CN101379111B - Polymerizable unsaturated compound and method for producing the same - Google Patents
Polymerizable unsaturated compound and method for producing the same Download PDFInfo
- Publication number
- CN101379111B CN101379111B CN2007800045509A CN200780004550A CN101379111B CN 101379111 B CN101379111 B CN 101379111B CN 2007800045509 A CN2007800045509 A CN 2007800045509A CN 200780004550 A CN200780004550 A CN 200780004550A CN 101379111 B CN101379111 B CN 101379111B
- Authority
- CN
- China
- Prior art keywords
- formula
- general formula
- group
- expression
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 CC[C@@]1C[C@@](C2)[C@@]2*C1 Chemical compound CC[C@@]1C[C@@](C2)[C@@]2*C1 0.000 description 6
- PWWSXAZZCKGJRF-ZPOWTRSPSA-N C/C=C(\C=C(\C)/C=C)/S(c1ccccc1)(=N)=O Chemical compound C/C=C(\C=C(\C)/C=C)/S(c1ccccc1)(=N)=O PWWSXAZZCKGJRF-ZPOWTRSPSA-N 0.000 description 1
- UTGJSPOKMBYZKF-UHFFFAOYSA-N CC1(C=NC=CC=C1)C(O)=O Chemical compound CC1(C=NC=CC=C1)C(O)=O UTGJSPOKMBYZKF-UHFFFAOYSA-N 0.000 description 1
- RIRARCHMRDHZAR-UHFFFAOYSA-N CC1C(C)CCC1 Chemical compound CC1C(C)CCC1 RIRARCHMRDHZAR-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/547—Hydroxy compounds containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Resins (AREA)
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
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, the adjustment such as polymerizable unsaturated compound and molecular weight, acid value that can form good pattern are easily, and the easy method of manufacture 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 resist or the PC board that can be used as liquid-crystal apparatus for example etc. made.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, methylacrylic 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, makes 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 property unsaturated compound (resin) and acid value etc.Under this situation, expectation is developed and can under the temperature condition of gentleness, be carried out, and molecular weight control is easy to have the method for manufacture of the polymerizable unsaturated compound (resin) of fluorene skeleton etc.
Patent documentation 1:JP spy opens flat 5-339356 communique
Patent documentation 2:JP spy opens flat 7-92674 communique
Patent documentation 3:JP spy opens flat 8-278630 communique
Patent documentation 4:JP spy opens the 2003-165830 communique
Patent documentation 5:JP spy opens flat 11-231523 communique
Summary of the invention
The problem that invention will solve
The present 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 method for manufacture of the polymerizable unsaturated compound (resin) of fluorene skeleton etc. at low temperatures.
Be used to solve the method for problem
The present invention provides and comprises 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 Wasserstoffatoms, halogen atom, alkyl or alkoxyl group, R independently of one another
3And R
4Represent Wasserstoffatoms 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 representes singly-bound or with the divalent group of any expression in the formula (1-1)～(1-8), V
1And V
2Represent independently of one another Sauerstoffatom or-the 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 representes the alkyl of 4 valencys, and a and b represent 0 or 1 independently of one another, and k representes natural number, wherein, and in the formula (1), R
6, R
8, R
9In any at least one be group with two keys;
-COOR
6(2)
In the formula (2), R
6Expression Wasserstoffatoms, 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 Wasserstoffatoms or halogen atom independently of one another;
In the formula (5), R
8Expression Wasserstoffatoms or R
7
In the formula (6), R
9Expression Wasserstoffatoms or R
7
In addition, the present invention provides and comprises the compound that the structural unit with general formula (7) expression forms,
In the formula (7), R
3' and R
4' represent Wasserstoffatoms, 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 present invention provides the method for manufacture 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 representes 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 method for manufacture that comprises the compound that structural unit forms shown in the above-mentioned general formula (7), it is characterized in that, makes compound shown in the general formula (13) and polyprotonic acid or its anhydride reaction with 3 above carboxyls; Wherein, Said polyprotonic acid comprises that the part of carboxyl is the material of carboxylicesters, and said 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 Wasserstoffatoms, alkali metal atom, general formula (14) or general formula (15) expression, R
11Be the group of Wasserstoffatoms, 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 Wasserstoffatoms or alkali metal atom, V
3The expression Sauerstoffatom or-the NH-group, T
1Same as described above;
In the formula (16), T
2Same as described above;
In the formula (17), M
2Expression Wasserstoffatoms or alkali metal atom, V
4The expression Sauerstoffatom or-the NH-group, T
2Same as described above.
The invention effect
Polymerizable unsaturated compound of the present invention is in structural unit, to have the xenyl skeleton; 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 through 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 and have, 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' alkyl of expression, can enumerate straight chain shape, branched or cyclic, usually carbonatoms is 1～4, 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' alkoxyl group of expression, can enumerate straight chain shape, branched or cyclic, usually carbonatoms is 1～4, 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', Wasserstoffatoms more preferably.
The bonding position of U and phenyl ring does not have special qualification 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 formula (1-1) and (1-7) shown in the divalent group, wherein, further be preferably with 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 Wasserstoffatoms.
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; Can be straight chain shape, branched 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-methylbutyl, 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; Like 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 representes 1～3 integer, wherein, in formula (31), 4 singly-bounds can be bonded on any carbon in the naphthenic base 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, the further preferred group of representing with formula (26 ').
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 formula (25), (29-1) or (29-3) group of expression, further preferred with formula (29-1) or the group (29-3) represented.
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.
As 4 valency alkyl with the aliphatic category of general formula (31) expression, can enumerate h usually 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.
In the method for manufacture of stating after 4 valency alkyl of these aromatic series or aliphatic category come from that comprises the compound that structural unit forms shown in the general formula (7) with the polyprotonic acid with 3 above carboxyls (part that comprises carboxyl is the material of carboxylicesters) of 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; Can be straight chain shape, branched 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-methylbutyl, 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 representing with general formula (3) or general formula (4).
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 straight chain shape, branched 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, positive propoxy carbonyl, isopropoxy carbonyl, ring propoxycarbonyl, n-butoxy carbonyl, isobutoxy carbonyl, sec.-butoxy carbonyl, tert-butoxycarbonyl, cyclobutoxy group carbonyl, n-pentyloxy carbonyl, isopentyloxy carbonyl, secondary pentyloxy carbonyl, tert-pentyloxy carbonyl, neopentyl oxygen carbonyl, 2-methyl butoxy carbonyl, 1-ethyl propoxycarbonyl, 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, positive propoxy carbonyl, isopropoxy carbonyl, ring propoxycarbonyl, n-butoxy carbonyl, isobutoxy carbonyl, sec.-butoxy carbonyl, tert-butoxycarbonyl, cyclobutoxy group carbonyl, more preferably methoxycarbonyl, ethoxy carbonyl.
As the Y in the general formula (7)
1', more preferably the group shown in Sauerstoffatom or the formula (8) further is preferably the group shown in the formula (8).
As the Y in general formula (7)
2', more preferably the group shown in Sauerstoffatom or the formula (9) further is preferably the 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
22 single bonded bonding positions of arylidene of expression do not have special qualification, 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, the group of especially preferably using general formula (14) to represent with general formula (14) or (15) 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, the group of especially preferably using general formula (16) to represent with general formula (16) or (17) expression.
As the M in general formula (15) and (17)
1And M
2, Wasserstoffatoms 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 with general formula (18) expression 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-the 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 and be with the formula (1-1) or (1-7) material of the divalent group of 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 Wasserstoffatoms.
In general formula (41); Usually so long as use 4 valency alkyl that Z representes 4 valency alkyl as aromatic series or aliphatic category; Just there is not special qualification; For example, in 4 valency alkyl, preferably use above-mentioned formula (25) or (26) with the aromatic series of above-mentioned general formula (25)～(33) expressions or aliphatic category, with above-mentioned general formula (29) or the group represented with above-mentioned formula (32), (33).
As the preferred especially 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 and be with the formula (1-1) or (1-7) structural unit of the divalent group of 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 Wasserstoffatoms.
In general formula (46); Usually so long as use 4 valency alkyl that Z representes 4 valency alkyl as aromatic series or aliphatic category; Just there is not special qualification; 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 preferred especially 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, do not have special qualification so long as be set at; But be generally 70～150mgKOH/g, be preferably 80～130mgKOH/g.At this,, then for example using the resin combination that obtains by this compound to prepare under the situation of colour filter if contain the not enough 70mgKOH/g of the acid value of the compound that structural unit forms shown in the general formula (1); 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 show with the mg numerical table of the necessary Pottasium Hydroxide of this compound of 1g, usually, can obtain through 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 is used at this compound under the situation of various uses shown in the general formula (1), can obtain suitable performance as long as be set at; Do not have special qualification, 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 not special qualification; 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 can be with other structural unit as composition, specifically except shown in the general formula (1) the structural unit; 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 the divalent alkyl of aromatic series or aliphatic category can be enumerated, specifically, the for example divalent alkyl of the fragrant same clan of formula (49)～(51), general formula (52) or (53) expression can be enumerated; 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 representes 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 divalent alkyl, more preferably use the group of formula (49 ') or (49 ") expression with the fragrant same clan of formula (49) expression.
As divalent alkyl, more preferably use the group of formula (50 '), (50 ") or (50 " ') expression with the fragrant same clan of formula (50) expression.
In the divalent alkyl of the fragrant same clan that representes 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 representes 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 representes 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 representes 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 representes 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 representes 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 representes 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 representes 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 representes 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, the group of promptly preferably using formula (49), (53-1) or (53-3) representing, the group of further preferably representing with formula (49).
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 representes 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 2, the divalent alkyl of the aliphatic category of 3-propenylidene (1-propane-2,3-two bases) can be enumerated the 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 divalent alkyl with the fragrant same clan of formula (56) expression, more preferably use the group of formula (56 ') or (56 ") expression, wherein, further be preferably the group of representing with formula (56 ').
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, that is, preferably use the group of formula (54-2 '), (54-2 "), (56 ') or (56 ") expression with the group of formula (56) expression.
The divalent alkyl of these aromatic series or aliphatic category the use by oneself aromatic series with 2 carboxyls or the aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) of general formula (57) expression 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 ") do not have special qualification, 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 Wasserstoffatoms.
In general formula (60); Usually; The 4 valency alkyl of representing with Z are not so long as 4 valency alkyl of aromatic series or aliphatic category just have special qualification, for example; In 4 valency alkyl of above-mentioned aromatic series or 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 not so long as the divalent alkyl of aromatic series or aliphatic category just has special qualification, 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 preferred especially 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 structural unit shown in the general formula (43) and the 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 Wasserstoffatoms.
In general formula (64); Usually; The 4 valency alkyl of representing with Z are not so long as 4 valency alkyl of aromatic series or aliphatic category just have special qualification, for example; In 4 valency alkyl of above-mentioned aromatic series or 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 not so long as the divalent alkyl of aromatic series or aliphatic category just has special qualification, 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, and for example; The k ' of the expression polymerization degree representes 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 to be used for the quantity of the structural unit of Z ' under the situation of various uses; can obtain suitable performance as long as set for, not have special qualification at this compound, 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)-random structure shown in repeating structure, the block structure shown in the general formula (66) or the general formula (67) of AB-constitutes this compound, further, can also be except A with the 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 with general formula (20) expression 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.
As the preferred concrete example of structural unit shown in the general formula (20), can enumerate U and be formula (1-1) or (1-7) shown in the structural unit of divalent group, 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 Wasserstoffatoms.
In general formula (71); Usually; The 4 valency alkyl of representing with Z are not so long as 4 valency alkyl of aromatic series or aliphatic category just have special qualification, 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 preferred especially 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.
As the preferred concrete example of structural unit shown in the general formula (21), can enumerate U and be formula (1-1) or (1-7) shown in the structural unit of divalent group, 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 Wasserstoffatoms.
In general formula (76); Usually; The 4 valency alkyl of representing with Z are not so long as 4 valency alkyl of aromatic series or aliphatic category just have special qualification, 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 preferred especially 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 representes in the entire infrastructure unit in this compound; Contain the quantity of 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; Do not have special qualification, 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 (7) is used under the situation of various uses at this compound; Can obtain suitable performance as long as set for; There is not special qualification; 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, be 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 as other 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 Wasserstoffatoms.
In general formula (80); Usually; The 4 valency alkyl of representing with Z are not so long as 4 valency alkyl of aromatic series or aliphatic category just have special qualification, 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 not so long as the divalent alkyl of aromatic series or aliphatic category just has special qualification, 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 preferred especially 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 structural unit shown in the general formula (73) and the compound that this structural unit forms, and 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 Wasserstoffatoms.
In general formula (84); Usually; The 4 valency alkyl of representing with Z are not so long as 4 valency alkyl of aromatic series or aliphatic category just have special qualification, 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 not so long as the divalent alkyl of aromatic series or aliphatic category just has special qualification, 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 like 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, and for example; The k ' of the expression polymerization degree representes to contain the structural unit quantity of Z, k in the entire infrastructure unit of this compound in general formula (78) and (82) " represent in the entire infrastructure unit of this compound; contain the structural unit quantity of Z ', be used at this compound under the situation of various uses, can obtain suitable performance as long as set for; do not have special qualification, 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 ' with the 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 method for manufacture that contains the compound that structural unit forms shown in general formula (1) and (7), promptly, method of manufacture of the present invention is carried out detailed explanation.As the method for manufacture 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 be selected from (methyl) acrylic acid derivative more than at least a kind in general formula (10), (11) and (12) as long as make; In the presence of solvent as required, react and get final product, as concrete method of manufacture, 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 in hydroxyl and/or carboxyl, imports the compound that the structural unit from the group of this (methyl) acrylic acid derivative forms 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 combination more than 2 of (methyl) acrylic acid derivative that will contain useful general formula (10) expression is used; Preferably at first make and contain that (methyl) acrylic acid derivative reacts 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 { material of for example, representing } reaction with general formula (11) or (12).If (methyl) acrylic acid derivative shown in the general formula (10) is mixed with other (methyl) acrylic acid derivative; Two kinds of verivates are reacted in the lump; Because the reactivity of (methyl) acrylic acid derivative shown in the general formula (10) is higher than other (methyl) acrylic acid derivative; 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, the result, the productive rate that causes containing the compound that structural unit forms shown in the general formula (18) reduces.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, follows and the reaction of (methyl) acrylic acid derivative shown in the general formula (10).
In addition; Use in combination under the situation of (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 method of manufacture 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) react, 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 use solvent cut as required with containing the compound 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 in the purpose purposes, use, and also can separate containing the compound that structural unit forms shown in the general formula (88), make with extra care through 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 article, also can suitably use through 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 not special the qualification, for example; Be generally 0～50 ℃, be preferably 10～30 ℃.If temperature of reaction surpasses 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 in solvent, carry out, but preferably in solvent, carries out.
As solvent; As long as each composition that uses in can solubilizing reaction and reaction product, can and be not water miscible to the bad influence of reaction generation; Just there is not special qualification, specifically, for example; Can enumerate N, aprotic polar solvents such as dinethylformamide, 1-Methyl-2-Pyrrolidone, propylene glycol methyl ether acetate, methyl-sulphoxide 、 diox, MIBK, gamma-butyrolactone, ethyl lactate, pimelinketone.These solvents can be distinguished independent use, or combination more than 2 kinds is used, about the usage quantity of above-mentioned solvent, so long as the amount of ability dissolving raw material does not just have special qualification.
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 independent use, or combination more than 2 kinds is used, and the equivalents of above-mentioned alkali is not had special qualification, 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 quaternary ammonium salt or the triphenylphosphine etc. of TBuA muriate, TBuA bromide, triethyl hexadecyldimethyl benzyl ammonium muriate, triethyl hexadecyldimethyl benzyl ammonium bromide etc.These catalyzer can be distinguished independent use; Or with combination use more than 2 kinds; Usage quantity to above-mentioned catalyzer does not have special qualification, 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 t butyl phenol, thiodiphenylamine, benzophenone etc.These stoppers can be distinguished independent use; Or with combination use more than 2 kinds; Usage quantity to above-mentioned stopper does not have special qualification, 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 through 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 through 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.Compound obtaining through present method is used under the situation of various uses; As long as setting for, the group import volume of acrylic acid derivative can obtain suitable performance from this (methyl); There is not special qualification; But the hydroxyl mol amount with respect to containing the compound that structural unit forms shown in the general formula (20) is generally 1～100mol%, is 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 make it to produce down in little light irradiation crosslinked, curing, 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 method of manufacture 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 situation 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 Wasserstoffatoms, a and b are 1 situation.
As the preferred concrete example of method of manufacture 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 method for manufacture that a and b in general formula (19) and (21) is the compound that forms of 1 formation unit.
Wherein, above-mentioned [V] method is carried out detailed explanation.For example; [V] method is to use solvent cut with containing the compound 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 like 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 in the purpose purposes, use, and also can through 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 with behind the solvent cut reaction solution, and as required with the residue of condensing agent through after filtering removal, filtrating 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) propenoate, 1,2-epoxy-4-butyl (methyl) propenoate, 1,2-epoxy-5-amyl group (methyl) propenoate, 1; 2-epoxy-6-hexyl (methyl) propenoate, 1,2-epoxy-7-heptyl (methyl) propenoate, 1,2-epoxy-8-octyl group (methyl) propenoate etc. 1; 2-epoxy-ω-alkyl (methyl) propenoate; Wherein, preferred glycidyl (methyl) propenoate, 1,2-epoxy-4-butyl (methyl) propenoate, 1; 2-epoxy-5-amyl group (methyl) propenoate, more preferably glycidyl (methyl) propenoate.
In [V] method; As (methyl) acrylic acid derivative shown in the general formula (12); For example; Can enumerate ω-hydroxyl-1-(methyl) alkyl acrylate of 1-hydroxyl (methyl) methyl acrylate, 2-hydroxyl-1-(methyl) ethyl propenoate, 3-hydroxyl-1-(methyl) propyl acrylate, 4-hydroxyl-1-(methyl) Bing Xisuandingzhi, 5-hydroxyl-1-(methyl) vinylformic acid pentyl ester, 6-hydroxyl-1-(methyl) NSC 11786 etc.; Wherein, preferred 2-hydroxyl-1-(methyl) ethyl propenoate, 3-hydroxyl-1-(methyl) propyl acrylate, 4-hydroxyl-1-(methyl) Bing Xisuandingzhi, 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 article, can also suitably use through normally used method of manufacture synthetic material in this field.
(methyl) acrylic acid derivative shown in the general formula (12) both can use commercially available article, can also suitably use through normally used method of manufacture 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 not special qualification; 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, be set in usually 0.5～50 hour, preferably set at 0.5～20 hour, more preferably be set in 0.5～10 hour scope.
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 Carbodiimides such as dicyclohexyl carbodiimide, 1-ethyl-3-[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 independent use, or combination more than 2 kinds is used, and the equivalents of above-mentioned condensing agent is not had special qualification, 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 quaternary ammonium salt or the triphenylphosphine etc. of TBuA muriate, TBuA bromide, triethyl hexadecyldimethyl benzyl ammonium muriate, triethyl hexadecyldimethyl benzyl ammonium bromide etc.These catalyzer can be distinguished independent use; Or with combination use more than 2 kinds; Usage quantity to above-mentioned catalyzer does not have special qualification, 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 and gets final product with the identical stopper of above-mentioned [III] method, and the usage quantity of stopper also can be and the identical amount of above-mentioned [III] method.
[V] method is through 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; Through 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 through 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 not special qualification; But the carboxyl mol amount with respect to containing the compound that structural unit forms shown in the general formula (91) is generally 1～100mol%, is 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 to 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 the little light irradiation, can make it crosslinked, solidify, 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 method of manufacture 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 situation.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 Wasserstoffatoms, Y
1And Y
2Be Sauerstoffatom or-NH-group, a and b are 1 situation.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 Wasserstoffatoms, Y
1And Y
2Be Sauerstoffatom or-NH-group, a and b are 1 situation.
As the method for manufacture that contains the compound that structural unit forms shown in the general formula (7) of the present invention; So long as can make compound shown in the general formula (13) and the polyprotonic acid (part that comprises carboxyl is the material of carboxylicesters) with 3 above carboxyls 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 method of manufacture; 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 Wasserstoffatoms, alkali metal atom or the group of representing with above-mentioned general formula (15), R
13Expression Wasserstoffatoms, 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 carried out detailed explanation.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 following normal general formula of 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 in the purpose purposes, use, and 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) through ordinary method.
In [VIII] method, as compound shown in the general formula (22), for example; Can enumerate compound and epoxy chloropropane, epoxy bromopropane, 4-chloro-1 through making the xenyl skeleton shown in (98) that has general formula, 2-butylene oxide ring, 4-bromo-1,2-butylene oxide ring, 5-chloro-1; 2-epoxy pentane, 5-bromo-1,2-epoxy pentane, 6-chloro-1,2-epoxy hexane, 6-bromo-1; 2-epoxy hexane, 7-chloro-1,2-epoxy heptane, 7-bromo-1,2-epoxy heptane, 8-chloro-1; 2-octylene oxide, 8-bromo-1, the compound that ω such as 2-octylene oxide-the halogenated epoxide reaction obtains, wherein; Preferably compound through making the xenyl skeleton shown in (98) that has general formula and epoxy chloropropane, epoxy bromopropane, 4-chloro-1,2-butylene oxide ring, 4-bromo-1,2-butylene oxide ring, 5-chloro-1; 2-epoxy pentane, 5-bromo-1; The compound that the ω of 2-epoxy pentane-halogenated epoxide reaction obtains is more preferably through making the compound of the compound of xenyl skeleton shown in (98) that has general formula and the ω of epoxy chloropropane, epoxy bromopropane-halogenated epoxide reaction acquisition
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 through the divalent group crosslinking structure shown in singly-bound or the 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 with this xenyl skeleton when being formula (1-1) as U for example, can enumerate 9, two (4-hydroxy phenyl) fluorenes, 9 of 9-; Two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3, the 5-dichlorophenyl) fluorenes, 9 of 9-; Two (4-hydroxyl-3, the 5-dibromo phenyl) fluorenes, 9 of 9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-chloro-phenyl-) fluorenes, 9 of 9-; Two (4-hydroxyl-3-bromophenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-fluorophenyl) fluorenes, 9 of 9-, two (the 4-hydroxy 3-methoxybenzene base) fluorenes, 9 of 9-, two (4-aminophenyl) fluorenes, 9 of 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, two (4-amino-3-aminomethyl phenyl) fluorenes, 9 of 9-, two (4-amino-3-chloro-phenyl-) fluorenes, 9 of 9-; Two (4-amino-3-bromophenyl) fluorenes, 9 of 9-, two (4-amino-3-fluorophenyl) fluorenes, 9 of 9-, two (4-amino-3-p-methoxy-phenyl) fluorenes of 9-etc.
In addition, this when having substituent fluorenes ring { formula (1-1) } such as halogen atom has the concrete example of the compound of xenyl skeleton, for example, can enumerate 2,7-two bromo-9, two (4-hydroxy phenyl) fluorenes, 2 of 9-; 7-two bromo-9, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) fluorenes, 2 of 9-, 7-two bromo-9, two (the 4-hydroxyls-3 of 9-; The 5-dichlorophenyl) fluorenes, 2,7-two bromo-9, two (4-hydroxyl-3, the 5-dibromo phenyl) fluorenes, 2 of 9-, 7-two bromo-9; Two (the 4-hydroxy-3-methyl phenyl) fluorenes, 2 of 9-, 7-two bromo-9, two (4-hydroxyl-3-chloro-phenyl-) fluorenes, 2 of 9-, 7-two bromo-9, two (4-hydroxyl-3-bromophenyl) fluorenes, 2 of 9-; 7-two bromo-9, two (4-hydroxyl-3-fluorophenyl) fluorenes, 2 of 9-, 7-two bromo-9, two (the 4-hydroxy 3-methoxybenzene base) fluorenes, 2 of 9-, 7-two bromo-9; Two (4-aminophenyl) fluorenes, 2 of 9-, 7-two bromo-9,9-two (4-amino-3,5-3,5-dimethylphenyl) fluorenes, 2,7-two bromo-9; 9-two (4-amino-3,5-dichlorophenyl) fluorenes, 2,7-two bromo-9,9-two (4-amino-3,5-dibromo phenyl) fluorenes, 2; 7-two bromo-9, two (4-amino-3-aminomethyl phenyl) fluorenes, 2 of 9-, 7-two bromo-9, two (4-amino-3-chloro-phenyl-) fluorenes, 2 of 9-, 7-two bromo-9; Two (4-amino-3-bromophenyl) fluorenes, 2 of 9-, 7-two bromo-9, two (4-amino-3-fluorophenyl) fluorenes, 2 of 9-, 7-two bromo-9, two (4-amino-3-p-methoxy-phenyl) fluorenes of 9-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; The 5-3,5-dimethylphenyl) ketone, two (4-hydroxyl-3; The 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; The 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; The 5-3,5-dimethylphenyl) sulfone, two (4-hydroxyl-3; The 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; The 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-236fas, two (4-hydroxyl-3,5-3,5-dimethylphenyl) HFC-236fa, two (4-hydroxyl-3,5-dichlorophenyl) HFC-236fa, two (4-hydroxyl-3; The 5-dibromo phenyl) HFC-236fa, two (4-aminophenyl) HFC-236fa, two (4-amino-3; The 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-hydroxyl-3,5-3,5-dimethylphenyl) dimethylsilane, two (4-hydroxyl-3,5-dichlorophenyl) dimethylsilane, two (4-hydroxyl-3; The 5-dibromo phenyl) dimethylsilane, two (4-aminophenyl) dimethylsilane, two (4-amino-3; The 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; The 5-3,5-dimethylphenyl) methane, two (4-hydroxyl-3; The 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; The 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, two (4-hydroxy phenyl) propane, 2 of 2-; Two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane, 2 of 2-, two (4-hydroxyl-3, the 5-dichlorophenyl) propane, 2 of 2-; Two (4-hydroxyl-3, the 5-dibromo phenyl) propane, 2 of 2-, two (the 4-hydroxy-3-methyl phenyl) propane, 2 of 2-, two (4-hydroxyl-3-chloro-phenyl-) propane, 2 of 2-; Two (4-hydroxyl-3-bromophenyl) propane, 2 of 2-, two (4-aminophenyl) propane, 2 of 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; Two (4-amino-3-aminomethyl phenyl) propane, 2 of 2-, two (4-amino-3-chloro-phenyl-) propane, 2 of 2-, two (4-amino-3-bromophenyl) propane of 2-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; The 5-3,5-dimethylphenyl) ether, two (4-hydroxyl-3; The 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; The 5-dichlorophenyl) ether, two (4-amino-3,5-dibromo phenyl) ether etc.
Have in the compound of xenyl skeleton at these, preferred 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, two (4-hydroxy phenyl) fluorenes of 9-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 article, also can suitably use the compound that will have xenyl skeleton shown in the general formula (98) and epoxy chloropropane, epoxy bromopropane, 4-chloro-1,2-butylene oxide ring, 4-bromo-1; 2-butylene oxide ring, 5-chloro-1,2-epoxy pentane, 5-bromo-1,2-epoxy pentane, 6-chloro-1; 2-epoxy hexane, 6-bromo-1; 2-epoxy hexane, 7-chloro-1,2-epoxy heptane, 7-bromo-1,2-epoxy heptane, 8-chloro-1; 2-octylene oxide, 8-bromo-1, the ω-halogenated epoxide of 2-octylene oxide etc. comes the synthetic material through the method for manufacture 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 representes 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, and 5-benzene tertacarbonic acid, 1,2,4,5-benzene tertacarbonic acid (PMA) etc., wherein preferred 1,2,4,5-benzene tertacarbonic acid (PMA).
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-dicarboxylicacid.
As the aliphatics tetracarboxylic acid shown in the general formula (109), can enumerate 5-(1,2-dicarboxyl ethyl)-3-methylcyclohexane-1, the 2-dicarboxylicacid.
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 article, for example also can suitably use the usual method synthetic material that reacts through 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 not special qualification; 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.
In reaction times in [VIII] method, so long as set the polymerization degree k that can make in the general formula (20) for, that is, set the weight-average molecular weight that can formula contains the compound that structural unit forms shown in the general formula (20) for and in suitable scope, get final product at the proper range inner casing.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 is not as long as the ability dissolving raw material just has special qualification.
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 quaternary ammonium salt or the triphenylphosphine etc. of TBuA muriate, TBuA bromide, triethyl hexadecyldimethyl benzyl ammonium muriate, triethyl hexadecyldimethyl benzyl ammonium bromide etc.These catalyzer can be distinguished independent use; Or with combination use more than 2 kinds; Usage quantity to above-mentioned catalyzer does not have special qualification, 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 method of manufacture 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).Compound shown in the general formula (110) is equivalent to the polyprotonic acid with 3 above carboxyls (part that comprises carboxyl is the material of carboxylicesters) is defined as 3,3 ', 4; 4 '-biphenyltetracarboxyacid acid, 3,3 ', 4; 4 '-benzophenone tetracarboxylic acid or 4-(1,2-dicarboxyl ethyl)-1,2; 3,4-naphthane-1, the situation of 2-dicarboxylicacid { the aliphatics tetracarboxylic acid shown in the following formula (108) }.Contain the compound that structural unit forms shown in the general formula (111) and be equivalent to the 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 representes 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 representes 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, dipicolimic acid 2,3,4-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 dicarboxylicacid, 2,4-xenyl ether dicarboxylicacid, 2,5-xenyl ether dicarboxylicacid, 2,6-xenyl ether dicarboxylicacid, 3,4-xenyl ether dicarboxylicacid, 3,5-xenyl ether dicarboxylicacid etc.In addition, as W
13Be the aromatic dicarboxylic acid of carbonyl, for example, can enumerate 2,3-benzophenone dicarboxylicacid, 2,4-benzophenone dicarboxylicacid, 2,5-benzophenone dicarboxylicacid, 2,6-benzophenone dicarboxylicacid, 3,4-benzophenone dicarboxylicacid, 3,5-benzophenone dicarboxylicacid etc.In addition, as W
13Be the aromatic dicarboxylic acid of alkylsulfonyl, for example, can enumerate 2,3-xenyl sulfone dicarboxylicacid, 2,4-xenyl sulfone dicarboxylicacid, 2,5-xenyl sulfone dicarboxylicacid, 2,6-xenyl sulfone dicarboxylicacid, 3,4-xenyl sulfone dicarboxylicacid, 3,5-xenyl sulfone dicarboxylicacid etc.In addition, as W
13Be 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 dicarboxylicacid, 2,3 '-xenyl ether dicarboxylicacid, 2,4 '-xenyl ether dicarboxylicacid, 3; 3 '-xenyl ether dicarboxylicacid, 3,4 '-xenyl ether dicarboxylicacid, 4,4 '-xenyl ether dicarboxylicacid etc.In addition, as W
14Be the aromatic dicarboxylic acid of carbonyl, for example, can enumerate 2,2 '-benzophenone dicarboxylicacid, 2,3 '-benzophenone dicarboxylicacid, 2,4 '-benzophenone dicarboxylicacid, 3,3 '-benzophenone dicarboxylicacid, 3,4 '-benzophenone dicarboxylicacid, 4,4 '-benzophenone dicarboxylicacid etc.In addition, as W
14Be the aromatic dicarboxylic acid of alkylsulfonyl, for example, can enumerate 2; 2 '-xenyl sulfone dicarboxylicacid, 2,3 '-xenyl sulfone dicarboxylicacid, 2,4 '-xenyl sulfone dicarboxylicacid, 3; 3 '-xenyl sulfone dicarboxylicacid, 3,4 '-xenyl sulfone dicarboxylicacid, 4,4 '-xenyl sulfone dicarboxylicacid.In addition, as W
14Be 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 2, the aliphatic dicarboxylic acid of 3-propenylidene (1-propylene-2,3-two bases) can be enumerated 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), can enumerate q usually and be 1～3 integer, be preferably 2～3 integer, 3 aliphatic dicarboxylic acid more preferably, specifically, for example; Can enumerate 1,2-CBDCA, 1,3-CBDCA, 1,2-pentamethylene dicarboxylicacid, 1; 3-pentamethylene dicarboxylicacid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid etc.; Wherein, preferred 1,2-pentamethylene dicarboxylicacid, 1,3-pentamethylene dicarboxylicacid, 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, anti-form-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; And if 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; And with the mol ratio under the sour situation shown in acid and the above-mentioned general formula (57) shown in the above-mentioned general formula (34) be generally 10: 90～99: 1, be preferably 40: 60～99: 1.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, be difficult to form fine pattern, in addition using the resin combination that obtains by this compound to prepare under the situation of colour filter; 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, can also it be reacted respectively and by stages.
As the more detailed concrete example of method of manufacture 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 compound shown in the general formula (121) is equivalent to aromatic series with 2 carboxyls or aliphatic carboxylic acid (aromatic series or aliphatic dicarboxylic acid) are defined as terephthalic acid, toxilic acid or cis-1,2,3, the situation of 6-tetrahydrophthalic acid.Contain the compound that structural unit forms shown in the general formula (122) and be equivalent to the 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 carried out detailed explanation.For example; [IX] method is that the compound shown in the general formula (23) is used solvent cut; And as required after wherein adding catalyzer; To adding in this mixing solutions, under the temperature of regulation, react the specified time as stating the multi-anhydride shown in the normal general formula of regulation (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.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 through 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 Wasserstoffatoms, 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 Wasserstoffatoms, for example, can enumerate through making the V in the compound shown in the above-mentioned general formula (98) with biphenyl backbone
1And V
2Compound and the carbonatomss such as compound with biphenyl backbone shown in the above-mentioned general formula (98) and formaldehyde that are Sauerstoffatom are the compound that 1 compound reaction obtains; The ω of compound with bis-phenol skeleton shown in the above-mentioned general formula (98) and 2-chloro-1-ethanol, 2-bromo-1-ethanol, trimethylene chlorohydrin, 3-bromo-1-propyl alcohol, 4-chloro-1-butanols, 4-bromo-1-butanols, 5-chloro-1-amylalcohol, 5-bromo-1-amylalcohol, 6-chloro-1-hexanol, 6-bromo-1-hexanol etc.-halohydrin reacts and the compound of acquisition; Wherein, The compound that preferably makes the ω-halohydrin reaction of compound with biphenyl backbone shown in the above-mentioned general formula (98) and 2-chloro-1-ethanol, 2-bromo-1-ethanol, trimethylene chlorohydrin, 3-bromo-1-propyl alcohol, 4-chloro-1-butanols, 4-bromo-1-butanols and obtain more preferably makes compound with biphenyl backbone shown in the above-mentioned general formula (98) and 2-chloro-1-ethanol, 2-bromo-1-alcoholic acid ω-halohydrin react and the compound of acquisition.
In [IX] method, as V in the compound shown in the general formula (23)
1And V
2Be-NH-is basic, R
12And R
13Be the compound of Wasserstoffatoms, 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-is basic, M
1And M
2Be the compound of Wasserstoffatoms, 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-the basic compound of NH-; The compound that obtains with the omega-halogenated alkyl groups amine reaction of the compound shown in the above-mentioned general formula (98) and 1-chloromethane amine, 1-bromine methylamine, 2-chloro-1-ethamine, 2-bromo-1-ethamine, 3-chloro-1-propylamine, 3-bromo-1-propylamine, 4-chloro-1-butylamine, 4-bromo-1-butylamine, 5-chloro-1-amylamine, 5-bromo-1-amylamine, 6-chloro-1-hexylamine, 6-bromo-1-hexylamine etc. with biphenyl backbone; Wherein, The compound that preferably makes the omega-halogenated alkyl groups amine reaction of compound with biphenyl backbone shown in the above-mentioned general formula (98) and 2-chloro-1-ethamine, 2-bromo-1-ethamine, 3-chloro-1-propylamine, 3-bromo-1-propylamine, 4-chloro-1-butylamine, 4-bromo-1-butylamine etc. and obtain more preferably makes omega-halogenated alkyl groups amine such as compound with biphenyl backbone shown in the above-mentioned general formula (98) and 2-chloro-1-ethamine, 2-bromo-1-ethamine react 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 in the alkali metal alcoholates such as hydrogenated alkali metal, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide etc. of the compound that makes the compound shown in the compound shown in the above-mentioned general formula (98), the above-mentioned general formula (98) and ω-halohydrin or the reaction of omega-halogenated alkyl groups amine and obtain and alkali metal hydroxides such as sodium hydroxide, Pottasium Hydroxide, sodium hydride, potassium hydride KH etc. any and react the compound that obtains through ordinary method with biphenyl backbone with biphenyl backbone; Wherein, The compound that compound that preferably makes the reaction of 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 omega-halogenated alkyl groups amine and obtain and sodium methylate or potassium methylate obtain through 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 representes 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 (PMA acid anhydride) etc., wherein preferred 1,2,4,5-benzene tertacarbonic acid dianhydride (PMA 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, the 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 article; 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 through 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 not special qualification; 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, and 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 not so long as the amount of ability dissolving raw material just has special qualification.
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 independent use, or combination more than 2 kinds is used, and the usage quantity of above-mentioned catalyzer is not had special qualification; 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 method of manufacture 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 Wasserstoffatoms, R
11Be general formula (17) and V
4Be Sauerstoffatom, M
2It is the situation of Wasserstoffatoms.Compound shown in the general formula (135) is equivalent to the multi-anhydride with 3 above carboxyls (is comprised 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; 4-naphthane-1, the situation of 2-dicarboxylic acid dianhydride { the aliphatics tetracarboxylic dianhydride shown in the following formula (132) }.Comprise the compound that structural unit forms shown in the general formula (136) and be equivalent to the 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 the multi-anhydride with 3 above carboxyls shown in general formula (35) or (36) (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 addition, can use can with the compound of compound polymerization shown in the general formula (23), specifically; For example; As using the method that has the aromatic series or the aliphatic carboxylic acid acid anhydride (aromatic series or aliphatic dicarboxylic acid acid anhydride) of 2 carboxyls shown in the general formula (58), 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 representes 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, pimelic acid acid anhydride, suberic acid acid anhydride, 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, pimelic acid acid anhydride, suberic acid acid anhydride, nonane diacid acid anhydride, sebacic anhydride, 1,10-sebacic anhydride, more preferably malonic anhydride, Succinic anhydried, Pyroglutaric acid, adipic anhydride, pimelic acid acid anhydride, 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 2, the aliphatic dicarboxylic acid acid anhydride of 3-propenylidene (1-propyl group-2,3-two bases) for example, can be enumerated 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-CBDCA 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, the 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 aliphatic carboxylic acid acid anhydride (aromatic series or aliphatic dicarboxylic acid acid anhydride) time these materials mol than in; And the mol ratio during with above-mentioned tetracarboxylic anhydride and above-mentioned dicarboxylic anhydride be generally 10: 90～99: 1, be 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, be difficult to form fine pattern using the resin combination that obtains by this compound to make under the situation of colour filter, 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 can their mixture have been 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.
Method of manufacture 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 shown in self-drifting (150), general formula (151), general formula (152) or the general formula (153) or its acid anhydrides, 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', 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
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 Wasserstoffatoms 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 abbreviate it as end structure compound sometimes.
Become the method for same group as two ends that make these structural units; That is,, get final product so long as import like above-mentioned end structure compound according to conventional methods as the introduction method of end structure compound; For example; Can through 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 through 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 brightly specifically, but the present invention is not limited to these embodiment.In addition, in the present embodiment, separate the compound that structural unit forms shown in the general formula (1) that contains of target, but also can the solution that obtain through reaction directly be used for 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; After to be compound that containing of will the method for manufacture through present embodiment obtaining, structural unit formed shown in the general formula (1) with the mixing solutions of propylene glycol methyl ether acetate and 1-Methyl-2-Pyrrolidone dilute; With phenolphthalein is indicator, determines with (the 50 weight %) aqueous solution titration of KOH ethanol.In addition, molecular weight is obtained through the gel permeation chromatography with RI (specific refractory power) detector through being elutriant with the 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.
In the formula, R
8' and R
9' represent Wasserstoffatoms or vinyl carbonyl, Z independently of one another
1Same as described above with k.
<1>Contain the 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), add the 1-Methyl-2-Pyrrolidone of 185.3g in two (the 4-glycidoxypropyl phenyl) fluorenes of 9-, dissolve this fluorene compound after; 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 the dilution of the 1-Methyl-2-Pyrrolidone of 102.9g, 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 the 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 ')
Contain in compound (resin) solution that structural unit forms shown in the general formula (156) what above-mentioned < 1>obtained, add 30mg thiodiphenylamine and 38.9g triethylamine, stirred 10 minutes down, in this solution, splash into 29.0g (0.320mol) acrylate chloride then at 0 ℃.After splashing into end, stirred 2 hours down, make it reaction at 25 ℃.In 3.8kg water, splash into the gained reaction solution, 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 the 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 through 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 unitary compound of 4 valency alkyl various structure of expression.In addition; Through 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 the H-NMR, can confirm 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
1The H-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-dicarboxylicacid
Table 2
| Embodiment No. | Resin No. | Acid value (mgKOH/g) | Weight-average molecular weight | Propylene rate (mol%) |
| |
Resin 1 | - | 6000 | 43 |
| |
Resin 2 | - | 8500 | 40 |
| |
|
112 | 4600 | 40 |
| |
|
113 | 6300 | 31 |
| |
|
111 | 8300 | 36 |
| |
|
103 | 9300 | 32 |
| |
|
102 | 10100 | 31 |
| |
|
132 | 4300 | 33 |
| |
|
132 | 5000 | 71 |
| |
|
131 | 6600 | 73 |
| |
|
126 | 9900 | 68 |
| |
|
104 | 7100 | 31 |
| |
|
94 | 7000 | 27 |
As above shown in the table 1 and 2; Result by embodiment 3～7 relatively can judge; Reaction times during through 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, clearly can know relatively from the result of embodiment 3,8,12 and 13; Through changing the usage quantity ratio of compound shown in tetracarboxylic acid shown in the general formula (110) and the formula (154), can easily synthesize different the containing of the acid value compound (resin) that structural unit forms shown in the general formula (157).Further; By the result of embodiment 3,4,6 and 9～11 relatively (especially embodiment 3 and 9, embodiment 4 and 10 and result's comparison of embodiment 6 and 11) can know; The reaction times of containing acrylic acid derivative shown in structural unit forms shown in the general formula (156) compound and the formula (89) through change; Easily the synthesizing propylene rate is different contains the compound (resin) that structural unit forms shown in the general formula (157), in addition, can be known by the comparison as a result of embodiment 1～3; 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 through changing the concentration of tetracarboxylic acid shown in compound shown in temperature of reaction and the formula (154) and the general formula (110) through change reaction times synthetic molecular weight different compounds.
In the formula, R
8', R
9', Z
1, Z
3, k ' and k " same as described above.
<1>Contain the 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), add the 1-Methyl-2-Pyrrolidone of 185.3g in two (the 4-glycidoxypropyl phenyl) fluorenes of 9-, 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 in this solution, add the 4-(1,2-dicarboxyl ethyl)-1,2,3 of 26.9g (0.080mol), 4-naphthane-1, the 2-dicarboxylicacid stirred 8 hours down at 80 ℃, made it reaction.With the 1-Methyl-2-Pyrrolidone of 102.9g 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 the 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 ')
Contain in compound (resin) solution that structural unit forms shown in the general formula (158) what above-mentioned < 1>obtained, add 30mg thiodiphenylamine and 38.9g triethylamine, and stirred 15 minutes down, in this solution, splash into 29.0g (0.320mol) acrylate chloride then at 0 ℃.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; Through 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 dicarboxylicacid shown in the above-mentioned general formula (121), the dicarboxylicacid of the regulation shown in the use table 3 replaces the CHEC of use among the embodiment 14, contains the Z in general formula (158) and (159) thereby synthesize
1And Z
3The compound that 4 shown valencys and divalent alkyl various structure unit form.In addition; Through 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 dicarboxylicacid; 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 likewise, 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 dicarboxylicacid reaction after zero hour, are added tetracarboxylic acid in this solution, and reaction △ hour (below identical).
Table 4
| Embodiment No. | Resin No. | Acid value (mgKOH/g) | Weight-average molecular weight | Propylene rate (mol%) |
| |
|
111 | 5100 | 64 |
| |
|
109 | 4800 | 72 |
| 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 |
| |
|
89 | 4900 | 35 |
| Embodiment 21 | Resin 21 | 92 | 6500 | 34 |
| Embodiment 22 | Resin 22 | 82 | 7700 | 28 |
| Embodiment 23 | Resin 23 | 76 | 7300 | 29 |
Shown in above-mentioned table 3 and 4, can know by the comparison as a result of embodiment 14～23, by being used in combination tetrabasic carboxylic acid and dicarboxylic acids, can, this compound molecular weight change acid value under almost keeping constant state.
Embodiment 24～38; Be through containing the compound that structural unit forms shown in the 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 method of manufacture of the present invention, the molecular end of synthesizing at structural unit has imported A ' and A " shown in the example of compound shown in formula (161) and (162) of group, according to each embodiment; the kind of end structure compound or the reaction conditions in temperature of reaction, reaction times etc. are different
In the formula, R
16And R
17The group of representing Wasserstoffatoms, formula (163) or formula (164) expression independently of one another; About A ' and A " shown in group; A when A ' is Wasserstoffatoms " 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, and 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 Wasserstoffatoms, 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), add the 1-Methyl-2-Pyrrolidone of 110.9g in two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes (BPEF) of 9-, thereby after dissolving this fluorene compound; In this solution, add the 4-(1,2-dicarboxyl ethyl)-1,2 of 30.0g (0.10mol); 3,4-naphthane-1, the dimethyl aminopyridine of 2-dicarboxylic anhydride (TDA) and 0.6g; Stirred 2 hours down at 80 ℃, make it reaction.Then in this solution, further add the BPEF and the 1-Methyl-2-Pyrrolidone of 13.2g of 8.8g (0.02mol), stirred 2 hours down, make it to react, 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 Wasserstoffatoms, 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 Wasserstoffatoms, A " shown in group be the compound synthetic (propylene reaction) of group shown in the formula (165)
Contain in compound (resin) solution that structural unit forms shown in the general formula (151) what above-mentioned < 1>obtained; Add 100mg thiodiphenylamine, the SY-Monomer G of 14.2g (0.10mol) and the 1-Methyl-2-Pyrrolidone of 21.3g; And under 80 ℃, stirred 6 hours, make it reaction.Behind the 1-Methyl-2-Pyrrolidone dilution gained reaction solution with 150.0g; Splash in the 1.6kg water; Crystallization is separated out, and filters, again with behind the clean gained crystallization precipitate of 50% methanol aqueous solution of 1.6kg and 1.6kg; 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 Wasserstoffatoms, 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; Through 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; Through changing reaction conditions { 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), the reaction times during condensation and the reaction times of propyleneization } as shown in table 5ly, 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; In the condensation reaction of < 1 >; Use the 1-Methyl-2-Pyrrolidone of 119.9g during reaction, in the propylene reaction of < 2 >, the thiodiphenylamine in the time of then will reacting and the usage quantity of 1-Methyl-2-Pyrrolidone increase and decrease according to the use mole number of GMA in proportion.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) | |
| |
|
| BPEF | GMA | 1/1/0.2/1.2 | 2+2 | 6 | |
| Embodiment 26 | Resin 26 | | BPEF | GMA | 1/1/0.2/1.4 | 2+2 | 6 | |
| Embodiment 27 | Resin 27 | | BPEF | GMA | 1/1/0.2/2 | 2+2 | 6 | |
| Embodiment 28 | Resin 28 | | BPEF | GMA | 1/1.2/0.2/1.2 | 2+2 | 6 | |
| Embodiment 29 | Resin 29 | | BPEF | GMA | 1/1.2/0.2/1.6 | 2+2 | 6 | |
| |
|
| BPEF | GMA | 1/1.2/0.2/2 | 2+2 | 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
The 1-Methyl-2-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 the 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 stirs down reaction in 0.5 hour at 80 ℃, thereby obtains 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
Contain in compound (resin) solution that structural unit forms shown in the general formula (161) what above-mentioned < 1>obtained, add 100mg thiodiphenylamine, the GMA of 14.2g (0.10mol) and the 1-Methyl-2-Pyrrolidone of 21.3g, and stirred 6 hours down and make it to react at 80 ℃.Behind the 1-Methyl-2-Pyrrolidone dilution gained reaction solution with 140.0g; Splash in the 1.5kg water; Crystallization is separated out, and filters, clean the gained crystallization precipitate with 50% methanol aqueous solution of the water of 1.5kg and 1.5kg again after; 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, through 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; Through 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, in addition, among the embodiment 32, in the propylene reaction of < 2 >, the thiodiphenylamine during with reaction and the usage quantity of 1-Methyl-2-Pyrrolidone increase and decrease according to the use mole number of GMA in proportion.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 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)
The 1-Methyl-2-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 to react.Then in this solution, further add the 1-Methyl-2-Pyrrolidone of 9.0g (0.03mol) TDA and 13.5g, stirred 2 hours down, make it to react, 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)
Contain in compound (resin) solution that structural unit forms shown in the general formula (161) what above-mentioned < 1>obtained; After adding the 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) NSC 57182.Then, make this solution reach 25 ℃ with 30 minutes, further stirred 2 hours down, make it reaction synthermal.With the 1-Methyl-2-Pyrrolidone dilution gained reaction solution of 130.0g, and filter this reaction solution, thereby after removing NSC 30023; This filtered liq is splashed in the 1.5kg water, carry out crystallization and separate out, filter; After cleaning the gained crystallization precipitate with 50% methanol aqueous solution of the water of 1.4kg and 1.4kg 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 through 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; Through 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, in the condensation reaction of < 1 >, the usage quantity of the 1-Methyl-2-Pyrrolidone during with reaction increases and decreases according to the use mole number of end structure compound in proportion.In the propylene reaction of < 2 >,, increase and decrease in proportion according to the use mole number of HEA with the usage quantity of thiodiphenylamine, NSC 57182 and the 1-Methyl-2-Pyrrolidone in when reaction.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 likewise can confirm characteristic peak with the foregoing description 1～13 situation.In addition, shown in Fig. 2 by embodiment 24 gained compounds
1The H-NMR data are in the data of IR shown in Fig. 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 34 | Resin 34 | - | | TDA | HEA | 1/1/0.3/1 | 2+2 | 2 | |
| |
|
Formula (56 ') | | CHEA | HEA | 1/1/0.8/1 | 2+2 | 2 | |
| Embodiment 36 | Resin 36 | Formula (56 ") | | THPA | HEA | 1/1/0.8/1 | 2+2 | 2 | |
| Embodiment 37 | Resin 37 | Formula (49 ") | | PAN | HEA | 1/1/0.8/1 | 2+2 | 2 |
CHEA=cis-1,2,3, the 6-Tetra Hydro Phthalic Anhydride
THPA=3,4,5, the 6-Tetra Hydro Phthalic Anhydride
The PAN=Tetra hydro Phthalic anhydride
*=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.
Table 8
| Embodiment No. | Resin No. | Acid value (mgKOH/g) | Weight-average molecular weight | Propylene rate (mol%) |
| Embodiment 24 | Resin 24 | 103 | 4600 | 21 |
| |
|
95 | 4600 | 26 |
| 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 |
| |
|
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 34 | Resin 34 | 118 | 7400 | 35 |
| |
|
107 | 4000 | 35 |
| Embodiment 36 | Resin 36 | 109 | 7100 | 31 |
| Embodiment 37 | Resin 37 | 134 | 3500 | 26 |
Shown in above-mentioned table 5～8; Comparison as a result by embodiment 24～27,28～30,31 and 32 and 33 and 34 can be known; Through changing the usage quantity ratio of acrylic acid derivative to formula (155) compound; Can easily synthesize different the containing of the acid value compound (resin) that structural unit forms shown in the general formula (162); And the result by embodiment 25 and 28 more clearly can know, through 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, can know, through the end structure compound is changed into TDA+H by BPEF by the comparison as a result of embodiment 24 and 31
2O; Need not to change under the situation of propylene rate; Just can obtain different the containing of the acid value compound (resin) that structural unit forms shown in the general formula (162), in addition, can know by the comparison as a result of embodiment 35～37; Through 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; Measure through sealing pond differential scanning calorimetric determination (SC-DSC) and differential scanning heat balance (TG-DSC); Its result; Even under 300 ℃, do not find exothermal peak, endotherm(ic)peak and weight change yet, can judge that thus also be stable under 300 ℃ high heat.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, the thermostability of gained compound (thermotolerance) data in embodiment shown in Fig. 53, the thermostability of gained compound (thermotolerance) data in embodiment shown in Fig. 6 24.
Embodiment 39
Use formation, hardness and the test of development property 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-the 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 mix, form uniform solution.Then, behind this solution of coating on the glass substrate, prebake on 90 ℃ hot plate (プ レ ベ one Network) 1 minute is filmed thereby form.Then, being formed with on this glass substrate of filming, through mask, with the UV lamp of wavelength 365nm exposure 3 minutes.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 one 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 the cured film that obtains in above-mentioned < 1>and < 2>is measured pencil hardness, in addition, through visual observation development property.As a result, the pencil hardness of all cured film is 4H, does not find residue at the development position.
Thus; Contain the compsn that this compound forms; Because its development property is excellent, 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 development property excellent pattern form in useful compound.
Utilizability in the industry
Polymerizable unsaturated compound of the present invention is in structural unit, to have the xenyl skeleton; Especially has fluorene skeleton; Alkali-soluble, and the compound of excellent heat resistance use and contain the compsn that this compound forms; When making it form pattern, just can easily form the good pattern of thermotolerance through light or heat.In addition; Manufacturing method according to the invention; Can not produce that existing method has for example because at high temperature react the control difficulty, owing to side reaction causes 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 structural unit shown in the general formula (1) of productive rate.
Claims (9)
1. compound, it is to comprise the compound that structural unit forms shown in the general formula (1),
In the formula (1), R
1, R
2, R
1' and R
2' represent the alkyl of Wasserstoffatoms, halogen atom, carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4, R independently of one another
3And R
4Represent Wasserstoffatoms 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 representes singly-bound or with the divalent group of any expression in the formula (1-1)～(1-8), V
1And V
2Represent independently of one another Sauerstoffatom or-the 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 representes the alkyl of 4 valencys, and a and b represent 0 or 1 independently of one another, and k representes natural number, wherein, and in the formula (1), R
3And R
4In at least one be the group of formula (2) expression, R
6, R
8, R
9In any at least one be group with two keys;
-COOR
6 (2)
In the formula (2), R
6Expression Wasserstoffatoms, carbonatoms are the group of 1～6 alkyl, general formula (3) or general formula (4) expression,
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 (1-1), R
5And R
5' represent Wasserstoffatoms or halogen atom independently of one another;
In the formula (5), R
8Expression Wasserstoffatoms or R
7
In the formula (6), R
9Expression Wasserstoffatoms or R
7
2. compound, it is to comprise the compound that structural unit forms shown in the general formula (20),
In the formula (20), R
1, R
2, R
1' and R
2' represent the alkyl of Wasserstoffatoms, halogen atom, carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4, R independently of one another
3' and R
4' represent the alkoxy carbonyl of Wasserstoffatoms, carboxyl or carbonatoms 2～7, 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 representes singly-bound or with the divalent group of any expression in the formula (1-1)～(1-8), V
1And V
2Represent independently of one another Sauerstoffatom or-the NH-group, Z representes the alkyl of 4 valencys, k representes natural number, wherein, in formula (20), R
3' and R
4' at least one be the alkoxy carbonyl of carboxyl or carbonatoms 2～7,
In the formula (1-1), R
5And R
5' represent Wasserstoffatoms or halogen atom independently of one another.
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-the 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. the method for manufacture of a compound, this compound is to comprise the compound that structural unit forms shown in the general formula (1),
In the formula (1), R
1, R
2, R
1' and R
2' represent the alkyl of Wasserstoffatoms, halogen atom, carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4, R independently of one another
3And R
4Represent Wasserstoffatoms 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 representes singly-bound or with the divalent group of any expression in the formula (1-1)～(1-8), V
1And V
2Represent independently of one another Sauerstoffatom or-the 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 representes the alkyl of 4 valencys, and a and b represent 0 or 1 independently of one another, and k representes natural number, wherein, and in the formula (1), R
3And R
4In at least one be the group of formula (2) expression, R
6, R
8, R
9In any at least one be group with two keys;
-COOR
6 (2)
In the formula (2), R
6Expression Wasserstoffatoms, carbonatoms are the group of 1～6 alkyl, general formula (3) or general formula (4) expression,
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 (1-1), R
5And R
5' represent Wasserstoffatoms or halogen atom independently of one another;
In the formula (5), R
8Expression Wasserstoffatoms or R
7
In the formula (6), R
9Expression Wasserstoffatoms 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,
In the formula (7), R
1, R
2, R
1' and R
2' represent the alkyl of Wasserstoffatoms, halogen atom, carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4, R independently of one another
3' and R
4' represent the alkoxy carbonyl of Wasserstoffatoms, carboxyl or carbonatoms 2～7, 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 representes singly-bound or with the divalent group of any expression in the formula (1-1)～(1-8), V
1And V
2Represent independently of one another Sauerstoffatom or-the 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 representes the alkyl of 4 valencys, and a and b represent 0 or 1 independently of one another, and k representes natural number, wherein, and in formula (7), R
3' and R
4' at least one be the alkoxy carbonyl of carboxyl or carbonatoms 2～7,
In the formula (1-1), R
5And R
5' represent Wasserstoffatoms or halogen atom independently of one another;
R
7-X (10)
In the formula (10), R
7Expression vinyl carbonyl or pseudoallyl carbonyl, X representes 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.
6. the method for manufacture of a compound, this compound is to comprise the compound that structural unit forms shown in the general formula (20),
In the formula (20), R
1, R
2, R
1' and R
2' represent the alkyl of Wasserstoffatoms, halogen atom, carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4, R independently of one another
3' and R
4' represent the alkoxy carbonyl of Wasserstoffatoms, carboxyl or carbonatoms 2～7, 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 representes singly-bound or with the divalent group of any expression in the formula (1-1)～(1-8), V
1And V
2Represent independently of one another Sauerstoffatom or-the NH-group, Z representes the alkyl of 4 valencys, k representes natural number, wherein, in formula (20), R
3' and R
4' at least one be the alkoxy carbonyl of carboxyl or carbonatoms 2～7,
In the formula (1-1), R
5And R
5' represent Wasserstoffatoms or halogen atom independently of one another,
It is characterized in that,
Compound shown in the general formula (22) and polyprotonic acid or its acid anhydrides with 3 above carboxyls are reacted; Wherein, Said polyprotonic acid comprises that the part of carboxyl is the material of carboxylicesters; Said 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 (22), R
1, R
2, R
1' and R
2' represent the alkyl of Wasserstoffatoms, halogen atom, carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4, T independently of one another
1And T
2Straight chain shape alkylidene group or the arylidene of representing carbonatoms 1～6 independently of one another, U are represented singly-bound or with the divalent group of any expression in the formula (1-1)～(1-8), V
1And V
2Represent independently of one another Sauerstoffatom or-the NH-group,
In the formula (1-1), R
5And R
5' represent Wasserstoffatoms or halogen atom independently of one another.
7. method of manufacture as claimed in claim 5, wherein, comprising the compound that structural unit forms shown in the general formula (7) is to obtain through the described method of manufacture of claim 6.
8. method of manufacture as claimed in claim 5, 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;
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.
9. method of manufacture as claimed in claim 5; 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), and the 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-the 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-the 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.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP109216/2006 | 2006-04-11 | ||
| JP2006109216 | 2006-04-11 | ||
| PCT/JP2007/057867 WO2007123017A1 (en) | 2006-04-11 | 2007-04-10 | Polymerizable unsaturated compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101379111A CN101379111A (en) | 2009-03-04 |
| CN101379111B true CN101379111B (en) | 2012-01-11 |
Family
ID=38624923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800045509A Expired - Fee Related CN101379111B (en) | 2006-04-11 | 2007-04-10 | Polymerizable unsaturated compound and method for producing the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2007123017A1 (en) |
| KR (1) | KR101050728B1 (en) |
| CN (1) | CN101379111B (en) |
| TW (1) | TW200801068A (en) |
| WO (1) | WO2007123017A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100725023B1 (en) * | 2006-10-16 | 2007-06-07 | 제일모직주식회사 | Cardo type resin-containing resist composition and method for preparing a pattern by the same and a color filter using the same |
| KR101520763B1 (en) * | 2008-03-25 | 2015-05-15 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Photosensitive resin and photosensitive resin composition comprising the same |
| KR101254054B1 (en) * | 2008-03-25 | 2013-04-12 | 오사까 가스 가부시키가이샤 | Photosensitive resin and photosensitive resin composition comprising the same |
| CN102344369A (en) * | 2010-07-30 | 2012-02-08 | 华东师范大学 | High oriented luminescent polyacetylene monomer with side chains containing fluorene group and preparation method thereof |
| JP6031807B2 (en) * | 2012-04-13 | 2016-11-24 | Jsr株式会社 | Coloring composition, color filter and display element |
| KR102054045B1 (en) * | 2017-03-03 | 2019-12-09 | 주식회사 엘지화학 | Polymer resion compound and photosensitive resin composition for black bank |
| KR102420415B1 (en) * | 2017-10-17 | 2022-07-15 | 덕산네오룩스 주식회사 | Adhesion enhanced photo sensitive resin composition and light blocking layer using the same |
| KR102227606B1 (en) | 2018-04-06 | 2021-03-12 | 주식회사 엘지화학 | Cardo-based binder resin, photo-sensitive resin composition comprising the same, black matrix, color filter and display device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200519081A (en) * | 2003-10-03 | 2005-06-16 | Nagase Chemtex Corp | An alkali soluble resin |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791365B2 (en) * | 1987-03-06 | 1995-10-04 | 新日鐵化学株式会社 | Epoxy resin composition |
| JP3148429B2 (en) * | 1992-02-04 | 2001-03-19 | 新日本製鐵株式会社 | Photopolymerizable unsaturated compound and alkali-developable photosensitive resin composition |
| JP3673321B2 (en) * | 1996-05-10 | 2005-07-20 | 新日鐵化学株式会社 | Photosensitive resin composition capable of alkali development |
| JP4036550B2 (en) * | 1998-11-25 | 2008-01-23 | 日本化薬株式会社 | Radiation sensitive polyester resin and negative resist composition using the same |
| JP2000338344A (en) * | 1999-03-25 | 2000-12-08 | Unitika Ltd | High-polymer optical material for optical device, high- polymer optical device and their production |
| JP4665189B2 (en) * | 2003-10-03 | 2011-04-06 | ナガセケムテックス株式会社 | Alkali-soluble resin |
| JP2005281620A (en) * | 2004-03-30 | 2005-10-13 | Sumitomo Bakelite Co Ltd | Functional resin and functional element |
-
2007
- 2007-03-27 TW TW096110466A patent/TW200801068A/en unknown
- 2007-04-10 KR KR1020087027522A patent/KR101050728B1/en not_active IP Right Cessation
- 2007-04-10 WO PCT/JP2007/057867 patent/WO2007123017A1/en active Application Filing
- 2007-04-10 CN CN2007800045509A patent/CN101379111B/en not_active Expired - Fee Related
- 2007-04-10 JP JP2008512066A patent/JPWO2007123017A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200519081A (en) * | 2003-10-03 | 2005-06-16 | Nagase Chemtex Corp | An alkali soluble resin |
Non-Patent Citations (4)
| Title |
|---|
| JP昭63-218725A 1988.09.12 |
| JP特开2000-159857A 2000.06.13 |
| JP特开2005-281620A 2005.10.13 |
| JP特开平9-304929A 1997.11.28 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101379111A (en) | 2009-03-04 |
| KR20090009236A (en) | 2009-01-22 |
| WO2007123017A1 (en) | 2007-11-01 |
| JPWO2007123017A1 (en) | 2009-09-03 |
| KR101050728B1 (en) | 2011-07-21 |
| TW200801068A (en) | 2008-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101379111B (en) | Polymerizable unsaturated compound and method for producing the same | |
| US9527962B2 (en) | Phosphorous-containing compounds and their preparation process and use | |
| KR100860433B1 (en) | Diamine, Acid Dianhydride, Polyimide Composition Having Reactive Group Obtained Therefrom, and Process for Producing These | |
| JP5198473B2 (en) | Fluorene resin polymer and method for producing the same | |
| CN103965764B (en) | Synthetic method of polyester polyurethane wire enamel with high heat-resistant grade | |
| CN110128611B (en) | Low-temperature curing bio-based benzoxazine resin and preparation method thereof | |
| CN104151535B (en) | A kind of polyester block copolymer and preparation method thereof | |
| CN111138423B (en) | Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof | |
| CN111057050B (en) | Monomer of bio-based benzoxazine resin, benzoxazine resin and preparation method thereof | |
| CN113603864A (en) | Photocuring phosphorus-nitrogen flame-retardant acrylic resin and photocuring coating prepared from same | |
| US5576399A (en) | Epoxy acrylates | |
| CN108752239A (en) | Oxime ester compound and its manufacturing method | |
| TWI555750B (en) | Cage cyclopentanoic acid dianhydride compounds, processes for their manufacture and polyimides | |
| TWI359152B (en) | Phosphorus-containing compounds with various subst | |
| CN115073735A (en) | Hyperbranched semi-aromatic polyester imide polymer and preparation method thereof | |
| JP4798749B2 (en) | Imide type epoxy resin curing agent composition and epoxy resin composition | |
| JP2005170818A (en) | Alicyclic tetracaboxylic acid dianhydride, its production method and polyimide | |
| CN102432699A (en) | Light trigger based on vegetable oil and preparation method thereof | |
| JP2524322B2 (en) | Novel polyester and method for producing the same | |
| KR101239047B1 (en) | Fluorene-based hyperbranched polymer resin | |
| JPS63241031A (en) | Novel copolymer and its production | |
| JP2005206651A (en) | Dicarboxylic acid-containing composition and thermoplastic resin produced by curing the same | |
| JP2005320383A (en) | Epoxy resin-curing agent and epoxy resin composition | |
| JP2003327695A (en) | Polyimide and manufacturing method therefor | |
| JPS63277235A (en) | Polyester based polymer and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120111 Termination date: 20120410 |