CN101300064A - Dispersing agent, method for producing same and pigment composition using same - Google Patents

Dispersing agent, method for producing same and pigment composition using same Download PDF

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CN101300064A
CN101300064A CNA2006800412151A CN200680041215A CN101300064A CN 101300064 A CN101300064 A CN 101300064A CN A2006800412151 A CNA2006800412151 A CN A2006800412151A CN 200680041215 A CN200680041215 A CN 200680041215A CN 101300064 A CN101300064 A CN 101300064A
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general formula
expression
group
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base system
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三上让司
有吉泰
立花友子
稻垣大
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Toyo Ink Mfg Co Ltd
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Abstract

The invention discloses a dispersing agent, production method thereof and pigment component containing such a dispersing agent. The dispersing agent contains a carboxyl group-containing unit (G) represented by the general formula (1) below in the main chain of a vinyl polymer on an average from 0.3 to 3.0 units per one vinyl polymer molecule.

Description

Dispersant, its manufacture method and use its color compositions
Technical field
The present invention relates to make dispersiveness, flowability and excellent storage stability dispersion dispersant, its manufacture method and use its color compositions.
Background technology
Known generally when making printing ink etc., be difficult to pigment is disperseed with high-concentration stable ground, thereby bring variety of issue to manufacturing process or goods itself.
For example, contain the dispersing of pigments body that comprises minuteness particle and often show high viscosity, not only be difficult to goods are taken out from dispersion machine, carry, and under the relatively poor situation even in preservation gelation take place, use difficulty.And then, the defective mode that produces on color development thing surface that gloss descends, levelling is bad etc.In addition, when pigment not of the same race is mixed use, owing to phenomenons such as the color distinction that causes because of aggegation, sedimentation make the color development thing the remarkable decline of color spot, tinting strength, tinting power occur.
Therefore generally use dispersant in order to keep good dispersity.Dispersant have the position that is adsorbed on the pigment, with structure as the high position of the solvent compatibility of decentralized medium, and decide the performance of dispersant with the balance of these two functional parts.Dispersant generally uses acid dispersant for the pigment with meta-alkalescence surface according to using various dispersants as the surface state of the pigment that is disperseed thing.At this moment, acidic functionality becomes the adsorption site of pigment.
Known have have phosphate or sulfonic group dispersant (for example patent documentation 1 or patent documentation 2) as acidic functionality.These known dispersants have high dispersibility, can make low viscous pigment dispersion with low use amount to a certain degree.But, have the situation of storage stability difference or exist because be derived from phosphate or sulfonic shortcoming, for example compatibility poor (problem is also arranged during fabrication), hear resistance is low or the resistance to chemical reagents situation that produces the problem in the use such as low, this have phosphate or sulfonic dispersant for shortage extensibilities such as applied printing ink or coating.
Having the carboxylic acid group does not exist as the dispersant of acidic functionality and has phosphate or the existing problem of sulfonic dispersant, but the tendency that the dispersibility difference is arranged also is difficult to realize using the lowering viscousity that can reach when having phosphate or sulfonic dispersant even increase use amount.
In recent years, proposed to use the carboxylic acid group and dispersant that the ability as dispersant is improved.The example that makes acrylic resin with carboxylic acid group carry out block copolymerization is for example arranged, or at the example (for example patent documentation 3 or patent documentation 4) with grafted polyester, polyethers or polyurethane etc. on carboxylic acid group's the acrylic resin.
Though comparing with the existing carboxylic acid group's of having dispersant, these dispersants have high dispersibility, if but with have phosphate or sulfonic dispersant is compared, then dispersibility is lower, in order to make low viscosity and stable dispersion, need use with amount to a certain degree.
On the other hand, in patent documentation 5, patent documentation 6 and patent documentation 7 etc., proposed in color compositions to mix and had acidic-group or basic group method as precursor skeleton and on side chain as substituent synergist with pigment.Only this might not obtain satisfied effect, thereby has proposed to have acidic-group, basic group as substituent synergist for above-mentioned, and then uses the dispersant (for example patent documentation 8 and patent documentation 9) with its counter ion counterionsl gegenions.Here, synergist is meant the material with following character, promptly, has the similar structure of chemical constitution to the pigment that forms pigment, can interact with π-π is adsorbed on the pigment securely, the ionic functional group of containing by synergist makes surface of pigments be acid or alkaline, and the dispersant with counter ion counterionsl gegenions or the effect of pigment carrier are increased.
Patent documentation 8 has been enumerated to contain has basic group as substituent synergist with have the color compositions of the dispersant of phosphate.Dispersant by will having phosphate with have basic group as substituent synergist and use, can have pigment-dispersing ability to a certain degree, but the situation of storage stability difference is arranged or have owing to come from the shortcoming of phosphoric acid, for example hear resistance is low, resistance to chemical reagents is low, compatibility difference etc. and situation about having problems.This is for having sulfonic dispersant too.This color compositions with phosphate or sulfonic dispersant that used lacks extensibility for applied printing ink or coating etc., on the other hand, to use the dispersant of carboxylic acid and have the color compositions that basic group combines as substituent synergist for existing, it is no problem aspect hear resistance, chemical proofing, compatibility, but viscosity height, poor stability, pigment differential bad etc. the problem of loosing is arranged.
No. 2633075 communique of patent documentation 1 Japan Patent
No. 2747769 communique of patent documentation 2 Japan Patents
Patent documentation 3 TOHKEMY 2005-194487 communiques
No. 3049407 communique of patent documentation 4 Japan Patents
Patent documentation 5 Japanese kokai publication sho 63-305173 communiques
Patent documentation 6 Japanese kokai publication hei 1-247468 communiques
Patent documentation 7 Japanese kokai publication hei 3-26767 communiques
Patent documentation 8 Japanese kokai publication sho 63-248864 communiques
Patent documentation 9 Japanese kokai publication hei 9-176511 communiques
Summary of the invention
The inventor makes great efforts research for the exploitation that contains the carboxyl dispersant with high dispersive ability, found that by in vinyl based polymer main chain (for example in the acrylic acid series polymeric compounds main chain) introduce have an ad hoc structure contain the carboxyl unit, can obtain having the dispersant of excellent dispersive property.In addition, also new discovery of the inventor: the effective ways of making dispersant with the extensive structure that comprises above-mentioned vinyl based polymer dispersant.
The present invention is based on above-mentioned knowledge and the invention made.
Therefore, the present invention relates to ethene base system dispersant [below be referred to as ethene base system dispersant (a)], it is characterized in that, in vinyl based polymer main chain (A), contain carboxyl unit (G) with what average amount more than 0.3, below 3.0 in per 1 molecule vinyl based polymer contained useful general formula (1) expression.
[Chemical formula 1]
In general formula (1), R 1Be hydrogen atom or methyl,
X 1For-C (=O) O-,-C (=O) NH-,-O-,-OC (=O)-or-CH 2O-,
X 2Be to use general formula:
-(-R a1-O-) m1-
(in the formula, R A1Be that carbon number is that the alkylidene of 2～8 straight or branched or carbon number are 3～8 ring alkylidene, m1 is 1～50 integer) group of expression,
X 3Be to use general formula:
-(-C(＝O)-R b1-O-) m2-
(R B1Be that carbon number is that the alkylidene of 4～8 straight or branched or carbon number are 4～8 ring alkylidene, m2 is 0～20 integer) group of expression,
Y 1Be with general formula (2):
[Chemical formula 2]
Figure A20068004121500131
[in the general formula (2),
(i) A is arranged 1～A 3In 1 to be hydrogen atom, other 2 be-C (=O) combination of OH, or (ii) A 1～A 3In 1 be-C (=O) OR c(wherein, R cBe that carbon number is 1～18 alkyl), other 2 be-C (=O) combination of OH, perhaps (iii) A 1～A 3In 1 be with general formula (2a):
[chemical formula 3]
Figure A20068004121500132
[in the general formula (2a),
X 21For-C (=O) O-,-C (=O) NH-,-O-,-OC (=O)-or-CH 2O-,
X 22Be to use general formula:
-(-R a21-O-) m21-
(in the formula, R A21Be that carbon number is that the alkylidene of 2～8 straight or branched or carbon number are 3～8 ring alkylidene, m21 is 1～50 integer) group of expression,
X 23Be to use general formula:
-(-C(＝O)-R b21-O-) m22-
(R B21Be that carbon number is that the alkylidene of 4～8 straight or branched or carbon number are 4～8 ring alkylidene, m22 is 0～20 integer) group of expression,
Z 21Be to contain useful general formula (21):
[chemical formula 4]
Figure A20068004121500141
[in the general formula (21), R 21Be hydrogen atom or methyl] the vinyl based polymer main chain (B) of group of expression, above-mentioned vinyl based polymer main chain (A) can be identical main chain or also can be respectively different main chains with above-mentioned vinyl based polymer main chain (B)]
The group, other 2 of expression be-and C (=O) combination of OH, perhaps, (iv) A 1～A 3In 3 be-C (=O) OH, k is 1 or 2] group of expression,
Or with general formula (3):
[chemical formula 5]
Figure A20068004121500142
[(v) A in the general formula (3), is arranged 5～A 7In 1 to be hydrogen atom, other 2 be-C (=O) combination of OH, perhaps (vi) A 5～A 7In 1 be-C (=O) OR d(wherein, R dBe that carbon number is 1～18 alkyl), other 2 be-C (=O) combination of OH, perhaps (vii) A 5～A 7In 1 be with general formula (3a):
[chemical formula 6]
Figure A20068004121500143
[in the general formula (3a),
X 31For-C (=O) O-,-C (=O) NH-,-O-,-OC (=O)-or-CH 2O-,
X 32Be to use general formula:
-(-R a31-O-) m31-
(in the formula, R A31Be that carbon number is that the alkylidene of 2～8 straight or branched or carbon number are 3～8 ring alkylidene, m31 is 1～50 integer) group of expression,
X 33Be to use general formula:
-(-C(＝O)-R b31-O-) m32-
(R B31Be that carbon number is that the alkylidene of 4～8 straight or branched or carbon number are 4～8 ring alkylidene, m32 is 0～20 integer) group of expression,
Z 31Be to contain useful general formula (31):
[chemical formula 7]
Figure A20068004121500151
[in the general formula (31), R 31Be hydrogen atom or methyl] the vinyl based polymer main chain (C) of group of expression, above-mentioned vinyl based polymer main chain (A) can be identical main chain or also can be respectively different main chains with above-mentioned vinyl based polymer main chain (C)] group, other 2 of expression for-C (=O) combination of OH, perhaps
(viii) A 5～A 73 be-C (=O) OH,
R 2Be Direct Bonding ,-CH 2-,-O-,-C (=O)-,-C (=O) OCH 2CH 2OC (=O)-,-C (=O) OCH (OC (=O) CH 3) CH 2OC (=O)-,-SO 2-,-C (CF 3) 2-, use formula:
[chemical formula 8]
Figure A20068004121500161
The expression group or use formula:
[chemical formula 9]
Figure A20068004121500162
The expression group] expression group.
In the preferred version of ethene base system dispersant of the present invention (a), the A in the general formula (2) 1～A 3Be combinations thereof (i), perhaps the A in the general formula (3) 5～A 7For combinations thereof (v).
In other preferred versions of ethene base system dispersant of the present invention (a), the A in the general formula (2) 1～A 3For combinations thereof (iii), the perhaps A in the general formula (3) 5～A 7For combinations thereof (vii).
Ethene base system dispersant of the present invention (a) so that other preferred version in, with the Y that contains carboxyl unit (G) of general formula (1) expression 1It is the group of general formula (2) expression.
Ethene base system dispersant of the present invention (a) so that other preferred version in, represent with general formula (4).
[Chemical formula 1 0]
Figure A20068004121500171
[in the general formula (4),
G be illustrated in above-mentioned with general formula (1) expression contain carboxyl unit (G),
R 4Expression hydrogen atom or methyl,
R 5Expression hydrogen atom or methyl,
R 6Be aromatic group or-C (=O)-X 7-R 7(wherein, X 7For-O-or-NH-, R 7Be that hydrogen atom or carbon number are the alkyl of 1～18 straight or branched, above-mentioned R 7Can have aromatic group as substituting group),
X 4For-C (=O) O-,-C (=O) NH-,-O-,-OC (=O)-or-CH 2O-,
X 5Be to use formula:
-(-R a2-O-) m3-
(in the formula, R A2Be that carbon number is that the alkylidene of 2～8 straight or branched or carbon number are 3～8 ring alkylidene, m3 is 1～50 integer) group of expression,
X 6Be to use formula:
-(-C-(＝O)-R b4-O-) m4-
(in the formula, R B2Be that carbon number is the alkylidene of 4～8 straight or branched, m4 is 0～20 integer) group of expression,
Above-mentioned in the general formula (4) contains carboxyl unit (G), contains-X 4-X 5-X 6The hydroxyl unit (J) of-H and containing-C (R 5) (R 6)-the configuration of backbone structure unit (K) be not limited to this order, in vinyl based polymer main chain with general formula (4) expression, expression can contain each unit G, J and K in any order, and then can contain each unit G, J and K in the mode of random or block type
For above-mentioned carboxyl unit (G), above-mentioned hydroxyl unit (J) and backbone structure unit (K) of containing that in general formula (4), contains, when they exist when a plurality of, can be identical each other or also can be different, in addition, p1, p2 and p3 represent the mean number of each construction unit in each molecule ethene base system dispersant, p1 is more than 0.3, below 3.0, and p2 is more than 0, below 180, and p3 is more than 6, below 250].
Ethene base system dispersant of the present invention (a) so that other preferred version in, number-average molecular weight is more than 500, below 40000.
The present invention relates to contain the color compositions of pigment and above-mentioned ethene base system dispersant (a).
In the preferred version of color compositions of the present invention, and then contain and be selected from pigment derivative, anthraquinone derivative, have the acridone derivatives of basic group and have alkaline builder at least a of the pyrrolotriazine derivatives of basic group with basic group with basic group.
In addition, the present invention relates to the manufacture method of ethene base system dispersant [below be referred to as ethene base system dispersant (A)], it contains
(A) make ethylenically unsaturated monomers (h) with hydroxyl and tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) reaction make ethylenically unsaturated monomers operation and
(B) operation that makes the ethylenically unsaturated monomers that in above-mentioned operation (A), obtains and other ethylenically unsaturated monomers carry out copolymerization.
In addition, the present invention relates to the manufacture method of ethene base system dispersant (A), it comprises:
(C) make ethylenically unsaturated monomers (h) with hydroxyl and other ethylenically unsaturated monomers carry out copolymerization operation and
(D) operation that the hydroxyl of tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) and the copolymerization that obtains in above-mentioned operation (C) is reacted.
In addition, the present invention relates to the manufacture method of ethene base system dispersant (A), its ethylenically unsaturated monomers (h) that will have hydroxyl on one side carries out copolymerization with other ethylenically unsaturated monomers, Yi Bian make tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) and this hydroxyl reaction simultaneously.
In the preferred version of above-mentioned each manufacture method, the acid anhydrides that reacts is a trimellitic anhydride.
In other preferred versions of above-mentioned each manufacture method, the acid anhydrides that reacts is aromatic tetracarboxylic acid's dianhydride.
In addition, the ethene base system dispersant (A) that the present invention relates to utilize any manufacture method of above-mentioned each manufacture method to make.
By in color compositions, using above-mentioned ethene base system dispersant of the present invention (a), can obtain dispersiveness, flowability and storage stability with low use amount, can obtain the hear resistance and the resistance to chemical reagents of color development thing simultaneously.
In addition, manufacturing method according to the invention can be made the above-mentioned ethene base system dispersant (A) with the extensive structure that comprises above-mentioned ethene base system dispersant (a) effectively.
The specific embodiment
The present invention relates to ethene base system dispersant (a), it is characterized in that, in vinyl based polymer main chain (for example in the acrylic acid series polymeric compounds main chain), contain with average amount more than 0.3, below 3.0 in per 1 molecule vinyl based polymer and to contain carboxyl unit (the G) [Y in the general formula (1) particularly with above-mentioned general formula (1) expression 1].
At first explanation is, general pigment dispersing agent have the position that is adsorbed on the pigment and with structure as the high position of the solvent compatibility of decentralized medium, decide the performance of dispersant with the balance of these 2 functional parts.That is, in order to show dispersiveness, the performance of dispersant adsorption on pigment and all extremely important for compatibility as the solvent of decentralized medium.In containing in the carboxyl unit (G) of representing with above-mentioned general formula (1), with the Y of above-mentioned general formula (2) or above-mentioned general formula (3) expression 1Have 2 or 3 carboxyls on the ring structure carbon atom that directly is combined in aromatic ring, this directly is combined in the adsorption site that a plurality of carboxyls on the ring structure carbon atom of aromatic ring have formed pigment.But, work as Y 1When only having 1 carboxyl (scope of the present invention outer), can not show high dispersiveness, flowability and storage stability, from rather than preferred.
Importantly, above-mentioned ethene base system dispersant of the present invention (a) contains in 1 molecule and on average contains carboxyl unit (G) [the group Y in the general formula (1) particularly with general formula (1) expression more than 0.3, below 3.0 1].And then preferred more than 0.35, below 2.0, most preferably more than 0.4, below 1.5.When the position that is adsorbed on the pigment is few than 0.3 after a little while, dispersibility reduces as a result.In addition, when having the position that is adsorbed on the pigment too to become many for a long time than 3.0, cause dispersed situation about reducing on the contrary.
For general formula (1), consider the preferred X of general formula (1) from the lowering viscousity of pigment dispersion and the angle of storage stability 1For-C (=O) general formula of O-(1 '):
[Chemical formula 1 1]
Figure A20068004121500201
And then, R A1Preferably carbon number is 1～4 alkyl (for example, the propylidene of methylene, ethylidene, straight or branched or the butylidene of straight or branched), and m1 is preferably 1～10 (and then preferred 1～3), R B1Be preferably pentamethylene, m2 is preferably 0～5 (and then preferred 0～3).
Especially, Y 1A in the general formula (2) preferably 1～A 3In 1 be hydrogen atom, other 2 for-C (=O) combination of OH group, or A in the general formula (3) 5～A 7In 1 to be hydrogen atom, other 2 be-C (=O) the combination of OH group.
In addition, as other modes, A in the preferred formula (2) 1～A 3In 1 be with the group, other 2 of general formula (2a) expression for-C (=O) combination of OH, perhaps A in the general formula (3) 5～A 7In 1 be to be-C (=O) the combination of OH with the group, other 2 of general formula (3a) expression.Containing a kind of scheme this combination, ethene base system dispersant of the present invention for example can represent with general formula (4A).
General formula (4A):
[Chemical formula 1 2]
Figure A20068004121500202
[in the general formula (4A), curved portion is described vinyl based polymer main chain,
R 1And X 1～X 3It is identical with each group in the above-mentioned general formula (1),
R 11And X 11～X 13Respectively with above-mentioned general formula (1) in R 1And X 1～X 3Identical (wherein, R 11With R 1, X 11With X 1, X 12With X 2, X 13With X 3Separate respectively),
Y 2Be with general formula (2 '):
[Chemical formula 1 3]
Figure A20068004121500211
[in the general formula (2 '), k ' is 1 or 2]
Perhaps use general formula (3 '):
[Chemical formula 1 4]
Figure A20068004121500212
[in the general formula (3 '), R 2' with above-mentioned general formula (3) in radicals R 2Identical]
Organic residue of 4 valencys of expression.
E 1～E 4The end of expression vinyl based polymer main chain.Here, E 1End or E 2End also can with E 3End or E 4Terminal combination.Wherein, E 1End and E 2Terminal can not being combined in simultaneously on the identical end].
In above-mentioned general formula (4A), work as E 1End or E 2End and E 3End or E 4Terminal in conjunction with the time [for example, vinyl based polymer main chain (B) is the situation of identical main chain with vinyl based polymer main chain (A) in above-mentioned general formula (2a), perhaps vinyl based polymer main chain (C) is the situation of identical main chain with vinyl based polymer main chain (A) in above-mentioned general formula (3a)], contain the backbone structure unit of representing with general formula (4B) at its vinyl based polymer main chain.
[Chemical formula 1 5]
Figure A20068004121500221
[in the formula, R 1And X 1～X 3, R 11And X 11～X 13, and Y 2It is identical with each group in the above-mentioned general formula (4A),
With general formula (4b):
[Chemical formula 1 6]
Figure A20068004121500222
The backbone structure unit (B) of expression be can constitute vinyl based polymer main chain construction unit [for example, contain carboxyl unit (G) (wherein with the hydroxyl unit (J) of following general formula (4j) expression or with the backbone structure unit (K) of general formula (4k) expression or with what general formula (1) was represented, in general formula (1), the A in the general formula (2) 1～A 3Not group with general formula (2A) expression, the A in the general formula (3) 5～A 7Be not group with general formula (3A) expression)],
M41 is more than 0, below 430].
In above-mentioned general formula (4A), work as E 1End or E 2End not with E 3End or E 4Terminal in conjunction with the time [for example, vinyl based polymer main chain (B) and vinyl based polymer main chain (A) are the situations of different main chain in above-mentioned general formula (2a), in the perhaps above-mentioned general formula (3a), vinyl based polymer main chain (C) and vinyl based polymer main chain (A) are the situations of different main chain], in this specification about vinyl based polymer main chain (A) even record for Z 21[that is the vinyl based polymer main chain (B) that, contains the group of useful general formula (21) expression] or Z 31[that is, containing the vinyl based polymer main chain (C) of the group of useful general formula (31) expression], also can be and directly suitable according to those skilled in the art's technology general knowledge.
And then in general formula (1), Y 1Preferably use the group of general formula (2) expression, and then preferred k is 1.In addition, work as Y 1When representing with general formula (3), R 2Be preferably Direct Bonding ,-C (=O) OCH 2CH 2OC (=O)-or use formula:
[Chemical formula 1 7]
Figure A20068004121500231
The group of expression.
Above-mentioned ethene base system dispersant of the present invention (a) can enumerate comprise with above-mentioned general formula (1) expression contain carboxyl unit (G), with general formula (4j):
[Chemical formula 1 8]
Figure A20068004121500232
[in the general formula (4j), R 4, X 4, X 5, and X 6Same as described above] the hydroxyl unit (J) of expression and with general formula (4k):
[Chemical formula 1 9]
Figure A20068004121500241
[in the general formula (4k), R 5And R 6Same as described above]
The block copolymer or the random copolymer of each construction unit of the backbone structure unit (K) of expression.
Therefore, preferred above-mentioned ethene base system dispersant (a) is with above-mentioned general formula (4) or general formula (4a) among the present invention:
-[G]p1-[J]p2-[K]p3-(4a)
The copolymer of expression.Here, G contains the carboxyl unit with above-mentioned general formula (1) expression, J is the hydroxyl unit with above-mentioned general formula (4j) expression, K is the backbone structure unit with above-mentioned general formula (4k) expression, p1 is (preferred more than 0.35, below 2.0 more than 0.3, below 3.0, and then preferred more than 0.4, below 1.5), p2 is (preferred more than 0.05, below 50) more than 0, below 180, p3 is (preferred more than 10, below 100) more than 6, below 250.In addition, in above-mentioned general formula (4a), contain carboxyl unit (G) and hydroxyl unit (J) and backbone structure unit (K), can exist with block copolymerization form or random copolymerization form respectively.And then, above-mentionedly contain carboxyl unit (G), above-mentioned hydroxyl unit (J) and backbone structure unit (K) can exist a plurality of respectively in above-mentioned general formula (4a).At this moment, unit separately can be identical each other, also can be different.For example, backbone structure unit (K) can contain the construction unit of the structure more than 2 kinds or 2 kinds.And, for the configuration that contains carboxyl unit (G), hydroxyl unit (J) and backbone structure unit (K) in the general formula (4a), not only mean and to contain [G] p1, [J] p2 and [K] p3 with this in proper order, can also random order contain each unit G, J and K respectively.
For the hydroxyl unit (J) that in of the present invention above-mentioned ethene base system dispersant (a), contains, preferred X with above-mentioned general formula (4) or general formula (4a) expression 4Be-C (=O) O-, preferred R A2Be that carbon number is 1～4 alkyl (for example: the propylidene of methylene, ethylidene, straight or branched or the butylidene of straight or branched), m3 is preferably 1～10 (and then 1～3), R B4Be preferably pentamethylene, m4 is preferably 0～5 (and then preferred 0～3).
Of the present invention above-mentioned ethene base system dispersant (a) with above-mentioned general formula (4) or general formula (4a) expression preferably contains R 5Be methyl, R 6For-C (=O)-O-CH 2The backbone structure unit (K1) of-Ar (wherein, Ar is an aromatic group, is in particular phenyl) is as above-mentioned backbone structure unit (K).This backbone structure unit (K1) preferably has average amount more than 1, below 100 in the ethene polymers of each molecule, the above-mentioned ethene base system dispersant (a) of this scheme has excellent dispersibility.
And then the of the present invention above-mentioned ethene base system dispersant of representing with above-mentioned general formula (4) or general formula (4a) (a) preferably contains R 5Be hydrogen atom or methyl, R 6For-C (=O)-O-R 7(wherein, R 7Be that carbon number is the alkyl of 2～12 straight or branched) backbone structure unit (K2) as above-mentioned backbone structure unit (K).More preferably in above-mentioned ethene base system dispersant (a), this backbone structure unit (K2) and above-mentioned backbone structure unit (K1) are also deposited.
And then, in addition, with the of the present invention above-mentioned ethene base system dispersant (a) of above-mentioned general formula (4) or general formula (4a) expression preferably to contain R separately or with above-mentioned backbone structure unit (K1) and/or above-mentioned backbone structure unit (K2) and the mode of depositing 5Be hydrogen atom, R 6For the backbone structure unit (K3) of aromatic group (being in particular phenyl) is used as above-mentioned backbone structure unit (K).And then, also can be used as above-mentioned backbone structure unit (K), make R 5Be hydrogen atom or methyl, R 6For the backbone structure unit (K4) of carboxyl with above-mentioned backbone structure unit (K1), backbone structure unit (K2) and/or backbone structure unit (K3) and deposit and contain.
When above-mentioned backbone structure unit (K1) and above-mentioned backbone structure unit (K2) and when depositing, their ratio (K1/K2) for example can be 0.01～100, preferred 0.1～10.In addition, when making above-mentioned backbone structure unit (K3) and above-mentioned backbone structure unit (K1) and/or above-mentioned backbone structure unit (K2) and depositing, its ratio [K3/ (K1+K2)] for example can be 0.01～10, preferred 0.05～2.And then when making above-mentioned backbone structure unit (K4) and above-mentioned backbone structure unit (K) in addition and depositing, its ratio [K4/K] for example can be 0～0.2, preferred 0～0.1.
Can have with the main chain end of the ethene base system dispersant (a) of above-mentioned general formula (4) expression and to think in the polymerization of known ethylenically unsaturated monomers or the structure in the polymerization process, for example from polymerization initiator, from chain-transferring agent, from solvent or from the chemical constitution of ethylenically unsaturated monomers etc.
The number-average molecular weight of ethene base system dispersant of the present invention (a) is preferably more than 500, below 40000, and then preferred more than 1000, below 20000, most preferably more than 1500, below 16000.No matter number-average molecular weight is less than 500 or surpass 40000, dispersiveness or the mobile situation about reducing of causing arranged all.
Above-mentioned ethene base system dispersant of the present invention (a) can utilize manufacture method of the present invention to make.According to following manufacture method of the present invention, not only can make above-mentioned ethene base system dispersant (a), can also make ethene base system dispersant (A) with the extensive structure that comprises above-mentioned ethene base system dispersant (a).That is, in following manufacture method of the present invention, can make above-mentioned ethene base system dispersant of the present invention (a) by selecting specific parent material.
As the manufacture method of ethene base system dispersant of the present invention (A), can enumerate following manufacture method 1～3.
Manufacture method 1:
Comprise
(A) make ethylenically unsaturated monomers (h) with hydroxyl and tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) react, make the operation of ethylenically unsaturated monomers in advance;
(B) operation that makes this ethylenically unsaturated monomers and other ethylenically unsaturated monomers carry out copolymerization.
Manufacture method 2:
Comprise
(C) will have the ethylenically unsaturated monomers (h) of hydroxyl and the operation that other ethylenically unsaturated monomers carries out copolymerization;
(D) make the operation of the hydroxyl reaction of tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) and this copolymer.
Manufacture method 3:
The ethylenically unsaturated monomers (h) that will have hydroxyl on one side carries out copolymerization with other ethylenically unsaturated monomers, Yi Bian make tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) and this hydroxyl reaction simultaneously.
As the ethylenically unsaturated monomers with hydroxyl (h) that in above-mentioned manufacture method, uses, so long as the monomer that has hydroxyl and have an ethylenic unsaturated double-bond gets final product, specifically, can enumerate (methyl) acrylic ester monomer, for example (methyl) acrylic acid 2-hydroxy methacrylate with hydroxyl, (methyl) acrylic acid 2 (or 3)-hydroxy propyl esters, (methyl) acrylic acid hydroxyalkyl acrylate of (methyl) acrylic acid 2 (or 3 or 4)-hydroxyl butyl ester and cyclohexanedimethanol list (methyl) acrylate etc., and the alkyl-Alpha-hydroxy alkyl acrylate of ethyl-Alpha-hydroxy methacrylate etc.; (methyl) acrylamide monomer that perhaps has hydroxyl, for example N-(hydroxy alkyl) (methyl) acrylamide of N-(2-hydroxyethyl) (methyl) acrylamide, N-(2-hydroxypropyl) (methyl) acrylamide, N-(2-hydroxybutyl) (methyl) acrylamide etc.; The vinyl ethers that perhaps has hydroxyl is a monomer, the hydroxy alkyl vinyl ethers of 2-hydroxyethyl vinyl ethers, 2-(or 3-) hydroxypropyl vinyl ethers, 2-(or 3-or 4-) hydroxybutyl vinyl ethers etc. for example, the allyl ether that perhaps has hydroxyl is a monomer, for example the hydroxy alkyl allyl ether of 2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, 2-(or 3-or 4-) hydroxybutyl allyl ether etc.
In addition, addition alkylene oxide and/or lactone in above-mentioned (methyl) acrylic acid hydroxyalkyl acrylate, alkyl-Alpha-hydroxy alkyl acrylate, N-(hydroxy alkyl) (methyl) acrylamide, hydroxy alkyl vinyl ethers or hydroxy alkyl allyl ether and the ethylenically unsaturated monomers that obtains in the methods of the invention also can be as the ethylenically unsaturated monomers (h) with hydroxyl.As the alkylene oxide of addition, can use oxirane, expoxy propane, 1,2-, 1,4-, 2,3-or 1, also the using more than 2 kinds of 3-epoxy butane and these compounds is.And the combining form during with the alkylene oxide more than 2 kinds can be in random and/or the block any one.As the lactone of addition, can use δ-Wu Neizhi, 6-caprolactone, with carbon number be the 6-caprolactone that replaces of 1～6 alkyl and these compounds more than 2 kinds and with system.Also can the two carries out addition with alkylene oxide and lactone.
As tricarboxylic acid anhydride (M3), at first can enumerate aliphatic tricarboxylic acids acid anhydride, aromatic tricarboxylic acids acid anhydride or polycycle tricarboxylic acid anhydride.
The aliphatic tricarboxylic acids acid anhydride can be enumerated for example 3-carboxyl methylglutaric acid acid anhydride, 1,2,4-butane tricarboxylic acids-1,2-acid anhydride, suitable-propylene-1,2,3-tricarboxylic acids-1,2-acid anhydride, 1,3,4-pentamethylene tricarboxylic acid anhydride etc.
The aromatic tricarboxylic acids acid anhydride for example can enumerate benzene tricarbonic acid's acid anhydride (1,2,3-benzene tricarbonic acid acid anhydride, trimellitic anhydride (1,2,4-benzenetricarboxylic anhydride) etc. naphthalene tricarboxylic acid anhydride (1,2),, 4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,3,4,4 8-naphthalene tricarboxylic acid anhydride etc.), '-benzophenone tricarboxylic acid anhydride, 3,4,4 '-diphenyl ether tricarboxylic acid anhydride, 3,4,4 '-biphenyl tricarboxylic acid anhydride, 2,3,2 '-biphenyl tricarboxylic acid anhydride, 3,4,4 '-biphenyl methane tricarboxylic acid anhydride, 3,4,4 '-the diphenyl sulphone (DPS) tricarboxylic acid anhydride etc.
In addition, in the methods of the invention, for following tetracarboxylic dianhydride (M4), with 1 acid anhydrides water in 1 molecule, carbon number is that 1～18 alcohol or carbon number are that 5～18 cyclic alcohol (for example can be enumerated methyl alcohol, ethanol, the propyl alcohol of straight or branched, the butanols of straight or branched, the amylalcohol of straight or branched or cyclopentanol, the hexanol of straight or branched or cyclohexanol, the enanthol of straight or branched or suberol, the octanol of straight or branched or ring octanol, the nonyl alcohol of straight or branched or ring nonyl alcohol, the decyl alcohol of straight or branched or ring decyl alcohol, the dodecanol of straight or branched or cyclododecanols, the tetradecanol of straight or branched or ring tetradecanol, the hexadecanol of straight or branched or ring hexadecanol, the octadecanol of straight or branched or ring octadecanol etc.) carry out the tetrabasic carboxylic acid list acid anhydride that open loop forms, also can use as tricarboxylic acid anhydride (M3) in the methods of the invention with tetrabasic carboxylic acid monoesters list acid anhydride.In this manual, aliphatic tetrabasic carboxylic acid monoesters list acid anhydride, aliphatic tricarboxylic acids acid anhydride, aromatic tetracarboxylic acid's monoesters list acid anhydride and aromatic tricarboxylic acids acid anhydride, polycycle tetracarboxylic anhydride monoesters list acid anhydride are described as the polycycle tricarboxylic acid anhydride.The object lesson of these tetracarboxylic anhydride monoesters list acid anhydrides can be known by following tetracarboxylic dianhydride for those skilled in the art.
Tetracarboxylic dianhydride (M4) can enumerate for example aliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride or polycycle tetracarboxylic dianhydride.
Aliphatic tetracarboxylic dianhydride for example can enumerate 1,2,3,4-butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 3,5,6-three carboxyls norbornane-2-acetate dianhydride, 2,3,4,5-oxolane tetracarboxylic dianhydride, 5-(2,5-dioxo oxolane)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, two rings [2,2,2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride etc.
Aromatic tetracarboxylic acid's dianhydride can be enumerated for example PMDA, two trimellitic anhydride glycol esters, two trimellitic anhydride propylene glycol esters, two trimellitic anhydride butanediol esters, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, connection (phthalic acid) phenyl phosphine oxide dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-the diphenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-the diphenyl methane dianhydride, 9,9-two (3,4-dicarboxyl phenyl) fluorenic acid dianhydride, 9, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] fluorenic acid dianhydrides of 9-etc.
Polycycle tetracarboxylic dianhydride for example can enumerate 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-6-methyl isophthalic acid-naphthalene succinic dianhydride etc.
For manufacture method 1 of the present invention and then be described in detail.
In manufacture method 1 of the present invention, at first make the operation A of ethylenically unsaturated monomers (h) with hydroxyl and tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) reaction.For this operation A, produce thermal polymerization in order not make monomer, preferably dry air is flow in the reaction unit, and meanwhile polymerization inhibitor added, and under 80～150 ℃, carry out.More preferably 90 ℃～130 ℃.As polymerization inhibitor, can enumerate quinhydrones, hydroquinone monomethyl ether, methylnaphthohydroquinone etc.
When in operation A, making ethylenically unsaturated monomers (h) with hydroxyl and tricarboxylic acid anhydride (M3) when reacting, as reaction ratio, preferred " molal quantity of molal quantity/tricarboxylic acid anhydride (M3) with ethylenically unsaturated monomers (h) of hydroxyl " is more than 0.8, below 10.More preferably more than 0.9, below 5, and then preferred more than 0.95, below 2.When less than 0.8 the time, tricarboxylic acid anhydride (M3) has residual, is not preferred therefore.When greater than 10 the time, the ethylenically unsaturated monomers (h) with hydroxyl is residual in a large number, and the amount that can carry out other ethylenically unsaturated monomers of copolymerization in process B thereafter reduces, from rather than preferred.
When in operation A, making ethylenically unsaturated monomers (h) with hydroxyl and tetracarboxylic dianhydride (M4) when reacting, as reaction ratio, preferred " molal quantity/tetracarboxylic dianhydride's (M4) the molal quantity with ethylenically unsaturated monomers (h) of hydroxyl " is more than 0.5, below 10.0.More preferably more than 1.0, below 5.0.When less than 0.5 the time, tetracarboxylic dianhydride (M4) is residual morely, is not preferred therefore.When greater than 10 the time, the ethylenically unsaturated monomers (h) with hydroxyl is residual in a large number, and the amount that can carry out other ethylenically unsaturated monomers of copolymerization in process B thereafter reduces, from rather than preferred.
In operation A, also can use catalyst.Catalyst preferably uses the tertiary amine based compound, can enumerate for example triethylamine, triethylenediamine, N, N-dimethyl benzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0]-7-hendecene, 1,5-diazabicyclo [4.3.0]-5-nonene etc.
And then, when making ethylenically unsaturated monomers (h) with hydroxyl and tetracarboxylic dianhydride (M4) with " molal quantity/tetracarboxylic dianhydride's (M4) molal quantity " when reacting less than 2.0 condition with ethylenically unsaturated monomers (h) of hydroxyl, can water or carbon number be that 1～18 alcohol makes residual anhydride group open loop (operation Aa) this moment, thereby can easily remove unwanted anhydride group.
Then, in manufacture method 1, make the ethylenically unsaturated monomers synthetic among the operation A and the process B of other ethylenically unsaturated monomers copolymerization.
Preferably following such ethylenically unsaturated monomers is carried out copolymerization as other ethylenically unsaturated monomers that uses in operation A, it is that 1～18 (methyl) alkyl acrylate, carbon number are 1～18 N-alkyl (methyl) acrylamide, styrene, have the ethylenically unsaturated monomers (h) (comprising compound residual among the operation A) of hydroxyl and have the ethylenically unsaturated monomers of carboxyl that described ethylenically unsaturated monomers is selected from the carbon number that can be replaced by aromatic group.
(methyl) alkyl acrylate of non-replacement can be enumerated (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate of straight or branched, (methyl) butyl acrylate of straight or branched, (methyl) acrylic acid pentyl ester of straight or branched, (methyl) acrylic acid ring pentyl ester, (methyl) Hexyl 2-propenoate of straight or branched, (methyl) cyclohexyl acrylate, (methyl) acrylic acid heptyl ester of straight or branched, (methyl) acrylic acid ring heptyl ester, (methyl) 2-ethyl hexyl acrylate of straight or branched, (methyl) acrylic acid ring monooctyl ester, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems of straight or branched, (methyl) acrylic acid ring ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate of straight or branched, (methyl) acrylic acid ring ester in the last of the ten Heavenly stems, (methyl) dodecylacrylate of straight or branched, (methyl) acrylic acid cyclo-dodecyl ester, (methyl) acrylic acid myristyl ester of straight or branched, (methyl) acrylic acid ring myristyl ester, (methyl) acrylic acid cetyl ester of straight or branched, (methyl) acrylic acid ring cetyl ester, (methyl) acrylic acid stearyl with straight or branched, or (methyl) acrylic acid ring stearyl.Can enumerate (methyl) benzyl acrylate with aromatic series cyclosubstituted (methyl) alkyl acrylate.
N-alkyl (methyl) acrylamide of non-replacement can be enumerated N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide of straight or branched, N-butyl (methyl) acrylamide of straight or branched, N-amyl group (methyl) acrylamide of straight or branched, N-cyclopenta (methyl) acrylamide, N-hexyl (methyl) acrylamide of straight or branched, N-cyclohexyl (methyl) acrylamide, N-heptyl (methyl) acrylamide of straight or branched, N-suberyl (methyl) acrylamide, N-octyl group (methyl) acrylamide of straight or branched, N-ring octyl group (methyl) acrylamide, N-nonyl (methyl) acrylamide of straight or branched, N-ring octyl group (methyl) acrylamide, N-decyl (methyl) acrylamide of straight or branched, N-ring decyl (methyl) acrylamide, N-dodecyl (methyl) acrylamide of straight or branched, N-cyclo-dodecyl (methyl) acrylamide, N-myristyl (methyl) acrylamide of straight or branched, N-ring myristyl (methyl) acrylamide, N-cetyl (methyl) acrylamide of straight or branched, N-ring cetyl (methyl) acrylamide, N-octadecyl (methyl) acrylamide of straight or branched, or N-ring octadecyl (methyl) acrylamide.As with the cyclosubstituted alkyl of aromatic series (methyl) acrylamide, can enumerate N-benzyl (methyl) acrylamide.And (methyl) acrylate is represented methacrylate or acrylate here, and (methyl) acrylamide is represented Methacrylamide or acrylamide.
Ethylenically unsaturated monomers with carboxyl can be enumerated caprolactone addition product (the addition molal quantity is 1～5) of for example acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, acrylic acid dimer, acrylic acid caprolactone addition product (the addition molal quantity is 1～5) and methacrylic acid etc.
In process B, while preferably make reaction vessel carry out nitrogen replacement, use polymerization initiator, under 50 ℃～150 ℃, carry out polymerisation.As polymerization initiator, can enumerate alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, the peroxidating isobutyl group, lauryl peroxide, 3,5,5-trimethyl acetyl base peroxide, the peroxidating decoyl, tert butyl isopropyl benzene peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, the cumyl peroxide base, peroxidating two-tert-butyl group, 1,1-bis(t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane, 3,3, the 5-trimethyl hexanone peroxide, methyl cyclohexanone peroxide, two (isobutyl group peroxies), two carbonic esters, two (2-ethylhexyl peroxies), two carbonic esters, organic peroxides such as t-butylperoxy isobutyrate; 2,2 '-azodiisobutyronitrile, dimethyl-2,2 '-azo-bis-iso-butyl, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2, the two azo-compounds such as (2-methylbutyronitriles) of 2-azo.In these compounds, preferably use azo-compound.With respect to the ethylenically unsaturated monomers that adds up to 100 weight portions, preferably use the polymerization initiator of 1～20 weight portion.
In process B, also can use chain-transferring agent.Chain-transferring agent can be enumerated the mercapto methyl acetate, the mercapto octyl acetate, the mercapto methoxy butyl acetate, two mercapto acetate glycol esters, two mercapto acetate butanediol esters, two mercapto acetate hexylene glycol esters, the trimethylolpropane tris Thioglycolate, pentaerythrite four Thioglycolates, mercapto-propionate, mercaptopropionic acid methoxyl group butyl ester, the mercaptopropionic acid monooctyl ester, mercaptopropionic acid tridecyl ester, dimercapto propionic acid glycol ester, the trimethylolpropane tris mercaptopropionic acid ester, pentaerythrite four mercaptopropionic acid esters, the AMS dimer.
The preferred solvent that uses in process B.Solvent can use the acetate esters of ethyl acetate, propyl acetate, butyl acetate, ethyl cellosolve acetate (ethyl cellosolve acetate), propylene glycol methyl ether acetate etc., the ketone of acetone, methyl ethyl ketone, cyclohexanone, methyl iso-butyl ketone (MIBK) etc., the aromatic series alkanes of dimethylbenzene, toluene, ethylbenzene etc. etc.
After operation A, when not carrying out operation Aa, can water or carbon number be that 1～18 alcohol makes acid anhydrides open loop (process B b) residual after process B.In operation Aa or process B b, the water of preferred reaction or carbon number are that the molal quantity of 1～18 alcohol is (preferred more than 1 times, below 2 times) more than 0.9 times, below 5 times with respect to the molal quantity of residual acid anhydrides.When less than 0.9 times, reactive high anhydride group is residual morely, when greater than 5 times, water or carbon number be 1～18 pure residual morely, no matter that a kind of situation when printing ink or coating are carried out the purposes expansion, all may have problems.Yet, when being 1～18 alcohol, the water that makes reaction or carbon number surpass 1 times when reacting with respect to the molal quantity of residual acid anhydrides, and can heat or reduce pressure except that water residual after the dereaction or carbon number is 1～18 alcohol.Preferred reaction operation Aa or process B b carry out under 80～150 ℃.
Then, be described in detail for manufacture method 2 of the present invention.
In manufacture method 2 of the present invention, the ethylenically unsaturated monomers (h) that at first carries out having hydroxyl and the operation C of other ethylenically unsaturated monomers copolymerization.Preferably following such ethylenically unsaturated monomers is carried out copolymerization as other ethylenically unsaturated monomers, described ethylenically unsaturated monomers is selected from can being (methyl) alkyl acrylate of 1～18, can being 1～18 N-alkyl (methyl) acrylamide, styrene and the ethylenically unsaturated monomers with carboxyl by the cyclosubstituted carbon number of aromatic series by the cyclosubstituted carbon number of aromatic series of enumerating in the process B of manufacture method 1.
Having the ethylenically unsaturated monomers (h) of hydroxyl and the copolymerization ratio of other ethylenically unsaturated monomers decides in the mode that on average adds the hydroxyl more than 0.3, below 177 in a part after polymerization at least.
Preferably the process B with manufacture method 1 is identical for the polymerizing condition of the kind of the kind of polymerization initiator, chain-transferring agent, solvent types, amount, reaction temperature etc. among the operation C.
Then, in manufacture method 2, make the step D of the hydroxyl reaction of the copolymer that obtains among tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) and the operation C.In step D, while preferably make nitrogen or dry air in reaction vessel, flow, under 80 ℃～150 ℃, carry out.Here, also can use the catalyst of in the operation A of manufacture method 1, enumerating.
For the situation of in the step D of manufacture method 2, using tetracarboxylic dianhydride (M4), when anhydride group is residual, can utilize the method identical with the process B b of manufacture method 1, water or carbon number are that 1～18 alcohol makes residual acid anhydrides open loop (step D d).
Below, be described in detail for manufacture method 3 of the present invention.
In manufacture method 3 of the present invention, on one side will have a hydroxyl ethylenically unsaturated monomers (h) carry out copolymerization with other ethylenically unsaturated monomers, make tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) and this hydroxyl reaction on one side simultaneously.Reaction is preferably while making nitrogen flow in reaction vessel, carry out under 80 ℃～150 ℃, preferred hydroxyl and anhydride group catalyst for reaction are at the catalyst shown in the operation A of manufacture method 1, and the polymerizing condition of the kind of preferred polymeric initator, the kind of chain-transferring agent, solvent types, amount, reaction temperature etc. is in the condition shown in the process B of manufacture method 1.
Other ethylenically unsaturated monomers that uses in the manufacture method 3 is identical with the compound that uses in the operation C of manufacture method 2.In manufacture method 3, when anhydride group is residual, also can utilize the method identical with the process B b of manufacture method 1, water or carbon number are that 1～18 alcohol makes residual anhydride group open loop (operation Ee).
Utilize these manufacture methods 1～3, can make ethene base system dispersant of the present invention (A).Wherein, consider preferable production process 2 from the angle that can easily control the number that contains carboxyl unit (G) a part dispersant.This is because can be determined at the number-average molecular weight of the copolymer that obtains among the operation C of manufacture method 2 in advance, decides the amount that makes tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) reaction thereby adapt with this value.For example, making in the process of ethene base system dispersant (A) with manufacture method 2, be determined at the number-average molecular weight of the copolymer that obtains among the operation C, when its measured value is [X], for the situation of using tricarboxylic acid anhydride (M3), can make with respect to resin [X] g is that tricarboxylic acid anhydride (M3) more than 0.3 mole, below 3.0 moles reacts.On the other hand, when using tetracarboxylic dianhydride (M4),, the tetracarboxylic dianhydride (M4) more than 0.15 mole, below 1.5 moles is reacted with respect to resin [X] g.This is because have 2 anhydride group among the tetracarboxylic dianhydride (M4), so in order to make the two molecule crosslinking copolymers that obtain in operation C, the amount of half is reacted and got final product during with use tricarboxylic acid anhydride (M3).
In addition, for the situation of in step D, using tetracarboxylic dianhydride (M4), when the number of the hydroxyl that contains in a part copolymer that obtains in operation C is 1.1 when above, the total amount＜OH of the hydroxyl that preferably in copolymer, contains〉with the total amount＜AH of the anhydride group that in tetracarboxylic dianhydride (M4), contains ratio:＜OH 〉/＜AH value less than 0.9 or be more than 1.1.As＜OH 〉/＜AH value more than 0.9 and less than 1.1 scope the time, have the number-average molecular weight of ethene base system dispersant (A) to surpass the situation of the upper limit 40000 of the preferred number-average molecular weight of the present invention.
When utilizing manufacture method 1 or 3 to make ethene base system dispersant of the present invention (A), carry out inverse by the number-average molecular weight [Y] of the ethene base system dispersant (A) that finally obtains and tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride's (M4) interpolation molal quantity, as its result, be that tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) more than 0.3 mole, below 3.0 moles reacts as long as make with respect to ethene base system dispersant (A) [Y] g.
For the situation of making ethene base system dispersant (A) with manufacture method of the present invention, when using tricarboxylic acid anhydride (M3), optimization aromatic tricarboxylic acid anhydride, further preferred trimellitic anhydride.In addition, when the tetracarboxylic dianhydride (M4) that uses in above-mentioned, preferably use aromatic tetracarboxylic acid's dianhydride, and then preferred PMDA, two trimellitic anhydride glycol esters, 9, two (3,4-dicarboxyl phenyl) the fluorenic acid dianhydrides, 3 of 9-, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride.
In arbitrary method of manufacture method 1～3, when to ethene base system dispersant (A) when making, preferably make following such ethylenically unsaturated monomers carry out copolymerization as other ethylenically unsaturated monomers, it is 1～12 (methyl) alkyl acrylate, (methyl) acrylic acid benzyl ester, the ethylenically unsaturated monomers with hydroxyl (h) as required, styrene as required, the ethylenically unsaturated monomers with carboxyl as required that described ethylenically unsaturated monomers has the non-alternate c atoms number that can have side chain.And then preferably making 1～50 carbon number that can have the non-replacement of side chain in a part ethene base system dispersant (A) is that (methyl) alkyl acrylate of 1～12,1～50 (methyl) benzyl acrylate carry out copolymerization.
In addition, in ethene base system dispersant of the present invention (A), also can not hinder the various ethylenically unsaturated monomers that make under the dispersed scope except that the illustrated compound so far to carry out copolymerization, for example can make have NCO, the ethylenically unsaturated monomers of the heat cross-linking groups such as ring-type ester group of blocked isocyanate base, alkoxysilane group, 3～5 yuan of rings carries out copolymerization.
By use suitable parent material of selecting from the above-mentioned parent material of having enumerated, and utilize above-mentioned manufacture method of the present invention, can make above-mentioned ethene base system dispersant (a).
Use above-mentioned ethene base system dispersant (A) [perhaps, particularly above-mentioned ethene base system dispersant (a)] and pigment (P), can obtain color compositions of the present invention.Here, by use ethene base system dispersant (A) [perhaps, particularly above-mentioned ethene base system dispersant (a)], and formation is dispersed, mobile and the color compositions of excellent storage stability.
Employed pigment (P) can use the various pigment that are used for printing ink etc. among the present invention.Such pigment has the dissolubility AZOpigments, insoluble azo colour, phthalocyanine color, quinacridone pigment, isoindolinone pigment, isoindoline pigment perylene dye perylene ketone (perinone) pigment triazine dioxin pigment, anthraquinone pigment, dianthraquinone pigment, anthrapyrimidine (anthrapyrimidine) pigment, anthanthrene diketone pigment, indanthrone pigment, flavanthrone pigment, pyranthrone pigments, diketo-pyrrolo pyrrole pigments etc., if and then represent object lesson with the generic name of pigment index, then can enumerate pigment black 7, alizarol saphirol 6,15,15:1,15:3,15:4,15:6,60, pigment Green 7,36, Pigment Red 9,48,49,52,53,57,97,122,144,146,149,166,168,177,178,179,185,206,207,209,220,221,238,242,254,255, pigment violet 19,23,29,30,37,40,50, pigment Yellow 12,13,14,17,20,24,74,83,86,93,94,95,109,110,117,120,125,128,137,138,139,147,148,150,151,154,155,166,168,180,185, pigment orange 13,36,37,38,43,51,55,59,61,64,71,74 etc.But, be not limited to these examples.
In addition, also can use the metal oxide of titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, silica etc., the inorganic pigment of cadmium sulfide, calcium carbonate, brium carbonate, barium sulfate, clay, talcum, chrome yellow, carbon black etc.For carbon black, can use all carbon blacks of neutrality, acidity, alkalescence etc.
The use of ethene base system dispersant of the present invention is not limited to above-mentioned pigment, can also be used for for example gold, silver, copper, platinum, iron, cobalt, nickel and/or contain the dispersion of solia particle of metal particle of their alloy etc.
Preferably in color compositions of the present invention, and then contain and be selected from pigment derivative, anthraquinone derivative, have the acridone derivatives of basic group and have at least a alkaline builder (Y) of the pyrrolotriazine derivatives of basic group with basic group with basic group.
Here, pigment derivative is meant introduces the compound that specified substituent forms in the organic pigment residue of recording and narrating in above-mentioned pigment index, use in the present invention to have the pigment derivative of basic group.
By containing alkaline builder (Y), the pigment (particularly organic pigment) that also is difficult to disperse can be made the color compositions of dispersiveness, flowability, excellent storage stability under the situation that does not have alkaline builder (Y), from but preferred.Utilize the synergy of ethene base system dispersant (A) and alkaline builder (Y), can effectively pigment (P) be made the color compositions of dispersiveness, flowability, excellent storage stability.
The alkaline builder (Y) that can use in color compositions of the present invention is selected from pigment derivative, the anthraquinone derivative with basic group with basic group, have the acridone derivatives of basic group and have the pyrrolotriazine derivatives of basic group.
The basic group of the alkaline builder (Y) that can use in color compositions of the present invention is selected from least one group with following general formula (5), (6), (7) and (8) expression.
General formula (5)
[Chemical formula 2 0]
Figure A20068004121500351
General formula (6)
[Chemical formula 2 1]
Figure A20068004121500361
General formula (7)
[Chemical formula 2 2]
Figure A20068004121500362
General formula (8)
[Chemical formula 2 3]
Figure A20068004121500363
In above-mentioned general formula (5)～(8),
X: expression-SO 2-,-C (=O)-,-CH 2NHC (=O) CH 2-,-CH 2-or Direct Bonding.
V: the integer of expression 1～10.
R 8, R 9: respectively independent expression can substituted alkyl, can substituted thiazolinyl, can substituted phenyl or R 8, R 9Be combined into one and and then contain nitrogen, oxygen or sulphur atom can substituted heterocyclic group.
R 10: expression can substituted alkyl, can substituted thiazolinyl or can substituted phenyl.
R 11, R 12, R 13, R 14: respectively independent expression hydrogen atom, can substituted alkyl, can substituted thiazolinyl or can substituted phenyl.
Y: expression-NR 15-Z-NR 16-or Direct Bonding.
R 15, R 16: respectively independent expression hydrogen atom, can substituted alkyl, can substituted thiazolinyl or can substituted phenyl.
Z: expression can substituted alkylidene, can substituted alkenylene or can substituted phenylene.
W: the expression substituting group of general formula (5) expression or the substituting group of representing with general formula (7).
Q: represent hydroxyl, alkoxyl, use the substituting group of general formula (5) expression or the substituting group of representing with general formula (7).
Substituent preferred version with above-mentioned general formula (5) expression is that X is-SO 2-or C (=O)-, v is 1～5 (and then preferred 2～4), R 8And R 9Independent respectively expression methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, perhaps R 8With R 9Nitrogen-atoms in formula forms morpholine.
Substituent preferred version with above-mentioned general formula (6) expression is R 8And R 9Represent methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group respectively independently.
Substituent preferred version with above-mentioned general formula (7) expression is that X is-CH 2NHC (=O) CH 2-, R 10Be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group, R 11～R 14Be hydrogen atom.
Substituent preferred version with above-mentioned general formula (8) expression is that X is Direct Bonding or SO 2-, Y is Direct Bonding or NH-Z-NH-, and Z is a phenylene, and Q is hydroxyl, methoxyl group, ethyoxyl, propoxyl group or butoxy, and W is the substituting group with above-mentioned general formula (8) expression, the X among this W is-SO 2-or C (=O)-, the v among this W is 1～5 (and then preferred 2～4), the R among this W 8And R 9Represent methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group respectively independently.
Can enumerate for example dimethylamine for forming with the amine component that formula (5)～substituting group of formula (8) expression uses, diethylamine, Methylethyl amine, N, N-ethyl isopropylamine, N, N-ethyl propylamine, N, the N-methylbutylamine, N, N-methyl isobutyl amine, N, N-butyl ethamine, N, N-tert-butyl group ethamine, diisopropylamine, di-n-propylamine, N, N-sec-butyl propylamine, dibutyl amine, two sec-butylamine, diisobutyl amine, N, N-isobutyl group sec-butylamine, diamyl amine, diisoamyl amine, dihexyl amine, dicyclohexyl amine, two (2-ethylhexyl) amine, dioctylamine, N, N-methyl octadecylamine, eicosyl amine, diallylamine, N, N-ethyl-1, the 2-dimethyl propylamine, N, the N-tuaminoheptane, two oil base amine, two (octadecyl) amine, N, N-dimethylamino methylamine, N, N-dimethylamino ethamine, N, N-dimethylamino amylamine, N, N-dimethylamino butylamine, N, the N-diethylamino-ethylamine, N, the N-diethylaminopropylamine, N, N-lignocaine hexylamine, N, N-lignocaine butylamine, N, N-lignocaine amylamine, N, the amino butylamine of N-dipropyl, N, the N-dibutylaminopropylamine, N, N-dibutylamino ethamine, N, N-dibutylamino butylamine, N, the amino amylamine of N-two isobutyls, N, the amino propylamine of N-methyl dodecyl, N, the own aminoethyl of N-ethyl, N, N-two (octadecyl amino) ethamine, N, N-two oil base aminoethyl, N, N-two (octadecyl amino) butylamine, piperidines, pipecoline, the 3-methyl piperidine, the 4-methyl piperidine, 2, the 4-lupetidine, 2, the 6-lupetidine, 3, the 5-lupetidine, the 3-piperidine carbinols, nipecotic acid, isonipecotic acid, the isonipecotic acid methyl esters, isonipecotic acid ethyl ester, 2-piperidines ethanol, pyrrolidines, the 3-hydroxyl pyrrolidine, the N-aminoethyl piperidine, N-aminoethyl-4-methyl piperidine, the N-aminoethyl morpholine, N-aminopropyl piperidines, N-aminopropyl-pipecoline, N-aminopropyl-4-methyl piperidine, the N-aminopropyl morpholine, N methyl piperazine, N-butyl piperazine, the high piperazine of N-methyl, the 1-cyclopentyl-based piperazine, 1-amino-4-methyl piperazine, 1-cyclopentyl-based piperazine etc.
It is pigment that the organic pigment that constitutes the pigment derivative with basic group for example has diketopyrrolopyrrolecocrystals, azo, two diazonium, the azo of poly-azo etc. is a pigment, phthalocyanine is a pigment, the diaminourea DIANTHRAQUINONE, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, the anthraquinone of violanthrone etc. is a pigment, quinacridone pigment dioxazine is that pigment perylene ketone is that pigment perylene is a pigment, and thioindigo is a pigment, isoindoline is a pigment, isoindolinone is a pigment, Kui phthalein ketone is pigment, the intellectual circle is a pigment, the pigment of metal complex system pigment etc.In addition, the acridone derivatives that has the anthraquinone derivative of basic group and have a basic group also can have the alkyl of methyl, ethyl etc., amino, nitro, the substituting group of the halogen of the alkoxyl of hydroxyl or methoxyl group, ethyoxyl etc. or chlorine etc. etc.
In addition, the triazine that constitutes the pyrrolotriazine derivatives with basic group is to have following substituent 1,3, the 5-triazine, described substituting group has alkyl (methyl, ethyl, butyl etc.), amino, alkyl amino (dimethylamino, lignocaine, dibutylamino etc.), nitro, hydroxyl, alkoxyl (methoxyl group, ethyoxyl, butoxy etc.), halogen (chlorine, bromine etc.), phenyl (can be used alkyl, amino, alkyl amino, nitro, hydroxyl, alkoxyl, replacements such as halogen), and phenyl amino (can be used alkyl, amino, alkyl amino, nitro, hydroxyl, alkoxyl, replacements such as halogen) etc.
Pigment derivative, anthraquinone derivative and acridone derivatives with above-mentioned basic group can synthesize by various synthesis paths.For example, can be by after in organic pigment, anthraquinone or acridone, introducing substituting group with formula (11)～formula (14) expression, make itself and amine component, for example N, N-dimethylaminopropylamine, N methyl piperazine, diethylamine or 4-[4-hydroxyl-6-[3-(dibutylamino) third amino]-1,3,5-triazine-2-base is amino] aniline etc. reacts and obtains, and described amine component can form substituting group with formula (5)～formula (8) expression with above-mentioned substitution reaction.
Formula (11) :-SO 2Cl
Formula (12) :-C (=O) Cl
Formula (13) :-CH 2NHC (=O) CH 2Cl
Formula (14) :-CH 2Cl
With the substituting group of formula (11)～formula (14) expression during with the reaction of above-mentioned amine component, the substituting group generation hydrolysis that a part is represented with formula (11)～formula (14) is replaced to hydroxyl thereby can mix existence with the chlorine atom.At this moment, the substituting group of representing with formula (11) or formula (12) is respectively sulfonic group or carboxylic acid group, and wherein any one can keep the state of free acid, perhaps, also can form salt with the metal or the above-mentioned monoamine of 1～3 valency.
In addition, when organic pigment is an azo when being pigment, also can carry out coupling reaction afterwards again and make the azo pigment derivative by in diazonium composition or coupling composition, introducing the substituting group of representing with above-mentioned general formula (5)～formula (8) in advance.
Pyrrolotriazine derivatives with above-mentioned basic group can synthesize by various synthesis paths.For example can obtain by following manner: with cyanuric chloride as initiation material, make the substituent amine component, for example N that form with formula (5)～formula (8) expression, at least one chlorine reaction of N-dimethylaminopropylamine or N methyl piperazine etc. and cyanuric chloride makes then that remaining chlorine and various amine or alcohol etc. react in the cyanuric chloride.
In color compositions of the present invention, the use level of alkaline builder (Y) is preferably 1～50 weight portion with respect to the pigment (P) of 100 weight portions, and then preferred 3～30 weight portions, most preferably 5～25 weight portions.When the pigment (P) with respect to 100 weight portions, alkaline builder (Y) has the situation of dispersed variation during less than 1 weight portion, when greater than 50 weight portions, the situation of hear resistance, light resistance variation is arranged.In addition, [perhaps, particularly above-mentioned ethene base system dispersant (a)] use level is preferably 0.1～100 weight portion with respect to the pigment (P) of 100 weight portions to ethene base system dispersant (A), and then preferred 0.5～75 weight portion, 1.0～50 weight portions most preferably.When the pigment (P) with respect to 100 weight portions, ethene base system dispersant (A) has the situation of dispersed variation during less than 0.1 weight portion, when greater than 100 weight portions, the situation of dispersed variation is arranged also.
Color compositions of the present invention can mix all kinds of solvents, resin, additive etc. as required, by use horizontal sand mill, vertically sand mill, ring-like ball mill, grater (attritor) etc. disperse, and can make the pigment dispersion that color compositions is dispersed in form in the varnish.For pigment (P), alkaline builder (Y), ethene base system dispersant (A) [perhaps, particularly above-mentioned ethene base system dispersant (a)], other resin, additive, disperse again after all compositions can being mixed, also can be at first only with pigment (P) and alkaline builder (Y), perhaps only with alkaline builder (Y) and ethene base system dispersant (A), perhaps only pigment (P) and alkaline builder (Y) and ethene base system dispersant (A) are disperseed, add other composition then and disperse once more.
In addition, before disperseing with horizontal sand mill, vertical sand mill, ring-like ball mill, grater etc., also can use mixing rolls such as kneader, 3 beaming roller grinding machines preceding dispersion, used the solid shape of 2 beaming roller grinding machines etc. to disperse, perhaps pigment (P) is carried out the processing of alkaline builder (Y) and/or ethene base system dispersant (A) [perhaps, particularly above-mentioned ethene base system dispersant (a)].In addition, all dispersion machine or mixers such as homogenizer, homogenizer, ball mill, roller mill, burrstone mill, ultrasonic dispersing machine all can be used for the dispersion that makes paints.The all kinds of solvents that can be used for above-mentioned pigment dispersion can be enumerated organic solvent, water etc.In addition, when being used for active energy ray-curable composition, also can use the instead medium of solvent of the aqueous monomer of active energy ray-curable or aqueous oligomer.
In addition, the example that can be used for the resin of above-mentioned pigment dispersion can be enumerated Petropols, casein, shellac, Abietyl modified maleic acid resin, the rosin modified phenol resin, nitrocellulose, cellulose acetate butyrate, thermoprene, chlorinated rubber, oxidized rubber, hydrochloride rubber, phenolic resin, alkyd resins, mylar, unsaturated polyester resin, amino resins, epoxy resin, vinylite, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, the metha crylic resin, polyurethane resin, silicones, fluororesin, drying oil, synthetic drying oil, phenylethene modified maleic acid, polyamide, chlorinated polypropylene, butyral resin, permalon etc.
Coating, gravure printing ink, hectographic printing printing ink (offset ink), jetted ink, ink for color filter, black matrix (black matrix) that above-mentioned pigment dispersion can be applied to non-water system, water system or solvent-free system with printing ink, numerical digit paper with in printing ink, the plastic cement colouring agent etc.Wherein, be preferred for jetted ink, ink for color filter and black matrix printing ink.Be particularly preferred for ink for color filter and black matrix printing ink, it is to be applicable to for example printing ink of multiple print processes such as photoetching process, lithography, woodburytype, toppan printing, screen printing method and ink jet printing method.
Embodiment
Below, specifically describe the present invention by embodiment, but the present invention is not limited to these embodiment.And, in an embodiment, " part " expression " weight portion ", " % " expression " weight % ".In addition, number-average molecular weight be when use TSKgel chromatographic column (eastern ソ one society's system), utilize the GPC that equipped the RI detector (eastern ソ one society's system, HLC-8120GPC), the polystyrene conversion molecular weight of measuring when in launching solvent, using THF.
Embodiment 1
(1) operation (A)
In reaction unit, add 192.1 parts of trimellitic anhydrides, 130.4 parts of 2-hydroxyethyl methacrylates and 0.3 part of Hydroquinone monomethylether with gas introduction tube, condenser, paddle and thermometer, while making dry air flow, under 100, make it to react 5 hours, obtained in 2-hydroxyethyl methacrylate addition the ethylenically unsaturated monomers of trimellitic acid (a1) (the operation A of embodiment 1).
(2) operation (B)
Has gas introduction tube, condenser, paddle, with add 60 parts of acetate methoxyl group propyl ester in the reactive tank of thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 38.5 parts of n-BMAs with 2 hours, 46.1 part benzyl methacrylate, 2.2 part 2-hydroxyethyl methacrylate, 13.2 part ethylenically unsaturated monomers (a1), 40 parts of acetate methoxyl group propyl ester, with 8 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (process B of embodiment 1).
So obtain number-average molecular weight and be 2450, the average copolymerization number (that is the mean number that, contains carboxyl unit (G)) of each molecule ethylenically unsaturated monomers (a1) is 1.0 ethene base system dispersant (A1).
Embodiment 2
(1) operation (C)
In reactive tank, add 60 parts of acetate methoxyl group propyl ester with gas introduction tube, condenser, paddle and thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove with dropping in 2 hours with 40 parts of n-BMAs, 48 parts of benzyl methacrylates, 12 parts of 2-hydroxyethyl methacrylates, 40 parts of acetate methoxyl group propyl ester and 6 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (the operation C of embodiment 2).
So obtain number-average molecular weight and be 3800, the mean number of the hydroxyl in a part is 3.5 vinyl resin intermediate (C1).
(2) operation (D)
In reaction unit, add 100 parts in solid acrylic resin intermediate (C1), 2.5 parts of trimellitic anhydrides and the 0.1 part of dimethyl benzylamine that divides that form, make its 6 hours (step D of embodiment 2) of reaction under 100 ℃ with gas introduction tube, condenser, paddle and thermometer.
The mean number (that is the mean number that, contains carboxyl unit (G)) that so obtains the trimellitic acid in each molecule is 0.5 an ethene base system dispersant (A2).
Embodiment 3
Except the addition with the trimellitic anhydride in the step D of embodiment 2 changes into 3.5 parts, other use the 2 identical methods with embodiment, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains trimellitic acid in each molecule is 0.7 an ethene base system dispersant (A3).
Embodiment 4
Except the addition with the trimellitic anhydride in the step D of embodiment 2 changes into 5.1 parts, other use the 2 identical methods with embodiment, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains trimellitic acid in each molecule is 1.0 an ethene base system dispersant (A4).
Embodiment 5
Except the addition with the trimellitic anhydride in the step D of embodiment 2 changes into 7.1 parts, other use the 2 identical methods with embodiment, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains trimellitic acid in each molecule is 1.4 an ethene base system dispersant (A5).
Embodiment 6
Except the addition with the trimellitic anhydride in the step D of embodiment 2 changes into 10.1 parts, other use the 2 identical methods with embodiment, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains trimellitic acid in each molecule is 2.0 an ethene base system dispersant (A6).
Embodiment 7
In reactive tank, add 60 parts of acetate methoxyl group propyl ester with gas introduction tube, condenser, paddle and thermometer, be warming up to 80 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 41.9 parts of n-BMAs, 50.0 parts of benzyl methacrylates, 6.8 parts of 2-hydroxyethyl methacrylates, 1.2 parts of trimellitic anhydrides, 40 parts of acetate methoxyl group propyl ester with 2 hours, with 2.0 part 2,2 '-mixed liquor that azodiisobutyronitrile evenly mixes in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction.So obtain number-average molecular weight and be 15400, the mean number (that is the mean number that, contains carboxyl unit (G)) of the trimellitic acid in a part is 1.0 vinyl resin intermediate (A7).
Embodiment 8
(1) operation (A)
In reactive tank, add 218.1 parts of PMDAs, 130.1 parts of 2-hydroxyethyl methacrylates and 0.3 part of hydroquinone monomethyl ether with gas introduction tube, condenser, paddle and thermometer, while making dry air flow, under 100 ℃, make it to react 5 hours, obtained in 2-hydroxyethyl methacrylate addition the ethylenically unsaturated monomers of PMA (a8 ') (the operation A of embodiment 8).
(2) operation (Aa)
By the water of 36 parts of interpolations in the ethylenically unsaturated monomers (a8 ') that in preceding paragraph (1), obtains, and under 90 ℃, make its reaction 5 hours, and will remain in the anhydride group hydrolysis in the above-mentioned ethylenically unsaturated monomers (a8 ').Then, residual water is removed in decompression, obtains ethylenically unsaturated monomers (a8) (the operation Aa of embodiment 8).
(3) operation (B)
Has gas introduction tube, condenser, paddle, with add 60 parts of acetate methoxyl group propyl ester in the reactive tank of thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 84.6 parts of n-BMAs with 2 hours, 0.7 part 2-hydroxyethyl methacrylate, 14.7 part ethylenically unsaturated monomers (a8), 40 parts of acetate methoxyl group propyl ester, with 6 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (process B of embodiment 8).。
So obtain number-average molecular weight and be 4000, the average copolymerization number (that is the mean number that, contains carboxyl unit (G)) of the ethylenically unsaturated monomers (a8) in each molecule is 0.5 ethene base system dispersion resin (A8).
Embodiment 9
(1) operation (C)
Has gas introduction tube, condenser, paddle, with add 60 parts of acetate methoxyl group propyl ester in the reactive tank of thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 30.0 parts of methacrylic acid 2-Octyl Nitrites with 2 hours, 68.3 part benzyl methacrylate, 1.7 part 2-hydroxyethyl methacrylate, 40 parts of acetate methoxyl group propyl ester, with 6 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (the operation C of embodiment 9).So obtain number-average molecular weight and be 4800, the mean number of the hydroxyl in a part is 0.5 vinyl resin intermediate (C2).
(2) operation (D)
In reactive tank, add 100 parts of acetate methoxyl group propyl ester, 4.3 parts of ethylene glycol bisthioglycolate trimellitic anhydride esters and 0.1 part of dimethyl benzylamine, be warming up to 100 ℃ with gas introduction tube, condenser, paddle and thermometer.From drip groove, 100 parts of vinyl resin intermediates (C2) (Gu formation divides) are added drop-wise in the reactive tank, after dropping finishes, react 4 hours (step D of embodiment 9) down at 100 ℃ with 2 hours.
(3) operation (Dd)
Add 10 parts of 2-Ethylhexyl Alcohols afterwards, under 90 ℃, make its reaction 5 hours, residual anhydride group is carried out alcohol decompose (the step D d of embodiment 9), the average copolymerization number (that is the mean number that, contains carboxyl unit (G)) that obtains ethylene glycol bisthioglycolate trimellitic acid skeleton is 0.5 an ethene base system dispersion resin (A9).
Embodiment 10
Except in the step D of embodiment 9, use 6.0 part 9,9-two (3,4-dicarboxyl phenyl) the fluorenic acid acid anhydride replaces beyond 4.8 parts of ethylene glycol bisthioglycolate trimellitic anhydride esters, other use the 9 identical methods with embodiment, obtain 9 in each molecule, and 9-two (3,4-dicarboxyl phenyl) mean number of fluorenes (that is the mean number that, contains carboxyl unit (G)) is 0.5 an ethene base system dispersion resin (A10).
Embodiment 11
(1) operation (C)
In reactive tank, add 60 parts of acetate methoxyl group propyl ester with gas introduction tube, condenser, paddle and thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove with dropping in 2 hours with 21.2 parts of n-BMAs, 30.0 parts of methacrylic acid 2-Octyl Nitrites, 30 parts of benzyl methacrylates, 10 parts of styrene, 8 parts of プ ラ Network セ Le FM-2D (in 1 mole of 2-hydroxyethyl methacrylate addition the ethylenically unsaturated monomers with hydroxyl of 2 moles of 6-caprolactones; ダ イ セ Le chemical industry society system), 0.8 part of acrylic acid, 40 parts of acetate methoxyl group propyl ester, with 5 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (the operation C of embodiment 11).So obtain number-average molecular weight and be 5500, the mean number of the hydroxyl in a part is 1.2 vinyl resin intermediate (C3).
(2) operation (D)
In reaction unit, add 100 parts of (dividing) acrylic resin intermediates (C3), 3.5 parts of trimellitic anhydrides and 0.1 part of dimethyl benzylamine, under 100 ℃, make 6 hours (step D of embodiment 11) of its reaction Gu form with gas introduction tube, condenser, paddle and thermometer.So, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains the trimellitic acid in each molecule is 1.0 an ethene base system dispersant (A11).
Embodiment 12
(1) operation (C)
In reactive tank, add 60 parts of acetate methoxyl group propyl ester with gas introduction tube, condenser, paddle and thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove with dripped in 2 hours with 22 parts of methyl methacrylates, 30 parts of methacrylic acid dodecane esters, 30 parts of benzyl methacrylates, 10 parts of styrene, 8 parts of Block レ Application マ-AE-200 (in 1 mol propylene acid 2-hydroxy methacrylate on average addition the ethylenically unsaturated monomers with hydroxyl of 3.5 mole ethylene oxides; Japan grease society system), 40 parts of acetate methoxyl group propyl ester and 6 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (the operation C of embodiment 12).So obtain number-average molecular weight and be 4400, the mean number of the hydroxyl in a part is 1.3 vinyl resin intermediate (C4).
(2) operation (D)
In reaction unit, add 100 parts of (dividing) acrylic resin intermediates (C4), 4.4 parts of trimellitic anhydrides and 0.1 part of dimethyl benzylamine, under 100 ℃, make 6 hours (step D of embodiment 12) of its reaction Gu form with gas introduction tube, condenser, paddle and thermometer.So, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains the trimellitic acid in each molecule is 1.0 an ethene base system dispersant (A12).
Embodiment 13
(1) operation (C)
Has gas introduction tube, condenser, paddle, with add 60 parts of acetate methoxyl group propyl ester in the reactive tank of thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 20 parts of methyl methacrylates with 2 hours, 37.6 part isobutyl methacrylate, 30 parts of methacrylic acid dodecane esters, 10 parts of benzyl methacrylates, 2.4 part N-ethoxy acrylamide (Xing people society system), 40 parts of acetate methoxyl group propyl ester, with 6 parts of dimethyl-2,2 '-mixed liquor that azo two (2 Methylpropionic acid esters) evenly mixes in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (the operation C of embodiment 13).So obtain number-average molecular weight and be 4900, the mean number of the hydroxyl in a part is 1.0 vinyl resin intermediate (C5).
(2) operation (D)
In reaction unit, add 100 parts of (dividing) acrylic resin intermediates (C5), 3.9 parts of trimellitic anhydrides Gu form with gas introduction tube, condenser, paddle and thermometer, with 0.1 part of dimethyl benzylamine, under 100 ℃, make 6 hours (step D of embodiment 13) of its reaction.So, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains the trimellitic acid in each molecule is 1.0 an ethene base system dispersant (A13).
Embodiment 14
(1) operation (C)
Has gas introduction tube, condenser, paddle, with add 60 parts of acetate methoxyl group propyl ester in the reactive tank of thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 30 parts of n-BMAs with 2 hours, 30 parts of methyl methacrylates, 35 parts of benzyl methacrylates, 5 parts of 2-hydroxyethyl methacrylates, 40 parts of acetate methoxyl group propyl ester, with 6 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (the operation C of embodiment 14).So obtain number-average molecular weight and be 3800, the mean number of the hydroxyl in a part is 1.5 vinyl resin intermediate (C6).
(2) operation (D)
In reaction unit, add 100 parts in solid acrylic resin intermediate (C1), 2.9 parts of PMDAs and the 0.1 part of dimethyl benzylamine that divides that form, under 100 ℃, make 6 hours (step D of embodiment 14) of its reaction with gas introduction tube, condenser, paddle and thermometer.So, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains the pyromellitic acid in each molecule is 1.0 an ethene base system dispersant (A14).
Embodiment 15
(1) operation (C)
Has gas introduction tube, condenser, paddle, with add 60 parts of acetate methoxyl group propyl ester in the reactive tank of thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 30 parts of n-BMAs with 2 hours, 20 parts of ethyl acrylates, 25 parts of benzyl methacrylates, 10 parts of methacrylic acids, 5 parts of 2-hydroxyethyl methacrylates, 40 parts of acetate methoxyl group propyl ester, with 6 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (the operation C of embodiment 15).So obtain number-average molecular weight and be 3900, the mean number of the hydroxyl in a part is 1.5 vinyl resin intermediate (C7).
(2) operation (D)
In reaction unit, add 100 parts in the solid acrylic resin intermediates (C1) that divide, 3.8 part 3 of forming with gas introduction tube, condenser, paddle and thermometer, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and 0.1 part of dimethyl benzylamine, under 100 ℃, make 6 hours (step D of embodiment 15) of its reaction.
So, obtain 3,3 in each molecule ', 4,4 '-mean number (that is the mean number that, contains carboxyl unit (G)) of biphenyltetracarboxyacid acid is 1.0 an ethene base system dispersant (A15).
Embodiment 16
(1) operation (C)
In reactive tank, add 100 parts of cyclohexanone with gas introduction tube, condenser, paddle and thermometer, be warming up to 95 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 50 parts of n-BMAs, 25 parts of benzyl methacrylates, 25 parts of 2-hydroxyethyl methacrylates, 125 parts of cyclohexanone and 2.5 portions of mixed liquors that azodiisobutyronitrile evenly mixes in advance with 2 hours, continuous stirring 3 hours under uniform temp afterwards, cessation reaction (the operation C of embodiment 16).
So obtain number-average molecular weight and be 5000, the mean number of the hydroxyl in a part is 9.6 vinyl resin intermediate (C8).
(2) operation (D)
In reaction unit, add 100 parts in solid acrylic resin intermediate (C8), 3.84 parts of trimellitic anhydrides and the 0.1 part of dimethyl benzylamine that divides that form, under 120 ℃, make 2 hours (step D of embodiment 16) of its reaction with gas introduction tube, condenser, paddle and thermometer.
So, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains the trimellitic acid in each molecule is 1.0 an ethene base system dispersant (A16).
As mentioned above, ethene base system dispersant of the present invention (a) can make tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4), have the ethylenically unsaturated monomers (h) of hydroxyl, react with the arbitrary method in the manufacture method 1～3 with other ethylenically unsaturated monomers and make by using the method identical with embodiment 1～13.
Production Example 1
Except the addition with the trimellitic anhydride in the step D of embodiment 2 changes into 0.5 part, other use the 2 identical methods with embodiment, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains trimellitic acid in each molecule is 0.1 a vinyl resin (B1).
Production Example 2
Except the addition with the trimellitic anhydride in the step D of embodiment 2 changes into 17.7 parts, other use the 2 identical methods with embodiment, the mean number (that is the mean number that, contains carboxyl unit (G)) that obtains trimellitic acid in each molecule is 3.5 a vinyl resin (B2).
Production Example 3
In reaction unit, add with gas introduction tube, condenser, paddle and thermometer 100 parts in solid form divide, the acrylic resin intermediate (C1) that in embodiment 2, obtains, 2.7 parts of succinyl oxides and 0.1 part of dimethyl benzylamine, under 100 ℃, make its reaction 6 hours.So, the mean number that obtains the butanedioic acid in each molecule is 1.0 a vinyl resin (B3).
Production Example 4
In reaction unit, add with gas introduction tube, condenser, paddle and thermometer 100 parts in solid form divide, the acrylic resin intermediate (C1) that in embodiment 2, obtains, 3.9 parts of phthalic anhydrides and 0.1 part of dimethyl benzylamine, under 100 ℃, make its reaction 6 hours.So, the mean number that obtains the phthalic acid in each molecule is 1.0 a vinyl resin (B4).
Production Example 5
In reactive tank, add 60 parts of acetate methoxyl group propyl ester with gas introduction tube, condenser, paddle and thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove with dropping in 2 hours with 40 parts of n-BMAs, 50 parts of benzyl methacrylates, 5 parts of 2-hydroxyethyl methacrylates, 5 parts of methacrylic acids, 40 parts of acetate methoxyl group propyl ester and 6 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction.So obtain number-average molecular weight and be 4000 vinyl resin (B5).
Production Example 6
Has gas introduction tube, condenser, paddle, with add 60 parts of acetate methoxyl group propyl ester in the reactive tank of thermometer, be warming up to 110 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 65 parts of methyl methacrylates with 2 hours, 10 parts of isobutyl methacrylates, 18 parts of methacrylic acid dodecane esters, 3 parts of 2-hydroxyethyl methacrylates, 1 part of methacrylic acid, 4 parts of methacrylic acid 2-sulfo group ethyl esters, 40 parts of acetate methoxyl group propyl ester, with 6 part 2,2 '-mixed liquor that the two two isobutyric acid dimethyl esters of azo evenly mix in advance, continuous stirring 3 hours under uniform temp afterwards, cessation reaction.So obtain number-average molecular weight and be 400 vinyl resin (B6).Vinyl resin (B6) solution produces muddy.
Production Example 7
In reactive tank, add 100 parts of cyclohexanone with gas introduction tube, condenser, paddle and thermometer, be warming up to 95 ℃, after carrying out nitrogen replacement in the reaction vessel, from drip groove, dripped 46.5 parts of n-BMAs, 25 parts of benzyl methacrylates, 25 parts of 2-hydroxyethyl methacrylates, 3.5 parts of methacrylic acids, 125 parts of cyclohexanone and 2.5 portions of mixed liquors that azodiisobutyronitrile evenly mixes in advance with 2 hours, continuous stirring 3 hours under uniform temp afterwards, cessation reaction.So obtain number-average molecular weight and be 5000 vinyl resin (B7).
Embodiment 17～31 and comparative example 1～6
The ethene base system dispersant (A), the titanium oxide (with the pure medicine system of light) as pigment, solvent, the bead (0.8mm) that obtain among the embodiment 1～15 are added in the vial of 140mL than (all being divided into benchmark with solid formation) with the weight shown in table 1 and the table 2 (g), place electromagnetic shaker (Shaker) (F﹠amp; FM corporate system ス キ ヤ Application デ Star Network ス SO400) (below be called ス キ ヤ Application デ Star Network ス) goes up and disperseed 3 hours.After placing 24 hours under 25 ℃, carry out following test.
And then, the acrylic resin that obtains in the Production Example 1～6 or commercially available dispersant (comparative example 7), solvent, bead (0.8mm) are added in the vial of 140mL than (all being divided into benchmark with solid formation) with the weight shown in the table 3 (g), utilize ス キ ヤ Application デ Star Network ス to carry out 3 hours dispersion.After placing 24 hours under 25 ℃, carry out following test.
(1) viscosimetric analysis
For the dispersion that obtains, use that to have diameter be 59 minutes the cone and plate viscometer of cone-plate of 0 degree as 60mm, angle, measure its viscosity under 25 ℃ with the rotary speed of 10rad/ second.The results are shown in table 1～table 3.
(2) through the time storage stability
For the dispersion that obtains, in 50 ℃ constant temperature machine, preserve 1 week with promote its through the time change after, with the method identical with preceding paragraph (1) " viscosimetric analysis " measure through the time after the viscosity of pigment dispersion, calculating divides 2 grades to estimate at 50 ℃ of viscosity rates of change of preserving 1 all front and back down according to following standard.
Zero: the viscosity rate of change ± 10% with interior and do not produce sedimentary situation.
*: the viscosity rate of change surpasses ± 10% situation, even perhaps the viscosity rate of change ± 10% with interior but produce sedimentary situation.
The results are shown in table 1～table 3.
[table 1]
Figure A20068004121500501
[table 2]
Figure A20068004121500502
[table 3]
Figure A20068004121500511
As mentioned above, use ethene base system dispersant of the present invention (A) will disperse the dispersion that forms as the titanium oxide of inorganic pigment, have low viscosity and through the time storage stability also good.On the other hand, when using the containing carboxy vinyl and be resin of usefulness relatively, viscosity height, a part through the time storage stability poor (comparative example 1～5).In addition, when use with embodiment 1 at patent documentation 2 in the dispersant recorded and narrated be identical (comparative example 6), commercially available phosphorous acid esters dispersant (the PVC Star Network ケ ミ-society's system that in the definition of the claim of patent documentation 1, contains when use in addition when containing the sulfonic group dispersant; Disperbyk-111) time (comparative example 7), can obtain having more low viscous dispersion, but through the time storage stability poor.
Embodiment 32 and comparative example 8
With the vinyl resin (B7) that obtains in the ethene base system dispersant (A16) that obtains among the embodiment 16 or the Production Example 7, zinc oxide (with the pure medicine system of light), cyclohexanone, bead (0.8mm) as pigment with the weight shown in the table 4 (g) than (all being divided into benchmark) with solid formation, be added in the vial of 140mL, place on the ス キ ヤ Application デ Star Network ス and carry out 3 hours dispersion.After placing 24 hours under 25 ℃, carry out following test.
(1) viscosimetric analysis
For the dispersion that obtains, use that to have diameter be 59 minutes the cone and plate viscometer of cone-plate of 0 degree as 60mm, angle, measure its viscosity under 25 ℃ with the rotary speed of 10rad/ second.The results are shown in table 4.
(2) through the time storage stability
For the dispersion that obtains, in 40 ℃ constant temperature machine, preserve 1 week with promote its through the time change after, with the method identical with preceding paragraph (1) " viscosimetric analysis " measure through the time after the viscosity of pigment dispersion, calculating divides 2 grades to estimate at 40 ℃ of viscosity rates of change of preserving 1 all front and back down according to following standard.
Zero: the viscosity rate of change ± 10% with interior and do not produce sedimentary situation.The results are shown in table 4.
[table 4]
Figure A20068004121500521
As mentioned above, use ethene base system dispersant of the present invention (A) will disperse the dispersion that forms as the zinc oxide of inorganic pigment, have low viscosity and through the time storage stability also good.On the other hand, when using the containing carboxy vinyl and be resin (B7) of usefulness relatively, the viscosity height, through the time storage stability poor.
[Production Example 1 of alkaline builder (Y)]
After 50 parts of copper phthalocyanines as pigment composition are carried out chlorosulfonation, make itself and 15 parts of N as amine component, the N-diethylaminopropylamine reacts, and obtains 62 parts of alkaline builder (Y1).Alkaline builder (Y1) is represented with following structural formula.
[Chemical formula 2 4]
Figure A20068004121500531
CuPc represents the copper phthalocyanine residue.
[Production Example 2 of alkaline builder (Y)]
After 50 parts of copper phthalocyanines as pigment composition are carried out chloromethylation, itself and 40 parts of dibutylamines as amine component are reacted, obtain 95 parts of alkaline builder (Y2).Alkaline builder (Y2) is represented with following structural formula.
[Chemical formula 2 5]
Figure A20068004121500532
CuPc represents the copper phthalocyanine residue.
[Production Example 3 of alkaline builder (Y)]
50 parts of quinacridones as pigment composition are carried out itself and 40 parts of N methyl piperazines as amine component being reacted after chloroacetamide methylates, obtain 103 parts of alkaline builder (Y3).Alkaline builder (Y3) is represented with following structural formula.
[Chemical formula 2 6]
Figure A20068004121500533
[Production Example 4 of alkaline builder (Y)]
Use diphenyl diketone base pyrrolopyrrole as pigment composition, use N-aminopropyl morpholine as amine component, utilize the method identical with Production Example 1, obtain alkaline builder (Y4).Alkaline builder (Y4) is represented with following structural formula.
[Chemical formula 2 7]
[Production Example 5～11 of alkaline builder (Y)]
Utilize the method identical, obtain alkaline builder shown below (Y5)～alkaline builder (Y11), that is, obtain pigment derivative, anthraquinone derivative and acridone derivatives with the Production Example 1～4 of above-mentioned alkaline builder (Y1)～alkaline builder (Y4).
Alkaline builder (Y5):
[Chemical formula 2 8]
Figure A20068004121500542
Alkaline builder (Y6):
[Chemical formula 2 9]
Figure A20068004121500551
Alkaline builder (Y7):
[chemical formula 30]
Alkaline builder (Y8):
[chemical formula 31]
Figure A20068004121500553
Alkaline builder (Y9):
[chemical formula 32]
Figure A20068004121500561
Alkaline builder (Y10):
[chemical formula 33]
Figure A20068004121500562
Alkaline builder (Y11):
[chemical formula 34]
Figure A20068004121500563
With the method identical with the Production Example 1～11 of above-mentioned alkaline builder (Y1)～(Y11), react with pigment composition, anthraquinone, acridone or triazine, with amine component, the compound that perhaps will have amine component carries out coupling reaction and comes synthetic dyestuff, can make various alkaline builder (Y) thus.
Embodiment 33
With 9 parts of pigment blue 15s as pigment (P): 3,1 part of alkaline builder (Y1), 1 part of ethene base system dispersant (A4), 29 parts of alkyd resins (Hitachi changes into society's system " Off Le キ Star De 133-60 "), 10 parts of melmacs (Hitachi changes into society's system " メ ラ Application 20 "), 50 parts of solvents (mixed diluent that comprises acetate methoxyl group propyl ester/dimethylbenzene/n-butanol=6/2/2 (weight ratio)) are added in the vial (addition all is divided into benchmark and adds with solid formation).With dispersion machine carry out pre-dispersed after, the zirconia bead that to add 250 parts of diameters be 0.5mm utilizes ス キ ヤ Application デ Star Network ス to carry out this dispersion as decentralized medium, obtains pigment dispersion.
Measure the viscosity of the pigment dispersion obtain with Brookfield viscometer, estimate the performance of dispersion with viscosity and TI value [=(in the viscosity under the 6rpm)/(viscosity under 60rpm)].Viscosity under 6rpm is 300mPas, and the viscosity under 60rpm is that 270mPas, TI value are 1.11.In addition, the pigment dispersion that obtains was preserved for 1 week in 50 ℃ of constant temperature machines, promote its through the time change after, for through the time before and after the viscosity of pigment dispersion change and measure, and judge storage stability.Viscosity under 6rpm is that 290mPas, rate of change are-3%.
In addition, be coated with machine #5 with rod the pigment dispersion that obtains is coated on the aluminium sheet, under 180 ℃, burnt till 1 hour, obtain coloring film.Be placed on concentration and be in 5% the saline solution dipping 24 hours, and estimated resistance to chemical reagents.The outward appearance of coloring film does not change before and after the dipping in saline solution, thereby resistance to chemical reagents is good.
Embodiment 34～51 and comparative example 9～25
The composition that use is recorded and narrated in following table 5～table 8 (addition all is divided into benchmark with solid formation to be added) utilizes with embodiment 33 identical operations and obtains pigment dispersion respectively, estimates with method same as described above.And the low more expression of viscosity is good more, and the TI value is good more near 1 expression more.In addition, in 50 ℃ constant temperature machine, preserve 1 week with promote its through the time the evaluation criterion of viscosity rate of change after changing as follows.
Zero: the viscosity rate of change ± 10% with interior and do not produce sedimentary situation.
*: the viscosity rate of change surpasses ± 10% situation, even perhaps the viscosity rate of change ± 10% with interior but produce sedimentary situation.
The results are shown in table 5～table 8.
[table 5]
Figure A20068004121500581
[table 6]
[table 7]
[table 8]
Figure A20068004121500592
" DB111 " that record and narrate in table 8 is commercial dispersants (PVC Star Network ケ ミ society system: Disperbyk-111).
Using pigment blue 15 as can be known: among 3 the embodiment 33～38, owing to use ethene base system dispersant of the present invention (a), so viscosity is low, viscosity stability is also good.On the other hand, at the comparative example 9 that does not use ethene base system dispersant of the present invention (a) with used in the comparative example 10 of relatively using vinyl resin (B), viscosity uprises.And then, in the comparative example 11 that does not use alkaline builder (Y) and ethene base system dispersant of the present invention (a), when disperseing, produce high viscosityization, thereby can not separate with bead with ス キ ヤ Application デ Star Network ス.
Even for the embodiment 39～51 that has used other pigment, comparative example 12～25, the excellent effect of being brought by ethene base system dispersant of the present invention (a) and color compositions also is tangible.
In addition, use with the pigment dispersion that obtains in embodiment 34～51, comparative example 9～25 with the same mode of embodiment 33 and estimate resistance to chemical reagents, the result produces foaming in the coating thing of comparative example 23 and 24.Hence one can see that, and for the coloring film that has used commercially available phosphorous acidic group dispersant, its resistance to chemical reagents is poor.
Industrial applicability
Dispersant of the present invention for example can be used for dispersible pigment dispersion or color compositions effectively Preparation. In addition, manufacturing method according to the invention can be made above-mentioned dispersant effectively.
More than, describe the present invention according to specified scheme, for a person skilled in the art Apparent distortion or improvement are also contained in the scope of the invention.

Claims (14)

1. ethene base system dispersant is characterized in that, in vinyl based polymer main chain (A), contains carboxyl unit (G) with what average amount more than 0.3, below 3.0 in per 1 molecule vinyl based polymer contained useful general formula (1) expression,
[Chemical formula 1]
Figure A20068004121500021
In general formula (1), R 1Be hydrogen atom or methyl,
X 1For-C (=O) O-,-C (=O) NH-,-O-,-OC (=O)-or-CH 2O-,
X 2Be to use general formula:
-(-R a1-O-) m1-
(in the formula, R A1Be that carbon number is that the alkylidene of 2～8 straight or branched or carbon number are 3～8 ring alkylidene, m1 is 1～50 integer) group of expression,
X 3Be to use general formula:
-(-C(＝O)-R b1-O-) m2-
(R B1Be that carbon number is that the alkylidene of 4～8 straight or branched or carbon number are 4～8 ring alkylidene, m2 is 0～20 integer) group of expression,
Y 1Be with general formula (2):
[Chemical formula 2]
Figure A20068004121500031
[in the general formula (2),
(i) A is arranged 1～A 3In 1 to be hydrogen atom, other 2 be-C (=O) combination of OH, or (ii) A 1～A 3In 1 be-C (=O) OR c(wherein, R cBe that carbon number is 1～18 alkyl), other 2 be-C (=O) combination of OH, perhaps (iii) A 1～A 3In 1 be with general formula (2a):
[chemical formula 3]
Figure A20068004121500032
[in the general formula (2a),
X 21For-C (=O) O-,-C (=O) NH-,-O-,-OC (=O)-or-CH 2O-,
X 22Be to use general formula:
-(-R a21-O-) m21-
(in the formula, R A21Be that carbon number is that the alkylidene of 2～8 straight or branched or carbon number are 3～8 ring alkylidene, m21 is 1～50 integer) group of expression,
X 23Be to use general formula:
-(-C(＝O)-R b21-O-) m22-
(R B21Be that carbon number is that the alkylidene of 4～8 straight or branched or carbon number are 4～8 ring alkylidene, m22 is 0～20 integer) group of expression,
Z 21Be to contain useful general formula (21):
[chemical formula 4]
Figure A20068004121500041
[in the general formula (21), R 21Be hydrogen atom or methyl] the vinyl based polymer main chain (B) of group of expression, above-mentioned vinyl based polymer main chain (A) can be identical main chain or also can be respectively different main chains with above-mentioned vinyl based polymer main chain (B)]
The group, other 2 of expression be-and C (=O) combination of OH, perhaps, (iv) A 1～A 3In 3 be-C (=O) OH, k is 1 or 2] group of expression,
Or with general formula (3):
[chemical formula 5]
Figure A20068004121500042
[(v) A in the general formula (3), is arranged 5～A 7In 1 to be hydrogen atom, other 2 be-C (=O) combination of OH, perhaps (vi) A 5～A 7In 1 be-C (=O) OR d(wherein, R dBe that carbon number is 1～18 alkyl), other 2 be-C (=O) combination of OH, perhaps (vii) A 5～A 7In 1 be with general formula (3a):
[chemical formula 6]
Figure A20068004121500043
[in the general formula (3a),
X 31For-C (=O) O-,-C (=O) NH-,-O-,-OC (=O)-or-CH 2O-,
X 32Be to use general formula:
-(-R a31-O-) m31-
(in the formula, R A31Be that carbon number is that the alkylidene of 2～8 straight or branched or carbon number are 3～8 ring alkylidene, m31 is 1～50 integer) group of expression,
X 33Be to use general formula:
-(-C(＝O)-R b31-O-) m32-
(R B31Be that carbon number is that the alkylidene of 4～8 straight or branched or carbon number are 4～8 ring alkylidene, m32 is 0～20 integer) group of expression,
Z 31Be to contain useful general formula (31):
[chemical formula 7]
Figure A20068004121500051
[in the general formula (31), R 31Be hydrogen atom or methyl] the vinyl based polymer main chain (C) of group of expression, above-mentioned vinyl based polymer main chain (A) can be identical main chain or also can be respectively different main chains with above-mentioned vinyl based polymer main chain (C)] group, other 2 of expression for-C (=O) combination of OH, perhaps
(viii) A 5～A 7In 3 be-C (=O) OH,
R 2Be Direct Bonding ,-CH 2-,-O-,-C (=O)-,-C (=O) OCH 2CH 2OC (=O)-,-C (=O) OCH (OC (=O) CH 3) CH 2OC (=O)-,-SO 2-,-C (CF 3) 2-, use formula:
[chemical formula 8]
Figure A20068004121500061
The expression group or use formula:
[chemical formula 9]
The expression group] expression group.
2. ethene base system dispersant as claimed in claim 1, the A in the general formula (2) 1～A 3Be combinations thereof (i), perhaps the A in the general formula (3) 5～A 7For combinations thereof (v).
3. ethene base system dispersant as claimed in claim 1, the A in the general formula (2) 1～A 3For combinations thereof (iii), the perhaps A in the general formula (3) 5～A 7For combinations thereof (vii).
4. as each described ethene base system dispersant in the claim 1～3, with the Y that contains carboxyl unit (G) of general formula (1) expression 1It is group with general formula (2) expression.
5. as each described ethene base system dispersant in the claim 1～4, it is with general formula (4) expression,
[Chemical formula 1 0]
Figure A20068004121500071
[in the general formula (4),
G be illustrated in claim 1 described with general formula (1) expression contain carboxyl unit (G),
R 4Expression hydrogen atom or methyl,
R 5Expression hydrogen atom or methyl,
R 6Be aromatic group or-C (=O)-X 7-R 7(wherein, X 7For-O-or-NH-, R 7Be that hydrogen atom or carbon number are the alkyl of 1～18 straight or branched, above-mentioned R 7Can have aromatic group as substituting group),
X 4For-C (=O) O-,-C (=O) NH-,-O-,-OC (=O)-or-CH 2O-,
X 5Be to use formula:
-(-R a2-O-) m3-
(in the formula, R A2Be that carbon number is that the alkylidene of 2～8 straight or branched or carbon number are 3～8 ring alkylidene, m3 is 1～50 integer) group of expression,
X 6Be to use formula:
-(-C(＝O)-R b4-O-) m4-
(in the formula, R B2Be that carbon number is the alkylidene of 4～8 straight or branched, m4 is 0～20 integer) group of expression,
Above-mentioned in the general formula (4) contains carboxyl unit (G), contains-X 4-X 5-X 6The hydroxyl unit (J) of-H and containing-C (R 5) (R 6)-the configuration of backbone structure unit (K) be not limited to this order, in vinyl based polymer main chain with general formula (4) expression, each unit G, J and K can be contained in any order, and then each unit G, J and K can be contained in the mode of random or block type
For above-mentioned carboxyl unit (G), above-mentioned hydroxyl unit (J) and backbone structure unit (K) of containing that in general formula (4), contains, when they exist when a plurality of, can identical each other or also can be different,
In addition, p1, p2 and p3 represent the mean number of each construction unit in each molecule ethene base system dispersant, and p1 is more than 0.3, below 3.0, and p2 is more than 0, below 180, and p3 is more than 6, below 250].
6. as each described ethene base system dispersant in the claim 1～5, its number-average molecular weight is more than 500, below 40000.
7. color compositions, it contains each described ethene base system dispersant in pigment and the claim 1～6.
8. color compositions as claimed in claim 7, it also contains alkaline builder at least a that is selected from pigment derivative, the anthraquinone derivative with basic group with basic group, has the acridone derivatives of basic group and have the pyrrolotriazine derivatives of basic group.
9. the manufacture method of ethene base system dispersant, it comprises:
(A) make ethylenically unsaturated monomers (h) with hydroxyl and tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) reaction make ethylenically unsaturated monomers operation and
(B) operation that makes the ethylenically unsaturated monomers that in above-mentioned operation (A), obtains and other ethylenically unsaturated monomers carry out copolymerization.
10. the manufacture method of ethene base system dispersant, it comprises:
(C) make ethylenically unsaturated monomers (h) with hydroxyl and other ethylenically unsaturated monomers carry out copolymerization operation and
(D) operation that the hydroxyl of tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) and the copolymerization that obtains in above-mentioned operation (C) is reacted.
11. the manufacture method of ethene base system dispersant, its ethylenically unsaturated monomers (h) that will have hydroxyl on one side carries out copolymerization with other ethylenically unsaturated monomers, Yi Bian make tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) and this hydroxyl reaction simultaneously.
12. as the manufacture method of each described ethene base system dispersant in the claim 9～11, the acid anhydrides that reacts is a trimellitic anhydride.
13. as the manufacture method of each described ethene base system dispersant in the claim 9～11, the acid anhydrides that reacts is aromatic tetracarboxylic acid's dianhydride.
14. ethene base system dispersant, it utilizes as each described manufacture method manufacturing in the claim 9～13.
CNA2006800412151A 2005-11-02 2006-11-01 Dispersing agent, method for producing same and pigment composition using same Pending CN101300064A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103374240A (en) * 2012-04-13 2013-10-30 Jsr株式会社 Coloring composition, color filter and display device
CN111221217A (en) * 2014-12-24 2020-06-02 Dnp精细化工股份有限公司 Color material dispersion liquid, photosensitive colored resin composition, color filter, liquid crystal display device, and organic light-emitting display device
CN111684320A (en) * 2018-02-27 2020-09-18 Jsr株式会社 Optical filter and device using the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103374240A (en) * 2012-04-13 2013-10-30 Jsr株式会社 Coloring composition, color filter and display device
CN111221217A (en) * 2014-12-24 2020-06-02 Dnp精细化工股份有限公司 Color material dispersion liquid, photosensitive colored resin composition, color filter, liquid crystal display device, and organic light-emitting display device
CN111221217B (en) * 2014-12-24 2024-03-12 Dnp精细化工股份有限公司 Color material dispersion, photosensitive coloring resin composition, color filter, liquid crystal display device, and organic light-emitting display device
CN111684320A (en) * 2018-02-27 2020-09-18 Jsr株式会社 Optical filter and device using the same
CN111684320B (en) * 2018-02-27 2023-03-31 Jsr株式会社 Optical filter, solid-state imaging device, and camera module

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