TW201105680A - Tetracarboxyic dianhydride and polymer - Google Patents

Abstract

The present invention provides a tetracarboxyic dianhydride represented by following formula (1), and a polyimade having excellent solvent soluability, Tg and low dielectric constant obtained by the tetracarboxyic dianhydride: In formula (1), A is at least a divalent linking group of a replaced or not replaced structure represented by following formulas (2)-(4), and Z, Z' independently represent an atom group for forming saturated or unsaturated carbon ring or heterocyclic with two carbon atoms of oxane ring.

Description

201105680l A VI. Description of the Invention: [Technical Field] The present invention relates to a tetracarboxylic dianhydride useful as a functional material such as a liquid crystal material, a nonlinear optical material, an electronic material, or an adhesive material, and The tetracarboxylic dianhydride is a polymer of a constituent component. [Prior Art] Polyimide has properties such as heat resistance, chemical resistance, insulation, and excellent mechanical properties, and thus is widely used for liquid crystal materials, nonlinear optical materials, electronic materials, and adhesives. Functional materials such as materials. However, since the polyimine which usually has a rigid skeleton is large, it is insoluble in an organic solvent, and the glass transition point (Tg) is also 300 C or more, the polyimine itself is molded and not easy. Therefore, a method of performing a molding process by using a polyimide precursor which exhibits high solubility to an amide organic solvent is usually used. Specifically, after the aprotic organic solvent solution of the polyimide precursor is coated and dried, it is heated at a high temperature of 250 ° C to 350 ° C to carry out a dehydration ring-closing reaction, thereby forming a reaction. Polyimine film. However, the temperature of the imidization reaction is so high that the above-mentioned film forming step is sometimes not applicable in some fields. For example, a color filter that is indispensable for colorization of a liquid crystal display has a heat-resistant temperature of about 2 ° C, and is intended to form a liquid crystal alignment film by a ruthenium imidization of a polyimide precursor. The imine film, at this temperature, could not complete the imidization reaction of the coating film of 醯1 1201105680. In recent years, the high integration of electronic materials has been remarkable, and the dielectric constant of the polyimine raw material has been reduced as the wiring pitch of the printed-circuit board has been miniaturized. In order to reduce the heat treatment temperature, it is expected to reduce the glass transition point of the polyimide pigment raw material as a countermeasure against the increase in density of the semiconductor element. A polyimide which has a high solvent solubility is known as a polyester ylide (for example, 曰 Patent Publication No. 2005-298623, Japanese Patent Laid-Open No. 2007-137960, and "High Performance Polymer" (Twisting) Performance P〇iymer), 2 〇〇 6 years, vol. 18, p 697 〜p wherein the polyester quinone imine having a lower glass transition point is exemplified by the polyester described in JP-A-2005-298623醯imine, etc. However, the solvent for dissolving polyimine can be limited to N-methyl pyrr〇iidone (NMp), N,N•dimethylacetamide (N, N -dimethylacetamide, DMAc) and other high-boiling guanamine solvents, which are soluble in methyl ethyl ketone (methyI ethyI ket〇ne, m, etc., are difficult to test by general-purpose sol- ing. Moreover, the yttrium imine is converted to multiple points. 200. (: The above 'and the dielectric constant is also 3 or more and the like ^ can fully satisfy the above-mentioned reduction of the dielectric constant, the drop-precise point. [Invention] The object of the present invention is to have a specific structure The group is incorporated into the aggregate, and the realization is (4) the polymerization (10) solvent solubility: low dielectric constant Lowering the glass transfer point. Falling 201105680 The inventors of the present invention have determined the specific _acid dianhydride in view of the above situation, and found out from the fruit: the people who discovered the use of the four Wei Erxuan = Er Bucheng: I Ming That is, the above-mentioned problem of the present invention is specifically achieved by the following technical means. <1> A tetrabasic acid dianhydride is represented by the following formula: [Chemical Formula 1]

In the general formula (1), 'A is a divalent linking group having at least one of the substituted or unsubstituted structures represented by the following general formulae (2) to (4)) , [Chemical 2] 7 201105680 00 General formula (2)

General formula (3)

CD General formula (4) (In the general formula (3), Z and Z' are independent of each other, and represent a saturated or unsaturated carbocyclic or heterocyclic atom group together with two carbon atoms of the oxane ring. ). &lt;2&gt; The tetracarboxylic dianhydride as described in <1>, wherein in the above formula (1), A is represented by any one of the following formulae (5) to (7). .

[化3] 8 201105680

O

General formula (5) 4

r General formula (6) • 2

L 2 general formula (7 - 1)

In the formula (7-2), 'Ll, Ll', L2, L2' are independent of each other, and represent a single bond, 2i/ydQdkylene gr〇up) or a divalent aromatic ring group; Z, Z, mutual. ^ represents not a saturated or unsaturated, ring or heterocyclic group together with two carbon atoms of the methane ring; R1, independently of each other, represents a chloroproton or a cyclic or acyclic (tetra) hydrocarbon; Ri, R2 They may also be bonded to each other to form a garment, and nl is independent, indicating an integer above. &lt;&gt; The tetraacid dianhydride as described in <2>, wherein in the above (5) to (7), L1, V, L2, ; l2 are independent of each other, and the formula is extended or extended. base. 4, 鞑, 9 201105680 &lt;4&gt; A polymer which is synthesized from at least one diamine compound, and the tetracarboxylic dianhydride as described in any one of &lt;1&gt; to &lt;3&gt;. &lt;5&gt; The polymer according to <3> or <4>, wherein the diamine compound is an aromatic diamine compound. &lt;6&gt; The polymer according to &lt;4&gt; or <5>, wherein the polymer is a polyester quinone imine or a polyether phthalimide. &lt;7&gt; A composition comprising the polymer according to any one of &lt;4&gt; to &lt;6&gt;. The above and other objects, features and advantages of the present invention will become more <RTIgt; [Embodiment] &lt;Description of tetracarboxylic dianhydride&gt; Hereinafter, the present invention will be described in detail. One form of the present invention is a tetracarboxylic dianhydride which is represented by the following general formula (1). [Chemical 4]

Hereinafter, A will be described. In the formula (1), A is a divalent linkage having at least one of the substituted or unsubstituted structures represented by the following general formulae (2) to (4);

rL

s#r

General formula (2) General formula (3) General formula (4) In the general formula (3), Z and Z' are independent of each other and represent a bond. The two carbon atoms of the cauterized ring together form a saturated or unsaturated carbocyclic or heterocyclic group. In particular, A is preferably a structure represented by any one of the following general formulae (5) to (7) from the viewpoint of allowing solvent solubility and low dielectric constant to coexist to a greater extent. Wherein the formula (7) refers to both the formula (7-1) and the formula (7-2). [化6] 11 201105680

General formula (s) general formula (6)

L2·. General formula (7 1)

1. Ll', L2, and L2' are independent of each other and represent an I-based or divalent aromatic ring group. z, 2, mutual _ 鏠, 伸 基 ' ::,, together with the formation of saturated or unsaturated carbon 戸ΐ. Oxane atomic group. R1 and R2 are independent of each other and represent a radical of a heterocyclic ring of a hydrogen atom. The three rings or non-rings indicate that the above number can be bonded to each other to form a ring. Μ are independent, (ml) two, Γ, 1, the extension of the base can be listed as: methylene ethyl (ethylene), triamethylene (trimethylene), tetramethylene (time Lanxian), Liuya Hyperthyroidism 12 201105680 (hexamethylene), etc. ° The cycloalkylene group represented by L], IV, L2, IV is a cyclohexyl group, a 1,3-cyclohexylene group or the like. Bovine, 4-extension The aromatic ring group represented by k, IV, L2, and L2' can be exemplified by phenylene, naphthylene, and thiophene. The main extension group, the exocyclic group and the aromatic ring group may be unsubstituted or have a substituent. Examples of the substituent include the substituents described below. Further, from the viewpoint of availability of raw materials, A is more preferably a structure represented by any one of (1) to (11). [化7] 13 201105680,

The general formulae (2) to (4) may be unsubstituted or substituted by other substituents. Examples of the substituent of the formula (2) to the formula (4) include a halogen atom (_F, -Br, -Cb-I), an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. (aralkyl), alkoxy, aryloxy, mercapto, alkylthio, arylthio, alkyldithio, aryldithio, N-alkylamino, N, N-diarylamino, N-alkyl-N-arylamine, acyioxy, amine methyl methoxy, N-alkylamine methyl methoxy, N-arylamine hydrazine Oxy, N,N-dialkylamine decyloxy, hydrazine, fluorene-diarylamine methyl methoxy, N-alkyl Ν aryl amine methyl methoxy, alkyl sulfonyloxy ( Alkyl sulf0xy), aryl fluorenyloxy, fluorenylthio, decylamino, N-alkylhydrazine, N-aryl 醯 201105680 λ ϊ 胺 、, ureido 'N,- Sodium carbazide, n, N,-dialkyl gland, Ν'-aryl ureido, N', N'-diaryl ureido, N,-alkyl-N,-aryl ureido , N-alkylurea group, N-arylureido group, ν'-alkyl-N-institutional gland group, N,-alkyl-indole-arylureido group, Ν·,Ν'_dialkyl group -Ν-alkylureido, ν,,Ν,-dialkyl- Ν-• arylureido, Ν'-aryl-Ν-alkylureido, fluorene,-aryl-fluorene-arylureido, Ν', Ν'-diaryl-fluorenyl-alkylureido ,Ν',Ν'-diaryl-fluorene-arylureido, Ν'-alkyl-oxime,-aryl-oxime-alkylureido, oxime,-alkyl-oxime,-aryl-oxime - aryl urea group, alkoxycarbonylamino group, aryloxycarbonylamino group, fluorenyl-fluorenyl-hydrazine-alkoxyamino group, fluorenyl-alkyl-aryloxyamino group, Aryl-fluorene-alkoxy group, fluorenyl-aryl-fluorenyl-aryloxyamino group, aryl (f〇rmy 1 ), aryl, decyloxy, alkoxycarbonyl, aromatic Carbocarbonyl, arylcarbonyloxy, aryloxycarbonyl, amine fluorenyl, N-alkylamine fluorenyl, N,N-dialkylamine fluorenyl, N-arylamine fluorenyl, N , N-diarylamine fluorenyl, N-alkyl-N-arylamine fluorenyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, aryl fluorenyl , alkoxy fluorenyl, aryloxy fluorenyl, sulfinamoyl, N-alkylamine sulfinyl, n,N-dialkylamine arsenyl, N-aryl Amidino, N,N-diarylamine, N-homo-N-square Alkyl sulphate, sulfamoyl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine sulfonyl, fluorene, fluorene-. Diarylamine sulfonyl, fluorenyl-alkyl-fluorene-arylsulfonyl, dialkylphosphonic acid, diarylphosphonic acid, alkylarylphosphonic acid, monoalkylphosphonic acid , mono-arylphosphonic acid, dialkyl phosphonooxy, diarylphosphoniumoxy, alkylarylphosphoniumoxy, monoalkylphosphoniumoxy, monoarylphosphine oxygen Base, morpholino, cyano, nitrate 15 201105680 nitro. Specific examples of the alkyl group in the substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, and isobutyl group. , a second butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1-decyl butyl group, an isohexyl group, a 2-ethylhexyl group, a 2-decylhexyl group, a cyclopentyl group and the like. Specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesylate group, and a cumyl group. Cumenyl), gas phenyl, phenyl, gas methylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, benzoquinone Phenylphenyl, methylthiophenyl, phenylthiophenyl, methylaminophenyl, dinonylaminophenyl, ethoxylated aminophenyl, carboxyphenyl, decyloxycarbonylphenyl, Ethoxyphenylcarbonyl, phenoxycarbonylphenyl, N-phenylamine, mercaptophenyl, cyanophenyl, sulfophenyl, suifonat phenyl, phosphonic acid Phosphonophenyl, phosphonatophenyl, and the like. Further, examples of the alkenyl group include vinyl (vinyl), 1-propenyl, 1-butyryl, cinnamyi, and 2-chloro-l-ettienyl. )Wait. G in the fluorenyl group (GfO-) includes hydrogen and the above alkyl group and aryl group. The aralkyl group may be a group obtained by substituting the above aryl group on the above alkyl group. From the viewpoints of availability of raw materials and ease of production, preferred among the substituents are a functional group atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, an alkoxy group, a decyloxy group, and a decyl group. An amine group, an aryl group having 6 to 1 Å, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxyl group, a cyano group, or an unsubstituted group, more preferably 201105680. is unsubstituted. Z, acetamidine in the formula (3). Sub-, p μ saturated or unsaturated carbon ring; atom-shaped ^ is a six-membered ring. Preferred are aromatic rings or heterocyclic rings. Preferred aromatic rings are: stupid, 喆r.j, phenyl, tetrahn, etc.; ^ indane, naphthalene, thiophene , pyrrole eight, can be listed. Furan (f), (thi〇Pyran), „比π定(=e), 吼 ( (Pyran), face (thiazole), σ米嗤 (丨丨)&quot;(GxazGle)&quot;triazine, ind:, Pyrimidine, triazine, quinone, quinoline, purine, (cajole) pyridine, 嗟 吻 。 。 。 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 吡 ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca Let the second, benzoquinone ° plug. Sit, seven evil, ten sitting, etc. Cai, material = is the aromatic ring of benzene, (four) full, better than the benzene. From the point of view of the convenience, ease of manufacture, Special ring. Good is a four-membered ring ~ six-membered ring, more preferably six-membered pyrimidine is strictly 1 ^ ring, ° than wow ring (Pyrazole Γ (four)), ° than bite ring, in the 疋::? Lin ring, dissipate Ring, etc. Particularly good is the (four) ring. The D heteroaromatic ring may also be substituted by other substituents. The substituent, ",", the original f (-f, _, -α, -1), alkyl, alkenyl, aromatic, alkoxy, aromatic Oxyl, fluorenyl, alkylthio, arylthio, 17 201105680. alkyl dithio, aryl disulfide, N-alkylamino, N,N-diarylamine, N-hospital N-arylamino, decyloxy, aminoxy, n-alkylamine decyloxy, N-arylamine methyl methoxy, ν, Νdialkylamine methyl methoxy, N,N-diarylaminemethyloxy, N-alkyl-N-arylamine oxime, alkylsulfonyloxy, arylsulfonyloxy, sulfonylthio, decylamino , N-alkyldecylamino, N-aryldecylamine, ureido, N'-alkylureido, N, N,-dialkylurea, N-arylurea, N,,N,-diarylureido, N,-alkyl-N,-arylureido, N-alkylureido, N-arylureido, N,-alkyl-N-alkyl Urea, Ν'-alkyl-N-arylureido, Ν', Ν'-alkyl-N-alkylureido, N, N,-dialkyl-N-arylureido, Ν'-Aryl-N-alkylureido, N,-aryl-N-arylureido, Ν', Ν '-Diaryl-fluorenyl-ureido group, ν, Ν,-diaryl-fluorene-arylureido, Ν'_alkyl-Ν'_aryl-Ν-systemylurea, Ν ,-alkyl-hydrazine,-aryl-fluorene-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, fluorenyl-alkyl-hydrazine-alkoxycarbonylamino, fluorenyl-alkyl - anthracene-aryloxycarbonylamino, fluorenyl-aryl-hydrazine-alkoxycarbonylamino, fluorenyl-aryl-fluorene-aryloxycarbonylamino, fluorenyl, fluorenyl, decyloxy, alkane Oxycarbonyl, arylcarbonyl, arylcarbonyloxy, aryloxycarbonyl, aminyl, fluorenyl-alkylamine, fluorene, hydrazine, dimethyl-dialkylamine, arylamine Base, hydrazine, fluorene-diarylamine fluorenyl, fluorenyl-alkyl-fluorene-arylamine, sulfinyl, arylsulfinyl, alkylsulfonyl, aryl Sulfonyl, alkoxysulfonyl, aryloxysulfonyl, amine sulfinyl, alkylamine sulfinyl, hydrazine, hydrazine-dialkylamine sulfinyl, hydrazine-arylamine Sulfosyl, anthracene, fluorene-diarylamine sulfinyl, fluorenyl-hydrazino-arylamine sulfinyl, amidoxime, hydrazine-alkylamine sulfonyl, hydrazine, hydrazine -dialkylamine sulfonyl, fluorene-aryl Amidoxime, hydrazine, hydrazine-diarylamine sulfonyl sulfonyl, fluorenyl-alkyl-hydrazine-aryl 18 201105680 } Amine, bis-phosphonate, diarylphosphonic acid, alkyl Aryl sulphate, mono phosphino, monoaryl, bis, aryl, diarylphosphonium A, hexamethyloxy, benzyl lysine, monoarylphosphonium oxy , morpholinyl, cyano, nitro. Specific examples of the alkyl group in the above substituents include a mercaptoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isopropyl group, an isobutyl group, a second butyl group, and a Tributyl, isopentyl, neopentyl, indenyl butyl, isohexyl, 2-ethylhexyl, 2-decylhexyl, cyclopentyl and the like. Specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a phenyl group, a xylyl group, a [bell+m] group, an isopropyl group, a chlorophenyl group, a bromophenyl group, and a benzylbenzene group. Base, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated, phenyloxyphenyl, methylthiophenyl, phenylthiophenyl , methylaminophenyl, dinonylaminophenyl, ethionylamino, carboxyphenyl, decyloxycarbonylphenyl, ethoxyphenylcarbonyl, phenoxycarbonylphenyl, N_ The benzylamine is a mercaptophenyl group, a cyanophenyl group, a phenyl group, a phenyl group, a phosphonic acid phenyl group, a phosphonic acid phenyl group, and the like. Further, examples of the alkenyl group include an ethylene group, a 1-propenyl group, a 1-butyl group, a phenylallyl group, a 2 gas group, and the like. G1 in the mercapto group (G1CO·) includes hydrogen and the above alkyl group and aryl group. The aryl group may be a group obtained by substituting the above aryl group on the above-mentioned alkyl group. From the viewpoints of availability of raw materials and ease of production, preferred among the substituents are a halogen atom, a carbon group having 1 to 8 carbon atoms, a cycloalkyl group, an alkoxy group, a decyloxy group, or a mercaptoamine. Base, carbon number 6 to 10 aryl, aryloxy, arylalkyl, aryloxy, thiol or cyano substituted or unsubstituted benzene, special 201105680 分丨~ ^ y Γ The methyl group or the unsubstituted benzene β is represented by L!, L! in the formula (5), and the exudyl group represented by the formula: methylene soil, exoethyl group: trimethylene group, tetramethylene group, and six Methylene and the like. Further, examples of the stretching ring group represented by 1, 1 and 2 are Μ-extension ring hexyl group, ^-extension ring hexyl group and the like. The aromatic ring group represented by k and L is preferably an onion group or the like, and preferably a phenyl group. The bases of the formula (6), R1 and R2, independently of each other, represent nitrogen, a cyclic or acyclic hydrocarbon group which may be optionally substituted, or a heteroalkyl group, and R1 and r2 may also be phase-bonded to form ruthenium. Examples of the unsubstituted tobacco group include a straight bond or a bond of carbon number: 20: an aliphatic group, an alicyclic group having a carbon number of 3 to 2 G, and an aromatic ring having a carbon number of 6 to 2 G. The above-mentioned linear or branched lipid group can be heard: a hospital base (for example, methyl, propyl, isopropyl, butyl, t-butyl, t-butyl, "if j 2 ethyl? Base: octyl, 12-yard base, etc.), stretching base (for example, producing T-alkenyl, etc.); alicyclic group can be exemplified by ring-based base (such as sulfhydryl, % hexyl, menthyl, etc.) , cycloalkenyl (such as cyclohexenyl, etc.), alicyclic polycyclic group (example domain (bQrayi), descending, ki-ηγ1), decaHnyl, admamyl Examples of the aromatic ring of the above aromatic ring group include benzene, naphthalene, g (flu), anthracene, anthracene, indane, biphenyl, and the like. Examples of the hydrocarbon group include a group which is touched by a fresh-scented ring or a collar compound. Examples of the heteroaromatic ring include a bite, a porphin, a scale, a _, a snail, a singe, a shot, a sputum, a sputum, a shot, and Triazine" bow Bu Duo, Yu Lin, 嗓 201105680 呤, benzoquinone saliva, benzoquinone &lt; 7 plug 0 sit, 啥. Evil Lin, Yuka Jun and so on. Examples of the heteroalicyclic compound include oxetane, thietane, azetidine, oxolane, and thiolane. , "&py; pyroline, pyrrolidine, 0 to 0 (pyrazoline), ° m alpha (imidazoline). Plug. Thiazoline, pyran, oxane, thiane, piperididine, morpholine, coumaran, chromane, D-bito-ketone. The hydrocarbyl or heterohydrocarbyl group which may be optionally substituted may be a hydrocarbyl group or a heterohydrocarbyl group having a structure in which a group is substituted at any position of the above-exemplified unsubstituted hydrocarbon group: a halogen atom (for example, a fluorine atom, a gas atom, or a bromine group) Atom of the atom 'moth atom, cyano, nitro, continuation base, decylamino group, alkoxy group having a carbon number of 〜2 〇 (for example, methoxy group, τ oxynoxy group), carbon number 2020 Amino group (e.g., ethenylamino group, benzylideneamino group, propylamino group, etc.), an aryl group having 6 to 20 carbon atoms (e.g., phenyl, decyl, etc.), hydroxy group, decyl group Wait. ★ R and R are preferably a hydrogen atom, a sulfhydryl group, a ring-based group, an alicyclic group, a phenyl group, a naphthyl group, or a phenyl group. From the viewpoint of workability, a hydrogen atom is particularly preferred ( Z and Z in 6) are the same as those described for z and z. in the above formula (soil 3), and the preferred ranges are also the same. It is the same as the general formula (7-1) or the general formula (7), and the preferred range is also (there is no particular limitation; in the case of an integer of two H1 or more of mechanical properties), a preferred one is preferable. It is 1 or more and 21 201105680 10 or less. It is more preferably 1 or more and 3 or less from the viewpoint of raw material availability. Specific examples of the tetracarboxylic dianhydride of the present invention are disclosed below, but the present invention is not This limitation. [Chemistry 8]

[Chem. 9] 22 201105680 . Yan * r

(2) one 10

[化 10] 23 20110568α

(3)-9 (3)-10 &lt;Explanation of a method for producing tetracarboxylic dianhydride&gt; Next, a method for producing the tetracarboxylic dianhydride of the present invention will be described. The tetracarboxylic dianhydride of the present invention is a diol represented by the following formula (19) and a trimellitic anhydride derivative represented by the following formula (20). [Chem. 11] 24 201105680 ho-a-oh General formula (19) 〇 〇

In the formula (19), A is the same as A in the formula (i), and preferably has the same circumference. In the formula (2〇), 'X' can be exemplified by a halogen atom (fluorene fluorene, gas (C1), ^^Γ), 峨(1)), and a fluorene group (then) (〇S(=0) 2CH3), tosyl (p 2C6h4CH3), etc., preferably a gas atom, a sulfonyl sulfhydryl group (〇S(=0)2CH3), a sulfonylsulfonyl group &lt;:P_〇 S(=〇)2C6H4CH3) 'The reason is that tetracarboxylic acid monoanhydride can be obtained in high yield, and a particularly good helium atom is obtained from the viewpoint of availability of raw materials or ease of production. And a trimellitic anhydride derivative represented by the formula (2G) in terms of the advantage that the amount of the unreacted material of each of the compounds represented by the general formulae (19) and (20) is low as a raw material The amount of use is preferably from 2 〇 kHz to ig 倍 moles, more preferably from 2G MPa to 3 〇 摩尔, more preferably疋 2.1 times the molar amount to 2 $ moles. As a solvent that can be used as a reaction, as long as it does not cause problems in the operation of the steps, etc., the sand is impaired, and in the process of _ _, 眺, thioacetate 25 201105680 χ Will not be decomposed after decomposition Should (4) reduce the impact (four) material limit, if the following solvents can be used alone or in combination: guanamine solvent (such as monoamine, hydrazine, hydrazine - dimethyl acetamide, 丨 曱 _2 _2 - - 比 比 咯 咯鲷), sulfone g solvent (eg sulfolane), sulfoxide solvent (eg one',

a sulfoxide, a urea (urea) solvent (for example, tetramethylurea), a snail system S (for example, dioxane, cyclopentyl oxime ether), a solvent such as acetone , cyclohexanone), candlestick solvent (eg, stupid, _-monomethylbenzene, n-decane), halogen solvent (eg tetrachloroethane, chloroform, dioxin, chloroform), 0 to 0 is a solvent (for example, 〇 ratio, gamma-picoline, 2,6-dimethyl-mouth (2,6-lmidine)), 酉^22 (such as acetic acid) Ethyl ester, butyl acetate), and a nitrile solvent (for example, B). Among them, preferred are a guanamine-based solvent, an oxime-based solvent, an anthraquinone-based solvent, a di-glycolic solvent, an ether-based solvent, an i-based solvent, a pyridine-based solvent, a nitrile-based solvent, and a solvent, and more preferably an amide-based compound. The solvent, the ether solvent, the γ-based solvent 2 and the solvent are more preferably a guanamine-based solvent or a nitrile-based solvent. These two are used singly or in combination of two or more. The reaction temperature is preferably in the range of -30 ° C to 20 (TC range, more preferably β-catch to 縦C, more preferably russaries to thief. The reaction amount and reaction temperature vary, preferably 05 The range of hours to 12 hours, more preferably the range of 0.5 hours to ό hours. The environment during the reaction is preferably a sufficiently dried inert gas atmosphere. The presence of moisture causes a decrease in the reaction rate, so that it is preferred. It is a salty knife as much as possible, and a water knife is a specific example of an inert gas, and a rare gas such as argon gas can be preferably used. - 26 201105680. B phthalic anhydride ==::: = structural unit _ acid, etc. The method of separation and refining is carried out by crystallization or re-knotting, but it can be made into four _: two-two; the precipitation can also be separated from the tetracarboxylic dianhydride by appropriate dissolution: the crystal is separated as ϊ: ϊ. , d-based, sputum-based basic ether solvents such as acetonitrile and other nitrile solvents, two production = two gas-based system: agent: === and other ester solvents, acetone, methyl 7 / acetamidine容 crystallization and other secrets, clever rules, crystallization or re-acquisition _ (10), compared to (four) should be, safety, aromatic hydrocarbon solvent. Also preferred is a phthalonitrile oxime agent, an ester solvent, (mw..., 甲甲甲本 (may be an o-(〇-) body, any green (, Γ) body or a mixture of the (4) _4_ It is ethyl b, ethyl, cumene (cumene), more preferably P, body 1L, two women, acetophenone, toluene, dimethyl stupid (may be 〇 _ body, m body, P - Any one of a mixture of a mixture or a ratio of _, ethylbenzene. The above solvents may be used alone or in combination of two or more. <Explanation of a polymer containing tetra-iso as a structural unit> 27 201105680 The following description includes the polymer constituting the tarenic acid dianhydride of the present invention. The type of the polymer containing the tetrahedral compound of the above formula (1) is as follows: polyacetamide , poly-caffeine, y: amine amine, polyacetic acid, polyacetate: polyacetate, poly-imine, polyamine, urethane Polyether oxime imine. The amine compound of the machine is not specifically limited, and it is §, ideally a diamine compound. The compound does not have a special mosquito, and for example, an aliphatic chain type stone compound, an alicyclic type diamine compound, an aromatic diamine compound, and a guanamine compound can be used. Among them, the reactivity is controlled and incorporated in the polymerization temple. The diamine compounding agent is preferably an aromatic diamine compound, from the viewpoint that the dielectric constant of the polymer is maintained at 3 Å or less, and the polymerization is found to have a solubility in a low-foam solvent. For the purpose of the description, the conjugate may be a homopolymer or a block copolymer. The backbone skeleton may be any of aliphatic or aliphatic, and the main chain or the side chain may contain polyfluorene, preferably an aromatic backbone. In two specific examples, the following diamine compounds may be exemplified. The following diamine compounds may be used alone or in abbreviated form: p-phenylenediamine, m-phenylenediamine, o-diamine =, 1,4- Diamine-based benzene, hydrazine, 3·diamine-based ice methyl benzene, 1,3-nine chlorobenzene, 1,3-diamino-4-(ethenylamino)benzene, a Bis (amine hexamethylene diamine, 3,3'-diamine 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4,-di Amino-3,3,-二气联28 201105680κ Benzene, 2,2·-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4·-diamine linkage, 2,2'- Difluoro-5,5'-diaminobiphenyl, 3,3'-di-f--5,5'-diaminobiphenyl, 2,2,-digas-4,4'-diamine linkage Benzene, 3,3'-digas-4,4'-diaminobiphenyl, 2,2'-dichloro-5J-diaminobiphenyl, 3,3'-dichloro-5,5·- Diaminobiphenyl, 2,2'-di-di-4, quinone diaminobiphenyl, 3,3'-dibromo-4,4'-diaminobiphenyl, 2,2,-dibromo- 5,5'-diamino phenyl, 3,3'-di-5,5,-diamino phenyl, 2,2,-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-5,5'-diaminobiphenyl , 3,3'-bis(trishydrazinyl)-5,5,-diaminobiphenyl, 2,2'-bis(trimethylsulfonyl)-4,4,-diamine, stupid, 3, 3,-bis(triseodecyl)-4,4·-diaminobiphenyl, 2,2,_bis(trichloromethyl)_5,5,-diaminobiphenyl, 3,3'- Bis(trichloromethyl)-5,5'-diaminobiphenyl, 2,2'-bis(tribromomethyl)-4,4.-diamine biphenyl, 3,3,-bis (three Bromoindolyl)_4,4,-diaminobiphenyl, 2,2,-bis (three deserts -5,5,-diaminobiphenyl, 3,3,-bis(tribromoindolyl)-5,5,-diaminobiphenyl, 3,3'-diaminodiphenyl ether, 3 , 4,-diaminodiphenyl ether, 4,4,-diaminodiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl ether, 3,3,- Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4,-diaminodiphenyl guaiacene, 3,3'-diaminodiphenyl hard, 3,4'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl sulfone, bis(4-amino-3-methylphenyl) sulfone, bis(4-amino-3) -^phenyl)sulfone, bis(4-aminophenyl)sulfone, bis(3-aminophenyl)sulfonium, bis(5-fluoroaminophenyl)sulfone, bis(5-fluoro-3-amino) Phenyl)sulfone, bis(5-chloro-4-indoylphenyl)sulfone, bis(5-aza-3-aminophenyl)sulfone, bis(5-bromo-4-aminophenyl) Bis(5--3-aminophenyl) hard, bis(5-trifluorodecyltomenidophenyl) j, bis(5-difluoroindolyl-3-ylamino)sulfone, double (5_trichloromethyl_4_amine-based) stone wind, bis(5·di-mercapto-3-ylaminophenyl) stone wind, bis(5-tribromoindolyl_4_ 29 201105680, Aminophenyl) hard, bis(5-trimethylmethyl-3-I-aminophenyl) stone, 3 3, diamine, a diphenyl Ketone, 4,4'-diaminobenzophenone, 3,4,-diaminobenzhydryl: 4,4-monoamino-3,3'-dimethyldiphenylpyrene, 4,4'-diamino-3,3,-dichlorobenzophenone, 3,3,-diaminodiphenyl fluorene, 4,4,-diaminodiphenylcarbamate: 3 , 4'-diaminodiphenyl decane, 2,2.di(3.amino)phenylpropane, 22 bis(4-aminophenyl)propane '2-(3-aminophenyl)_2 -(4_Aminophenyl)propane, 2 2_bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 22-bis(4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)_2_(4-aminophenyl)-1,1,1,3,3-hexafluoropropane , 2,2-bis(4-amino-3.methylphenyl)propane, 2,2-bis(4-amino-3-phenylphenyl)propane, 151_bis(3-aminobenzene) Small phenyl, 1,1-di(4.aminophenyl)succinylethane, 丨-(3amino)yl-1-(4-aminophenyl)-1- Phenylethane, hydrazine bis-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, i,4-bis(3-aminophenoxy)benzene,丨, 4 bis(4-aminophenoxy)benzene, 1,3 bis (3-amino cumyl) phenyl, bis-bis-aminophenyl phenyl) benzene , 1,4-bis(3-aminophenylhydrazino)benzene, 〗 4, bis (4-aminol fluorenyl) benzene, 1,3-bis(3-amino-α,α-dimethyl Benzyl)benzene, iota, 3_bis(4-amino-α,α-dimethylbenzyl)benzene, iota, 4_bis(3_amino-α,α_:decylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene, deuterated bis-amino-α,α-di-trifluorodecylbenzyl)benzene, 13-bis (4 _Amino-α,α_Ditrifluorodecylbenzyl)benzene, 1,4-bis(3-amino-α,α_:-trifluorodecylbenzyl) stupid, 14•bis(4·amine Base-α,α-di-trifluorodecylbenzyl)benzene, 2 6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxybenzidine , 4,4,_bis(3-aminophenoxy)biphenyl, 4,^-bis(4-aminophenoxy)biphenyl, bis[4_(3-aminophenoxy)phenyl Ketone, bis[4-(4-aminophenoxy)phenyl]one, bis[4_(3-aminophenoxy)benzene 201105680 —· — W ^ yl] thioether, bis [4_(4 _Amino- phenyloxy) stupyl] sulphur, bis[4_(4·aminophenyl, yl), yl] sulfone, bis[4-(3-aminophenyloxy)phenyl]sulfone, bis[ 4_(5_Fluoro-4_aminophenoxy)phenyl]sulfone, bis[4-(5-fluoro-3-aminophenoxy)phenyl]sulfone Bis[4-(5-a-4-aminophenoxy)phenyl]sulfone, bis[4-(5-chloro-3-aminophenoxy)phenyl]sulfone, bis[4-(5-bromo) 4-aminophenoxy)phenyl]sulfone, bis[4-(5-j-3-aminophenoxy)phenyl]sulfone, bis[4_(5-trifluoromethyl-4-aminobenzene) Oxy)phenyl]sulfone, bis[4-(5-trifluorodecyl-3.aminophenoxy)phenyl]anthracene, bis[4_(5_di-methylmethyl-4-aminophenoxy) Phenyl]milled, bis[4_(5-trichloromethyl_3_aminophenoxy)phenyl]sulfone, bis[4-(5-tribromomethyl-4-aminophenoxy) Phenyl] stone, bis[4-(5-dibromomethyl-3-aminophenoxy)phenyl] milled, bis[4-(3-aminophenoxy)phenyl], double [ 4-(4-Aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[4-(3-aminophenoxy)phenyl Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1 , 3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1, 3_bis[4_(3-aminophenoxy)phenylindenyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzylidene]benzene, anthracene, 4_double [4-(3-amine basic oxy) this Benzyl]benzene, 1,4_bis[4_(4_Amine-based, phenylhydrazine)benzene, 1,3-bis[4-(3-aminophenoxy)_α, α_: A Benzoylbenzene, 1,3-bis[4_(4-aminophenoxy)·α,α·dimercaptobenzyl]benzene, μ bis[4-(3-amine basic oxy)-α,α -didecylbenzyl]benzene, 1,4-bis[4_(4.aminophenoxy)-α,α-dimercaptobenzyl]benzene, 4,4'-bis[4-(4- Aminophenoxy)benzhydryl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4 , 4'-bis[4-(4-amino-α,α-dimercaptobenzyl)phenoxy]dipyridylium, 4,4'-bis[4_(4-aminophenoxy) Phenoxy]diphenyl sulfone, 3,3,-diamine 201105680

.A base-4,4'-diphenoxydibenzophenone, 3,3'-diamino-4,4L diphenoxy bis-mercapto ketone, 3,3'.diamino-4 -phenoxybenzophenone, 3,3,-diamine-based chilled phenoxy benzophenone, 6,6,-bis(3-aminophenoxy)-3,3,3/3 ^Tetramethyl-1,1'-spirobiindane, 6,6,_bis(4-aminophenoxy)_3 3,3,,3,_tetramethyl]^ snail , 3-bis(aminopropyl)tetramethyldiazepine, 1,3-bis(4-aminobutyl)tetramethyldioxane, α,ω-bis(3-amino Propyl) polydimethyloxime, α,ω-bis(3-aminobutyl)polydimethyloxane, diamine polyoxyalkylene, and the like. The above-exemplified amine compounds can be suitably used singly or in combination. Further, the amine compound may be a part or all of a hydrogen atom on the aromatic ring of the above amine compound, which may be a substituent selected from a fluorine atom, a fluorenyl group, a methoxy group, a trifluoromethyl group and a trifluoromethoxy group. Substituting the resulting diamine. Further, in order to introduce a branch, a part of the amine compound may be replaced with a triamine compound or a tetraamine compound. Specific examples of the triamine compound include pararosaniline and the like. &lt;Explanation of a method for producing a polymer containing tetracarboxylic dianhydride as a structural unit&gt; The method for producing the polymer of the present invention is not particularly limited, and a monomer or monomer using the above tetracarboxylic dianhydride can be used. The mixture, a monomer or a monomer mixture with the above amine compound, is used to prepare the polymer of the present invention. For example, a method for producing the polyamidene-based polymer of the present invention can be utilized. A method of ring-opening and ruthenium imidization via polyphthalic acid; a method of polyisocyanine; Further, a method for forming a block polyimine by argon polyacrylic acid; and the like for producing the poly 32 201105680 amide compound of the present invention ===== 繊==Solution_acid: Formula:: = a method in which an acid needle is dissolved and/or dispersed in an organic solvent, and a method in which a mixture of an acid anhydride and an amine compound is reacted in an organic solvent to polymerize.醯亚^化+, 醯麟环环化纽成水, preferably by yt, A, and II? Benzene or naphthalene scale L and (4) water are removed to the outside of the reaction system to promote ruthenium iodization, and when a dehydrating agent such as an acetic acid aliphatic acid anhydride or an aromatic acid anhydride is used, the ruthenium imidization reaction proceeds easily. Further, if necessary, a polycondensation accelerator may be added to the reaction system to complete the reaction rapidly. The polycondensation accelerator may be exemplified by a basic polycondensation accelerator and an acidic polycondensation accelerator, and the two may be used in combination. Polycondensation accelerator. Examples of the above-mentioned test polycondensation accelerator include n, n-dimethylaniline, N,N-diethylaniline, pyridine, 嗤琳, 啥啥琳, (X- Is the methyl η ratio σ, β-methyl U ratio bite, γ_methyl 0 ratio bite, 2,4 dimethyl 11 pyridine, triethylamine, tributylamine, triamylamine, Ν-fluorenyl? Morpholine, diazabicycloundecene, diazabicyclononene, etc.; acidic polycondensation accelerators, for example, benzoic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid , p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenylacetic acid, 4·hydroxyphenylpropionic acid, phosphoric acid, p-phenolsulfonic acid, p-toluenesulfonic acid, crotonic acid, and the like. The amount of the above polycondensation accelerator used is 33 201105680 1 mol% to 50 mol %, preferably 5 mol % to the diamine or diamine component. The reaction temperature can be set lower = preventing W from becoming The cause of coloring is due to heating, and the reaction time can be greatly shortened, which is economical. 2: The polymerization temperature is better. It is 60° or less, and it is more preferable that the degree is easy to rise. The solvent can be used because of the reaction efficiency, and the solvent which can be used for the adhesion of the poly-proline is, for example, dimethylethyl gland Such as urea, dimethyl terminal diphenyl::: methyl stone wind and other sub-like, Ν, Ν · dimercapto (tetra) amine (DMAe), N, N_ methyl formazan (N, N-dimethylf 〇rmamide ' DMF), N,N'_diethyl ethanoamine, Ν·methyl-2- squamous (NMp), 丫_butyl vinegar, hexamethylphosphoric triamide (hexamethylphosphoric triamide) a protic solvent of the class, or a phosphophilamide; a gas, a gas, a gas, a methane, etc., an aromatic hydrocarbon such as stupid or toluene, a phenol such as benzene, cresol, or the like. An ether such as oxime ether, diethyl ether or p-cresol methyl ether. Usually these solvents are used alone, but they may be combined as needed.

, come up to use. Among these, guanamines such as DMF, DMAc, and NMP can be preferably used. The molecular weight of the obtained polymer is preferably 100 Å or more from the viewpoint of maintaining self-sustainability when the polymer composition is formed into a film. In addition, from the viewpoint of the strength of the ruthenium and the solvent solubility of the polymer, the molecular enthalpy is preferably 20,000 or more and loooooo or less, and is more preferable from the viewpoint of easiness of liquid preparation and coating operation. It is 2〇00〇 or more, 300000 34 201105680. Below. <Description of a composition containing a polymer containing a tetracarboxylic dianhydride as a structural unit> The following description contains a composition comprising a polymer constituting the tetracarboxylic dianhydride of the present invention. Another aspect of the present invention is a composition comprising a polymer comprising at least one of tetrazoic acid dianhydride represented by the above formula (1) as a structural unit. Examples of the composition that can be used include a solution of a polymer, a mixture of a solution of the above polymer and particles such as a filler, an age of particles such as a polymer and a filler, and a solution of the polymer. The composition obtained from the material is obtained. From the viewpoint of the hardening treatment, the composition is preferably a solution of a polymer. The solvent of the solution for the polymer is not particularly limited, and is, for example, usable; a chelating agent: a guanamine-based solvent (for example, N,N-dimethylformamide, 'ban-diethyl hydrazine, 1-methyl·2· Material phase), hard solvent t sulfoxide f agent (such as dimethyl sulfoxide), gland solvent (such as dimethyl f =, ether solvent (such as diwei, cyclopental agent such as acetone, cyclohexane _ ), a flue solvent, a solvent, a solvent (for example, tetrachloroethane, benzene, dioxane, milk imitation), a bite-based solvent (for example, a bite, γ-methyl: :, preferably, 醢Amine solvent, Thai two: = view: 糸 solvent, _, 丨, Chen solvent, solvent and nitrile: 35

20110568 (^ X agent' is more preferably an amine-based solvent, an ether solvent, a halogen solvent, and a solvent, and more preferably a guanamine solvent and a nitrile solvent. These solvents may be used alone or in combination. The above disclosure is incorporated herein by reference in its entirety, the entire disclosure of which is hereby incorporated by reference in its entirety in the the the the the the the the the the The present invention, but the present invention is not limited to the examples. In order to evaluate the characteristics of the obtained compound, various spectra of nuclear magnetic resonance (H-NMR) and mass spectrometry (MS) were performed. The measurement conditions of each characteristic are as follows. <Test method> (1) Nuclear magnetic resonance spectrum analysis (1H-NMR): Measurement was carried out at a resonance frequency of 400 MHz using AV400M manufactured by BRUKER Co., Ltd. Gasified dimercaptopurine as a solvent for DMSO-d6 ° (2) Mass spectrometry (MS): using APIQSTAR Pulsar i manufactured by Applied Biosystems, using electrospray ionization (elec) The measurement was carried out by trospray ionization method, ESI method. Example 1 The exemplified compound (1)-1 was synthesized according to the following formula: [Chem. 12] 36 201105680

(1) — 1—Under a chaotic airflow, a trihydrate anhydride helium gas 46.42 g (〇·22 丨) was added to a 5000 mL three-necked flask, and tetrahydrocyanate was shaken, and the mixture was stirred for 10 minutes in an ice bath. In the solution, 3,9_bis(u,_dimethyl-2-hydroxyethyl hydrazine, 4,8,^tetraoxaspiro[5 octadecane 4' g three 0.10 mol] was added dropwise. And a solution obtained by dissolving 39.6 g (0.50 m〇i) of pyridine in 100 mL of methylpyrrolidone. After stirring for 3 hours, 3 〇〇〇 mL of acetonitrile was added dropwise and stirred! hour. The solid obtained was separated by filtration and applied to milk. The vacuum was dried under vacuum for 4 hours, whereby 55.4 g (yield: 85%) of the exemplified compound (yttrium) solid was obtained. White 1H-NMR (4〇〇MHz, CDC13) : δ 9.05 (s, 2H), δ 8.45 (d, 2Η), δ 8.27 (d, 2Η), δ 4.67 (s, 2Η), δ 4.17 (s 4 Η), δ 3.77 〜 3.67 (m, 8 Η), δ l.ll (s, 12 Η) MS : M+ = 652.60 Example 2 The exemplified compound (2)-1 was synthesized according to the following formula. [Chem. 13]

(2)-1 In addition to 3,9-bis(1,1-dimercapto-2-hydroxyethyl)-2,4,8,10-tetrazed 37 201105680 Oxyspiro[5.5]undecane 30.4 g (0.10 mol), and using 7,7,-dihydroxy-4,4,4',4,-tetramethyl-2,2,-spirochrome 34.0 g (0.10 mol), and synthesis examples 1 In the same operation, 53.1 g (yield: 77%) of the white solid of the compound (2). 1H-NMR (400 MHz, CDC13) : δ 9.22 (s, 2H), δ 8.49 (d, 2Η), δ 8.44 (d, 2Η), δ 7.17 (d, 2Η), δ 6.63 (d, 2Η), δ 6.58 (s, 2 Η), δ 2.42 〜 2.17 (m, 4H), 5 1.39 (s, 12H) MS: M+ = 688.16 Example 3 The exemplified compound (2)-2 was synthesized according to the following formula. [Chem. 14]

In addition to replacing 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5] eleven-burning 30.4 g (0.10 mol), and using The same procedure as in Synthesis Example 1 except that 7,7,-dihydroxy-4,4,4',4',6,6'-hexamethylene-2,2,-spirochrome was 36.8 g (0.10 mol). The operation of the compound (2)-2 was obtained as a white solid (yield: 69%). 1H-NMR (400 MHz, CDC13): δ 9.22 (s, 2H), δ 8.49 (d, 2Η), δ 8.44 (d, 2Η), δ 7.05 (d, 2Η), δ 6.46 (d, 2Η), δ 2·42 〜 2·17 (m, 10 Η), δ 1.39 (s, 12 Η) MS: M+ = 716.19 38 201105680 Example 4 The exemplified compound (3)-1 was synthesized according to the following formula. [化15]

(3) — 1 In addition to 3,9-bis(1,1-dimercapto-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane 30.4 g ( The same procedure as in Synthesis Example 1 was carried out except that the compound (3)-1 was obtained as a white solid (yield: 0.10 mol). 82%). 1H-NMR (400 MHz, CDC13): δ 9.05 (s, 2H), δ 8.45 (d, 2H), δ 8.274 (d, 2H), δ 4.34 (d, 2H), δ 4.09 (d, 2H), δ 2.15 〜 2 〇 2 (m, 2 Η), δ 1.52 to 1.27 (m, 10 Η), MS: M+ = 536.17 Example 5 The exemplified compound (3)-2 was synthesized according to the following formula. [Chemistry 16]

Compound A

In addition to replacing 3,9-bis(1,1-dimercapto-2-hydroxyethyl)-2,4,8,10-tetra 39 201105680, oxaspiro[5·5]undecane 3〇.4 G (0.10 mol) was used in the same manner as in Synthesis Example 1 except that the compound A21 g (0.10 mol) was used, and 38.8 g (yield: η%) of the white solid of γ 'non-compound (3) -2 was selected. NMR (400 MHz, CDC13): δ 9.05 (s, 2H) (m, 2H), δ 8.27 (d, 2H), δ 3.54~3.22 (m, 3H), δ i 82'~i 235 (d, 13H MS: M+ = 546.19 Example 6 The exemplified compound (3) -3 was synthesized according to the following formula. [Chem. 17]

Compound B

(3)-3 used in place of 3,9-bis(1,1·dimethyl-2-hydroxyethyl)·2,48 ^oxaspiro[5.5]undecane 30.4 g (0.10 mol)' The same procedure as in Synthesis Example 1 was carried out except that the compound β was § (0.10 mol), and 46.1 g (yield: 74%) of the white solid of the compound (3) -3 was obtained as the compound 1H-NMR. (400 MHz, CDC13) : δ 9.05 (s, 211) § 8 2Η), δ 8.27 (d, 2Η), δ 3.56~3.21 (m, 4Η), δ 185' 2 5 (d, 20H) 22 (m MS: M+ = 642.25 Example 7 The exemplified compound (3) -4 was synthesized according to the following formula: 201105680

- -- I

[Chem. 18]

Compound c

(3) —4

In addition to 3,9-bis(1,1-dimethyl-2-hydroxyethyl)_2 4,8,1 〇tetraoxaspiro[5.5] eleven burned 30.4 g (〇.1〇mol)' The same procedure as in Synthesis Example 1 was carried out except that Compound c 36 jg (0.10 mol) was used to obtain 46.1 g (yield: 65%) of the white solid of the compound (3)-4. 1H-NMR (400 MHz, CDC13) : δ 9.05 (S) 2Η), δ 8 45 (d 2H), δ 8.27 (d, 2H), δ 3.58^3.17 (m, 4H), δ 1.86^ι 19 26H MS: M+ = 708.29 Example 8 1. Preparation of a polyimine oxime containing compound (1)-1 as a constituent component and preparation of a composition containing the polyamidene 1, σ成(聚醯亚Synthesis of amine) A 200 mL three-necked flask of diamine-based 4-methylbenzene (DAT) 〇.02 _, N_methyl~biridine-(10) mL· was dissolved in a gas-substituted gas. While stirring the reaction solution at room temperature, the compound (1)·i _ _ was added to the oxime body at room temperature under _ 2 ^ to add acetic anhydride 0.05 mol, (4) _5 mGl at ^. After an hour and then heating to 3 hours, a solution of the polyimine 1 having a structure of 1 was obtained. Even repeating the knot 201105680 [Chem. 19]

Polyimine 1 MW: 76000 The obtained solution was added dropwise to 3 〇〇 mL of sterol, and the resulting precipitate was filtered and dried, whereby a powder of polyimine was obtained. (Preparation of composition containing polyimine) 10 g of this powder was dissolved in 50 mL of N,N-dimercaptoacetamide (DMAc) to obtain a polyimine solution. 2. Physical property measurement The polyimine solution obtained above was applied onto a quartz glass plate using a blade and dried at 200. (The dielectric constant of the polyimide film obtained on the quartz glass plate was measured after 1 hour of heat hardening treatment. The dielectric constant was measured using a precision bridge method using Precision LCRMeter E4980A manufactured by Agilent Technologies. In addition, the glass transition point of the above polyimide pigment powder was measured, and the solvent solubility was confirmed. The glass transition point was measured using DSC 7200 manufactured by SII NanoTechnology, and 5 mg of the above polyimine powder sample was used. 10 mg of the alumina powder of the target sample was placed in an aluminum cell for measurement and was carried out at a temperature increase rate of HTC/min. It was confirmed that the solvent solubility was 1 g of the above polyimine powder dissolved at room temperature. In 20 mL of methyl ethyl ketone, it was confirmed by illuminating whether or not the above polyimine powder was dissolved. 42 201105680 The results of the above are shown in Table i. Example 9 Fish: 1 化合物 Compound (7)] was used instead of Compound (1) In addition, the poly 8 was obtained in the same manner, and a powder smear solution of L amine 2 having a repeating unit shown below was obtained.

Similarly, the powder of the polyimine 2 and the DMAe solution were confirmed by the measurement of the dielectric constant, the glass complementation, and the solvent solubility of Example 8. The results are shown in Table 10. Example 10 Polyimine 2 MW: 83000 The same procedure as in Example 8 was carried out except that the compound (2)-2 was used instead of the compound (1)-1 to obtain a polyfluorene having the repeating unit shown below. A powder of amine 3 and a DMAc solution. [Chem. 21]

Polyimine 3 MW: 88,000 Examples The powders of the polyimine 3 and the DMAc solution were measured for the dielectric constant, the glass transition point, and the solvent solubility in the same manner as in the case of 430,056,080. The results are shown in Table 1. Example 11 The same procedure as in Example 8 was carried out except that the compound (3)-1 was used instead of the compound (1)-1, and a powder of the polyimine 4 having a repeating unit shown below and a DMAc solution were obtained. [化22]

The powder of the polyimine 4 and the DMAc solution were measured for dielectric constant, glass transition point, and solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Example 12 The same procedure as in Example 8 was carried out except that the compound (3)-2 was used instead of the compound (1)-1, to obtain a powder 5 of a polyimine having a repeating unit shown below and a DMAc solution. [Chem. 23]

44 201105680 The powder of the polyimine 5 and the DMAc solution were measured for dielectric constant, glass transition point, and solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Example 13 The same procedure as in Example 8 was carried out except that the compound (3) -3 was used instead of the compound (1) _1 to obtain a powder of the polyimine 6 having a repeating unit shown below and a DMAc solution. [Chem. 24]

Polyimine 6 MW: 97000 The powder of the polyimine 6 and the DMAc solution were measured for dielectric constant, glass transition point, and solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Example 14 A powder of polyimine 7 having a repeating unit shown below and a DMAc solution were obtained in the same manner as in Example 8 except that the compound (3)_4 was used instead of the compound (1). [Chem. 25]

Polyimine 7 MW: 118000 45 201105680 The powdered dragon wt of the polyimine 7 is similarly subjected to the clear reduction of dielectric green' and the determination of the sputum, the transfer point of the glaze, the solvent, and the metamaterial Confirmation. The results are shown in Table 丨. Ridge W Ridge Example 15 The same operation as in Example 8 was carried out except that 2,2'-dimercapto-4,4L-diaminobiphenyl (mTB) was used to obtain 'repeated early it's shown below. Amine 8 material seams [Chemistry 26]

In the powder of the polyimine 8 and the DMAc solution, the measurement of the dielectric constant, the measurement of the glass transition point, and the solvent solubility were confirmed in the same manner as in Example 8. The results are shown in Table 1. Example 16 A powder of the polyimine 9 having the repeating unit shown below was obtained in the same manner as in Example 8 except that the 4,4-amino group-based barrier (4DAS) was used instead of DAT. DMAc solution. [化27]

Polyimine 9 MW: 89000 46 201105680 = powder of silk fibroin 9 and DMAe, and the determination of the solution number of Example 8, the enthalpy of the glass transition point, and the solvent solution. The results are shown in Table 1. Example 17 The same operation as in Example 8 was carried out by using bis[4_(3-aminophenoxy)phenyl]bowls BAPS) to obtain a polyglycan having the following repeating units. Powder of quinone imine 10 and DMAc solution. [化 28]

Polyimine 10 MW: 94000 The powder of the polyimine 10 and the DMAc solution were measured for dielectric constant, glass transition point, and solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Example 18 In addition to using 2,2-bis[4-(3-aminophenyloxy)phenyl]_1,1,1,3,3,3-hexafluoropropane (HFBAPP) instead of DAT, In the same manner as in Example 8, a powder of the polyimine U having the repeating unit shown below and a DMAc solution were obtained. [化 29] 47 201105680 φ〇Λ〇:Κ Eight points. . MW: 99000 Polyacrylimide 11 The powder of the polyimine 11 and the DMAc solution were measured for dielectric constant, glass transition point, and solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Example 19 The same procedure as in Example 9 was carried out except that 3,3'-diaminodiphenyl hydrazide (3DAS) was used instead of dat, to obtain a powder of the polyimine 12 having the repeating unit shown below. And DMAc solution. [化30]

The powder of the polyimine 12 and the DMAc solution were measured for dielectric constant, glass transition point, and solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Example 20 In addition to using 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexa 48 201105680 fluoropropane (HFBAPP) instead of DAT The same operation as in Example 1 was carried out to obtain a powder of (IV) imine η having a repeating unit shown below and a DMAc solution. [化31]

The powder of the polyimine 13 and the DMAc solution were subjected to measurement of dielectric constant, transfer measurement, and solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Example 21 The same procedure as in Example 12 was carried out except that bis[4-(4-aminophenoxy)phenyl](4BAps) was used for DAT to obtain a polyimine having the repeating unit shown below. 14 powder and DMAc solution. [化32]

Polyimine 14 MW: 124000 49 201105680 The same: the amine, the end and the DMAc solution, and the confirmation of the solution of the example 8: the determination of the crusting, the transfer point of the glass, the solvent solution example 22 except the use of 2 2, - two A4 /1, 〇AT ri recognition, society / one, 4'-diaminobiphenyl (mTB) instead of 卜' carried out the same operation as in Example 13, to obtain the imine 15 Powder and legs ^ ^ [化33]

The powder of the polyimine 15 and the DMAc solution were measured for the dielectric constant, the glass transition point, and the solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Comparative Example A1 to Comparative Example A6 Using the following comparative acid anhydride and diamine compound (shown in Table 1), Comparative Polyimine 1 to Comparative Polyimine 6 was obtained in the same manner as in Example 8. . [化 34] 50 201105680

[化35] 51 201105680

52 201105680 The powder obtained is almost insoluble in the solvent. The measurement of the dielectric constant and the measurement of the glass transition point were carried out in the same manner as in Example 8. The results are shown in Table 1. 53 20110568〇ι Table 1 Polyimine tetracarboxylic dianhydride diamine compound glass transition temperature [°c] Solvent solubility dielectric constant [-] Example 8 Polyimine 1 Compound (1)-1 DAT 155 Uniform 2.7 Example 9 Polyimine 2 Compound (2)-1 DAT 169 Uniform 2.6 Example 10 Polyimine 3 Compound (2)-2 DAT 161 Uniform 2.6 Example 11 Polyimine 4 Compound (3)-1 DAT 175 Uniform 2,9 Example 12 Polyimine 5 Compound (3)-2 DAT 167 Uniform 2,7 Example 13 Polyimine 6 Compound (3)-3 DAT 162 Uniform 2.6 Example 14 Polyimine 7 Compound (3)- 4 DAT 159 Uniform 2.6 Example 15 Polyimine 8 Compound (1)-1 mTB 161 Uniform 2.7 Example 16 Polyimine 9 Compound (1)-1 4DAS 157 Uniform 2.8 Example 17 Polyimine 10 Compound (1)-1 3BAPS 151 Uniform 2.7 Example 18 Polyimine 11 Compound (1)-1 HFBAPP 164 Uniform 2.6 Example 19 Polyimine 12 Compound (2)-1 3DAS 154 Uniform 2.8 Example 20 Polyimine 13 Compound (2)-2 HFBAPP 162 Uniform 2.7 Example 21 Polyimine 14 Compound (3)-2 4BAPS 158 Uniform 2.7 Example 22 Polyimine 15 Compound (3)-3 mTB 16 3 Uniform 2.8 Comparative Example A1 Comparative Polyimine 1 Comparative Acid A DAT 259 Solid Residue 3.2 Comparative Example A2 Comparative Polyimine 2 Comparative Anhydride A HFBAPP 277 Solid Residue 3.0 Comparative Example A3 Comparison Polyimine 3 Comparative anhydride A 4DAS 244 Solid residue 3.2 Comparative Example A4 Comparative Polyimine 4 Comparative Anhydride B DAT 177 Solid Residue 3.1 Comparative Example A5 Comparative Polyimine 5 Comparison Anhydride B mTB 185 Solid Residue 3.2 Comparative Example A6 Comparative Polyimine 6 Comparative Anhydride B 3BAPS 165 Solid Residue 3.0 According to Table 1 above, polyfluorene imine introduced with the tetracarboxylic dianhydride of the present invention It has superior solvent solubility, low Tg and low dielectric constant compared to the previously known polyimine. According to the present invention, there is provided a tetracarboxylic dianhydride having a specific structure, and further, a polymer using the tetracarboxylic dianhydride, which can improve the solvent solubility of the polymer 54 20110568, reduce the dielectric constant, and lower the glass. Transfer point. [Industrial Applicability] The field of use of the polyimine which is introduced with the tetracarboxylic dianhydride provided by the present invention is exemplified as a lens or a diffraction grating in the field of optical materials. Such precision optical parts, hologram, compact disc (CD), mini disc 'MD', digital versatile disc (called versatjie disc, DVD), optical disc, etc. A disk substrate, an optical adhesive, a substrate for a liquid crystal display (LCD) for a display device, a support film for a polarizing plate, a transparent resin moon, a retardation film, a light diffusion film, and a ruthenium (prism) Sheet), an adhesive for LCD, a spacer for LCD, an electrode substrate for LCD, a transparent protective film for color filters, a color filter, an alignment film, a transparent protective film, etc., as a visible material other than LCD Screen for a projector, substrate or film for a plasma display, optica fiiter, electro-luminescence (EL) coating material As optical fiber, optical waveguide, optical multiplexer, optical switching element, optical modulator, filter, wavelength splitter, optical amplifier (light amplifier) in the field of optical communication or optical components ), an optical attenuator, an optical wavelength converter, an insulating tape in the field of electrical and electronic equipment, various laminated boards, a flexible printed circuit board, an adhesive film for a multilayer printed circuit board, and a printed circuit board A cover film, a surface protective film of a semiconductor integrated circuit element, a coating type cover layer, a photosensitive cover layer, a coating agent for electric wires, or the like, or a thermal feeling 55 201105680 4 1 Parts for thermal head, flash memory Body (flash mem〇ry), charge-coupled device (CCD), photodiode (PD), laser diode (laserdiode, LD) and other optical semiconductor sealing materials, photodiode Body, die b〇nding with adhesive, wafer surface lead package (lead 〇n chip, L〇c) with adhesive tape, lead frame (lead f Rame) using a fixing tape, a film for a multilayer lead frame, a film for tape automated bonding (TAB), and a raw material polymerization of a buffer coating film, a passivation film, an interlayer insulating film, and a photosensitive polymer in the semiconductor field Various protective films such as base p〇iymer and semiconductor coating agents, under-film agents, flattening films, and sealants; solar cells (solar cells in the aerospace industry), thermal control systems, and other special aerospace applications. The coating material of the module and the like may be used, and the coating material or the base film substrate for a solar cell, an adhesive, other coating materials, and the like may be used in addition to the characteristics of the material. Further, the above polyimine may be used for: heat-resistant adhesive material, epoxy resin modifier, heat-resistant paint, resin for composite materials, coated metal (steel, copper, aluminum, etc.), thermoplastic or thermosetting plastic. (plastic), ceramics (ceramics) and other surface coating agents, chemical plants or automotive engine reservoirs, medical equipment that requires autoclaving (aut〇dave) sterilization, alpha radiation blocking, prepreg Body (Qing), varnish (vanish), etc. The above description of the specific form of the present invention is provided for the purpose of description and description. The invention is not intended to be limited to the disclosed forms, and is not intended to be exhaustive. Of course, those skilled in the art can carry out the decoration or deformation of 56 20110568α. This type is selected to best illustrate the application of the present invention in order to provide a variety of types of applications in the art that are suitable for other applications contemplated by those skilled in the art. State or various changes. = All the financial technical standards described in this manual 'When turning these clusters, ^ ^ and using the literature, they are specifically incorporated into the same limit wire circumference as the g-technical 3 and ^ cited documents. And people. The present invention is determined in accordance with the scope of the following claims and their equivalents.疋 [Simple description of the diagram] X is subject to. &quot;,, [Main component symbol description] Helmet η», 57

Claims (1)

201105680 x 1 VII. Patent application scope: 1. A tetracarboxylic dianhydride which is represented by the following general formula (1): [Chemical 1] 〇 (In the formula (1), hydrazine is a divalent linking group having at least one of a substituted or unsubstituted structure represented by the following general formula (2) to the general formula (4); [Chemical 2] General formula (2) In the formula (4), in the formula (3), Z and Z' are independent of each other, and represent a saturated or unsaturated carbocyclic or heterocyclic atom group together with two carbon atoms of the methane ring. 2. The tetracarboxylic dianhydride according to claim 1, wherein in the above formula (1), A is any one of the following formulas (5) to (7). To indicate: Π匕3] 1' one formula (5) (wherein, In, V, L2, and L2' are independent of each other, and represent a single bond, an alkyl group, a cycloalkyl group, or a divalent aromatic ring group; Z and Z' are independent of each other, and represent two of the ring of the methane. The carbon atoms together form a saturated or unsaturated carbocyclic or heterocyclic atomic group; R1, R2 are independent of each other, and represent a hydrogen atom, or a cyclic or acyclic hydrocarbon group; and R1, R2 may also be bonded to each other to form a ring; nl Independently, indicating an integer of 1 or more). 3. The tetracarboxylic dianhydride according to claim 2, wherein in the above formula (5) to formula (7), Li, Li', L2, and L2' are independent of each other. Single bond, alkyl or cycloalkyl. A polymer which is synthesized from at least one diamine compound and a tetracarboxylic dianhydride as described in any one of claims 1 to 3. 5. The polymer of claim 4, wherein the diamine compound is an aromatic diamine compound. 6. The polymer of claim 4, wherein the polymer is a polyester quinone imine or a polyether oxime imine. 7. The polymer of claim 5, wherein the polymer is a polyester quinone imine or a polyether oxime imine. A composition comprising the polymer as described in claim 4 of the patent application. A composition comprising the polymer as described in claim 7 of the patent application. 201105680i IV. Designated representative: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇 4 201105680 For the Chinese manual No. 99114936, no scribe correction page, invention patent specification revision date + September 2, 佟 年 年 & & . & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & Do not fill in. ※Application number: (zoocuvi, ※Application date: ※IPC classification: I. Invention name: (Chinese/English) m % f2G〇g,.〇j) Tetracarboxylic dianhydride and poly rush c^T 2006(2006..01) TETRACARBOXYIC DIANHYDRIDE AND POLYMER 2. Abstract: The tetracarboxylic dianhydride represented by the following general formula (1) and the solvent obtained by using the tetracarboxylic dianhydride are excellent in solubility. Tg, low dielectric constant polyimine: In the formula (1), A is a divalent linking group having at least one of the substituted or unsubstituted structures represented by the following general formulae (2) to (4): 201105680 - JI ^ A. Amendment date: 99 years. § 2nd day is the 99114930 Chinese manual without line correction page [Chem. 18] [Chem. 1 8] In addition to replacing 3,9-bis(1,1-didecyl-2-hydroxyethyl)-2,4,8,1〇-tetraoxaspiro[5.5] eleven-burning 30.4 g (〇.1〇mol) The lg (yield of 65%) was obtained as a white solid of the compound (3) -4 as the compound (3) -4. 1H-NMR (400 MHz, CDC13): δ 9.05 (s, 2H), δ 8.45 (d, 2H), S8.27 (d, 2H), 53.58~3.17 (m, 4H), 3l.86~1.19 ( m, '26H) MS : M+ = 708.29 Example 8 1. Synthesis of polyiphthalimide 1 using compound (1)-1 as a constituent component, ^ and preparation of a composition containing the same Synthesis of imine) In a 200 mL three-necked flask substituted with an inert gas, 1, decylamino-4-mercaptobenzene (DAT) 〇.〇2 mcd, N-methyl-2-° bilu Bite _ 11 〇 mL and dissolve. While stirring the reaction solution at room temperature, the compound (1) -1 〇·〇2 m〇l was directly added as a solid, and the mixture was stirred at room temperature for 2 hours. Then add 0.05 mol of acetic anhydride, absorb 〇 〇〇 5 m〇i, and disturb for 1 hour at room temperature, then heat to 60. (: Stirring for 3 hours, obtaining a solution of the polyimine 1 having the following repeating structure. 41 201105680 Γ·» W^/XJL X Revision date: September 2, 1999, No. 99114936 Chinese manual without scribe correction Page [Chem. 19] Polyimine 1 MW: 76000 The obtained solution was added dropwise to 3 〇〇 mL of sterol, and the resulting precipitate was dried and dried to obtain a powder of polyimine. (Preparation of composition containing polyimine) 10 g of this powder was dissolved in 50 mL of hydrazine, hydrazine-dimercaptoacetamide (DMAc) to obtain a polyimine solution. 2. Physical property measurement The polyimine solution obtained above was applied onto a quartz glass plate using a blade, dried, and subjected to a heat hardening treatment at 2 ° C for 1 hour, and then the quartz glass plate was measured. The dielectric constant of the obtained polyimide film. The dielectric constant was measured using a balanced bridge method using a Precision LCR Meter E4980A manufactured by Agilent Technologies. Further, the glass transition point of the above polyimide pigment powder was measured, and the solvent solubility was confirmed. The glass transition point was measured by using DSC 7200 manufactured by SII NanoTechnology, and 5 mg of the above polyimine powder sample and 1 〇mg of the alumina powder as a control sample were respectively placed in an aluminum cell for measurement. 'It is carried out at a temperature increase rate i〇°c/min. It was confirmed that the solvent solubility was such that 1 g of the above-mentioned polyamidimide powder was dissolved in 20 mL of mercaptoethyl ketone at room temperature. It was visually confirmed whether or not the above polyimine powder was dissolved. 42 201105680, Revision date: September 2, 1999. No. 99114936 Chinese manual without line correction page The results of these are shown in Table 1. Example 9 A powder having the heavy polyimine 2 shown below and a DMAc solution were obtained except that the compound (2) _1 was used instead of the compound (1) to give the same operation as in Example 8. [化20] 〇 P-polyimine 2 MW: 83000, the powder of the polyacrylonitrile 2 and the DMAc solution were measured for the dielectric constant, the glass transition point, and the impurities in the same manner as in Example 8. The silk is shown in the table. Example 10 A powder of the polyimine 3 having a repeating unit shown below and a DMAc solution were obtained by the same operation as in Example 8 except that the compound (2)-2 was used instead of the compound (1). [Chem. 21] 43 201105680 Revision date: September 2, 1999, 388 34388ριί1 No. 99114936 Chinese manual No scribe correction page The dielectric constant measurement, the glass transition point measurement, and the solvent solubility are confirmed. The results are shown in Table 1. Example 11 The same procedure as in Example 8 was carried out except that the compound (3)-1 was used instead of the compound (1)-1, and a powder of the polyimine 4 having a repeating unit shown below and a DMAc solution were obtained. [化22] The powder of the polyimine 4 and the DMAc solution were measured for dielectric constant, glass transition point, and solvent solubility in the same manner as in Example 8. The results are shown in Table 1. Example 12 The same procedure as in Example 8 was carried out except that the compound (3)-2 was used instead of the compound (1)-1, and a powder of the polyimine 5 having a repeating unit shown below and a DMAc solution were obtained. [Chem. 23] Polyimine 5 MW: 85000 201105680 No. 99114936 Chinese manual no scribe correction page invention patent specification revision date + September 2nd 佟 年 年 H . . . . . & & & & & & & & & & & & & & & & & & & & & & & & & & & & For any change, please do not fill in the ※ mark. ※Application number: (zoocuvi, ※Application date: ※IPC classification: 1. Invention name: (Chinese/English) m % f2G〇g,.〇j) Tetracarboxylic acid II Anhydride and poly rush c^T〇(2006..01) TETRACARBOXYIC DIANHYDRIDE AND POLYMER II. Abstract of Chinese Abstract: A tetracarboxylic dianhydride represented by the following general formula (1), and the use of the tetracarboxylic dianhydride Excellent solvent solubility, Tg, low dielectric constant polyimine: In the formula (1), A is a divalent linking group having at least one of a substituted or unsubstituted structure represented by the following general formula (2) to the general formula (4): 201105680 is the Chinese Patent No. 99114936 The instructions have no strokes. Revision period: September 2, 1999 通式 General formula (2) The formula (4) CD Z, Z' are independent of each other, and represent a saturated or unsaturated carbocyclic ring or a heterocycle; == aft atom-formed to form a third, the present invention summary: the present invention provides a tetracarboxyic dianhydride represented by the following formula (1), and a polyimade having excellent solvent soluability , Tg and low dielectric constant obtained by the tetracarboxyic dianhydride: 〇 Formula (1)