaphthylfurfural polymer used in the present invention can introduce an epoxy group into a phenolic hydroxyl group. The epoxy group-containing compound such as a resin having a phenolic hydroxyl group and a surface alcohol can be introduced into the epoxy group by the action of a base. The alkylnaphthalene aldehyde polymer used in the present invention may be used singly or in combination of two or more kinds. Further, the alkyl phthalocyanine polymer may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers, and the like. The organic solvent used in the present invention is not particularly limited as long as it is an organic solvent which is not arbitrarily mixed with water. It is preferably an organic solvent which can be safely used in a semiconductor manufacturing process. The amount of the organic solvent to be used is usually from about 1 to 100 times by weight relative to the poly 2:field used. Examples of the ethers and acetic acid oxime agents 2 include diethyl ether, diisopropyl ether, etc., esters such as n-butyl acrylate and isoamyl acetate, methyl 2 2 m diisobutyl ketone, and ethyl isobutyl ketone. , cyclohexanone, cyclopentanone, di: pentane: et al. bis-ethylene glycol monoethyl ether B, ethylene glycol monoethyl ether acetate r cage: 7 early methyl ether acetate vinegar (PGMEA), propylene glycol mono, hydrazine-alcohol ether Acetate, aliphatic such as n-hexane or n-heptane: hydrocarbons, etc., such aromatic hydrocarbons, dichloromethane, chloroform (tetra)pentanone, anthraquinone, preferably toluene, 2-heptanone , cyclohexanone, ring » soil isobutyl ketone, propylene glycol monoterpene ether acetate, ethyl acetate, etc., especially good Cyclohexyl, propylene glycol mono-acetic acid sleep. The mixture may be used alone or in combination. The acidic aqueous solution used in the invention may be suitably cooled in an aqueous solution obtained by dissolving a generally known organic compound or inorganic compound in water. . For example, an aqueous solution obtained by diluting a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid with water may be used, or acetic acid, propionic acid, oxalic acid, and propylene disulfide may be changed to X butyl bis. An aqueous solution obtained by dissolving an organic acid such as enedic acid, maleic acid, tartaric acid, citric acid, m-acid acid, p-toluene acid or trifluoroacetic acid. These acidic aqueous solutions may be used singly or in combination of two or more kinds. The acidic aqueous solution is preferably sulfuric acid, nitric acid, and acetic acid, oxalic acid, tartaric acid, lemon, and several water-based liquids, more preferably water-cooled liquids of sulfuric acid, oxalic acid, tartaric acid, and lemon. Particularly preferred is an aqueous solution of oxalic acid. It is generally believed that since the polycarboxylic acid such as B 21 201144342 diacid, tartaric acid or citric acid is coordinated with a metal ion, a chelation effect is produced, and the metal can be further removed. Further, the water used herein is preferably a water having a small metal content, such as ion exchange water or the like, according to the object of the present invention. The pH of the acidic aqueous solution used in the present invention is not particularly limited, and if the acidity of the aqueous solution is too large, the alkylnaphthalene formaldehyde resin is adversely affected and is not preferable. Usually, the pH range is about 〇~5, and more preferably the pH is about 0~3. The amount of the acidic aqueous solution used in the present invention is not particularly limited. When the amount used is too small, the number of extractions for removing the metal must be increased. On the other hand, if the amount of the aqueous solution is too large, the amount of the entire liquid is increased to cause an operational problem. The amount of the aqueous solution to be used is usually 10% by weight to 2% by weight, preferably 20% by weight to 100% by weight based on the alkylnaphthalene resin in the organic solvent. The present invention is characterized in that the metal component is extracted by bringing the acidic aqueous solution as described above into contact with a solution containing an alkylnaphthalene formaldehyde resin and an organic solvent. . The temperature at the time of the extraction treatment is usually 2 (rc 〜 9 〇 &lt; t, preferably in the range of 3 〇 ° C to 803 ⁄4. The extraction operation is carried out, for example, by thoroughly mixing by stirring or the like, followed by standing. The metal component contained in the solution containing the naphthalene resin and the organic solvent is transferred to the aqueous phase. - The resulting mixture is separated by a cold liquid phase and an aqueous phase containing an alkylnaphthalene formaldehyde resin and an organic solvent. There is no particular limitation on the time for the precipitation of the sulfhydryl-based resin and the organic solute solution. 22 201144342 == too short 'The solution phase containing the organic solvent and the aqueous phase are usually left standing. The time should be: more than minutes, more preferably: several times... it is also effective to repeat the line = acid = liquid for this extraction treatment, preferably, after the extraction process, the aqueous solution is extracted from the aqueous solution. The liquid of the package 3 pits of the amylose and the organic solvent is further subjected to the extraction with water.:: After the mixture is sufficiently mixed, the bath is allowed to stand still and I is immersed in the bath. Phase-reducing and water containing calcined naphthene and resin Therefore, the phase containing the naphthoquinone and the organic solvent solution is recovered by decantation or the like. Further, the water used herein is preferably water having a small metal content, such as ion-exchanged water, etc., according to the object of the present invention. The extraction treatment may be carried out only once, and it is also effective to repeat the operations of mixing, standing, and separating several times. In addition, the ratio of the solution containing the thioglycolic acid resin and the organic solvent to the acidic aqueous solution during the extraction treatment, or The conditions such as temperature and time are not particularly limited, and may be the same as in the case of the contact treatment with the prior acidic aqueous solution. The water mixed in the solution containing the alkylnaphthalene f-aldehyde resin and the organic solvent thus obtained may be reduced by the implementation. It is easy to remove by pressurization and other operations. In addition, an organic solvent may be added as needed to adjust the concentration of the naphthoquinone resin to an arbitrary concentration. Only the alkane is obtained from the obtained solution containing an alkylnaphthalene formaldehyde resin and an organic solvent. The method of the naphthaldehyde formaldehyde resin can be carried out by a known method such as separation of 23 201144342 by pressure reduction or reprecipitation, and a combination of these methods. EXAMPLES Hereinafter, the embodiments of the present invention will be more specifically described by way of examples. However, the present invention is not limited to the examples. In the following synthesis examples, compounds were confirmed by H-NMR (nuclear magnetic resonance) measurement. <Synthesis Example> Synthesis of alkylnaphthalene formaldehyde polymer (synthesis of dinonylnaphthalene resin (DMN resin)) • Synthesis example of DMN resin i Four ports with a Dairy cooling tube, a thermometer, and a stirring blade In a flask (2000 mL), under the nitrogen flow, ι,5·didecylnaphthalene (1,5DMN) (218 g, 1.4 mol) manufactured by Mitsubishi Gas Chemical, and Formalin 40 manufactured by Mitsubishi Gas Chemical The % aqueous solution (42 〇g, 5.6 mol) and 98% sulfuric acid (194 g) manufactured by Kanto Chemicals were refluxed at 100 ° C for 7 hours under normal pressure. After dilution with ethylbenzene, neutralization and water washing were carried out to remove &gt; granules and 1,5DMN was removed under reduced pressure to obtain a light brown solid (1,5DMN-R) 250 g. The results of GPC (gel_permead 〇n chromatography, gel permeation chromatography) were Mn: 550, Mw: 1130, and Mw/Mn: 2.05. (Synthesis of Naphthol-modified DMN-R) • Synthesis Example 1 of Modified Resin In a four-necked flask (5 〇〇 mL) equipped with a Dairy Cooling Officer, a thermometer, and a wing-removing blade, a synthesis example was added under a nitrogen stream. g) obtained in 1 and α-naphthol (71.1 g, 0.49 m〇i) manufactured by Kanto Chemical Co., Ltd., and p-toluene 24 201144342 (1,6 g) were heated to 185 ° C for 4 hours to carry out a reaction. After the solvent was diluted, the mixture was neutralized and washed with water, the solvent was removed, and the residue was removed under reduced pressure to give a pale brown solid (e.g.) 16 (^. 〇? (: The result of the measurement was ] ^11: 848, Mw: 1630, Mw/Mn: 1.93, and a hydroxyl value of 175 mgKOH/g. Further, the above NF-1 is a naphthoquinone acid polymer containing the structural unit represented by the above formula (1) and formula (5). - Synthetic Example 2 of the modified resin: The amount of α-naphthol in the synthesis example 1 of the modified resin was changed to (5 〇·1 g, 0.35 mol), and the modified resin was used. Synthesis Example i was synthesized in the same manner to obtain 125 g of a light brown solid (NF 2 ). The results of Gpc measurement were Μ η : 871, Mw : 2174, Mw / Mn : 2.50, and the hydroxyl value was 122 mg KOH / g. Manufacture of cyclohexanone solution of modified resin with reduced metal content (Example 1) In a 1000 mL capacity four-necked flask (round bottom type), a solution in which NF-1 was dissolved in cyclohexane (15% by weight) was charged. 4〇〇g, while stirring, heated to 75 ° C. Then, add oxalic acid aqueous solution (1) 11 value 丨 3) 4 〇〇 g 'stirring for 3 minutes, then stand for 丨 hours ^ After the oil phase and the aqueous phase were separated, and the aqueous phase was removed one by two times, 400 g of ultrapure water was added to the obtained oil phase, and after mixing for 3 minutes, the mixture was allowed to stand for 1 hour to remove the aqueous phase. This operation was repeated 3 times to obtain a NIM cyclohexanone solution with a reduced metal content. (Example 2) Aqueous sulfuric acid solution (pH value! 3) _ g instead of input example] 25 A solution of oxalic acid in PH. Upper P value 13) 400 g 'In addition to this, the treatment was carried out in the same manner, and the NF-1 cyclohexanone solution having a reduced total metal content was obtained. <Example> pgmea of the modified resin having a reduced amount of metal s The solution (Example 3) was put into a four-necked flask (round bottom type) of a 1000 mL capacity, and the solution (1%%) _g obtained by dissolving the PGMEA was heated to the side while being removed. Oxalic acid hydrazine (pH L3) 0〇g ' After 3 minutes, stand still, then. Separate into oil phase and water 1 ' and remove water phase · #. Repeat 2 times after this operation , 100 g of ultrapure water was added to the obtained oil phase, and after stirring for 3 minutes, it was left to stand for a few hours to bring the water phase.

Remove. This operation was repeated 3 times to obtain a NF 2 pGMEA > trough solution having a reduced metal content. (Example 4) An aqueous solution of citric acid (pH 1.3) was placed in the same manner except that 1 〇〇g was used instead of the aqueous solution of oxalic acid (pH 13) in Example 3, except that it was treated in the same manner. Obtaining a decrease in the metal content] ^1?_没有(^^£八溶液. (Example 5) Putting an aqueous solution of sulfuric acid (pH 1.3) 1〇〇g instead of the aqueous solution of acetic acid (pH 1.3) in Example 3 100 g In addition, the treatment is performed in the same manner to obtain a metal content reducing liquid. 26 201144342 The NF-1 ring before treatment is measured by an inductively coupled plasma mass spectrometer (ICP-MS). The ketone solution and the contents of various metals in Example 1, Example 2. The results of the measurement are shown in Table 1. [Table 1] Metal Λ i content (ppb) Na K Cr Fe Zn Treatment 刖 44.7 1.5 0.6 3.2 1.9 Example 1 ^0.2 $0.2 ^0.2 ^ 0.2 &lt; 0.2 Example 2 0.8 ^ 0.2 0.7 ^ 0.2 0.5 The NF 2 PGMEA solution before treatment and the various metal contents in Example 3, Example 4, and Example 5 were determined by ICP-MS. 2]

Na 'metal> &amp; quantity (ppb) before treatment, apricot, 16., 16.7 IV 0.4 Lr 0.3 re 2.2 Zn 1.4 1 column J Example 4 Example 5 ^0.2 ^0.2 ^0.2 &lt;0.2 &lt;0.2 &lt;0.2 &lt;0.2 &lt;0.2 &lt;0.2 $0.2 $0.2 0.4 $0.2 ^0.2 Guest 0.2 Each 0.2 [Industrial Applicability] This month, it is industrially advantageous to manufacture a naphthoic acid resin with a reduced metal content. The present invention has been disclosed in the above preferred embodiments, and is not intended to limit the invention, and may be modified and modified without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims. [Simple description of the diagram] None. [Main component symbol description] None 0 28

Claims (1)

201144342 VII. Patent application scope: 1. A method for purifying an alkylnaphthylfurfural polymer, characterized in that: a solution comprising an alkylnaphthylfurfural polymer and an organic solvent is contacted with an acidic aqueous solution, and the alkylnaphthalene formaldehyde is polymerized. The substance is obtained by reacting an alkylnaphthalene with furfural. The purification method according to the first aspect of the invention, wherein the acidic aqueous solution is one or more inorganic acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. 3. The purification method according to claim 1, wherein the acidic aqueous solution is selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid An aqueous solution of one or more organic acids in the group consisting of tartaric acid, citric acid, citric acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. 4. The purification method according to claim 2, wherein the acidic aqueous solution is an aqueous solution of sulfuric acid. 5. The method of purifying according to item 3 of the patent application, wherein the acidic aqueous solution is an aqueous solution of oxalic acid. The purification method according to any one of the items 1 to 5, wherein the organic solvent is toluene, 2-g-indene, cyclohexanone methyl isobutyl ketone, propylene glycol Single shouts of acetate or ethyl acetate. 7. The method of purifying according to item 6 of the patent application, wherein the organic solvent is a cyclohexane or a propylene glycol monomethyl ether acetate. 〃 ^ ^ ^ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ (In the formula (1), X is -(OCH2)t-, t is 0 to 2; η is 0 to 4). The finishing method according to any one of claims 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (2): [Chemical 2] (In the formula (2), X is the same as above; and R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The refining method according to any one of claims 1 to 7, wherein the alkylnaphthalene formaldehyde polymer comprises a unit represented by the following formula (3): 30 201144342 [Chem. 3] (In the formula (3), X is the same as the above; R1 each independently represents a hydrogen atom or a group selected from a carbon number of 1 to a carbon number of 4, a deuteration group, a cyclohexyl group, a tricyclodecanyl group, an adamantyl group, or a decahydrogen group. One or more functional groups in the group consisting of naphthyl, bicyclooctyl and ethanenaphthyl; in addition, in the formula (3), Y represents -CO- or a single bond, and Z represents an oxygen atom or a sulfur atom; It is 0~3). The refining method according to any one of claims 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (4): [Chemical 4] 31 201144342 (In the formula (4), X, γ, and z are the same as the above; and R2 each independently represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to a carbon number of 4, and R3 each independently represents a group selected from a thiol group, a cyclohexyl group, and a third group. One or more functional groups in the group consisting of a cyclodecyl group, an adamantyl group, a decahydronaphthyl group, and a bicyclooctyl group; 丨 is 〇~3). The refining method according to any one of claims 1 to 7, wherein the alkylnaphthalene formaldehyde polymer comprises a unit represented by the following formula: [Chemical 5] 卜W(7) towel, χ, γ, ζ are the same as above; R4 is independently a ruthenium atom or an alkyl group selected from carbon number 丨 to carbon number 3, thiol group, cyclohexyl group, tricyclodecyl group, adamantyl group, ten One or more functional groups in the group consisting of hydronaphthyl, bicyclooctyl and ethane; For i~2, ρ is 〇~4). The refining method according to any one of the preceding claims, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula: [Chem. 6] 32 201144342 (In the formula (6), X, Υ, Z, and R3 are the same as above; and R5 each independently represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to a carbon number of 3; q is 1 to 2, and r is 0 4 ) 〇 14. The purification method according to any one of the items 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (7): [Chem. 7] (In the formula (7), X and R5 are the same as above; s is 0 to 4). The purification method according to any one of the items 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (8): [Chemical 8] 33 201144342 (In the formula (8), X, R5, and s are the same as described above). 34 201144342 IV. Designated representative circle: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 0 2 201144342 ______ The date of revision 7 years is selected from acetic acid, propylene, ethyl acetate, maleic acid, wine acid, anti The method for purifying the above-mentioned acidic aqueous solution, wherein the above-mentioned acidic aqueous solution is 5. The above-mentioned acidic aqueous solution is 5. The purification method according to the item 3, wherein the oxalic acid is the oxalic acid The aqueous solution of the mixture is as described in any one of items 1 to 5, which is a scorpion, a 2-heptanone, a cyclohexanone, a cyclopentanone: a butyl butyl ketone. The propylene glycol monomethyl acetate or the acetic acid acetonitrile. The purification method according to the above item 6, wherein the organic hexanyl or propylene glycol monoterpene bond B is intended to be. The above-mentioned = formazan according to any one of the items 7 includes the military unit represented by the following formula (1) wherein G (In the formula (1), X is _ (0CH, t is 〇~2; η is 〇9. The purification method according to any one of items 1 to 7, which is 201104342. The specification has no scribing correction page. Correction date: July 15 of the following year: The above alkylnaphthalene aldehyde polymer contains a unit represented by the following formula (2): [Chemical 2] (In the formula (2), X is the same as above; and R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The purification method according to any one of the items 1 to 7, wherein the alkylnaphthalene aldehyde polymer comprises a unit represented by the following formula (3): [Chemical 3] ZH (In the formula (3), X is the same as the above; R1 each independently represents a hydrogen atom or is selected from an alkyl group having a carbon number of 1 to a carbon number of 4, a decyl group, a cyclohexyl group, and a third 201144342 - a revised date · 100 years of July On the 15th, the Chinese manual of No. 100112054 is one of the groups of the unscented gastric octyl naphthalene, or =1: excellent = resin-made == special = dimethyl phthalene or ethyl phthalene, W And r is preferably 1,5-dimethylnaphthalene. The surname i is in the second, and the two aromatic rings of the naphthalene ring each have one methyl group, and the two are in the presence of a catalyst. To form a polyfunctional resin. When dimethyl 1,3- and 1,3-dimethylnaphthalene which are dimethylated without a single aromatic ring are used as a raw material, as long as a special reaction form such as an interfacial reaction is not employed When a naphthyl compound is substituted with a dimercapto group, the reaction point is reduced and a polyfunctional resin is not obtained. The alkylnaphthylfurfural polymer used in the present invention is preferably The structural unit represented by the following formula (1) is contained. (In the formula (1), X is -(〇CH2)r, t is 0 to 2. η is 0 to 4.) The alkylnaphthalene formaldehyde polymer used in the present invention may have the following formula (2) The structural unit shown. 11 201144343⁄4 For the Chinese manual No. 100112054, there is no scribe correction page. Revision date: July 15, 100 [Chem. 10] (In the formula (2), X is the same as above. R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) The modified alkyl group of the present invention comprising the structural unit represented by the formula (2) A naphthylfurfural polymer which can be condensed under acidic or basic catalyst by a polymer comprising a structural unit represented by the formula (1) and a modifying agent comprising a compound represented by the following formula (9) The reaction comes. The compound represented by the formula (9) is particularly preferably an alkylene naphthalene. [Reference 11] RRR R- 12 (9 201144342. For the Chinese manual No. 100112054, there is no scribe correction page. Revision date: July 15, 1 sulfonic acid (0.36 g) 'When 4 hours, the temperature is raised to i85〇c The reaction was carried out. After solvent dilution, neutralization and washing with water were carried out, the solvent was removed, and unreacted α-naphthol was removed under reduced pressure to obtain a pale brown solid (NF_i) g. The result of GPC measurement was Μη: 848, Mw: 1630, Mw/Mn: 1.93, and the 'passage value is 175 mgKOH/g. Further, the above NF-1 is a hospital-based naphthaldehyde polymer containing the structural unit represented by the above formula (1) and formula (5). Synthesis Example 2 of Modified Resin fS The amount of α-naphthol in the synthesis example 1 of the modified resin was changed to (50.1 g, 0.35 mol), and the same as the synthesis example i of the modified resin. The method was synthesized to obtain a light brown solid (NF_2) U5g. The results of GPC measurement were Mn: 871, Mw. 2174, Mw/Mn: 2 50, and the hydroxyl value was 122 mgKOH/g. Manufacture of reduced cyclopentene solution of modified resin (Example 1) 四 four burners in 1〇〇〇inL capacity In the (round bottom type), a solution (15 wt%) of 400 g of NF-1 dissolved in cyclohexanone is charged, and the mixture is heated to 75 C while being dropped. Then, an aqueous solution of ethylic acid (pH 13) is added. g, after stirring for 3 minutes, let stand for 1 hour, thereby separating the oil phase and the water phase, and removing the water phase. After repeating this operation twice, 400 g of ultrapure water was added to the obtained oil phase, and stirring was carried out. After a minute, it was allowed to stand for 1 hour to remove the aqueous phase. This operation was repeated 3 times to obtain a NF-1 cyclohexanide solution having a reduced metal content. (Example 2) 25 201144342 is the Chinese version of the 100112054曰期: On July 15th, 1st, (8), 400 g of sulfuric acid aqueous solution (pH 1.3) was put into place, instead of 400 g of the aqueous solution of oxalic acid (卩: value L3) in Example 1, except that it was treated in the same manner. NF_i cyclohexanone solution with reduced metal content was obtained. <Example> Production of PGMEA solution of modified resin with reduced metal content (Example 3) In a 1000 mL capacity four-necked flask (round bottom type), NF-2 was introduced. Solution (10 wt%) dissolved in PGMEA 4 〇〇g while stirring The mixture was heated to 4 (TC. Then an aqueous solution of oxalic acid (1) was added to have a value of 13). After 100 minutes of dispersing for 3 minutes, the mixture was allowed to stand for 1 hour, whereby the oil phase and the aqueous phase were separated, and the aqueous phase was removed. After repeating this operation twice, 100 g of ultrapure water was added to the obtained oil phase, and the mixture was stirred for 3 minutes, and then allowed to stand for a few hours to remove the aqueous phase. This operation was repeated 3 times to obtain a NF-2pGMEA solution having a reduced metal content. (Example 4) Aqueous citric acid solution (positive value 13) 1GGg was used instead of the aqueous solution of oxalic acid (positive value 丨3) in Example 3, except that it was treated in the same manner to obtain a reduced metal content wNF_2PGMEA solution. . (Example 5) An aqueous solution of sulfuric acid (pH i 3) was charged in place of 100 g of the aqueous solution of oxalic acid (pH 1.3) in Example 3, except that the treatment was carried out in the same manner to obtain a metal content. Reduced dissolution 26 201144342 I.A · Revision period: July 15th of the following year is No. 100112054 Chinese patent scope is not seven, application for patent garden: 1. - Refining method of seed naphthoquinone (tetra) The method according to the first aspect of the invention, wherein the above-mentioned liquid is one or more inorganic acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Aqueous solution. 3. The method according to claim 1, wherein the aqueous solution is selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, dibutyl succinyl-acid, and maleic acid. An aqueous solution of one or more organic acids in the group consisting of acid, tartaric acid, citric acid, citric acid, phenolsulfonic acid, p-benzoic acid, and trifluoroacetic acid. 4. The purification method according to claim 2, wherein the acidic aqueous solution is an aqueous solution of sulfuric acid. 5. The purification method according to claim 3, wherein the acidic aqueous solution is an aqueous solution of oxalic acid. 6. The purification method according to claim 1, wherein the organic solvent is toluene, 2-heptanone, cyclohexanone, cyclopentanone, decyl isobutyl hydrazine, propylene glycol monoterpene ether acetate or Ethyl acetate. 7. The purification method according to claim 6, wherein the organic solvent is cyclohexanone or propylene glycol monomethyl ether acetate. 8. The purification method according to any one of claims 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (1): 29 201144342 L Revision date :1〇〇15715曰#100112054 Chinese Patent Range Without Scribe Revision [Chemical 1] (In the formula (1), X is -(OCH2)t-, t is 0 to 2; η is 0 to 4). 9. The finishing method according to any one of claims 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (2): 2] (In the formula (2), X is the same as above; and R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The purification method according to any one of the items 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (3): 30 201144342 . Chinese Patent No. 100112054 No slash correction This revision date: July 15th, 1st year [Chemical 3] Ο (In the formula (3), X is the same as the above; R1 each independently represents a hydrogen atom or an alkyl group selected from a carbon number of 1 to a carbon number of 4, a decyl group, a cyclohexyl group, a tricyclodecyl group, an adamantyl group, and ten One or more functional groups in the group consisting of hydronaphthyl, bicyclooctyl and ethanenaphthyl; in addition, in the formula (3), Y represents • -CO- or a single bond, and Z represents an oxygen atom or a sulfur atom. ;m is 0~3). The refining method according to any one of claims 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (4): (4) 31. 201144342 is the Chinese patent scope of No. 100112054. There is no slash correction. The date of this amendment is: July 1st, i5th day (in equation (4), X, γ, z are the same as above; R2 represents the 虱 atom independently. Or a hydrocarbon group having a carbon number of 1 to a carbon number of 4, and each of R3 independently represents one or more selected from the group consisting of a ash group, a cyclohexyl group, a tricyclodecanyl group, an adamantyl group, a decahydronaphthyl group, and a bicyclooctyl group. Functional group; 丨 is 〇~3). The refining method according to any one of claims 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula: [Chemical 5] In the formula (5), X, Y, and z are the same as above; R4 is independently a hydrogen atom or an alkyl group selected from carbon number 1 to carbon number 3, a decyl group, a cyclohexyl group, a tricyclodecyl group, and a diamond. One or more functional groups in the group consisting of an alkyl group, a decahydronaphthyl group, a bicyclooctyl group, and an ethane naphthyl group; 〇 is 1 to 2, and p is 〇~:) = 13. The purification method according to any one of item 7, wherein the alkylnaphthalene formaldehyde polymer comprises a unit represented by the following formula (6): [Chemical 6] 32 201144342.. Chinese Patent No. 100112054 The range is not corrected by the line. The date of this revision: 100 years, July 15 (6) (In the formula (6), X, Y, Z, and R3 are the same as defined above; and R5 each independently represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to a carbon number of 3; q is 1 to 2, and r is 0 〇14. The purification method according to any one of the items 1 to 7, wherein the alkylnaphthylfurfural polymer comprises a unit represented by the following formula (7): [Chem. 7] (In the formula (7), X and R5 are the same as above; s is 0 to 4). The purification method according to any one of the items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer comprises a unit represented by the following formula (8): [Chem. 8] 33 201144342 For the Chinese patent scope of No. 100112054, there is no slash correction. The date of this amendment: July 15 of the following year (In the formula (8), X, R5, and s are the same as described above). 34