KR20060043745A - Stable organosol dispersion and liquid inks comprising the same - Google Patents

Abstract

The liquid ink may comprise (a) a wet carrier having a kauri-butanol number of 30 or less; (b) a graft copolymer containing a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier; And (c) a colorant, wherein the steric stabilizer comprises units derived from 3,3,5-trimethylcyclohexyl methacrylate, wherein the thermoplastic (co) polymer core comprises an aliphatic amino radical (meth) ) Acrylates, nitrogen-containing heterocyclic vinyl monomers, N-vinyl substituted cyclic amide monomers, aromatic substituted ethylene monomers containing amino radicals, and nitrogen-containing vinyl ether monomers Unit derived from at least one polymerizable monomer selected. The organosol provides improved wet electrophotographic and electrographic ink compositions having improved dispersion stability, chargeability, and blocking resistance, resulting in improved print quality or ink delivery performance.

Description

Stable organosol dispersion and liquid inks comprising the same

The present invention relates to a stable organosol dispersion and a wet ink comprising the same, more particularly, a wet ink useful in a printing process. In particular, the present invention relates to a wet ink that exhibits improved dispersion stability, improved blocking resistance, and improved charge performance when used in a given image processing process, wherein the image processing process comprises an ink transfer process, an ionographic (ionographic), inkjet, bubblejet, electrographic and electrophotographic color printing or proofing processes.

Wet inks are widely used in a variety of image processing and printing processes such as offset, bubblejet, inkjet, engraving, rotogravure, electrographic, and electrophotographic printing processes. Many of the features required for pigment dispersants for wet inks are the same as for individual processes, even if the final ink composition and treatment process are different. For example, the stability of discarded pigment dispersants under shear conditions and under high voltage electric fields is an important consideration, whether or not the final use of a wet ink. In order to provide more flexibility in ink composition, a lot of research is being conducted on more stable pigment dispersants to provide better efficiency and waste reduction effect in various printing processes.

In the field of electrophotography including devices such as photocopiers, laser printers, facsimiles and the like, liquid ink is also referred to as liquid toner or liquid developer. In general, the electrophotographic processing includes exposing a photoconductor to radiation in an image pattern to form an electrostatic latent image on a charged photoconductor, and contacting the photoconductor with a wet developer to develop a temporary image on the photoconductor. And finally transmitting the temporary picture to a receptor. The final transmission step may be performed directly from the photoconductor or indirectly through an intermediate transmission member. The burn developed above is generally heat treated and / or pressurized to fuse the burn permanently to the receptor.

Liquid toners include an insulating liquid that is generally used as a carrier for dispersing charged particles, known as toner particles. The toner particles include at least colorants (eg pigments or dyes) and polymer binders. Charge control agents are often used as one phase of a wet developer to control the polarity and size of the charge on the toner particles. Liquid toners can be divided into two major categories. For convenience, the two classes are defined as liquid toners and organosol toners. Of these two liquid toners, organosol toners are more preferred in the field of electrophotography in terms of stability.

Stable organosols include colloidal (approximately 0.1-1 micron diameter) particles of a polymer binder. Generally, the organosol particles can be synthesized by non-aqueous dispersion polymerization in a low dielectric hydrocarbon solvent. These organosol particles are stericly stabilized by the use of physically adsorbed or chemically grafted soluble polymers to inhibit aggregation. Such steric stabilization mechanisms are described in more detail in Napper, DH, Polymeric Stabilization of Colloidal Dispersions , Academic Press, New York, NY, 1983. Processes affecting the synthesis of self-stable organosol are known to those skilled in the art and are described in Dispersion Polymerization in Organic Media , KEJ Barrett, ed., John Wiley: New York, NY, 1975.

The most commonly used non-aqueous dispersion polymerization method is free radical polymerization, which is a method of the preparation of a lipophilic polymer prepared in advance of one or more ethylenically unsaturated (typically acrylic or methacrylic) monomers that are soluble in a hydrocarbon medium. It is a method of polymerizing in presence. Preformed lipophilic polymers (commonly referred to as stabilizers) comprise two different units, one of which is essentially insoluble in the hydrocarbon medium and the other is soluble. If the polymerization process for preparing the organosol particles proceeds to fractional conversion of the monomer corresponding to the critical molecular weight, the solubility limit of the polymer is exceeded, and the polymer forms a precipitate with a solution to form "core particles. The lipophilic polymer then adsorbs to the core by ionic or covalent bonds, whereby the core continues to grow as other particles, which continue to grow until the monomer runs out, and the bound parent The matrix polymer “shell” serves to stabilize the growing core particles sterically against aggregation The resulting non-aqueous colloidal dispersion (organosol) can be used for core / shell polymer particles having a number average diameter of about 0.05 to 5 microns. Include.

The resulting organosol is then converted to a liquid toner by simple integration and mixing of colorants (pigments) and charge directors, followed by high shear homogenization, ball milling, attritor milling, and high energy bead (sand) milling. Or other micronization process or mixing means known in the art to affect particle size reduction in dispersion formation. The application of mechanical energy to the dispersion during the milling process serves to inhibit the pigment from agglomerating to the base particles (e.g. about 0.05 to 1.0 micron number average diameter) and to cut the organosol adsorbed onto the newly created pigment surface. It plays a role and stericly stabilizes the pigment particles against aggregation. The charge director adsorbs physically or chemically to the pigment, organosol, or both. The result is a non-aqueous pigment dispersion that is stericly stabilized, charged, and has particles of a number average diameter size ranging from about 0.05 to 5.0 microns (normal toner particles have a number average diameter of 0.15 to 1.0 micron). The steric stabilized dispersion can be ideally used for high resolution printing.

The problem with producing wet inks is that the image is viscous on the final receptor. If viscosity remains in the image, peeling or embossing may occur when the image is left in contact with another surface. This phenomenon is called blocking. This is especially a problem when the printed sheets are placed on the stack, such as when printed sheets come out of the printer and are fed into the drawers. If the image is viscous, the image portion may be adsorbed or transferred to the back side of the neighboring sheet. In view of this aspect, the film laminate or protective layer is generally located on the surface of the image. This requires separate material costs and processing steps to form the protective layer.

Another problem in producing fast self-fixing wet inks is that it is difficult to obtain wet inks that have both good cohesive and precipitation stability upon standing. It is known in the art that film-forming wet inks comprising stable organosols generally exhibit either good coagulation stability or precipitation stability, but not all of them. Aggregation stability of the organosol is related to the tendency of the core / shell particles to effectively aggregate into larger clusters of particles. Precipitation stability of the organosol is related to the tendency to precipitate from a particular component (particularly colorant component) dispersion or suspension of the organosol. Accordingly, there is a need for a wet ink composition having both good cohesive stability and precipitation stability.

An important point in preparing a wet ink is the charging ability of the wet ink. Due to the difference based on the difference in charge on the photoreceptor, there is a need for a wet ink with high charge ability to move under an electric field to obtain a sufficient amount of charge to be deposited on the image area on the photoreceptor. The charging ability of a wet ink is measured by its conductivity and mobility. Generally, wet inks having high ink conductivity and high ink mobility are preferred.

It is an object of the present invention to provide a stable organosol dispersion having a novel composition exhibiting improved dispersion stability, improved blocking resistance and improved chargeability and a wet ink comprising the same.

One aspect of the present invention to achieve the above technical problem,

(a) a wet carrier comprising a Kauri-Butanol number of 30 or less; And

(b) providing an organosol dispersion comprising a graft copolymer comprising a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier,

The thermoplastic (co) polymer core contains 1) a (meth) acrylate with an aliphatic amino group, 2) a nitrogen-containing heterocyclic vinyl monomer, 3) an N-vinyl substituted cyclic amide monomo, 4) an amino group An aromatic substituted ethylene monomer and 5) a (co) polymer comprising units derived from at least one polymerizable monomer selected from the group consisting of nitrogen-containing vinyl ether monomers.

The second aspect of the present invention,

(a) a wet carrier comprising a Kauri-Butanol number of 30 or less; And

(b) providing an organosol dispersion comprising a graft copolymer comprising a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier,

Such steric stabilizers include polymers comprising units derived from 3,3,5-trimethylcyclohexyl methacrylate.

According to a third aspect of the present invention,

(a) a wet carrier comprising a Kauri-Butanol number of 30 or less; And

(b) providing an organosol dispersion containing a graft copolymer comprising a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier,

The steric stabilizer contains a polymer comprising units derived from 3,3,5-trimethylcyclohexyl methacrylate, wherein the thermoplastic (co) polymerized core comprises: 1) (meth) acrylate having an aliphatic amino group, 2 At least one selected from the group consisting of a nitrogen-containing heterocyclic vinyl monomer, 3) an N-vinyl substituted cyclic amide monomo, 4) an aromatic substituted ethylene monomer containing an amino group, and 5) a nitrogen-containing vinyl ether monomer. It contains a (co) polymer comprising units derived from one polymerizable monomer.

The fourth aspect of the present invention,

(a) a wet carrier comprising a Kauri-Butanol number of 30 or less;

(b) a graft copolymer comprising a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier; And

(c) providing a liquid ink containing a colorant,

The thermoplastic (co) polymer core contains 1) a (meth) acrylate with an aliphatic amino group, 2) a nitrogen-containing heterocyclic vinyl monomer, 3) an N-vinyl substituted cyclic amide monomo, 4) an amino group An aromatic substituted ethylene monomer and 5) a (co) polymer comprising units derived from at least one polymerizable monomer selected from the group consisting of nitrogen-containing vinyl ether monomers.

The fifth aspect of the present invention,

(a) a wet carrier comprising a Kauri-Butanol number of 30 or less;

(b) a graft copolymer comprising a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier; And

(c) providing a liquid ink containing a colorant,

Such steric stabilizers include polymers comprising units derived from 3,3,5-trimethylcyclohexyl methacrylate.

According to a sixth aspect of the present invention,

(a) a wet carrier comprising a Kauri-Butanol number of 30 or less;

(b) a graft copolymer comprising a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier; And

(c) providing a liquid ink containing a colorant,

The steric stabilizer contains a polymer comprising units derived from 3,3,5-trimethylcyclohexyl methacrylate, wherein the thermoplastic (co) polymerized core comprises: 1) (meth) acrylate having an aliphatic amino group, 2 At least one selected from the group consisting of a nitrogen-containing heterocyclic vinyl monomer, 3) an N-vinyl substituted cyclic amide monomo, 4) an aromatic substituted ethylene monomer containing an amino group, and 5) a nitrogen-containing vinyl ether monomer. It contains a (co) polymer comprising units derived from one polymerizable monomer.

Although the liquid ink according to the present invention is basically described for electrophotographic office printing, these liquid toners are not limited to their use, but are not intended for other image processing processes, other printing processes, other ink delivery processes such as high speed printing processes, Photocopy apparatuses, microfilm reproducing apparatuses, fax machines, inkjet printers, mechanical recording apparatuses and the like.

The liquid ink composition according to the present invention comprises a liquid dispersed organosol and a colorant comprising a kauri-butanol (KB) number of 30 or less. The wet ink compositions are particularly useful for electrophotographic, ionographic or electrostatic image processing and other conventional printing processes because they are resistant to both aggregation and precipitation and are capable of fast film formation (rapid self-fixing).

"Kaury-butanol" refers to ASTM measurement method D1133-54T. The kauri butanol number (KB) is a measure of the resistance of the 1-butanol standard solution of the Kauri resin to the added hydrocarbon diluent, and produces a certain turbidity when added to 20 g of the standard kauri-1-butanol solution. It is measured as a volume (unit: milliliters) at 25 ° C. of the solvent required for the purpose. The standard value is toluene (KB = 105) and 75 vol% heptane with 25 vol% toluene (KB = 40).

The polymer particles in the organosol of the invention are lipophilic copolymers. The lipophilic copolymers comprise soluble or somewhat insoluble high molecular weight (co) polymer steric stabilizers covalently bonded to the insoluble, thermoplastic (co) polymer core. Stability against aggregation and precipitation of the dispersed toner particles is particularly excellent when the stabilizer comprises 3,3,5-trimethylcyclohexyl methacrylate.

Table 1 below shows Kauri-Butanol number and Hilderbrand solubility parameters for some common wet carriers used in electrophotographic toners, and Table 2 shows Hilderbrand solubility parameters and glass transition temperatures of common monomers.

TABLE 1

Solvent value at 25 ℃

Solvent name Kauri-Butanol Number by ASTM Method D1133-54T (mL) Hilderbrand Solubility Parameters (MPa ^1/2 ) Norpar ^TM 15 18 13.99 Norpar ^TM 13 22 14.24 Norpar ^TM 12 23 14.30 Isopar ^TM V 25 14.42 Exxsol ^TM D80 28 14.60

Source: calculated according to equation # 31 described in Polymer Handbook , 3rd Ed., J. Brandrup EH Immergut, Eds. John Wiley, NY, p. VII / 522 (1989).

TABLE 2

Monomer name Hilderbrand Solubility Parameters (MPa ^1/2 ) Glass transition temperature (℃) n-octadecyl methacrylate 16.77 -100 n-octadecyl acrylate 16.82 -55 Lauryl methacrylate 16.84 -65 Lauryl acrylate 16.95 -30 2-ethylhexyl methacrylate 16.97 -10 2-ethylhexyl acrylate 17.03 -55 n-hexyl methacrylate 17.13 -5 t-butyl methacrylate 17.16 107 n-butyl methacrylate 17.22 20 n-hexyl acrylate 17.30 -60 n-butyl acrylate 17.45 -55 Ethyl methacrylate 17.90 66 Ethyl acrylate 18.04 -24 Methyl methacrylate 18.17 105 Vinyl acetate 19.40 30 Methyl acrylate 20.2 5

Calculated by Small Group Contribution Method (Small, PA, Journal of Applied Chemistry 3 p. 71 (1953) Polymer Handbook , 3rd Ed., J. Brandrup EH Immergut, Eds. John Wiley, NY, p. VII / 525 (1989)).

Polymer Handbook , 3rd Ed., J. Brandrup EH Immergut, Eds. John Wiley, NY, p. VII / 209-277 (1989).

The wet carrier may be selected from a variety of materials known in the art, but preferably has a kauri-butanol number of less than 30. The liquid is preferably lipophilic, chemically stable under various conditions, and electrically insulating. Electrical insulation means a liquid having a low dielectric constant and a high electrical resistivity. Preferably, the liquid has a dielectric constant of less than 5; More preferably less than 3. The electrical resistivity of the wet carrier is typically greater than 10 ⁹ Ohm-cm; More preferably greater than 10 ¹⁰ Ohm-cm. The wet carrier is preferably relatively non-viscous enough to allow the movement of charged particles during the development process and is preferably volatile enough to allow timely removal from the final image processing substrate, but in a preserved developer It is desirable to be non-volatile enough to minimize evaporation losses at. The wet carrier should also be chemically inert in most embodiments with respect to the components used to formulate the toner particles.

Examples of suitable wet carriers include aliphatic hydrocarbons (n-pentane, hexane, heptane, etc.), cyclic aliphatic hydrocarbons (cyclopentane, cyclohexane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbon solvents (chlorinated) Alkanes, fluorinated alkanes, chlorofluorocarbons, etc.), silicone oils and mixtures of these solvents. Preferred wet liquids include branched paraffinic solvent mixtures such as Isopar ^™ G, Isopar ^™ H, Isopar ^™ K, Isopar ^™ L, Isopar ^™ M and Isopar ^™ V (available from Exxon Corporation, NJ), Most preferred carriers are aliphatic hydrocarbon solvent mixtures such as Norpar ^™ 12, Norpar ^™ 13 and Norpar ^™ 15 (purchased from Exxon Corporation, NJ).

The composition of the graft stabilizer is generally chosen such that the Hilderbrand solubility parameter of the graft stabilizer (shell) is closely matched with that of the wet carrier so that the stabilizer is sufficiently solvated and reliably dissolved in the wet carrier. Substantially any polymerizable compound exhibiting a Hilderbrand solubility parameter of less than 3.0 MPa ^1/2 compared to the wet carrier may be used in the graft stabilizer preparation. In addition, preparation of the stabilizer and less than 3.0 MPa ^1/2 the effective hildeo Brandt solubility parameter difference between the liquid carrier, 3.0 MPa ^1/2 hildeo Brandt solubility polymerizable compound is a copolymer of the graft stabilizer represents the parameter difference greater than the Can be used. The absolute difference in Hilderbrand solubility parameter between the graft stabilizer (shell) and the wet carrier is preferably less than 2.6 MPa ^1/2 .

Generally graft stabilizers derived from C ₆ -C ₃₀ acrylates and methacrylates, such as lauryl methacrylate (LMA) and octadecyl acrylate (ODA), have their Hilderbrand solubility parameters associated with hydrocarbon carriers. Close proximity and therefore very soluble in hydrocarbon carriers. However, graft stabilizers completely derived from C ₆ -C ₃₀ acrylates and methacrylates have very low Tg values and are therefore not suitable for commercial wet inks due to their stickiness and low blocking resistance. Nevertheless, when the graft stabilizers are modified by copolymerization with 3,3,5-trimethylcyclohexyl methacrylate (TCHMA), their stickiness and blocking resistance can be significantly improved. Homopolymers of 3,3,5-trimethylcyclohexyl methacrylate (TCHMA) have high Tg at 125. However, it is soluble in most common wet carriers. Copolymerization of TCHMA with at least one C ₆ -C ₃₀ acrylate and / or methacrylate to form a graft stabilizer increases the Tg value of the graft stabilizer but does not cause side effects on solubility in the wet carrier. In order to obtain good offset transfer efficiency and excellent blocking resistance of the transferred image, a graft stabilizer having a Tg between -10 ° C and 30 ° C is preferred, and more preferably between -5 ° C and 15 ° C.

Non-limiting examples of C ₆ -C ₃₀ acrylic and methacrylic esters suitable for use in the graft stabilizer compositions include hexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl (lauryl) acrylate, octa Decyl (stearyl) acrylate, behenyl acrylate, hexyl methacrylate, 2-ethylhexyl (methacrylate), decyl acrylate, dodecyl (lauryl) methacrylate, octadecyl (stearyl) methacrylate Examples include rates, isobornyl acrylate, isobornyl methacrylate, and other acrylates and methacrylates that meet the above solubility parameters.

The graft stabilizer is capable of chemically bonding to the resin core (i.e., grafted to the core) and remains as an essential component adsorbed on the core and physically bonded to the resin core. Many reactions known to those skilled in the art can be used to influence the reaction of grafting soluble polymer stabilizers to the organosol core during free radical polymerization. Typical graft reactions include random graft reactions of multifunctional free radicals; Ring-opening polymerization of cyclic ethers, esters, amides or acetals; Epoxidation reactions; Reaction of a hydroxyl or amino chain transfer agent with an end-unsaturated end group; Esterification reaction (ie, glycidyl methacrylate performs an esterification reaction catalyzed by methacrylic acid and tertiary amine); And condensation or polymerization reactions. The preferred weight average molecular weight of the graft stabilizer is 50,000 to 1,000,000 Daltons (Da), preferably 100,000 to 500,000 Da, most preferably 100,000 to 300,000 Da.

Multiple dispersions of the graft stabilizer also affect the image processing and delivery performance of the liquid toner. In general, it is preferable to maintain a multiple dispersion degree (ratio of weight average molecular weight to number average molecular weight) of preferably 15 or less, more preferably 5 or less, and most preferably 2.5 or less.

The present invention also provides a new grafting site used to covalently bond the stabilizer to the insoluble core. The grafting site incorporates hydroxyl groups into the graft stabilizer during the first free radical polymerization process and incorporates some or all of these hydroxyl groups into ethylenically unsaturated aliphatic isocyanates (e.g. meta-isopropenyldimethylbenzyl isocyanate). By catalytic reaction with [TMI] or 2-cyanatoethyl methacrylate [IEM]) to form a polyurethane linkage in the subsequent non-free radical reaction step. The graft stabilizer is then used in the subsequent free radical polymerization process to unsaturated vinyl groups and ethylenically unsaturated core monomers of the grafting site (e.g. vinyl esters, in particular acrylic and methacrylic esters or vinyl acetates having up to 7 carbon atoms; Vinyl aromatics, such as acrylonitrile; n-vinyl pyrrolidone; vinyl chloride and vinylidene chloride), and covalently bonded to the initial insoluble acrylic (co) polymer core.

Other methods of influencing the grafting of previously prepared polymer stabilizers to the initial insoluble core particles are known to those skilled in the art. For example, other grafting protocols are described in sections 3.7-3.8 of Barrett Dispersion Polymerization in Organic Media , KEJ Barrett , ed., (John Wiley: New York, 1975), pp. 79-106. A particularly useful method of grafting the polymer stabilizer onto the core is to use an anchoring group. The function of the anchoring group is to provide a covalent bond between the core portion of the particle and the soluble component of the steric stabilizer. Suitable monomers comprising a fixing group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, pentaerythritol triacrylate, 4-hydroxybutyl vinyl ether, 9-octa Additives of alkenylazlactone comonomers having unsaturated nucleophiles such as decene-1-ol, cinnamil alcohol, allyl mercaptan, metallylamine; And azlactones such as 2-alkenyl-4,4-dialkylazlactone of the formula:

Food,

R ¹ represents H or an alkyl group having 1 to 5 carbon atoms, preferably 1 carbon atoms,

R ² and R ³ each independently represent a lower alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

Most preferably, however, the grafting mechanism is commercially available from ethylenically unsaturated isocyanates (e.g., dimethyl-m-isopropenyl benzyl isocyanate, American cyanamide) with hydroxyl groups previously incorporated into the graft stabilizer precursor. ) Is achieved by grafting (eg using hydroxy ethyl methacrylate).

The core polymer may be prepared in situ by copolymerization with the stabilizer monomer. The composition of the insoluble resin core is preferably prepared such that the resin core exhibits a low glass transition temperature (Tg), so that the ink composition comprising the resin is at a temperature higher than the glass transition temperature (Tg) of the core, Preferably, the film may be manufactured to perform rapid film formation (rapid magnetic fixing) in a printing or image processing process performed at a temperature of 23 ° C. or higher. Rapid self-fixing helps to prevent print defects (stains or lags) and incomplete transmission in high speed printing. The Tg of the core should be 23 ° C. or less, more preferably 10 ° C. or less, most preferably −10 ° C.

Non-limiting examples of polymerizable organic compounds suitable for use in the organosol core include methyl acrylate, ethyl acrylate, butyl acrylate, methyl (methacrylate), ethyl (methacrylate), butyl (methacrylate), and Other acrylates and methacrylates are mentioned, Methyl methacrylate and ethyl acrylate are the most preferable.

In order to form a stable ink dispersion, the organosol particles should be able to interact strongly with the colorant pigment particles. This requires that the organosol particles comprise a moiety capable of chemically bonding or physically adsorbing to the pigment surface. The present invention reveals that the nitrogen-containing polymerizable organic compound incorporated into the organosol core enhances the interaction between the organosol and the pigment and as a result stabilizes the ink dispersion. Non-limiting examples of nitrogen-containing polymerizable organic compounds include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylic Latex, N, N-hydroxyethylaminoethyl (meth) acrylate, N-benzyl, N-ethylaminoethyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, n-octyl, (Meth) acrylates containing aliphatic amino radicals such as N, N-dihexylaminoethyl (meth) acrylate and the like; N-vinylimidazole, N-vinylindazole, N-vinyltetrazole, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2- Nitrogen-containing heterocyclic vinyl monomers such as vinylpyrazine, 2-vinyloxazole, 2-vinylbenzoxazole and the like; N-vinyl substituted cyclic amide monomers structured as N-vinyl groups bonded to a ring structure having an internal amide group, such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinyloxazolidone, etc. As disclosed in patent 5,953,566); N-methylacrylamide, N-octylacrylamide, N-phenylmethacrylamide, N-cyclohexylacrylamide, N-phenylethylacrylamide, Np-methoxy-phenylacrylamide, acrylamide, N, N-dimethyl (Meth) acrylamides such as acrylamide, N, N-dibutylacrylamide, N-methyl, N-phenylacrylamide, piperidine acrylate, morpholine acrylate and the like; Aromatic substituted ethylene monomers containing amino radicals such as dimethylaminostyrene, diethylaminostyrene, diethylaminomethylstyrene, dioctylaminostyrene and the like; And vinyl-N-ethyl-N-phenylaminoethyl ether, vinyl-N-butyl-N-phenylamino ethyl ether, triethanolamine divinyl ether, vinyldiphenylaminoethyl ether, vinylpyrrolidylamino ether, vinyl- Nitrogen-containing vinyl ether monomers such as beta-morpholinoethyl ether, N-vinylhydroxyethylbenzamide, m-aminophenylvinylether and the like.

Examples of other polymers that can be used alone or in combination with the above-mentioned materials include melamine and melamine formaldehyde resins, phenol formaldehyde resins, epoxy resins, polyester resins, styrene and styrene / acrylic copolymers. , Vinyl acetate and vinyl acetate / acrylic copolymers, acrylic and methacrylic esters, cellulose acetate and cellulose acetate-butyrate copolymers, and poly (vinyl butyral) copolymers. Suitable weight ratios of the resin core to the stabilizer shell have orders of 1/1 to 15/1, preferably 2/1 to 10/1, and most preferably 4/1 to 8/1. Core / shell ratios outside these ranges can involve undesirable effects. For example, at high core / shell ratios (above 15), there will be insufficient graph stabilizer to stericly stabilize the organosol against aggregation. At low core / shell ratios (1 or less), the polymerization reaction has insufficient driving force to form discrete particulates, thereby forming a copolymer solution rather than a self-stable organosol dispersion.

The particle size of the organosol will also affect the image processing, drying and transfer characteristics of the wet ink. Preferably, the basic particle size of the organosol (which may be measured by, for example, dynamic light scattering measurement) is preferably about 0.05 to 5.0 microns, more preferably 0.15 to 1 micron, and 0.20 to 0.50 micron. Most preferred.

The wet ink using the above-mentioned organosol includes colorant particles embedded in the thermoplastic organosol resin. Useful colorants are well known in the art and include materials such as dyes, stains, pigments and the like. Preferred colorants are pigments that can be incorporated into the polymer resins and are generally insoluble and nonreactive in the wet carrier and are useful and effective for visualizing the electrostatic latent image. In general, non-limiting examples of proper coloring include phthalocyanine blue (CI Pigment Blue 15: 1, 15: 2, 15: 3 and 15: 4), monoarylide yellow (CI Pigment Yellow 1,3, 65, 73 and 74). , Diarylide yellow (CI Pigment yellow 12, 13, 14, 17 and 83), arylamide (Hansa) yellow (CI Pigment Yellow 10, 97, 105, 138 and 111), azo red (CI Pigment Red 3, 17 , 22, 23, 38, 48: 1, 48: 2, 52: 1, 81, 81: 4 and 179), quinacridone magenta (CI Pigment Red 122, 202 and 209) and finely divided carbon (Cabot Black pigments such as Monarch 120, Cabot Regal 300R, Cabot Regal 350R, Vulcan X72) and the like.

Suitable weight ratios of the resin to the colorant in the toner particles have orders of 1/1 to 20/1, preferably 3/1 to 10/1, and most preferably 5/1 to 8/1. All materials dispersed in the wet carrier are generally from 0.5 to 70% by weight, preferably from 1 to 25% by weight and most preferably from 2 to 12% by weight, based on the total wet developer composition.

Electrophotographic liquid toners can be prepared by incorporating a charge control agent into the liquid ink. The charge control agent, also called the charge director, imparts a homogeneously improved charge polarity to the toner particles. The charge director is a method of chemically reacting the toner particles with the charge director, a method of chemically or physically adsorbing the charge director on the toner particles (resin or pigment), or a functional group incorporated into the toner particles. Various methods can be incorporated into the toner particles, such as by cheating the charge director. The preferred method is to bind through the functional groups formed in the graft stabilizer. The charge director serves to distribute charge of the selected polarity to the toner particles. Most of the charge directors described in the prior art can be used. For example, the charge director may be introduced in the form of a metal salt consisting of organic anions such as counterions and polyvalent metal ions. Non-limiting examples of suitable metal ions include Ba (II), Ca (II), Mn (II), Zn (II), Zr (IV), Cu (II), Al (III), Cr (III), Fe (II) ), Fe (III), Sb (III), Bi (III), Co (II), La (III), Pb (II), Mg (II), Mo (III), Ni (II), Ag (I ), Sr (II), Sn (IV), V (V), Y (III) and Ti (IV). Non-limiting examples of suitable organic anions include carboxylates or sulfonates derived from aliphatic or aromatic carboxylic acids or sulfonic acids, preferably stearic acid, behenic acid, neodecanoic acid, diisopropylsalicylic acid, jade Aliphatic fatty acids such as carbonic acid, abietic acid, naphthenic acid, octanoic acid, lauric acid, tallic acid and the like are preferred. Preferred positive charge directors are the metal carboxylates disclosed in US Pat. No. 3,411,936, incorporated herein by reference, and include cyclic aliphatic acids comprising fatty acids and naphthenic acids containing at least 6-7 carbon atoms. Alkaline earth metal salts and heavy metal salts of acids are preferred; Zirconium salt of octanoic acid (zirconium HEX-CEM from Mooney Chemicals, Cleveland, Ohio).

The preferred charge direction level for a given toner formulation depends on many factors, including, for example, the composition of the graft stabilizer and organosol, the molecular weight of the organosol, the particle size of the organosol, the core / shell ratio of the graft stabilizer, the toner Pigments used in the preparation, and the ratio of organosol to pigment, and the like. Further, preferred charge direction levels depend on the nature of the electrophotographic image processing process, in particular the design of the developing hardware and photosensitive components. However, those skilled in the art know how to adjust the level of charge direction based on the enumerated parameter values in order to obtain the desired result in a particular field.

The conductivity of liquid toners is well known in the art as a method of measuring the efficiency of toner in developing electrophotographic images. The most useful conductivity range is about 1 × ^{10 −11} mho / cm to 10 × ^{10 −10} mho / cm. High conductivity generally means insufficient charge coupled to the toner particles, which means that there is a low association between the current density and the toner deposited during development. Low conductivity indicates little or no charging of the toner particles, resulting in very low development rates. It is common practice to use charge director compounds to ensure sufficient charge associated with each particle. Recently, it has been recognized that even with the use of charge directors, many undesired charges can be located on the charged species in the solution of the wet carrier. This undesired charge causes inefficiency, instability and inconsistency in the development process.

Many efforts to concentrate charge on the toner particles, substantially eliminate the transfer of charge from such particles to the liquid, and to ensure that no other undesired charge moieties are present in the liquid result in substantial improvements. The measurement of the required property uses the ratio between the conductivity of the liquid carrier appearing in the liquid toner and the overall conductivity of the liquid toner (fully configured toner dispersion). This ratio is at most 0.6, preferably at most 0.4, and most preferably at most 0.3. Many toners according to the prior art, which have been examined through experiments, are in the range of 0.95, a much larger proportion.

Various methods may be used to influence the particle size reduction of the pigment in the preparation of the gel liquid toner. Suitable methods include high shear homogenization, ball milling, attrition milling, high energy bead (sand) milling, or other methods according to the prior art.

In electrophotography, an electrostatic image is generally formed on a belt, sheet or drum coated with a photosensitive component, the forming method comprising: (1) homogeneously charging the photosensitive component to an applied voltage, (2) the radiation source Exposing and discharging a portion of the photosensitive component to form a latent image, (3) applying toner to the latent image to form a toned image, and delivering the toned image to a final receiving paper through one or more steps It includes a step. In some applications, it is desirable to fix the toned image using a hot pressing roller or other fixing method known in the art.

While the electrostatic charge of the toter particles or photosensitive component is positive or negative, the electrophotographic employed in the present invention preferably disperses the charge on the positively charged photosensitive component. The positively charged toner is then applied to the area where the positive charge is dispersed using the wet ink impregnation technique. Such development can be performed using a uniform electric field located adjacent to the photosensitive component surface and generated by the development electrode. A bias voltage that is halfway between the initially charged surface voltage and the exposed surface voltage level is applied to the electrode. The voltage is adjusted to obtain the maximum density level and tone reproduction stale required for the halftone dots without leaving any residue in the background. The liquid toner then flows between the electrode and the photosensitive component. The charged toner particles are movable in the electric field and are attracted to the discharge region on the photosensitive component, but are rejected from the discharged non-image region. The high amount of liquid toner remaining on the photosensitive component is removed according to methods known in the art. Thereafter, the photosensitive component surface is forcibly dried or dried at ambient conditions.

The substrate that receives the image from the photosensitive component can be any acceptor material commonly used, including, for example, paper, coated paper, polymer film, and primed or coated polymer film. Treated metal or metallized surfaces can also be used as acceptors. Polymeric films include plasticized and complexed polyvinyl chloride (PVC), acrylic, polyurethane, polyethylene / acrylic acid copolymers, and polyvinyl butyral. Commercially available composite materials such as the trade names Scotchcal ^™ , Scotchlite ^™ , and Panaflex ^™ film materials are also suitable for the preparation of the substrates described above.

The process of transferring the formed image from the charged surface to the final receptor or delivery medium can be enhanced by the incorporation of the release-promoting material in the dispersed particles used to form the image. The incorporation of a silicon containing material or a fluorine containing material into the outer (shell) layer of the particles makes the effective transfer of the image easier.

In color image processing, the toner may be applied to the surface of the dielectric or photoreceptor in any order, but inversion may occur during delivery in terms of color, and in some cases, the image is popular in a particular order according to the transparency and intensity of the color. It may be desirable to. Preferred sequences for the direct image processing or dual delivery process are yellow, magenta and black; Preferred sequences in a single delivery process are black, cyan, magenta and yellow. Yellow is generally first imaged on the photoconductor to prevent contamination from other toners and to become the top color layer upon delivery. Black is generally the latest imaged on the photoconductor due to the black toner acting as a filter of the radiation source, becoming the bottom layer after delivery.

In order to work most effectively, the liquid toner should have a conductance value of 50 to 1200 picomho-cm ^-1 . The liquid toner prepared according to the present invention has a conductance value of 100 to 500 picomho-cm ^-1 for dispersions containing 2.5% by weight solids.

Overcoating of the transferred image can optionally be done to protect the image from physical damage and / or actinic damage. Overcoating compositions are well known in the art and generally comprise a clear film polymer dissolved or suspended in a volatile solvent. UV absorbers may be optionally added to the coating composition. Laminating a protective layer on the image-beating surface is also known in the art and can be used in the present invention.

The present invention is explained in more detail by the following examples. These examples are intended to illustrate specific materials within the broad disclosure set forth above and are not intended to limit the scope of the invention.

Example

Glossary of Compound Abbreviations and Compound Manufacturers

The following raw materials were used to prepare the polymers of the following examples:

Catalysts used in the examples include azobisisobutyronitrile (called AIBN, available from DuPont Chemicals, Wilmington, DE as VAZO ^™ ); Dibutyl tin dilaurate (called DBTDL, available from Aldrich Chemical Co., Milwaukee, WI); And 2,2'-azobisisobutyronitrile (called AZDN, available from Elf Atochem, Phliadelphia, PA). Monomers can be purchased from the manufacturer (Scientific Polymer Products, In., Ontario, NY) unless otherwise noted.

The monomers used in the examples are referred to by the following abbreviations: dimethyl-m-isopropenyl benzyl isocyanate (available from TMI, CYTEC Industries, Wet Paterson, NJ); Ethyl acrylate (EA); 2-ethylhexyl methacrylate (EHMA); 2-hydroxyethyl methacrylate (HEMA); 3,3,5-trimethylcyclohexyl methacrylate (TCHMA); Lauryl methacrylate (LMA); Methyl methacrylate (MMA); Isobornyl methacrylate (IBMA); Octadecyl methacrylate (ODA); And N, N-dimethylaminoethyl methacrylate (DMAEMA).

Test Methods

The following test methods were used to analyze the polymers and inks of the following examples:

Solids Percentage of Graft Stabilizer, Organosol, and Liquid Toner

The graft stabilizer solution, and the percentage of solids of the organosol and ink dispersion color, were weighed using a halogen lamp drying oven (Mettler instruments Inc., higntstown, NJ) attached to a precision analytical balance. In this sample drying measurement, about 2 grams of samples were used for each percent solids measurement.

Graft Stabilizer Molecular Weight

Various properties of graft stabilizers such as molecular weight and molecular weight polydispersity have been known to be important for the performance of such stabilizers. Graft stabilizer molecular weights are generally expressed in terms of weight average molecular weight (M _w ), but molecular weight polydispersity is obtained as the ratio of weight average molecular weight (M _w / M _n ) to number average molecular weight. Molecular weight parameters for the graft stabilizer were determined by gel permeation chromatography (GPC) using tetrahydrofuran as the carrier solvent. Complete MW was measured using a Dawn DSP-F light dispersion detector (available from Wyatt Technology Corp, Santa Barbara, CA) and polydispersity is Obtilab 903 differential refractometer detector (available from Wyatt Technology Corp, Santa Barbara, CA) It was evaluated as the ratio of Mw measured to Mn value measured by.

Particle size

Toner particle size dispersibility was measured using a Horiba LA-900 laser diffraction particle size analyzer (commercially available from Horiba Instrument, Inc., Irving, Calif.). The toner sample was diluted to approximately 1/500 and then sonicated for one minute at 150 watts and 20 kHz before measurement. Toner particle size was expressed on a number average basis to represent the basic (basic) particle size of the ink particles.

Toner conductivity

The conductivity (bulk conductivity, k _b ) of the liquid toner was measured at approximately 18 hz using a conductivity meter (Scientifica model 627, available from Scientifica Instruments, Inc., Princeton, NJ). In addition, the free (diffusion) phase conductivity (k _f ) in the absence of toner particles was also measured. Toner particles were removed in a wet environment by centrifugation at 6,000 rpm (6,110 relative centrifugal force) for 1-2 hours in a Jouan MR1822 centrifuge (commercially available from Jouan Inc., Winchester, VA) for 1-2 hours. The supernatant was then carefully decanted and the conductivity of this liquid was measured using a Scientifica Model 627 Conductance Meter. Next, the percentage of free phase conductivity relative to the bulk toner conductivity was measured as 100% (k _f / k _b ).

Particle mobility

The electrical mobility (dynamic mobility) of the toner particles was measured using Matec MBS-8000 Electrokinetic Sonic Amplitude Analyser (commercially available from Matte Applied Sciences, Inc., Hopkinton, MA). Unlike electrokinetic measurements based on microelectrophoresis, the MBS-800 device has the advantage that it is not necessary to dilute the toner sample to obtain the mobility value. Therefore, it was possible to measure the dynamic mobility of the toner particles at substantially the solid content concentration desirable for printing. The MBS-8000 measures the response of particles charged with a high frequency (1.2 MHz) alternating current (AC) electric field. In a high frequency AC electric field, the relative movement between the charged toner position and the surrounding dispersion medium (including counter ions) causes an ultrasonic wave in the applied electric field of the same frequency. At 1.2 MHz, the size of this ultrasonic wave can be measured using a piezoelectric quartz transducer; The electrokinetic ultrasonic magnitude (ESA) is directly proportional to the low electric field AC electrophoretic mobility of the particles. The zeta potential of the particles can then be calculated by the instrument from the measured dynamic mobility and known toner particle size, diffuser liquid viscosity, and liquid dielectric constant.

Particle charge

Toner charge / mass is a useful parameter that is difficult to measure as a useful parameter in predicting development characteristics (eg optical density, color uniformity) for liquid toners. The difficulty in measuring the charge / mass for a liquid toner is due to the low developing toner mass (typically 50-200 micrograms / cm ² ) associated with the required developing optical density (typically> 1.2 reflectance optical density unit). A related parameter that is directly proportional to toner charge / mass is toner charge / developing optical density. This parameter was measured by applying ink particles in various bands containing a known range of plating potential on a dielectric sheet coated with a silicon release layer while simultaneously monitoring the entire current flow with a high sensitivity electrometer. The applied toner layer, which was then obtained, was dried with air and delivered to plain paper using an offset transfer process. The reflective optical density of the toner film completely delivered to the paper was measured using the registered Gretag SPM50 reflective optical density meter (Gretag Instrument Inc., Regensdorf, Switzerland). The ratio of the total current to the product of applied toner area and developed archeological density is based on the charge / ROD value for the toner, i.e., charge / ROD = (total current) / [(application area) (reflective optical density)]. To get.

Blocking resistance test

Laser printed solid blocks (100% printing, optical density = 1.3) of the toner obtained in Example 3 and Comparative Example B were printed on a general uncoated A4 paper (Zerox 4200 copy paper), and at 48 ± 1 ° C. for 24 hours and It was measured according to ASTM test method D1146 in a chamber at 75% relative humidity.

Later in this period, an ink image printed using the toner obtained in Example 3 showed little adsorption blocking or image loss when the image and paper were separated. Some cohesive defects were observed for the ink, but no image loss was observed when the sheet was separated.

In contrast, an ink image printed using the toner obtained from Comparative Example B exhibited adsorptive blocking (cross-section image blocking from ink to paper, ie from front to back, as observed in the receipt of printed paper), However, no image loss was seen when the image and paper were separated. As observed in the bin in which the double paper was printed, a defect in the town was observed for the ink image (blocking from ink to ink), and image loss was also observed when the paper was separated.

Various embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are also within the scope of the following claims.

Preparation of Graft Stabilizers

In the following examples relating to the preparation of graft stabilizers, the specific composition of each particular graft stabilizer or graft stabilizer precursor can be described simply and conveniently by listing the weight percentage of monomers used in the synthesis. A graft stabilizer, for example EHMA / HEMA-TMI (97 // 3-4.7% w / w), is obtained from a graft stabilizer precursor which is a copolymer consisting of 97% by weight EHMA and 3% by weight HEMA, In the graft site consisting of 4.7% by weight TMI based on the total weight of the graph stabilizer precursor is covalently bonded.

Comparative Example A

Norpar ^TM 12 2560g, EHMA 849g, 96% HEMA 27g, and AIBN 8.8g in a 5,000 ml three-necked round bottom flask equipped with a chiller, a thermocouple connected to a digital thermostat, a nitrogen input tube connected to a dry nitrogen source, and a magnetic stirrer A mixture was added. While stirring the mixture magnetically, the reaction flask was purged with dry nitrogen for 30 minutes at a flow rate of approximately 2 liters / minute. A hollow glass stopper was then inserted into the open end of the cooler and the nitrogen flow rate was reduced to approximately 0.5 liters / minute. The mixture was heated to 70 ° C. for 16 h. The transformation was quantitative.

The mixture was heated to 90 ° C. and maintained at that temperature for 1 hour to decompose the remaining AIBN and then cooled back to 70 ° C. After removing the nitrogen input tube, 13.6 g of 95% DBTDM was added to the mixture followed by 41.1 g of TMI. TMI was added dropwise over approximately 5 minutes while stirring the mixture magnetically. The nitrogen feed tube was reinserted, the used glass stopper of the cooler was removed and the reaction flask was purged with dry nitrogen for 30 minutes at a flow rate of approximately 2 liters / minute. The hollow glass stopper was reinserted into the open end of the cooler and the nitrogen flow rate was lowered to approximately 0.5 liters / minute. The mixture was reacted at 70 ° C. for 6 hours and then cooled to room temperature. The cooling mixture was a sticky clear liquid containing no visible impurities. The transformation was political.

The product is suitable for gel organosol preparation as a copolymer of EHMA and HEMA comprising a random side chain of TMI. Referred to herein as EHMA / HEMA-TMI (97 / 3-4.7% w / w). It measured according to the method described in the test method section. The percentage of solids was 27.42%. The copolymer showed an M _w of 202,100 Da and M _w / M _n of 2.17 based on two independent measurements.

Comparative Example B

Using the same method as ^{Norpar TM 12 2372g, LMA 1019g,} 96% HEMA 33g, and the ^{AIBN 10.5g Norpar TM 12 2560g, EHMA} 849g, 96% HEMA 27g, and Comparative Example A, except that AIBN was changed to 8.8g Comparative Example B was prepared; The content of 95% DBTDL was increased to 16.3 g. The cooled mixture was a viscous, clear solution that contained no visible impurities.

The product is suitable for the preparation of non-gel organosols as copolymers of LMA and HEMA comprising random side chains of TMI. Named herein LMA / HEMA-TMI (97 / 3-4.7% w / w). It measured according to the method described in the test method section. The percentage of solids was 30.0%. The copolymer showed an M _w of 197,750 Da and M _w / M _n of 1.84 based on two independent measurements.

Example 1

In a sediment vial (32 oz; 907 ml) was added 483 g Norpar ^™ 12, 80 g LMA, 80 g TCHMA, 3 g 98% HEMA, and 0.95 g AZDN. The bottle was purged with dry nitrogen at a rate of approximately 1.5 liters / minute for 1 minute and then sealed using a screw cap appropriately adjusted with a Teflon liner. Tighten the stopper tightly using electrical tape. The sealed bottle was then inserted into a metal cage assembly and installed in an agitator assembly (available from Atlas Electric Devices Company, Chicago, IL) of an Atlas Launder-Ometer. The washfastness tester was run at a fixed stirring speed of 42 rpm in a water bath at a temperature of 70 ° C. The mixture was reacted at 70 ° C. for 17 hours and heated to 90 ° C. for 1 hour to decompose the residual AZDN, and then cooled to room temperature. The conversion of monomers to polymers was quantitative. The bottle was then opened and 2.6 g of 95% DBTDL and 7.8 g of TMI were added to the mixture. The bottle was purged with dry nitrogen for 1 minute at a rate of approximately 1.5 liters / minute and sealed with a screw cap appropriately adjusted with a Teflon liner. The stopper was tightly screwed using an electrical tape. The sealed bottle was then inserted into a metal cage assembly and installed on the stirring assembly of the atlas laundry fastness tester. The wash fastness tester was operated at a fixed stirring speed of 42 rpm in a water bath at a temperature of 70 ° C. The mixture was allowed to react at 70 ° C. for 5 hours and then cooled to room temperature. The cooled mixture was a clear solution that contained no visible impurities and was viscous. The transformation was quantitative.

The product is a copolymer of LMA, TCHMA and HEMA comprising a random side chain of TMI. The copolymer obtained can be used to prepare a non-gel organosol. In the present specification, it is referred to as LMA / TCHMA / HEMA-TMI (48.5 / 48.5 / 3-4.7w / w%). The test was carried out according to the method described in the Test Method section. The percentage of solids was 25.76. The copolymer exhibited M _w of 181,100 Da and M _w / M _n of 1.92.

Example 2

Example 2 was prepared in the same manner as in Example 1, except that TCHMA was changed to IBMA and the contents of 98% HEMA and AZDN were increased to 5.1 g and 1.57 g, respectively. The cooled mixture was a viscous, clear solution containing no visible impurities.

The product can be used to prepare non-gel organosols as copolymers of LMA, IBMA, and HEMA comprising random side chains of TMI. Named herein LMA / IBMA / HEMA-TMI (48.5 / 48.5 / 3-4.7w / w%). It was tested by the method described in the test method section above. The percentage of solids was 25.55%. The copolymer exhibited M _w of 146,500 Da and M _w / M _n of 1.97.

Example 3

Example 3 was prepared in the same manner as in Example 2, except that IBMA was changed to ODA. The cooled mixture was a viscous, clear solution containing no visible impurities.

The product can be used to prepare non-gel organosols as copolymers of LMA, ODA, and HEMA comprising random side chains of TMI. In this specification, it is referred to as LMA / ODA / HEMA-TMI (48.5 / 48.5 / 3-4.7w / w%). It was tested by the method described in the test method section. The percentage of solids was 26.57%. The copolymer exhibited M _w of 179,200 Da and M _w / M _n of 2.00.

Example 4

Example 4 The same procedure as in Example 1 was performed except that LMA 107g, TCHMA 53g, 98% HEMA 5.1g, and AZDN 1.57g were used instead of LMA 80g, TCHMA 80g, 98% HEMA 3g, and AZDN 0.95g. Was performed. The cooled mixture was a viscous, clear solution containing no visible impurities.

The product can be used to prepare non-gel organosols as copolymers of LMA, TCHMA, and HEMA comprising random side chains of TMI. In the present specification, it is named LMA / TCHMA / HEMA-TMI (32/65 / 3-4.7w / w%). It was tested by the method described in the test method section. The percentage of solids was 25.87%. The copolymer exhibited M _w of 204,000 Da and M _w / M _n of 2.26.

Graft stabilizer sample Graft Stabilizer Composition (% w / w) Molecular Weight Tg (℃) Mw Mw / Mn Comparative Example A EHMA / HEMA-TMI (97 / 3-4.7) 202,100 2.17 -10 Comparative Example B LMA / HEMA-TMI (97 / 3-4.7) 197,750 1.84 -65 Example 1 LMA / TCHMA / HEMA-TMI (48.5 / 48.5 / 3-4.7) 181,110 1.92 0 Example 2 LMA / IBMA / HEMA-TMI (48.5 / 48.5 / 3-4.7) 146,500 1.97 -7 Example 3 LMA / ODA / HEMA-TMI (48.5 / 48.5 / 3-4.7) 179,200 2.00 35 (mp) Example 4 LMA / TCHMA / HEMA-TMI (32/65 / 3-4.7) 204,000 2.26 33

Preparation of Organosol

In the preparation of the organosol of the following examples, it is simple and convenient to express the composition of the organosol in terms of the ratio of the total weight of the monomer comprising the organosol core relative to the total weight of the monomer comprising the organosol shell. This ratio is referred to as the core / shell ratio of the organosol. It is also useful to express the specific composition of each particular organosol by proportioning the weight percentage of monomers used to make the shell and core. For example, the organosol named EHMA / HEMA-TMI / MMA / EA (97 / 3-4.7 // 25/75% w / w) is a graph stable which is a copolymer consisting of 97% EHMA and 3% HEMA by weight. It is formed from a shell consisting of a topical precursor, to which a grafting site consisting of 4.7% by weight of TMI based on the total weight of the graft stabilizer precursor is covalently bonded. The graft stabilizer is covalently bound to the core comprising 25% MMA and 75% EA.

Comparative Example C

Norpar ^TM 12 2950g, EA 281g, MMA 93g, 27.42% solids in a 5000 ml three-necked round bottom flask equipped with a chiller, a thermocouple connected to a digital thermostat, a nitrogen input tube connected to a source of anhydrous nitrogen, and a magnetic stirrer 170 g of Comparative Example A and 6.3 g of AIBN were added. While stirring the mixture magnetically, the reaction flask was purged with dry nitrogen for 30 minutes at a flow rate of approximately 2 liters / minute. The hollow glass stopper was then inserted into the open end of the cooler and the nitrogen flow rate was reduced to approximately 0.5 liters / minute. The mixture was heated to 70 ° C. for 16 h and cooled to rt. The transformation was quantitative.

Approximately 350 g of n-heptane was added to the cooled mixture. The reaction mixture was separated from the residual monomer using a dry ice / acetone cooler and a rotary evaporator with a water bath at a temperature of 90 ° C. in a vacuum of approximately 15 mm Hg. The separated mixture was cooled to room temperature to give a white opaque dispersion that formed a weak gel after approximately 2 hours. The gel organosol is named EHMA / HEMA-TMI // MMA / EA (97 // 3-4.7 // 25/75% w / w) and can be used to prepare rapid self-fixing gel ink compositions. It was tested according to the method described in the Test Method section above. The percentage of solids was 12.70%.

Comparative Example D

Comparative Example D was prepared by the same procedure as Comparative Example C, except that Comparative Example A having a solid content of Norpar ^TM 12 529.77 g, EA 36.27 g, MMA 19.95 g, and 27.42% was used, and AIBN 0.94 g. It was.

This gel organosol is named EHMA / HEMA-TMI // MMA / EA / DMAEMA (97 / 3-4.7 // 22.5 / 67.5 / 10% w / w) and can be used in rapid self-fixing gel ink compositions. . It was tested according to the method described in the test method section above. The percentage of solids was 17.02%.

Example 5

To the glass sphere (32 ounces, 907 ml) was added 527 g of Norpar ^™ 12, 22.14 g of MMA, 40.26 g of EA, 60 g of Example 1 at 25.76% solids, and 0.94 g of AIBN. The bottle was purged with dry nitrogen for 1 minute at a rate of approximately 1.5 liters / minute and then sealed with a screw cap appropriately adjusted with a Teflon liner. The stopper was tightened securely in place using electrical tape. The sealed bottle was installed in a metal cage assembly and in a stirring assembly of an Atlas Laundry Fastness Tester (available from Atlas Electric Devices Company, Chicago, Il). The wash fastness tester was operated at a fixed stirring speed of 42 rpm in a water bath at a temperature of 70 ° C. The mixture was reacted for 17 hours and then cooled to room temperature. The conversion of monomers to polymers was quantitative. The mixture obtained above was separated from the remaining monomers by using a rotary evaporator with a dry ice / acetone cooler at a temperature of 90 ° C. with a vacuum of approximately 15 mm Hg. The separated organosol was cooled to room temperature, yielding an ungelled white opaque dispersion.

This organosol is termed LMA / TCHMA / HEMA-TMI // MMA / EA (48.4 / 48.5 / 3-4.7 // 25/75% w / w) and is used to prepare rapid self-fixing non-gel ink compositions. Can be used. The percentage of solids was 17.00% by weight.

Example 6

Example 6 was prepared in the same manner as in Example 5, except that 527 g of Norpar ^™ 12, 22.14 g of MMA, 40.26 g of EA, 60 g of Example 2 with 25.55% solids, and 0.94 g of AIBN were used. An ungelled white opaque dispersion was obtained.

This organosol is termed LMA / IBMA / HEMA-TMI // MMA / EA (48.4 / 48.5 / 3-4.7 // 25/75% w / w) and is used to prepare rapid self-fixing non-gel ink compositions. Can be used. The percentage of solids was 15.4% by weight.

Example 7

Example 7 was prepared in the same manner as in Example 5, except that 527 g of Nopar ^™ 12, 22.14 g of MMA, 40.26 g of EA, 60 g of Example 3 having a solid content of 26.57%, and 0.94 g of AIBN were used. A white opaque dispersion was obtained, which did not gel.

The resulting organosol is named LMA / ODA / HEMA-TMI // MMA / EA (48.4 / 48.5 / 3-4.7 // 25/75 /% w / w) to prepare a rapid self-fixing non-gel ink composition Can be used to The percentage of solids was 18.31 wt%.

Example 8

Example 8 was prepared by the same process as Example 5 except for using 527 g of Nopar ^TM 12, 20 g of MMA, 36 g of EA, 6.18 g of DMAEMA, 60 g of Example 1 having a solid content of 25.76%, and 0.94 g of AIBN. It was. A white opaque dispersion was obtained, which did not gel.

The resulting organosol is named LMA / TCHMA / HEMA-TMI // MMA / EA-DMAEMA (48.5 / 48.5 / 3-4.7 // 22.5 / 67.5 / 10% w / w) and is a rapid self-fixing non-gel ink It can be used to prepare the composition. The percentage of solids was 17.36 wt%.

Example 9

Example 9 was prepared by the same process as Example 5 except for using 527 g of Nopar ^TM 12, 20 g of MMA, 36 g of EA, 6.18 g of DMAEMA, 60 g of Example 2 having a solid content of 25.55%, and 0.94 g of AIBN. It was. A white opaque dispersion was obtained, which did not gel.

The resulting organosol is named LMA / IBMA / HEMA-TMI // MMA / EA-DMAEMA (48.5 / 48.5 / 3-4.7 // 22.5 / 67.5 / 10% w / w) and is a rapid self-fixing non-gel ink It can be used to prepare the composition. The percentage of solids was 17.5% by weight.

Example 10

Example 10 was prepared by the same process as Example 5 except for using 527 g of Nopar ^TM 12, 20 g of MMA, 36 g of EA, 6.18 g of DMAEMA, 60 g of Example 2 having a solid content of 25.55%, and 0.94 g of AIBN. It was. A white opaque dispersion was obtained, which did not gel.

The resulting organosol is named LMA / IBMA / HEMA-TMI // MMA / EA-DMAEMA (48.5 / 48.5 / 3-4.7 // 22.5 / 67.5 / 10% w / w) and is a rapid self-fixing non-gel ink It can be used to prepare the composition. The percentage of solids was 17.87 wt%.

Example 11

Example 11 was prepared by the same procedure as in Example 5 except for using 527 g of Nopar ^TM 12, 20 g of MMA, 36 g of EA, 6.18 g of DMAEMA, 60 g of Example 4 having a solid content of 25.87%, and 0.94 g of AIBN. It was. A white opaque dispersion was obtained, which did not gel.

The resulting organosol is named LMA / TCHMA / HEMA-TMI // MMA / EA-DMAEMA (32/65 / 3-4.7 // 22.5 / 67.5 / 10% w / w) and is a rapid self-fixing non-gel ink It can be used to prepare the composition.

Example 12

Same process as in Example 5, except 527 g of Nopar ^TM 12, 20 g of MMA, 36 g of EA, 6.18 g of vinylpyrrolidinone, 60 g of Example 4 having a polymer solids of 25.87%, and 0.94 g of AIBN in a reaction vessel Example 12 was prepared by following the steps. A white opaque dispersion was obtained, which did not gel.

The resulting organosol is named LMA / TCHMA / HEMA-TMI // MMA / EA / VP (32/65 / 3-4.7 // 22.5 / 67.5 / 10% w / w) and is a rapid self-fixing non-gel ink It can be used to prepare the composition.

Example 13

Example 5 The same procedure as in Example 5 was carried out except that 527 g of Nopar ^TM 12, 20 g of MMA, 36 g of EA, 6.18 g of vinylimidazole, 60 g of Example 4 having a solid content of 25.87%, and 0.94 g of AIBN were used. 13 was prepared. A white opaque dispersion was obtained, which did not gel.

The resulting organosol is named LMA / TCHMA / HEMA-TMI // MMA / EA / VIM (32/65 / 3-4.7 // 22.5 / 67.5 / 10% w / w) and is a rapid self-fixing non-gel ink It can be used to prepare the composition.

sample Organosol Composition (% w / w) Visual observation Comparative Example C EHMA / HEMA-TMI // MMA / EA (97 / 3-4.7 // 25/75) Gel Comparative Example D EHMA / HEMA-TMI // MMA / EA / DMAEMA (97 / 3-4.7 // 22.5 / 67.5 / 10) Slightly gelling Example 5 LMA / TCHMA / HEMA-TMI // MMA / EA (48.5 / 48.5 / 3-4.7 // 25/75) Non-gel Example 6 LMA / IBMA / HEMA-TMI // MMA / EA (48.5 / 48.5 / 3-4.7 // 25/75) Non-gel Example 7 LMA / ODA / HEMA-TMI // MMA / EA (48.5 / 48.5 / 3-4.7 // 25/75) Non-gel Example 8 LMA / TCHMA / HEMA-TMI // MMA / EA / DMAEMA (48.5 / 48.5 / 3-4.7 // 22.5 / 67.5 / 10) Non-gel Example 9 LMA / IBMA / HEMA-TMI // MMA / EA / DMAEMA (48.5 / 48.5 / 3-4.7 // 22.5 / 67.5 / 10) Non-gel Example 10 LMA / ODA / HEMA-TMI // MMA / EA / DMAEMA (48.5 / 48.5 / 3-4.7 // 22.5 / 67.5 / 10) Non-gel Example 11 LMA / TCHMA / HEMA-TMI // MMA / EA / DMAEMA (32/65 / 3-4.7 // 22.5 / 67.5 / 10) Non-gel Example 12 LMA / TCHMA / HEMA-TMI // MMA / EA / Vinylpyrrolidinone (32/65 / 3-4.7 // 22.5 / 67.5 / 10) Non-gel Example 13 LMA / TCHMA / HEMA-TMI // MMA / EA / vinylimidazole (32/65 / 3-4.7 // 22.5 / 67.5 / 10) Non-gel

Manufacture of ink

Comparative Example E

Comparative Example D (Norpar ^TM solid in 12 17.02% (w / w) , 169g) of ^{Norpar TM 12 122g, Pigment Red 122} 3.6g ( available from Sun Chemical Company, Cincinnati, Ohio) , Pigment Red 81: 4 3.6g (Commercially available from Sun Chemical Company, Cincinnati, Ohio), 2.02 g of 6.15% zirconium HEX-CEM solution (commercially available from OMG Chemical Company, Cleveland, Ohio) were mixed in a glass vessel (8 oz., 227 ml). This mixture was then filled with a 0.1 liter vertical bead mill (Model 6TSG-1 / 4, Amex Co., Ltd.) filled with 390 g of Potters glass beads of 1.3 mm diameter (available from Potter Industries, Inc., Parsippany, NJ). Ltd., available from Tokyo, Japan). The mill was run at 2,000 RPM for 1.5 hours without using cooling water circulating through the cooling jacket of the milling chamber.

A portion of the 12% (w / w) solid toner concentrate was diluted to approximately 3.0% (w / w). The properties of such diluted toner samples were measured according to the test process described in the test method section, and are shown in Tables 3 and 4.

Example 14

Example 5 (17.00% solids in Norpar ^TM 12 (w / w), 169 g) 119 g Norpar ^TM 12, 7.2 g Pigment Red 122 (available from Sun Chemical Company, Cincinnati, Ohio), 6.15% zirconium HEX-CEM solution 4.39 g (commercially available from OMG Chemical Company, Cleveland, Ohio) was mixed in a glass vessel (8 oz., 227 ml). This mixture was then filled with a 0.1 liter vertical bead mill (Model 6TSG-1 / 4, Amex Co., Ltd.) filled with 390 g of Potters glass beads of 1.3 mm diameter (available from Potter Industries, Inc., Parsippany, NJ). Ltd., available from Tokyo, Japan). The mill was run at 2,000 RPM for 1.5 hours without using cooling water circulating through the cooling jacket of the milling chamber.

A portion of the 12% (w / w) solid toner concentrate was diluted to approximately 3.0% (w / w). The properties of such diluted toner samples were measured according to the test process described in the test method section, and are shown in Table 3.

Example 15

Example 8 Example 6 (187g, solid content of 15.40% (w / w) in Norpar ^TM 12) by replacing, and to perform the same process as in Example 14 except for reducing the amount of Norpar ^TM 12 to 101g Example 15 was prepared.

The properties of the obtained diluted sample were measured by the test method described in the Test Method section, and are shown in Table 3.

Example 16

Example 5 was replaced with Example 7 (157 g, 18.31% solids in Norpar ^TM 12 (w / w)) and the same procedure as in Example 14 was carried out except that the content of Norpar ^TM 12 was increased to 131 g. Example 16 was prepared.

The properties of the obtained diluted sample were measured by the test method described in the Test Method section, and are shown in Table 3.

Example 17

Example 5 was replaced with Example 8 (166 g, 17.36% solids in Norpar ^TM 12 (w / w)) and the same procedure as in Example 14 was carried out except that the content of Norpar ^TM 12 was increased to 124 g Example 17 was prepared.

The properties of the obtained diluted sample were measured by the test method described in the Test Method section, and are shown in Table 3.

Example 18

Example 5 was replaced with Example 9 (165g, 17.50% solids in Norpar ^TM 12 (w / w)) and the same procedure as in Example 14 was carried out except that the content of Norpar ^TM 12 was increased to 126 g. Example 18 was prepared.

The properties of the obtained diluted sample were measured by the test method described in the Test Method section, and are shown in Table 3.

Example 19

Example 5 was replaced with Example 10 (161 g, 17.87% solids in Norpar ^TM 12 (w / w)) and the same procedure as in Example 14 was carried out except that the content of Norpar ^TM 12 was increased to 130 g. Example 19 was prepared.

The properties of the obtained diluted sample were measured by the test method described in the Test Method section, and are shown in Table 3.

Example 20

Example 5 (163g, solid content of 17.68% (w / w) in Norpar ^TM 12) of Norpar ^TM 12 136g, Monarch 120 carbon black, 7.2g (Cabot Corp., Billerica, available from Mass.), 6.15% zirconium HEX- 4.32 g of CEM solution (commercially available from OMG Chemical Company, Cleveland, Ohio) was mixed in a glass vessel (8 oz., 227 ml). This mixture was then filled with a 0.1 liter vertical bead mill (Model 6TSG-1 / 4, Amex Co., Ltd.) filled with 390 g of Potters glass beads of 1.3 mm diameter (available from Potter Industries, Inc., Parsippany, NJ). Ltd., available from Tokyo, Japan). The mill was run at 2,000 RPM for 1.5 hours without using cooling water circulating through the cooling jacket of the milling chamber.

A portion of the 12% (w / w) solid toner concentrate was diluted to approximately 3.0% (w / w). The properties of such diluted toner samples were measured according to the test process described in the test method section, and are shown in Table 4.

Example 21

Example 5 (175 g, 17.68% solids in Norpar ^TM 12 (w / w)), 116 g Norpar ^TM 12, 5.14 g Pigment Blue 15: 4 available from Sun Chemical Company, Cincinnati, Ohio, 6.15% zirconium HEX- 4.32 g of CEM solution (commercially available from OMG Chemical Company, Cleveland, Ohio) was mixed in a glass vessel (8 oz., 227 ml). This mixture was then filled with a 0.1 liter vertical bead mill (Model 6TSG-1 / 4, Amex Co., Ltd.) filled with 390 g of Potters glass beads of 1.3 mm diameter (available from Potter Industries, Inc., Parsippany, NJ). Ltd., available from Tokyo, Japan). The mill was run at 2,000 RPM for 1.5 hours without using cooling water circulating through the cooling jacket of the milling chamber.

A portion of the 12% (w / w) solid toner concentrate was diluted to approximately 3.0% (w / w). The properties of such diluted toner samples were measured according to the test process described in the test method section, and are shown in Table 4.

Example 22

Example 5 (163 g, 17.68% solids in Norpar ^TM 12 (w / w)) was added to 126 g Norpar ^TM 12, 6.48 g Pigment Yellow 83 and 0.72 g Pigment Yellow 138 (available from Sun Chemical Company, Cincinnati, Ohio), 6.15 4.32 g of% zirconium HEX-CEM solution (commercially available from OMG Chemical Company, Cleveland, Ohio) was mixed in a glass vessel (8 oz., 227 ml). This mixture was then filled with a 0.1 liter vertical bead mill (Model 6TSG-1 / 4, Amex Co., Ltd.) filled with 390 g of Potters glass beads of 1.3 mm diameter (available from Potter Industries, Inc., Parsippany, NJ). Ltd., available from Tokyo, Japan). The mill was run at 2,000 RPM for 1.5 hours without using cooling water circulating through the cooling jacket of the milling chamber.

A portion of the 12% (w / w) solid toner concentrate was diluted to approximately 3.0% (w / w). The properties of such diluted toner samples were measured according to the test process described in the test method section, and are shown in Table 4.

Magenta ink sample Dynamic mobility (m ² / Vsec) Conductivity (pMho / cm) Pigment size (um) Reflective optical density (@ 600 dev) Blocking (vs. control) bulk Free Prize Dv Dn Comparative Example E 1.35E-10 133 20.8 1.528 0.689 - Control Example 14 1.15E-10 40.5 0.77% 1.398 0.407 0.72 - Example 15 0.35E-10 49.9 0.66% 1.464 0.399 0.75 - Example 16 0.78E-10 53.4 2.68% 1.081 0.342 0.45 - Example 17 2.58E-10 129.3 1.06% 1.267 0.388 1.18 Improving Example 18 2.12E-10 98 0.52% 1.164 0.411 1.25 same Example 19 1.51E-10 125 0.97% 0.977 0.321 1.34 same

Different color inks sample color* Dynamic mobility (m ² / Vsec) Conductivity (pMho / cm) Particle size (um) Optical density (@ 600dev) Blocking (vs. control) bulk Free Prize Dv Dn Comparative Example E M 4.35E-10 133 20.8% 1.528 0.689 - Control Example 17 M 2.58E-10 129.3 1.06% 1.267 0.388 1.18 Improving Example 20 K 0.93E-10 292 13.9% 0.456 0.196 1.40 Improving Example 21 C 2.59E-10 300 5.13% 0.507 0.174 1.31 Improving Example 22 Y 2.87E-10 292 3.81% 0.690 0.243 0.87 Improving

Example 23

Carbon black pigment (20.0 g, Monarch 120, lot 485-732, available from Carbot, Billerica, N.Y.) and modified ethanol (60.0 g) were added to a 400 mL polyethylene beaker. The mixture was homogenized using a Polytron laboratory disperser (available from Polytron laboratory disperser, Model # PT 10/35, Kinematica, Littau, Switzerland) for about 3 minutes to give a viscous paste. Poly (2-vinylpyridine-co-styrene) solution in a modified alcohol (2.5% by weight solution 20.0 g, Mw approximately 220,000 (where the weight average molecular weight was used even if the number average molecular weight was used), 30% styrene content, Aldrich Chemical Company, available from Milwaukee, Wis.) Was added to the carbon black dispersion. The homogenization process was continued until a low viscosity black dispersion was obtained. 2.5 wt% poly (2-vinylpyridine-co-styrene) was further added to the dispersion and homogenization was continued for approximately 10 minutes with the number 5 fixed. The weight ratio of pigment to polymer is 10/1. The black dispersion was slowly added to 2600 g of deionized water stirred with a laboratory stirrer. The pigment suspension in water was filtered through filter paper (Whatman # 54) and washed twice with approximately 150 g of deionized water. The combined pigments were dried at 50 ° C. for approximately 20 hours and then ground by hand using a laboratory mortar and bowl to obtain poly (2-vinylpyridine-co-styrene) treated with Monarch 120 pigment.

Zr Hexcem solution (14.20 g, 6.15 wt.%, Available from OMG Americas Inc., Westlake, Ohio) and trade name Norpar 12 (951.8 g) in organosol EHMA / HEMA-TMI // MMA / A (1034.0 g) Add, and shake the mixture for about 30 minutes with a laboratory shaker to prepare an organosol / charge control additive / registered Norpar premix. 390 g of 0.5 L Igarashi cell with Potters glass beads, 294.9 g of the organosol / charge control additive / NoNor premix, and Monarch 120 pigment, poly (2-vinylpyridine-co-styrene) 5.65 filled with g. The composition was milled at 2000 rpm for 90 minutes to obtain a black ink with a charge control additive (CCA) level corresponding to 25 mg CCA / g of a poly (2-vinylpyridine-co-styrene) free pigment.

The particle size and conductivity of the black ink were measured according to the above-described process. The results showed that the 3 wt% black ink had a conductivity of 185 pmho / cm, a free phase conductivity of 9.71 pmho / cm (5.2% free phase conductivity), and a volume average particle size (Horiba 910) of 2.56 microns. The particle size distribution was a two-peak structure with a maximum at approximately 1.25 microns and 4 microns (shoulder, approximately 30% by volume of toner). The toner was satisfactorily printed with a reflective optical density of 1.44 at a 500V developer bias.

The experiment showed that the treatment of the carbon black pigment with poly (2-vinylpyridine-co-styrene) improves the charging performance of the pigment, so that the ink has a conductivity of 135 pmho or more and a CCA level corresponding to 25 mg CCA / g of the pigment. Effective in providing

Example 24

Carbon black pigment (20.0 g, Monarch 120, lot 485-732, Carbot, Billerica, NY) and modified ethanol (60.0 g), and poly (2-vinylpyridine-co-butyl methacrylate) (approximately 60 g 2.5 weight % Solution, 10% butyl methacrylate content, available from Aldrich Chemical Company, Milwaukee, WI) was added to a 400 mL polyethylene beaker. The mixture was homogenized for 3 minutes using a polytron laboratory disperser (available from Model # PT 10/35, Kinematica, Littau, Switzerland) to obtain a carbon black dispersion. To the dispersion was further added a poly (2-vinylpyridine-co-butyl methacrylate) solution (2.5% by weight in denatured alcohol, 100.0 g) and the homogenization treatment was continued for approximately 10 minutes with the number set to 5. The weight ratio of pigment to polymer was 5/1. The black dispersion was slowly added to 2200 g of deionized water stirred with a laboratory stirrer. The pigment suspension in water was filtered through filter paper (Whatman # 54) and washed twice with approximately 150 g of deionized water. The resulting pigment was dried at 50 ° C. for approximately 20 hours and then ground by hand using a laboratory pestle and bowl to obtain poly (2-vinylpyridine-co-butyl methacrylate) treated with Monarch 120 pigment.

Zr Hexcem solution (14.20 g, 6.15 wt.%, Available from OMG Americas Inc., Westlake, Ohio) and trade name Norpar 12 (951.8 g) in organosol EHMA / HEMA-TMI // MMA / EA (1034.0 g) Add, and shake the mixture for about 30 minutes with a laboratory shaker to prepare an organosol / charge control additive / registered Norpar premix. Poly (2-vinylpyridine-co-butyl methacrylate treated with 0.5 L Igarashi cell with 390 g of Potters glass beads, 294.9 g of the organosol / charge control additive / registered Norapr premix, and Monarch 120 pigment ) 6.16 g. The composition was milled at 2000 rpm for 90 minutes to give a black ink free of poly (2-vinylpyridine-co-butyl methacrylate) and having a charge control additive (CCA) level corresponding to 25 mg CCA / g of pigment.

The particle size and conductivity of the black ink were measured according to the above-described process. The obtained results showed that the 3 wt% black ink had a conductivity of 233 pmho / cm, a free phase conductivity of 11.74 pmho / cm (5.0% free phase conductivity), and a volume average particle size (Horiba 910) of 11.0 microns. The particle size distribution was a two-peak structure with maximums at approximately 13 microns (dir 85 weight percent) and 1.5 microns (about 15 weight percent). The process of treating the carbon black pigment with poly (2-vinylpyridine-co-butyl methacrylate) is also effective for increasing the toner particle size distribution.

 The experiment showed that the step of treating the carbon black pigment with poly (2-vinylpyridine-co-butyl methacrylate) improved the charging performance of the pigment to achieve a conductivity of at least 135 pmho and a CCA level corresponding to 25 mg CCA / g of the pigment. It is shown to be effective in providing the ink having.

Example 25

An aqueous solution of poly (1-vinylpyrrolidinone-co-2-dimethylaminoethylmethacrylate) (10.0 g, 19% by weight solution, average Mw = 1,000,000, Aldrich Chemical Company, Milwaukee, Wis) was added to a 400 mL beaker, 190 g of boiling deionized water was added to obtain a hot dilute solution of the polymer. The resulting hot solution was added to a carbon black pigment (20.0 g, Monarch 120, lot 485-732, Carbot, Billerica, N.Y.) and the mixture was stirred for 10 minutes with a laboratory magnetic stirrer. The resulting slurry was filtered through filter paper (Whatman # 5) to reduce the volume to approximately 100 mL. At this point, the filtration process was very slow and the material remaining on the filter paper was found to be black thixotropic gelatinous material. The filtered material was left to dry in a 50 ° C. oven for 7 days, dried, and ground by hand using a mortar and pestle to be treated with carbon black pigment poly (1-vinylpyrrolidinone-co-2-dimethylaminoethyl methacrylate). Got.

Zr Hexcem solution (14.20 g, 6.15 wt.%, Available from OMG Americas Inc., Westlake, Ohio) and trade name Norpar 12 (951.8 g) in organosol EHMA / HEMA-TMI // MMA / EA (1034.0 g) Add, and shake the mixture for about 30 minutes with a laboratory shaker to prepare an organosol / charge control additive / registered Norpar premix. Poly (2-vinylpyridine-co-butyl methacrylate treated with 0.5 L Igarashi cell with 390 g of Potters glass beads, 294.9 g of the organosol / charge control additive / registered Norapr premix, and Monarch 120 pigment ) 6.16 g. The composition was milled at 2000 rpm for 90 minutes to give a black ink free of poly (2-vinylpyridine-co-butyl methacrylate) and having a charge control additive (CCA) level corresponding to 25 mg CCA / g of pigment.

The particle size and conductivity of the black ink were measured according to the above-described process. The results showed that the 3 wt% black ink had a conductivity of 167 pmho / cm, a free phase conductivity of 7.11 pmho / cm (4.3% free phase conductivity), and a volume average particle size (Horiba 910) of 5.291 microns. The particle size distribution was a two-peak structure with maximums at approximately 1.3 microns (approximately 40 volume percent of toner) and 8.5 microns (approximately 60 volume percent of toner). The toner was satisfactorily printed with an optical density of 1.29 reflected at a 500V developer bias.

The experiment showed that the treatment of the carbon black pigment with poly (1-vinyl pyrrolidone-co-2-dimethylaminoethylmethacrylate) improved the charging performance of the pigment, resulting in conductivity of at least 135 pmho and 25 mg CCA / g of pigment. It is shown to be effective in providing an ink having a corresponding CCA level.

Example 26

A carbon black pigment (20.0 g, Monarch 120, lot 485-732, Carbot, Billerica, NY) was added 100 g of poly (vinyl pyrrolidone-co-vinyl acetate) solution (PVP / VA E-335, 0.67 weight of modified alcohol) % Solution, available from ISP Technologies, Inc., Wayne, NJ). The mixture was homogenized using a polytron laboratory disperser for about 10 minutes to give a black dispersion. The weight ratio of pigment to polymer is 30/1. The black dispersion was added to an aluminum pan and dried at 80 ° C. for about 20 hours, then ground by hand using a laboratory pestle and bowl to obtain poly (vinyl pyrrolidone-co-vinyl acetate) treated with Monarch 120 pigment.

Zr Hexcem solution (14.20 g, 6.15 wt.%, Available from OMG Americas Inc., Westlake, Ohio) and trade name Norpar 12 (951.8 g) in organosol EHMA / HEMA-TMI // MMA / EA (1034.0 g) Add, and shake the mixture for about 30 minutes with a laboratory shaker to prepare an organosol / charge control additive / registered Norpar premix. 390 g of 0.5 L Igarashi cell with Potters glass beads, 294.9 g of the organosol / charge control additive / registered Norapr premix, and Monarch 120 pigment, poly (vinyl pyrrolidone-co-vinyl acetate) 5.31 filled with g. The composition was milled at 2000 rpm for 90 minutes to give a black ink free of poly (vinyl pyrrolidone-co-vinyl acetate) and having a charge control additive (CCA) level corresponding to 25 mg CCA / g of pigment.

The particle size and conductivity of the black ink were measured according to the above-described process. The results showed that the 3 wt% black ink had a conductivity of 145 pmho / cm, a free phase conductivity of 6.77 pmho / cm (4.7% free phase conductivity), and a volume average particle size (Horiba 910) of 1.04 micron. The particle size dispersion was a one-peak structure.

The experiment showed that the step of treating the carbon black pigment with poly (vinyl pyrrolidone-co-vinyl acetate) improves the charging performance of the pigment to have a conductivity of at least 135 pmho and a CCA level corresponding to 25 mg CCA / g of pigment. It is effective in providing ink. The experiment also shows that treating carbon black pigments to improve conductivity does not increase the size of the toner particles as compared to untreated control black pigments when milling under the above-mentioned conditions.

Although specific materials, concentrations, devices, times, temperatures, and conditions have been shown in the examples required by due process, the scope of the techniques disclosed and claimed herein is not limited to these specific examples. Rather, these embodiments are to be understood as one example within the scope of the general disclosure.

The present invention provides organosol dispersions and wet inks useful in the printing process. The wet ink exhibits improved dispersion stability, improved blocking resistance, and improved charging performance when used in certain image processing processes, wherein the image processing process includes ink delivery processes, ionographic, inkjet, Bubble jet, electrographic and electrophotographic color printing or proofing processes.

Claims (27)

(a) a wet carrier having a kauri-butanol number of 30 or less; And (b) a graft copolymer comprising a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier, Wherein said thermoplastic (co) polymer cores are (meth) acrylates containing aliphatic amino radicals, nitrogen-containing heterocyclic vinyl monomers, N-vinyl substituted cyclic amide monomers, aromatic substituted amino acids containing amino radicals An organosol dispersion, comprising units derived from at least one polymerizable monomer selected from the group consisting of ethylene monomers, and nitrogen-containing vinyl ether monomers. The (meth) acrylates according to claim 1, wherein the (meth) acrylates containing the aliphatic amino radicals are N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N -Dibutylaminoethyl (meth) acrylate, N, N-hydroxyethylaminoethyl (meth) acrylate, N-benzyl, N-ethylaminoethyl (meth) acrylate, N, N-dibenzylaminoethyl ( Meta) acrylate, and N-octyl, N, N-dihexylaminoethyl (meth) acrylate. The organosol dispersion characterized by the above-mentioned. The method of claim 1, wherein the nitrogen-containing heterocyclic vinyl monomer is N-vinylimidazole, N-vinylimidazole, N-vinyltetrazole, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5 -Organosol dispersions selected from the group consisting of -vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylpyrazine, 2-vinyloxazole and 2-vinylbenzoxazole. The compound according to claim 1, wherein the N-vinyl substituted cyclic amide monomer is N-vinylpyrrolidone, N-vinylpiperidone, N-vinyloxazolidone; N-methylacrylamide, N-octylacrylamide, N-phenylmethacrylamide, N-cyclohexylacrylamide, N-phenylethylacrylamide, Np-methoxy-phenylacrylamide, acrylamide, N, N-dimethyl An organosol dispersion, which is selected from the group consisting of acrylamide, N, N-dibutylacrylamide, N-methyl, N-phenylacrylamide, piperidine acrylate, and morpholine acrylate. The organosol dispersion according to claim 1, wherein the aromatic substituted ethylene monomer is selected from the group consisting of dimethylaminostyrene, diethylaminostyrene, diethylaminomethylstyrene and dioctylaminostyrene. The method of claim 1, wherein the nitrogen-containing vinyl ether monomer containing the amino radical is vinyl-N-ethyl-N-phenylaminoethyl ether, vinyl-N-butyl-N-phenylaminoethyl ether, triethanolamine divinyl ether , Vinyldiphenylaminoethyl ether, vinylpyrrolidylamino ether, vinyl-beta-morpholinoethyl ether, N-vinylhydroxyethylbenzamide, and m-aminophenylvinyl ether. Organosol dispersions. The organosol dispersion according to claim 1, wherein the steric stabilizer has a weight average molecular weight of 100,000 and 300,000 Daltons. The organosol dispersion according to claim 1, wherein the weight ratio of the core to the stabilizer is 1/1 to 15/1. The organosol dispersion according to claim 1, wherein the weight ratio of the core to the stabilizer is 2/1 to 10/1. The organosol dispersion according to claim 1, wherein the weight ratio of the core to the stabilizer is 4/1 to 8/1. (a) a wet carrier having a kauri-butanol number of 30 or less; And (b) a graft copolymer containing a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier, (Meth) acrylates, nitrogen-containing heterocythes, wherein the steric stabilizer comprises units derived from 3,3,5-trimethylcyclohexyl methacrylate and the thermoplastic (co) polymer core comprises an aliphatic amino radical Derived from at least one polymerizable monomer selected from the group consisting of click vinyl monomers, N-vinyl substituted cyclic amide monomers, aromatic substituted ethylene monomers comprising amino radicals, and nitrogen-containing vinyl ether monomers Organosol dispersion, characterized in that it comprises an integrated unit. The (meth) acrylates according to claim 11, wherein the (meth) acrylates containing aliphatic amino radicals are N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N -Dibutylaminoethyl (meth) acrylate, N, N-hydroxyethylaminoethyl (meth) acrylate, N-benzyl, N-ethylaminoethyl (meth) acrylate, N, N-dibenzylaminoethyl ( Meta) acrylate, and N-octyl, N, N-dihexylaminoethyl (meth) acrylate. The organosol dispersion characterized by the above-mentioned. 12. The method of claim 11, wherein the nitrogen-containing heterocyclic vinyl monomer is N-vinylimidazole, N-vinylimidazole, N-vinyltetrazole, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5 An organosol dispersion, which is selected from the group consisting of -vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylpyrazine, 2-vinyloxazole, and 2-vinylbenzoxazole. 12. The method of claim 11, wherein the N-vinyl substituted cyclic amide monomers are N-vinylpyrrolidone, N-vinylpiperidone, N-vinyloxazolidone; N-methylacrylamide, N-octylacrylamide, N-phenylmethacrylamide, N-cyclohexylacrylamide, N-phenylethylacrylamide, Np-methoxy-phenylacrylamide, acrylamide, N, N-dimethyl An organosol dispersion, which is selected from the group consisting of acrylamide, N, N-dibutylacrylamide, N-methyl, N-phenylacrylamide, piperidine acrylate, and morpholine acrylate. The organosol dispersion according to claim 11, wherein the aromatic substituted ethylene monomer is selected from the group consisting of dimethylaminostyrene, diethylaminostyrene, diethylaminomethylstyrene and dioctylaminostyrene. The method of claim 11, wherein the nitrogen-containing vinyl ether monomer containing the amino radical is vinyl-N-ethyl-N-phenylaminoethyl ether, vinyl-N-butyl-N-phenylaminoethyl ether, triethanolamine divinyl ether , Vinyldiphenylaminoethyl ether, vinylpyrrolidylamino ether, vinyl-beta-morpholinoethyl ether, N-vinylhydroxyethylbenzamide, and m-aminophenylvinyl ether. Organosol dispersions. The organosol dispersion according to claim 11, wherein the granule stabilizer further comprises a polymerizable monomer having a Hilderbrand solubility parameter of 17.14 MPa ^1/2 or less. 12. The method of claim 11 wherein the steric stabilizer further comprises a polymerizable monomer selected from the group consisting of lauryl acrylate, lauryl methacrylate, n-octadecyl acrylate, and n-octadecyl methacrylate. An organosol dispersion characterized by the above-mentioned. The organosol dispersion according to claim 11, wherein the steric stabilizer has a weight average molecular weight of 100,000 and 300,000 Daltons. The organosol dispersion according to claim 11, wherein the weight ratio of the core to the stabilizer is 1/1 to 15/1. The organosol dispersion according to claim 11, wherein the weight ratio of the core to the stabilizer is 2/1 to 10/1. The organosol dispersion according to claim 11, wherein the weight ratio of the core to the stabilizer is 4/1 to 8/1. (a) a wet carrier having a kauri-butanol number of 30 or less; (b) a graft copolymer containing a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier; And (c) a colorant, Wherein said thermoplastic (co) polymer cores are (meth) acrylates containing aliphatic amino radicals, nitrogen-containing heterocyclic vinyl monomers, N-vinyl substituted cyclic amide monomers, aromatic substituted amino acids containing amino radicals And a unit derived from at least one polymerizable monomer selected from the group consisting of ethylene monomers, and nitrogen-containing vinyl ether monomers. The method according to claim 23, wherein the (meth) acrylate comprising an aliphatic amino radical is N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N- Dibutylaminoethyl (meth) acrylate, N, N-hydroxyethylaminoethyl (meth) acrylate, N-benzyl, N-ethylaminoethyl (meth) acrylate, N, N-dibenzylaminoethyl (meth ) Acrylate and N-octyl, N, N-dihexylaminoethyl (meth) acrylate. (a) a wet carrier having a kauri-butanol number of 30 or less; (b) a graft copolymer containing a (co) polymer steric stabilizer covalently bonded to a thermoplastic (co) polymer core insoluble in the wet carrier; And (c) a colorant, (Meth) acrylates, nitrogen-containing heterocythes, wherein the steric stabilizer comprises units derived from 3,3,5-trimethylcyclohexyl methacrylate and the thermoplastic (co) polymer core comprises an aliphatic amino radical Derived from at least one polymerizable monomer selected from the group consisting of click vinyl monomers, N-vinyl substituted cyclic amide monomers, aromatic substituted ethylene monomers comprising amino radicals, and nitrogen-containing vinyl ether monomers Wet ink comprising a unit. The (meth) acrylates according to claim 25, wherein the (meth) acrylates containing aliphatic amino radicals are N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N -Dibutylaminoethyl (meth) acrylate, N, N-hydroxyethylaminoethyl (meth) acrylate, N-benzyl, N-ethylaminoethyl (meth) acrylate, N, N-dibenzylaminoethyl ( Meta) acrylate and N-octyl, N, N-dihexylaminoethyl (meth) acrylate. The wet ink characterized by the above-mentioned. (a) dissolving a polymer comprising units derived from at least one nitrogen-containing polymerizable monomer in a solvent having a kauri-butanol number of at least 30 to form a polymer solution; (b) dispersing the colorant pigment particles in the polymer solution to form a colorant pigment dispersion; (c) removing at least a portion of the solvent from the colorant pigment dispersion to form treated colorant pigment particles; And (d) dispersing the treated colorant pigment particles in an organosol comprising a wet ink having a kauri-butanol number of 30 or less, Wherein the nitrogen atom is present in a functional group selected from the group consisting of amide, amido, amino and amine groups, the dispersion obtained in step (b) further comprises a charge director, and the nitrogen-containing polymerizable monomer is an aliphatic amino radical Methacrylates or acrylates, nitrogen-containing heterocyclic vinyl monomers, N-vinyl substituted cyclic amide monomers, aromatic substituted ethylene monomers containing nitrogen radicals, and nitrogen-containing vinyl ether monomers A method for producing a liquid ink, wherein the colorant pigment is carbon black.