CN101185039A - Liquid developing agent and process for producing the same - Google Patents
Liquid developing agent and process for producing the same Download PDFInfo
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- CN101185039A CN101185039A CNA2006800184723A CN200680018472A CN101185039A CN 101185039 A CN101185039 A CN 101185039A CN A2006800184723 A CNA2006800184723 A CN A2006800184723A CN 200680018472 A CN200680018472 A CN 200680018472A CN 101185039 A CN101185039 A CN 101185039A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/122—Developers with toner particles in liquid developer mixtures characterised by the colouring agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/12—Developers with toner particles in liquid developer mixtures
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
- G03G9/131—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
- G03G9/132—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/12—Developers with toner particles in liquid developer mixtures
- G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
- G03G9/133—Graft-or block polymers
Abstract
This invention provides a liquid developing agent for electrophotography or electrostatic recording that can realize a high solid content and has excellent developing properties. The liquid developing agent is characterized in that colored chips produced by heat kneading a pigment with a thermoplastic resin are dispersed by wet pulverization in an electrically insulating hydrocarbon solvent containing at least one pigment dispersant selected from the group consisting of specific modified novolak resins(A) having an aromatic ring and a ring opened structure of an epoxy group by a hydroxycarboxylic acid-derived carboxyl group, and copolymers (B).
Description
Technical field
The present invention relates to be used for electrofax or the electrostatic recording liquid developer and the manufacture method thereof of equipment such as printing machine, duplicating machine, printer, facsimile recorder.
Background technology
The electrofax or the electrostatic recording that use in the equipment such as duplicating machine, printer, facsimile recorder roughly are divided into dry process development agent and liquid developer with developer, but the particle diameter of toner particle that it has been generally acknowledged that liquid developer is little, and this is very big advantage for obtaining high quality image.Owing to this reason, the liquid developer that need to form the image color height on the market, blurs few high quality image.
Usually, as liquid developer, use toner particle is dispersed in the electrical insulating property solvent and the developer that obtains, described toner particle coats colorant such as pigment and forms with thermoplastic resin.
Be relatively easy to one of manufacture method as what obtain this liquid developer, method by following so-called case of wet attrition manufactured liquid developer has been proposed, promptly, the following heating edge of temperature more than melting point resin is mediated with colorant and resin, carry out mixing with mixing rolls such as three-roll mill, the cooling back is carried out dry type to the potpourri that obtains and is pulverized, use spreading agent and electrical insulating property non-aqueous solvent that described crushed material is carried out case of wet attrition, make the dense magma of toner, be scattered in again in the non-water kind solvent of the electrical insulating property that contains charge adjusting agent, obtain liquid developer (for example, referring to Japanese kokai publication sho 60-021056 communique, Te Kaiping 05-134468 communique).
But, recovery from the high speed of developing powder in recent years, profit, electrical insulating property solvent, also need liquid developer to reach higher-solidization, for described manufacture method, be difficult to guarantee fully basic dispersion stabilization and charged characteristic, if the solid component concentration of liquid developer raises, then have to cause tackify and the low problem of resistance.
Summary of the invention
Therefore, problem of the present invention provides and can reach higher-solidization, and development excellent liquid developer and manufacture method thereof.
In order to solve described problem, the inventor furthers investigate, found that pigment and thermoplastic resin added hot milling after, carry out case of wet attrition in the electrical insulating property varsol that behind the specific pigment dispersing agent of dissolving, forms again and make liquid developer, the epoxy ring-opening structure that wherein specific pigment dispersing agent has aromatic rings and causes from the carboxyl of hydroxycarboxylic acid, thereby can solve described problem, thereby finish the present invention.
That is to say, the invention provides following liquid developer and manufacture method thereof.
[1] liquid developer, it is characterized in that, be will to pigment and thermoplastic resin add hot milling and obtain carry out case of wet attrition in the electrical insulating property varsol that behind the dissolving pigment dispersing agent, forms of color chips, thereby its dispersion is formed, and pigment dispersing agent wherein is selected from least a in the following modified linear phenol-aldehyde resin (A) of the epoxy ring-opening structure that has aromatic rings and cause from the carboxyl of hydroxycarboxylic acid and the multipolymer (B).
Modified linear phenol-aldehyde resin (A): have in the molecule from the aromatic rings of linear phenol-aldehyde resin and at least a carboxyl and cause epoxy ring-opening and the modified linear phenol-aldehyde resin of the group of general formula (1) expression that forms from hydroxycarboxylic acid.
[changing 1]
(in the formula, the oxygen atom that the oxygen atom of left end is contained from the aromatic series hydroxyl of linear phenol-aldehyde resin, W
1And X
1Represent that independently of one another carbon number is 1～19 bivalent hydrocanbon radical, i and j represent the integer of i=1～30, j=0～30, R independently of one another
1Expression hydrogen atom or methyl)
Multipolymer (B): weight-average molecular weight is 3,000～100,000 multipolymer is the multipolymer that more than one that wherein contain the structural unit of general formula (2) expression that is equivalent at least 10 moles of % and be equivalent at least 10 moles of % are selected from the structural unit that general formula (3) and general formula (4) represent.
[changing 2]
[changing 3]
[changing 4]
(in the formula, W
2And X
2Represent that independently of one another carbon number is 1～19 bivalent hydrocanbon radical, p and q represent the integer of p=1～30, q=0～30, R independently of one another
2, R
3And R
4Represent hydrogen atom or methyl independently of one another, R
5Expression hydrogen atom or halogen atom, R
6And R
7Represent that independently of one another hydrogen atom, carbon number are that 1～5 alkyl, carbon number are that 1～5 alkoxy, carbon number are 6～10 aryloxy group or halogen atom, R
8Expression hydrogen atom or methyl, R
9Expression is combination or methylene directly.)
[2] liquid developer described in described [1], the total solid constituent concentration in the liquid developer are 13～50 quality %.
[3] liquid developer described in described [1] or [2] cooperates pigment dispersing agent 2～100 mass parts and forms with respect to color chips 100 mass parts.
[4] any described liquid developer in described [1]～[3] wherein uses higher boiling paraffinic solvent as described electrical insulating property varsol.
[5] manufacture method of any described liquid developer in described [1]～[4], it is characterized in that, for pigment and thermoplastic resin are added hot milling and obtain color chips, carrying out dry type pulverizing formation meal in advance minces, then in being dissolved with the electrical insulating property varsol that is selected from least a pigment dispersing agent in described modified linear phenol-aldehyde resin (A) and the multipolymer (B), described meal being minced carry out case of wet attrition.
Embodiment
Below the present invention will be described in more detail.
At first, the constituent material that uses in the liquid developer of the present invention is described.
As the pigment that uses among the present invention, can use inorganic pigment, the organic pigment that all the time is used in the liquid developer with being not particularly limited, for example can enumerate inorganic pigments such as carbon black, graphite, iron oxide red, chrome yellow, ultramarine such as acetylene carbon black, and organic pigment such as azo class pigment, condensation azo class pigment, mordant pigment, phthalocyanine pigment, isoindoline class pigment, anthraquinone class pigment, quinacridine ketone pigment.As the organic pigment of various tones, pinkish red class organic pigment can be enumerated the red perylene kinds pigment such as condensation azo class pigment such as azo class pigment, condensation azophloxine such as quinacridine ketone pigment, permanent bordeaux, pyrene are red etc. that wait of quinacridone.Cyan class pigment can be enumerated phthalocyanine pigments such as metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue etc.Yellow class organic pigment can be enumerated condensation azo class pigment such as two azo class pigment, condensation azophosphine such as monoazo class pigment, benzidine yellow, permanent Huang such as hansa yellow etc.Green class pigment can be enumerated phthalocyanine pigment such as phthalocyanine green etc.These pigment can be used alone or mixed use of two or more.
Pigment content in the liquid developer is not particularly limited, but considers preferably finally in liquid developer 100 mass parts 1～20 mass parts is arranged from the image color aspect.
As the thermoplastic resin that uses among the present invention, can adopt the known thermoplastic resin that is used to liquid developer, be to be insoluble to electrical insulating property varsol, preferably low kind to the swellbility of electrical insulating property varsol.If the swellbility height of thermoplastic resin then is not easy to reach higher-solidization, in addition, if developing powder is accelerated, problems such as photographic fog, stain appear in the non-image part that then is easy to generate on the image.
As thermoplastic resin, for example can enumerate polyester resin, epikote, synthetic resin such as acrylic resin, styrene resin, styrene-propene acid copolymer resin, Corvic, polyvinyl acetate resin, polyvinyl resin, acrylic resin, polyurethanes resin, polyvinyl butyral resin, abietic resin, modified rosin resin, terpene resin, phenolics, aliphatic category hydrocarbon resin, fragrant same clan petroleum resin or natural resin etc.These thermoplastic resins can be used alone or mixed use of two or more.
Also have, pigment and thermoplastic resin shared total ratio in liquid developer of the present invention is preferably 10～50 quality %, more preferably 15～40 quality %.If the total ratio of pigment and thermoplastic resin is lower than described scope, then can not obtain having the liquid developer of enough concentration sometimes, if be higher than described scope, the problem that the viscosity of liquid developer rises too high then can appear.
As the electrical insulating property varsol that uses among the present invention, can use as the aliphatic hydrocarbon that does not dissolve the solvent of described thermoplastic resin, ester ring type hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon etc. to have the specific insulation (10 that can not upset the electrostatic latent image degree
11～10
16About Ω cm) solvent.Wherein, on foul smell, innocuousness, cost, preferred n-paraffin kind solvent, isoalkane kind solvent, cycloalkane solvent or the paraffinic solvent of the higher boilings such as potpourri (boiling point under the normal pressure is more than 150 ℃) of two or more wherein.As the n-paraffin kind solvent, the isoalkane kind solvent, the commercially available product of cycloalkane solvent or their paraffinic solvents such as potpourri, for example preferred Isopar G, Isopar H, IsoparL, Isopar M, Exxsol D130, Exxsol D140 (more than be Exxon chemistry (strain) system), Shellsol 71 (Shell petrochemistry (strain) system), IP Solvent 1620, IP Solvent 2080, IPSolvent 2835 (more than be bright dipping petrochemistry (strain) system), Moresco White P-40, MorescoWhite P-55, Moresco White P-80 (more than be (strain) loose village oil institute system), whiteruss No.40-S, whiteruss No.55-S (more than be central authorities change into (strain) system).
Pigment dispersing agent used in the present invention is at least a pigment dispersing agent that is selected from described modified linear phenol-aldehyde resin (A) and the multipolymer (B), can use the pigment dispersing agent that dissolves in the electrical insulating property varsol.
Also have, described multipolymer (B) has the larger side chain of general formula (2) expression that is suspended on the main chain, and this structure is regarded as graft copolymer.From described viewpoint, described multipolymer (B) is called graft copolymer (B) in this manual.
At first, described modified linear phenol-aldehyde resin (A) is described.
As the linear phenol-aldehyde resin that is used to obtain modified linear phenol-aldehyde resin (A), can use the linear phenol-aldehyde resin of deriving by polyatomic phenols such as monobasic phenols or trihydroxy benzene and aldehydes.As monohydric phenol wherein, can use no substituted benzene phenols or alkyl substituted benzene phenols such as phenol, cresols, xylenols, pseudocuminol, propylphenol, butylphenol, amyl phenol, hexylphenol, octyl phenol, nonyl phenol, dodecyl phenol, monohydroxy diphenylmethyl alkanes or phenylphenol etc. have the phenol of aromatic substituents.As polyatomic phenol, can use catechol, resorcinol, p-dihydroxy-benzene or trihydroxy benzene etc. two or trihydroxy benzene class, or the alkyl substituent of these materials or aromatic series substituent.In addition, also can use dihydroxy diphenylmethyl alkanes, dihydroxybiphenyl classes etc. such as bisphenol-A, Bisphenol F.In addition, also can use the halogen substituent of described phenols, for example can enumerate chlorination or brominated phenols etc.These phenols can be used alone or mixed use of two or more.
As phenols, consider the phenols that the phenol in the preferred monobasic phenols, a position are replaced by an alkyl etc., the resorcinol in the preferred polyatomic phenol etc. from reactive aspect.
As aldehydes, can not have especially restrictedly to use and make normally used kind in the linear phenol-aldehyde resin.Specifically, can enumerate aromatic series aldehydes such as formaldehyde, paraformaldehyde, three _ alkane and cyclic formals class, acetaldehyde, propionic aldehyde, hutanal, iso-butyraldehyde, glyoxal etc. lower aliphatic aldehydes, furfural, benzaldehyde etc.These aldehydes can be used alone or mixed use of two or more.
In synthetic linear phenol-aldehyde resin, in the presence of acid catalysts such as p-methylphenyl sulfonic acid, perchloric acid, hydrochloric acid, nitric acid, sulfuric acid, chloroacetic acid, oxalic acid, phosphoric acid, these phenols and aldehydes are reacted under 80～130 ℃ get final product according to a conventional method.Can be by following the tracks of reaction with gel permeation chromatography (GPC) determining molecular weight.
In addition, also can synthesize linear phenol-aldehyde resin by the method for using the such phenol derivatives of such phenol derivatives of saligenin or o-chloromethyl phenol with halogenated methyl with methylol.
Then, linear phenol-aldehyde resin and chloropropylene oxide or Beta-methyl chloropropylene oxide are reacted, obtain having the linear phenol-aldehyde resin resin of epoxy radicals according to conventional method.Certainly, also can use commercially available linear phenol-aldehyde resin with epoxy radicals.
At last, linear phenol-aldehyde resin with epoxy radicals and carboxylic acids described later or amine are reacted, obtain target modified linear phenol-aldehyde resin (A).For this reaction, can use solvent in case of necessity, can use catalyzer such as fatty amine, aromatic amine, ammonium salt in case of necessity in addition, be heated to 60～160 ℃ and react.Can be by following the tracks of reaction process with gel permeation chromatography (GPC) determining molecular weight, mensuration epoxide equivalent.
Except behind synthetic linear phenol-aldehyde resin, carrying out the method for modification as mentioned above, aromatic series hydroxyl by at first making described monohydric phenol or polyatomic phenol and chloropropylene oxide or Beta-methyl chloropropylene oxide react, form glycidoxypropyl or 2,3-epoxy radicals-2-methyl propoxyl group, and itself and carboxylic acids described later or amine are reacted, add new phenols then as required, use aldehydes to carry out the linear phenol-aldehyde resin reaction, thereby also can obtain modified linear phenol-aldehyde resin (A).
The group of general formula (1) expression in the modified linear phenol-aldehyde resin (A) can obtain in the following manner, promptly, chloropropylene oxide or Beta-methyl chloropropylene oxide and aromatic series hydroxyl are reacted, and making the carbon number that can have unsaturated link and branched structure then is 2～20 hydroxycarboxylic acid, their potpourri or condensed polymer and its reaction.
In general formula (1), the oxygen atom that the oxygen atom of left end is contained from the aromatic series hydroxyl of linear phenol-aldehyde resin, W
1And X
1Expression can have unsaturated link and/or the bivalent hydrocanbon radical of branched structure carbon number in 1～19 scope, R
1Expression hydrogen atom or methyl.
In general formula (1), general formula (5)
[changing 5]
_OCOW
1_
iOH (5)
(in the formula, W
1And i is with described identical) group and the general formula (6) represented
[changing 6]
_OCOX
1_
jOH (6)
(X in the formula
1And j is with described identical) group represented can be derived from hydroxycarboxylic acid, their potpourri or their condensed polymer of the carbon number that can have unsaturated link and/or branched structure in 2～20 scopes.
As described hydroxycarboxylic acid, can enumerate glycollic acid, lactic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid, Hydroxyoctanoic acid, hydroxydecanoic acid, hydroxylauric acid, hydroxyl myristic acid, hydroxy-palmitic acid, comb fiber crops acid or castor oil fatty acid, and their hydride, 12-hydroxy stearic acid etc.Wherein, preferably use the hydroxycarboxylic acid of carbon number in 12～20 scopes, especially preferably use comb fiber crops acid or the castor oil fatty acid of carbon number in 16～20 scopes, and hydroxycarboxylic acids such as their hydride, 12-hydroxy stearic acid.
Repeat number i represents the integer in 1～30 scope, and j represents the integer in 0～30 scope.But suitable value changes according to the specific surface area of employed pigment type, pigment particles and particle diameter, the character of surface of pigments treating agent, the kind of thermoplastic resin, the polarity of dispersion medium etc., need be according to various situations selection optimum values.But, usually preferred i or j 〉=2 and i+j 〉=2.Even exceeding described scope, the value of i or j also can not further improve dispersiveness.
The group of general formula (5) in the general formula (1) or general formula (6) expression can form by the following method, for example, pass through the polycondensation synthesizing polyester of hydroxycarboxylic acid in advance, and the method that its terminal carboxyl group and described epoxy radicals are reacted, or after making the carboxyl and described epoxy reaction of hydroxycarboxylic acid monomer, make hydroxycarboxylic acid carry out method of polycondensation etc. again.
Polycondensation reaction as described hydroxycarboxylic acid, can catalyzer such as p-methylphenyl sulfonic acid, stannous octoate, dibutyltin diacetate, tetra-n-butyl titanate exist or not in the presence of with reaction system 180～220 ℃ of following heated and stirred, on one side remove generation by azeotropic solvents such as toluene or dimethylbenzene water react on one side.Reaction can be by the GPC mode molecular weight determination and acid value measuring etc. follow the tracks of.
The group that must have general formula (1) expression in the molecule of modified linear phenol-aldehyde resin (A).The group number of preferred formula (1) expression is 1～20.Can not obtain enough dispersivenesses during this group.Even this group number also tells on when exceeding described scope, but the molecular weight of the many linear phenol-aldehyde resin of required nucleome quantity this moment is very wayward, thus in the reality on be limited to 20.But, suitable value according to the specific surface area of pigment type, pigment particles and particle diameter, surface of pigments treating agent have or not and character, the kind of thermoplastic resin, the polarity of dispersion medium etc. change, need select optimum value according to purposes.
In addition, can also have general formula (7) in the molecule of modified linear phenol-aldehyde resin (A)
[changing 7]
[in the formula, the oxygen atom of left end is from the contained oxygen atom of the aromatic series hydroxyl of linear phenol-aldehyde resin, and Y represents any monovalent organic radical group in 1～20 scope of carbon number that link has oxygen atom or a nitrogen-atoms (still, the group of general formula (5) expression except), R
10Expression hydrogen atom or methyl] group of expression.
The group of general formula (7) expression can obtain in the following manner, that is, chloropropylene oxide or Beta-methyl chloropropylene oxide and aromatic series hydroxyl are reacted, and makes monocarboxylic acid class or monobasic amine and its reaction then.Also have, make the reaction of monobasic amine and the basic group that forms produces harmful effect to charged characteristic easily, therefore preferably do not use the monobasic amine.Under the situation of using the monobasic amine, should be noted that its use amount.
Object lesson as the monocarboxylic acid class, can use saturated fat acids such as acetic acid, propionic acid, butyric acid, caproic acid, sad, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, leukotrienes, arachidonic acid, eleostearic acid and their hydride etc.
As the monobasic amine, can use aliphatics unary primary amines such as methylamine, ethamine, propylamine, butylamine, amylamine, octylame, dodecyl amine, stearmide, benzylamine, aromatic series such as aniline, naphthylamines unary primary amine, and they are by the monobasic secondary amine class of N-monoalkyl replacement formation, and monoethanolamine, N-monoalkyl ethanolamine, diethanolamine etc. have the chain alcohol monoamine of primary amino radical or secondary amino group.
In addition, can also have general formula (8) in the molecule of modified linear phenol-aldehyde resin (A)
[changing 8]
(in the formula, the oxygen atom of left end is from the contained oxygen atom of the aromatic series hydroxyl of linear phenol-aldehyde resin, R
12Expression hydrogen atom or methyl) group and the aromatic series hydroxyl of expression.
This situation represents that glycidoxypropyl or 2 can be arranged, 3-epoxy radicals-2-methyl propoxyl group and aromatic series hydroxyl residual.But the linear phenol-aldehyde resin (A) of preferred modification does not have the group and the aromatic series hydroxyl of general formula (8) expression simultaneously.Have at the same time under both situations, gelation takes place easily.
The group of the group of general formula (7) expression, general formula (8) expression and the group number of aromatic series hydroxyl get final product in 0～19 scope respectively.Though also tell on when exceeding this scope, the molecular weight of the linear phenol-aldehyde resin that nucleome quantity is many is very wayward, in addition, must have the group of a general formula (1) expression, considers that from these aspects the upper limit in the reality is respectively 19.But, suitable value according to the specific surface area of pigment type, pigment particles and particle diameter, surface of pigments treating agent have or not and character, the kind of thermoplastic resin, the polarity of dispersion medium etc. change, preferably according to purposes selection optimum value.
Modified linear phenol-aldehyde resin (A) can also be with general formula (9)
[changing 9]
[in the formula, the oxygen atom of right-hand member is from the contained oxygen atom of the aromatic series hydroxyl of same or different linear phenol-aldehyde resins, Z represents that link has the organic group of 2～6 officials energy of carbon number in 1～40 scope of oxygen atom or nitrogen-atoms, and k represents the integer in 2～6 scopes, R
11Expression hydrogen atom or methyl] crosslinked group of expression carry out intermolecular or molecule in replace.
In order to replace with the intermolecular or intramolecular crosslinking chemical of general formula (9) expression reactive hydrogen to the aromatic series hydroxyl, chloropropylene oxide or Beta-methyl chloropropylene oxide and aromatic series hydroxyl are reacted, and then with 2～6 officials can carboxylic acids, amine (comprising unary primary amine) or amino acids react and get final product.Also have, the basic group that amine, amino acids reaction are formed produces harmful effect to charged characteristic easily, does not therefore preferably use amine, amino acids.Under the situation of using amine, amino acids, should be noted that use amount.
Object lesson as polyfunctional carboxylic acids, can use succinic acid, maleic acid, itaconic acid, cyclohexane dicarboxylic acid, hexane diacid, azelaic acid, decanedioic acid, 1,10-decane dicarboxylic acid, dodecylene succinic acid, dimer acid, 3, methine tetrahydrophthalic acid, 3 in the 6-, aliphatics polycarboxylic acid's classes such as the interior methine tetrahydrophthalic acid of 6-methyl, aromatic carboxylic acid classes such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trihemellitic acid, pyromellitic acid, benzophenone tetrabasic carboxylic acid, ethylene glycol bisthioglycolate trimellitate, glycerine three trimellitates.
Object lesson as multifunctional amine, can enumerate ethylenediamine, diethylene triamine, trien, tetren, penten, propane diamine, (dimethylamino) propylamine, (lignocaine) propylamine, hexamethylene diamine, the hexa-methylene triamine, N, two (aminopropyl) methyl amine of N-, isophorone diamine, the norbornane diamines, diamino-dicyclohexyl methane, N-(aminoethyl) piperazine, N, two (aminoethyl) piperazines of N-, the xylylene diamines, aliphatic poly amines such as dimerization diamines, and melamine, the phenyl guanamines, m-phenylene diamine, aromatic series polyamine classes such as diaminodiphenyl-methane.
In addition, can also use polyether diamine, N-aminoethyl ethanolamine, and so-called polyaminoamide etc.
In addition, the primary amino radical of two functionalities and epoxy radicals are reacted and form cross-linked structure.In this case, also can use described unary primary amine.
In addition, can also use amino acid such as leucine, threonine.
As described reaction, can use suitable organic solvent in case of necessity, adopt the catalyzer such as ammonium salt of aliphatic tertiary amine, aromatic nitrile base or tertiary amine in case of necessity, be heated under 60～160 ℃ and react.Can be by following the tracks of reaction process with GPC method determining molecular weight, mensuration epoxide equivalent.
Owing to the molecular weight of the many linear phenol-aldehyde resins of nucleome quantity is very wayward, so the total of the aromatic series hydroxyl that modified linear phenol-aldehyde resin had (total of the aromatic series hydroxyl that does not replace or replace, down together) is preferably below 20.
Below, (B) describes to described graft copolymer.
Graft copolymer (B) can obtain in the following manner: (I) for general formula (10)
[changing 10]
(in the formula, R
2And R
3With described identical) expression 10～90 moles of % of the ethylene unsaturated monomer that contains epoxy radicals, general formula (11)
[changing 11]
(in the formula, R
4, R
5, R
6And R
7With described identical) expression monomer and/or general formula (12)
[changing 12]
(in the formula, R
8And R
9With described identical) 10～90 moles of % of monomer of expression and adopt in case of necessity do not have 0～80 mole of % of other ethylene unsaturated monomer to the high functional group of epoxy reaction, use radical polymerization initiators such as superoxide or azo-compound, obtain containing the multipolymer of epoxy radicals according to a conventional method, the carboxylic acids or the amine that make the epoxy radicals of this multipolymer and hydroxycarboxylic acid then, adopt in case of necessity react; Or (II) for general formula (13)
[changing 13]
(in the formula, R
2, R
3, W
2, X
2With described identical.M and n represent the integer of m=1～30, n=0～30 independently of one another) monomer of expression and the general formula (14) that adopts when needing
[changing 14]
(in the formula, V is any monovalent organic radical group (still, the general formula (15) of carbon number in 1～20 scope that link has oxygen atom or nitrogen-atoms
[changing 15]
_OCOW
2_
pOH (15)
(in the formula, W
2And p is with described identical) except the group represented), R
13And R
14Represent hydrogen atom or methyl independently of one another) monomer of 10～90 moles of % of monomer, general formula (11) expression of expression and/or 10～90 moles of % of monomer of general formula (12) expression and adopt in case of necessity do not have 0～80 mole of % of other ethylene unsaturated monomer to the high functional group of epoxy reaction, use radical polymerization initiators such as superoxide or azo-compound, it is reacted.
Also have, react and obtain general formula (2) or general formula (16) for the epoxy radicals that in described method (1), makes the multipolymer that obtains and carboxylic acids described later or amine
[changing 16]
(in the formula, V, R
13And R
14With described identical) reaction of structural unit of expression, or react with hydroxycarboxylic acid, the carboxylic acids that adopts in case of necessity or amine and obtain the reaction of the monomer that general formula (13) or general formula (14) represent for the epoxy radicals of the vinyl unsaturated monomer that contains epoxy radicals that in described method (II), makes general formula (10) expression, can use solvent in case of necessity, use catalyzer such as fatty amine, aromatic amine or ammonium salt in addition in case of necessity, be heated to 60～160 ℃ and react.
In the structural unit of described general formula (3) expression, as R
5The halogen atom of expression can be enumerated the chlorine atom.As R
6Or R
7The carbon number of expression is 1～5 alkyl, for example can enumerate alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, amyl group, it as carbon number 1～5 alkoxy, for example can enumerate methoxyl, butoxy etc., it as carbon number 6～10 aryloxy group, for example phenoxy group etc. be can enumerate,, fluorine atom, chlorine atom, bromine atoms etc. for example can be enumerated as halogen atom.
At the monomer that is used for making graft copolymer (B), as the styrene derivative in the monomer of general formula (11) expression, can use alkyl-substituted styrenes such as vinyltoluene, α-Jia Jibenyixi, dimethyl styrene, ethyl styrene, cumene ethene, t-butyl styrene, halogen-substituted styrenes such as chlorostyrene, dichlorostyrene, bromstyrol, fluorobenzene ethene, alkoxy substituted ethene such as methoxy styrene, butyl phenyl ether ethene, aryloxy group substituted phenylethylenes such as phenoxy group styrene, β-chlorostyrene etc.
As the monomer of general formula (2) expression, can enumerate (methyl) acrylic acid benzyl ester, (methyl) phenyl acrylate.
The ethylene unsaturated monomer that contains epoxy radicals as general formula (10) expression can use (methyl) glycidyl acrylate, (methyl) acrylic acid-2,3-epoxy radicals-2-methyl-propyl ester etc.
Do not have other ethylene unsaturated monomer as what adopt in case of necessity, can use not have the ethylene unsaturated monomer to the high functional group of epoxy reaction such as carboxyl, phenolic hydroxyl group, primary amino radical, secondary amino group the high functional group of epoxy reaction.For example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) 2-ethyl hexyl acrylate, (methyl) lauryl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid cetyl ester, (methyl) stearyl acrylate acid esters, (methyl) acrylic acid Shan Yu ester, (methyl) acrylic acid Arrcostabs such as (methyl) acrylic acid norborneol ester, (methyl) tetrahydrofurfuryl acrylate etc. has (methyl) acrylate of cyclic ethers base, (methyl) acrylic acid-2-hydroxyl ethyl ester etc. has (methyl) esters of acrylic acid of aliphatics hydroxyl, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester etc. has (methyl) esters of acrylic acid of uncle's amino, methyl vinyl ether, dodecyl vinyl, vinyl ethers such as propenyl ether propylene carbonate, hydroxy butyl vinyl ethers etc. have the vinyl ethers of aliphatics hydroxyl, the allyl ester of various acid such as allyl acetate etc.
Also have, the epoxy radicals of the ethylene unsaturated monomer that contains epoxy radicals and hydroxycarboxylic acid, the carboxylic acids that adopts in case of necessity or amine are reacted and the general formula (13) that obtains or the monomer of general formula (14) expression form under the situation of graft copolymer in use, can also use to have carboxyl, phenolic hydroxyl group, primary amino radical, secondary amino group etc. have the functional group of high response to epoxy radicals ethylene unsaturated monomer.
The structural unit of general formula (2) in the graft copolymer (B) expression can be that 2～20 hydroxycarboxylic acid, their potpourri or its condensed polymer obtain from the structural unit of being derived by the ethylene unsaturated monomer that contains epoxy radicals of described general formula (10) expression and the carbon number that can have unsaturated link or branched structure.Perhaps, can be formed by the monomer derived of general formula (13) expression, the monomer of its formula of (13) expression is to be that 2～20 hydroxycarboxylic acid, their potpourri or its condensed polymer obtain by the ethylene unsaturated monomer that contains epoxy radicals of described general formula (10) expression and the carbon number that can have unsaturated link or a branched structure.
In general formula (2), W
2And X
2Expression can have the bivalent hydrocanbon radical of carbon number in 1～19 scope of unsaturated link and/or branched structure, R
2And R
3Represent hydrogen atom or methyl independently of one another.
In general formula (2), general formula (15)
[changing 17]
_OCOW
2_
pOH (15)
(in the formula, W
2And p is with described identical) group and the general formula (17) represented
[changing 18]
_OCOX
2_
qOH (17)
(in the formula, X
2And q is with described identical) group represented can be derived and formed by the hydroxycarboxylic acid of the carbon number that can have unsaturated link and/or branched structure in 2～20 scopes, their potpourri or its condensed polymer.
As described hydroxycarboxylic acid, can enumerate glycollic acid, lactic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid, Hydroxyoctanoic acid, hydroxydecanoic acid, hydroxylauric acid, hydroxyl myristic acid, hydroxy-palmitic acid, comb fiber crops acid or castor oil fatty acid, and their hydride, 12-hydroxy stearic acid etc.Wherein, preferably use the hydroxycarboxylic acid of carbon number in 12～20 scopes, especially preferably use comb fiber crops acid or the castor oil fatty acid of carbon number in 16～20 scopes, and hydroxycarboxylic acids such as their hydride, 12-hydroxy stearic acid.
Repeat number p represents the integer in 1～30 scope, and q represents the integer in 0～30 scope.But suitable value changes according to the specific surface area of employed pigment type, pigment particles and particle diameter, the character of surface of pigments treating agent, the kind of thermoplastic resin, the polarity of dispersion medium etc., preferably according to purposes selection optimum value.But, usually preferred p or q 〉=2 and p+q 〉=2.Even exceeding described scope, the value of p or q also can not further improve dispersiveness.
The group of general formula (15) in the general formula (2) or general formula (17) expression can form by the following method, for example, pass through the polycondensation synthesizing polyester of hydroxycarboxylic acid in advance, and the method that its terminal carboxyl group and described epoxy radicals are reacted, or after making the carboxyl and described epoxy reaction of hydroxycarboxylic acid monomer, make hydroxycarboxylic acid carry out method of polycondensation etc. again.
Polycondensation reaction as described hydroxycarboxylic acid, can catalyzer such as p-methylphenyl sulfonic acid, stannous octoate, dibutyltin diacetate, tetra-n-butyl titanate exist or not in the presence of with reaction system 180～220 ℃ of following heated and stirred, on one side remove generation by azeotropic solvents such as toluene or dimethylbenzene water react on one side.Reaction can be followed the tracks of by the molecular weight determination and the acid value measuring of GPC mode.
Graft copolymer (B) must have the structural unit of general formula (2) expression and the structural unit of general formula (3) and/or general formula (4) expression.As they content with respect to graft copolymer (B), in graft copolymer, the structural unit of preferred formula (2) expression is equivalent at least 10 moles of %, particularly be equivalent to 10～90 moles of %, and be selected from general formula (3) and general formula (4) expression structural unit in more than one structural units be equivalent at least 10 moles of %, particularly be equivalent to 10～90 moles of %.Also have, the structural unit content of general formula (2) expression is equivalent at least 10 moles of % and is meant graft copolymer is divided into structural unit from ethylene unsaturated monomer, in the entire infrastructure unit, contains the structural unit of 10 moles of % general formulas (2) expression at least.That is,, just mean that the number of the structural unit of this graft copolymer formula of (2) expression of a part is at least 0.1 * n when graft copolymer is n ethylene unsaturated monomer copolymerization when obtaining.In addition, the content of more than one structural units that is selected from the structural unit of general formula (3) and general formula (4) expression is equivalent at least 10 moles of % and is meant graft copolymer is divided into structural unit from ethylene unsaturated monomer, in the entire infrastructure unit, contain more than one structural units that 10 moles of % are selected from the structural unit of general formula (3) and general formula (4) expression at least.That is,, just mean that the number of more than one structural units of the structural unit that is selected from general formula (3) and general formula (4) expression in this graft copolymer of a part is at least 0.1 * n when graft copolymer is n ethylene unsaturated monomer copolymerization when obtaining.
The structural unit of general formula (2) expression, to be selected from any or both in more than one structural units of structural unit of general formula (3) and general formula (4) expression be not that molar weight with regulation contains sometimes, can not obtain enough dispersivenesses.But, suitable value according to the specific surface area of pigment type, pigment particles and particle diameter, surface of pigments treating agent have or not and character, the kind of thermoplastic resin, the polarity of dispersion medium etc. change, preferably according to purposes selection optimum value.
The structural unit that can also further have in addition, general formula (16) expression in the graft copolymer (B).
The structural unit of general formula (16) expression can be by containing epoxy radicals ethylene unsaturated monomer or the epoxy radicals of multipolymer and the reaction of monocarboxylic acid or monobasic amine obtain.Also have, make the reaction of monobasic amine and the basic group that forms produces harmful effect to charged characteristic easily, therefore preferably do not use the monobasic amine.Under the situation of using the monobasic amine, should be noted that its use amount.
Object lesson as the monocarboxylic acid class, can use saturated fat acids such as acetic acid, propionic acid, butyric acid, caproic acid, sad, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, leukotrienes, arachidonic acid, eleostearic acid and their hydride etc.
As the monobasic amine, can use aliphatics unary primary amines such as methylamine, ethamine, propylamine, butylamine, amylamine, octylame, dodecyl amine, stearmide, benzylamine, aromatic series such as aniline, naphthylamines unary primary amine, and they are by the monobasic secondary amine class of N-monoalkyl replacement formation, and monoethanolamine, N-monoalkyl ethanolamine, diethanolamine etc. have the chain alcohol monoamine of primary amino radical or secondary amino group.
In addition, graft copolymer (B) can also have general formula (18)
[changing 19]
(in the formula, R
15And R
16Represent hydrogen atom or methyl independently of one another) expression structural unit.
The glycidoxypropyl or 2 that this situation represents to exist the ethylene unsaturated monomer that contains epoxy radicals to cause, 3-epoxy radicals-2-methyl propoxyl group residual.
The weight-average molecular weight of described graft copolymer (B) is 3,000～100,000.If weight-average molecular weight does not reach described scope, though then dispersed enough, be difficult to regulate polymerization, on the other hand,, then be not easy to obtain enough dispersivenesses if surpass described scope.
For the present invention, in using the system of electrical insulating property varsol as solvent, by using described specific pigment dispersing agent, can obtain resistance value (specific insulation) and not descend, the liquid developer of the higher-solid concentration that dispersion stabilization, redispersibility are good.
As the use amount of pigment dispersing agent among the present invention, preferably with respect to pigment and thermoplastic resin are added hot milling obtains color chips 100 mass parts be 2～100 mass parts, 2～50 mass parts more preferably.If the use amount of pigment dispersing agent does not reach described scope, then cause dispersiveness, redispersibility to descend easily, on the other hand,, then cause resistance to descend easily if surpass described scope.
As the charged controlling agent that uses in case of necessity among the present invention, (1) that roughly is divided into the following stated reaches (2) two types.
(1) constitutes by the material that can carry out ionization or ionic adsorption, and coat the type of surfaces of toner particles with it
As such charged controlling agent, the oxidative condensation thing of greases such as preferred linseed oil, soya-bean oil, alkyd resin, halogen polymer, aromatic series poly carboxylic acid, the water-soluble dye that contains acidic-group, aromatic series polyamine etc.
(2) can carry out ion with toner particle and receive the substance dissolves award in the electrical insulating property solvent and reach the type of coexistence
As such charged controlling agent, metallic soap classes such as preferred cobalt naphthenate, nickel naphthenate, iron naphthenate, zinc naphthenate, zirconium caprylate, cobalt octoate, nickel octoate, zinc octoate, dodecoic acid cobalt, dodecoic acid nickel, zinc laurate, 2 ethyl hexanoic acid cobalt, the metal organic sulfonate classes such as slaine of petroleum-type metal organic sulfonate, sulfosuccinate, phosphatide such as lecithin, cephalin, salicylic acid metal salts such as tert-butyl group salicylic acid metal complex, the polyvinyl pyrrolidone resin, polyamide, contain sulfonic resin, hydroxybenzoic acid derivative etc.
Below the manufacture method of liquid developer of the present invention is described.
In the present invention, as long as finally can by the case of wet attrition method make to pigment and thermoplastic resin add that hot milling obtains color chips reach imperceptibly and pulverize, and be dispersed in the electrical insulating property solvent that is dissolved with described pigment dispersing, then combination of the kind of comminutor and dispersion machine, pulverizing process etc. has no particular limits.Herein, for combination more easy, that color chips dry type pulverize and the manufacture method of case of wet attrition describes.
At first, described pigment and described thermoplastic resin are added hot milling with three-roll mill, biaxial extruder etc., cooling back with Dry-crusher to obtain color chips carry out dry type and pulverize.Preferably pulverizing the mean grain size that the meal obtain minces by dry type is about 7～12 μ m.Also have, when dry type crushed material when being soft, for example softening point is below 100 ℃ the time, with liquid nitrogen or solid carbon dioxide cool off, embrittlement and pulverizing.As described Dry-crusher, preferably use hammer crusher, jet pulverizer, draw point muller, turbo-mill, cutting machine, bowl mill etc.
Then, use wet crushing mill, in the electrical insulating property varsol that is dissolved with at least a pigment dispersing agent that is selected from described modified linear phenol-aldehyde resin (A) and multipolymer (B), pulverize the meal obtain by dry type and mince and carry out case of wet attrition described, thereby can obtain liquid developer of the present invention.Also have, the charged correctives that can add in case of necessity in the liquid developer can add when case of wet attrition and/or after the case of wet attrition.As described wet crushing mill, for example be fit to use Eiger grinding machine, masher (atoreiter), puddle mixer, refiner (dinomill), bowl mill, DCP grinding machine, Apex grinding machine, ball mill medium type dispersion machines such as (pearl mill), Ultimizer ((strain) Sugino Machine system), Nanomizer (Nanomizer (strain) system), Microfuldizer (Mizuho industry (strain) system), DeBee2000 non-medium comminutors such as (DeBee corporate systems) etc.Consider that from obtaining high precise image the mean grain size of the toner particle in the liquid developer that obtains by case of wet attrition is preferably 0.1～5 μ m, more preferably 0.1～3 μ m.
The liquid developer that is obtained by above material and manufacture method can reach higher-solidization, and the development excellence.
For example, concerning liquid developer of the present invention, the all solids composition of crushed material (being toner particle), pigment dispersing agent and other solid constituent that will comprise color chips is as object, and the solid component concentration in the liquid developer is preferably 13～50 quality %.Basically we can say, from use be difficult for to guarantee dispersion stabilization and charged characteristic the case of wet attrition method of color chips, till reaching 50 quality %, solid component concentration all kept having reached unexistent in the past fabulous effect and effect on the good flowability and development.
Embodiment
Below, by embodiment liquid developer of the present invention is elaborated.Also have, remove nonspecific pointing out, " part " reaches " % " and refers to that respectively " mass parts " reaches " quality % ".
Pigment, pigment dispersing agent, the thermoplastic resin that uses in following embodiment and the comparative example described.
＜pigment 〉
Pigment blue 15: 3 (industry (strain) systems of refining big day)
＜pigment dispersing agent 1 〉
(this likes Lu epoxy resin (シ エ Le エ Port キ シ) (strain) system oiling to add epoxide modified linear phenol-aldehyde resin in reaction vessel, Epicoat154) 30 parts, the acid number 30, the weight-average molecular weight 4 that obtain by the polycondensation of 12-hydroxy stearic acid, the potpourri that 75 parts of 500 polyester, 35 parts of stearic acid and tetraethylammonium bromide are 0.2 part, in nitrogen stream with 130～150 ℃ of heated and stirred 3 hours, remove catalyzer by filtration under diminished pressure then, obtain weight-average molecular weight and be 8,000 modified linear phenol-aldehyde resin (pigment dispersing agent 1).
＜pigment dispersing agent 2 〉
In reaction vessel, add 100 parts of 12-hydroxy stearic acids, 10 parts of dimethylbenzene, 0.1 part of tetra-n-butyl titanate, flow down on one side at nitrogen that azeotropic heats up in a steamer the water that generates, 180～200 ℃ under carry out condensation reaction on one side.Heat up in a steamer removal xylene when reaching the regulation acid number, obtain the acid number 33 as light brown polymkeric substance, the polyester of weight-average molecular weight 4,400.Then,, make 74.3 parts of this polyester and under 130～150 ℃, react for 25.7 parts as solvent with 40 parts of dimethyl formamides as the styrene of multipolymer and the multipolymer (containing ratio is respectively 80 moles of %, 20 moles of %) of glycidyl methacrylate with epoxy radicals.Measure acid number and epoxy radicals, reach determination limit when following in the residual quantity of carboxyl and epoxy radicals, decompression is heated up in a steamer and is desolvated, and obtains graft copolymer (pigment dispersing agent 2).The weight-average molecular weight of measuring by GPC is 35,000.
＜comparison pigment dispersing agent 〉
Use Solsparse 17000 (Abesia society system) pigment dispersing agent as a comparison.
＜thermoplastic resin 1 〉
Use epoxy resin (AER6064, Asahi Chemical Industry's (strain) system).
＜thermoplastic resin 2 〉
Mix for 1.5 parts with 76.7 parts of styrene (St), 14.7 parts of methacrylic acid stearates (SMA), 8.6 parts of DMAAs (DMAA), 160 parts of toluene and as the azoisobutyronitrile of initiating agent, under 80 ℃, carried out free radical polymerization 10 minutes.Again for the resin solution that obtains, the decompression heating is 8 hours under 150 ℃, the condition of 70cmHg (about 93kPa), thereby heats up in a steamer toluene, unreacted monomer and low molecule oligomer, obtains thermoplastic resin 2.The thermoplastic resin 2 that obtains consist of that (St: SMA: DMAA=85: 5: 10 mol ratios), weight-average molecular weight is 45800, and fusing point is 92 ℃.
Embodiment 1
Use three hot rolls under 140 ℃ to 250 parts of pigment blue 15s: 3 and 750 parts of thermoplastic resins 1 carry out melting mixing, and the mixing thing (color chips) that obtains is cooled off, and use jet pulverizer (Japanese Pneumatic (strain) system) to pulverize then.Then use and filled the Eiger grinding machine (trade name M-250) of diameter as the zirconia microballon of 0.5mm, under 40 ℃ temperature to 140 parts of these meal mince, 8.8 parts of 1,551.2 parts of higher boiling paraffinic solvents of pigment dispersing agent (MorescoWhite P-40) carry out about 90 minutes case of wet attrition, obtain solid component concentration and be 21.3% liquid developer 1.
Embodiment 2
Use three hot rolls under 140 ℃ to 250 parts of pigment blue 15s: 3 and 750 parts of thermoplastic resins 1 carry out melting mixing, and the mixing thing (color chips) that obtains is cooled off, and use jet pulverizer (Japanese Pneumatic (strain) system) to pulverize then.Then use and filled the Eiger grinding machine (trade name M-250) of diameter as the zirconia microballon of 0.5mm, under 40 ℃ temperature to 140 parts of these meal mince, 5.3 parts of 1,554.7 parts of higher boiling paraffinic solvents of pigment dispersing agent (MorescoWhite P-40) carry out about 90 minutes case of wet attrition, obtaining solid component concentration is the liquid developer 2 of 20.8 amount %.
Embodiment 3
Use three hot rolls under 140 ℃ to 333 parts of pigment blue 15s: 3 and 667 parts of thermoplastic resins 1 carry out melting mixing, and the mixing thing (color chips) that obtains is cooled off, and use jet pulverizer (Japanese Pneumatic (strain) system) to pulverize then.Then use and filled the Eiger grinding machine (trade name M-250) of diameter as the zirconia microballon of 0.5mm, under 40 ℃ temperature to 210 parts of these meal mince, 5.3 parts of 1,484.7 parts of higher boiling paraffinic solvents of pigment dispersing agent (MorescoWhite P-40) carry out about 90 minutes case of wet attrition, obtain solid component concentration and be 30.8% liquid developer 3.
Embodiment 4
Use three hot rolls under 140 ℃ to 250 parts of pigment blue 15s: 3 and 750 parts of thermoplastic resins 1 carry out melting mixing, and the mixing thing (color chips) that obtains is cooled off, and use jet pulverizer (Japanese Pneumatic (strain) system) to pulverize then.Then use and filled the Eiger grinding machine (trade name M-250) of diameter as the zirconia microballon of 0.5mm, under 40 ℃ temperature, 140 parts of these crushed materials, 8.8 parts of 2,551.2 parts of higher boiling paraffinic solvents of pigment dispersing agent (MorescoWhite P-40) are carried out about 90 minutes case of wet attrition, obtain solid component concentration and be 21.3% liquid developer 4.
Embodiment 5
Use thermoplastic resin 2 to replace thermoplastic resin 1, use higher boiling paraffinic solvent (IPSolvent 2835) to replace higher boiling paraffinic solvent (Moresco White P-40), in addition, obtaining solid component concentration by the method identical with embodiment 1 is 21.3% liquid developer 5.
Comparative example 1
Use three hot rolls under 140 ℃ to 250 parts of pigment blue 15s: 3 and 750 parts of thermoplastic resins 1 carry out melting mixing, and the mixing thing (color chips) that obtains is cooled off, and use jet pulverizer (Japanese Pneumatic (strain) system) to pulverize then.Then use and filled the Eiger grinding machine (trade name M-250) of diameter as the zirconia microballon of 0.5mm, under 40 ℃ temperature to 140 parts of these meal mince, 560 parts of higher boiling paraffinic solvents (Moresco White P-40) carry out about 90 minutes case of wet attrition, obtain solid component concentration and be 20% liquid developer 6.
Comparative example 2
Use three hot rolls under 140 ℃ to 250 parts of pigment blue 15s: 3 and 750 parts of thermoplastic resins 1 carry out melting mixing, and the mixing thing (color chips) that obtains is cooled off, and use jet pulverizer (Japanese Pneumatic (strain) system) to pulverize then.Then use and filled the Eiger grinding machine (trade name M-250) of diameter as the zirconia microballon of 0.5mm, under 40 ℃ temperature to 140 parts of these meal mince, 8.8 parts of Solsperse 17000 (Abecia society system), 551.2 parts of higher boiling paraffinic solvents (Moresco White P-40) carry out about 90 minutes case of wet attrition, obtain solid component concentration and be 21.3% liquid developer 7.
＜estimate
For the liquid developer 1～7 of preparation in embodiment 1～5 and the comparative example 1～2, measure viscosity, resistance value, particle size range.The results are shown in the table 1.
(viscosity)
Use E type viscosity meter (for viscosity as more than the 10mPas, the material of not enough 100mPas measures under 20rpm, the material that surpasses 100mPas for viscosity is measured under 5rpm), measure the viscosity of liquid developer under 25 ℃, wherein adopt the viscosity after 60 seconds.Also have, the viscosity of the liquid developer of comparative example 1 is too high, can not measure.
(resistance value)
For liquid developer (can viscometric those), the R834 that makes by Advance society measures resistance value.
(particle size range)
For liquid developer, by the particle size range of the visual mensuration toner particle of optical microscope (Olympus (strain) system).
Table 1
| Viscosity (mPas) | Specific insulation (Ω cm) | Particle size range (μ m) | |
| Embodiment 1 | 16 | 6.0×10 13 | 1～2 |
| Embodiment 2 | 20 | 3.0×10 14 | 1～2 |
| Embodiment 3 | 100 | 5.0×10 14 | 1～2 |
| Embodiment 4 | 21 | 4.0×10 13 | 1～2 |
| Embodiment 5 | 50 | 5.0×10 14 | 1～2 |
| Comparative example 1 | - | - | ＞5 |
| Comparative example 2 | 15 | 8.0×10 12 | 1～4 |
Industrial applicibility
For added by pigment and thermoplastic resin that hot milling obtains color chips, use has aromatic rings and the specific pigment dispersant of the epoxy ring-opening structure that causes from the carboxyl of hydroxycarboxylic acid is pulverized, obtain liquid developer, although what adopt is the case of wet attrition method, but the liquid developer viscosity that obtains is low, can reach higher-solid, and resistance value is high, development is good.
Claims (5)
1. a liquid developer is characterized in that,
Described liquid developer be will pigment and thermoplastic resin be added hot milling and obtain color chips in being dissolved with the electrical insulating property varsol of pigment dispersing agent, carry out case of wet attrition, thereby make its dispersion and form, described pigment dispersing agent is selected from least a in the following modified linear phenol-aldehyde resin (A) of the epoxy ring-opening structure that has aromatic rings and cause from the carboxyl of hydroxycarboxylic acid and the multipolymer (B);
Modified linear phenol-aldehyde resin (A): have in the molecule from the aromatic rings of linear phenol-aldehyde resin and at least a carboxyl and cause epoxy ring-opening and the modified linear phenol-aldehyde resin of the group of general formula (1) expression that forms from hydroxycarboxylic acid;
[changing 1]
(in the formula, the oxygen atom that the oxygen atom of left end is contained from the aromatic series hydroxyl of linear phenol-aldehyde resin, W
1And X
1Represent that independently of one another carbon number is 1～19 bivalent hydrocanbon radical, i and j represent the integer of i=1～30, j=0～30, R independently of one another
1Expression hydrogen atom or methyl)
Multipolymer (B): weight-average molecular weight is 3,000～100,000 multipolymer, this multipolymer are the multipolymers that more than one that wherein contain the structural unit of general formula (2) expression that is equivalent at least 10 moles of % and be equivalent at least 10 moles of % are selected from the structural unit that general formula (3) and general formula (4) represent;
[changing 2]
[changing 3]
[changing 4]
(in the formula, W
2And X
2Represent that independently of one another carbon number is 1～19 bivalent hydrocanbon radical, p and q represent the integer of p=1～30, q=0～30, R independently of one another
2, R
3And R
4Represent hydrogen atom or methyl independently of one another, R
5Expression hydrogen atom or halogen atom, R
6And R
7Represent that independently of one another hydrogen atom, carbon number are that 1～5 alkyl, carbon number are that 1～5 alkoxy, carbon number are 6～10 aryloxy group or halogen atom, R
8Expression hydrogen atom or methyl, R
9Expression is combination or methylene directly).
2. liquid developer according to claim 1, wherein,
Total solid constituent concentration in the liquid developer is 13～50 quality %.
3. liquid developer according to claim 1 and 2, wherein,
Described liquid developer cooperates pigment dispersing agent 2～100 mass parts with respect to color chips 100 mass parts and forms.
4. according to any described liquid developer in the claim 1～3, wherein,
Use higher boiling paraffinic solvent as described electrical insulating property varsol.
5. according to the manufacture method of any described liquid developer in the claim 1～4, it is characterized in that,
For pigment and thermoplastic resin are added hot milling and obtain color chips, carrying out dry type pulverizing formation meal in advance minces, then in being dissolved with the electrical insulating property varsol that is selected from least a pigment dispersing agent in described modified linear phenol-aldehyde resin (A) and the multipolymer (B), described meal being minced carry out case of wet attrition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP154073/2005 | 2005-05-26 | ||
| JP2005154073 | 2005-05-26 |
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| JP (1) | JP5175547B2 (en) |
| KR (1) | KR20080018869A (en) |
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| CN102269948A (en) * | 2010-05-27 | 2011-12-07 | 京瓷美达株式会社 | Liquid developer, liquid developing device, and wet image forming device and method |
| CN103988131A (en) * | 2011-12-19 | 2014-08-13 | 惠普深蓝有限责任公司 | Liquid electrophotographic inks |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2640288B2 (en) * | 1989-09-28 | 1997-08-13 | 富士写真フイルム株式会社 | Non-aqueous dispersant and liquid developer for electrostatography |
| JPH0485551A (en) * | 1990-07-30 | 1992-03-18 | Fuji Photo Film Co Ltd | Nonaqueous dispersant and liquid developer for electrostatic photography |
| JP4382274B2 (en) * | 2000-10-31 | 2009-12-09 | サカタインクス株式会社 | Liquid developer |
| JP4527308B2 (en) * | 2001-03-27 | 2010-08-18 | サカタインクス株式会社 | Method for producing liquid developer |
| JP4021253B2 (en) * | 2002-06-18 | 2007-12-12 | サカタインクス株式会社 | Liquid developer |
-
2006
- 2006-05-24 EP EP06756517A patent/EP1884834A1/en not_active Withdrawn
- 2006-05-24 WO PCT/JP2006/310311 patent/WO2006126566A1/en active Application Filing
- 2006-05-24 CA CA002609825A patent/CA2609825A1/en not_active Abandoned
- 2006-05-24 AU AU2006250500A patent/AU2006250500A1/en not_active Abandoned
- 2006-05-24 CN CNA2006800184723A patent/CN101185039A/en active Pending
- 2006-05-24 KR KR1020077026956A patent/KR20080018869A/en not_active Application Discontinuation
- 2006-05-24 JP JP2007517850A patent/JP5175547B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102269948A (en) * | 2010-05-27 | 2011-12-07 | 京瓷美达株式会社 | Liquid developer, liquid developing device, and wet image forming device and method |
| CN102269948B (en) * | 2010-05-27 | 2014-05-14 | 京瓷办公信息系统株式会社 | Liquid developer, liquid developing device, and wet image forming device and method |
| CN103988131A (en) * | 2011-12-19 | 2014-08-13 | 惠普深蓝有限责任公司 | Liquid electrophotographic inks |
| CN103988131B (en) * | 2011-12-19 | 2017-09-22 | 惠普深蓝有限责任公司 | Liquid electrophotographic ink |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2006250500A1 (en) | 2006-11-30 |
| JPWO2006126566A1 (en) | 2008-12-25 |
| KR20080018869A (en) | 2008-02-28 |
| WO2006126566A1 (en) | 2006-11-30 |
| CA2609825A1 (en) | 2006-11-30 |
| EP1884834A1 (en) | 2008-02-06 |
| JP5175547B2 (en) | 2013-04-03 |
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