CN101379111A

CN101379111A - Polymerizable unsaturated compound and method for producing the same

Info

Publication number: CN101379111A
Application number: CNA2007800045509A
Authority: CN
Inventors: 保坂幸宏; 岛村信孝; 井上健一
Original assignee: Wako Pure Chemical Industries Ltd
Current assignee: Fujifilm Wako Pure Chemical Corp
Priority date: 2006-04-11
Filing date: 2007-04-10
Publication date: 2009-03-04
Anticipated expiration: 2027-04-10
Also published as: KR20090009236A; KR101050728B1; TW200801068A; CN101379111B; JPWO2007123017A1; WO2007123017A1

Abstract

The present invention relates to a compound comprising structural unit represented by general formula (1) and preparing method thereof, in the general formula (1), R<1>, R<2>, R<1>' and R<2>' respectively represent hydrogen atom, halogen atom, alkyl or alkoxyl independently. R<3> and R<4> respectively represent hydrogen atom or group represented by general formula (2). T1 and T2 respectively represent straight-chain alkylidene group or arylidene with 1-6 carbon atoms independently. U represents single bound or a random 2-valence group represented by a general formula selected from general formula (1-1) to (1-8). V1 and V2 respectively represent oxygen atom or -NH- group independently. Y1 represents oxygen atom, -NH- group or group represented by general formula (5). Y2 represents oxygen atom, -NH- group or group represented by general formula (6). Z represents 4-valence alkyl, a and b respectively represent 0 or 1 independently, and k represents a natural number, wherein, at least random one group selected from R<6>, R<8> and R<9> is a group with double bond.

Description

Polymerizable unsaturated compound and manufacture method thereof

Technical field

The present invention relates to a kind of new polymerizable unsaturated compound and the new manufacturing method of this compound.In more detail, relate to a kind of fluorene skeleton etc. that in structural unit, has, and excellent heat resistance can form the polymerizable unsaturated compound of good pattern and molecular weight, acid value etc. and adjust easily, and the easy manufacture method of this compound of synthetic at low temperatures.

Background technology

The polymer resin composition that contains various polymerizable unsaturated compounds (resin), the welding resist when can be used as the resist of liquid-crystal apparatus for example etc. or printed-wiring board (PWB) and making.In recent years, be accompanied by the densification of instrument, require for example excellent polymer resin composition such as the transparency, thermotolerance, adhesivity, resistance.So, especially nearest as the polymerizable unsaturated compound with above-mentioned performance (resin), the polymerizable compound with bis-phenol skeleton or fluorene skeleton (resin) of the transparency when having proposed cured article and excellent heat resistance.

As the method for making these polymerizable unsaturated compounds (resin), known have a following method, promptly at first make the acrylic acid derivative reaction of epoxy compounds with bis-phenol skeleton and for example vinylformic acid, methacrylic acid etc., synthetic epoxy acrylic ester cpds with bis-phenol skeleton, then, the method that itself and carboxylic acid derivative or carboxylic acid anhydride are reacted.

Concrete example as this existing method, known for example (1) makes epoxy compounds and acrylic acid derivative with bis-phenol skeleton react down at 90～120 ℃, synthetic epoxy acrylic ester cpds with bis-phenol skeleton, then, make it 90～130 ℃ of following and carboxylic acid anhydride and acid dianhydride reactions, thereby the method (for example, patent documentation 1, patent documentation 2, patent documentation 3 etc.) of synthetic this polymerizable unsaturated compound; (2) epoxy compounds with fluorene skeleton is reacted down at 90～120 ℃ with (methyl) vinylformic acid, synthetic (methyl) acrylate derivative with fluorene skeleton, then, make itself and tetracarboxylic dianhydride 100～130 ℃ of reactions down, again 80～110 ℃ down with the dicarboxylic anhydride reaction, thereby the method (for example patent documentation 4 etc.) of synthesizing this polymerizability unsaturated polyester; (3) make epoxy acrylic ester cpds and acid anhydrides 100～130 ℃ of down reaction and synthetic methods (for example patent documentation 5 etc.) etc.

Yet, in these methods, exist and must under the high temperature more than 80 ℃, react, and, in order to suppress because the thermopolymerization that two keys of acrylic acid derivative cause, problem that must the excessive stopper of interpolation.In addition, owing to need under higher temperature, react for a long time, therefore be difficult to the control reaction, cause side reactions such as two key crackings easily, as a result, has the reaction solution gelation, the problems such as adjustment difficulty of the molecular weight of target polymerization unsaturated compound (resin) and acid value etc.Under this situation, expectation is developed and can be carried out under the temperature condition of gentleness, and molecular weight control is easy to have the manufacture method of the polymerizable unsaturated compound (resin) of fluorene skeleton etc.

Patent documentation 1:JP spy opens flat 5-No. 339356 communiques

Patent documentation 2:JP spy opens flat 7-No. 92674 communiques

Patent documentation 3:JP spy opens flat 8-No. 278630 communiques

Patent documentation 4:JP spy opens communique 2003-No. 165830

Patent documentation 5:JP spy opens flat 11-No. 231523 communiques

Summary of the invention

The problem that invention will solve

The invention provides a kind of xenyl structure that in structural unit, has, especially have fluorene structured, and excellent heat resistance, can form the polymerizable unsaturated compound (resin) of good pattern, in addition, provide the adjustment of a kind of molecular weight, acid value etc. easy, and synthetic have the manufacture method of the polymerizable unsaturated compound (resin) of fluorene skeleton etc. at low temperatures.

Be used to solve the method for problem

The invention provides and comprise the compound that the structural unit with general formula (1) expression forms,

In the formula (1), R ¹, R ², R ¹' and R ²' represent hydrogen atom, halogen atom, alkyl or alkoxyl group, R independently of one another ³And R ⁴Represent hydrogen atom or the group of representing with general formula (2) independently of one another, T ₁And T ₂Represent that independently of one another carbonatoms is 1～6 straight chain shape alkylidene group or arylidene, U represents singly-bound or with the divalent group of any expression in formula (1-1)～(1-8), V ₁And V ₂Represent independently of one another Sauerstoffatom or-NH-group, Y ₁The expression Sauerstoffatom ,-NH-group or the group represented with general formula (5), Y ₂The expression Sauerstoffatom ,-NH-group or the group represented with general formula (6), Z represents the alkyl of 4 valencys, and a and b represent 0 or 1 independently of one another, and k represents natural number, wherein, and in the formula (1), R ⁶, R ⁸, R ⁹In any one is the group with two keys at least;

—COOR ⁶ (2)

In the formula (2), R ⁶Expression hydrogen atom, carbonatoms are the group of 1～6 alkyl, general formula (3) or general formula (4) expression,

In the formula (3), R ⁷Be vinyl carbonyl or pseudoallyl carbonyl, T ₃The expression carbonatoms is 1～6 straight chain shape alkylidene group,

In the formula (4), T ₄The expression carbonatoms is 1～6 straight chain shape alkylidene group, R ⁷Same as described above;

In the formula (1-1), R ⁵And R ⁵' represent hydrogen atom or halogen atom independently of one another;

In the formula (5), R ⁸Expression hydrogen atom or R ⁷

In the formula (6), R ⁹Expression hydrogen atom or R ⁷

In addition, the invention provides and comprise the compound that the structural unit with general formula (7) expression forms,

In the formula (7), R ³' and R ⁴' represent hydrogen atom, carboxyl or alkoxy carbonyl, Y independently of one another ₁' the expression Sauerstoffatom ,-group of NH-group or formula (8) expression, Y ₂' the expression Sauerstoffatom ,-NH-group or the group represented with formula (9), R ¹, R ², R ¹', R ²', T ₁, T ₂, U, V ₁, V ₂, Z, a, b and k be same as described above, wherein, in formula (7), R ³' and R ⁴' at least one be carboxyl base or alkoxy carbonyl,

In addition, the invention provides the manufacture method that comprises the compound that structural unit forms shown in the above-mentioned general formula (1), it is characterized in that, at least a above (methyl) acrylic acid derivative that contains the compound that structural unit forms shown in the above-mentioned general formula (7) and be selected from general formula (10), general formula (11) and the general formula (12) is reacted

R ⁷—X　　　　　　　　　　(10)

In the formula (10), X represents halogen atom, R ⁷Same as described above;

In the formula (11), R ⁷And T ₃Same as described above;

In the formula (12), R ⁷And T ₄Same as described above.

Further, the present invention provides the manufacture method that comprises the compound that structural unit forms shown in the above-mentioned general formula (7), it is characterized in that, make compound shown in the general formula (13) and polyprotonic acid or its anhydride reaction with 3 above carboxyls, wherein, described polyprotonic acid comprises that the part of carboxyl is the material of carboxylicesters, and described acid anhydrides comprises the material of the part of carboxyl through dehydrating condensation formation anhydride group, and a part that also comprises carboxyl is the material of carboxylicesters;

In the formula (13), R ¹⁰Be the group of hydrogen atom, alkali metal atom, general formula (14) or general formula (15) expression, R ¹¹Be the group of hydrogen atom, alkali metal atom, general formula (16) or general formula (17) expression, R ¹, R ², R ¹', R ²', U, V ₁And V ₂Same as described above;

In the formula (14), T ₁Same as described above;

In the formula (15), M ₁Expression hydrogen atom or alkali metal atom, V ₃The expression Sauerstoffatom or-NH-group, T ₁Same as described above;

In the formula (16), T ₂Same as described above;

In the formula (17), M ₂Expression hydrogen atom or alkali metal atom, V ₄The expression Sauerstoffatom or-NH-group, T ₂Same as described above.

The invention effect

Polymerizable unsaturated compound of the present invention is to have the xenyl skeleton in structural unit, especially the demonstration alkali-soluble that has fluorene skeleton, and the compound of excellent heat resistance, when use contains this compound compositions, make it form pattern by light or heat it, just can easily form the good pattern of thermotolerance.In addition, manufacturing method according to the invention, can not produce existing method has, for example owing at high temperature reacting the control difficulty, because side reaction causes problems such as productive rate reduction, the adjustment that can produce molecular weight, acid value etc. is easy, and productive rate is good contains the target compound that structural unit forms shown in the general formula (1).

Description of drawings

Fig. 1 is a gained compound among the expression embodiment 3 ¹The figure of H-NMR data.

Fig. 2 is a gained compound among the expression embodiment 24 ¹The figure of H-NMR data.

Fig. 3 is the figure of gained Compound I R data among the expression embodiment 3.

Fig. 4 is the figure of gained Compound I R data among the expression embodiment 24.

Fig. 5 is the figure of expression embodiment 3 gained compound thermostability (thermotolerance) data.

Fig. 6 is the figure of expression embodiment 24 gained compound thermostability (thermotolerance) data.

Embodiment

As using R in general formula (1), (7) and (13) ¹, R ², R ¹' and R ²' halogen atom of expression, can enumerate for example fluorine atom, chlorine atom, bromine atoms, iodine atom etc., wherein, preferred chlorine atom, bromine atoms, wherein, more preferably chlorine atom.

As using R ¹, R ², R ¹' and R ²' expression alkyl, can enumerate straight chain shape, chain or cyclic, carbonatoms is 1～4 usually, preferred carbonatoms is 1～2, more preferably carbonatoms is 1 alkyl, specifically, can enumerate for example methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl etc., wherein, preferable methyl, ethyl, wherein, more preferably methyl.

As using R ¹, R ², R ¹' and R ²' expression alkoxyl group, can enumerate straight chain shape, chain or cyclic, carbonatoms is 1～4 usually, preferred carbonatoms is 1～2, more preferably carbonatoms is 1 alkoxyl group, specifically, can enumerate for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, ring propoxy-, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, cyclobutoxy group etc., wherein, preferred methoxyl group, oxyethyl group, more preferably methoxyl group.

As these R ¹, R ², R ¹' and R ²', hydrogen atom more preferably.

There is no particular limitation for the bonding position of U and phenyl ring in the mutual-through type (1), but with respect to the V1 and the V2 of bonding on the phenyl ring, preferred bonding in a position and on to bit position, wherein, more preferably bonding on to bit position.Specifically, shown in general formula (24), with the carbon of the phenyl ring of U bonding in, when bonding is had V ₁Carbon as 4, bonding V is arranged ₂Carbon as under 4 ' the situation, as the bonding position of U on phenyl ring, can enumerate carbon with the U bonding and be any the combination among any and 1 ', 2 ', 3 ', 5 ', 6 ' in 1,2,3,5,6, wherein, the combination of any among any in preferred 1,2,6 and 1 ', 2 ', 6 ', more preferably 1 and 1 ' 's combination

In the formula (24), R ¹, R ², R ¹', R ²', V ₁, V ₂Same as described above with U.

As the U in the general formula (1), more preferably use the divalent group shown in formula (1-1) and (1-7), wherein, more preferably use the divalent group shown in the formula (1-1).

As R in the formula (1-1) ⁵And R ⁵' shown in halogen atom, can enumerate for example fluorine atom, chlorine atom, bromine atoms, iodine atom etc., wherein, preferred chlorine atom, bromine atoms, more preferably chlorine atom.

As these R ⁵And R ⁵', more preferably hydrogen atom.

As the V in general formula (1), (7) and (13) ₁And V ₂, more preferably Sauerstoffatom.

As the Y in the general formula (1) ₁, the more preferably group shown in Sauerstoffatom or the general formula (5), the further group shown in the preferred formula (5).

As the Y in the general formula (1) ₂, the more preferably group shown in Sauerstoffatom or the general formula (6), the further group shown in the preferred formula (6).

As R ³Or R ⁴General formula (2) in R ⁶Shown carbonatoms is 1～6 alkyl, it can be the straight chain shape, chain or cyclic any, specifically, can enumerate for example methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, neo-pentyl, 2-methyl butyl, 1-ethyl propyl, cyclopentyl, n-hexyl, isohexyl, Sec-Hexyl, uncle's hexyl, new hexyl, 2-methyl amyl, 1,2-dimethylbutyl, 1-ethyl-butyl, cyclohexyl etc., wherein, preferred carbonatoms is 1～4 alkyl, specifically, can enumerate for example methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl, wherein, more preferably carbonatoms is 1～2 alkyl, specifically, can enumerate methyl, ethyl.

In general formula (1) and (7) second month in a season, as 4 valency alkyl shown in the Z, usually 4 valency alkyl of aromatic series or aliphatic category can be enumerated, specifically, for example 4 valency alkyl of the fragrant same clan of formula (25), formula (26), general formula (27), general formula (28) or general formula (29) expression can be enumerated; As the aliphatic category 4 valency alkyl of general formula (30), general formula (31), formula (32) or formula (33) expression,

Wherein, in formula (26), 4 singly-bounds can be bonded on any carbon in 1～8 carbon of naphthalene nucleus;

In the formula, W ₁, W ₂And W ₃Expression singly-bound, Sauerstoffatom, carbonyl, alkylsulfonyl or vinylidene;

In the formula, W ₄Expression ethane four bases, propane four bases, butane four bases or ethene four bases, h represents 1～3 integer, wherein, in formula (31), 4 singly-bounds can be bonded on any carbon in the cycloalkyl carbon;

As the W in general formula (27)～(29) ₁～W ₃, more preferably singly-bound or carbonyl.

The integer of the h ordinary representation 1～3 in the general formula (31), wherein, preferred 2～3 integer, more preferably 3.

As 4 valency alkyl of the fragrant same clan of formula (25) expression, more preferably use the alkyl of formula (25 ') expression.

As 4 valency alkyl of the fragrant same clan of formula (26) expression, more preferably use the alkyl of formula (26 '), (26 ") expression, wherein, further preferred group with formula (26 ') expression.

As W in the fragrant same clan 4 valency alkyl of general formula (27) expression ₁Be 4 valency alkyl of the single bonded fragrant same clan, can enumerate group with formula (27-1) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (27) expression ₁Be 4 valency alkyl of the fragrant same clan of Sauerstoffatom, can enumerative (27-2) group of expression.

As W in the fragrant same clan 4 valency alkyl of general formula (27) expression ₁Be 4 valency alkyl of the fragrant same clan of carbonyl, can enumerate group with formula (27-3) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (27) expression ₁Be 4 valency alkyl of the fragrant same clan of alkylsulfonyl, can enumerate group with formula (27-4) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (27) expression ₁Be 4 valency alkyl of the fragrant same clan of vinylidene, can enumerate group with formula (27-5) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (28) expression ₂Be 4 valency alkyl of the single bonded fragrant same clan, can enumerate group with formula (28-1) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (28) expression ₂Be 4 valency alkyl of the fragrant same clan of Sauerstoffatom, can enumerate group with formula (28-2) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (28) expression ₂Be 4 valency alkyl of the fragrant same clan of carbonyl, can enumerate group with formula (28-3) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (28) expression ₂Be 4 valency alkyl of the fragrant same clan of alkylsulfonyl, can enumerate group with formula (28-4) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (28) expression ₂Be 4 valency alkyl of the fragrant same clan of vinylidene, can enumerative (28-5) group of expression.

As W in the fragrant same clan 4 valency alkyl of general formula (29) expression ₃Be 4 valency alkyl of the single bonded fragrant same clan, can enumerate group, wherein, preferably use the group of formula (29-1 '), (29-1 ") expression, more preferably use the group of formula (29-1 ') expression with formula (29-1) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (29) expression ₃Be 4 valency alkyl of the fragrant same clan of Sauerstoffatom, can enumerate group, wherein, preferably use the group of formula (29-2 '), (29-2 ") expression, more preferably use the group of formula (29-2 ') expression with formula (29-2) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (29) expression ₃Be 4 valency alkyl of the fragrant same clan of carbonyl, can enumerate group, wherein, preferably use the group of formula (29-3 '), (29-3 ") expression, more preferably use the group of formula (29-3 ') expression with formula (29-3) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (29) expression ₃Be 4 valency alkyl of the fragrant same clan of alkylsulfonyl, can enumerate group, wherein, preferably use the group of formula (29-4 '), (29-4 ") expression, more preferably use the group of formula (29-4 ') expression with formula (29-4) expression.

As W in the fragrant same clan 4 valency alkyl of general formula (29) expression ₃Be 4 valency alkyl of the fragrant same clan of vinylidene, can enumerate group, wherein, preferably use the group of formula (29-5 '), (29-5 ") expression, more preferably use the group of formula (29-5 ') expression with formula (29-5) expression.

In 4 valency alkyl of the above-mentioned fragrant same clan, preferably use the group of formula (25), (26) or general formula (29) expression, wherein, more preferably W in formula (25) or the general formula (29) ₃Be the group of singly-bound or carbonyl, that is, preferably use the group of formula (25), (29-1) or (29-3) expression, further preferred group with formula (29-1) or (29-3) expression.

As W in 4 valency alkyl of the aliphatic category shown in the general formula (30) ₄Be 4 valency alkyl of the aliphatic category of ethane four bases, can enumerate group with formula (30-1) expression.

As W in 4 valency alkyl of the aliphatic category shown in the general formula (30) ₄Be 4 valency alkyl of the aliphatic category of propane four bases, can enumerate group with formula (30-2) expression.

As W in 4 valency alkyl of the aliphatic category shown in the general formula (30) ₄Be 4 valency alkyl of the aliphatic category of butane four bases, can enumerate group with formula (30-3) expression.

4 valency alkyl as the aliphatic category of representing with general formula (31), usually can enumerate h and be 1～3 integer, be preferably 2～3 integer, 4 valency alkyl of 3 aliphatic category more preferably, specifically, can enumerate group, wherein with expressions such as formula (31-1), (31-2), (31-3), preferably use the group of formula (31-2), (31-3) expression, more preferably use the group of formula (31-3) expression.

In 4 valency alkyl of above-mentioned aliphatic category, preferably use the group of formula (32) or (33) expression, wherein, more preferably use the group of formula (32) expression.

4 valency alkyl of these aromatic series or aliphatic category come from the manufacture method that comprises the compound that structural unit forms shown in the general formula (7) described later the polyprotonic acid with 3 above carboxyls (part that comprises carboxyl is the material of carboxylicesters) with general formula (34) expression, with the multi-anhydride with 3 above carboxyls (comprise the material of the part of carboxyl through dehydrating condensation formation anhydride group, a part that also comprises carboxyl is the material of carboxylicesters) of general formula (35) or (36) expression;

In the formula (34), R3 ', R4 ' and Z are same as described above;

In the formula, R3 ', R4 ' and Z are same as described above.

In addition, wherein said carboxylicesters is meant the group with general formula (37) expression,

—COOR ¹⁴　　　　　　(37)

In the formula (37), R ¹⁴The expression carbonatoms is 1～6 alkyl.

As in general formula (37), using R ¹⁴The carbonatoms of expression is 1～6 alkyl, it can be the straight chain shape, chain or cyclic any, specifically, can enumerate for example methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, neo-pentyl, 2-methyl butyl, 1-ethyl propyl, cyclopentyl, n-hexyl, isohexyl, Sec-Hexyl, uncle's hexyl, new hexyl, 2-methyl amyl, 1,2-dimethylbutyl, 1-ethyl-butyl, cyclohexyl etc., wherein, preferred carbonatoms is 1～4 alkyl, specifically, can enumerate for example methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl, more preferably carbonatoms is 1～2 alkyl, specifically, can enumerate methyl, ethyl.

As a and the b in general formula (1) and (7), more preferably 1.

K in general formula (1) and (7) can enumerate 1～100 integer usually in natural number, wherein, and preferred 2～50 integer, more preferably 2～20 integer.

Said in the general formula (1) " in the formula, R ⁶, R ⁸, R ⁹At least 1 be group with two keys " in " group " with two keys, be meant group from (methyl) acrylic acid derivative, specifically, be meant and use R ⁷The group of expression, that is, and expression vinyl carbonyl or pseudoallyl carbonyl, the group of using general formula (3) or general formula (4) to represent.

In addition, at this said (methyl) acrylic acid derivative, be meant acrylic acid derivative and/or methacrylic acid derivative.

As in general formula (7), using R ³' and R ⁴' expression alkoxy carbonyl, can enumerate the straight chain shape, prop up chain or cyclic, usually carbonatoms is 2～7, preferred carbonatoms is 2～5, more preferably carbonatoms is 2～3 alkoxy carbonyl, specifically, can enumerate methoxycarbonyl, ethoxy carbonyl, the positive propoxy carbonyl, isopropoxy carbonyl, the ring propoxycarbonyl, the n-butoxy carbonyl, isobutoxy carbonyl, the sec-butoxy carbonyl, tert-butoxycarbonyl, the cyclobutoxy group carbonyl, the n-pentyloxy carbonyl, the isopentyloxy carbonyl, secondary pentyloxy carbonyl, tert-pentyloxy carbonyl, the neopentyl oxygen carbonyl, 2-methyl butoxy carbonyl, 1-ethyl propoxycarbonyl, the cyclopentyloxy carbonyl, positive hexyloxy carbonyl, different hexyloxy carbonyl, secondary hexyloxy carbonyl, uncle's hexyloxy carbonyl, new hexyloxy carbonyl, 2-methyl pentyloxy carbonyl, 1,2-dimethyl butoxy carbonyl, 1-ethyl butoxy carbonyl, cyclohexyloxy carbonyl etc., wherein, preferred methoxycarbonyl, ethoxy carbonyl, the positive propoxy carbonyl, isopropoxy carbonyl, the ring propoxycarbonyl, the n-butoxy carbonyl, isobutoxy carbonyl, the sec-butoxy carbonyl, tert-butoxycarbonyl, cyclobutoxy group carbonyl, more preferably methoxycarbonyl, ethoxy carbonyl.

As the Y in the general formula (7) ₁', the more preferably group shown in Sauerstoffatom or the formula (8), the more preferably group shown in the formula (8).

As the Y in general formula (7) ₂', the more preferably group shown in Sauerstoffatom or the formula (9), the more preferably group shown in the formula (9).

As the halogen atom of in general formula (10), representing with X, can enumerate for example fluorine atom, chlorine atom, bromine atoms, iodine atom etc., wherein, preferred chlorine atom, bromine atoms, more preferably chlorine atom.

As in general formula (1), (7), (14), (15), (16) and (17), using T ₁And T ₂The carbonatoms of expression is 1～6 straight chain shape alkylidene group, can enumerate for example methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene etc., wherein, preferred carbonatoms is 1～4 straight chain shape alkylidene group, specifically, can enumerate methylene radical, ethylidene, propylidene, butylidene, wherein, more preferably carbonatoms is 1～2 straight chain shape alkylidene group, specifically, can enumerate methylene radical, ethylidene, wherein, further preferred carbonatoms is 1 straight chain shape alkylidene group, specifically, can enumerate methylene radical.

To using T ₁And T ₂There is no particular limitation for 2 single bonded bonding positions of arylidene of expression, but with respect to phenyl ring, and position and to the bit position relation between 2 single bonded positions relations are preferably more preferably concerns bit position.

As these T ₁And T ₂, more preferably carbonatoms is 1～6 straight chain shape alkylidene group.

As in general formula (3) and (11), using T ₃The carbonatoms of expression is 1～6 straight chain shape alkylidene group, can enumerate for example methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene etc., wherein, preferred carbonatoms is 1～3 straight chain shape alkylidene group, specifically, can enumerate methylene radical, ethylidene, propylidene, wherein, more preferably carbonatoms is 1 straight chain shape alkylidene group, specifically, can enumerate methylene radical.

As in general formula (4) and (12), using T ₄The carbonatoms of expression is 1～6 straight chain shape alkylidene group, can enumerate for example methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene etc., wherein, preferred carbonatoms is 2～4 straight chain shape alkylidene group, specifically, can enumerate ethylidene, propylidene, butylidene, wherein, more preferably carbonatoms is 2 straight chain shape alkylidene group, specifically, can enumerate ethylidene.

As R at general formula (3), (4), (10), (11), (12), general formula (5) ⁸And the R of general formula (6) ⁹In R ⁷, more preferably vinyl carbonyl.

As the R in general formula (13) ¹⁰And R ¹¹, the M in the general formula (15) ₁And the M in the general formula (17) ₂The alkali metal atom of expression can be enumerated for example lithium atom, sodium atom, potassium atom, rubidium atom, caesium atom, francium atom etc., wherein, and preferred lithium atom, sodium atom, potassium atom, caesium atom, more preferably sodium atom, potassium atom.

As the R in general formula (13) ¹⁰, more preferably alkali metal atom, with the group of general formula (14) or (15) expression, wherein, further preferred group with general formula (14) or (15) expression is especially preferably used the group of general formula (14) expression.

As the R in general formula (13) ¹¹, more preferably alkali metal atom, with the group of general formula (16) or (17) expression, wherein, further preferred group with general formula (16) or (17) expression is especially preferably used the group of general formula (16) expression.

As the M in general formula (15) and (17) ₁And M ₂, hydrogen atom more preferably.

As the V in general formula (15) and (17) ₃And V ₄, Sauerstoffatom more preferably.

Contain in the compound that structural unit forms shown in the above-mentioned general formula (1) of the present invention, as comprising the compound that structural unit more specifically forms, for example can enumerate and comprise the compound that the structural unit with general formula (18) expression forms or comprise the compound that the structural unit represented with general formula (19) forms, wherein, the structural unit of representing with general formula (18) is the Y in the general formula (1) ₁Be group, Y with general formula (5) expression ₂Being that group, a and b with general formula (6) expression is 1 structural unit, is the middle Y of general formula (1) with the structural unit of general formula (19) expression ₁And Y ₂Be Sauerstoffatom or-structural unit of NH-group;

In the formula (18), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁸, R ⁹, T ₁, T ₂, U, V ₁, V ₂, Z and k be same as described above;

In the formula (19), Y ₁" and Y ₂" represent independently of one another Sauerstoffatom or-NH-group, R ¹, R ², R ¹', R ²', R ³, R ⁴, T ₁, T ₂, U, V ₁, V ₂, Z, a, b and k be same as described above.

As the Y in the general formula (19) ₁" and Y ₂", more preferably Sauerstoffatom.

Preferred concrete example as structural unit shown in the general formula (18), can enumerate U is the material of using the divalent group of formula (1-1) or (1-7) expression, more particularly, can enumerate with the material of general formula (38) expression or the material of representing with general formula (39), wherein, more preferably U is the material with the divalent group of formula (1-1) expression, more particularly, can enumerate the material with general formula (38) expression;

In the formula (38), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', R ⁸, R ⁹, T ₁, T ₂, V ₁, V ₂, Z and k be same as described above;

In the formula (39), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁸, R ⁹, T ₁, T ₂, V ₁, V ₂, Z and k be same as described above.

As the preferred concrete example of structural unit shown in the general formula (38), can enumerate V ₁And V ₂Be the material of Sauerstoffatom, more particularly, can enumerate material with general formula (40) expression;

In the formula (40), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', R ⁸, R ⁹, T ₁, T ₂, Z and k be same as described above.

As the preferred concrete example of structural unit shown in the general formula (40), can enumerate T ₁And T ₂Be that carbonatoms is the material of 1～3 straight chain shape alkylidene group, more particularly, can enumerate material with general formula (41) expression;

In the formula (41), T ₁' and T ₂' represent that independently of one another carbonatoms is 1～3 straight chain shape alkylidene group, R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', R ⁸, R ⁹, Z and k be same as described above.

As using T in the general formula (41) ₁' and T ₂' carbonatoms of expression is 1～3 straight chain shape alkylidene group, for example, can enumerate methylene radical, ethylidene, propylidene etc., wherein, more preferably carbonatoms is 1 straight chain shape alkylidene group, specifically, can enumerate methylene radical.

In general formula (41), preferred R ¹, R ², R ¹', R ²', R ⁵, R ⁵It all is the material of hydrogen atom.

In general formula (41), usually so long as the 4 valency alkyl of representing with Z are 4 valency alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in 4 valency alkyl, preferably use above-mentioned formula (25) or (26), with above-mentioned general formula (29) or the group represented with above-mentioned formula (32), (33) with the aromatic series of above-mentioned general formula (25)～(33) expressions or aliphatic category.

As the particularly preferred concrete example of structural unit shown in the general formula (41), can enumerate structural unit with general formula (42) expression;

In the formula (42), Z ₁Be with above-mentioned formula (29-1 '), (29-3 ') or aromatic series of (32) expression or 4 valency alkyl of aliphatic category, R ³, R ⁴, R ⁸, R ⁹Same as described above with k.

Preferred concrete example as the structural unit of representing with general formula (19), can enumerate U is the structural unit of using the divalent group of formula (1-1) or (1-7) expression, more particularly, can enumerate with the structural unit of general formula (43) expression or the structural unit of representing with general formula (44), wherein, more preferably U is the structural unit with the divalent group of formula (1-1) expression, more particularly, can enumerate the structural unit with general formula (43) expression;

In the formula (43), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', T ₁, T ₂, V ₁, V ₂, Y ₁", Y ₂", Z, a, b and k be same as described above;

In the formula (44), R ¹, R ², R ¹', R ²', R ³, R ⁴, T ₁, T ₂, V ₁, V ₂, Y ₁", Y ₂", Z, a, b and k be same as described above.

As the preferred concrete example of structural unit shown in the general formula (43), can enumerate V ₁, V ₂, Y ₁" and Y ₂" be Sauerstoffatom, and a and b be 1 structural unit, more particularly, can enumerate the structural unit with general formula (45) expression;

In the formula (45), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', T ₁, T ₂, Z and k be same as described above.

As the preferred concrete example of structural unit shown in the general formula (45), can enumerate T ₁And T ₂Be that carbonatoms is the structural unit of 2～4 straight chain shape alkylidene group, more particularly, can enumerate structural unit with general formula (46) expression;

In the formula (46), T ₁" and T ₂" represent that independently of one another carbonatoms is 2～4 straight chain shape alkylidene group, R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', Z and k be same as described above.

As using T in the general formula (46) ₁" and T ₂" carbonatoms of expression is 2～4 straight chain shape alkylidene group, for example, can enumerate ethylidene, propylidene, butylidene etc., wherein, preferred carbonatoms is 2 straight chain shape alkylidene group, specifically, can enumerate ethylidene.

In general formula (46), preferred R ¹, R ², R ¹', R ²', R ⁵, R ⁵' all be the structural unit of hydrogen atom.

In general formula (46), usually so long as the 4 valency alkyl of representing with Z are 4 valency alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in 4 valency alkyl with the aromatic series of above-mentioned general formula (25)～(33) expressions or aliphatic category, the group of preferably using above-mentioned formula (25) or (26), representing with above-mentioned general formula (29) or above-mentioned formula (32), (33).

As the particularly preferred concrete example of structural unit shown in the general formula (41), can enumerate structural unit with general formula (47) expression;

In the formula (47), Z ₂Be 4 valency alkyl with the aliphatic category of above-mentioned formula (32) expression, R ₃, R ₄Same as described above with k.

As the acid value that contains the compound that structural unit forms shown in the general formula (1), be used at this compound under the situation of various uses, can obtain suitable performance and get final product so long as be set at, there is no particular limitation, but be generally 70～150mgKOH/g, be preferably 80～130mgKOH/g.At this, if contain the not enough 70mgKOH/g of the acid value of the compound that structural unit forms shown in the general formula (1), then for example using the resin combination that obtains by this compound to prepare under the situation of colour filter, for example the alkali development time after light or the thermofixation is elongated, in addition, if acid value surpasses 150mgKOH/g, in the time of then can being created in the alkali development, the problem that fine pattern is peeled off etc. easily, therefore not preferred.In addition, acid value with in and the mg numerical table of the necessary potassium hydroxide of this compound of 1g show, usually, can obtain by the mixing solutions titration of using alcohol such as potassium hydroxide aqueous solution or ethanol and water.

In containing the compound that structural unit forms shown in the general formula (1), the k of the expression polymerization degree is illustrated in the entire infrastructure unit in this compound, the number of structural unit shown in the general formula (1), be used at this compound under the situation of various uses, can obtain suitable performance as long as be set at, there is no particular limitation, but be generally 1～100, be preferably 2～50, more preferably 2～20 integer.

The polystyrene conversion weight-average molecular weight that contains the compound that structural unit forms shown in the general formula (1) is used under the situation of various uses at this compound, can obtain suitable performance as long as be set at, there is no particular limitation, but be generally 1000～5,000,000, be preferably 2000～100,000, more preferably 2000～50,000.

Contain in the compound that structural unit forms shown in the general formula (1) of the present invention, this compound is except structural unit shown in the general formula (1), can be with other structural unit as composition, specifically, for example, other structural unit is that the Z in the general formula (38) is the unit of divalent hydrocarbon, as containing structural unit shown in the general formula (38) and containing the compound that this structural unit forms, can enumerate the compound that comprises structural unit shown in the general formula (48);

In the formula (48), Z ' expression divalent alkyl, k ' and k " the expression natural number, R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', R ⁸, R ⁹, T ₁, T ₂, V ₁, V ₂And Z is same as described above.

In general formula (48), as the divalent alkyl of using Z ' expression, usually can enumerate the divalent alkyl of aromatic series or aliphatic category, specifically, can enumerate for example divalent alkyl of the fragrant same clan of formula (49)～(51), general formula (52) or (53) expression, perhaps, the divalent alkyl of the aliphatic category of general formula (54), (55) or formula (56) expression;

Wherein, in formula (50), two singly-bounds can be bonded on any carbon in 1～8 carbon of naphthalene nucleus;

In the formula, W ₅And W ₆Expression singly-bound, Sauerstoffatom, carbonyl, alkylsulfonyl or vinylidene;

In the formula, W ₇Expression singly-bound, carbonatoms are 1～18 straight chain shape alkylidene group, vinylidene, 2,3-propenylidene (1-propylene-2,3-two bases), ethynyl or 2-oxo propylidene, and i represents 1～3 integer.Wherein, in formula (55), 2 singly-bounds can be bonded on any carbon in the carbon of cycloalkyl ring;

In the formula, 2 singly-bounds can be bonded on any carbon in the tetrahydrobenzene basic ring carbon.

As the W in general formula (52) and (53) ₅And W ₆, more preferably singly-bound or carbonyl.

As the W in the general formula (54) ₇, more preferably singly-bound, carbonatoms are 1～18 straight chain shape alkylidene group or vinylidene, wherein, and further preferred vinylidene.

The integer of the i ordinary representation 1～3 in the general formula (55), wherein, preferred 2～3 integer, more preferably 3.

As the divalent alkyl of the fragrant same clan, more preferably use the group of formula (49 ') or (49 ") expression with formula (49) expression.

As the divalent alkyl of the fragrant same clan, more preferably use the group of formula (50 '), (50 ") or (50 " ') expression with formula (50) expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (52), as W ₅Be the divalent alkyl of the single bonded fragrant same clan, can enumerate group with formula (52-1) expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (52), as W ₅Be the divalent alkyl of the fragrant same clan of Sauerstoffatom, can enumerate group with formula (52-2) expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (52), as W ₅Be the divalent alkyl of the fragrant same clan of carbonyl, can enumerate group with formula (52-3) expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (52), as W ₅Be the divalent alkyl of the fragrant same clan of alkylsulfonyl, can enumerate group with formula (52-4) expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (52), as W ₅Be the divalent alkyl of the fragrant same clan of vinylidene, can enumerate group with formula (52-5) expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (53), as W ₆Be the divalent alkyl of the single bonded fragrant same clan, can enumerate group with formula (53-1) expression, wherein, the more preferably group of formula (53-1 ') expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (53), as W ₆Be the divalent alkyl of the fragrant same clan of Sauerstoffatom, can enumerative (53-2) group of expression, wherein, the more preferably group of formula (53-2 ') expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (53), as W ₆Be the divalent alkyl of the fragrant same clan of carbonyl, can enumerate group, wherein, more preferably use the group of formula (53-3 ') expression with formula (53-3) expression.

In the divalent alkyl of the fragrant same clan that represents with general formula (53), as W ₆Be the divalent alkyl of the fragrant same clan of alkylsulfonyl, can enumerate group with formula (53-4) expression, wherein, the more preferably group of formula (53-4 ') expression.

In the divalent alkyl of the fragrant same clan that general formula (53) is represented, as W ₆Be the divalent alkyl of the fragrant same clan of vinylidene, can enumerative (53-5) group of expression, wherein, the more preferably group of formula (53-5 ') expression.

In the divalent alkyl of the above-mentioned fragrant same clan, preferably use the alkyl of formula (49) or general formula (53) expression, wherein, more preferably using the W6 in formula (49) or the general formula (53) is the group of singly-bound or carbonyl, promptly preferred group with formula (49), (53-1) or (53-3) expression, further preferred group with formula (49) expression.

In divalent alkyl, as W with general formula (54) expression ₇Be that carbonatoms is the divalent alkyl of the aliphatic category of 1～18 straight chain shape alkylidene group, can enumerate alkyl with general formula (54-1) expression,

—(CH ₂) _j— (54-1)

In the formula (54-1), j represents 1～18 integer.

As the j in the general formula (54-1), can enumerate 1～18 integer usually, be preferably 1～10 integer, more preferably 1～6 integer.

In the divalent alkyl of general formula (54) expression, as W ₇Be the divalent alkyl of the aliphatic category of vinylidene, can enumerate alkyl, wherein, preferably use the alkyl of formula (54-2 ') expression with formula (54-2 ') or (54-2 ") expression.

In divalent alkyl, as W with general formula (54) expression ₇Be the divalent alkyl of the aliphatic category of 2,3-propenylidene (1-propane-2,3-two bases), can enumerate alkyl with formula (54-3) expression.

In divalent alkyl, as W with general formula (54) expression ₇Be the divalent alkyl of the aliphatic category of ethynyl, can enumerate alkyl with formula (54-4) expression.

In divalent alkyl, as W with general formula (54) expression ₇Be the divalent alkyl of the aliphatic category of 2-oxo propylidene, can enumerate alkyl with formula (54-5) expression.

Divalent alkyl as the aliphatic category of representing with general formula (55), usually can enumerate i and be 1～3 integer, be preferably 2～3 integer, the divalent alkyl of 3 aliphatic category more preferably, specifically, for example, can enumerate group with expressions such as formula (55-1), (55-2), (55-3), wherein, preferably use the group of formula (55-2), (55-3) expression, more preferably use the group of formula (55-3) expression.

As the divalent alkyl of the fragrant same clan with formula (56) expression, more preferably use the group of formula (56 ') or (56 ") expression, wherein, more preferably use the group of formula (56 ') expression.

In the divalent alkyl of above-mentioned aliphatic category, preferably use the group of general formula (54) or formula (56) expression, wherein, the more preferably W in the general formula (54) ₇Be that singly-bound, carbonatoms are 1～18 straight chain shape alkylidene group or the group of vinylidene or the group of representing with formula (56), wherein, the W in the further preferred formula (54) ₇Be the group of vinylidene or with the group of formula (56) expression, that is, preferably use the group of formula (54-2 '), (54-2 "), (56 ') or (56 ") expression.

The divalent alkyl of these aromatic series or aliphatic category the use by oneself aromatic series with 2 carboxyls of general formula (57) expression or aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) or the aromatic series of representing with general formula (58) or the group of aliphatic carboxylic acid acid anhydride (aromatic series or aliphatic dicarboxylic acid acid anhydride) with 2 carboxyls

In the formula (57), Z ' is same as described above;

In the formula (58), Z ' is same as described above.

K ' and k in the mutual-through type (48) " ratio (k ': k ") there is no particular limitation, for example, can enumerate k ': k "=10:90～99:1.

As the preferred concrete example of structural unit shown in the general formula (48), can enumerate V ₁And V ₂Be the structural unit of Sauerstoffatom, more particularly, can enumerate the structural unit shown in the general formula (59),

In the formula (59), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', R ⁸, R ⁹, T ₁, T ₂, Z, Z ', k ' and k " same as described above.

As the preferred concrete example of structural unit shown in the general formula (59), can enumerate T ₁And T ₂Be that carbonatoms is the structural unit of 1～3 straight chain shape alkylidene group, more particularly, can enumerate the structural unit shown in the general formula (60),

In the formula (60), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', R ⁸, R ⁹, T ₁', T ₂', Z, Z ', k ' and k " same as described above.

In general formula (60), preferred R ¹, R ², R ¹', R ²', R ⁵, R ⁵' all be hydrogen atom.

In general formula (60), usually, the 4 valency alkyl of representing with Z are so long as 4 valency alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in above-mentioned aromatic series or 4 valency alkyl of aliphatic category with general formula (25)～(33) expressions, the group of preferably using above-mentioned formula (25) or (26), representing with above-mentioned general formula (29) or above-mentioned formula (32), (33).

In general formula (60), usually, the divalent alkyl of using Z ' expression is so long as the divalent alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in the divalent alkyl of above-mentioned aromatic series of representing with general formula (49)～(56) or aliphatic category, preferably use the group of above-mentioned formula (49), above-mentioned general formula (53) or (54) or formula (56) expression.

As the particularly preferred concrete example of structural unit shown in the general formula (60), can enumerate structural unit with general formula (61) expression,

In the formula (61), Z ₃The aromatic series shown in expression following formula (49 ') (54-2 ') or (56 ') or the divalent alkyl of aliphatic category, R ³, R ⁴, R ⁸, R ⁹, Z ₁, k ' and k " same as described above.

In addition, for example, be that Z in the general formula (43) is the unit of divalent hydrocarbon and contains the structural unit shown in the general formula (43) and compound that this structural unit forms as other structural unit, can enumerate and contain the compound that structural unit forms shown in the general formula (62),

In the formula (62), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', T ₁, T ₂, V ₁, V ₂, Y ₁", Y ₂", Z, Z ', a, b, k ' and k " same as described above.

As the preferred concrete example of structural unit shown in the general formula (62), can enumerate V ₁, V ₂, Y ₁" and Y ₂" be Sauerstoffatom, and a and b be 1 structural unit, more particularly, can enumerate the structural unit shown in the general formula (63),

In the formula (63), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', T ₁, T ₂, Z, Z ', k ' and k " same as described above.

As the preferred concrete example of structural unit shown in the general formula (63), can enumerate T ₁And T ₂Be that carbonatoms is the structural unit of 2～4 straight chain shape alkylidene group, more particularly, can enumerate the structural unit shown in the general formula (64),

In the formula (64), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁵, R ⁵', T ₁", T ₂", Z, Z ', k ' and k " same as described above.

In general formula (64), preferred R ¹, R ², R ¹', R ²', R ⁵, R ⁵' all be hydrogen atom.

In general formula (64), usually, the 4 valency alkyl of representing with Z are so long as 4 valency alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in above-mentioned aromatic series or 4 valency alkyl of aliphatic category with general formula (25)～(33) expressions, the group of preferably using above-mentioned formula (25) or (26), representing with above-mentioned general formula (29) or above-mentioned formula (32) or (33).

In general formula (64), usually, the divalent alkyl of using Z ' expression is so long as the divalent alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in the divalent alkyl of aromatic series of representing with above-mentioned general formula (49)～(56) or aliphatic category, preferably use the group of above-mentioned formula (49), above-mentioned general formula (53) or above-mentioned formula (54) or formula (56) expression.

In addition, in containing the compound that structural unit forms shown in the general formula (1), as the unit beyond this structural unit, be not limited to as in the above-mentioned structural unit, in addition, as long as contain the structural unit shown in the general formula (1), other structural unit just can contain with ratio arbitrarily, specifically, for example, the k ' of the expression polymerization degree represents to contain in the entire infrastructure unit in this compound the quantity of the structural unit of Z, k in general formula (48) and (62) " represent to contain in the entire infrastructure unit in this compound the quantity of the structural unit of Z '; be used at this compound under the situation of various uses; can obtain suitable performance as long as set for, there is no particular limitation, but k ' and k " ratio (k ': k "); for example, can enumerate is k ': k "=10:90～99:1.

In addition, in containing the compound that structural unit forms shown in the general formula (1), when with structural unit shown in the general formula (1) as A, with other structural unit during as B, A and B can by shown in the general formula (65)-AB-repeating structure, the block structure shown in the general formula (66) or general formula (67) shown in random structure constitute this compound, further, can also be except A and B, with other structural units such as C, D as composition, with 3 compositions with on constitute this compound.

In containing the compound that structural unit forms shown in the above-mentioned general formula of the present invention (7), as containing the compound of structural unit more specifically, for example can enumerate and comprise the compound that the structural unit with general formula (20) expression forms or comprise the compound that the structural unit represented with general formula (21) forms, wherein, the structural unit of representing with general formula (20) is the Y in the general formula (7) ₁' be group, Y with formula (8) expression ₂' be that group, a and b with formula (9) expression is 1 structural unit, be the middle Y of general formula (7) with the structural unit of general formula (21) expression ₁' and Y ₂' be Sauerstoffatom or-structural unit of NH-group,

In the formula (20), R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z and k be same as described above;

In the formula (21), R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Y ₁", Y ₂", Z, a, b and k be same as described above.

Preferred concrete example as structural unit shown in the general formula (20), can enumerate U is the structural unit of divalent group shown in formula (1-1) or (1-7), more particularly, can enumerate the structural unit shown in structural unit shown in the general formula (68) or the general formula (69), wherein, more preferably U is the unit of the divalent group shown in the formula (1-1), more particularly, can enumerate the structural unit shown in the general formula (68)

In the formula (68), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁, T ₂, V ₁, V ₂, Z and k be same as described above;

In the formula (69), R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, V ₁, V ₂, Z and k be same as described above.

As the preferred concrete example of structural unit shown in the general formula (68), can enumerate V ₁And V ₂Be the structural unit of Sauerstoffatom, more particularly, can enumerate the structural unit shown in the general formula (70),

In the formula (70), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁, T ₂, Z and k be same as described above.

As the preferred concrete example of structural unit shown in the general formula (70), can enumerate T ₁And T ₂Be that carbonatoms is the structural unit of 1～3 alkylidene group, more particularly, can enumerate the structural unit shown in the general formula (71),

In the formula (71), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁', T ₂', Z and k be same as described above.

In general formula (71), preferred R ¹, R ², R ¹', R ²', R ⁵, R ⁵' all be hydrogen atom.

In general formula (71), usually, the 4 valency alkyl of representing with Z are so long as 4 valency alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in 4 valency alkyl of aromatic series of representing with above-mentioned general formula (25)～(33) or aliphatic category, preferably use the group of above-mentioned formula (25) or (26), above-mentioned general formula (29) or above-mentioned formula (32) or (33) expression.

As the particularly preferred concrete example of structural unit shown in the general formula (71), can enumerate the structural unit shown in the general formula (72),

In the formula (72), R ³', R ⁴', Z ₁And k is same as described above.

Preferred concrete example as structural unit shown in the general formula (21), can enumerate U is the structural unit of divalent group shown in formula (1-1) or (1-7), more particularly, can enumerate the structural unit shown in structural unit shown in the general formula (73) or the general formula (74), wherein, more preferably U is the unit of the divalent group shown in the formula (1-1), more particularly, can enumerate the structural unit shown in the general formula (73)

In the formula (73), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁, T ₂, V ₁, V ₂, Y ₁", Y ₂", Z, a, b and k be same as described above;

In the formula (74), R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, V ₁, V ₂, Y ₁", Y ₂", Z, a, b and k be same as described above.

As the preferred concrete example of structural unit shown in the general formula (73), can enumerate V ₁, V ₂, Y ₁" and Y ₂" be Sauerstoffatom, and a and b be 1 structural unit, more particularly, can enumerate the structural unit shown in the general formula (75),

In the formula (75), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁, T ₂, Z and k be same as described above.

As the preferred concrete example of structural unit shown in the general formula (75), can enumerate T ₁And T ₂Be that carbonatoms is the structural unit of 2～4 straight chain shape alkylidene group, more particularly, can enumerate the structural unit shown in the general formula (76),

In the formula (76), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁", T ₂", Z and k be same as described above.

In general formula (76), preferred R ¹, R ², R ¹', R ²', R ⁵, R ⁵' all be hydrogen atom.

In general formula (76), usually, the 4 valency alkyl of representing with Z are so long as 4 valency alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in 4 valency alkyl of aromatic series of representing with above-mentioned general formula (25)～(33) or aliphatic category, preferably use the group of above-mentioned formula (25) or (26), above-mentioned general formula (29) or above-mentioned formula (32) or (33) expression.

As the particularly preferred concrete example of structural unit shown in the general formula (76), can enumerate the structural unit shown in the general formula (77),

In the formula (77), R ³', R ⁴', Z ₂And k is same as described above.

In containing the compound that structural unit forms shown in the general formula (7), the k of the expression polymerization degree represents in the entire infrastructure unit in this compound, the quantity that contains structural unit shown in the general formula (7), be used at this compound under the situation of various uses, can obtain suitable performance as long as set for, there is no particular limitation, is generally 1～100, is preferably 2～50, more preferably 2～20 integer.

The polystyrene conversion weight-average molecular weight that contains the compound that structural unit forms shown in the general formula (7) is used under the situation of various uses at this compound, can obtain suitable performance as long as set for, there is no particular limitation, be generally 1000～5,000,000, be preferably 2000～100,000, more preferably 2000～50,000.

Contain in the compound that structural unit forms shown in the general formula (7) of the present invention, this compound can be with other structural unit beyond the structural unit shown in the general formula (7) as composition, specifically, for example, as other structural unit is that Z in the general formula (68) is the structural unit of divalent hydrocarbon and contains structural unit shown in the general formula (68) and the compound of this structural unit, can enumerate and contain the compound that structural unit forms shown in the general formula (78)

In the formula (78), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁, T ₂, V ₁, V ₂, Z, Z ', k ' and k " same as described above.

As the preferred concrete example of structural unit shown in the general formula (78), can enumerate V ₁And V ₂Be the structural unit of Sauerstoffatom, more particularly, can enumerate the structural unit shown in the general formula (79),

In the formula (79), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁, T ₂, Z, Z ', k ' and k " same as described above.

As the preferred concrete example of structural unit shown in the general formula (79), can enumerate T ₁And T ₂Be that carbonatoms is the structural unit of 1～3 straight chain shape alkylidene group, more particularly, can enumerate the structural unit shown in the general formula (80),

In the formula (80), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁', T ₂', Z, Z ', k ' and k " same as described above.

In general formula (80), preferred R ¹, R ², R ¹', R ²', R ⁵, R ⁵' all be hydrogen atom.

In general formula (80), usually, the 4 valency alkyl of representing with Z are so long as 4 valency alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in 4 valency alkyl of aromatic series of representing with above-mentioned general formula (25)～(33) or aliphatic category, preferably use the group of above-mentioned formula (25) or (26), above-mentioned general formula (29) or above-mentioned formula (32) or (33) expression.

In general formula (80), usually, the divalent alkyl of using Z ' expression is so long as the divalent alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in the divalent alkyl of aromatic series of representing with above-mentioned general formula (49)～(56) or aliphatic category, preferably use the group of above-mentioned formula (49), above-mentioned general formula (53) or above-mentioned formula (54) or formula (56) expression.

As the particularly preferred concrete example of structural unit shown in the general formula (80), can enumerate the structural unit shown in the general formula (81),

In the formula (81), R ³', R ⁴', Z ₁, Z ₃, k ' and k " same as described above.

In addition, for example, as other structural unit is that Z in the general formula (73) is the structural unit of divalent hydrocarbon and contains the structural unit shown in the general formula (73) and compound that this structural unit forms, can enumerate and contain the compound that structural unit forms shown in the general formula (82)

In the formula (82), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁, T ₂, V ₁, V ₂, Y ₁", Y ₂", Z, Z ', a, b, k ' and k " same as described above.

As the preferred concrete example of structural unit shown in the general formula (82), can enumerate V ₁, V ₂, Y ₁" and Y ₂" be Sauerstoffatom, and a and b be 1 structural unit, more particularly, can enumerate the structural unit shown in the general formula (83),

In the formula (83), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁, T ₂, Z, Z ', k ' and k " same as described above.

As the preferred concrete example of structural unit shown in the general formula (83), can enumerate T ₁And T ₂Be that carbonatoms is the structural unit of 2～4 straight chain shape alkylidene group, more particularly, can enumerate the structural unit shown in the general formula (84),

In the formula (84), R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁵, R ⁵', T ₁", T ₂", Z, Z ', k ' and k " same as described above.

In general formula (84), preferred R ¹, R ², R ¹', R ²', R ⁵, R ⁵' all be hydrogen atom.

In general formula (84), usually, the 4 valency alkyl of representing with Z are so long as 4 valency alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in 4 valency alkyl of aromatic series of representing with above-mentioned general formula (25)～(33) or aliphatic category, preferably use the group of above-mentioned formula (25) or (26), above-mentioned general formula (29) or above-mentioned formula (32) or (33) expression.

In general formula (84), usually, the divalent alkyl of using Z ' expression is so long as the divalent alkyl of aromatic series or aliphatic category, just there is no particular limitation, for example, in the divalent alkyl of aromatic series of representing with above-mentioned general formula (49)～(56) or aliphatic category, preferably use the group of above-mentioned formula (49), above-mentioned general formula (53) or (54) or formula (56) expression.

In addition, in containing the compound that structural unit forms shown in the general formula (7), as the unit beyond this structural unit, be not limited to as above-mentioned structural unit, in addition, as long as contain the structural unit shown in the general formula (7), other structural unit just can contain with ratio arbitrarily, specifically, for example, the k ' of the expression polymerization degree represents in the entire infrastructure unit of this compound in general formula (78) and (82), the structural unit quantity that contains Z; k " represent to contain the structural unit quantity of Z ' in the entire infrastructure unit of this compound, be used at this compound under the situation of various uses, can obtain suitable performance as long as set for, there is no particular limitation, for example, k ' and k " ratio (k ': k ") can to enumerate be k ': k "=10:90～99:1.

In addition, in containing the compound that structural unit forms shown in the general formula (7), when with structural unit shown in the general formula (7) as A ', with other structural unit during as B ', A ' and B ' can by shown in the general formula (85)-A ' B '-repeating structure, the block structure shown in the general formula (86), general formula (87) shown in random structure constitute this compound, further, except A ' and B ', can also be with structural units such as C ', D ' as composition, thus with 3 compositions with on constitute this compound.

Below, to the manufacture method that contains the compound that structural unit forms shown in general formula (1) and (7), promptly, manufacture method of the present invention is described in detail.As the manufacture method that contains the compound that structural unit forms shown in the general formula (1) of the present invention, contain the compound that structural unit forms shown in the general formula (7) and (methyl) acrylic acid derivative more than at least a kind that is selected from general formula (10), (11) and (12) as long as make, in the presence of solvent as required, react and get final product, as concrete manufacture method, for example, can enumerate following [I] method or following [II] method

In the formula [I], R ¹, R ², R ¹', R ²', R ³, R ⁴, R ³', R ⁴', R ⁷, R ⁸, R ⁹, T ₁, T ₂, T ₃, T ₄, U, V ₁, V ₂, X, Z and k be same as described above;

In the formula [II], R ¹, R ², R ¹', R ²', R ³, R ⁴, R ³', R ⁴', R ⁷, T ₁, T ₂, T ₃, T ₄, U, V ₁, V ₂, X, Y ₁", Y ₂", Z, a, b and k be same as described above.

Above-mentioned [I] method is to make to comprise to have hydroxyl and R ³', R ⁴' shown in the structural unit of the carboxyl compound that forms and (methyl) acrylic acid derivative more than at least a kind that is selected from general formula (10), (11) and (12) react, contain the method that imports the compound that the structural unit from the group of this (methyl) acrylic acid derivative forms in hydroxyl and/or carboxyl thereby make, above-mentioned [II] method is to make to comprise to have R ³' and R ⁴' shown in the structural unit of the carboxyl compound that forms and (methyl) acrylic acid derivative more than at least a kind that is selected from general formula (11) and (12) react, thereby make the method that contains the compound that in carboxyl importing forms from the structural unit of the group of this (methyl) acrylic acid derivative.

In addition, wherein so-called group from (methyl) acrylic acid derivative, be meant the group of (methyl) acrylic acid derivative of self-drifting (10), (11) and (12) expression, specifically, the group of (methyl) acrylic acid derivative of the general formula (10) of using by oneself expression is meant uses R ⁷The group of expression promptly refers to vinyl carbonyl or pseudoallyl carbonyl, and the group of (methyl) acrylic acid derivative of the general formula (11) of using by oneself expression is meant uses R ³The group of expression, the group of (methyl) acrylic acid derivative of the general formula (12) of using by oneself expression is meant uses R ⁴The group of expression.

In addition, in above-mentioned [I] and [II] method, (methyl) acrylic acid derivative with general formula (10), (11) and (12) expression can use a kind or multiple, in addition, should can on the structure of structural unit shown in the above-mentioned general formula (20), import 1～4k group by (methyl) acrylic acid derivative, can on the structure of structural unit shown in the above-mentioned general formula (21), import 1～2k group.

Under the situation that (methyl) acrylic acid derivative more than 2 of (methyl) acrylic acid derivative that will contain useful general formula (10) expression is used in combination, preferably at first make and contain that (methyl) acrylic acid derivative is reacted shown in structural unit forms shown in the general formula (20) compound and the general formula (10), then, with gained reactant and other (methyl) acrylic acid derivative { for example, the material of representing with general formula (11) or (12) } reaction.If (methyl) acrylic acid derivative shown in the general formula (10) is mixed with other (methyl) acrylic acid derivative, two kinds of derivatives are reacted in the lump, because the reactivity of (methyl) acrylic acid derivative is than other (methyl) acrylic acid derivative height shown in the general formula (10), therefore between (methyl) acrylic acid derivative shown in the general formula (10) and other (methyl) acrylic acid derivative, react, generate the by product of (methyl) acrylic acid derivative, as a result, cause containing the productive rate reduction of the compound that structural unit forms shown in the general formula (18).In order to prevent this problem, preferably make (methyl) acrylic acid derivative reach reaction by stages respectively.

In addition, in above-mentioned, make and contain the compound that structural unit forms shown in the general formula (20) and at first react with (methyl) acrylic acid derivative shown in the general formula (10), (methyl) acrylic acid derivative with other reacts then, but after can certainly at first making other (methyl) acrylic acid derivative reaction, then with (methyl) acrylic acid derivative reaction shown in the general formula (10).

In addition, under the situation that is used in combination (methyl) acrylic acid derivative shown in general formula (11) and (12), when containing structural unit forms shown in general formula (20) or (21) compound and react, both can mix these (methyl) acrylic acid derivatives and reaction in the lump, and these (methyl) acrylic acid derivatives had been reached stage by stage respectively react.

As the preferred concrete example of manufacture method shown in [I] method, for example, can enumerate the method shown in following [III] method,

In the formula [III], R ¹, R ², R ¹', R ²', R ³', R ⁴', R ⁷, R ⁸, R ⁹, T ₁, T ₂, U, V ₁, V ₂, X, Z and k be same as described above.

Above-mentioned [III] method is to make to comprise to have hydroxyl and R ³' and R ⁴' shown in the compound that forms of the structural unit of carboxyl and (methyl) acrylic acid derivative shown in the general formula (10) reacted, contain the method that on hydroxyl, imports the compound that the structural unit from the group of this (methyl) acrylic acid derivative forms thereby make.

At this, above-mentioned [III] method is elaborated.For example, above-mentioned [III] method is to contain the compound usefulness solvent cut as required that structural unit forms shown in the general formula (20), after adding alkali, stopper and catalyzer as required therein, in this mixing solutions, splash into (methyl) acrylic acid derivative shown in the normal general formula of following regulation (10), under the temperature of regulation, react the specified time.Wherein the solution of gained need not to separate, make with extra care, and just can use in the purpose purposes, also can separate containing the compound that structural unit forms shown in the general formula (88), make with extra care by ordinary method according to purposes.As concrete separation, process for purification, therefore owing to reaction solution is splashed into this compound crystal is separated out, it is filtered, after for example water etc. is further cleaned to the gained crystallization precipitate, drying under reduced pressure, thereby to separating, make with extra care this compound.

In [III] method, as (methyl) acrylic acid derivative shown in the general formula (10), for example, can enumerate (methyl) acryloyl halide compounds such as (methyl) acrylate chloride, (methyl) propylene acylbromide, wherein, preferred (methyl) acrylate chloride,

As the equivalent of (methyl) acrylic acid derivative shown in the general formula (10), with respect to the hydroxyl that contains in the compound that structural unit forms shown in the general formula (20), can enumerate 0.1～3 equivalent usually, wherein, preferred 0.5～2 equivalent, more preferably 0.8～1.5 equivalent.

(methyl) acrylic acid derivative shown in the general formula (10) both can use commercially available product, also can suitably use by making the usual method synthetic material of (methyl) vinylformic acid and halogenating agent reaction.

About the temperature of reaction in [III] method, so long as can make the hydroxyl that contains in the compound that structural unit forms shown in the general formula (20) and the temperature of (methyl) acrylic acid derivative quantitative reaction shown in the general formula (10), just be not particularly limited, for example, be generally 0～50 ℃, be preferably 10～30 ℃.If temperature of reaction is above 50 ℃, then can cause the partially polymerized of this (methyl) acrylic acid derivative, become the rapid cause of increased of molecular weight, in addition, if 0 ℃ of less than, then reaction is carried out slowly, produces in order to make group from this (methyl) acrylic acid derivative import volume that achieves the goal, therefore needing the long period, is problem such as not preferred.

About the reaction times in [III] method, only need make the import volume of the group of (methyl) acrylic acid derivative shown in the self-drifting (10) to be controlled in the proper range and the decision reaction times gets final product.Because this reaction times is depended on the equivalent and the temperature of reaction of (methyl) acrylic acid derivative that uses in the reaction, therefore cannot treat different things as the same, usually be set in 0.5～50 hour, and preferably set, more preferably be set in 0.5～10 hour the scope at 0.5～20 hour.

[III] method is usually solvent-free or carry out in solvent, but preferably carries out in solvent.

As solvent, as long as each composition that uses in can solubilizing reaction and reaction product, can not produce bad influence and be water miscible to reaction, just there is no particular limitation, specifically, for example, can enumerate N, non-proton property polar solvents such as N-dimethyl formamide, 1-methyl-2-pyrrolidone, propylene glycol methyl ether acetate, methyl-sulphoxide, diox, methyl iso-butyl ketone (MIBK), γ-butyrolactone, ethyl lactate, pimelinketone.These solvents can be distinguished use separately, or will be used in combination more than 2 kinds, and about the usage quantity of above-mentioned solvent, so long as the amount of energy dissolving raw material, just there is no particular limitation.

In [III] method, preferably use alkali, thereby hydroxyl and (methyl) acrylic acid derivative shown in the general formula (10) of containing in the compound that structural unit forms shown in the general formula (20) quantitatively and are reposefully reacted.As these alkali, for example, can enumerate alkali such as normally used tertiary amine such as triethylamine, pyridine, dimethyl aminopyridine.These alkali can be distinguished separately and to use, or will be used in combination more than 2 kinds, and there is no particular limitation to the equivalents of above-mentioned alkali, with respect to (methyl) acrylic acid derivative shown in the general formula (10), can enumerate 1～2 equivalent usually.

In addition, in [III] method, can use catalyzer.As these catalyzer, for example, can enumerate the catalyzer such as organic phosphine compound of the quaternary ammonium salt of TBuA muriate, TBuA bromide, triethyl hexadecyldimethyl benzyl ammonium muriate, triethyl hexadecyldimethyl benzyl ammonium bromide etc. or triphenylphosphine etc.These catalyzer can be distinguished use separately, or will be used in combination more than 2 kinds, there is no particular limitation to the usage quantity of above-mentioned catalyzer, with respect to the mol amount that contains the compound that structural unit forms shown in the general formula (20), can enumerate more than the 0.001mol%, in order to improve speed of response, can also use about 200mol%.

And in [III] method, in preventing to react because the polymerization that two keys cause can be used stopper.As stopper, for example, can enumerate quinhydrones, hydroquinone monomethyl ether, pyrogallol, 4-tert-butyl catechol, 2,6-DI-tert-butylphenol compounds, thiodiphenylamine, benzophenone etc.These stoppers can be distinguished use separately, or will be used in combination more than 2 kinds, there is no particular limitation to the usage quantity of above-mentioned stopper, with respect to the mol amount that contains the compound that structural unit forms shown in the general formula (20), can enumerate 0.001mol%～2mol% usually.

[III] method is by under appropriate reaction conditions, in containing the compound that structural unit forms shown in the general formula (20), import the group of (methyl) acrylic acid derivative shown in the self-drifting (10), promptly by above-mentioned reaction conditionss such as control as equivalent that should (methyl) acrylic acid derivative, temperature of reaction, reaction times, thereby can at random regulate import volume from the group of this (methyl) acrylic acid derivative.Be used under the situation of various uses at the compound that obtains by present method, as long as setting for, the group import volume of acrylic acid derivative can obtain suitable performance from this (methyl), there is no particular limitation, but with respect to the hydroxyl mol amount that contains the compound that structural unit forms shown in the general formula (20), be generally 1～100mol%, be preferably the ratio of 10～80mol%.Should be from (methyl) if the group ratio of acrylic acid derivative be less than 10mol%, then for example prepare under the situation of colour filter using by containing the resin combination that compound that this structural unit forms obtains, for example the alkali development time after light or the thermofixation is elongated, in addition, should be from (methyl) if the group ratio of acrylic acid derivative surpasses 80mol%, though then can under a little light irradiation, make it to produce crosslinked, solidify, but cross-linking density is too high, thereby producing fine pattern and problem such as peel off easily, is not preferred therefore.

As the more detailed concrete example of manufacture method shown in [III] method, for example, can enumerate the method shown in following [IV] method,

In the formula, R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z and k be same as described above.

In addition, the compound shown in the formula (89) is equivalent to R in the general formula (10) ⁷Be that vinyl carbonyl, X are the situations of chlorine atom.Compound shown in the general formula (90) is equivalent to the Y in the general formula (1) ₁Be group and R shown in the general formula (5) ⁸Be vinyl carbonyl, Y ₂Be group and R shown in the general formula (6) ⁹Be that hydrogen atom, a and b are 1 situations.

As the preferred concrete example of manufacture method shown in [II] method, for example, can enumerate the method shown in following [V] method,

In the formula, R ¹, R ², R ¹', R ²', R ³, R ⁴, R ³', R ⁴', R ⁷, T ₁, T ₂, T ₃, T ₄, U, V ₁, V ₂, Y ₁', Y ₂", Z and k be same as described above.

Above-mentioned [V] method is and the identical method of above-mentioned [II] method, is to contain the manufacture method that a in general formula (19) and (21) and b are the compound that forms of 1 formation unit.

Wherein, above-mentioned [V] method is described in detail.For example, [V] method is to contain the compound solvent cut that structural unit forms shown in the general formula (91), and after wherein adding stopper and as required condensing agent and/or catalyzer, in this mixing solutions, splash into as normal (methyl) acrylic acid derivative more than at least a kind that is selected from general formula (11) and (12) of following regulation, under the temperature of regulation, react the specified time.Wherein the solution of gained need not to separate, make with extra care, and just can use in the purpose purposes, also can by ordinary method the compound that contains structural unit shown in the general formula (92) be separated, make with extra care according to purposes.As concrete separation, process for purification, because behind the solvent cut reaction solution, and after as required the residue of condensing agent being removed by filtration, filtrate is splashed in water and this compound crystal is separated out, therefore it is filtered, to the gained crystallization precipitate further with after for example water, alcohol etc. are cleaned, drying under reduced pressure, thus can separate, refining this compound.

In [V] method, as (methyl) acrylic acid derivative shown in the general formula (11), for example, can enumerate glycidyl (methyl) acrylate, 1,2-epoxy-4-butyl (methyl) acrylate, 1,2-epoxy-5-amyl group (methyl) acrylate, 1,2-epoxy-6-hexyl (methyl) acrylate, 1,2-epoxy-7-heptyl (methyl) acrylate, 1,2-epoxy-8-octyl group (methyl) acrylate etc. 1,2-epoxy-ω-alkyl (methyl) acrylate, wherein, preferred glycidyl (methyl) acrylate, 1,2-epoxy-4-butyl (methyl) acrylate, 1,2-epoxy-5-amyl group (methyl) acrylate, more preferably glycidyl (methyl) acrylate.

In [V] method, as (methyl) acrylic acid derivative shown in the general formula (12), for example, can enumerate 1-hydroxyl (methyl) methyl acrylate, 2-hydroxyl-1-(methyl) ethyl propenoate, 3-hydroxyl-1-(methyl) propyl acrylate, 4-hydroxyl-1-(methyl) butyl acrylate, 5-hydroxyl-1-(methyl) vinylformic acid pentyl ester, ω-hydroxyl-1-(methyl) alkyl acrylate of 6-hydroxyl-1-(methyl) Ethyl acrylate etc., wherein, preferred 2-hydroxyl-1-(methyl) ethyl propenoate, 3-hydroxyl-1-(methyl) propyl acrylate, 4-hydroxyl-1-(methyl) butyl acrylate, more preferably 2-hydroxyl-1-(methyl) ethyl propenoate.

Equivalent as (methyl) acrylic acid derivative shown in general formula (11) and (12), carboxyl with respect to containing in the compound that structural unit forms shown in the general formula (91) can be enumerated as 0.1～3 equivalent, wherein usually, be preferably 0.5～2 equivalent, more preferably 0.8～1.5 equivalent.

(methyl) acrylic acid derivative shown in the general formula (11) both can use commercially available product, can also suitably use by normally used manufacture method synthetic material in this field.

(methyl) acrylic acid derivative shown in the general formula (12) both can use commercially available product, can also suitably use by normally used manufacture method synthetic material in this field.

About the temperature of reaction in [V] method, so long as can make carboxyl that contains in the compound that structural unit forms shown in the general formula (91) and the temperature that is selected from (methyl) acrylic acid derivative quantitative reaction more than at least a kind in general formula (11) and (12), just there is no particular limitation, for example, be generally-10～150 ℃, be preferably 0～120 ℃.If temperature of reaction is above 150 ℃, then can cause the partially polymerized of this (methyl) acrylic acid derivative, thereby become the rapid cause of increased of molecular weight, in addition, if not enough-10 ℃, then reaction is carried out slowly, produces in order to make group from this (methyl) acrylic acid derivative import volume required time that achieves the goal longer, therefore is problem such as not preferred.

About the reaction times in [V] method, be controlled in the proper range as long as be set to making from the group import volume that is selected from (methyl) acrylic acid derivative more than at least a kind in general formula (11) and (12).Because this reaction times is depended on the equivalent and the temperature of reaction of (methyl) acrylic acid derivative that uses in the reaction, therefore cannot treat different things as the same, usually be set in 0.5～50 hour, and preferably set, more preferably be set in 0.5～10 hour scope at 0.5～20 hour.

About the solvent in [V] method, as long as use and the identical solvent of above-mentioned [III] method, the usage quantity of solvent also can be and the identical amount of above-mentioned [III] method.

In [V] method, preferably use condensing agent, contain structural unit forms shown in the general formula (91) compound and (methyl) acrylic acid derivative shown in the general formula (12) quantitatively and reaction reposefully thereby make.As these condensing agents, for example, can enumerate dicyclohexyl carbodiimide, 1-ethyl-3-Carbodiimides such as [3-(N, N-dimethylamino) propyl group] carbodiimide hydrochloride; The condensing agent of carbonates such as two-2-pyridyl carbonic ether, two-2-pyridylthio carbonic ether etc.These condensing agents can be distinguished separately and to use, or will be used in combination more than 2 kinds, and there is no particular limitation to the equivalents of above-mentioned condensing agent, with respect to (methyl) acrylic acid derivative shown in the general formula (12), can enumerate 1～2 equivalent usually.

In addition, in [V] method, can use catalyzer.As these catalyzer, for example, can enumerate the catalyzer such as organic phosphine compound of the quaternary ammonium salt of TBuA muriate, TBuA bromide, triethyl hexadecyldimethyl benzyl ammonium muriate, triethyl hexadecyldimethyl benzyl ammonium bromide etc. or triphenylphosphine etc.These catalyzer can be distinguished use separately, or will be used in combination more than 2 kinds, there is no particular limitation to the usage quantity of above-mentioned catalyzer, with respect to the mol amount that contains the compound that structural unit forms shown in the general formula (91), can enumerate more than the 0.001mol%, and, can also use about 200mol% in order to improve speed of response.

In addition, in [V] method, in preventing to react because the polymerization that two keys cause can be used stopper.Stopper in [V] method uses the stopper identical with above-mentioned [III] method to get final product, and the usage quantity of stopper also can be and the identical amount of above-mentioned [III] method.

[V] method is by under appropriate reaction conditions, in containing the compound that structural unit forms shown in the general formula (91), import from the group of (methyl) acrylic acid derivative more than at least a kind that is selected from general formula (11) and (12), promptly, by the above-mentioned reaction conditions in control as equivalent that should (methyl) acrylic acid derivative, temperature of reaction, reaction times etc., thereby can at random regulate import volume from the group of this (methyl) acrylic acid derivative.When the compound that obtains by present method is used under the situation of various uses, from this (methyl) as long as the import volume of the group of acrylic acid derivative can obtain suitable performance setting for, there is no particular limitation, but with respect to the carboxyl mol amount that contains the compound that structural unit forms shown in the general formula (91), be generally 1～100mol%, be preferably the ratio of 10～80mol%.Should be from (methyl) if the group ratio of acrylic acid derivative be less than 10mol%, then for example use by containing the resin combination that compound that this structural unit forms obtains and prepare under the situation of colour filter, for example the alkali development time after light or the thermofixation is elongated, in addition, should be from (methyl) if the group ratio of acrylic acid derivative surpasses 80mol%, though then under a little light irradiation, can make it crosslinked, solidify, but cross-linking density is too high, thereby producing fine pattern and problem such as peel off easily, is not preferred therefore.

As the more detailed concrete example of manufacture method shown in [V] method, for example, can enumerate the method shown in the method shown in following [VI] method or following [VII] method,

In the formula, R ¹, R ², R ¹', R ²', T ₁, T ₂, U, V ₁, V ₂, Y ₁", Y ₂", Z and k be same as described above;

In the formula, R ¹, R ², R ¹', R ²', T ₁, T ₂, U, V ₁, V ₂, Y ₁", Y ₂", Z and k be same as described above.

In addition, the compound shown in the general formula (93) is equivalent to the R in the general formula (7) ³' and R ⁴' be carboxyl, Y ₁' and Y ₂' be Sauerstoffatom or-NH-group, a and b are 1 situations.Compound shown in the formula (94) is equivalent to the R in the general formula (11) ⁷Be pseudoallyl carbonyl, T ₃It is the situation of methyl.Compound shown in the general formula (95) is equivalent to the R in the general formula (1) ³Be group and R with general formula (2) expression ⁶Be group, R with general formula (3) expression ⁷And T ₃Be group, R same as described above ⁴Be group, the R shown in the general formula (2) ⁶Be hydrogen atom, Y ₁And Y ₂Be Sauerstoffatom or-NH-group, a and b are 1 situations.Compound shown in the general formula (96) is equivalent to the R in the general formula (12) ⁷Be vinyl carbonyl, T ₄It is the situation of ethyl.Compound shown in the general formula (97) is equivalent to the R in the general formula (1) ³Be group, R with general formula (2) expression ⁶Be group, R with general formula (4) expression ⁷And T ₄Be group, R same as described above ⁴Be group, the R shown in the general formula (2) ⁶Be hydrogen atom, Y ₁And Y ₂Be Sauerstoffatom or-NH-group, a and b are 1 situations.

As the general formula that contains of the present invention, the manufacture method of the compound that structural unit forms (7), so long as can make general formula, (13) compound shown in and polyprotonic acid with 3 above carboxyls, (part that comprises carboxyl is the material of carboxylicesters) or its acid anhydrides, (comprise that the part of carboxyl forms the material of anhydride group through dehydrating condensation, a part that also comprises carboxyl is the material of carboxylicesters) in the presence of solvent, react and get final product, as concrete manufacture method, for example, can enumerate the method shown in the method shown in following [VIII] method or following [IX] method

In the formula, R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z and k be same as described above;

In the formula, R ¹²Expression hydrogen atom, alkali metal atom or the group of representing with above-mentioned general formula (15), R ¹³Expression hydrogen atom, alkali metal atom or the group of representing with above-mentioned general formula (17), R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Y ₁", Y ₂", Z, a, b and k be same as described above.

Above-mentioned [VIII] method is to make material and the polyprotonic acid with 3 above carboxyls shown in the general formula (34) (part that comprises carboxyl is the material of the carboxylicesters) reaction that has epoxy group(ing) in the compound shown in the general formula (13), thereby make the method that contains the compound that structural unit forms shown in the general formula (20) with hydroxyl and carboxyl, above-mentioned [IX] method is to make to have hydroxyl and/or the amino material (an alkali metal salt that comprises these materials in the compound shown in the general formula (13).) (comprise that the part of carboxyl forms the material of anhydride group through dehydrating condensation with the multi-anhydride shown in general formula (35) or (36) with 3 above carboxyls, a part that also comprises carboxyl is the material of carboxylicesters) reaction, thus make the method that contains the compound that structural unit forms shown in the general formula (21) with carboxyl.

In addition, in above-mentioned [VIII] and [IX] method, can use the compound shown in one or more general formulas (22) and (23), in addition, can use the multi-anhydride shown in the polyprotonic acid shown in one or more general formulas (34) (part that comprises carboxyl is the material of carboxylicesters) and general formula (35) or (36) (comprise the material of the part of carboxyl through dehydrating condensation formation anhydride group, a part that also comprises carboxyl is the material of carboxylicesters) with 3 above carboxyls with 3 above carboxyls.

Wherein, above-mentioned [VIII] method is described in detail.For example, [VIII] method is with the compound shown in the solvent cut general formula (22), and as required to wherein adding catalyzer, in this mixing solutions, add the polyprotonic acid with 3 above carboxyls (part that comprises carboxyl is the material of carboxylicesters) shown in the normal general formula of following regulation (34) then, under specified temperature, react the specified time.Wherein the solution of gained need not to separate, make with extra care, and just can use in the purpose purposes, also can further dilute this solution with solvent according to purposes, separates, makes with extra care and contain the compound that structural unit forms shown in the general formula (20) by ordinary method.

In [VIII] method, as compound shown in the general formula (22), for example, can enumerate by making the compound and the epoxy chloropropane of the xenyl skeleton shown in (98) that has general formula, epoxy bromopropane, 4-chlorine-1,2-butylene oxide ring, 4-bromine-1,2-butylene oxide ring, 5-chlorine-1,2-epoxy pentane, 5-bromine-1,2-epoxy pentane, 6-chlorine-1,2-epoxy hexane, 6-bromine-1,2-epoxy hexane, 7-chlorine-1,2-epoxy heptane, 7-bromine-1,2-epoxy heptane, 8-chlorine-1,2-octylene oxide, 8-bromine-1, the compound that ω such as 2-octylene oxide-the halogenated epoxide reaction obtains, wherein, preferably by making the compound and the epoxy chloropropane of the xenyl skeleton shown in (98) that has general formula, epoxy bromopropane, 4-chlorine-1,2-butylene oxide ring, 4-bromine-1,2-butylene oxide ring, 5-chlorine-1,2-epoxy pentane, 5-bromine-1, the compound that the ω of 2-epoxy pentane-halogenated epoxide reaction obtains is more preferably by making the compound and the epoxy chloropropane of the xenyl skeleton shown in (98) that has general formula, the compound that the ω of epoxy bromopropane-the halogenated epoxide reaction obtains

In the formula, R ¹, R ², R ¹', R ²', U, V ₁And V ₂Same as described above.

In addition, wherein said compound with xenyl skeleton for example is meant shown in the general formula (98) compound of 2 phenyl by the divalent group crosslinking structure shown in singly-bound or formula (1-1)～(1-8) any.

Concrete example when U is singly-bound in the compound with xenyl skeleton shown in the general formula (98) for example, can enumerate 4,4 '-bis-phenol, 3,3 '-bis-phenol, 4,4 '-p-diaminodiphenyl, 3,3 '-p-diaminodiphenyl etc.

The concrete example of the compound when being formula (1-1) with this xenyl skeleton as U, for example, can enumerate 9,9-two (4-hydroxy phenyl) fluorenes, 9,9-two (4-hydroxyls-3,5-3,5-dimethylphenyl) fluorenes, 9,9-two (4-hydroxyls-3,5-dichlorophenyl) fluorenes, 9,9-two (4-hydroxyls-3,5-dibromo phenyl) fluorenes, 9,9-two (4-hydroxyl-3-aminomethyl phenyl) fluorenes, 9,9-two (4-hydroxyl-3-chloro-phenyl-) fluorenes, 9,9-two (4-hydroxyl-3-bromophenyl) fluorenes, 9,9-two (4-hydroxyl-3-fluorophenyl) fluorenes, 9,9-two (4-hydroxyl-3-p-methoxy-phenyl) fluorenes, 9,9-two (4-aminophenyl) fluorenes, 9,9-two (4-amino-3,5-3,5-dimethylphenyl) fluorenes, 9,9-two (4-amino-3,5-dichlorophenyl) fluorenes, 9,9-two (4-amino-3,5-dibromo phenyl) fluorenes, 9,9-two (4-amino-3-aminomethyl phenyl) fluorenes, 9,9-two (4-amino-3-chloro-phenyl-) fluorenes, 9,9-two (4-amino-3-bromophenyl) fluorenes, 9,9-two (4-amino-3-fluorophenyl) fluorenes, 9,9-two (4-amino-3-p-methoxy-phenyl) fluorenes etc.

In addition, when having substituent fluorenes rings { formula (1-1) } such as halogen atom this has the concrete example of the compound of xenyl skeleton, for example, can enumerate 2,7-dibromo-9,9-two (4-hydroxy phenyl) fluorenes, 2,7-dibromo-9,9-two (4-hydroxyl-3,5-3,5-dimethylphenyl) fluorenes, 2,7-dibromo-9,9-two (4-hydroxyls-3,5-dichlorophenyl) fluorenes, 2,7-dibromo-9,9-two (4-hydroxyl-3,5-dibromo phenyl) fluorenes, 2,7-dibromo-9,9-two (4-hydroxyl-3-aminomethyl phenyl) fluorenes, 2,7-dibromo-9,9-two (4-hydroxyl-3-chloro-phenyl-) fluorenes, 2,7-dibromo-9,9-two (4-hydroxyl-3-bromophenyl) fluorenes, 2,7-dibromo-9,9-two (4-hydroxyl-3-fluorophenyl) fluorenes, 2,7-dibromo-9,9-two (4-hydroxyl-3-p-methoxy-phenyl) fluorenes, 2,7-dibromo-9,9-two (4-aminophenyl) fluorenes, 2,7-dibromo-9,9-two (4-amino-3,5-3,5-dimethylphenyl) fluorenes, 2,7-dibromo-9,9-two (4-amino-3,5-dichlorophenyl) fluorenes, 2,7-dibromo-9,9-two (4-amino-3,5-dibromo phenyl) fluorenes, 2,7-dibromo-9,9-two (4-amino-3-aminomethyl phenyl) fluorenes, 2,7-dibromo-9,9-two (4-amino-3-chloro-phenyl-) fluorenes, 2,7-dibromo-9,9-two (4-amino-3-bromophenyl) fluorenes, 2,7-dibromo-9,9-two (4-amino-3-fluorophenyl) fluorenes, 2,7-dibromo-9,9-two (4-amino-3-p-methoxy-phenyl) fluorenes etc.

When being formula (1-2) as U this has the concrete example of the compound of xenyl skeleton, for example, can enumerate two (4-hydroxy phenyl) ketone, two (4-hydroxyl-3,5-3,5-dimethylphenyl) ketone, two (4-hydroxyl-3,5-dichlorophenyl) ketone, two (4-hydroxyl-3,5-dibromo phenyl) ketone, two (4-aminophenyl) ketone, two (4-amino-3,5-3,5-dimethylphenyl) ketone, two (4-amino-3,5-dichlorophenyl) ketone, two (4-amino-3,5-dibromo phenyl) ketone etc.

When being formula (1-3) as U this has the concrete example of the compound of xenyl skeleton, for example, can enumerate two (4-hydroxy phenyl) sulfones, two (4-hydroxyl-3,5-3,5-dimethylphenyl) sulfone, two (4-hydroxyl-3,5-dichlorophenyl) sulfone, two (4-hydroxyl-3,5-dibromo phenyl) sulfone, two (4-aminophenyl) sulfone, two (4-amino-3,5-3,5-dimethylphenyl) sulfone, two (4-amino-3,5-dichlorophenyl) sulfone, two (4-amino-3,5-dibromo phenyl) sulfone etc.

When being formula (1-4) as U this has the concrete example of the compound of xenyl skeleton, for example, can enumerate two (4-hydroxy phenyl) HFC-236fa, two (4-hydroxyls-3,5-3,5-dimethylphenyl) HFC-236fa, two (4-hydroxyls-3,5-dichlorophenyl) HFC-236fa, two (4-hydroxyls-3,5-dibromo phenyl) HFC-236fa, two (4-aminophenyl) HFC-236fa, two (4-amino-3,5-3,5-dimethylphenyl) HFC-236fa, two (4-amino-3,5-dichlorophenyl) HFC-236fa, two (4-amino-3,5-dibromo phenyl) HFC-236fa etc.

When being formula (1-5) as U this has the concrete example of the compound of xenyl skeleton, for example, can enumerate two (4-hydroxy phenyl) dimethylsilane, two (4-hydroxyls-3,5-3,5-dimethylphenyl) dimethylsilane, two (4-hydroxyls-3,5-dichlorophenyl) dimethylsilane, two (4-hydroxyls-3,5-dibromo phenyl) dimethylsilane, two (4-aminophenyl) dimethylsilane, two (4-amino-3,5-3,5-dimethylphenyl) dimethylsilane, two (4-amino-3,5-dichlorophenyl) dimethylsilane, two (4-amino-3,5-dibromo phenyl) dimethylsilane etc.

When being formula (1-6) as U this has the concrete example of the compound of xenyl skeleton, for example, can enumerate two (4-hydroxy phenyl) methane, two (4-hydroxyl-3,5-3,5-dimethylphenyl) methane, two (4-hydroxyl-3,5-dichlorophenyl) methane, two (4-hydroxyl-3,5-dibromo phenyl) methane, two (4-aminophenyl) methane, two (4-amino-3,5-3,5-dimethylphenyl) methane, two (4-amino-3,5-dichlorophenyl) methane, two (4-amino-3,5-dibromo phenyl) methane etc.

When being formula (1-7) as U this has the concrete example of the compound of xenyl skeleton, for example, can enumerate 2,2-two (4-hydroxy phenyl) propane, 2,2-two (4-hydroxyls-3,5-3,5-dimethylphenyl) propane, 2,2-two (4-hydroxyl-3,5-dichlorophenyl) propane, 2,2-two (4-hydroxyls-3,5-dibromo phenyl) propane, 2,2-two (4-hydroxyl-3-aminomethyl phenyl) propane, 2,2-two (4-hydroxyl-3-chloro-phenyl-) propane, 2,2-two (4-hydroxyl-3-bromophenyl) propane, 2,2-two (4-aminophenyl) propane, 2,2-two (4-amino-3,5-3,5-dimethylphenyl) propane, 2,2-two (4-amino-3,5-dichlorophenyl) propane, 2,2-two (4-amino-3,5-dibromo phenyl) propane, 2,2-two (4-amino-3-aminomethyl phenyl) propane, 2,2-two (4-amino-3-chloro-phenyl-) propane, 2,2-two (4-amino-3-bromophenyl) propane etc.

When being formula (1-8) as U this has the concrete example of the compound of xenyl skeleton, for example, can enumerate two (4-hydroxy phenyl) ethers, two (4-hydroxyl-3,5-3,5-dimethylphenyl) ether, two (4-hydroxyl-3,5-dichlorophenyl) ether, two (4-hydroxyl-3,5-dibromo phenyl) ether, two (4-aminophenyl) ether, two (4-amino-3,5-3,5-dimethylphenyl) ether, two (4-amino-3,5-dichlorophenyl) ether, two (4-amino-3,5-dibromo phenyl) ether etc.

Have in the compound of xenyl skeleton at these, preferably U is that more preferably U is the divalent group with formula (1-1) expression with the divalent group of formula (1-1) or formula (1-7) expression, wherein, and the V in the further preferred formula (98) ₁And V ₂Be the group of Sauerstoffatom,, specifically, for example, can enumerate 9,9-two (4-hydroxy phenyl) fluorenes etc. particularly preferably in not having substituent group on phenyl ring and the fluorenes ring.

Compound shown in the general formula (22) both can use commercially available product, also can suitably use the compound and the epoxy chloropropane that will have xenyl skeleton shown in the general formula (98), epoxy bromopropane, 4-chlorine-1,2-butylene oxide ring, 4-bromine-1,2-butylene oxide ring, 5-chlorine-1,2-epoxy pentane, 5-bromine-1,2-epoxy pentane, 6-chlorine-1,2-epoxy hexane, 6-bromine-1,2-epoxy hexane, 7-chlorine-1,2-epoxy heptane, 7-bromine-1,2-epoxy heptane, 8-chlorine-1,2-octylene oxide, ω-the halogenated epoxide of 8-bromine-1,2-octylene oxide etc. comes the synthetic material by the manufacture method that adopts in common this field.

As the polyprotonic acid shown in the general formula (34) (part that comprises carboxyl is the material of carboxylicesters) with 3 above carboxyls, usually can enumerate aromatic series or aliphatic carboxylic acid (part that comprises carboxyl is the material of carboxylicesters) with 3 above carboxyls, specifically, for example, the aromatic tricarboxylic acids shown in can enumerative (99); Aromatic tetracarboxylic acid shown in formula (100), (101) or general formula (102)～(104); Aliphatic tricarboxylic acids shown in the general formula (105); Or the aliphatics tetracarboxylic acid shown in general formula (106), (107), formula (108) or (109),

Wherein, in formula (101), 4 carboxyls can with the bond with carbon arbitrarily in 1～8 carbon of naphthalene nucleus;

In the formula, W ₈, W ₉And W ₁₀Expression singly-bound, Sauerstoffatom, carbonyl, alkylsulfonyl or inferior ethylene group;

In the formula (105), W ₁₁Expression ethane three bases, propane three bases or butane three bases;

In the formula, W ₁₂Expression ethene four bases or butane four bases, p represents 1～3 integer, wherein, in formula (107), 4 carboxyls also can be bonded on the carbon arbitrarily in the cycloalkyl ring carbon;

As the W in general formula (102)～(104) ₈～W ₁₀, more preferably singly-bound or carbonyl.

The integer of the p ordinary representation 1～3 in the general formula (107), wherein, preferred 2～3 integer, more preferably 3.

As aromatic tricarboxylic acids with formula (99) expression, specifically, for example, can enumerate 1,2,3-benzene tricarbonic acid, 1,2,4-benzene tricarbonic acid (trimellitic acid), 1,3,5-benzene tricarbonic acid etc., wherein preferred 1,2,4-benzene tricarbonic acid (trimellitic acid).

Aromatic tetracarboxylic acid as with formula (100) expression specifically, for example, can enumerate 1,2,3,4-benzene tertacarbonic acid, 1,2,3,5-benzene tertacarbonic acid, 1,2,4,5-benzene tertacarbonic acid (pyromellitic acid) etc., wherein, preferred 1,2,4,5-benzene tertacarbonic acid (pyromellitic acid).

Aromatic tetracarboxylic acid as with formula (101) expression specifically, for example, can enumerate 1,2,3,4-naphthalene tetracarboxylic acid, 1,2,3,5-naphthalene tetracarboxylic acid, 1,2,3,6-naphthalene tetracarboxylic acid, 1,2,3,7-naphthalene tetracarboxylic acid, 1,2,3,8-naphthalene tetracarboxylic acid, 1,2,4,5-naphthalene tetracarboxylic acid, 1,2,4,6-naphthalene tetracarboxylic acid, 1,2,4,7-naphthalene tetracarboxylic acid, 1,2,4,8-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,2,5,7-naphthalene tetracarboxylic acid, 1,2,5,8-naphthalene tetracarboxylic acid, 1,2,6,7-naphthalene tetracarboxylic acid, 1,2,6,8-naphthalene tetracarboxylic acid, 1,3,5,7-naphthalene tetracarboxylic acid, 1,3,5,8-naphthalene tetracarboxylic acid, 1,3,6,7-naphthalene tetracarboxylic acid, 1,3,6,8-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 1,4,6,7-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid etc., wherein, preferred 1,4,5,8-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, more preferably 1,4,5,8-naphthalene tetracarboxylic acid.

As W among the aromatic tetracarboxylic acid shown in the general formula (102) ₈Be single bonded aromatic tetracarboxylic acid, for example, can enumerate 2,3,4,5-biphenyltetracarboxyacid acid, 2,3,4,6-biphenyltetracarboxyacid acid, 2,3,5,6-biphenyltetracarboxyacid acid etc.In addition, as W ₈Be the aromatic tetracarboxylic acid of Sauerstoffatom, for example, can enumerate 2,3,4,5-xenyl ether tetracarboxylic acid, 2,3,4,6-xenyl ether tetracarboxylic acid, 2,3,5,6-xenyl ether tetracarboxylic acid etc.In addition, as W ₈Be the aromatic tetracarboxylic acid of carbonyl, for example, can enumerate 2,3,4,5-benzophenone tetracarboxylic acid, 2,3,4,6-benzophenone tetracarboxylic acid, 2,3,5,6-di-benzophenone tetracarboxylic acid etc.In addition, as W ₈Be the aromatic tetracarboxylic acid of alkylsulfonyl, for example, can enumerate 2,3,4,5-xenyl sulfone tetracarboxylic acid, 2,3,4,6-xenyl sulfone tetracarboxylic acid, 2,3,5,6-xenyl sulfone tetracarboxylic acid etc.In addition, as W ₈Be the aromatic tetracarboxylic acid of vinylidene, for example, can enumerate cis-2,3,4,5-toluylene tetracarboxylic acid, trans-2,3,4,5-toluylene tetracarboxylic acid, cis-2,3,4,6-toluylene tetracarboxylic acid, trans-2,3,4,6-toluylene tetracarboxylic acid, cis-2,3,5,6-toluylene tetracarboxylic acid, trans-2,3,5,6-toluylene tetracarboxylic acid etc.

As W among the aromatic tetracarboxylic acid shown in the general formula (103) ₉Be single bonded aromatic tetracarboxylic acid, for example, can enumerate 2,2 ', 3,4-biphenyltetracarboxyacid acid, 2,3,3 ', 4-biphenyltetracarboxyacid acid, 2,3,4,4 '-biphenyltetracarboxyacid acid, 2,2 ', 3,5-biphenyltetracarboxyacid acid, 2,3,3 ', 5-biphenyltetracarboxyacid acid, 2,3,4 ', 5-biphenyltetracarboxyacid acid, 2,2 ', 3,6-biphenyltetracarboxyacid acid, 2,3,3 ', 6-biphenyltetracarboxyacid acid, 2,3,4 ', 6-biphenyltetracarboxyacid acid, 2,2 ', 4,5-biphenyltetracarboxyacid acid, 2,3 ', 4,5-biphenyltetracarboxyacid acid, 2,4,4 ', 5-biphenyltetracarboxyacid acid, 2,2 ', 4,6-biphenyltetracarboxyacid acid, 2,3 ', 4,6-biphenyltetracarboxyacid acid, 2,4,4 ', 6-biphenyltetracarboxyacid acid etc.In addition, as W ₉Be the aromatic tetracarboxylic acid of Sauerstoffatom, for example, can enumerate 2,2 ', 3,4-xenyl ether tetracarboxylic acid, 2,3,3 ', 4-xenyl ether tetracarboxylic acid, 2,3,4,4 '-xenyl ether tetracarboxylic acid, 2,2 ', 3,5-xenyl ether tetracarboxylic acid, 2,3,3 ', 5-xenyl ether tetracarboxylic acid, 2,3,4 ', 5-xenyl ether tetracarboxylic acid, 2,2 ', 3,6-xenyl ether tetracarboxylic acid, 2,3,3 ', 6-xenyl ether tetracarboxylic acid, 2,3,4 ', 6-xenyl ether tetracarboxylic acid, 2,2 ', 4,5-xenyl ether tetracarboxylic acid, 2,3 ', 4,5-xenyl ether tetracarboxylic acid, 2,4,4 ', 5-xenyl ether tetracarboxylic acid, 2,2 ', 4,6-xenyl ether tetracarboxylic acid, 2,3 ', 4,6-xenyl ether tetracarboxylic acid, 2,4,4 ', 6-xenyl ether tetracarboxylic acid etc.In addition, as W ₉Be the aromatic tetracarboxylic acid of carbonyl, for example can enumerate 2,2 ', 3,4-benzophenone tetracarboxylic acid, 2,3,3 ', 4-benzophenone tetracarboxylic acid, 2,3,4,4 '-benzophenone tetracarboxylic acid, 2,2 ', 3,5-benzophenone tetracarboxylic acid, 2,3,3 ', 5-benzophenone tetracarboxylic acid, 2,3,4 ', 5-benzophenone tetracarboxylic acid, 2,2 ', 3,6-benzophenone tetracarboxylic acid, 2,3,3 ', 6-benzophenone tetracarboxylic acid, 2,3,4 ', 6-benzophenone tetracarboxylic acid, 2,2 ', 4,5-benzophenone tetracarboxylic acid, 2,3 ', 4,5-benzophenone tetracarboxylic acid, 2,4,4 ', 5-benzophenone tetracarboxylic acid, 2,2 ', 4,6-benzophenone tetracarboxylic acid, 2,3 ', 4,6-benzophenone tetracarboxylic acid, 2,4,4 ', 6-benzophenone tetracarboxylic acid etc.In addition, as W ₉Be the aromatic tetracarboxylic acid of alkylsulfonyl, for example, can enumerate 2,2 '; 3,4-xenyl sulfone tetracarboxylic acid; 2,3,3 '; 4-xenyl sulfone tetracarboxylic acid; 2,3,4,4 '-xenyl sulfone tetracarboxylic acid; 2; 2 ', 3,5-xenyl sulfone tetracarboxylic acid; 2,3; 3 ', 5-xenyl sulfone tetracarboxylic acid; 2,3,4 '; 5-xenyl sulfone tetracarboxylic acid; 2,2 ', 3,6-xenyl sulfone tetracarboxylic acid; 2; 3,3 ', 6-xenyl sulfone tetracarboxylic acid; 2,3; 4 ', 6-xenyl sulfone tetracarboxylic acid; 2,2 ', 4; 5-xenyl sulfone tetracarboxylic acid; 2,3 ', 4,5-xenyl sulfone tetracarboxylic acid; 2; 4,4 ', 5-xenyl sulfone tetracarboxylic acid; 2,2 '; 4,6-xenyl sulfone tetracarboxylic acid; 2,3 ', 4; 6-xenyl sulfone tetracarboxylic acid; 2,4,4 ', 6-xenyl sulfone tetracarboxylic acid etc.In addition, as W ₉Be the aromatic tetracarboxylic acid of vinylidene, for example, can enumerate cis-2,2 ', 3,4-toluylene tetracarboxylic acid, trans-2,2 ', 3,4-toluylene tetracarboxylic acid, cis-2,3,3 ', 4-toluylene tetracarboxylic acid, trans-2,3,3 ', 4-toluylene tetracarboxylic acid, cis-2,3,4,4 '-toluylene tetracarboxylic acid, trans-2,3,4,4 '-toluylene tetracarboxylic acid, cis-2,2 ', 3,5-toluylene tetracarboxylic acid, trans-2,2 ', 3,5-toluylene tetracarboxylic acid, cis-2,3,3 ', 5-toluylene tetracarboxylic acid, trans-2,3,3 ', 5-toluylene tetracarboxylic acid, cis-2,3,4 ', 5-toluylene tetracarboxylic acid, trans-2,3,4 ', 5-toluylene tetracarboxylic acid, cis-2,2 ', 3,6-toluylene tetracarboxylic acid, trans-2,2 ', 3,6-toluylene tetracarboxylic acid, cis-2,3,3 ', 6-toluylene tetracarboxylic acid, trans-2,3,3 ', 6-toluylene tetracarboxylic acid, cis-2,3,4 ', 6-toluylene tetracarboxylic acid, trans-2,3,4 ', 6-toluylene tetracarboxylic acid, cis-2,2 ', 4,5-toluylene tetracarboxylic acid, trans-2,2 ', 4,5-toluylene tetracarboxylic acid, cis-2,3 ', 4,5-toluylene tetracarboxylic acid, trans-2,3 ', 4,5-toluylene tetracarboxylic acid, cis-2,4,4 ', 5-toluylene tetracarboxylic acid, trans-2,4,4 ', 5-toluylene tetracarboxylic acid, cis-2,2 ', 4,6-toluylene tetracarboxylic acid, trans-2,2 ', 4,6-toluylene tetracarboxylic acid, cis-2,3 ', 4,6-toluylene tetracarboxylic acid, trans-2,3 ', 4,6-toluylene tetracarboxylic acid, cis-2,4,4 ', 6-toluylene tetracarboxylic acid, trans-2,4,4 ', 6-toluylene tetracarboxylic acid etc.

As W among the aromatic tetracarboxylic acid shown in the general formula (104) ₁₀Be single bonded aromatic tetracarboxylic acid, for example, can enumerate 2,2 ', 3,3 '-biphenyltetracarboxyacid acid, 2,2 ', 3,4 '-biphenyltetracarboxyacid acid, 2,2 ', 3,5 '-biphenyltetracarboxyacid acid, 2,2 ', 3,6 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 5 '-biphenyltetracarboxyacid acid, 2,2 ', 4,4 '-biphenyltetracarboxyacid acid, 2,2 ', 4,5 '-biphenyltetracarboxyacid acid, 2,2 ', 4,6 '-biphenyltetracarboxyacid acid, 2,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3 ', 4,5 '-biphenyltetracarboxyacid acid, 2,2 ', 5,5 '-biphenyltetracarboxyacid acid, 2,2 ', 5,6 '-biphenyltetracarboxyacid acid, 2,3 ', 4 ', 5-biphenyltetracarboxyacid acid, 2,3 ', 5,5 '-biphenyltetracarboxyacid acid, 2,2 ', 6,6 '-biphenyltetracarboxyacid acid, 2,3 ', 4 ', 6-biphenyltetracarboxyacid acid, 2,3 ', 5 ', 6-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,5 '-biphenyltetracarboxyacid acid, 3,3 ', 5,5 '-biphenyltetracarboxyacid acid etc.Wherein, preferred 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 5,5 '-biphenyltetracarboxyacid acid, more preferably 3,3 ', 4,4 '-biphenyltetracarboxyacid acid.In addition, as W ₁₀Be the aromatic tetracarboxylic acid of Sauerstoffatom, for example, can enumerate 2,2 ', 3,3 '-xenyl ether tetracarboxylic acid, 2,2 ', 3,4 '-xenyl ether tetracarboxylic acid, 2,2 ', 3,5 '-xenyl ether tetracarboxylic acid, 2,2 ', 3,6 '-xenyl ether tetracarboxylic acid, 2,3,3 ', 4 '-xenyl ether tetracarboxylic acid, 2,3,3 ', 5 '-xenyl ether tetracarboxylic acid, 2,2 ', 4,4 '-xenyl ether tetracarboxylic acid, 2,2 ', 4,5 '-xenyl ether tetracarboxylic acid, 2,2 ', 4,6 '-xenyl ether tetracarboxylic acid, 2,3 ', 4,4 '-xenyl ether tetracarboxylic acid, 2,3 ', 4,5 '-xenyl ether tetracarboxylic acid, 2,2 ', 5,5 '-xenyl ether tetracarboxylic acid, 2,2 ', 5,6 '-xenyl ether tetracarboxylic acid, 2,3 ', 4 ', 5-xenyl ether tetracarboxylic acid, 2,3 ', 5,5 '-xenyl ether tetracarboxylic acid, 2,2 ', 6,6 '-xenyl ether tetracarboxylic acid, 2,3 ', 4 ', 6-xenyl ether tetracarboxylic acid, 2,3 ', 5 ', 6-xenyl ether tetracarboxylic acid, 3,3 ', 4,4 '-xenyl ether tetracarboxylic acid, 3,3 ', 4,5 '-xenyl ether tetracarboxylic acid, 3,3 ', 5,5 '-xenyl ether tetracarboxylic acid etc., wherein, preferred 3,3 ', 4,4 '-xenyl ether tetracarboxylic acid, 3,3 ', 5,5 '-xenyl ether tetracarboxylic acid, more preferably 3,3 ', 4,4 '-xenyl ether tetracarboxylic acid.In addition, as W ₁₀Be the aromatic tetracarboxylic acid of carbonyl, for example, can enumerate 2,2 ', 3,3 '-benzophenone tetracarboxylic acid, 2,2 ', 3,4 '-benzophenone tetracarboxylic acid, 2,2 ', 3,5 '-benzophenone tetracarboxylic acid, 2,2 ', 3,6 '-benzophenone tetracarboxylic acid, 2,3,3 ', 4 '-benzophenone tetracarboxylic acid, 2,3,3 ', 5 '-benzophenone tetracarboxylic acid, 2,2 ', 4,4 '-benzophenone tetracarboxylic acid, 2,2 ', 4,5 '-benzophenone tetracarboxylic acid, 2,2 ', 4,6 '-benzophenone tetracarboxylic acid, 2,3 ', 4,4 '-benzophenone tetracarboxylic acid, 2,3 ', 4,5 '-benzophenone tetracarboxylic acid, 2,2 ', 5,5 '-benzophenone tetracarboxylic acid, 2,2 ', 5,6 '-benzophenone tetracarboxylic acid, 2,3 ', 4 ', 5-benzophenone tetracarboxylic acid, 2,3 ', 5,5 '-benzophenone tetracarboxylic acid, 2,2 ', 6,6 '-benzophenone tetracarboxylic acid, 2,3 ', 4 ', 6-benzophenone tetracarboxylic acid, 2,3 ', 5 ', 6-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,5 '-benzophenone tetracarboxylic acid, 3,3 ', 5,5 '-benzophenone tetracarboxylic acid etc.Wherein, preferred 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 5,5 '-benzophenone tetracarboxylic acid, more preferably 3,3 ', 4,4 '-benzophenone tetracarboxylic acid.In addition, as W ₁₀Be the aromatic tetracarboxylic acid of alkylsulfonyl, for example, can enumerate 2,2 '; 3,3 '-xenyl sulfone tetracarboxylic acid; 2,2 ', 3; 4 '-xenyl sulfone tetracarboxylic acid; 2,2 ', 3,5 '-xenyl sulfone tetracarboxylic acid; 2; 2 ', 3,6 '-xenyl sulfone tetracarboxylic acid; 2,3; 3 ', 4 '-xenyl sulfone tetracarboxylic acid; 2,3,3 '; 5 '-xenyl sulfone tetracarboxylic acid; 2,2 ', 4,4 '-xenyl sulfone tetracarboxylic acid; 2; 2 ', 4,5 '-xenyl sulfone tetracarboxylic acid; 2; 2 ', 4,6 '-xenyl sulfone tetracarboxylic acid; 2; 3 ', 4,4 '-xenyl sulfone tetracarboxylic acid; 2; 3 ', 4,5 '-xenyl sulfone tetracarboxylic acid; 2; 2 ', 5,5 '-xenyl sulfone tetracarboxylic acid; 2; 2 ', 5,6 '-xenyl sulfone tetracarboxylic acid; 2; 3 ', 4 ', 5-xenyl sulfone tetracarboxylic acid; 2; 3 ', 5,5 '-xenyl sulfone tetracarboxylic acid; 2; 2 ', 6,6 '-xenyl sulfone tetracarboxylic acid; 2; 3 ', 4 ', 6-xenyl sulfone tetracarboxylic acid; 2; 3 ', 5 ', 6-xenyl sulfone tetracarboxylic acid; 3; 3 ', 4,4 '-xenyl sulfone tetracarboxylic acid; 3; 3 ', 4,5 '-xenyl sulfone tetracarboxylic acid; 3; 3 ', 5,5 '-xenyl sulfone tetracarboxylic acid etc.; wherein, preferred 3,3 '; 4,4 '-xenyl sulfone tetracarboxylic acid; 3,3 '; 5,5 '-xenyl sulfone tetracarboxylic acid, more preferably 3; 3 ', 4,4 '-xenyl sulfone tetracarboxylic acid.In addition, as W ₁₀Be the aromatic tetracarboxylic acid of vinylidene, for example, can enumerate cis-2,2 ', 3,3 '-toluylene tetracarboxylic acid, trans-2,2 ', 3,3 '-toluylene tetracarboxylic acid, cis-2,2 ', 3,4 '-toluylene tetracarboxylic acid, trans-2,2 ', 3,4 '-toluylene tetracarboxylic acid, cis-2,2 ', 3,5 '-toluylene tetracarboxylic acid, trans-2,2 ', 3,5 '-toluylene tetracarboxylic acid, cis-2,2 ', 3,6 '-toluylene tetracarboxylic acid, trans-2,2 ', 3,6 '-toluylene tetracarboxylic acid, cis-2,3,3 ', 4 '-toluylene tetracarboxylic acid, trans-2,3,3 ', 4 '-toluylene tetracarboxylic acid, cis-2,3,3 ', 5 '-toluylene tetracarboxylic acid, trans-2,3,3 ', 5 '-toluylene tetracarboxylic acid, cis-2,2 ', 4,4 '-toluylene tetracarboxylic acid, trans-2,2 ', 4,4 '-toluylene tetracarboxylic acid, cis-2,2 ', 4,5 '-toluylene tetracarboxylic acid, trans-2,2 ', 4,5 '-toluylene tetracarboxylic acid, cis-2,2 ', 4,6 '-toluylene tetracarboxylic acid, trans-2,2 ', 4,6 '-toluylene tetracarboxylic acid, cis-2,3 ', 4,4 '-toluylene tetracarboxylic acid, trans-2,3 ', 4,4 '-toluylene tetracarboxylic acid, cis-2,3 ', 4,5 '-toluylene tetracarboxylic acid, trans-2,3 ', 4,5 '-toluylene tetracarboxylic acid, cis-2,2 ', 5,5 '-toluylene tetracarboxylic acid, trans-2,2 ', 5,5 '-toluylene tetracarboxylic acid, cis-2,2 ', 5,6 '-toluylene tetracarboxylic acid, trans-2,2 ', 5,6 '-toluylene tetracarboxylic acid, cis-2,3 ', 4 ', 5-toluylene tetracarboxylic acid, trans-2,3 ', 4 ', 5-toluylene tetracarboxylic acid, cis-2,3 ', 5,5 '-toluylene tetracarboxylic acid, trans-2,3 ', 5,5 '-toluylene tetracarboxylic acid, cis-2,2 ', 6,6 '-toluylene tetracarboxylic acid, trans-2,2 ', 6,6 '-toluylene tetracarboxylic acid, cis-2,3 ', 4 ', 6-toluylene tetracarboxylic acid, trans-2,3 ', 4 ', 6-toluylene tetracarboxylic acid, cis-2,3 ', 5 ', 6-toluylene tetracarboxylic acid, trans-2,3 ', 5 ', 6-toluylene tetracarboxylic acid, cis-3,3 ', 4,4 '-toluylene tetracarboxylic acid, trans-3,3 ', 4,4 '-toluylene tetracarboxylic acid, cis-3,3 ', 4,5 '-toluylene tetracarboxylic acid, trans-3,3 ', 4,5 '-toluylene tetracarboxylic acid, cis-3,3 ', 5,5 '-toluylene tetracarboxylic acid, trans-3,3 ', 5,5 '-toluylene tetracarboxylic acid etc., wherein, preferred cis-3,3 ', 4,4 '-toluylene tetracarboxylic acid, trans-3,3 ', 4,4 '-toluylene tetracarboxylic acid, cis-3,3 ', 5,5 '-toluylene tetracarboxylic acid, trans-3,3 ', 5,5 '-toluylene tetracarboxylic acid, more preferably cis-3,3 ', 4,4 '-toluylene tetracarboxylic acid, trans-3,3 ', 4,4 '-toluylene tetracarboxylic acid.

In above-mentioned aromatic tetracarboxylic acid, the material shown in preferred formula (100) or the general formula (104), wherein, the more preferably W in formula (100) or the general formula (104) ₁₀It is the material of singly-bound or carbonyl.

In the aliphatic tricarboxylic acids shown in the general formula (105), as W ₁₁Be the aliphatic tricarboxylic acids of ethane three bases, for example, can enumerate ethane tricarboxylic acid etc.In addition, as W ₁₁Be the aliphatic tricarboxylic acids of propane three bases, for example, can enumerate tricarballylic acid etc.In addition, as W ₁₁Be the aliphatic tricarboxylic acids of butane three bases, for example, can enumerate butane tricarboxylic acid etc.

In the aliphatics tetracarboxylic acid shown in the general formula (106), as W ₁₂Be the aliphatics tetracarboxylic acid of ethene four bases, for example, can enumerate ethene tetracarboxylic acid etc.In addition, as W ₁₂Be the aliphatics tetracarboxylic acid of butane four bases, for example, can enumerate BTCA etc.

As the aliphatics tetracarboxylic acid shown in the general formula (107), usually can enumerate p and be 1～3 integer, be preferably 2～3 integer, 3 aliphatics tetracarboxylic acid more preferably, specifically, for example, can enumerate tetramethylene tetracarboxylic acid, pentamethylene tetracarboxylic acid, hexanaphthene tetracarboxylic acid etc., wherein, optimization cyclopentane tetracarboxylic acid, hexanaphthene tetracarboxylic acid, more preferably hexanaphthene tetracarboxylic acid.

As the aliphatics tetracarboxylic acid shown in the general formula (108), can enumerate 4-(1,2-dicarboxyl ethyl)-1,2,3,4-naphthane-1,2-dicarboxylic acid.

As the aliphatics tetracarboxylic acid shown in the general formula (109), can enumerate 5-(1,2-dicarboxyl ethyl)-3-methylcyclohexane-1,2-dicarboxylic acid.

In above-mentioned aliphatics tetracarboxylic acid, the material shown in preferred formula (108) or (109), wherein, the more preferably material shown in the formula (108).

In addition, carboxyl in above-mentioned aromatic series or the aliphatic carboxylic acid, it can be the carboxylicesters shown in the above-mentioned general formula (37), compound with this carboxylicesters both can use commercially available product, for example also can suitably use the usual method synthetic material that reacts by at the aromatic series shown in above-mentioned general formula (99)～(109) or aliphatic carboxylic acid and alcohol such as methyl alcohol, ethanol.

As the equivalent of the polyprotonic acid shown in the general formula (34) (part that comprises carboxyl is the material of carboxylicesters) with 3 above carboxyls, can enumerate with respect to the compound shown in the general formula (22), be generally 0.5～2 equivalent.

Temperature of reaction in [VIII] method, so long as can make the temperature of the carboxyl quantitative reaction in the polyprotonic acid shown in epoxy group(ing) in the compound shown in the general formula (22) and the general formula (34) (part that comprises carboxyl is the material of carboxylicesters) with 3 above carboxyls, just there is no particular limitation, for example, be generally 60～120 ℃, be preferably 70～90 ℃.If temperature of reaction is above 120 ℃, then can cause the intramolecularly and the intermolecular part acid anhydridesization of this polyprotonic acid, thereby become the rapid cause of increased of molecular weight, in addition, if be lower than 60 ℃, reaction is carried out slowly, and the residual worry of compound shown in the unreacted general formula (22) and this polyprotonic acid etc. is arranged, and is not preferred therefore.

Reaction times in [VIII] method, so long as set the polymerization degree k that can make in the general formula (20) at the proper range inner casing, that is, setting the weight-average molecular weight that can formula contains the compound that structural unit forms shown in the general formula (20) for gets final product in suitable scope.This reaction times is depended on the equivalent or the temperature of reaction of the polyprotonic acid (part that comprises carboxyl is the material of carboxylicesters) that uses in the reaction, therefore cannot treat different things as the same, usually be set in 0.5～50 hour, and preferably set, more preferably be set in 2～15 hours scope at 1～24 hour.

Solvent in [VIII] method is as long as use and the identical solvent of above-mentioned [III] method, and the usage quantity of solvent needs only the energy dissolving raw material, and just there is no particular limitation.

In [VIII] method, preferably use catalyzer, contain quantitatively and reposefully reaction of the polyprotonic acid shown in compound shown in the general formula (22) and the general formula (34) (part that comprises carboxyl is the material of carboxylicesters) thereby make with 3 above carboxyls.As these catalyzer, for example, can enumerate the catalyzer such as organic phosphine compound of the quaternary ammonium salt of TBuA muriate, TBuA bromide, triethyl hexadecyldimethyl benzyl ammonium muriate, triethyl hexadecyldimethyl benzyl ammonium bromide etc. or triphenylphosphine etc.These catalyzer can be distinguished use separately, or will be used in combination more than 2 kinds, there is no particular limitation to the usage quantity of above-mentioned catalyzer, with respect to the mol amount that contains the compound shown in the general formula (22), can enumerate more than the 0.001mol%, in order to improve speed of response, can also use about 200mol%.

As the more detailed concrete example of manufacture method shown in [VIII] method, for example, can enumerate the method shown in following [X] method,

In the formula, R ¹, R ², R ¹', R ²', T ₁, T ₂, U, V ₁, V ₂, Z ₁And k is same as described above.

In addition, the compound shown in the general formula (22) is equivalent to the R in the general formula (13) ¹⁰Be general formula (14), R ¹¹It is the situation of general formula (16).The polyprotonic acid (part that comprises carboxyl is the material of carboxylicesters) that compound shown in the general formula (110) is equivalent to have 3 above carboxyls is defined as 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid or 4-(1,2-dicarboxyl ethyl)-1,2, the situation of 3,4-naphthane-1,2-dicarboxylic acid { the aliphatics tetracarboxylic acid shown in the following formula (108) }.Contain structural unit forms shown in the general formula (111) compound and be equivalent to R in the general formula (7) ³' and R ⁴' be carboxyl, Y ₁' be group, the Y shown in the formula (8) ₂' be the group shown in the formula (9), 4 valency alkyl, a and the b that will be defined as aromatic series shown in following formula (29-1 '), (29-3 ') or (32) or aliphatic category with the 4 valency alkyl that Z represents be 1 situation.

In above-mentioned [VIII] method, except the polyprotonic acid (part that comprises carboxyl is the material of carboxylicesters) that has 3 above carboxyls shown in the general formula (34), can also use can with the compound of compound polymerization shown in the general formula (22), specifically, for example, as using the aromatic series shown in the general formula (57) or the method for aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid), can enumerate the method shown in following [XI] method with 2 carboxyls

In the formula, R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z, Z ', k ' and k " same as described above.

As aromatic series shown in the general formula (57) or aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) with 2 carboxyls, specifically, for example, can enumerative (113)～(115), the aromatic dicarboxylic acid shown in general formula (116) or (117), or the aliphatic dicarboxylic acid shown in general formula (118), (119) or the formula (120)

Wherein, in the formula (114), 2 carboxyls can be bonded on any carbon in 1～8 carbon of naphthalene nucleus;

In the formula, W ₁₃And W ₁₄Expression singly-bound, Sauerstoffatom, carbonyl, alkylsulfonyl or vinylidene;

In the formula, W ₁₅Expression singly-bound, carbonatoms are 1～18 straight chain shape alkylidene group, vinylidene, 2,3-propenylidene (1-propylene-2,3-two bases), ethynyl or 2-oxo propylidene, q represents 1～3 integer, wherein, in the formula (119), 2 carboxyls can be bonded in the cycloalkyl ring arbitrarily on the carbon;

In the formula, 2 carboxyls can be bonded on the carbon arbitrarily in the cyclohexene ring carbon.

As the W in general formula (116) and (117) ₁₃And W ₁₄, more preferably singly-bound or carbonyl.

As the W in the general formula (118) ₁₅, more preferably singly-bound, carbonatoms are 1～18 straight chain shape alkylidene group or vinylidene, wherein, and further preferred vinylidene.

The integer of the q ordinary representation 1～3 in the general formula (119), wherein, preferred 2～3 integer, more preferably 3.

As the aromatic dicarboxylic acid shown in the formula (113), specifically, for example, can enumerate phthalic acid, m-phthalic acid, terephthalic acid etc., wherein, preferred phthalic acid, terephthalic acid.

As the aromatic dicarboxylic acid shown in the formula (114), specifically, for example, can enumerate 1,2-naphthalene dicarboxylic acids, 1,3-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 1,6-naphthalene dicarboxylic acids, 1,7-naphthalene dicarboxylic acids, 1,8-naphthalene dicarboxylic acids, 2,3-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids etc., wherein, preferred 1,8-naphthalene dicarboxylic acids, 2,3-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids.

As the aromatic dicarboxylic acid shown in the formula (115), specifically, for example, can enumerate 2,3-pyridine dicarboxylic acid, 2,4-pyridine dicarboxylic acid, 2,5-pyridine dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 3,4-pyridine dicarboxylic acid, 3,5-pyridine dicarboxylic acid etc.

As W in the aromatic dicarboxylic acid shown in the formula (116) ₁₃Be single bonded aromatic dicarboxylic acid, for example, can enumerate 2,3-diphenyl dicarboxylic acid, 2,4-diphenyl dicarboxylic acid, 2,5-diphenyl dicarboxylic acid, 2,6-diphenyl dicarboxylic acid, 3,4-diphenyl dicarboxylic acid, 3,5-diphenyl dicarboxylic acid etc.In addition, as W ₁₃Be the aromatic dicarboxylic acid of Sauerstoffatom, for example, can enumerate 2,3-xenyl ether dicarboxylic acid, 2,4-xenyl ether dicarboxylic acid, 2,5-xenyl ether dicarboxylic acid, 2,6-xenyl ether dicarboxylic acid, 3,4-xenyl ether dicarboxylic acid, 3,5-xenyl ether dicarboxylic acid etc.In addition, as W ₁₃Be the aromatic dicarboxylic acid of carbonyl, for example, can enumerate 2,3-benzophenone dicarboxylic acid, 2,4-benzophenone dicarboxylic acid, 2,5-benzophenone dicarboxylic acid, 2,6-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, 3,5-benzophenone dicarboxylic acid etc.In addition, as W ₁₃Be the aromatic dicarboxylic acid of alkylsulfonyl, for example, can enumerate 2; 3-xenyl sulfone dicarboxylic acid, 2,4-xenyl sulfone dicarboxylic acid, 2,5-xenyl sulfone dicarboxylic acid, 2; 6-xenyl sulfone dicarboxylic acid, 3,4-xenyl sulfone dicarboxylic acid, 3,5-xenyl sulfone dicarboxylic acid etc.In addition, as W ₁₃It is the aromatic dicarboxylic acid of vinylidene, for example, can enumerate cis-2,3-stilbenedicarboxylicacid acid, trans-2,3-stilbenedicarboxylicacid acid, cis-2,4-stilbenedicarboxylicacid acid, trans-2,4-stilbenedicarboxylicacid acid, cis-2,5-stilbenedicarboxylicacid acid, trans-2,5-stilbenedicarboxylicacid acid, cis-2,6-stilbenedicarboxylicacid acid, trans-2,6-stilbenedicarboxylicacid acid, cis-3,4-stilbenedicarboxylicacid acid, trans-3,4-stilbenedicarboxylicacid acid, cis-3,5-stilbenedicarboxylicacid acid, trans-3,5-stilbenedicarboxylicacid acid etc.

As W in the aromatic dicarboxylic acid shown in the formula (117) ₁₄Be single bonded aromatic dicarboxylic acid, for example, can enumerate 2,2 '-diphenyl dicarboxylic acid, 2,3 '-diphenyl dicarboxylic acid, 2,4 '-diphenyl dicarboxylic acid, 3,3 '-diphenyl dicarboxylic acid, 3,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid etc., wherein, preferred 3,3 '-diphenyl dicarboxylic acid, 3,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, more preferably 4,4 '-diphenyl dicarboxylic acid.In addition, as W ₁₄Be the aromatic dicarboxylic acid of Sauerstoffatom, for example, can enumerate 2,2 '-xenyl ether dicarboxylic acid, 2,3 '-xenyl ether dicarboxylic acid, 2,4 '-xenyl ether dicarboxylic acid, 3,3 '-xenyl ether dicarboxylic acid, 3,4 '-xenyl ether dicarboxylic acid, 4,4 '-xenyl ether dicarboxylic acid etc.In addition, as W ₁₄Be the aromatic dicarboxylic acid of carbonyl, for example, can enumerate 2,2 '-benzophenone dicarboxylic acid, 2,3 '-benzophenone dicarboxylic acid, 2,4 '-benzophenone dicarboxylic acid, 3,3 '-benzophenone dicarboxylic acid, 3,4 '-benzophenone dicarboxylic acid, 4,4 '-benzophenone dicarboxylic acid etc.In addition, as W ₁₄Be the aromatic dicarboxylic acid of alkylsulfonyl, for example, can enumerate 2; 2 '-xenyl sulfone dicarboxylic acid, 2,3 '-xenyl sulfone dicarboxylic acid, 2,4 '-xenyl sulfone dicarboxylic acid, 3; 3 '-xenyl sulfone dicarboxylic acid, 3,4 '-xenyl sulfone dicarboxylic acid, 4,4 '-xenyl sulfone dicarboxylic acid.In addition, as W ₁₄It is the aromatic dicarboxylic acid of vinylidene, for example, can enumerate cis-2,2 '-stilbenedicarboxylicacid acid, trans-2,2 '-stilbenedicarboxylicacid acid, cis-2,3 '-stilbenedicarboxylicacid acid, trans-2,3 '-stilbenedicarboxylicacid acid, cis-2,4 '-stilbenedicarboxylicacid acid, trans-2,4 '-stilbenedicarboxylicacid acid, cis-3,3 '-stilbenedicarboxylicacid acid, trans-3,3 '-stilbenedicarboxylicacid acid, cis-3,4 '-stilbenedicarboxylicacid acid, trans-3,4 '-stilbenedicarboxylicacid acid, cis-4,4 '-stilbenedicarboxylicacid acid, trans-4,4 '-stilbenedicarboxylicacid acid etc.

In above-mentioned aromatic dicarboxylic acid, the material shown in preferred formula (113) or the general formula (117), wherein, the more preferably W in formula (113) or the general formula (117) ₁₄It is the material of singly-bound or carbonyl.

As W in the aliphatic dicarboxylic acid shown in the general formula (118) ₁₅Be single bonded aliphatic dicarboxylic acid, can enumerate oxalic acid etc.In addition, as W ₁₅Be that carbonatoms is the aliphatic dicarboxylic acid of 1～18 straight chain shape alkylidene group, for example, can enumerate propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 1,10-sebacic acid, 1,18-octadecane diacid etc., wherein, preferred propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 1,10-sebacic acid, more preferably propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid.In addition, as W ₁₅Be the aliphatic dicarboxylic acid of vinylidene, for example, can enumerate toxilic acid, fumaric acid etc., wherein, preferred fumaric acid.In addition, as W ₁₅Be the aliphatic dicarboxylic acid of 2,3-propenylidene (1-propylene-2,3-two bases), can enumerate methylene-succinic acid etc.In addition, as W ₁₅Be the aliphatic dicarboxylic acid of 2-oxo propylidene, can enumerate 1,3-Bing Tongersuosuan etc.

As the aliphatic dicarboxylic acid shown in the general formula (119), usually can enumerate q and be 1～3 integer, be preferably 2～3 integer, 3 aliphatic dicarboxylic acid more preferably, specifically, for example, can enumerate 1,2-cyclobutane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,2-pentamethylene dicarboxylic acid, 1,3-pentamethylene dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid etc., wherein, preferred 1,2-pentamethylene dicarboxylic acid, 1,3-pentamethylene dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, more preferably 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid.

As the aliphatic dicarboxylic acid shown in the formula (120), specifically, can enumerate cis-1,2,3,6-tetrahydrophthalic acid, trans-1,2,3,6-tetrahydrophthalic acid, 34,5,6-tetrahydrophthalic acid etc., wherein, preferred cis-1,2,3,6-tetrahydrophthalic acid.

In above-mentioned aliphatic dicarboxylic acid, the material shown in preferred formula (118) or the formula (120), wherein, the more preferably W in the general formula (118) ₁₅Be that singly-bound, carbonatoms are 1～18 the straight chain shape alkylidene group or the material of vinyl, or the material shown in the formula (120), the further W in the preferred formula (118) ₁₅Be the material of vinyl, or the material shown in the formula (120).

In [XI] method, if and during their mol during with aromatic series with 2 carboxyls shown in polyprotonic acid with 3 above carbonyls shown in the general formula (34) (part that comprises carboxyl is the material of carboxylicesters) and the general formula (57) or aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) compares, also being generally 10:90～99:1, be preferably 40:60～99:1 with the mol ratio under the situation of acid shown in acid and the above-mentioned general formula (57) shown in the above-mentioned general formula (34).When the ratio of acid shown in the general formula (34) is lower than 10 moles of % of all acid, the acid value and the molecular weight of gained compound diminish, for example using the resin combination that obtains by this compound to prepare under the situation of colour filter, be difficult to form fine pattern, in addition, on thermotolerance or solvent resistance etc., probably can have problems, therefore not preferred.

In [XI] method, as and with the method for the aromatic series or the aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) that have 2 carboxyls shown in polyprotonic acid that has 3 above carbonyls shown in the general formula (34) (part that comprises carboxyl is the material of carboxylicesters) and the general formula (57), both can in the solution that comprises the compound shown in the general formula (22), add they mixture and in the lump the reaction, it can also be reacted respectively and by stages.

As the more detailed concrete example of manufacture method shown in [XI] method, for example, can enumerate the method shown in following [XII] method,

In the formula, R ¹, R ², R ¹', R ²', T ₁, T ₂, U, V ₁, V ₂, Z ₁, Z ₃, k ' and k " same as described above.

In addition, the aromatic series or the aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) that are equivalent to have 2 carboxyls of the compound shown in the general formula (121) is defined as terephthalic acid, toxilic acid or cis-1,2, the situation of 3,6-tetrahydrophthalic acid.Contain structural unit forms shown in the general formula (122) compound and be equivalent to R in the above-mentioned general formula (112) ³' and R ⁴' be carboxyl, will with 4 valency alkyl shown in the Z be defined as aromatic series shown in following formula (29-1 '), (29-3 ') or (32) or aliphatic category 4 valency alkyl, will use the divalent alkyl shown in the Z ' to be defined as the situation of the divalent alkyl of aromatic series shown in following formula (49 '), (54-2 ') or (56 ') or aliphatic category.

Below, above-mentioned [IX] method is described in detail.For example, [IX] method is with the compound solvent cut shown in the general formula (23), and as required after wherein adding catalyzer, (comprise that the part of carboxyl forms the material of anhydride group through dehydrating condensation to adding in this mixing solutions as stating the multi-anhydride shown in the normal general formula of regulation (35) or (36) with 3 above carboxyls, a part that also comprises carboxyl is the material of carboxylicesters), under the temperature of regulation, react the specified time.Wherein the solution of gained need not to separate, refining, just can in the purpose purposes, use, also can further dilute this solution with solvent, or separate, make with extra care and contain the compound that structural unit forms shown in the general formula (21) and get final product by ordinary method according to purposes.

In [IX] method, as V in the compound shown in the general formula (23) ₁And V ₂Be Sauerstoffatom, R ¹²And R ¹³Be the compound of hydrogen atom, and R ¹²Be group, the R shown in the general formula (15) ¹³Be group and the V shown in the general formula (17) ₃And V ₄Be Sauerstoffatom, M ₁And M ₂Be the compound of hydrogen atom, for example, can enumerate by making the V in the compound shown in the above-mentioned general formula (98) with biphenyl backbone ₁And V ₂Be that the compound of Sauerstoffatom and carbonatomss such as compound with biphenyl backbone shown in the above-mentioned general formula (98) and formaldehyde are the compound that 1 compound reaction obtains; Compound shown in the above-mentioned general formula (98) and 2-chlorine-1-ethanol with bis-phenol skeleton, 2-bromine-1-ethanol, 3-chlorine-1-propyl alcohol, 3-bromine-1-propyl alcohol, 4-chlorine-1-butanols, 4-bromine-1-butanols, 5-chlorine-1-amylalcohol, 5-bromine-1-amylalcohol, 6-chlorine-1-hexanol, the ω of 6-bromine-1-hexanol etc.-halohydrin reacts and the compound of acquisition, wherein, preferably make the compound shown in the above-mentioned general formula (98) and 2-chlorine-1-ethanol with biphenyl backbone, 2-bromine-1-ethanol, 3-chlorine-1-propyl alcohol, 3-bromine-1-propyl alcohol, 4-chlorine-1-butanols, the ω of 4-bromine-1-butanols-halohydrin reacts and the compound of acquisition, more preferably makes the compound with biphenyl backbone shown in the above-mentioned general formula (98) and 2-chlorine-1-ethanol, 2-bromine-1-alcoholic acid ω-halohydrin reacts and the compound of acquisition.

In [IX] method, as V in the compound shown in the general formula (23) ₁And V ₂Be-NH-base, R ¹²And R ¹³Be the compound of hydrogen atom, and R ¹²Be group, the R shown in the general formula (15) ¹³Be group and the V shown in the general formula (17) ₃And V ₄Be-NH-base, M ₁And M ₂Be the compound of hydrogen atom, for example, can enumerate the V that makes in the compound shown in the above-mentioned general formula (98) with biphenyl backbone ₁And V ₂Be-compound of NH-base, with the compound with biphenyl backbone and the 1-chloromethane amine shown in the above-mentioned general formula (98), 1-bromine methylamine, 2-chlorine-1-ethamine, 2-bromine-1-ethamine, 3-chlorine-1-propylamine, 3-bromine-1-propylamine, 4-chlorine-1-butylamine, 4-bromine-1-butylamine, 5-chlorine-1-amylamine, 5-bromine-1-amylamine, 6-chlorine-1-hexylamine, the ω of 6-bromine-1-hexylamine etc.-haloalkyl amine reacts and the compound of acquisition, wherein, preferably make the compound shown in the above-mentioned general formula (98) and 2-chlorine-1-ethamine with biphenyl backbone, 2-bromine-1-ethamine, 3-chlorine-1-propylamine, 3-bromine-1-propylamine, 4-chlorine-1-butylamine, the ω of 4-bromine-1-butylamine etc.-haloalkyl amine reacts and the compound of acquisition, more preferably makes the compound with biphenyl backbone shown in the above-mentioned general formula (98) and 2-chlorine-1-ethamine, ω such as 2-bromine-1-ethamine-haloalkyl amine reacts and the compound of acquisition.

In [IX] method, as R in the compound shown in the general formula (23) ¹²And R ¹³Be the compound of alkali metal atom, and R ¹²Be group, the R shown in the general formula (15) ¹³Be group and the M shown in the general formula (17) ₁And M ₂It is the compound of alkali metal atom, for example, can enumerate and make the compound shown in the above-mentioned general formula (98) with biphenyl backbone, the compound with biphenyl backbone shown in the above-mentioned general formula (98) and ω-halohydrin or ω-haloalkyl amine reacts and the compound and the sodium hydroxide of acquisition, alkali metal hydroxides such as potassium hydroxide, sodium hydride, the hydrogenated alkali metal of potassium hydride KH etc., sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, the compound that in the alkali metal alcoholates such as potassium tert.-butoxide etc. any obtains by the ordinary method reaction, wherein, the compound that compound that preferably makes the compound with biphenyl backbone shown in compound with biphenyl backbone shown in the above-mentioned general formula (98) and the above-mentioned general formula (98) and ω-halohydrin or ω-haloalkyl amine reaction and obtain and sodium methylate or potassium methylate obtain by the ordinary method reaction.

(comprise that the part of carboxyl forms the material of anhydride group through dehydrating condensation as the multi-anhydride shown in general formula (35) or (36) with 3 above carboxyls, a part that also comprises carboxyl is the material of carboxylicesters), usually can enumerate aromatic series or aliphatic carboxylic acid acid anhydride and (comprise that the part of carboxyl forms the material of anhydride group through dehydrating condensation with 3 above carboxyls, a part that also comprises carboxyl is the material of carboxylicesters), specifically, for example, the aromatic tricarboxylic acids acid anhydride shown in can enumerative (123); Aromatic tetracarboxylic acid's acid anhydride shown in formula (124), (125) or general formula (126)～(128); Aliphatic tricarboxylic acids acid anhydride shown in the general formula (129); Or the aliphatics tetracarboxylic dianhydride shown in general formula (130), (131), formula (132) or (133),

Wherein, in the formula (125), can form anhydride group, just can be bonded on any carbon in 1～8 carbon of naphthalene nucleus as long as form 4 carboxyls of anhydride group;

In the formula, W ₁₆, W ₁₇And W ₁₈Expression singly-bound, Sauerstoffatom, carbonyl, alkylsulfonyl or vinylidene;

In the formula, W ₁₉Expression ethane three bases, propane three bases or butane three bases;

In the formula, W ₂₀Expression ethene four bases or butane four bases, r represents 1～3 integer.Wherein, in the formula (131), can form anhydride group, just can be bonded on any carbon in the cycloalkyl ring carbon as long as form 4 carboxyls of anhydride group;

As the W in general formula (126)～(128) ₁₆～W ₁₈, more preferably singly-bound or carbonyl.

The integer of the r ordinary representation 1～3 in the general formula (131), wherein, preferred 2～3 integer, more preferably 3.

As the aromatic tricarboxylic acids acid anhydride shown in the formula (123), specifically, for example, can enumerate 1,2,3-benzene tricarbonic acid acid anhydride, 1,2,4-benzene tricarbonic acid acid anhydride (trimellitic acid 1,2-anhydride) etc., wherein, preferred 1,2,4-benzene tricarbonic acid acid anhydride (trimellitic acid 1,2-anhydride).

As the aromatic tetracarboxylic acid's dianhydride shown in the formula (124), specifically, for example, can enumerate 1,2,3,4-benzene tertacarbonic acid dianhydride, 1,2,4,5-benzene tertacarbonic acid dianhydride (pyromellitic acid acid anhydride) etc., wherein, preferred 1,2,4,5-benzene tertacarbonic acid dianhydride (pyromellitic acid acid anhydride).

As the aromatic tetracarboxylic acid's dianhydride shown in the formula (125), specifically, for example, can enumerate 1,2,3,4-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 1,2,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,7,8-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc., wherein, preferred 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, more preferably 1,4,5,8-naphthalene tetracarboxylic acid dianhydride.

As W in aromatic tetracarboxylic acid's dianhydride shown in the general formula (126) ₁₆Be single bonded aromatic tetracarboxylic acid's dianhydride, for example, can enumerate 2,3,4,5-biphenyl tetracarboxylic dianhydride, 2,3,5,6-biphenyl tetracarboxylic dianhydride etc.In addition, as W ₁₆Be aromatic tetracarboxylic acid's dianhydride of Sauerstoffatom, for example, can enumerate 2,3,4,5-xenyl ether tetracarboxylic dianhydride, 2,3,5,6-xenyl ether tetracarboxylic dianhydride etc.In addition, as W ₁₆Be aromatic tetracarboxylic acid's dianhydride of carbonyl, for example, can enumerate 2,3,4,5-benzophenone tetracarboxylic dianhydride, 2,3,5,6-benzophenone tetracarboxylic dianhydride etc.In addition, as W ₁₆Be aromatic tetracarboxylic acid's dianhydride of alkylsulfonyl, for example, can enumerate 2,3,4,5-xenyl sulfone tetracarboxylic dianhydride, 2,3,5,6-xenyl sulfone tetracarboxylic dianhydride etc.In addition, as W ₁₆Be aromatic tetracarboxylic acid's dianhydride of vinylidene, for example, can enumerate cis-2,3,4,5-toluylene tetracarboxylic dianhydride, trans-2,3,4,5-toluylene tetracarboxylic dianhydride, cis-2,3,5,6-toluylene tetracarboxylic dianhydride, trans-2,3,5,6-toluylene tetracarboxylic dianhydride etc.

As W in aromatic tetracarboxylic acid's acid anhydride shown in the general formula (127) ₁₇Be single bonded aromatic tetracarboxylic acid's acid anhydride, for example, can enumerate 2,2 ', 3,4-biphenyltetracarboxyacid acid acid anhydride, 2,3,3 ', 4-biphenyltetracarboxyacid acid acid anhydride, 2,3,4,4 '-biphenyltetracarboxyacid acid acid anhydride, 2,2 ', 3,5-biphenyltetracarboxyacid acid acid anhydride, 2,3,3 ', 5-biphenyltetracarboxyacid acid acid anhydride, 2,3,4 ', 5-biphenyltetracarboxyacid acid acid anhydride, 2,2 ', 3,6-biphenyltetracarboxyacid acid acid anhydride, 2,3,3 ', 6-biphenyltetracarboxyacid acid acid anhydride, 2,3,4 ', 6-biphenyltetracarboxyacid acid acid anhydride, 2,2 ', 4,5-biphenyltetracarboxyacid acid acid anhydride, 2,3 ', 4,5-biphenyltetracarboxyacid acid acid anhydride, 2,4,4 ', 5-biphenyltetracarboxyacid acid acid anhydride etc.In addition, as W ₁₇Be aromatic tetracarboxylic acid's acid anhydride of Sauerstoffatom, for example, can enumerate 2,2 ', 3,4-xenyl ether tetracarboxylic anhydride, 2,3,3 ', 4-xenyl ether tetracarboxylic anhydride, 2,3,4,4 '-xenyl ether tetracarboxylic anhydride, 2,2 ', 3,5-xenyl ether tetracarboxylic anhydride, 2,3,3 ', 5-xenyl ether tetracarboxylic anhydride, 2,3,4 ', 5-xenyl ether tetracarboxylic anhydride, 2,2 ', 3,6-xenyl ether tetracarboxylic anhydride, 2,3,3 ', 6-xenyl ether tetracarboxylic anhydride, 2,3,4 ', 6-xenyl ether tetracarboxylic anhydride, 2,2 ', 4,5-xenyl ether tetracarboxylic anhydride, 2,3 ', 4,5-xenyl ether tetracarboxylic anhydride, 2,4,4 ', 5-xenyl ether tetracarboxylic anhydride etc.In addition, as W ₁₇Be aromatic tetracarboxylic acid's acid anhydride of carbonyl, for example, can enumerate 2,2 ', 3,4-benzophenone tetracarboxylic anhydride, 2,3,3 ', 4-benzophenone tetracarboxylic anhydride, 2,3,4,4 '-benzophenone tetracarboxylic anhydride, 2,2 ', 3,5-benzophenone tetracarboxylic anhydride, 2,3,3 ', 5-benzophenone tetracarboxylic anhydride, 2,3,4 ', 5-benzophenone tetracarboxylic anhydride, 2,2 ', 3,6-benzophenone tetracarboxylic anhydride, 2,3,3 ', 6-benzophenone tetracarboxylic anhydride, 2,3,4 ', 6-benzophenone tetracarboxylic anhydride, 2,2 ', 4,5-benzophenone tetracarboxylic anhydride, 2,3 ', 4,5-benzophenone tetracarboxylic anhydride, 2,4,4 ', 5-benzophenone tetracarboxylic anhydride etc.In addition, as W ₁₇Be the aromatic carboxylic acid acid anhydride of alkylsulfonyl, for example, can enumerate 2,2 '; 3,4-xenyl sulfone tetracarboxylic anhydride; 2,3,3 '; 4-xenyl sulfone tetracarboxylic anhydride; 2,3,4,4 '-xenyl sulfone tetracarboxylic anhydride; 2; 2 ', 3,5-xenyl sulfone tetracarboxylic anhydride; 2,3; 3 ', 5-xenyl sulfone tetracarboxylic anhydride; 2,3,4 '; 5-xenyl sulfone tetracarboxylic anhydride; 2,2 ', 3,6-xenyl sulfone tetracarboxylic anhydride; 2; 3,3 ', 6-xenyl sulfone tetracarboxylic anhydride; 2,3; 4 ', 6-xenyl sulfone tetracarboxylic anhydride; 2,2 ', 4; 5-xenyl sulfone tetracarboxylic anhydride; 2,3 ', 4,5-xenyl sulfone tetracarboxylic anhydride; 2; 4,4 ', 5-xenyl sulfone tetracarboxylic anhydride etc.In addition, as W ₁₇Be aromatic tetracarboxylic acid's acid anhydride of vinylidene, for example, can enumerate cis-2,2 ', 3,4-toluylene tetracarboxylic anhydride, trans-2,2 ', 3,4-toluylene tetracarboxylic anhydride, cis-2,3,3 ', 4-toluylene tetracarboxylic anhydride, trans-2,3,3 ', 4-toluylene tetracarboxylic anhydride, cis-2,3,4,4 '-toluylene tetracarboxylic anhydride, trans-2,3,4,4 '-toluylene tetracarboxylic anhydride, cis-2,2 ', 3,5-toluylene tetracarboxylic anhydride, trans-2,2 ', 3,5-toluylene tetracarboxylic anhydride, cis-2,3,3 ', 5-toluylene tetracarboxylic anhydride, trans-2,3,3 ', 5-toluylene tetracarboxylic anhydride, cis-2,3,4 ', 5-toluylene tetracarboxylic anhydride, trans-2,3,4 ', 5-toluylene tetracarboxylic anhydride, cis-2,2 ', 3,6-toluylene tetracarboxylic anhydride, trans-2,2 ', 3,6-toluylene tetracarboxylic anhydride, cis-2,3,3 ', 6-toluylene tetracarboxylic anhydride, trans-2,3,3 ', 6-toluylene tetracarboxylic anhydride, cis-2,3,4 ', 6-toluylene tetracarboxylic anhydride, trans-2,3,4 ', 6-toluylene tetracarboxylic anhydride, cis-2,2 ', 4,5-toluylene tetracarboxylic anhydride, trans-2,2 ', 4,5-toluylene tetracarboxylic anhydride, cis-2,3 ', 4,5-toluylene tetracarboxylic anhydride, trans-2,3 ', 4,5-toluylene tetracarboxylic anhydride, cis-2,4,4 ', 5-toluylene tetracarboxylic anhydride, trans-2,4,4 ', 5-toluylene tetracarboxylic anhydride etc.

As W in aromatic tetracarboxylic acid's dianhydride shown in the general formula (128) ₁₈Be single bonded aromatic tetracarboxylic acid's dianhydride, for example, can enumerate 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride etc., wherein, preferred 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride.In addition, as W ₁₈Be aromatic tetracarboxylic acid's dianhydride of Sauerstoffatom, for example, can enumerate 2,2 ', 3,3 '-xenyl ether tetracarboxylic dianhydride, 2,3,3 ', 4 '-xenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-xenyl ether tetracarboxylic dianhydride etc., wherein, preferred 3,3 ', 4,4 '-xenyl ether tetracarboxylic dianhydride.In addition, as W ₁₈Be aromatic tetracarboxylic acid's dianhydride of carbonyl, for example, can enumerate 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride etc., wherein, preferred 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride.In addition, as W ₁₈Be aromatic tetracarboxylic acid's dianhydride of alkylsulfonyl, for example, can enumerate 2; 2 ', 3,3 '-xenyl sulfone tetracarboxylic dianhydride, 2; 3,3 ', 4 '-xenyl sulfone tetracarboxylic dianhydride, 3; 3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride etc.; wherein, preferred 3,3 '; 4,4 '-xenyl sulfone tetracarboxylic dianhydride.In addition, as W ₁₈Be aromatic tetracarboxylic acid's dianhydride of vinylidene, for example, can enumerate cis-2,2 ', 3,3 '-toluylene tetracarboxylic dianhydride, trans-2,2 ', 3,3 '-toluylene tetracarboxylic dianhydride, cis-2,3,3 ', 4 '-toluylene tetracarboxylic dianhydride, trans-2,3,3 ', 4 '-toluylene tetracarboxylic dianhydride, cis-3,3 ', 4,4 '-toluylene tetracarboxylic dianhydride, trans-3,3 ', 4,4 '-toluylene tetracarboxylic dianhydride etc., wherein, preferred cis-3,3 ', 4,4 '-toluylene tetracarboxylic dianhydride, trans-3,3 ', 4,4 '-toluylene tetracarboxylic dianhydride.

In above-mentioned aromatic tetracarboxylic acid's acid anhydride, the material shown in preferred formula (124) or the general formula (128), wherein, the more preferably W in formula (124) or the general formula (128) ₁₈It is the material of singly-bound or carbonyl.

As W in the aliphatic tricarboxylic acids acid anhydride shown in the general formula (129) ₁₉Be the aliphatic tricarboxylic acids acid anhydride of ethane three bases, for example, can enumerate ethane tricarboxylic acid anhydride etc.In addition, as W ₁₉Be the aliphatic tricarboxylic acids acid anhydride of propane three bases, for example, can enumerate tricarballylic acid's acid anhydride etc.In addition, as W ₁₉Be the aliphatic tricarboxylic acids acid anhydride of butane three bases, for example, can enumerate butane tricarboxylic acid anhydride etc.

In the aliphatics tetracarboxylic dianhydride shown in the general formula (130), W ₂₀Be the aliphatics tetracarboxylic dianhydride of ethene four bases, can enumerate ethene tetracarboxylic dianhydride etc.In addition, as W ₂₀Be the aliphatics tetracarboxylic dianhydride of butane four bases, for example, can enumerate butane tetracarboxylic acid dianhydride etc.

As the aliphatics tetracarboxylic dianhydride shown in the general formula (131), usually can enumerate r and be 1～3 integer, be preferably 2～3 integer, 3 aliphatics tetracarboxylic dianhydride more preferably, specifically, for example, can enumerate tetramethylene tetracarboxylic dianhydride, pentamethylene tetracarboxylic dianhydride, hexanaphthene tetracarboxylic dianhydride etc., wherein, optimization cyclopentane tetracarboxylic dianhydride, hexanaphthene tetracarboxylic dianhydride, more preferably hexanaphthene tetracarboxylic dianhydride.

As the aliphatics tetracarboxylic dianhydride shown in the formula (132), for example, can enumerate 4-(1,2-dicarboxyl ethyl)-1,2,3,4-naphthane-1,2-dicarboxylic acid dianhydride.

As the aliphatics tetracarboxylic dianhydride shown in the formula (133), for example, can enumerate 5-(1,2-dicarboxyl ethyl)-3-methylcyclohexane-1,2-dicarboxylic acid dianhydride.

In above-mentioned aliphatics tetracarboxylic dianhydride, the material shown in preferred formula (132) or (133), wherein, the more preferably material shown in the formula (132).

In addition, carboxyl in above-mentioned aromatic series or the aliphatic carboxylic acid acid anhydride can be the carboxylicesters with above-mentioned general formula (37) expression, compound with this carboxylicesters both can use commercially available product, after can also suitably using alcohol reactions such as aromatic series shown in for example above-mentioned general formula (99)～(109) or aliphatic carboxylic acid and methyl alcohol, ethanol, carry out the synthetic material by usual methods such as intramolecular dehydration or intramolecularly dealcoholysis condensations.

(comprise that the part of carboxyl forms the material of anhydride group through dehydrating condensation as the multi-anhydride shown in general formula (35) or (36) with 3 above carboxyls, a part that also comprises carboxyl is the material of carboxylicesters) equivalent, compound with respect to shown in the general formula (23) can be enumerated as 0.5～2 equivalent usually.

About the temperature of reaction in [IX] method, so long as can make hydroxyl in the compound shown in the general formula (23) and/or the amino (metal-salt that comprises them.) and general formula (35) or (36) shown in the multi-anhydride with 3 above carboxyls (part that comprises carboxyl forms the material of anhydride group through dehydrating condensation, a part that also comprises carboxyl is the material of carboxylicesters) in the temperature of anhydride group quantitative reaction, just there is no particular limitation, for example be generally 60～120 ℃, be preferably 70～90 ℃.If temperature of reaction is lower than 60 ℃, reaction is carried out slowly, and the worry of compound shown in the general formula (23) of remained unreacted and this multi-anhydride is arranged, and therefore produces not preferred.

Reaction times in [IX] method, get final product in suitable scope so long as set the polymerization degree k that can make in the general formula (21) for, that is, set for and the weight-average molecular weight that comprises the compound that structural unit forms shown in the general formula (21) is controlled at get final product in the proper range.Because this reaction times is depended on the multi-anhydride that uses in the reaction and (comprises that the part of carboxyl forms the material of anhydride group through dehydrating condensation, a part that also comprises carboxyl is the material of carboxylicesters) equivalent or temperature of reaction, therefore cannot treat different things as the same, usually be set in 0.25～50 hour, be preferably 0.25～15 hour, more preferably 0.5～8 hour scope.

Solvent in [IX] method is as long as use and the identical solvent of above-mentioned [III] method, and the usage quantity of solvent is so long as the amount of energy dissolving raw material, with regard to there is no particular limitation.

In [IX] method, the preferred catalyzer that uses, thereby the multi-anhydride with 3 above carboxyls shown in compound shown in the general formula (23) and general formula (35) or (36) (comprise the material of the part of carboxyl through dehydrating condensation formation anhydride group, a part that also comprises carboxyl is the material of carboxylicesters) quantitatively and is reposefully reacted.As such catalyzer, for example, can enumerate the tertiary amine of triethylamine, pyridine, dimethyl aminopyridine etc.; Perhaps, the quaternary ammonium salt of TBuA muriate, TBuA bromide, triethyl hexadecyldimethyl benzyl ammonium muriate, triethyl hexadecyldimethyl benzyl ammonium bromide etc.; Or the catalyzer such as organic phosphine compound of triphenylphosphine etc.These catalyzer can be distinguished separately and to use, or will be used in combination more than 2 kinds, and there is no particular limitation to the usage quantity of above-mentioned catalyzer, mol amount with respect to compound shown in the general formula (23), can enumerate more than the 0.001mol%,, can also use about 200mol% in order to improve speed of response.

As the more detailed concrete example of manufacture method shown in [IX] method, for example, can enumerate the method shown in following [XIII] method,

In the formula, R ¹, R ², R ¹', R ²', T ₁, T ₂, U, V ₁, V ₂, Z ₂Same as described above with k.

In addition, the compound shown in the general formula (134) is equivalent to the R in the general formula (13) ¹⁰Be general formula (15), and V ₃Be Sauerstoffatom, M ₁Be hydrogen atom, R ¹¹Be general formula (17) and V ₄Be Sauerstoffatom, M ₂It is the situation of hydrogen atom.The multi-anhydride that compound shown in the general formula (135) is equivalent to have 3 above carboxyls (comprises that the part of carboxyl forms the material of anhydride group through dehydrating condensation, a part that also comprises carboxyl is the material of carboxylicesters) be defined as 4-(1,2-dicarboxyl ethyl)-1,2,3, the situation of 4-naphthane-1,2-dicarboxylic acid dianhydride { the aliphatics tetracarboxylic dianhydride shown in the following formula (132) }.Comprise structural unit forms shown in the general formula (136) compound and be equivalent to R in the general formula (7) ³' and R ⁴' be carboxyl, Y ₁' and Y ₂' be Sauerstoffatom, 4 valency alkyl, a and b that 4 valency alkyl shown in the Z are defined as the aliphatic category shown in the following formula (32) be 1 situation.

In above-mentioned [IX] method, except general formula, (35) or, (36) the multi-anhydride shown in 3 above carboxyls, (comprise that the part of carboxyl forms the material of anhydride group through dehydrating condensation, a part that also comprises carboxyl is the material of carboxylicesters) in addition, can use energy and general formula, the compound of compound polymerization (23), specifically, for example, as using general formula, (58) aromatic series or the aliphatic carboxylic acid acid anhydride that have 2 carboxyls shown in, the method of (aromatic series or aliphatic dicarboxylic acid acid anhydride), can enumerate the method shown in following [XIV] method

In the formula, R ¹, R ², R ¹', R ²', R ³', R ⁴', R ¹², R ¹³, T ₁, T ₂, U, V ₁, V ₂, Y ₁", Y ₂", Z, Z ', a, b, k ' and k " same as described above.

As aromatic series that has 2 carboxyls shown in the general formula (58) or aliphatic carboxylic acid acid anhydride (aromatic series or aliphatic dicarboxylic acid acid anhydride), specifically, for example, can enumerative (138)～(140) or general formula (141) shown in the aromatic dicarboxylic acid acid anhydride; Perhaps, the aliphatic dicarboxylic acid acid anhydride shown in general formula (142), (143) or the formula (144),

Wherein, in formula (139), can form anhydride group, just can be bonded on any carbon in 1～8 carbon of naphthalene nucleus as long as form 2 carboxyls of anhydride group;

In the formula, W ₂₁Expression singly-bound, Sauerstoffatom, carbonyl, alkylsulfonyl or vinylidene;

In the formula, W ₂₂Expression singly-bound, carbonatoms are 1～18 straight chain shape alkylidene group, vinylidene, 2,3-propenylidene (1-propylene-2,3-two bases) or 2-oxo propylidene, s represents 1～3 integer, wherein, in formula (143), can form anhydride group as long as form 2 carboxyls of anhydride group, just can be bonded on any carbon in the cycloalkyl ring carbon;

In the formula, can form anhydride group, just can be bonded on any carbon in the tetrahydrobenzene basic ring carbon as long as form 2 carboxyls of anhydride group.

As the W in the general formula (141) ₂₁, more preferably singly-bound or carbonyl.

As the W in the general formula (142) ₂₂, more preferably singly-bound, carbonatoms are 1～18 straight chain shape alkylidene group or vinylidene, wherein, and further preferred vinylidene.

The integer of the s ordinary representation 1～3 in the general formula (143), wherein, preferred 2～3 integer, more preferably 3.

As the aromatic dicarboxylic acid acid anhydride shown in the formula (138), specifically, for example, can enumerate Tetra hydro Phthalic anhydride etc.

As the aromatic dicarboxylic acid acid anhydride shown in the formula (139), specifically, for example, can enumerate 1,2-naphthalene dicarboxylic acids acid anhydride, 1,8-naphthalene dicarboxylic acids acid anhydride, 2,3-naphthalene dicarboxylic acids acid anhydride etc.

As the aromatic dicarboxylic acid acid anhydride shown in the formula (140), specifically, for example, can enumerate 2,3-pyridine dicarboxylic acid acid anhydride, 3,4-pyridine dicarboxylic acid acid anhydride etc.

In the aromatic dicarboxylic acid acid anhydride shown in the general formula (141) as W ₂₁Be single bonded aromatic dicarboxylic acid acid anhydride, for example, can enumerate 2,3-diphenyl dicarboxylic acid acid anhydride, 3,4-diphenyl dicarboxylic acid acid anhydride etc.In addition, as W ₂₁Be the aromatic dicarboxylic acid acid anhydride of Sauerstoffatom, for example, can enumerate 2,3-xenyl ether dicarboxylic anhydride, 3,4-xenyl ether dicarboxylic anhydride etc.In addition, as W ₂₁Be the aromatic dicarboxylic acid acid anhydride of carbonyl, for example, can enumerate 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride etc.In addition, as W ₂₁Be the aromatic dicarboxylic acid acid anhydride of alkylsulfonyl, for example, can enumerate 2,3-xenyl sulfone dicarboxylic anhydride, 3,4-xenyl sulfone dicarboxylic anhydride etc.In addition, as W ₂₁Be the aromatic dicarboxylic acid acid anhydride of vinylidene, for example, can enumerate cis-2,3-stilbenedicarboxylicacid acid acid anhydride, trans-2,3-stilbenedicarboxylicacid acid acid anhydride, cis-3,4-stilbenedicarboxylicacid acid acid anhydride, trans-3,4-stilbenedicarboxylicacid acid acid anhydride etc.

In above-mentioned aromatic dicarboxylic acid acid anhydride, the material shown in the preferred formula (138).

In the aliphatic dicarboxylic acid acid anhydride shown in the general formula (142) as W ₂₂Be single bonded aliphatic dicarboxylic acid acid anhydride, for example, can enumerate oxalic anhydride.In addition, as W ₂₂Be that carbonatoms is the aliphatic dicarboxylic acid acid anhydride of 1～18 straight chain shape alkylidene group, for example, can enumerate malonic anhydride, Succinic anhydried, Pyroglutaric acid, adipic anhydride, the pimelic acid acid anhydride, the suberic acid acid anhydride, the nonane diacid acid anhydride, sebacic anhydride, 1,10-sebacic anhydride, 1,18-octadecane diacid acid anhydride etc., wherein, preferred malonic anhydride, Succinic anhydried, Pyroglutaric acid, adipic anhydride, the pimelic acid acid anhydride, the suberic acid acid anhydride, the nonane diacid acid anhydride, sebacic anhydride, 1,10-sebacic anhydride, more preferably malonic anhydride, Succinic anhydried, Pyroglutaric acid, adipic anhydride, the pimelic acid acid anhydride, the suberic acid acid anhydride.In addition, as W ₂₂Be the aliphatic dicarboxylic acid acid anhydride of vinylidene, for example, can enumerate maleic anhydride etc.In addition, as W ₂₂Be the aliphatic dicarboxylic acid acid anhydride of 2,3-propenylidene (1-propyl group-2,3-two bases), for example, can enumerate itaconic anhydride etc.In addition, as W ₂₂Be the aliphatic dicarboxylic acid acid anhydride of 2-oxo propylidene, for example, can enumerate 1,3-oxomalonic acid acid anhydride etc.

As the aliphatic dicarboxylic acid acid anhydride shown in the general formula (143), can enumerate s usually and be 1～3 integer, be preferably 2～3 integer, 3 aliphatic dicarboxylic acid acid anhydride more preferably, specifically, for example, can enumerate 1,2-cyclobutane dicarboxylic acid acid anhydride, 1,2-pentamethylene dicarboxylic anhydride, 1,2-cyclohexane dicarboxylic acid acid anhydride, wherein, preferred 1,2-pentamethylene dicarboxylic anhydride, 1,2-cyclohexane dicarboxylic acid acid anhydride, more preferably 1,2-cyclohexane dicarboxylic acid acid anhydride.

As the aliphatic dicarboxylic acid acid anhydride shown in the formula (144), specifically, for example, can enumerate cis-1,2,3,6-Tetra Hydro Phthalic Anhydride, 3,4,5,6-Tetra Hydro Phthalic Anhydride, wherein, preferred cis-1,2,3,6-Tetra Hydro Phthalic Anhydride.

In above-mentioned aliphatic dicarboxylic acid acid anhydride, the material shown in preferred formula (142) or the formula (144), wherein, the more preferably W in the general formula (142) ₂₂Be the material of vinylidene, or the material shown in the formula (144).

In [XIV] method, when also (comprising that the part of carboxyl forms the material of anhydride group through dehydrating condensation with the multi-anhydride shown in general formula (35) or (36) with 3 above carboxyls, a part that also comprises carboxyl is the material of carboxylicesters) and general formula (58) shown in the aromatic series with 2 carboxyls or the mol of these materials during aliphatic carboxylic acid acid anhydride (aromatic series or aliphatic dicarboxylic acid acid anhydride) than in, and the mol ratio during with above-mentioned tetracarboxylic anhydride and above-mentioned dicarboxylic anhydride is generally 10:90～99:1, is preferably 40:60～99:1.When the ratio of tetracarboxylic anhydride is lower than 10 moles of % of all acid, the acid value and the molecular weight of gained compound reduce, thereby for example using the resin combination that obtains by this compound to make under the situation of colour filter, be difficult to form fine pattern, and, the worry that on thermotolerance or solvent resistance, can have problems in addition, therefore not preferred.

In [XIV] method, as also (comprising that the part of carboxyl forms the material of anhydride group through dehydrating condensation with the multi-anhydride shown in general formula (35) or (36) with 3 above carboxyls, a part that also comprises carboxyl is the material of carboxylicesters) and general formula (58) shown in have the method for the aromatic series or the aliphatic carboxylic acid acid anhydride (aromatic series or aliphatic dicarboxylic acid acid anhydride) of 2 carboxyls, both their mixture can be added in the solution comprise compound shown in the general formula (23) and reaction in the lump can also be reacted them respectively and by stages.

Manufacture method according to containing the compound that above structural unit forms can make two ends of structural unit become same group according to the purposes of this compound.Specifically, for example, two ends of structural unit can be from the group with compound of xenyl skeleton shown in general formula (146), general formula (147), general formula (148) or the general formula (149); Or come the polyprotonic acid with 3 above carboxyls or its acid anhydrides shown in self-drifting (150), general formula (151), general formula (152) or the general formula (153) or have the aromatic series of 2 carboxyls or the group of aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) or its acid anhydrides

In the formula, R ¹, R ², R ¹', R ²', U, V ₁And V ₂Same as described above;

In the formula, R ¹, R ², R ¹', R ²', T ₁, T ₂, U, V ₁, V ₂, V ₃And V ₄Same as described above;

In the formula, R ³', R ⁴' and Z same as described above;

In the formula, Z is same as described above;

In the formula, R ¹⁵Expression hydrogen atom or alkyl, Z is same as described above;

In the formula, Z ' is same as described above.

In addition, as the compound that is used to end is used for same group, preferably enumerate as raw materials of compound of the present invention, for example have biphenyl backbone compound, have polyprotonic acid (part that comprises carboxyl is the material of carboxylicesters) or their acid anhydrides, aromatic series or aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) or their acid anhydrides of 3 above carboxyls with 2 carboxyls, below sometimes it is abbreviated as the end structure compound.

Become the method for same group as two ends that make these structural units, promptly, introduction method as the end structure compound, get final product so long as import as above-mentioned end structure compound according to conventional methods, for example, can by condensation reaction synthetic have the compound (resin) of purpose structural unit after, make the method for end structure compound reaction again, or when condensation reaction the method etc. of excessive use end structure compound.In addition, be under the situation of the compound of group shown in the above-mentioned general formula (151) at two ends, can be by water, alcohol etc. be acted in this compound, thus form compound with group shown in the above-mentioned general formula (152).

Embodiment

Below, based on embodiment and comparative example the present invention is carried out specific description, but the present invention is not limited to these embodiment.In addition, in the present embodiment, separated the compound that structural unit forms shown in the general formula (1) that contains of target, but also the solution that obtains by reaction can be directly used in the suitable purposes.The acid value that contains the compound that structural unit forms shown in the general formula (1) (importing compound) from the group of acrylic acid derivative, be will the manufacture method by present embodiment obtain contain the mixing solutions dilution of compound that structural unit forms shown in the general formula (1) with propylene glycol methyl ether acetate and 1-methyl-2-pyrrolidone after, with phenolphthalein is indicator, determines with (the 50 weight %) aqueous solution titration of KOH ethanol.In addition, molecular weight is obtained by the gel permeation chromatography with RI (specific refractory power) detector by being elutriant with the tetrahydrofuran (THF).The molecular weight that below illustrates all is the weight-average molecular weight of polystyrene conversion.In addition, pass through from the importing rate of acrylic acid derivative group (after, only abbreviate the propylene rate sometimes as) ¹H-NMR (400MHz) obtains by whole proton areas of structural unit shown in the general formula (1) with from the distinctive peak area of the group of acrylic acid derivative.

Embodiment 1～13rd, and by the method shown in following [XV] method of manufacture method of the present invention, the synthetic example that contains the compound that structural unit forms shown in the following general formula (157) of the present invention is according to each embodiment, Z ₁The kind or the reaction conditions in temperature of reaction, reaction times etc. of 4 shown valency alkyl are different,

In the formula, R ⁸' and R ⁹' represent hydrogen atom or vinyl carbonyl, Z independently of one another ₁Same as described above with k.

Embodiment 1

＜1〉contains Z in the general formula (156) ₁Be synthetic (condensation reaction) of the compound that forms of the structural unit of 4 valency alkyl shown in the formula (29-1 ')

At 9 of 80.4g (0.160mol), 1-methyl-2-the pyrrolidone that adds 185.3g in 9-two (4-glycidoxypropyl phenyl) fluorenes, after dissolving this fluorene compound, in this solution, add 3 of 42.3g (0.128mol), 3 ', 4, the triethyl hexadecyldimethyl benzyl ammonium muriate of 4 '-biphenyltetracarboxyacid acid (BPTC) and 3.6g, stirred 4 hours down at 80 ℃, make it reaction.With the gained reaction solution with 1-methyl of 102.9g-2-pyrrolidone dilution, thereby obtain faint yellow transparent, contain the Z in the general formula (156) ₁Be the solution of the compound (resin) that forms of the structural unit of 4 valency alkyl shown in the formula (29-1 ').

＜2〉contain Z in the general formula (157) ₁Be synthetic (the propylene reaction) of the compound that forms of the structural unit of 4 valency alkyl shown in the formula (29-1 ')

In above-mentioned＜1〉containing in compound (resin) solution that structural unit forms shown in the general formula (156) of obtaining, add 30mg thiodiphenylamine and 38.9g triethylamine, stirred 10 minutes down at 0 ℃, in this solution, splash into 29.0g (0.320mol) acrylate chloride then.After splashing into end, stirred 2 hours down, make it reaction at 25 ℃.Splash into the gained reaction solution in 3.8kg water, crystallization is separated out, and filters, again with behind the 3.8kg washing net income crystallization precipitate, 25 ℃ of following drying under reduced pressure 20 hours, thus obtain 123g (yield: 98%) white, contain the Z in the general formula (157) ₁Be the compound (resin) that forms of the structural unit of 4 valency alkyl shown in the formula (29-1 ') in addition, by based on ¹The propylene rate that H-NMR data are obtained, when with the quantity of the biphenyl fluorenes in the entire infrastructure unit of general formula (157) during as 100mol, the propylene rate is 43mol% in the compound that obtains in the present embodiment.}。It is a resin 1.

In embodiment 2～13, as the tetracarboxylic acid shown in the above-mentioned general formula (110), the tetracarboxylic acid by the regulation shown in the use table 1 replaces the BPTC that uses among the embodiment 1, thereby synthetic containing in general formula (156) and (157) used Z ₁The compound of the structural unit that 4 valency alkyl of expression are different.In addition, by with reaction conditions { with respect to the usage quantity ratio of this tetracarboxylic acid of compound shown in the formula (154), reaction times when reaction times during condensation and propylene } according to changing shown in the table 1, thus different various of synthesising resistance (acid value of this compound, weight-average molecular weight and propylene rate) contain the compound that structural unit forms shown in the general formula (157).In addition, above-mentioned condition is in addition then carried out according to the method for embodiment 1.

Reaction conditions in each embodiment shown in the table 1 in addition, illustrates the rerum natura of the compound among the embodiment 1～13 in the lump in table 2.

In addition, mensuration is passed through embodiment 1～13 gained compound ¹H-NMR and IR. ¹Among H-NMR, can determine with from the proton peak and the distinctive proton peak of carboxyl of the distinctive vinylidene bonding of the group of acrylic acid derivative.In addition, in IR, can be at 1700cm ^-1Near the distinctive peak of affirmation carboxyl.In addition, with gained compound among the embodiment 3 ¹H-NMR data are shown among Fig. 1, and the IR data are shown among Fig. 3.

Table 1

Yield among these embodiment 2～13 is 95～100%.

(for the following embodiment that illustrates 14～37, its yield also is similarly 95～100% with above-mentioned, below yield is omitted record.)

BzPTC=3,3 ', 4,4 '-benzophenone tetracarboxylic acid

TTC=4-(1,2-dicarboxyl ethyl)-1,2,3,4-naphthane-1,2-dicarboxylic acid

Table 2

Embodiment No.	Resin No.	Acid value (mgKOH/g)	Weight-average molecular weight	Propylene rate (mol%)
Embodiment No.	Resin No.	Acid value (mgKOH/g)	Weight-average molecular weight	Propylene rate (mol%)	Embodiment 1	Resin 1	—	6000	43
Embodiment 2	Resin 2	—	8500	40	Embodiment 1	Resin 1	—	6000	43
Embodiment 2	Resin 2	—	8500	40	Embodiment 3	Resin 3	112	4600	40
Embodiment 4	Resin 4	113	6300	31	Embodiment 3	Resin 3	112	4600	40
Embodiment 4	Resin 4	113	6300	31	Embodiment 5	Resin 5	111	8300	36
Embodiment 6	Resin 6	103	9300	32	Embodiment 5	Resin 5	111	8300	36
Embodiment 6	Resin 6	103	9300	32	Embodiment 7	Resin 7	102	10100	31
Embodiment 8	Resin 8	132	4300	33	Embodiment 7	Resin 7	102	10100	31
Embodiment 8	Resin 8	132	4300	33	Embodiment 9	Resin 9	132	5000	71
Embodiment 10	Resin 10	131	6600	73	Embodiment 9	Resin 9	132	5000	71
Embodiment 10	Resin 10	131	6600	73	Embodiment 11	Resin 11	126	9900	68
Embodiment 12	Resin 12	104	7100	31	Embodiment 11	Resin 11	126	9900	68
Embodiment 12	Resin 12	104	7100	31	Embodiment 13	Resin 13	94	7000	27

As above shown in the table 1 and 2, result by embodiment 3～7 relatively can judge, reaction times during by the change condensation, easily synthetic molecular weight is different contains the compound (resin) that structural unit forms shown in the general formula (157), in addition, as can be known clear and definite relatively from the result of embodiment 3,8,12 and 13, by changing the usage quantity ratio of compound shown in tetracarboxylic acid shown in the general formula (110) and the formula (154), can easily synthesize acid value different contain the compound (resin) that structural unit forms shown in the general formula (157).Further, by embodiment 3,4,6 and 9～11 result is (embodiment 3 and 9 especially relatively, embodiment 4 and 10 and the result of embodiment 6 and 11 relatively) as can be known, the reaction times of containing acrylic acid derivative shown in structural unit forms shown in the general formula (156) compound and the formula (89) by change, easily the synthesizing propylene rate is different contains the compound (resin) that structural unit forms shown in the general formula (157), in addition, by the result of embodiment 1～3 more as can be known, even change the kind of tetracarboxylic acid, equally also can obtain to contain the compound (resin) that structural unit forms shown in the general formula (157) with good yield.

In addition, in the foregoing description 3～7,, but, also can control molecular weight by changing the concentration of tetracarboxylic acid shown in compound shown in temperature of reaction and the formula (154) and the general formula (110) by the different compound of change reaction times synthetic molecular weight.

Embodiment 14～23, are by synthesizing the example that contains the compound that structural unit forms shown in the following general formula (159) of the present invention as method shown in following [XVI] method of manufacture method of the present invention, according to each embodiment, Z ₁And Z ₃The 4 shown valency alkyl and the kind or the reaction conditions in temperature of reaction, reaction times etc. of divalent alkyl are different,

In the formula, R ⁸', R ⁹', Z ₁, Z ₃, k ' and k " same as described above.

Embodiment 14

＜1〉contains Z in the general formula (158) ₁Be 4 valency alkyl, Z shown in the formula (32) ₃Be synthetic (condensation reaction) of the compound that forms of the structural unit of divalent alkyl shown in the formula (56 ')

At 9 of 80.4g (0.160mol), 1-methyl-2-the pyrrolidone that adds 185.3g in 9-two (4-glycidoxypropyl phenyl) fluorenes, thereby after dissolving this fluorene compound, in this solution, add the cis-1 of 13.6g (0.080mol), 2,3, the triethyl hexadecyldimethyl benzyl ammonium muriate of 6-tetrahydrophthalic acid (CHEC) and 3.6g, and under 80 ℃, stirred 1 hour, make it reaction.Then add 4 of 26.9g (0.080mol)-(1,2-dicarboxyl ethyl)-1,2 in this solution, 3,4-naphthane-1,2-dicarboxylic acid stirred 8 hours down at 80 ℃, made it reaction.With 1-methyl of 102.9g-2-pyrrolidone dilution gained reaction solution, thus obtain faint yellow transparent, contain the Z in the general formula (158) ₁Be 4 valency alkyl, Z shown in the formula (32) ₃Be compound (resin) solution that the structural unit of divalent alkyl shown in the formula (56 ') forms.

＜2〉contain Z in the general formula (159) ₁Be 4 valency alkyl, Z shown in the formula (32) ₃Be synthetic (the propylene reaction) of the compound that forms of the structural unit of divalent alkyl shown in the formula (56 ')

In above-mentioned＜1〉containing in compound (resin) solution that structural unit forms shown in the general formula (158) of obtaining, add 30mg thiodiphenylamine and 38.9g triethylamine, and under 0 ℃, stirred 15 minutes, in this solution, splash into 29.0g (0.320mol) acrylate chloride then.After splashing into end, stirred 6 hours down, make it reaction at 25 ℃.The gained reaction solution is splashed in 3.8kg water, and crystallization is separated out, and filters, again with behind the 3.8kg washing net income crystallization precipitate, 25 ℃ of following drying under reduced pressure 20 hours, thus obtain white, contain the Z in the general formula (159) ₁Be 4 valency alkyl, Z shown in the formula (32) ₃Be the compound (resin) that forms of the structural unit of divalent alkyl shown in the formula (56 ') in addition, by based on ¹The propylene rate that H-NMR obtains, the quantity of the unitary biphenyl fluorenes of entire infrastructure of the compound formula of (159) that obtains in present embodiment are during as 100mol%, and the propylene rate is 64mol%}.With it as resin 14.

In embodiment 15～23, by as the tetracarboxylic acid shown in the above-mentioned general formula (110), the TTC that the tetracarboxylic acid of the regulation shown in the use table 3 replaces embodiment 14 to use, as the dicarboxylic acid shown in the above-mentioned general formula (121), the dicarboxylic acid of the regulation shown in the use table 3 replaces the CHEC of use among the embodiment 14, thus the synthetic Z that contains in general formula (158) and (159) ₁And Z ₃The compound that the 4 shown valencys structural unit different with the divalent alkyl forms.In addition, by change reaction conditions as shown in table 3ly { with respect to this tetracarboxylic acid of compound shown in the formula (154) and the usage quantity ratio of this dicarboxylic acid, reaction times during condensation and the reaction times of propyleneization }, thus different various of synthesising resistance (acid value of this compound, weight-average molecular weight and propylene rate) contain the compound that structural unit forms shown in the general formula (159).In addition, above-mentioned condition is in addition then carried out according to the method for embodiment 14.

Reaction conditions in each embodiment shown in the table 3, in addition, the rerum natura that contains the compound that structural unit forms shown in the general formula (159) in embodiment shown in the table 4 14～23.

In addition, to embodiment 14～23 gained compounds, also carried out ¹H-NMR and IR measure, its result, with the situation of the foregoing description 1～13 similarly, can confirm characteristic peak.

Table 3

The MA=toxilic acid

The TPA=terephthalic acid

^*=in the reaction times, so-called " zero+△ " is meant at first the compound shown in the formula (154) and dicarboxylic acid reaction after zero hour, are added tetracarboxylic acid in this solution, and △ hour (following identical) of reaction.

Table 4

Embodiment No.	Resin No.	Acid value (mgKOH/g)	Weight-average molecular weight	Propylene rate (mol%)
Embodiment No.	Resin No.	Acid value (mgKOH/g)	Weight-average molecular weight	Propylene rate (mol%)	Embodiment 14	Resin 14	111	5100	64
Embodiment 15	Resin 15	109	4800	72	Embodiment 14	Resin 14	111	5100	64
Embodiment 15	Resin 15	109	4800	72	Embodiment 16	Resin 16	97	4500	63
Embodiment 17	Resin 17	91	5500	34	Embodiment 16	Resin 16	97	4500	63
Embodiment 17	Resin 17	91	5500	34	Embodiment 18	Resin 18	98	6900	34
Embodiment 19	Resin 19	94	5300	33	Embodiment 18	Resin 18	98	6900	34
Embodiment 19	Resin 19	94	5300	33	Embodiment 20	Resin 20	89	4900	35
Embodiment 21	Resin 21	92	6500	34	Embodiment 20	Resin 20	89	4900	35
Embodiment 21	Resin 21	92	6500	34	Embodiment 22	Resin 22	82	7700	28
Embodiment 23	Resin 23	76	7300	29	Embodiment 22	Resin 22	82	7700	28

Shown in above-mentioned table 3 and 4, more as can be known,, can almost keep changing acid value under the constant state at this compound molecular weight by being used in combination tetracarboxylic acid and dicarboxylic acid by the result of embodiment 14～23.

Embodiment 24～38; By containing the compound that construction unit forms shown in the following general formula (160) with respect to of the present invention; Use various end structure compounds; And with as the method shown in following [XVII] method of manufacture method of the present invention; The molecular end of synthesizing at construction unit has imported A ' and A " shown in the example of compound shown in the following general formula (161) of group and (162); According to each embodiment; The kind of end structure compound or the reaction condition in reaction temperature, reaction time etc. are different

In the formula, R ¹⁶And R ¹⁷The group of representing hydrogen atom, formula (163) or formula (164) expression independently of one another; About A ' and A " shown in group; A when A ' is hydrogen atom " be the group shown in the formula (165), A when A ' is group shown in the general formula (166) " be hydroxyl; A when A ' is group shown in the general formula (167) " be group shown in the general formula (168), perhaps, A when A ' is group shown in the general formula (169) " be group shown in the general formula (170); Z ₂It is same as described above with k,

In the formula (166), Z ₂Same as described above;

In the formula (167), Z ₂Same as described above;

In the formula (168), Z ₂Same as described above;

In the formula (169), Z ₄Be group with formula (49 "), (56 ') or (56 ") expression;

In the formula (170), Z ₄Same as described above.

Embodiment 24

＜1〉Z in the general formula (161) ₂Be the structural unit of 4 valency alkyl shown in the formula (32), the group shown in the A ' is a hydrogen atom, A " shown in group be synthetic (condensation reaction) of the compound of group shown in the formula (165)

At 9 of 43.9g (0.10mol), 1-methyl-2-the pyrrolidone that adds 110.9g in 9-two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes (BPEF), thereby after dissolving this fluorene compound, in this solution, add 4 of 30.0g (0.10mol)-(1,2-dicarboxyl ethyl)-1,2, the dimethyl aminopyridine of 3,4-naphthane-1,2-dicarboxylic anhydride (TDA) and 0.6g, stirred 2 hours down at 80 ℃, make it reaction.Then in this solution, further add the BPEF of 8.8g (0.02mol) and 1-methyl-2-pyrrolidone of 13.2g, stirred 2 hours down, make it reaction, thereby obtain the Z in faint yellow transparent, the general formula (161) at 80 ℃ ₂Be the structural unit of 4 valency alkyl shown in the formula (32), the group shown in the A ' is a hydrogen atom, A " shown in group be the solution of the compound (resin) of group shown in the formula (165).

＜2〉Z in the general formula (162) ₂Be the structural unit of 4 valency alkyl shown in the formula (32), the group shown in the A ' is a hydrogen atom, A " shown in group be the compound synthetic (propylene reaction) of group shown in the formula (165)

In above-mentioned＜1〉containing in compound (resin) solution that structural unit forms shown in the general formula (151) of obtaining, add 100mg thiodiphenylamine, the glycidyl methacrylate of 14.2g (0.10mol) and 1-methyl-2-pyrrolidone of 21.3g, and under 80 ℃, stirred 6 hours, make it reaction.Behind 1-methyl-2-pyrrolidone dilution gained reaction solution with 150.0g, splash in the 1.6kg water, crystallization is separated out, and filter, after cleaning the gained crystallization precipitate with 50% methanol aqueous solution of 1.6kg and 1.6kg again, 25 ℃ of following drying under reduced pressure 20 hours, thereby obtain Z white, in the general formula (162) ₂The structural unit, the group shown in the A ' that are 4 valency alkyl shown in the formula (32) are hydrogen atom, A " shown in group be group shown in the formula (165) compound (resin) in addition, by based on ¹The propylene rate that H-NMR obtains, when will be in the quantity of the biphenyl fluorenes in the entire infrastructure unit of the compound formula of (162) that present embodiment obtains during as 100mol%, the propylene rate be 21mol%}.With it as resin 24.

In embodiment 25～30, by using TDA as the tetracarboxylic dianhydride shown in the above-mentioned general formula (135), use BPEF as the end structure compound, thereby synthesize the compound that has with embodiment 24 same structures, by change reaction conditions as shown in table 5ly { with respect to the usage quantity ratio of this tetracarboxylic dianhydride, end structure compound and the acrylic acid derivative of compound shown in the formula (155), reaction times during condensation and the reaction times of propyleneization }, thus this different compound of synthesising resistance (acid value of this compound, weight-average molecular weight and propylene rate).

In addition, reaction conditions in each embodiment shown in the table 5, in addition, among the embodiment 28～30,＜1〉condensation reaction in, use 1-methyl-2-pyrrolidone of 119.9g during reaction,＜2〉the propylene reaction in, the usage quantity of the thiodiphenylamine in the time of then will reacting and 1-methyl-2-pyrrolidone increases and decreases in proportion according to the use mole number of GMA.In addition, carry out according to the method for embodiment 24.

Table 5

Embodiment No.	Resin No.	Tetracarboxylic dianhydride's kind	The kind of end structure compound	The kind of acrylic acid derivative	Usage quantity is than { compound/tetracarboxylic dianhydride shown in the formula (155)/end structure compound/acrylic acid derivative }	Reaction times during condensation (h) ^*	Reaction times during propylene (h)
Embodiment No.	Resin No.	Tetracarboxylic dianhydride's kind	The kind of end structure compound	The kind of acrylic acid derivative		Reaction times during condensation (h) ^*	Reaction times during propylene (h)	Embodiment 25	Resin 25	TDA	BPEF	GMA	1/1/0.2/1.2	2+2	6
Embodiment 26	Resin 26	TDA	BPEF	GMA		1/1/0.2/1.4	2+2	Embodiment 25	Resin 25	TDA	BPEF	GMA	1/1/0.2/1.2	2+2	6	6
Embodiment 26	Resin 26	TDA	BPEF	GMA		1/1/0.2/1.4	2+2	Embodiment 27	Resin 27	TDA	BPEF	GMA	1/1/0.2/2	2+2	6	6
Embodiment 28	Resin 28	TDA	BPEF	GMA		1/1.2/0.2/1.2	2+2	Embodiment 27	Resin 27	TDA	BPEF	GMA	1/1/0.2/2	2+2	6	6
Embodiment 28	Resin 28	TDA	BPEF	GMA		1/1.2/0.2/1.2	2+2	Embodiment 29	Resin 29	TDA	BPEF	GMA	1/1.2/0.2/1.6	2+2	6	6
Embodiment 30	Resin 30	TDA	BPEF	GMA		1/1.2/0.2/2	2+2	Embodiment 29	Resin 29	TDA	BPEF	GMA	1/1.2/0.2/1.6	2+2	6	6

^*=in the reaction times, so-called " zero+△ ", be meant at first the compound shown in the formula (155) and tetracarboxylic dianhydride reacted zero hour after, in this solution, add the end structure compound, reacted △ hour.

Embodiment 31

＜1〉Z in the general formula (161) ₂Be the structural unit of 4 valency alkyl shown in the formula (32), the group shown in the A ' is the group shown in the general formula (166), A " be the compound synthetic (condensation reaction) of hydroxyl

1-methyl-2-the pyrrolidone that in the BPEF of 43.9g (0.10mol), adds 119.9g, thereby after dissolving this fluorene compound, in this solution, add the TDA of 30.0g (0.10mol) and the dimethyl aminopyridine of 0.6g, and stirred 2 hours down, make it reaction at 80 ℃.Then in this solution, further add the TDA of 6.0g (0.02mol) and 1-methyl-2-pyrrolidone of 9.0g, stirred 2 hours down at 80 ℃, make it reaction, the water that adds 2.16g (0.12mol) again, stir down reaction in 0.5 hour at 80 ℃, thereby obtain the Z in faint yellow transparent, the general formula (161) ₂Be the structural unit of 4 valency alkyl shown in the formula (32), the group shown in the A ' is the group shown in the general formula (166), A " be the solution of the compound (resin) of hydroxyl.

＜2〉Z in the general formula (162) ₂Be the structural unit of 4 valency alkyl shown in the formula (32), the group shown in the A ' is the group shown in the general formula (166), A " be synthetic (the propylene reaction) of the compound of hydroxyl

In above-mentioned＜1〉containing in compound (resin) solution that structural unit forms shown in the general formula (161) of obtaining, add 100mg thiodiphenylamine, the GMA of 14.2g (0.10mol) and 1-methyl-2-pyrrolidone of 21.3g, and make it reaction 80 ℃ of following stirrings 6 hours.Behind 1-methyl-2-pyrrolidone dilution gained reaction solution with 140.0g, splash in the 1.5kg water, crystallization is separated out, and filter, after 50% methanol aqueous solution of the water of usefulness 1.5kg and 1.5kg is cleaned the gained crystallization precipitate again, 25 ℃ of following drying under reduced pressure 20 hours, thereby obtain Z white, in the general formula (162) ₂Structural unit, the group shown in the A ' that is 4 valency alkyl shown in the formula (32) is group, the A shown in the general formula (166) " be hydroxyl compound (resin) in addition, by based on ¹The propylene rate that H-NMR obtains, the quantity of the biphenyl fluorenes in the entire infrastructure unit of the compound formula of (162) that obtains in present embodiment are during as 100mol%, and the propylene rate is 18mol%}.With it as resin 31.

In embodiment 32, by TDA+H as use among use of end structure compound and the embodiment 31 ₂TDA that O is identical and H ₂O, thereby the group shown in the A ' of synthetic this compound is group, the A shown in the general formula (166) " be the compound of hydroxyl.In addition, by change reaction conditions as shown in table 6ly { with respect to the usage quantity ratio of this tetracarboxylic dianhydride, end structure compound and the acrylic acid derivative of compound shown in the formula (155), reaction times during condensation and the reaction times of propyleneization }, thus this different compound of synthesising resistance (acid value of this compound, weight-average molecular weight and propylene rate).

In addition, the reaction conditions in embodiment shown in the table 6 32 is in addition, among the embodiment 32,＜2〉the propylene reaction in, the thiodiphenylamine during with reaction and the usage quantity of 1-methyl-2-pyrrolidone increase and decrease in proportion according to the use mole number of GMA.In addition, carry out according to the method for embodiment 31.

Table 6

Embodiment No.	Resin No.	Tetracarboxylic dianhydride's kind	The kind of end structure compound	The kind of acrylic acid derivative	Usage quantity is than { compound/tetracarboxylic dianhydride shown in the formula (155)/end structure compound/acrylic acid derivative }	Reaction times during condensation (h) ^*	Reaction times during propylene (h)
Embodiment No.	Resin No.	Tetracarboxylic dianhydride's kind	The kind of end structure compound	The kind of acrylic acid derivative		Reaction times during condensation (h) ^*	Reaction times during propylene (h)	Embodiment 32	Resin 32	TDA	TDA+H ₂O	GMA	1/1/0.2(TDA) +1.2(H ₂O)/2	2+2+0.5	6

^*=in the reaction times, so-called " 2+2+0.5 ", be meant at first the compound shown in the formula (155) and tetracarboxylic dianhydride reacted 2 hours after, in this solution, add end structure compound (TDA) and reacted 2 hours, add water at last and reacted 0.5 hour, thus to A ' and A " shown in the anhydride group of group be hydrolyzed.

Embodiment 33

＜1〉Z in the general formula (161) ₂Be the structural unit of 4 valency alkyl shown in the formula (32), the group shown in the A ' is the group shown in the general formula (167), A " be synthetic (condensation reaction) of the compound of group shown in the general formula (168)

1-methyl-2-the pyrrolidone that in 43.9g (0.10mol) BPEF, adds 110.9g, dissolve this fluorene compound after, in this solution, add 30.0g (0.10mol) TDA and 0.6g dimethyl aminopyridine, stirred 2 hours down at 80 ℃, make it reaction.Then in this solution, further add 1-methyl-2-pyrrolidone of 9.0g (0.03mol) TDA and 13.5g, stirred 2 hours down, make it reaction, thereby obtain the Z in faint yellow transparent, the general formula (161) at 80 ℃ ₂Structural unit, the group shown in the A ' that is 4 valency alkyl shown in the formula (32) is group, the A shown in the general formula (167) " be the solution of the compound (resin) of group shown in the general formula (168).

＜2〉Z in the general formula (162) ₂Be the structural unit of 4 valency alkyl shown in the formula (32), the group shown in the A ' is the group shown in the general formula (167), A " be synthetic (the propylene reaction) of the compound of group shown in the general formula (168)

In above-mentioned＜1〉containing in compound (resin) solution that structural unit forms shown in the general formula (161) of obtaining, after adding 1-methyl-2-pyrrolidone of 60mg thiodiphenylamine, 7.0g (0.06mol) Hydroxyethyl acrylate (HEA) and 10.5g, when 0 ℃ is stirred this solution down, add 12.4g (0.06mol) dicyclohexylcarbodiimide.Then, make this solution reach 25 ℃ with 30 minutes, further stirred 2 hours down, make it reaction synthermal.1-methyl-2-pyrrolidone dilution gained reaction solution with 130.0g, and filter this reaction solution, thereby after removing dicyclohexylurea (DCU), this filtered liquid is splashed in the 1.5kg water, carry out crystallization and separate out, filter, after 50% methanol aqueous solution of the water of usefulness 1.4kg and 1.4kg is cleaned the gained crystallization precipitate again, 25 ℃ of following drying under reduced pressure 20 hours, thereby obtain white, the Z in the general formula (162) ₂Structural unit, the group shown in the A ' that is 4 valency alkyl shown in the formula (32) is group, the A shown in the general formula (167) " be group shown in the general formula (168) compound (resin) in addition, by based on ¹The propylene rate that H-NMR obtains, in the compound that obtains in the present embodiment, under the situation of quantity as 100mol% of biphenyl fluorenes, the propylene rate is 17mol%} in the entire infrastructure unit of general formula (162).With it as resin 33.

In embodiment 34～37, the TDA that replaces use among the embodiment 33 by carboxylic acid anhydride as regulation shown in the end structure compound use table 7, thereby synthesized the group shown in the A ' is group, the A shown in the formula (167) " be the compound of group shown in the general formula (168), or the group shown in the A ' is group, the A shown in the formula (169) " be the compound of group shown in the general formula (170).In addition, by change reaction conditions as shown in table 7ly { with respect to the usage quantity ratio of this tetracarboxylic dianhydride, end structure compound and the acrylic acid derivative of compound shown in the formula (155), reaction times during condensation and the reaction times of propyleneization } as, thereby this different compound of rerum natura (acid value of this compound, weight-average molecular weight and propylene rate) synthesized.In addition, among the embodiment 34～37,＜1〉condensation reaction in, the usage quantity of the 1-methyl-2-pyrrolidone during with reaction increases and decreases in proportion according to the use mole number of end structure compound.＜2〉the propylene reaction in, with the usage quantity of thiodiphenylamine, dicyclohexylcarbodiimide and the 1-methyl-2-pyrrolidone in when reaction, increase and decrease in proportion according to the use mole number of HEA.In addition, carry out according to the method for embodiment 33.

Reaction conditions in each embodiment shown in the table 7 in addition, illustrates the rerum natura that contains the compound that structural unit forms shown in the general formula (162) among the embodiment 24～37 in the lump in table 8.

In addition, to embodiment 24～37 gained compounds, also carried out ¹H-NMR and IR measure, and its result similarly can confirm characteristic peak with the foregoing description 1～13 situation.In addition, shown in Figure 2 by embodiment 24 gained compounds ¹H-NMR data, IR data shown in Figure 4.

Table 7

Embodiment No.	Resin No.	Z ₄Kind	Tetracarboxylic dianhydride's kind	The kind of end structure compound	The kind of acrylic acid derivative	Usage quantity is than { compound/tetracarboxylic dianhydride shown in the formula (155)/end structure compound/acrylic acid derivative }	Reaction times during condensation (h) ^*	Reaction times during propylene (h)
Embodiment No.	Resin No.	Z ₄Kind	Tetracarboxylic dianhydride's kind	The kind of end structure compound	The kind of acrylic acid derivative		Reaction times during condensation (h) ^*	Reaction times during propylene (h)	Embodiment 34	Resin 34	—	TDA	TDA	HEA	1/1/0.3/1	2+2	2
Embodiment 35	Resin 35	Formula (56 ')	TDA	CHEA	HEA		1/1/0.8/1	2+2	Embodiment 34	Resin 34	—	TDA	TDA	HEA	1/1/0.3/1	2+2	2	2
Embodiment 35	Resin 35	Formula (56 ')	TDA	CHEA	HEA		1/1/0.8/1	2+2	Embodiment 36	Resin 36	Formula (56 ")	TDA	THPA	HEA	1/1/0.8/1	2+2	2	2
Embodiment 37	Resin 37	Formula (49 ")	TDA	PAN	HEA		1/1/0.8/1	2+2	Embodiment 36	Resin 36	Formula (56 ")	TDA	THPA	HEA	1/1/0.8/1	2+2	2	2

CHEA=cis-1,2,3,6-Tetra Hydro Phthalic Anhydride

THPA=3,4,5,6-Tetra Hydro Phthalic Anhydride

The PAN=Tetra hydro Phthalic anhydride

Table 8

Embodiment No.	Resin No.	Acid value (mgKOH/g)	Weight-average molecular weight	Propylene rate (mol%)
Embodiment No.	Resin No.	Acid value (mgKOH/g)	Weight-average molecular weight	Propylene rate (mol%)	Embodiment 24	Resin 24	103	4600	21
Embodiment 25	Resin 25	95	4600	26	Embodiment 24	Resin 24	103	4600	21
Embodiment 25	Resin 25	95	4600	26	Embodiment 26	Resin 26	89	4600	28
Embodiment 27	Resin 27	62	4600	41	Embodiment 26	Resin 26	89	4600	28
Embodiment 27	Resin 27	62	4600	41	Embodiment 28	Resin 28	113	6600	25
Embodiment 29	Resin 29	101	6100	34	Embodiment 28	Resin 28	113	6600	25
Embodiment 29	Resin 29	101	6100	34	Embodiment 30	Resin 30	87	6300	42
Embodiment 31	Resin 31	151	3400	18	Embodiment 30	Resin 30	87	6300	42
Embodiment 31	Resin 31	151	3400	18	Embodiment 32	Resin 32	126	3400	35
Embodiment 33	Resin 33	138	7000	17	Embodiment 32	Resin 32	126	3400	35
Embodiment 33	Resin 33	138	7000	17	Embodiment 34	Resin 34	118	7400	35
Embodiment 35	Resin 35	107	4000	35	Embodiment 34	Resin 34	118	7400	35
Embodiment 35	Resin 35	107	4000	35	Embodiment 36	Resin 36	109	7100	31
Embodiment 37	Resin 37	134	3500	26	Embodiment 36	Resin 36	109	7100	31

Shown in above-mentioned table 5～8, by the result of embodiment 24～27,28～30,31 and 32 and 33 and 34 more as can be known, by changing the usage quantity ratio of acrylic acid derivative to formula (155) compound, can easily synthesize acid value different contain the compound (resin) that structural unit forms shown in the general formula (162), and the result by embodiment 25 and 28 is as can be known clearer and more definite, by changing the usage quantity ratio of tetracarboxylic anhydride to formula (155) compound, easily synthetic molecular weight is different contains the compound (resin) that structural unit forms shown in the general formula (162).In addition, by the result of embodiment 24 and 31 more as can be known, by the end structure compound is changed into TDA+H by BPEF ₂O, need not to change under the situation of propylene rate, just can obtain acid value different contain the compound (resin) that structural unit forms shown in the general formula (162), in addition, by the result of embodiment 35～37 more as can be known, by the end structure compound is changed into dicarboxylic anhydride by tetracarboxylic anhydride, can obtain acid value, the molecular weight compound (resin) that contain general formula (162) shown in structural unit different with the propylene rate.

Embodiment 38

The thermal test of gained compound among the embodiment 3 and 24

Thermostability (thermotolerance) for gained compound in embodiment 3 and 24, by sealing pond differential scanning calorimetric measurement (SC-DSC) and differential scanning heat balance (TG-DSC) measure, its result, even under 300 ℃, do not find exothermal peak, endotherm(ic)peak and changes in weight yet, can judge under 300 ℃ high heat it is stable thus yet.Especially in embodiment 3, in the gained compound, also be stable about 350 ℃.Therefore, to contain pattern that this compound compositions solidify to form under 300 ℃ high heat condition, especially among the embodiment 3 the gained compound under 350 ℃ high heat condition, its thermotolerance is also excellent, and polymerizable unsaturated compound of the present invention is a useful compound in forming the high pattern of thermotolerance like this.In addition, thermostability (thermotolerance) data of gained compound among the embodiment 3 shown in Figure 5, thermostability (thermotolerance) data of gained compound among the embodiment 24 shown in Figure 6.

Embodiment 39

Use formation, hardness and the development test of the cured film of gained compound among the embodiment 3 and 24

＜1〉in 2.5g embodiment 3, adds 15g poly glycol monomethyl ether acetic ester in the gained compound, thereby after dissolving this compound, add the dilution of 1.5g pimelinketone again.Further, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1 (IRGCURE369 that チバスペシヤ Le テイケミカ Le ズ makes) that in this solution, adds 1.1g dipentaerythritol acrylate and 0.05g, and mixed, form uniform solution.Then, behind this solution of coating on the glass substrate, prebake on 90 ℃ hot plate (プレベ-Network) 1 minute is filmed thereby form.Then, being formed with on this glass substrate of filming,, use the UV lamp of wavelength 365nm to expose 3 minutes by mask.It was developed 1 minute in the potassium hydroxide aqueous solution of 0.05 weight %, after on 180 ℃ the hot plate, cured (Port ストベ-Network) 3 minutes, thereby obtain cured film.

＜2〉according to above-mentioned＜1 〉, use 2.5g by the compound that obtains among the embodiment 24, obtain same cured film.

＜3〉respectively to above-mentioned＜1〉and＜2〉the middle cured film mensuration pencil hardness that obtains, in addition, by the visual observation development.As a result, the pencil hardness of all cured film is 4H, does not find residue at the development position.

Thus, contain the composition that this compound forms, because its development excellence, therefore can not only form good pattern, and the gained pattern also has good hardness, polymerizable unsaturated compound of the present invention is to have good hardness, and the development excellent pattern form in useful compound.

Industrial utilizability

Polymerizable unsaturated compound of the present invention is to have the xenyl skeleton in construction unit, especially has fluorene skeleton, alkali-soluble, and the compound of excellent heat resistance, use contains the composition that this compound forms, when making it form pattern by light or heat, just can easily form the good pattern of heat resistance. In addition, manufacturing method according to the invention, can not produce that existing method has such as because at high temperature react the control difficulty, owing to side reaction causes the problems such as productive rate reduction, the adjustment that can produce molecular weight, acid value etc. is easy, and the good target compound that contains construction unit shown in the general formula (1) of productive rate.

Claims

1. compound, it is to comprise the compound that structural unit forms shown in the general formula (1),

—COOR ⁶ (2)

In the formula (3), R ⁷Expression vinyl carbonyl or pseudoallyl carbonyl, T ₃The expression carbonatoms is 1～6 straight chain shape alkylidene group,

In the formula (4), R ⁷Expression vinyl carbonyl or pseudoallyl carbonyl, T ₄The expression carbonatoms is 1～6 straight chain shape alkylidene group;

In the formula (5), R ⁸Expression hydrogen atom or R ⁷

In the formula (6), R ⁹Expression hydrogen atom or R ⁷

2, a kind of compound, it is to comprise the compound that structural unit forms shown in the general formula (7),

In the formula (7), R ¹, R ², R ¹' and R ²' represent hydrogen atom, halogen atom, alkyl or alkoxyl group, R independently of one another ³' and R ⁴' represent hydrogen atom, carboxyl or alkoxy carbonyl, T independently of one another ₁And T ₂Represent that independently of one another carbonatoms is 1～6 straight chain shape alkylidene group or arylidene, U represents singly-bound or with the divalent group of any expression in formula (1-1)～(1-8), V ₁And V ₂Represent independently of one another Sauerstoffatom or-NH-group, Y ₁' the expression Sauerstoffatom ,-NH-group or the group represented with formula (8), Y ₂' the expression Sauerstoffatom ,-NH-group or the group represented with formula (9), Z represents the alkyl of 4 valencys, and a and b represent 0 or 1 independently of one another, and k represents natural number, wherein, and in formula (7), R ³' and R ⁴' at least one be carboxyl or alkoxy carbonyl,

3, compound as claimed in claim 1, wherein, the structural unit shown in the general formula (1) is the structural unit with general formula (18) expression,

In the formula (18), R ¹, R ², R ¹', R ²', R ³, R ⁴, R ⁸, R ⁹, T ₁, T ₂, U, V ₁, V ₂, Z is identical with above-mentioned definition with k.

4, compound as claimed in claim 1, wherein, the structural unit shown in the general formula (1) is the structural unit with general formula (19) expression,

In the formula (19), Y ₁", Y ₂" represent independently of one another Sauerstoffatom or-NH-group, R ¹, R ², R ¹', R ²', R ³, R ⁴, T ₁, T ₂, U, V ₁, V ₂, Z, a, b be identical with above-mentioned definition with k.

5, compound as claimed in claim 2, wherein, the structural unit shown in the general formula (7) is the structural unit with general formula (20) expression,

In the formula (20), R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z is identical with above-mentioned definition with k.

6, compound as claimed in claim 2, wherein, structural unit shown in the general formula (7) is the structural unit with general formula (21) expression,

In the formula (21), Y ₁", Y ₂" represent independently of one another Sauerstoffatom or-NH-group, R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z, a, b be identical with above-mentioned definition with k.

7, a kind of manufacture method of compound, this compound are to comprise the compound that structural unit forms shown in the general formula (1),

—COOR ⁶ (2)

In the formula (5), R ⁸Expression hydrogen atom or R ⁷

In the formula (6), R ⁹Expression hydrogen atom or R ⁷, it is characterized in that,

At least a above (methyl) acrylic acid derivative that comprises the compound that structural unit forms shown in the general formula (7) and be selected from general formula (10), general formula (11) and the general formula (12) is reacted,

R ⁷—X (10)

In the formula (10), R ⁷Expression vinyl carbonyl or pseudoallyl carbonyl, X represents halogen atom;

In the formula (11), R ⁷Expression vinyl carbonyl or pseudoallyl carbonyl, T ₃The straight chain shape alkylidene group of expression carbonatoms 1～6;

In the formula (12), R ⁷Expression vinyl carbonyl or pseudoallyl carbonyl, T ₄The straight chain shape alkylidene group of expression carbonatoms 1～6.

8, a kind of manufacture method of compound, this compound are to comprise the compound that structural unit forms shown in the general formula (7),

In the formula (1-1), R ₅And R ⁵' represent hydrogen atom or halogen atom independently of one another;

It is characterized in that,

Compound shown in the general formula (13) and polyprotonic acid or its acid anhydrides with 3 above carboxyls are reacted, wherein, described polyprotonic acid comprises that the part of carboxyl is the material of carboxylicesters, described acid anhydrides comprises that the part of carboxyl forms the material of anhydride group through dehydrating condensation, a part that also comprises carboxyl is the material of carboxylicesters

In the formula (13), R ¹, R ², R ¹' and R ²' represent hydrogen atom, halogen atom, alkyl or alkoxyl group, R independently of one another ¹⁰The group of expression hydrogen atom, alkali metal atom, general formula (14) or general formula (15) expression, R ¹¹The group of expression hydrogen atom, alkali metal atom, general formula (16) or general formula (17) expression, U are represented singly-bound or with the divalent group of any expression in formula (1-1)～(1-8), V ₁And V ₂Represent independently of one another Sauerstoffatom or-NH-group,

In the formula (14), T ₁The expression carbonatoms is 1～6 straight chain shape alkylidene group or arylidene;

In the formula (15), M ₁Expression hydrogen atom or alkali metal atom, T ₁The expression carbonatoms is 1～6 straight chain shape alkylidene group or arylidene, V ₃The expression Sauerstoffatom or-NH-group;

In the formula (16), T ₂The expression carbonatoms is 1～6 straight chain shape alkylidene group or arylidene;

In the formula (17), M ₂Expression hydrogen atom or alkali metal atom, T ₂The expression carbonatoms is 1～6 straight chain shape alkylidene group or arylidene, V ₄The expression Sauerstoffatom or-NH-group;

In the formula (1-1), R ⁵And R ⁵' represent hydrogen atom or halogen atom independently of one another.

9, manufacture method as claimed in claim 7 wherein, comprises the compound that structural unit forms shown in the general formula (7) and obtains by the described manufacture method of claim 8.

10, manufacture method as claimed in claim 7, wherein, structural unit shown in the general formula (7) is the structural unit shown in the general formula (20), structural unit shown in the general formula (1) is the structural unit shown in the general formula (18),

In the formula (20), R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z is identical with above-mentioned definition with k;

11, manufacture method as claimed in claim 7, wherein, structural unit shown in the general formula (7) is the structural unit shown in the general formula (21), (methyl) acrylic acid derivative is at least a above material that is selected from general formula (11) and the general formula (12), structural unit shown in the general formula (1) is the structural unit shown in the general formula (19)

In the formula (21), Y ₁" and Y ₂" represent independently of one another Sauerstoffatom or-NH-group, R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z, a, b be identical with above-mentioned definition with k;

In the formula (11), R ⁷And T ₃Identical with above-mentioned definition;

In the formula (12), R ⁷And T ₄Identical with above-mentioned definition;

In the formula (19), Y ₁" and Y ₂" represent independently of one another Sauerstoffatom or-NH-group, R ¹, R ², R ¹', R ²', R ³, R ⁴, T ₁, T ₂, U, V ₁, V ₂, Z, a, b be identical with above-mentioned definition with k.

12, manufacture method as claimed in claim 8, wherein, compound shown in the general formula (13) is the compound shown in the general formula (22), the acid of reacting with this compound is the polyprotonic acid with 3 above carboxyls, described polyprotonic acid comprises that the part of carboxyl is the material of carboxylicesters, structural unit shown in the general formula (7) is the structural unit shown in the general formula (20)

In the formula (22), R ¹, R ², R ¹', R ²', T ₁, T ₂, U, V ₁And V ₂Identical with above-mentioned definition;

13, manufacture method as claimed in claim 8, wherein, compound shown in the general formula (13) is the compound shown in the general formula (23), the acid of reacting with this compound is the multi-anhydride with 3 above carboxyls, described acid anhydrides comprises that a part of dehydrating condensation of carboxyl forms the material of anhydride group, a part that also comprises carboxyl is the material of carboxylicesters, and structural unit shown in the general formula (7) is the structural unit shown in the general formula (21)

In the formula (23), R ¹²Group shown in expression hydrogen atom, alkali metal atom or the general formula (15), R ¹³Group shown in expression hydrogen atom, alkali metal atom or the general formula (17), R ¹, R ², R ¹', R ²', U, V ₁And V ₂It is identical with above-mentioned definition,

In the formula (15), M ₁, T ₁And V ₃Identical with above-mentioned definition;

In the formula (17), M ₂, T ₂And V ₄Identical with above-mentioned definition;

In the formula (21), Y ₁" and Y ₂" represent independently of one another Sauerstoffatom or-NH-group, R ¹, R ², R ¹', R ²', R ³', R ⁴', T ₁, T ₂, U, V ₁, V ₂, Z, a, b be identical with above-mentioned definition with k.