TW201200538A - Polybenzoxazole resin and precursor resin thereof - Google Patents

Abstract

A polybenzoxazole precursor resin and a polybenzoxazole resin are provided. The polybenzoxazole precursor resin, wherein the content of ionic impurities is decreased, is useful in applications of electric and electronic parts. The polybenzoxazole resin is obtained by cyclodehydration of the polybenzoxazole precursor resin. The polybenzoxazole precursor resin is obtained by polymerizing a dicarboxylic acid triazine active ester represented by the following formula (A) (in formula (A), R1 represents a divalent aromatic residue containing one or more elements selected from O, N, S, F and Si in the structure, or a divalent organic group having 1 to 12 carbons; R2 represents an alkyl group having 1 to 4 carbons or an aromatic residue having 6 to 8 carbons.) with a bisaminophenol compound, wherein the weight average molecular weight is in a range of 10, 000 to 1, 000, 000, and the content of ionic impurities is 10 ppm or less.

Description

201200538 VI. Description of the Invention: [Technical Field] The present invention relates to a polybenzoic acid obtained by reacting a dicarboxylic acid triazine active ester with a bisamine benzoin compound. The oxo-? sitting precursor resin and the polybenzoxazole resin obtained by dehydrating and ring-closing the precursor resin. [Prior Art] As a method for synthesizing a polybenzoxazole precursor resin, a helium gas method in which a dicarboxylic acid dichloride and a bisaminophenol compound are reacted is known, but obtained by the method In the precursor resin, gas ions derived from the synthesis reaction remain in the resin, and when used in electrical/electronic parts, the residual ionic impurities may cause deterioration in electrical characteristics. Further, as a method for synthesizing a polyamide resin, a polycondensation reaction of a di-acid compound and an amine compound is widely carried out, but a condensing agent, a catalyst, an additive, or a by-product added from the purpose of carrying out the reaction is known. The ionic impurities derived from these are generated in the like. For example, in a method of polycondensing a dicarboxylic acid compound and a diamine compound in the presence of an aromatic linoleate and a pyridine derivative, a large amount of phosphorus-based ionic impurities derived from an aromatic phosphite remain. In the obtained polyamide resin, the electrical properties of the obtained polyamine resin are lowered, and thus the use in applications requiring electrical insulation is limited. For this reason, for example, Patent Document 1 proposes a technique for reducing the content of _ in the aromatic polyamide resin to reduce impurities, but even if the polyamine resin is used for electrical and electronic parts, the residual ionicity Impurities may still be responsible for the deterioration of electrical characteristics. 4 201200538 In addition, 'recently used in recent years' is a triazine-based condensing agent of methoxy (tetra) or (tetra) porphyrin chloride. ·) 々Methyl? The carbaryl condensate can be synthesized inexpensively, and the thiol syrup is affected by the post-treatment water after the reaction = recycling, for example, in the patent literature = Text, :::,: The application of polystyrene and oxazole precursor resin or aromatic polyamide resin was discussed. , a 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族Chloride ions are liable to remain in the resin. 'The obtained tree is not well-formed and cannot fully exhibit the characteristics'. In addition, when it is used for electrical and electronic parts, it may cause deterioration of electrical characteristics. CITATION LIST Patent Literature Patent Literature 1. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Semponf, Polymer Proceedings, Vol. 64, p. 231 (2〇〇7) [Invention] It is an object of the present invention to provide a ionic impurity-reducing content which is useful especially for electrical and electronic parts. Polybenzoxazole precursor 201200538 A resin, and a polyphenyl resin obtained by dehydrating and ring-closing the precursor resin. As a result of intensive studies to solve the above problems, the inventors of the present invention have obtained a polystyrene (tetra)-driven which has a small content of ionic impurities by making a specific two-three-handed g|histamine-based fine compound poly-'. The fat' thus completes the invention. τ h ie 'the polybenzoic precursor precursor resin of the present invention is characterized in that the retanning compound is represented by the following formula (A) ^, R2 R2, R2, A〇W: V2 (6) F and S (itIA) In the recording, the number of alkyl groups or carbon number phenol compounds selected from the group consisting of 芳香族, N, S, and 6 to 8 is agglomerated: Triple Qin f sex, ^000-1,000,000 ^ lls, ~ 4 ^ This fresh branch (four) • body resin towel, is carbon number] In addition, preferably R! is selected from the following formula (1) 6 201200538 [Chemical 2] - Except where R4 represents Η, 〇, N, S, F or Si 9 or de-stained contains a carbon number of 1L of 7L selected from the group consisting of 〇, N, S, and Fasi: a substituent of 6; χ represents a direct bond, 〇, N, s, F or Si, or a structure having a carbon number of 1 to 6 selected from the group consisting of 〇, N, s, F, and other groups a divalent binding group; a, b, 〇, and d are the average number of substituents, and a, b&c respectively represent an integer of 〇~4, and ^ is not an integer of ～6, and the divalent group in the group represented by Aromatic residues. Further, I is preferably a hydrogen atom of the formula (1), and χ is a direct bond, 〇, so2 or CO. Further, a polybenzoxazole resin can be obtained by dehydrating and ring-closing the polyphenylene oxazole precursor resin. [Effects of the Invention] The polybenzoxazole precursor resin of the present invention and the polybenzoxazole resin obtained by dehydrating and ring-closing the precursor resin are compared with those obtained by a conventionally known method. The content of ionic impurities is small, and it is useful for electrical and electronic parts. The above and other objects, features, and advantages of the present invention will become more apparent from the understanding of the appended claims appended claims 201200538 ·»» W / · ip 丨t [Embodiment] The polybenzoxazole precursor resin of the present invention is a dicarboxylic acid triazine active ester and a bisaminophenol represented by the following formula (A > The compound obtained by the polymerization of the compound. [Chemical 3] r2

(8) As a raw material of the polybenzoxazole precursor resin of the present invention, Ri of the dicarboxylic acid triazine active ester represented by P (A) may be in the form of a formula: selected from 0, .8, ? And a divalent ^*-containing group residue of the above-mentioned elements. The term "divalent aromatic residue" as used herein refers to a residue obtained by removing two hydrogen atoms from an aromatic group. For example, in a compound having a cerium ring or a ring-like ring such as diphenyl ether, it is different. Residues in the aromatic ring are also included in the category of divalent aromatic residues. Examples of the divalent aromatic residue include a strepyl ether, a biphenyl sulfone, a biphenyl ketone, and a residue of naphthalene. In addition, the formula (A) can be a carbon number] ~ 12 Specifically, it can be exemplified: anthracene, exoethyl, extens: machine diyl, pentylene, hexyl, and exo Base, extension of octyl soil, stretching of butane and exfoliating base. Hyperthyroidism, extension 12 8 201200538

R L is preferably a monovalent aromatic residue selected from the group. [4] A group represented by the following formula (1)

0) 中二: Λ , , 8, heart, or structure: two: one of the groups consisting of free 〇, n, s, f, and Si: the carbon number of the halogen on the halogen, the substituent of 6 , b, e, and d are flat, the numbers 'a, b, and c represent integers of 〇~4, respectively, and d represents two = words, and the carbon number is 1 to fluorenyl or the oxy group, and the like is preferable. X represents a direct bond, 〇, N, s, F or 々m containing a divalent bond group selected from the group consisting of ruthenium, N, s, and FASi, and may be: 〇, 〇, S〇 2. The carbon number b 6 is extended, the carbon number is 6, etc., more preferably a direct bond, 〇, S〇2 or CO, and more preferably... - and, the formula (A) & The residue after removing two hydrogen atoms from benzene, biphenyl, phenyl azide, biphenyl hydrazine, conjugated or naphthalene towel, and more preferably a residue of benzene and diphenyl ether, particularly preferably a stupid position And a residue after the hydrogen atom is removed at the 4-position and the 4'-position of the diphenyl ether. Further, R2 of the formula (A) may be an alkyl group having a carbon number of i to 4, and specific examples thereof include a mercapto group. , ethyl, n-propyl, isopropyl, n-butyl ^ isobutyl 9 201200538, etc. and · ^ (A) # R2 can be The aromatic residue of 6 to 8 may be a residue of benzene, toluene or xylene, etc. The 6 to 8 _ thief base of the card I and 8 means a carbon number 6 to a fragrance. The residue of the side of the raw material of the polystyrene (tetra) saliva precursor resin of the present invention is not particularly limited, and for example, it can be used in an organic solvent = milk dimer, three The amine compound and the dioxan are obtained by the reaction of the recrystallization product, and the gas triazine compound is obtained by, for example, 2-gas·4,6-dimethylzinc-1,3. 5-III. Qin, 2 gas-4,6-diethoxy_13,5-triazine, 2 gas _4,6-propoxy-1,3,5-tri. Qin, 2-chloro- 4,6-diisopropoxymethoxy],3,5-diazine^gas_4,6-dibutoxy-oxime, 3,5-triazine, 2-chloro-4-4,6-diphenyl Oxygen jU, 5-triazine, etc., among which 2 gas · 4,6 dimethoxy ΐ 3,5·= azine, helium _4,6-diethoxy_ι, 3,5 are preferred. Triazine, 2-gas-4,6-di-p-oxyl j'3,5-diazine, etc. It is used in an amount of 2 moles per mole of the dicarboxylic acid compound used in the reaction. 4 moles, preferably 2 moles ~ 26 moles. Examples of the tertiary amine compound include triethylamine, quinone methyl phenanthrene, hydrazine-ethyl morpholine, hydrazine-isobutyl morpholine, pyridine, 2-methylpyridyl, and 3-methylpyridinium. 4-pyridylpyridine, 2,4-dimethylpyridine, 1,8-diazabicyclo[5.4.〇]_7_ 々>seven>, etc., wherein 'preferably triethylamine, Ν-mercaptomorpholine Pyr

201200538 --· -- χ- -I pyridine and so on. The amount thereof to be used is usually from 0.5 mol to 6 mol, preferably from 1 mol to 5 mol, based on 1 mol of the dicarboxylic acid compound used in the reaction. Examples of the dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, oxydiphenyl phthalic acid, and thiodiphenyl hydrazine. Acid, dithiodibenzoic acid, carbonyl dibenzoic acid, sulfonyldibenzoic acid, fluorenylene dibenzoic acid, isopropylidene dibenzoic acid, or hexafluoroisopropylidene diphenyl Dicarboxylic acid such as formic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, eleven-burned dicarboxylic acid, dodecanedicarboxylic acid An acid or the like, among which, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, oxydiphenyl phthalic acid, carbonyl dibenzoic acid, sulfonyl dibenzoic acid, naphthalene dicarboxylic acid, etc. are preferable. . As the organic solvent which can be used in the synthesis reaction, it is preferred to use a dicarboxylic acid as a good solvent. The solvent is not particularly limited, and examples thereof include an alcohol such as water or decyl alcohol, ethanol or isopropyl alcohol, and a ketone system such as acetone, mercaptoethyl ketone or decyl isobutyl ketone, and N-mercapto-2- Pyrrolidone, N,N-dimethylacetamide, hydrazine, hydrazine-didecyl decylamine, N-decyl caprolactam, N,N-dimercaptoimidazolidinone, dimercapto An aprotic polar solvent such as tetramethyl gland, N-mercapto, or 0 to 0, γ-butyrolactone, apolar solvent such as toluene, hexane or heptane, tetrahydrofuran, An ether solvent such as diglyme, dioxo or trioxane, or a mixed solvent thereof. For a specific production method of the dicarboxylic acid triazine active ester, for example, the dicarboxylic acid compound may be stirred and dissolved in an organic solvent, and then a triazine compound or a tertiary amine compound may be added to carry out the reaction, and then the reaction may be carried out. A dicarboxylic acid triazine active ester is obtained by crystallization or the like. The reaction temperature is usually -10 ° C to 80 ° C, 11 201200538 V / · I soil X storm i · preferably 0 ° C ~ 30 ° C. The reaction time is from 5 minutes to 24 hours, preferably from 15 minutes to 3 hours. After completion of the reaction, the reaction mixture is poured into a poor solvent such as water or decyl alcohol to separate the product, and then purified by recrystallization or the like to remove by-products and the like, whereby the dicarboxylic acid triazine active ester can be obtained with high purity. . Further, the dicarboxylic acid triazine active ester can be obtained by, for example, adding a hydroxytriazine compound, a tertiary amine compound, and a dioxon compound to an organic solvent, followed by purification by recrystallization or the like. As the above hydroxytriazine compound, for example, 2-hydroxy-46 dimethoxy-1,3,5-trianthene, 2-pyridyl-4,6·diethoxy-l,3,5- may be mentioned. Triterpenoid, 2_hydroxy-4,6-dipropoxy-1,3,5-triazine, 2-hydroxy-4,6-diisopropoxy-1,3,5-diazine, 2-hydroxyl -4,6-dibutoxy-l,3,5-triazine, 2-hydroxydiphenoxy-1,3,5-triazine, etc., wherein 2-hydroxyldioxy- is preferred. 1,3,5-triazine, 2-hydroxy-4,6-diethoxy-1,3,5-triazine, 2-hydroxy-4,6-diphenyloxy_ι,3,5- Triazine and the like. It is used in an amount of 2 moles to 4 moles, preferably 2 moles to 2.6 moles, per mole of the dioxane compound used in the reaction. Examples of the tertiary amine compound include triethylamine, N-methylmorphine, N-ethylmorphine, N-isobutylmorpholine, n-pyridine, 2·methylpyridinium, and 12 201200538 - ----Γ 醯 醯, bismuthene phthalate, ruthenium dibenzoate, bisphosphonium chloride, naphthalene dioxane, dioxonium oxydibenzoate, thiodi Diphenylphosphonium benzoate, dioxonium dithiodibenzoate, dioxonium carbonyl dibenzoate, diterpene chloride of sulfonyldibenzoate, diterpene chloride of fluorenylene dibenzoate, sub Di-n-propyl diphenyl phthalate dichloride, hexafluoroisopropylidene dibenzoate dichlorohydrazone, malonic acid di-branched chlorine, succinic acid dioxane, glutaric acid di-energy, adipic acid II Antimony chloride, dioxonium diphosphonate, dioxonium dioctate, dioxonium azelaic acid, diterpene diammonium dichloride, eleven antimony diacetate dioxonium chloride, dicalcium diacetate dioxonium chloride Dioxane, etc., among which, it is preferably dioxonium isophthalate, dioxonium terephthalate, diterpene chloride dimethic acid, dioxonium oxydibenzoate, carbonyl dick Dioxane acid, sulfonyl dibenzoic acid diterpene gas, naphthalene dioxane gas, and the like. As the organic solvent which can be used in the reaction, it is preferred to use an inert solvent with respect to ruthenium chloride. The solvent is not particularly limited, and examples thereof include a ketone solvent such as acetone, methyl ethyl ketone or decyl isobutyl ketone, and fluorenyl-fluorenyl-2-pyrrolidone, anthracene, fluorenyl-dimercaptoacetone. Amine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, dimethyl hydrazine, tetramethyl carbazide, azeotropic, gamma-butyrolactone, aprotic polar solvent, toluene, hexane , non-polar solvent such as heptane, tetrahydrogen. An ether solvent such as flurane, dimethylglycol, dioxane or trioxane, or a mixed solvent thereof. In addition, the bisaminophenol compound which is a raw material of the polybenzoxazole precursor resin of the present invention is not particularly limited as long as it is a compound having at least two amine groups and at least one phenolic hydroxyl group in one molecule. Specific examples of the bisaminophenol compound include 4,6··diaminoresorcin, 2,5-diaminohydroquinone, 3,3′-dihydroxybenzidine, 4,4′. -diamine 13

201200538 L-based-3,3'-dihydroxydiphenyl ether, 3,3,-diamino-4,4,4-dihydroxydiphenyl ether, 3,3,_monoamine-4,4'-di Hydroxybiphenylmethane, 4,4,-diamino-3,3,-dihydroxybenzidine, 3,3'-diamino-4,4,-dihydroxydiphenyl sulfone, 3,3, _Diamino-4,4,-dihydroxybiphenyl, 3,3,-dihydroxy-4,4,-diaminobiphenyl, 2,2-bis(3-amino-4-phenyl) )propane, 1,3-hexa-2,2-bis(3-amino-4-phenyl)propyl, 9,9'-amino-4-hydroxyphenyl) oxime, and 13_bis(4amino-3-hydroxyphenoxy)benzene or the like, but is not limited thereto. These may be used alone or in combination of two or more. It is used in an amount of usually from 0.5 mol to 2.0 mol, preferably from 0.9 mol to U mol, relative to the dicarboxylic acid triazine active ester component i. The reaction of the triterpenoid bismuth succinate active ester with the bisamino phenol compound is usually carried out in an inert solvent which is preferably substantially not reacted with the triterpenoid active ester of dicarboxylic acid and has the above bisamino group In addition to the property that the phenol compound is well dissolved, the polyphenylene azole precursor resin as a reaction product is a good solvent. The inert solvent is not particularly limited, and examples thereof include N-fluorenyl-2-pyrrolidinone, N,N-dimercaptoacetamide, anthracene, fluorenyl-didecylguanamine, and N-methylhexene. An aprotic polar solvent such as guanamine, hydrazine, hydrazine-dimercaptoimidazolidinone, dimercaptosulfoxide, tetramethylurea, hydrazine-methylmorpholine, pyridine, γ-butyrolactone, sulfolane, Non-polar solvents such as toluene, hexane, heptane, tetrahydrofuran, digan, and one shout, one. A scaly solvent such as oxalate or dioxin, a ketone solvent such as cupronyl, decylethyl fluorene or decyl isobutyl ketone, or a mixed solvent thereof. The amount of the solvent used is usually from 0 mL to 1000 mL, preferably from 50 mL to 800 mL, relative to the dimethylaminophenol compound used. 201200538 In addition, in order to obtain a polybenzoxazole precursor resin having a large degree of polymerization, an inorganic salt such as a chlorination clock or a gasification dance is also added. The amount of the inorganic salt to be used is usually 1% by mass or less, preferably 5% or less, based on the amount of the solvent to be used. As a specific production method of the polybenzoxazole precursor resin, for example, a diamine basic compound is dissolved in an inert solvent, and the above dicarboxylic acid triazine active ester is added with respect to the bisamine phenol compound 1 mole. The component 〇5 mol to 2.0 mol, and then reacted while heating and stirring in an inert atmosphere such as nitrogen, thereby obtaining a polyphenylene oxazole precursor resin. The reaction temperature is usually -10 ° C to 80 ° C, preferably 2 ° ° C to 60 ° C. The reaction time is usually from 5 minutes to 24 hours, preferably from minute to 15 hours. After the completion of the reaction, the hydroxytriazine compound as a by-product is water-soluble. Therefore, the reaction mixture is placed in a poor solvent such as water or methanol to separate the polymer, and then purified by a reprecipitation method or the like to easily remove the reaction. A product or an inorganic salt or the like can thereby obtain a polybenzoxazole precursor resin having an ionic impurity content of 1 〇 ppm or less. In addition, the polystyrene of the present invention. The ruthenium precursor resin does not use a previously known phosphorus compound, and the dicarboxylic acid triazine active ester of the present invention as a raw material has a small chloride ion content, so that a high purity polyphenylene can be obtained as compared with the prior art. Oxazole precursor resin. The polybenzoxazole precursor resin of the present invention is a polybenzazole precursor resin having a weight average molecular weight of from 1 Torr to 1,000,00 G. When the weight average molecular weight is less than 10, _, the film forming property is poor and the properties of the polybenzoxazole precursor resin are not sufficiently expressed. The other side 15 201200538, the surface 'when more than 1, 〇〇〇, 〇〇〇 When the molecular weight is too high, the solvent solubility may be deteriorated, and the moldability may be deteriorated. As a simple method for adjusting the molecular weight of the polyphenylene oxazole precursor resin, a method of using any one of the dicarboxylic acid triazine active ester component or the bisaminophenerene compound component in excess is exemplified. Here, the term "weight average molecular weight (MW) and number average molecular weight (?η)" refers to a value calculated by gel permeation chromatography (GPC) and calculated by polystyrene conversion. . Further, the polybenzoxazole precursor resin of the present invention can be subjected to dehydration ring closure between the guanamine structure and the phenolic hydroxyl group by heating to form a polybenzoxazole resin. The heating condition is not particularly limited, and is usually heated at 15 Torr to 4 Torr for 30 minutes to 24 hours, preferably at 170 ° C to 35 ° C for 1 hour and 12 hours, more preferably for heating. The temperature is set to a decomposition temperature of the thiotriazine compound as a by-product, that is, 1 7 〇〇c or more. The polybenzoxazole precursor resin and the polybenzoxazole resin of the present invention have less ionic impurities than 10 ppm, and therefore, when used for electrical and electronic parts, electrical characteristics are not deteriorated. Suitable for semiconductors such as electrical and electronic parts, heat-resistant bag filters, secondary battery separators, insulation materials, various filters, food packaging and clothing. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. 201200538 Synthesis Example 1 <Synthesis of dicarboxylic acid triazine active ester> 4.2 parts of isophthalic acid and 2-gas-4,6-dioxin were added to a flask equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. 9.7 parts of oxy-1,3,5-triazine and 100 parts of N-mercapto-2-pyrrolidone were cooled to 0 °C. Thereafter, 7.6 parts of N-mercaptomorpholine was added dropwise with stirring, and the reaction was carried out for 15 minutes to obtain the following formula (2) [Chemical 5]

A reaction liquid of the dicarboxylic acid triazine active ester represented. The reaction solution was poured into 1000 parts of ion-exchanged water, and the precipitated product was separated by filtration, and then recrystallized by a mixed solvent of ethyl acetate and n-hexane, and dried to obtain a white dicarboxylic acid triazine active ester. Powdery crystalline resin powder 1 (yield 23%). Synthesis Example 2 <Synthesis of dicarboxylic acid triazine active ester> To a flask equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 6.5 parts of diphenyl ether-4,4'-dicarboxylic acid, 2-gas- 9.7 parts of 4,6-dimethoxy-1,3,5-triazine and 100 parts of N-decyl-2-pyrrolidone were cooled to 0 °C. Thereafter, 7.6 parts of N-mercaptomorpholine was added dropwise with stirring, and the reaction was carried out for 15 minutes to obtain the following formula (3) [Chemical 6] 17 (3) 201200538

A reaction liquid of the dicarboxylic acid triazine active ester represented. The reaction solution was poured into 1000 parts of ion-exchanged water, and the precipitated product was separated by filtration, and then recrystallized from a mixed solvent of ethyl acetate and n-hexane, and dried to obtain a white powder of a dicarboxylic acid triazine active ester. Crystalline resin powder 2 (yield 43%). Synthesis Example 3 <Synthesis of Dicarboxylic Acid Triazine Active Ester> 2-Carpet-4,6-monomethoxy-1,3,5 was added to a flask equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. - 3.1 parts of triazine, 50 parts of N-mercapto-2-0 than loidone and 2 parts of triethylamine, and cooled to 〇 °c. Thereafter, 2.0 parts of dioxonium phthalate was added and reacted for 20 minutes to obtain the following formula (2) [Chem. 7] h3co

(2) A reaction liquid of the dicarboxylic acid triazine active ester of the present invention shown. The reaction solution was poured into 500 parts of ion-exchanged water, and the precipitated product was separated by filtration and then recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain a white powder of a dicarboxylic acid triazine active ester. Crystalline resin powder 3 (yield 60%). 201200538 Example l &lt;Synthesis of Polypyrazole and Oxazole Precursor Resin&gt; Nitrogen-oxygen flushing of a flask equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer was carried out to dissolve 3,3'-di-perylene-4,4 '-Diamine-based 22 parts, methylpyrrolidone 205 parts' and then 54 parts of the above-obtained resin powder 2' of the above-mentioned di-barbital acid, the reaction product 2' was reacted at 20 C for 12 hours to obtain polyphenylene. And a reaction solution of an oxazole precursor resin. The reaction solution was poured into 2000 parts of methanol, and the precipitated resin was separated by filtration, washed with 2 parts of methanol, and then purified by refluxing with methanol. Then, after cooling to room temperature, it was filtered, and the filtrate was dried to obtain polyphenylene. Oxazole precursor resin powder 1 (yield 98%). The molecular weight (Mw) and the molecular weight distribution (Mw/Mn) determined by gel permeation chromatography (hereinafter, GPC) in terms of polystyrene were 114,000 and 2.4, respectively. Further, 4 g of the resin powder and 40 g of Millipore water were treated at 12 TC for 20 hours, and then ionic impurities (p-type ions, C1 ions) were analyzed by ion chromatography on the extract. The results are shown in Table 1. Comparative Example 1 &lt;Synthesis of polybenzoxazole precursor resin by a conventionally known method&gt;#, Nitrogen flushing of a flask equipped with a thermometer, a helium gas introduction tube, and a stirrer Parts, 3,3,_di-based _4,4,-diamino group ^ 21 injury, 1 part of gasification, N-methylpyrrolidone 1 〇 8 parts, „ pyridine 23 Αϋ stir to dissolve After adding '% linoleic acid vinegar and reacting at 9 Torr for 8 hours' to obtain a reaction solution of a polystyrene and a precursor resin. The reaction solution was poured into a 1 GGG portion, and the precipitated resin was filtered. After the mixture was washed with a fine portion of decyl alcohol, it was purified by refluxing with methanol. Then, after cooling to room temperature, the mixture was dried, and the filtrate was dried to obtain a comparative resin powder 1 (yield: 82%). The molecular weight (stealing) and molecular weight distribution (Mw/Mn) obtained by GPC and calculated according to polystyrene were 3, 80 Å and 24, respectively. At 12 Γ (^ 4 g of the resin powder and 40 g of microporous water) Perform 2 hours of treatment, and then analyze the ionic impurities (p-series, C1 ions) using the ion chromatogram for the extract. The results are shown in Table 1. Comparative Example 2 &lt;_Synthesis of the former male (tetra) branched benzene (tetra) salic precursor resin&gt; In addition to the comparative example resin powder, the isophthalic acid % (four) was _ -4, The resin powder 2 (yield 85%) of the same formula was used in the same manner as in the case of 25's of 2'-two lin. The molecular weight (and molecular weight distribution (Mw/Mn) obtained by using GPC and converted according to polystyrene was 5, 〇〇〇 and 26. In (2) 4 g of the resin powder and microporous water 4 〇 g into the rod 9, = extraction fine separation ion _ = = post C1 ion). The results are shown in Table 1. Comparative Example 3 &lt;Synthesis of a conventionally known rectangular resin> Polybenzophenone saliva precursor of α Μ was attached with a thermometer, a nitrogen introduction tube, gas flushing, addition of isophthalic acid 8 parts 4k bottle of nitrogen Stupid 11 parts, 2-chloro-4,6-dimethoxy]3 5':; light base _4,4'-diamine group ~ specific material fraction. Thereafter, run; ^ 19 parts And then, N-mercaptomorpholine 15 201200538^ was added dropwise, and then reacted at 2 (TC for 12 hours to obtain a reaction liquid of polybenzoxazole precursor resin. The reaction solution was poured into hydrazine. 2_ parts of alcohol, will be precipitated The lipid was separated and further separated by methanol, _, and methanol reflux to purify. Then, it was cooled to room temperature to be diced &gt; After washing, the filtrate was dried to obtain a comparative resin powder. Filtration, 93%). β 3 (Production is calculated by using GPC and calculated according to polystyrene and molecular weight distribution (Mw/Mn) is 4, 1 〇〇 and 2 sub-quantities (] VIW) 121 ° C 4 g of the resin powder and 4 μg of water were used for the microporous water. In addition, the ion and C1 ions were separated by an ion chromatogram for 2 hours. The results are shown in Table 1. Sub-contaminant (ρ Comparative Example 4 <Poly-knotwood using a previously known method. Synthesis of an antitussive precursor resin> Except 13 parts of isophthalic acid α dicarboxylic acid of Comparative Example Resin Powder 3 In the same way, the same method is used to treat the resin powder 4 (yield 85%) in the same manner as the other two -4,4'-dicarboxylic acid 13 parts. t匕 uses GPC and is calculated according to the polystyrene conversion, and the molecular weight distribution (^1\¥/]^11) is 6,3〇() and 23 molecules of car---. '.~V vvy for a long time 2 g of the resin powder 4 g and 40 g of microporous water were subjected to an ionic heterochronous treatment for the extract using an ion chromatogram 'then C1 ion'. The results are shown in Table 1 - Prepared Red ~ W) Department ions, 201200538.

[Table i]

[Industrial Applicability] ... This is the polyphenylene-based resin and the semiconductor field such as polyphenylene 9-ton ionic two-electron parts that are dehydrated and closed. Miscellaneous bag filter and: ί insulation material, and various sputum, food package Although the present invention has been disclosed in the preferred embodiment as above, 鈥 二 2 Anyone skilled in the art, without departing from the essence of the invention, 辄In the area, you can make some changes and refinements, because the range of i should be defined by the full-time g. , stay 濩 [Simple diagram] Benefits. #**&gt; [Main component symbol description] None. twenty two

Claims (1)

201200538 VII. Patent application scope: The following formula (A): 1. A polybenzopyrene precursor resin [Chemical 1] (A) (Formula (A) +, &amp; represents a divalent aromatic residue or a carbon number of 1 to 12 which contains a halogen or more selected from the group consisting of 〇, N, s, F, and Si The divalent organic group % indicates a carbon number of 4 or an aromatic residue having a carbon number of 6 to 8), and a tetacid diazine active is obtained by polymerization of a bisaminophenyl hydrazine compound. And the weight average molecular weight of the polystyrene and the salivary precursor resin is 1 〇 〜1 ,, the range of deletion, and the content of the ionic impurity f is 10 ppm or less. , ^^° The material of the polyphenylene-precursor precursor tree described in item 1 of the lining material, and R2 of the formula (A) is a sulfhydryl group having a carbon number of 1 to 4. The polybenzoin oxime (4) according to claim 1 or 2, wherein Ri of the formula (4) is selected from the following formula (1) [Chemical 2] 23 201200538 (In the formula, '4' denotes h, 〇, n containing a group consisting of 碳, N or &amp; or a group of carbon HS, F&amp;Sl of the symplectic symplectic In the group &amp; p and s L, Λ咏 Λ咏 丝, a, b and e are divided into W~4, two residues. π~6 integer) silk track group (four) divalent aromatic ^ ... () R4 is a ruthenium atom, X is a direct bond, 〇, and ICJ 0 5. A type I is a stupid and stagnation resin, which is a polybenzoic acid as described in any one of the claims i. Um, the precursor resin is obtained by dehydration ring closure. 24 201200538 IV. Designated representative map: (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: 201200538 is the Chinese manual of the l5〇l 19541 without a slash correction. The date of this amendment: the invention patent specification of September 15, 100 (the format, order and bold type of this manual are not allowed to be changed, please do not fill in the ※ part) ※Application No. ※Application date: /0,( ' Classification: I. Name of the invention: (Chinese / English) Polybenzopyrene and its precursor resin POLYBENZOXAZOLE RESIN AND PRECURSOR RESIN THEREOF O II. Chinese Abstract: The present invention provides a polyphenylene fluorene precursor resin which is useful for reducing the content of ionic impurities, which is useful for electrical and electronic parts, and a decarburization of the front = resin to obtain a (b) benzoate. The noise-resisting resin is obtained by the following formula (A) Ο f and η η indicate that the structure contains a divalent material group residue selected from 〇, n, s, or 素, or an aromatic shell residue having a carbon number of 6 to 8 represents a carbon number of 1 to 4 Polyalkyl group, or carbon number stupid poly: anti = = slow: triazine active (four) and diamine based! 〇, 〇 00~1 〇〇〇 _ reaction obtained 'its weight average molecular weight of 5 range, And the content of ionic impurities is 10 ppm 201200538 • JO is No. 100119541 Chinese manual without scribe correction This revision date: September 15th, 1996. Invention: Technical Field of the Invention The present invention has A polybenzoxazole precursor resin obtained by reacting a tricarboxylic acid of a dicarboxylic acid with a bisamino compound, and a polybenzoxazole resin obtained by dehydrating and ring-closing the precursor resin. [Prior Art] As a method for synthesizing a polybenzoxazole precursor resin, a ruthenium chloride method in which dicarboxylic acid dichloride is reacted with a bisaminophenol compound is known, but obtained by the method In the precursor resin, gas ions derived from the synthesis reaction remain in the resin, and when used in electrical and electronic parts, residual ionic impurities may cause deterioration in electrical characteristics. Further, as a method for synthesizing a polyamide resin, a polycondensation reaction of a dicarboxylic acid compound and a diamine compound is widely performed, but a condensing agent, a catalyst, an additive, or a by-product added to carry out the reaction is known. The ionic impurities derived from these are generated in the like. For example, in the method of polycondensing a dicarboxylic acid compound and a diamine compound in the presence of an aromatic phosphite and a pyridine derivative, a phosphorus-based ionic impurity derived from an aromatic phosphite remains in a large amount. In the obtained polyamide resin, the electrical properties of the obtained polyamine resin are lowered, and thus the use in applications requiring electrical = is limited. Therefore, for example, Patent Document 1 proposes a technique for reducing the content of the dish of the aromatic polyamine resin t to reduce impurities, but when the polyamine is used for electrical and electronic parts, the residual ion ^ It may become a cause of a decline in electrical characteristics. &quot;, 201200538 Ϊ第·; 19541 Chinese manual without a slash correction. In addition, in recent years, as a condensing agent for peptide synthesis, the phosphonium compound 4-(4, 卜二 A i _ χ has a non-lining chloride Triwei condensing agent minus -1,3,5·:azine_2·yl) ice methyl? The triazine-based condensing agent can be synthesized inexpensively, and the hydroxytriazine compound, therefore, the field II, 7 / capacitive =: 二Ο _Resin combined with two-two forests to open the precursor resin or if the fragrance is = yes, by the method disclosed in the document towel (4), the synthesis is easy to remain in the resin towel, _ 彳 3 ^ source Self-condensation _ gas ion distribution performance (four), the eager money can not be charged for the decline of electrical characteristics. ^ In _. Electronic parts may become Ο Revision date: September 15th, 100 曰 技术 文献 曰 曰 曰 曰 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 邦 邦 邦 邦 邦 邦 邦 邦 邦 邦 邦Dashi good line, jan〇ravec, Sen [invention content] Wei Di 64, (3) page (10)? Year) The purpose of the present invention is to use a polybenzoxazole precursor which is used in the middle of a pile to reduce the content of the cup for the electric and electronic parts. 201200538 is the 100th η 9541 Chinese manual. Date: Resin of September 15, 1GG, and a polybenzoxazole resin obtained by dehydrating and ring-closing the precursor resin. (4) As a result of intensive studies to solve the above problems, the inventors of the present invention have obtained a polyphenylene having a small content of ionic impurities by polycondensing a specific dicarboxylic acid triazine active ester with a bisaminophenol compound. The oxazole precursor resin, thereby completing the present invention. The β 4 , i.e., the polybenzoxazole precursor resin of the present invention is characterized in that it is represented by the following formula (Α1) the following. (In the formula (R), R represents a divalent aromatic residue having one or more elements selected from the group consisting of ruthenium, N, s, F, and Si, or a divalent carbon number of 1 to 12; An organic group; I represents a carbon number of 〜4 alkyl group, or a carbon number of 8 sulphur residue), and the diterpene triazine activity is obtained by polymerization of a bisamine-based compound. The weight average molecular weight is 1 〇, 〇00 to 1,000,000, and the ionic impurity content is 卯m, more preferably in the polybenzopyrene saliva precursor resin, the alkyl group having 1 to 4 carbon atoms. . In addition, the preferred heart is selected from the following formula (i) (1) 201200538 I · A yA A &lt;1 Revision date: September 15, 100, No. 100119541 Chinese manual without scribe correction [Chemistry 2 ] (Ri)a (wherein 'represents ^:^小以&amp;' or the junction contains a carbon number of 1 to 6 of an element selected from the group consisting of 0, N, S, F, and Si a substituent; X represents a direct bond, 〇, N, s, F or Si ' or a carbon number i~6 in the structure containing an element selected from the group consisting of 〇, N, s, F, and &amp; a divalent binding group; a, b, c, and d are the average number of substituents, and a, b, and c represent an integer of 〇~4, respectively, and d represents an integer of ～6, and the divalent group in the group represented by Aromatic residues. Further, it is preferred that the &amp; of the formula (1) is a hydrogen atom, and hydrazine is a direct bond, hydrazine, so2 or CO. Further, Q can be made into a polybenzoxazole resin by dehydrating and ring-closing the polyphenylene oxazole precursor resin. [Effects of the Invention] The polybenzazole precursor resin of the present invention, and the polypyramid resin obtained by dehydrating and ring-closing the precursor resin, are compared with the resins obtained by a previously known method. The content of sexual impurities is small, and it is useful for electrical and electronic parts. The above and other objects, features, and advantages of the present invention will become more apparent from the description of the appended claims. 7 201200538 /^χρχιι Date of revision: September 15, 1st, stomach H 1GGU9541 Chinese manual without scribe correction [Embodiment] The polybenzoxazole precursor resin of the present invention is obtained by the following formula (A) The obtained dicarboxylic acid triazine active ester and the bisaminophenol compound are obtained by polymerization. (A) As a raw material (4) of the polyphenylene L-precursor resin of the present invention, (IV) di-mirror triazine activity _ = selected from the group consisting of ruthenium, N, S, F, and Si Family residue. The divalent aromatics of the above-mentioned halogens, the divalent aromatic residues herein refer to the residues after the removal of two hydrogen atoms, for example, in the compounds of the four (four) (4) The residue of the silk in the aromatic surface is also included in the category of divalent aromatic residues. Specific examples of the divalent aromatic residue in the case of a flying atom include residues of benzene, hydrazine, biphenyl, hydrazine, and naphthalene. In addition, the formula (AWl may be a carbon number (IV) specifically, a methylene group, an ethyl group, a group, a group, a pentyl group, a hexyl group, a heptyl group, an exograin, a soil, and a Butane alkyl and hydrazine base, etc. Soil, extension 1220120053⁄4 ""195" Chinese manual without line correction This revision date: K) September 15th, the formula (Α) R! is preferably selected from A divalent aromatic residue in the group represented by the following formula (1). ° R4 of the formula (1) represents Η, Ο, Ν, S, F or Si, or the slave number of the structure containing one or more elements selected from the group consisting of 〇, N, S, F and Si The substituents of ～6, a, b, c and d are the average number of substituents, a, b and c each represent an integer of 0 to 4, and d represents an integer of 〇~6. Specific examples of δ include a burnt group having 1 to 6 carbon atoms, a hospitaloxy group, and the like, and more preferably a nitrogen atom. X of the formula (1) represents a direct bond, 〇, \, 8, 1, or ^, and the structure includes a group selected from the group consisting of 〇, ^4, and 31 = 碳 的 的 carbon number 1 to 6 A divalent binding group. Specific examples thereof include 〇', s, CO, S02, an alkylene group having 1 to 6 carbon atoms, a strict carbon number of J to 6, and the like, and more preferably a direct bond, hydrazine, S〇2 or C0. Further preferably, it is = decane, and the heart of the formula (4) is more preferably a residue obtained by removing two hydrogen atoms from the benzene, the phenyl ketone, the biphenyl ketone and the naphthalene, and the Z is a benzene. And the residue of the diphenyl ether, particularly preferably the residue after removal of a hydrogen atom from the benzene position and the 3 position, the 4th position and the 4' position of the best. In addition, R2 of the formula (A) may be an alkyl group having a carbon number of i to 4, and, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, or an n-butyl group 201200538. Revision date: 1〇 On September 15th of the following year, the Chinese manual for i 10P011954 无 has no underline correction base. R2 of the formula (A) may be a specific example of the carbon, and examples thereof include a stupid, tried-and-recognized residue, and the residue of the carbon number 6 to the eighth of the present invention. The "aromatic residue" removed by the aromatic aromatic ring of 8 means a residue obtained by removing one oxygen atom from the carbon number 6 to. And &amp;&gt; is preferably a methyl group, an ethyl group and a stupid residue, more preferably a methyl group and an ethyl group, and still more preferably a mercapto group. ^ As the polybenzoic acid of the present invention. The method for producing the di-low-acid diazine active ester of the raw material of the parent-salt resin is not particularly limited. For example, a chlorotriazine compound, a tertiary amine compound, and a dicarboxylic acid compound may be added to an organic solvent to carry out a reaction. It is obtained by purification by recrystallization or the like. Examples of the chloropyridazine compound include, for example, 2·chloro-4,6-dimethyllacyl-1,3,5-trinaphthyl, and gas-4,6-ethane-ethyl-1,3,5. - triterpenoid, 2-chloro-4-6_dipropoxy-1,3,5-pyridazine, 2_gas diisopropoxy methoxy dioxime, 2-gas-4,6-dibutoxy -1,3,5-diindole, 2-chloro-4,6-diphenoxy-1,3,5-three-noise, etc., among which 2-pyr-4,6-didecyloxy is preferred. _1,3,5_3 0 Qin, 2-chloro-4,6-di-6-oxy-1,3,5-tripa, 2-gas-4,6·di-phenyloxy-1,3, 5-triazine and the like. It is used in an amount of 2 moles to 4 moles, preferably 2 moles to 2 6 moles, per mole of the bis-acid compound used in the reaction. Examples of the tertiary amine compound' include, for example, triethylamine, sulfhydryl, N-ethyloximine, N-isobutylphosphonate, bite, and 2-oxime. ratio. , 3-pyridylpyridine, 4-anthracenepyridine, 2,4-dipyridylpyridine, 1,8-diazabicyclo[5.4 〇]-7. Base, shower, etc. 201200538 is the Chinese manual No. 100119541. There is no slash correction. The date of this revision is: September 15, 100. The amount of use is 1 mol relative to the dicarboxylic acid compound used in the reaction, usually 0.5 mol to 6 mol. Good for 1 mole ~ 5 moles. Examples of the dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, oxydibenzoic acid, and thiodiphenyl. Tannic acid, dithiodibenzoic acid, carbonyl dibenzoic acid, sulfonyldibenzoic acid, fluorenylene dibenzoic acid, isopropylidene dibenzoic acid, or hexafluoroisopropylidene Benzoic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, barium-dicarboxylic acid, hydrazine-dodecanedicarboxylate A dicarboxylic acid or the like such as an acid, among which, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, oxydiphenyl phthalic acid, carbonyl dibenzoic acid, sulfonyl dibenzoic acid, naphthalene are preferred. Dicarboxylic acid, etc. As the organic solvent which can be used in the synthesis reaction, it is preferred to use a dicarboxylic acid as a good solvent. The solvent is not particularly limited, and examples thereof include an alcohol such as water or decyl alcohol, ethanol or isopropyl alcohol, and a ketone system such as acetone, mercaptoethyl ketone or methyl isobutyl ketone, and fluorenyl-fluorenyl-2- Pyrrolidone, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-dimethyl decylamine, hydrazine-mercaptocaprolamine, hydrazine, hydrazine-dimercaptoimidazolidinone, dimercapto Aprotic polar solvents such as sulfoxide, tetradecylurea, fluorenyl-mercaptomorpholine, pyridine, γ-butyrolactone, non-polar solvents such as toluene, hexane, and gargene, tetrahydrofuran, di-glycin An ether solvent such as diglyme, dioxane or trioxane, or a mixed solvent thereof. For a specific production method of the dicarboxylic acid triazine active ester, for example, the dicarboxylic acid compound may be stirred and dissolved in an organic solvent, and then a triazine compound or a tertiary amine compound may be added to carry out the reaction, and then the reaction may be carried out. A dicarboxylic acid triazine active ester is obtained by crystallization or the like. The reaction temperature is usually -10 ° C ~ 80 ° C, 11 201200538 is the 100119119 Chinese manual without a slash correction. This correction date: September 15th, preferably or ~ 3 〇 ° C. The reaction time is from 5 minutes to 24 hours', preferably from 15 minutes to 3 hours. After the completion of the reaction, the reaction mixture is poured into a poor solvent such as water or decyl alcohol to separate the product, and then purified by recrystallization or the like to remove by-products and the like, whereby the dicarboxylic acid triazine active ester can be obtained with high purity. . Further, the dicarboxylic acid triazine active ester can be obtained, for example, by adding a hydroxytriazine compound, a tertiary amine compound, and a di-si compound to an organic solvent, followed by purification by recrystallization or the like. As the above-mentioned base triterpene compound, for example, 2-carbyl-4,6-dimethoxy-1,3,5-triazine, 2-yl-4,6-diethoxy_1 can be cited. , 3,5-triazine, 2_# to yl-4,6-dipropoxy-1,3,5-triazine, 2-hydroxy-4,6-diisopropoxy-1,3,5 - triterpenoid, 2-carbyl-4,6-dibutoxy-1,3,5-trioxane, 2_trans-base-4,6-diphenoxy-1,3,5-triazine, etc. Among them, preferred is 2-hydroxy-4,6-dimethoxyl_1,3,5-triazine, 2-hydroxy-4,6-diethoxy-oxime, 3,5 triazine, oxime hydroxyl group. -4,6-a stupidoxy-(3)·diterone, etc. The amount used is 1 mol of the dioxane compound used in the reaction, and is usually 2 mol to 4 mol for 2 mol to 2.6 mol. Examples of the tertiary amine compound include triethylamine and the amount of the group which are used in the reaction. = Lin, N. ethyl phenanthrene, N-isobutyl phenanthrene, shouting, 2_曱吼Bite, 3-mouth ratio. Ding '4-a 吼 定 、, 2, 4- 曱. Biha, _! p ten-ene, etc., straight, preferably - yin' _ two chaos double ring [5.4.0 Κ 7-i Wei Tianyi ~ for fine, team methyl lin, bite and so on. The fluorinated compound 1 mole, usually ο, 5 moles to 6 moles, is used as the above-mentioned diterpene chlorine compound, for example, for example, phthalic acid II 12 201200538 t Ί XL/Axl is 100119M1 No. Chinese manual, no revision period: September 15 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢 曰醢, biphenyl dichloride, dithiodibenzoic acid di-dibenzoic acid dimercapto dibenzoic acid dioxane, methylene hydrazine, carbonyl dibenzoic acid dioxane, sulfonyl benzoic acid diterpene Chlorine, hexafluoropyrene = this: dioxane acid, isopropylidene dioxane, dioxane succinate, pentane == formic acid di-'malonate dioxonium dichloride, suberic acid Diterpene chlorine, dioxonium adipic acid, heptyl chloride, undecane dinonanoic acid dioxane: diterpene dioxalate dichloride, diammonium diphosphate, etc., among which, preferably, meta-benzoic acid milk ^ Diterpenic acid diterpene gas, etc., two brewing gas, biphenyl dihydric acid diterpene chloride, oxy diterpenoid milk, p-dicarboxylic acid di-branched chlorine, diterpene chloride, sulfonyl diphenyl glycol: 1 acid, Chlorofluoride, carbonyl dibenzoic acid as available The reaction include inert solvents ° acyl chloride. This kind of _ and ^ special = think about dimethyl ketone, decyl isobutyl _ and other purchase agent ketone, hydrazine, hydrazine - dimethyl acetamide, Ν _ methyl: two JQ lazy, , gland, ~ butyl _ such as non-quality; = solvent 'Aben, hexane, glutinous material non-polar solvent, Fu Er thief or Sanwei et al. _ Solvent, etc., or the ^ ^ In addition, as the present invention The benzopyrene pre-diamine fine compound is not particularly limited as long as it is a compound having an oxime in the i molecule; 〃 As a specific example of the bisaminobenzene compound, there are 4,6-diaminoisophthalene, 2,5-diaminohydroquinone, 3,3'-di-diphenylaniline, 4, 4,_Diamine 13 201200538 JO /lipill Revision date: September 15, 100 is the 100119541 Chinese manual without underline correction of the base 3,3 _ by the base of the benzene shout, 3,3 · _ diamine _ 4,4,_di-based benzene test, 3,3,-diamino group _4,4, · di-based phenyl group, 4,4, · diamino group · 3,3, _ Base benzene, methane, 3/-diamino-4, dihydroxydiphenyl sulfone '3,3,-diamino-4, dibasic biphenyl, 3,3'·:·_4,4,_ Diaminobiphenyl, 2,2•bis(3_amino-4_phenyl)propyl, 1,3-hexafluoro-2,2_bis(3_aminophenyl)propyl, 9 , 9, bis (3-amino phenyl), and bis (4) amino phenyloxy) benzene, etc. 'but are not limited thereto. These may be used in combination or in combination of two or more. Its use (four) in the second ship three sisters (four) ingredients! Mohr' is usually from 0.5 moles to 2.0 moles, preferably from 9 to 1; 1 mole. The reaction of the dicarboxylic acid triazine active ester with the bisaminophenol compound is usually carried out in an inert solvent which is preferably substantially not reacted with the dicarboxylic acid diazine active ester and has the above diamine group. The polybenzoxazole precursor resin as a reaction product is a good solvent in addition to the property that the phenol compound is well dissolved. The inert solvent is not particularly limited, and examples thereof include N-fluorenyl-2-pyrrolidine, N,N-monomethylammonium, N,N-diindenyl anthracene, and N-fluorenyl group. Aprotic amines such as decylamine, hydrazine, hydrazine, dimercapto imidazolidinone, dimercaptosulfoxide, tetradecylurea, fluorenyl-mercaptomorpholine, pyridine, γ-butyrolactone, and cyclobutanthine Sexual polarity / gluten, non-polar solvent such as benzene, hexagram, geng, etc., tetrahydrofuran, di-glycolyl ether, di-alpha or three &quot; smoldering, etc., acetone, methyl b A ketone solvent such as a ketone or a decyl isobutyl ketone or the like, or a mixed solvent thereof. These solvents are used in an amount of 0.1 mol based on the bisaminophenol compound to be used, and are usually from 0 mL to 1000 mL', preferably from 50 mL to 800 mL. 14 201200538 Amendment date: September 15, 100, No. 100119541 Chinese manual, no sizing correction. In addition, in order to obtain a polyphenyl sulfonate precursor resin with a high degree of polymerization, chlorination, gasification, etc. may be added. Inorganic salts, the amount of the inorganic cerium is usually 1% by mass or less based on the amount of the solvent to be used, and is preferably a good mass. /〇The following. As a specific production method of the polybenzoxazole precursor resin, the bisaminobenzene compound can be dissolved in an inert solvent to form the above-mentioned dicarboxylic acid triazine activity with respect to the diphenyl-prone compound 1 molar The material is ~2.Q Moer, and then in an inert environment such as nitrogen, the surface force is 1 and the reaction is carried out to obtain a polystyrene and oxazole precursor resin. The reaction temperature is usually -l〇. °C~80°c, preferably 2(rc~6(rc.^ should be 5 minutes to 24 hours, preferably 3 minutes to 15 hours, % after the end of the reaction, as a by-product) Since the hydroxytriazine compound is water-soluble, the reaction mixture is put into a poor solvent such as water or methanol to separate the polymer, and then purified by a reprecipitation method or the like to easily remove by-products or inorganic salts. This is a polybenzoxazole precursor resin having a ionic impurity content of 1 or less. PPm 〇 In addition, the polybenzoxazole precursor resin of the present invention does not use a previously known filling compound and is used as a raw material. The two-rebel acid three-noise, tongue ester of the present invention The chlorine ion content is small. Therefore, a highly pure polybenzofluorene precursor resin can be obtained as compared with the prior art. The polybenzoxazole precursor resin of the present invention has a weight average molecular weight of 10,000 to 1,000,000. Polybenzoxazole precursor nucleus ruthenium. ~ When the weight average molecular weight is less than 10,000, the film forming property is poor and the performance of the polyphenylene sulfonium precursor resin is not sufficient, and -·', '方15 201200538 JO /Η·ΐρ丄Xi is the Chinese manual of No. 100119541. There is no slash correction. The date of this revision is: September 15th, 1st, when the temperature exceeds 1,000,000, the molecular weight is too high and the solvent solubility is deteriorated. Further, there is a possibility that the moldability is deteriorated. As a simple method for adjusting the molecular weight of the polyphenylene oxazole precursor resin, an excessive use of a tricarboxylic acid active ester component or a bisamino benzene compound component may be mentioned. Here, the weight average molecular weight (Mw) and the number average molecular weight (?η) refer to the determination by Gel Permeati〇 Chromatography (GPC). The value calculated by the polystyrene conversion is further calculated. Further, the polybenzoxazole precursor resin of the present invention can be dehydrated and closed between the guanamine structure and the phenolic hydroxyl group by heating to form polyphenylene. The oxazole resin is not particularly limited, and is usually 150. (: ~400. (: heating for 30 minutes to 24 hours, preferably at 17CTC to 350. (: heating for 1 hour to 12 hours) More preferably, the heating temperature is set to a decomposition temperature of the thiotriazine compound as a by-product, that is, 170 ° C or more. The benzoic acid contained in the polybenzoxazole precursor resin and the polybenzoxazole resin of the present invention It is less than 1 〇 ppm, so when it is used for electrical and electronic parts, it is suitable for semiconductors such as electrical and electronic parts, heat-resistant bag filters, secondary battery separators, and heat insulating materials without deteriorating electrical characteristics. , various filters, food packaging and clothes. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. 16 201200538 • j I i ^/4 jl JL is the Chinese manual of No. 100119541. There is no slash correction. This revision date: September 15th, 100th Synthesis Example 1 &lt;Synthesis of diteric acid triazine active vinegar&gt; 4.2 parts of isophthalic acid, 2-chloro-4,6-didecyloxy-1,3,5-triazine 9·7 parts and fluorenyl-fluorenyl group were added to the flask of the thermometer, nitrogen inlet tube and stirrer. The 2-π ratio 11 bites _ 100 parts each and is cooled to 〇°c. Thereafter, 7.6 parts of N-methyl hydrazine was added dropwise under the administration of the reaction for 15 minutes to obtain the following formula (2) &quot; A reaction liquid of the dicarboxylic acid triazine active ester represented. The reaction solution was poured into 1000 parts of ion-exchanged water, and the precipitated product was separated by filtration, and then recrystallized by a mixed solvent of ethyl acetate and n-hexane, and dried to obtain a white dicarboxylic acid triazine active ester. Powdery crystalline resin enamel powder 1 (yield 23%). Synthesis Example 2 &lt;Synthesis of Dicarboxylic Acid Triazine Active Vinegar> I-Adding 6·5 parts of diphenyl^-4,4'-dicarboxylic acid to a flask equipped with a thermometer, a nitrogen introduction tube, and a stirrer - Benzene-4,6-dimethoxy-1,3,5-triazine 9·7 parts and hydrazine-methyl 2_ oxalidone 1 part, and cooled to hydrazine. Hey. Thereafter, 7.6 parts of hydrazine-methyl phenanthrene was added dropwise under stirring, and the reaction was carried out for 15 minutes to obtain the following formula (3) [Chemical 6] 17 201200538 30 / ΗΐρΐΙΙ No. 100119541 Chinese manual No straight line correction This correction Date: September 15, 100 A reaction solution of a dicarboxylic acid triazine active ester represented by OCH3 N human N 〇An and OCH3 (3). The reaction solution was poured into 1000 parts of ion-exchanged water, and the precipitated product was separated by filtration, and then recrystallized from a mixed solvent of ethyl acetate and n-hexane, and dried to obtain a white powder of a dicarboxylic acid triazine active ester. Crystalline resin powder 2 (yield 43%). Synthesis Example 3 &lt;Synthesis of dicarboxylic acid triazine active ester&gt; To a flask equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 2-hydroxy-4,6-dimethoxy-1,3,5- was added. 3.1 parts of triazine, 50 parts of N-mercapto-2-pyrrolidone and 2.0 parts of triethylamine, and cooled to 0 °C. Thereafter, 2.0 parts of dioxonium chlorohydrazine dichloride was added, and the reaction was carried out for 20 minutes to obtain the following formula (2) [Chemical 7] The reaction liquid of the dicarboxylic acid triazine active ester of the present invention represented by OCHa 〇 Q η3οοαν^〇^0Λ 0 . The reaction solution was poured into 500 parts of ion-exchanged water, and the precipitated product was separated by filtration. Then, it was recrystallized by a mixed solvent of ethyl acetate and n-hexane, and dried to obtain a white powder of di-s-acid-activated active ester. Crystalline resin powder 3 (yield 60%). 18 20120053 8i Si 100119541 Chinese saying duck without scribing correction This revision period: September 15th, 100th Example 1 &lt;Synthesis of polybenzoxazole precursor resin&gt; ^Installation of thermometer, nitrogen inlet tube, The flask of the agitator was subjected to a nitrogen purge. 'Stirring dissolved 3 parts of 3,3,-dihydroxy-4,4'-diaminobiphenyl, 205 parts of fluorenyl-pyridylpyridone' and then adding 54 parts of the above obtained The resin powder 2 of the carboxylic acid triazine active ester was reacted at 20 ° C for 12 hours to obtain a reaction liquid of a poly-peptidic resin. The reaction solution was poured into 2000 parts of decyl alcohol, and the precipitated resin was separated by filtration and further washed with 2 parts of decyl alcohol and then subjected to methanol reflux to purify. Then, filtration was carried out after cooling to room temperature. The filtrate was dried to obtain a polybenzoxazole precursor resin powder 1 (yield 98%). The molecular weight (Mw) and the molecular weight distribution (Mw/Mn) determined by gel permeation chromatography (hereinafter, GPC) in terms of polystyrene were 114,000 and 2.4, respectively. Further, 4 g of the resin powder and 40 g of Millipore water were treated at 121 ° C for 20 hours, and then ionic impurities (P-type ions, C1 ions) were analyzed by ion chromatography on the extract. The results are shown in Table 1. ^Comparative Example 1 <Synthesis of polybenzoxazole precursor resin by a conventionally known method> A flask equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer was subjected to nitrogen purge, and 16 parts of isophthalic acid were added, 3 21 parts of 3'-dihydroxy-4,4'-diaminobiphenyl, 1 part of lithium hydride, N-methylpyrrolidone part, 23 parts of acridine, and stirred and dissolved, then added triphenyl phosphite 50 parts of the ester was reacted at 90 ° C for 8 hours to obtain a reaction liquid of a polystyrene and an oxazole precursor resin. The reaction solution was poured into 1000 parts of methanol, and the precipitated resin was filtered. 19 201200538 JO /^ιριιι is the 100119119 Chinese manual without a slash correction. The correction date _ September 15 is separated, and then 200 parts of methanol are used. After washing, it was purified by refluxing with methanol. Then, after cooling to room temperature, it was dried to obtain a comparative resin powder 1 (yield was /.). ‘477·7 The molecular weight (_) and molecular weight distribution (Mw/Mn) obtained by using GPC in terms of polystyrene were 3, _ and 24, respectively. At 121. . Next, 4 g of the resin powder and 4 μg of microporous water were treated for 2 hours, and after the absence, the ionic impurity pattern (C1 ion) was analyzed by ion chromatography for the extract. The results are shown in Table 1. Comparative Example 2 &lt;Synthesis of Polystyrene and Presence Resin Resin by a Previously Known Method&gt; In addition to changing the meta-dicarboxylic acid of the comparative resin powder i to diphenyl ether-4, 4'-two thief 25 parts The reaction liquid and the comparative resin powder 2 (yield 85%) were obtained in the same manner. The molecular weight (Mw) and the molecular weight distribution (Mw/Mn) determined by using GPC and converted according to the poly(ethylene) were 5, 〇〇〇 and 26. 4 g of the resin powder and 40 g of microporous water were treated at 121 Torr for 2 hours, and then the ionic hetero-C1 ion was analyzed by ion chromatography for the extract. The results are shown in Table H ^ + Comparative Example 3 &lt;Synthesis of Polybenzoxazole Precursor Resin by a Previously Known Method&gt; A flask equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer was subjected to nitrogen purge, and added. 8 parts of isophthalic acid, 3,3,-dihydroxy-4,4,-diamino group, 11-injection, 2-gas-4,6-monomethyl-lactyl-1,3,5-triazine 19 Parts and Ν-mercapto-2-pyrrolidone 200 parts. Thereafter, Ν_methylmorpholine was added dropwise with stirring. 15 20 201200538 Revision date: September 15, 100, No. 100119541 Chinese manual, no slash correction, and then reacted at 20 C for 12 hours to obtain a poly A reaction solution that is stupid and devastating to the precursor resin. The reaction solution was poured into 2 parts of decyl alcohol, and the precipitated resin was separated by filtration, washed with 2 parts of decyl alcohol, and then refluxed with methanol to purify. Then, after cooling to room temperature, it was filtered, and the filtrate was dried to obtain a comparative resin powder 3^' of 93%).分子量 Ο The molecular weight (Mw) and molecular weight distribution (Mw/Mn) determined by polystyrene conversion using GPC were 4, 1 and 22, respectively. Further, 4 g of the tree end and 4 g g of the microporous water were treated at 121 ° C for 2 () hours and then ionic impurities (p-type ions, Cl ions) were analyzed for the extract ion chromatogram. The results are shown in Table 1. Comparative Example 4 &lt;Kurtz-known method Synthesis of bismuth benzopyrene precursor resin&gt; In addition to changing the terephthalic acid of Comparative Example Resin Powder 3 to diphenyl scale: 4 2, New U 份 卜 ' _ The reaction liquid and the comparative resin powder 4 (yield 85%) were obtained. The molecular weight (Mw) and the distribution of the sub-$ (Mw/Mn) determined by GPC in terms of polystyrene were 6, 3 and 23, respectively. Under 121 force =, 4 g of powder and 40 g of microporous water were subjected to 2 (H, time treatment, for the stroke liquid ion layer _ analysis ion _ system C1 ion). The results are shown in Table 1. ’ 21 201200538 ^δ/^ιριιΐ Revision date: September 15th, 100th The Chinese manual No. 100119541 has no scribe correction [Table 1] Example resin powder 1 Comparative Example Resin Powder 3 Comparative Example Resin Powder 4 6200 | The limit value is below the limit value below the ionic impurity/ppm value C1 ion Ϊ~ 130 150 ~~5~ ~6~ [Industrial availability] (4) It is suitable for electrical and electronic parts such as semiconductors or energy-saving bag I I I 细 细 细 细 细 I I I I I I I I I I I I I I I 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 笨 I , secondary battery separators, insulation materials, and a variety of (four), food packaging and clothing. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of coverage is subject to the definition of the scope of the patent application. [Simple description of the picture] Blood. "*, [Description of main component symbols] 益〇22 201200538 is the Chinese manual of the l5〇l 19541 without a slash correction. Amendment date: September 15, 100 invention patent specification (this specification format, order and bold type ' Please do not change it arbitrarily, please do not fill in the ※ mark ※※Application number ※Application date: /0,( ' Classification: I. Invention name: (Chinese / English) Polybenzopyrene resin and its precursor resin POLYBENZOXAZOLE RESIN AND PRECURSOR RESIN THEREOF O II. SUMMARY OF THE INVENTION The present invention provides a polybenzofluorene precursor resin useful for reducing the content of ionic impurities in electrical and electronic parts, and a dehydration ring closure of the former = resin. (4) Benzoin. The polybenzoic noise is obtained by using the following formula (A) Ο f and η η indicate that the structure contains a divalent material group residue selected from 〇, n, s, or 素, or an aromatic shell residue having a carbon number of 6 to 8 represents a carbon number of 1 to 4 Polyalkyl group, or carbon number stupid poly: anti = = slow: triazine active (four) and diamine based! 〇, 〇 00~1 〇〇〇 _ reaction obtained 'its weight average molecular weight of 5 range, And the content of ionic impurities is 10 ppm 201200538 Revision date: September 15th, 1st, 1st, 2015, No. 100119541 Chinese manual, no underline correction. The polybenzoxazole precursor resin and a polybenzoxazole precursor are provided. The polybenzoxazole precursor resin, the content of ionic impurities is decreased, is useful in applications of electric and electronic parts. The polybenzoxazole resin is obtained by cyclodehydration of the The polybenzoxazole precursor resin is obtained by polymerizing a dicarboxylic acid triazine active ester represented by the following formula (A) (in formula (A), Rj represents a divalent aromatic residue containing one or more elements selected from Ο, N, S, F and Si in the structure, or a divalent organic group having 1 to 12 carbons; R2 represents an alkyl group having 1 to 4 carbons or an aromatic residue having 6 to 8 carbons.) with a bisaminophenol compound, wherein the weight average molecular weight is in a range of 10,000 to 1,000,000, and the content of ionic impurities is 10 ppm or less. 2 201200538" Amendment date: September 15th, 100th is the Chinese manual No. 1 &amp;0119541. There is no slash correction. 7. The scope of application: 1. A polybenzazole and 11 sputum precursor resin, which is the following ] A lA) 〇 (A) I (in the formula (Α) represents a divalent aromatic residue having one or more elements selected from the group consisting of ο, Ν, s, F, and Si, or a enthalpy of carbon number 12 An organic group of a shell; &amp; represents an alkyl group having a carbon number of 1 to 4 or an aromatic residue having a carbon number of 6 to 8), wherein the represented dicarboxylic acid triazine active ester is reacted with a bisaminophenol compound to obtain Further, the poly-benzoxazole precursor resin has a weight average molecular weight of 10,000 to 1,000,000 and an ionic impurity content of 1 〇 ppm 0 or less. 2. The polybenzoxene salivary precursor resin according to claim 1, wherein r2 of the formula (A) is an alkyl group having 1 to 4 carbon atoms. 3. The polybenzoxazole precursor resin as described in claim 1 or 2 wherein the formula (A) is selected from the following formula (1) [Chemical 2] 23 201200538 JO / H-lpili is the Chinese manual of No. 100119541. There is no slash correction. This revision period: September 15, 100 (wherein R4 represents a group selected from the group consisting of *0, N, S, F, and Si; a substituent having a carbon number of 1 to 6 in the structural element; \ means direct bonding, hydrazine, a carbon number of S, F or Si ' or an element comprising a group selected from the group consisting of 〇, N, s, 卩N, 二, N, s, 卩N, and the bivalent combination of ～6 and Si b, c and d For the average number of substituents, a, b, and e represent the divalent aromatic aryl group in the group represented by the heart '^, which represents an integer of G 1-6, respectively. 4. The polyphenylene group as described in claim 3 Chewing saliva, wherein R4 of the formula (1) is a hydrogen atom, and hydrazine is a direct bond, a sulphur or a CO. And a benzoxazole resin obtained by dehydrating a polybenzoxazole precursor resin according to any one of the above claims. 24 201200538 ί ΐ 〇 〇 541 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 (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: 3