JPH11349877A - Phase-change ink carrier composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phase-change ink carrier compsn. which has a low mol.wt. and a low viscosity in the liq. state, is thermally reversible between the liq. state and the solid state, and exhibits polymeric properties in the solid state. SOLUTION: This compsn. contains a component selected from the group consisting of thermally reversible Diels-Alder polymn. products, Diels-Alder polymn. precursors, and their mixtures, is a low-viscosity liq. in the temp. range from about 90 deg.C to about 160 deg.C, is a high-viscosity malleable substance in the temp. range from about 40 deg.C to about 80 deg.C, and is solid at a temp. lower than about 30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to selected phase change ink carrier compositions and to phase change ink compositions containing these carrier compositions. In particular, the invention relates to a phase change ink carrier composition and a phase change ink composition containing at least one compatible colorant. The phase change ink carrier composition contains a thermally reversible Diels-Alder polymerization precursor or a reaction product.
It becomes a low viscous liquid at temperatures from 0 ° C. to at least about 160 ° C., becomes a high viscous polymer at temperatures from about 40 ° C. to about 80 ° C., and becomes a solid polymer at temperatures below about 30 ° C.

[0002]

BACKGROUND OF THE INVENTION Phase change inks (sometimes called solid inks or hot melt inks) in digital printing applications have been used for offset printing, flexo printing,
It has been widely used by consumers as an alternative to conventional printing systems such as gravure printing and letterpress printing. Phase change inks are particularly desirable for printing devices as a peripheral device associated with computer technology, and are also suitable for use in other printing technologies, such as gravure printing applications. For such technology,
egwerk Farbenfabrik Keller, U.S. Pat. No. 5,496,879, assigned to Dr. Rung and Co., German Patent Publications DE 4205636AL and DE 4205.
713AL.

[0003] In general, phase change inks are in a solid phase at ambient temperatures, but exist in a liquid phase at elevated operating temperatures in ink jet printing devices. At the firing operating temperature, liquid ink drops are fired from the printing device.
When the ink drops contact the surface of the print media or the intermediate transfer surface, they quickly solidify to form a predetermined pattern of solidified ink drops.

[0004] Phase change inks are easy to handle and safe. Also, phase change inks are generally solids of a hardness similar to crayon used by children, and are in the form of yellow, magenta, cyan and black solid sticks, which are easy for a user to load into a printer. . Inside the printer, these inks melt at the elevated temperatures in the print head. The print head has a number of orifices through which the dissolved ink is ejected onto the desired final receiving substrate, ie, the media, such as paper or a transparent film for an overhead projector. Alternatively, the dissolved ink may be supplied to a rotating drum and then transferred to a substrate. As the ink cools on the substrate,
Coagulate again to the desired image. This resolidification process, ie,
The phase change is instantaneous. Therefore, the printed dried image is formed by the printer, and the user can immediately use the dried image.

[0005] These phase change inks do not contain solvents or diluents that cause undesirable jetting. In all respects, the use and specific formulations of phase change inks are limited in many ways to conventional ink and printing processes. In particular, the promising directions for the development of phase change inks are reducing environmental problems of pollutant sources, preventing pollution, standardizing jets, contaminating groundwater, reducing airborne particulates, waste, workers and consumers. And non-renewable consumables.

Further, when the user is actually touched by the ink in a cold state, the ink is always solid,
Since this ink is in a dissolved state only inside the printer, it is inaccessible to the user and can be used safely. Also, these inks are stable for long periods of time during shipping and interpolation. Further, phase change inks are relatively safe during manufacture.

[0007] These phase change inks generally include a phase change ink carrier composition which is combined with at least one compatible (co-soluble) phase change ink colorant. I have. The carrier composition generally comprises a resin, a fatty acid amide (fatty amid).
e), and a resin-derived material. In addition, the carrier composition contains a softener, a wax, an antioxidant (antioxidant).
ant) and the like. Generally, the resin used is water-insoluble and the carrier composition does not contain any volatile components at the injection temperature used. In addition, these carrier components are chemically stable and do not lose their chemical integrity over time and / or under elevated temperature conditions.

Preferably, the colored phase change ink is formed by combining the desired ink carrier composition described above with a compatible subtractive colorant. The subtractive color phase change inks of the present invention are composed of four component dyes, namely, cyan, magenta, yellow and black. United States Patent No. 48895
Nos. 60 and 5372852 disclose the use of subtractive colorants and typically use color index (CI) soluble dyes, C.I. I. Dispersion
se) Dyes, modified C.I. I. Acid and direct dyes, and C.I. I.
Dyes of the basic dye class may be provided. Also suitable as colorants are suitable polymer dyes. These are described, for example, in US Pat. No. 5,621,022.
And available from Milliken & Company.
Ink Yellow (Milliken InkYellow) 869, Milliken Ink Blue (Milliken Ink Blue) 92, Milliken Ink Red (357),
Milliken Ink Yellow
1800, Milliken Ink Black
Black) 8915-67, uncut reactant orange X
-38, uncut reactant blue X-17, uncut reactant violet X-80, and the like. It is also described in U.S. Pat. No. 5,231,135.
Further, the colored resin reaction products described in U.S. Pat. No. 5,780,528 are also suitable colorants.

[0009] The specially selected components and their associated amounts are very important to achieve the desired application performance properties of the phase change ink. Specific physical and chemical properties required of these inks include, but are not limited to, viscosity (viscosity), surface tension, flexibility, durability, thermal stability, and coloring ability. .

In practice, two desirable properties of phase change inks are (1) the durability of the printed image and (2) the ability to eject the ink to create an image on a substrate. Alternatively, a polymeric material is added to the carrier composition to achieve the desired durability.

The following US patents describe certain phase change ink compositions. U.S. Pat. No. 5,372,852 describes an optional phase change ink composition containing a phase change ink carrier composition comprising a fatty acid amide containing material (tetraamide compound or monoamide, or mixtures thereof). The U.S. patent also describes that preferred tetraamide compounds are made by reacting fatty acids, diamines (ethylene diamine) and dimer acids. A preferred fatty acid is stearic acid, and a preferred dimer acid is hydrogenation, known as EMPOL 1008 dimer acid, produced by the Emery Division of Henkel Corporation of Cincinnati, Ohio. Oleic acid dimer product. Witco Chemical Company KE
Secondary monoamides such as behenyl behenamide and stearyl stearamide, produced under the trademark MAMIDE, are described as preferred monoamides.

US Pat. Nos. 5,782,966, 5,827,918 and 583, assigned to the assignee of the present invention.
Nos. 0942, 5783658 and 5750064 describe a number of urethanes, ureas and mixed urethane / urea resins suitable for use in phase change ink compositions.

Although the phase change ink compositions described in the aforementioned US patents have been successful in the market, there is a need to constantly improve these inks to suit many processing conditions and different applications. In addition to the properties of the printed substrate, the inks and the individual components that go into them must be evaluated according to their cost, manufacturability, and how they operate in a separate printer. In addition, the safety and environmental issues of each component and the entire ink must be considered. The ideal phase change ink for plain paper printers has achieved the highest quality with all printing techniques.

[0014] Alternatively, the Diels-Alder reaction (also referred to as a 4 + 2 cycloaddition reaction) is a well-known technique for the synthesis of six-membered rings. This reaction involves a 1,4 addition of a dienophile double bond to the conjugated diene to generate a 6-membered ring. This reaction is often used to create relatively small molecular weight materials, which have been extended to polymeric materials. Furthermore, the choice of dienes and dienophiles includes cyclic, heterocyclic and highly substituted materials containing complex and / or protective or latent functional groups. Diels-Alder-Adults are typically stable.

[0015] Japanese Patent Laid-Open No. Hei 7 published on March 7, 1995
JP-A-61117 describes an ink jet recording method using the Diels-Alder reaction. However, the Diels-Alder reaction product is not a polymer product.

[0016] Journal of Polymer Scienc published in 1994
e) Part A Polymer Chemistry; Volume 32, 2501
Noriyuki Kuramoto et al., “Thermoreversible Reaction of Diels-Alder Pol of Diels-Alder Polymer Consisting of Difurfuryl Adipate with Bismaleimidodiphenylmethane”
ymer Composed of Difurfurylapidate with Bismaleimi
dodiphenylmethan) "describes details of several thermoreversible reactions of different Diels-Alder polymers and studies of this reaction. This class of polymer is
Produced by Diels-Alder reaction at 60 ° C,
It can be decomposed (depolymerized) into monomers by heating to 90 ° C.

[0017]

However, all of the above-mentioned conventional ink compositions have a low molecular weight and a low viscosity in a liquid state, and are thermally reversible between a liquid state and a solid state. It does not have the properties of a polymer in the solid state.

[0018]

SUMMARY OF THE INVENTION The present invention is based on the use of component classes useful in ink jet printing applications. These components are polymers that are solid at room temperature, but when dissolved form non-volatile, low viscosity components that facilitate ink ejection. In addition, after jetting the ink onto the substrate and during re-solidification of the ink, this class of components forms a polymeric material that provides a more durable printed image. This transition occurs by a thermally reversible chemical reaction.

By using this class of reaction products, when the phase change ink is stored as a solid at room temperature and dissolved at an elevated jetting temperature, the reaction products undergo a reversible chemical reaction and become non-volatile. To form a low viscosity phase change ink carrier composition. This carrier composition allows the ink to be easily jetted onto the intermediate transfer surface or directly onto the final substrate. As the jetted image cools, the carrier composition returns to the polymeric material, improving the durability of the image on the substrate.

This new class of carrier components, besides the utility provided by various other known carrier components, generally has a very low vapor pressure so that the components do not become undesirably volatile. Also, this class of reaction products is preferably water-insoluble.

Thus, one aspect of the present invention is a phase change ink carrier composition having a thermally reversible Diels-Alder polymerization precursor, wherein the reaction product is at about 80 ° C.
A non-volatile, low viscosity precursor at temperatures from about to about 40 ° C. to ambient room temperature (ie, less than about 20 ° C. to about 3 ° C.).
(0 ° C.) is a solid polymer.

Another aspect of the present invention is a phase change ink containing a phase change carrier composition and at least one compatible colorant, wherein the carrier composition is a thermally reversible Diels-Alder®. It is a polymerization precursor or a reaction product.

Yet another aspect of the invention is a hot melt gravure ink, such as a thermally reversible Diels-Alder polymerisation precursor or reaction product.

Furthermore, one of the preferred concepts of the present invention is that difurfuryladipate (DFA)
And bismaleimidodiphenylmethane (bismaleimidodi
phenylmethane (BMD) is a phase change carrier composition comprising a polymer made by the Diels-Alder reaction. Solid polymers can be made from these two monomers at temperatures below 60 ° C., and these polymers undergo a reactive Diels-Alder reaction above about 90 ° C.

A feature of the present invention is that Diels-Alder precursors or reaction products can be added to existing amide-based phase change inks or completely replaced with the tetra-amide component of such inks. It has improved durability and toughness, as well as reduced coefficient of friction when applied to substrates that slide over glass or metal surfaces.

An advantage of the present invention is that the Diels-Alder polymerization precursor can be processed to achieve desired properties, and when mixed with a phase change ink, the ink
Compatible with the base, images printed with this ink have similar properties.

Another advantage of the present invention is that the Diels-Alder reaction product, when added to a phase change ink formulation,
That is, the ink can be prepared, that is, technically compounded to obtain an ink having desired characteristics.

[0028]

DETAILED DESCRIPTION OF THE INVENTION As used herein, the expression "thermally reversible Diels-Alder polymerization reaction precursor or reaction product" refers to any diene precursor and / or any dienophile precursor, or Any chemical reaction product made by a reaction sequence including the Diels-Alder reaction. Here, the reaction product is from about 0 ° C. to about 60 ° C.
At temperatures up to 10 ° C., it is in the form of a high viscosity liquid or solid polymer, and at temperatures from about 90 ° C. to about 160 ° C., in the form of a low viscosity liquid.

For example, the diene and dienophile precursors can be added to a molten (dissolved) phase change ink carrier composition or a phase change ink composition. Upon cooling to room temperature, the ink along with the diene and dienophile undergo a Diels-Alder reaction to form a high molecular weight resin material that is a Diels-Alder-Adducts (adduct). Further, when the phase change ink is heated to the firing temperature, the polymer reaction product undergoes a reverse Diels-Alder reaction to produce a low viscosity, low molecular weight, jettable ink in the liquid state at the firing temperature. . Alternatively, one precursor can be formulated into the ink and the other precursor can be applied to a sacrificial release layer. This sacrificial release layer acts as an intermediate transfer surface of the transfer drum of the ink jet printer. Thus, when the ink is ejected onto the drum, the two precursors react within the liquid release layer on the drum to form a thermally reversible, high molecular weight resin reaction product.

Also, the reaction product of the two precursors can itself be prepared in a phase change carrier system so that the ink stick is in a solid form when inserted into an ink jet printer by a user. In this example, the solid reaction product becomes liquid at the jetting temperature and returns to a dry solid when cooled to a solid form on the substrate.

The Diels-Alder reaction product within this concept definition may be the reaction product of two or more Diels-Alder reactions, or the reaction sequence is limited to a single Diels-Alder reaction. Note that, or, the reaction may be the first or last reaction in the overall reaction sequence. Further, of course, this definition includes the compounding of one or more Diels-Alder precursors with a Diels-Alder reaction product or a mixture of different Diels-Alder reaction products in a phase change ink. Other possibilities include molecular weight preparation, symmetric or asymmetric dienes or dienophiles,
And combinations thereof, there is a chain termination component.

This concept definition does not include Diels-Alder precursors that do not tolerate the polymer species chain extension or reaction products. Note that the polymer species does not undergo a thermally reversible reaction over a temperature range of about 0 ° C to about 160 ° C.

The term "solid" as applied to a polymer type reaction product at a temperature of less than about 40 ° C. refers to solids in an ink jet printer apparatus and printed images dried on a substrate such as plain paper. Any solid form suitable for use in both.

The term "low viscosity liquid" as applied to reverse reaction products in liquid form from 90 ° C. to about 160 ° C. refers to the ink
Any suitable liquid state that can be jetted by a jet printer. The cracking Diels-Alder reaction is a reverse or retrograde reaction that cuts a molten solid polymer to make a low viscosity material that can be jetted with an ink jet printer. In the context of the printing process described in connection with indirect transfer printing, the Diels-Alder reaction produces an adduct that is mixed with the phase change ink. This is about 80 ° C. once repolymerization begins.
And while being cooled to a temperature range between about 40 ° C., while becoming more viscous and exhibiting malleable properties. When printed on a final receiving substrate, as the ink is further cooled to an ambient temperature of less than about 20 ° C. to about 30 ° C., it becomes harder and more robust and durable in the printing process.
The preparation of the Diels-Alder adducts and the resulting inks with the adducts allows the desired properties to be set technically in both the adducts and the inks. For example, placing a linear hydrocarbon chain, such as a polyethylene molecular chain, between multiple reactive diene units or components produces a more crystalline, harder, and more resistant material. In contrast to this, the glass transition point (Tg) is determined using a polyoxyalkylene component between a plurality of reaction units.
Produces a low, soft, flexible product. Of course, an important factor in using any diene or dienophile in phase change ink preparation is the compatibility of the compound with the ink base.

As mentioned above, the Diels-Alder reaction involves the reaction of dienes and dienophiles. For the purposes of the present invention, suitable dienes and dienophiles are
Any material capable of participating in the Diels-Alder reaction leading to a thermally reversible polymer may be used. Diels is any common diene, two double bonds separated by a single single bond, and dienophile can be understood as a double bond compound. For polymerization, if it contains at least two diene or dienophile reactive sites,
The condition of the diene and dienophile molecules is that they are each separated by one or more linking groups. In addition, the thermally reversible Diels-Alder polymerisation reaction product can be a linear copolymer (copolymer), a branched polymer or copolymer, a block copolymer, a star or dendrimeric with a functionalized termini. A polymer, or a plurality of polymers. These polymers may also be covalently linked to colorant materials (eg, diene or dienophil-capped Milliken polymer colorants), UV or IR absorbers, antioxidants, fungicides, and the like. Such bifunctionalized materials can provide certain desired properties (eg, certain colors, enhanced lightfastness, conductivity, oxidative stability, environmental or biodegradability, or reproducibility).
Alternatively, the linking group between the diene groups or dienophile groups in the precursor molecule may be altered to impart other functions and / or properties to the phase change ink. For example, functionalization can be introduced into these precursor molecules to provide the desired color, antioxidant, strengthening, UV stability, infrared absorption, plasticity, and other properties. In particular, it is desirable to prepare these precursors so that the desired glass transition temperature (Tg), melting point, yield stress, modulii and heat of fusion properties are obtained.

More preferably, the diene precursor may be comprised of any 5- to 8-membered ring containing a co-diene, wherein all of the ring members are nitrogen atoms in the conjugated diene system. , Oxygen, sulfur and carbon atoms having a heteroatom selected from mixtures thereof, or a mixture of carbon atoms. Also preferably, the ring (ring) atoms can be unsubstituted or electron donor substituents (eg, alkyl, aryl,
Arylalkyl, alkoxy, aryloxy
y), alkylthio, arylthio
thio), amino, alkyl-substituted amino, aryl-substituted amino, alkoxy-substituted amino, etc.).
Also, the linking moiety between the terminal diene components may be a natural or synthetic fatty acid (particularly dibasic, hydrogenated fatty acid containing 4 to 50 carbon atoms), 1
It may be selected from homopolymers or copolymers of alkyleneoxy substituents ranging from 1 to 100 repeat units, or similarly prepared functional groups to balance the softness of the incipient polymer. .

Optimally, the diene is difurfuryladipate (DFA). More preferably, the dienophile is an endcycli
c) Dienophili, which may contain olefins or is attached to the ring structure but is exo
c) Any 5- to 8-membered ring having a component may be used. Preferably, the dienophile can be unsubstituted or substituted with an electron withdrawing group such as a cyano, amide, carboxy, carboxy ester, nitro, aromatic ring including electron withdrawing groups. Alternatively, the dienophile may be a double bond in a ring structure conjugated to one or more electron withdrawing groups. The condition for ring polymerization is that the dienophile contains a link between the two dienophile components, the linking moiety comprising:
Diamines, aromatic diamines, bi-aryl diamines, or alkylenoxy diamines (Huntsman) separated by 4 to 50 carbon atoms, carbon chain lengths in the range of 2 to 50 carbon atoms・ Chemical (Hu
ntsman Chemical) (commonly referred to as Jeffamines).

Most preferably, the dienophile is bismaleimidodiphenyhlmethane:
BMD). The reaction of converting the diene and dienophile into a thermally reversible reaction product can be performed depending on the reaction conditions generally used for the Diels-Alder reaction.

The use of Diels-Alder reaction precursors, or reaction products, or both, is that these materials are liquid and non-polymeric at the jetting temperature, and are polymerized (due to clogged nozzles) in the print head. There is an important advantage that the injection operation is not defective or damaged. These materials also have the added advantage that at room temperature, i.e., ambient temperature, the properties of the polymer allow the formation of durable images. Further, the thermally reversible Diels-Alder polymer products of the present invention include:
Generally thermally stable (ie, not degraded by alternative or undesirable mechanisms) for use in hot melt print heads, and generally other conventional phase change ink jet carriers and pigments It is mutually compatible with the material and is generally inert so as to be compatible with environmental and consumer safety.

In addition to using these Diels-Alder precursors directly in print phase change inks,
It can also be used for print processing. For example, one precursor can be formulated into an offset ink and the other precursor can be formulated into a material to be used as a release layer in an offset process. Polymerization occurs during the transfix or post-processing steps of the offset printing process. Alternatively, both precursors of the Diels-Alder reaction product can be included in the offset ink or release layer material.

Preferably, the Diels-Alder polymer reaction product can be made from a chemical reaction that is completed without forming significant amounts of undesirable by-products. More preferably, these reaction products can be made by reactions that do not require volatile organic solvents,
Optimally, the reaction product is “straight” (ie, freed from the solvent). Further, in the present invention, the phase change ink / carrier composition allows a “solvent” to be used for the reaction.
Select Finally, these Diels-Alder reaction products do not require extensive purification operations.

Preferably, the present invention contains an optional phase change ink composition that is applied directly to the final receiving surface or substrate or indirectly via an intermediate transfer surface. These preferred phase change ink compositions of the present invention have a specific phase change ink colorant and a specific phase change ink carrier composition, the carrier composition comprising at least one thermally reversible deal. Contains Alder or thermally reversible Diels-Alder precursors. A specific phase change ink carrier composition is prepared to produce a selective ink composition. The selective ink composition has predetermined fluid and mechanical (mechanical) properties that meet the parameters needed to indirectly supply the ink composition to the final receiving surface through the intermediate transfer surface.

The colorant used in the phase change ink composition of the present invention may be any subtractive colorant that is compatible with the particular phase change ink carrier composition used. The subtractive color phase change inks of the present invention generally have four basic colors,
That is, it contains cyan, magenta, yellow and black dyes. Dyes used as subtractive colors may be of the following dye classes: color index (CI) dyes; solvent dyes; disperse dyes; modified acid and direct dyes; In addition to these classes of dyes, the ink compositions of the present invention also preferably include a selective polymeric dye as one or more colorants. Suitable polymeric dye colorants are described in U.S. Pat.
No. 80528.

The synthesis of organic chromophores suitable for use in suitable polymeric dye colorants containing a polyoxyalkylene substituent is described in Kuhn, US Pat. No. 3,157.
No. 633, U.S. Pat. No. 4,167,510 to Brendle, U.S. Pat. No. 4,284,729 to Cross et al., Baumga.
rtner), US Pat. Nos. 4,732,570 and 5,231,135.

Suitable polymeric dye colorants are Milliken®
Available from Milliken Corporation. Examples include Meriken Ink Yellow 869, Milliken Ink Yellow
Blue (Milliken Ink Blue) 92, Milliken Ink Red 357, Milliken Ink Yellow 1800, Milliken Ink Black 891
5-67. Other yellow, cyan, magenta and black polymeric dyes are those that can be used within the scope of the present invention. These polymer dyes may be used alone or in combination with a conventional coloring agent described in US Pat. No. 5,372,852. In addition, phase change inks containing polymer dyes may be used in ink jet printers with conventional phase change inks containing powdered dyes.

Various modifiers may be preferably added to the phase change ink carrier composition. These include tetraamide compounds, hydroxyl functional
There are fatty amide containing materials such as tetraamide compounds, monoamides and hydroxyl functional monoamides and mixtures thereof. Preferred tetraamides and monoamides are also described in the aforementioned US patents.

A preferred hydroxyl functional tetraamide compound for forming the modified phase change ink carrier composition is a dimer acid base tetraamide. Preferably,
These include the reaction products of hydroxyl functional fatty acids;
There are reaction products of diamines (eg, ethylene diamine) and dimer acids or fatty acids; diamines (eg, ethylene diamine) and hydroxyl functional dimer acids.
As used herein, the term "hydroxyl-functional fatty acid amide containing material" is a compound having a hydroxyl group and a fatty acid amide component. A preferred hydroxyl functional fatty acid precursor is 12 hydroxy stearic acid. For the purposes of the present invention, the term “dimer acid” preferably means a hydrogenated oleic acid dimer product. A suitable example of such a dimer acid is Emily Division, Cincinnati, Ohio, USA
Of Henkel Corporation (Emery Division o
f Henkel Corporation) and manufactures Empol
A product known as 1008 dimer acid. 10
Fatty acids having up to 22 carbon atoms can be preferably used for the formation of the dimer acid base tetraamide. These dimer acid tetraamides are produced at Union Camp and include the reaction products of ethylene diamine, dimer acid and the following fatty acids. These fatty acids include decanoic acid (Union Camp X32023-23), myristic acid (Union Camp X3202-56), stearic acid (Union Camp X3202-56).
Cap X3138-43, X3164-23, X32
02-44, X3202-46, X3222-655,
X3261-37, X3261-53 and X3290-
72), and docosanoic acid (Union Camp X320
2-36). For the purposes of the present invention, an optimal dimer acid base tetraamide is a dimer acid having a theoretical ratio of 1: 2: 2,
It is a reaction product of ethylene diamine and stearic acid. Stearic acid is a preferred fatty acid reactant. This is because the adduct with dimer acid and ethylene diamine,
It has the lowest viscosity dimeric acid-base tetraamide. The component is the cheapest because it is the easiest to obtain.

The hydroxyl-functional fatty acid amide-containing substance may preferably contain a hydroxyl-functional monoamide. In fact, in the preferred case, the phase change ink carrier composition contains both a hydroxyl functional tetraamide compound and a hydroxyl functional monoamide compound. Hydroxyl monoamide compounds are
Typically, it contains a hydroxyl functional primary or secondary monoamide, but is preferably a hydroxyl functional secondary monoamide. Hydroxy of primary monoamide
Stearamide can also be used. In the secondary monoamide, the hydroxyl functional behenyl benenamide (bene
namide) and hydroxyl functional stearyl stearamide are useful hydroxyl functional monoamides.

Preferred hydroxyl functional fatty acid amide containing compounds include a plurality of fatty acid amide materials,
It is compatible with each other. Typically, even when using a plurality of hydroxyl functional fatty acid amide-containing compounds to produce a phase change ink carrier composition, the carrier composition will have a substantially single melting point transition. The melting point of the phase change ink carrier composition is preferably at least about 85 ° C. Other suitable modifiers include certain tackifiers. Suitable tackifiers include those that are compatible with the fatty acid amide containing material. These include
For example, KE-100 resin, a glycerol ester of hydrogenated abietic (rosin) acid, produced by Alaska Chemical Industry Limited; and hydrogenated abietin (rosin, produced by Hercules Chemical Company) ) Foral 85, which is a glycerol ester of acid, Foral 105, which is a pentaerythritol ester of hydrogenated abietic (rosin) acid, and celloline, a hydrogenated abieticin (rosin) alcohol ester of phthalic acid (Cell
olyn) 21 or; Neevak 2300 and Nebutac 80, synthetic polyterpene resins produced by Neville Chemical Company; and modified synthetic polyterpene resins produced by Goodyear Chemical Company. A Wing Tack
tack) 86. However, the best tackifier is K
E-100.

Other suitable modifiers which can be added to the preparation are:
A softener. In this case, many phthalate softeners sold under the trade name "Santicizer" are suitable for this purpose. However, a preferred softener is Stunch Sizer 278, which comprises
Benzyl alcohol and Texano
l) "and diesters of phthalic acid.

Other additives may be combined with the phase change ink carrier composition. In a typical phase change ink, a chemical composition antioxidant is added to prevent discoloration of the carrier composition. Suitable antioxidants include Irganox (Irgaox) produced by Ciba Geigy.
nox) 1010; Uniroyal Chemical
Naugard 7 produced by the company
6, Now guard 445, Now guard 512, Now guard 524. However, the best antioxidant is Nowgard 445.

[0052] A viscosity reducing agent may be used in the ink composition of the present invention. By using a viscosity curing agent, the viscosity of the ink composition can be adjusted to a desired value. Suitable viscosity hardeners for use in the ink compositions of the present invention include stearyl monoethanolamide stearate (ester), ethylene glycol distearate (EGDS). The viscosity hardener can be present in an amount from about 0% to about 50% by weight of the ink composition. Further, the predetermined amount of the viscosity curing agent used in the predetermined ink composition is determined by the viscosity desired by the user.

An ink having a desired hardness at room temperature may be obtained by using a curing agent in the ink composition of the present invention. Useful curing agents include ricinolamide, hydroxysteaamide, hydrogenated castor oil, EGDS (ethylene glycol distearate), esters of propylene glycol, esters of glycerin, stearyl esters of 12 hydroxystearic acid. , 12-hydroxydodecanoic acid and its derivatives.

Ricinolamide and hydroxylstearamide can be used as preferred hardeners, with N (2-hydroxyethyl) -12-hydroxystearamide (Paricin 220 from CasChem, Inc.) being most suitable. It is. Other suitable hydroxystearamides include Palysin 210 and Palysin 285 available from Caschem, Inc. These compounds sufficiently cure the ink composition at room temperature and maintain the ink composition in a liquid state.

[0055] Viscosity hardeners and / or hardeners may or may not be necessary for use in the ink compositions of the present invention.

The above-described modifiers may be used in the preferred embodiment of the present invention, or may be combined with another material having similar properties, or
May be used to produce different phase change ink compositions having mechanical and fluid properties similar to those outlined above. These other materials include paraffin; microcrystalline wax,
Polyester wax; Ester wax; Oligomer (low polymer) or low molecular weight polymer, and copolymers such as polyethylene vinyl acetate (EVA); Ethylene acrylic acid copolymer; EVA /
Acrylic acid copolymers; ionomers; copolymers of acrylic acid with polyamide, and the like.

When cooled to ambient temperature, a uniform thickness thin film of the phase change ink composition on the final receiving substrate must be ductile and maintain sufficient flexibility. Therefore, the image has no crack even when bent, and has high brightness, saturation, transparency, and thermal stability.

It has been found that in indirect application processing using an intermediate transfer surface, a phase change ink composition must have certain fluid and mechanical properties in order to produce high quality prints on a substrate. Desirable solid state properties of the phase change ink compositions of the present invention can be identified and measured using several analytical techniques.
One such technique is dynamic mechanical analysis (DMA). This DMA is disclosed in US Pat. No. 5,389,955.
This is the technique described in No. 8.

Another of the mechanical analysis techniques described above is compressive yield testing on bulk samples of the phase change ink composition. Yield stress (y
The ieldstress is the point on the stress-strain curve where the material continues to deform without increasing stress, and is important in the printing process described above. This is because it determines the pressure required to spread solid, malleable ink droplets into a continuous thin film during the transfer process.

There are various types of deformation in which the ink is compressed according to the temperature or the rate of change (rate). Hard but brittle if broken by shearing or cracking
Grade the inks into classes. This means that in typification, the elongation (which is proportional to the strain) is low and the high stress is weak to relax. Since integrating the area in the stress-strain curve is a measure of the toughness of the material, a hard but brittle material is strong but not tough. The hard but brittle nature is
It is not preferable for the durability of the ink on the substrate. This is due to the low elongation (ie, very little ductility and flexibility) and low tenacity / toughness (ie, the ability to dissipate energy). The material of the present invention has good durability, ductility and toughness.

When the phase change ink composition of the present invention is finally supplied to a substrate, the finished print shows excellent color properties. As shown in commonly assigned U.S. Pat. No. 5,389,958, a uniform thickness thin film of this phase change ink composition transmits straight light and exhibits exemplary C * ab and L * values. .

Another important property of phase change inks is viscosity (viscosity). The viscosity of the molten ink must meet the requirements of the ink jet device and must be optimized for other physical properties of the ink. For the purposes of the present invention, the viscosity of the phase change ink is measured on a Bohlin CS-50 rheometer (flow meter) using a C-25 cup and Bob. The viscosity of the phase change ink carrier composition at 140 ° C., and with the ink compositions of the present invention, is from about 5 to about 30 centipoise (centipoise), more preferably from about 10 to about 20 centipoise. Optimally from about 11 to about 15 centipoise.

As mentioned above, phase change inks formed from the phase change ink carrier compositions of the present invention exhibit excellent physical properties. For example, unlike the conventional phase change ink, the phase change ink of the present invention exhibits a high level of lightness, saturation, and straight light transmission when a thin film having a substantially uniform thickness is used. Can be used to project a color image. Further, suitable phase change ink compositions exhibit the above-mentioned good mechanical and fluid properties as measured by DMA, compression yield test and viscosity measurement. More importantly, US Pat.
It works well when used in indirect printing as described in US Pat.

The inks used in the processes and systems of the present invention are preferably initially in the solid state, but can be dissolved (melted) when heat energy is applied to raise the temperature from about 85 ° C. to about 160 ° C. Change to a state. The melted ink is supplied (jetted) from an ink jet in the print head in a raster format to an exposed surface of a liquid phase forming an intermediate transfer surface. The supplied ink is cooled to an intermediate temperature and solidifies in a malleable state. This ink is placed in the nip between the pressure and fusing roller and the liquid layer forming the intermediate transfer surface on the drum which is the support surface, and is transferred to the final receiving surface by contact transfer. The intermediate temperature at which the molten ink is maintained in a malleable state is between about 30C and about 80C. At this temperature, the Diels-Alder polymer is reformed.

When an individual, malleable ink image enters the nip, the ink image is transformed into the form of the final image. And, by the pressure acting on the ink image on the final receiving medium only by the pressure and the fusing roller, or
The combination of heat and pressure applied by a suitable heating device causes the ink image to adhere to the final receiving medium. An additional heating device may optionally be used, at which point heat may be applied to facilitate the process. The pressure acting on the ink image is from about 10 to about 200
It is between 0 pounds per square inch (psi), more preferably between about 500 and about 1000 psi, and most preferably between about 750 and about 850 psi. Attaching the ink image to the final receiving medium, and if the final receiving medium is transparent, ensure that light travels straight through the ink image and passes through, i.e., from when the light enters the ink image until it is output. To make sure they do n’t change
This pressure must be sufficient. As the ink image adheres to the final receiving medium, the ink image is cooled to an ambient temperature from about 20C to about 25C. The inks that make up the ink image must be ductile and, when kept above the crow transition temperature, must be able to undergo, ie, undergo, plastic strain without cracking. Below the glass transition temperature, the ink is hard but brittle. The temperature of the ink image in the ductile state is about -1.
Between 0 ° C. and about the melting point, ie, less than about 85 ° C.

The coefficient of friction of the ink can be measured in an image device such as an electrophotographic or electrographic copying machine.
Affects automatic document feed capability for printed substrates. High coefficient of friction causes ink to “stick” when media slides across a support surface, such as glass
Or the printed medium is in a jam (paper jam) state. This coefficient of friction is defined as the ratio of the tangential force to the normal load when the surface of the material moves relative to another surface. For a printed substrate at rest on a support surface, the coefficient of friction is about 0.
Less than 7, preferably less than about 0.5, optimally about 0.3
Must be less than.

The following examples are not intended to limit the invention to the particular materials, treatments or configurations used, and to illustrate the preparation of phase change inks with or without a liquid intermediate transfer surface. Things.

[0068]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Ink Components The following ink formulations consist of components used in Tektronix phase change inks, except for the materials specifically used in the present invention. Formulation techniques and auxiliary materials are also described in patents and patents of Tektronix. These ingredients include viscosity modifiers, colorants, dyes, pigments, antioxidants, tougheners, waxes (esters, amides,
For example, natural and synthetic products such as polywax 850 polyethylene described in U.S. Patent Application Serial No. 09/033366 filed on February 13, 1998), softeners, functional components, color formers, resins (urethane, urea and urethane). / Urea), a polymer colorant, and a resin derived from the polymer colorant, but are not limited thereto.

These examples use the Diels-Alder reaction products and their precursors as the formulated components in the phase change ink. In addition, these components were described above in this specification. These components are used in a total ink formulation of 5
And within 90% by weight of the phase change ink. The expected average molecular weight of the Diels-Alder product ranges from 700 to 25000, optimally 700.
And 3500.

The Diels-Alder reaction product is formed from bisdienophiles and bisdienes. Here, the reaction components of each component are separated by a connection group. Each of these reaction components is characterized by an average molecular weight in the range of 200 to 15000, optimally between 300 and 3000. The polymerization (polymerization) of dienes and dienophiles is carried out at temperatures in the range of -20 to 80 ° C,
It is expected to occur optimally at temperatures between 0 and 50 ° C. The polymer is expected to return to its original components by heating to a temperature of 70 and 160 ° C, optimally 80 and 150 ° C. Dienes and dienophiles are at their melting points and, in the case of crystalline, in the expected range of 50 and 150 ° C.
The non-crystalline case is characterized by a glass transition temperature in the range of 25 to 125 ° C.

2. Ink formulation Melt the desired ingredients in a stainless steel beaker,
Prepare the ink by mechanical stirring. Using a temperature control mantle, a typical stirring temperature range of 80 to 140 ° C.
And stir for about 1 hour. A sample of the ink is taken and characterized by several selected physical properties, such as spectral intensity, viscosity, glass transition temperature, melting point, and the like. These properties are adjusted, if necessary, by readjusting the inks to work with a Tektronix phasor color printer or other printing or marker applicator.

3. Ink Treatment The final ink is filtered through a heated Mott apparatus (available from Mott Metallurgical) under # 3 Whatman filter paper and nitrogen pressure of 15 psi. The filtered phase change ink
Pour into molded HIPSSMA (High Impact Polysulene / Maleic Anhydride) plastic cups or tubs to form ink sticks. The completed solid ink is
Compared to compatible formulations that do not use polyethylene wax additives or Diels-Alder adducts, they have a significantly better surface finish and can be easily peeled off plastic cups.

4. Ink Analysis and Characterization The finished ink product is characterized by the following physical properties. These physical properties were measured at about 140 ° C. on a Ferrant-Shirley cone plate viscometer prepared with stearyl stearamide or a polymer tested according to the present invention, decreasing or increasing the viscosity, respectively. Viscosity of about 13 cPs; DuPont 2100
(8) measured by differential scanning calorimetry using a scanning calorimeter.
Predicted range of 5 to 160 ° C.); temperature in glass shop (-25 ° C. to 100 ° C.) measured by dynamic mechanical analysis using a rheometry (flowability) solid analyzer (RSAII)
Prediction range). Using a spectrophotometric procedure based on the melting of the solid ink in butanol, Perkin Elmer Lambda was used.
Lambda) Measure the colorant solution absorbance with a 2SUV / Vis spectrometer to determine the spectral intensity of the ink. Adjust the spectral intensity to suit your printing application.

5. Test of Ink Performance in Print Head and Transfer Fixing Process In order to obtain stable ejection characteristics, the ink was evaluated on a Tektronix phase change color printer using a Tektronix piezoelectric drive print head. The measurement items are the mass of the ink droplet used for ejection, the ejection frequency response,
It is a supply voltage and a waveform. The desired measurement object is an ink that can be ejected and generate ink drops at a useful mark rate. In addition, after several printhead operating cycles of freeze-thaw, printhead operation was undisturbed. That is, neither clogging of the orifice nor deterioration of the injection characteristics was observed.

In the offset printing process using a phase change color printer manufactured by Tektronix, Inc., Feather 340, the film split characteristics of the ink were evaluated. A general description of physical conditions can be found, for example, in the minutes of IS &T's 11th International Conference on Non-Impact Printing Technologies (1995), L. Bu.
i) et al., "Rheological, thermomechanical, viscoelastic conditions of phase change inks for offset ink jet printing". These inks are jetted onto a rotating drum containing a sacrificial silicone oil layer. Next, the image is transferred to a desired substrate by a transfer fixing process. These inks are used in the printing process after the printed image is prepared.
sheet), more than 90% of the transfer from the drum to the substrate is expected. In addition, these inks are evaluated for the absence of cohesive failure between the plurality of ink layers formed on the rotating drum before transfer fixation. A reversible polymer prepared by Diels-Alder-Adducts into inks by adjusting the substrate preheating, drum temperature, and transfer pressure parameters to optimize the image and print quality of the finished printed product Use the chemical properties.

6. Printing and Performance Testing The inks are tested on a Tektronix Phaser 340 printer using an offset transfer printing system. These inks have been found to transfer completely and produce good color and durable images for the primary colors, or in combination with each other, or when combined with commercially available Phasor 340 printer inks. Was.

The prints made in these examples are:
Shows good blocking resistance (anti-adhesion) at high temperatures when compared to the compatibility formulation without Diels-Alder-Adducts. This blocking test was conducted by Society for Imaging Science and
Technology (Society for Imaging Science and Tech)
5th of the NIP12 Bulletin of the 12th International Conference on Digital Printing Technology issued by
It is described on page 6.

The prints made in the following examples are expected to be as durable as laser printer hard copies, ie, prints, made by aqueous ink jet equipment or commercial offset printing techniques. Quantitative comparisons using the Taber abrasion method (ATSM D4060) provide improved durability due to the polymer properties of the Diels-Alder products in the ink. Also, these inks have improved resistance to cracking when folded printed articles.

The hard copy output using the ink of the present invention is also suitable for an automatic document feed function. This is 1 to 500
Using the automatic duplication mode selected between prints, the measurement can be made by the print copy function of a commercial photocopier.

Example 1 Preparation of a Phase Change Ink Carrier Base According to the general procedure described above, about 25% by weight of a Diels-Alder polymer prepared from difurfuryl adipate with bismaleimidodiphenylmethane was prepared. About 50% by weight of stearyl stearamide, about 25% by weight of a urethane / urea resin described in Example 4 of U.S. Pat. No. 5,782,966, and commercially available from Uniroyal Chemical Company of Oxford, Conn. Melt 2% of Naugard 445 antioxidants together
Dispensing a common phase change ink carrier base.
The master batch is used to dispense the phase change inks of Examples 2, 3, 4 and 5.

Example 2: Cyan-colored phase-change ink base formulated from Diels-Alder Products About 500 of the clear ink base formulated in Example 1.
The gram is combined with about 25 grams of Millijet Blue 28 colorant and the dispensed ink and processed to determine characteristics according to the general description above. As described above, the final ink is evaluated for superior properties in a Tektronix Phasor Color Printer.

Example 3: Cyan ink made from a cyan colored urethane resin and a thermoreversible polymer. About 500 of the clear ink base prepared in Example 1.
Grams were measured at about 125 grams of the cyan-colored urethane resin described in Example 2 of US Pat. No. 5,782,966.
Combine with gram. It shows the properties expected from the contained Diels-Alder thermoreversible polymer.

Example 4: Cyan ink formulated from cyan-colored urethane resin, urethane / urea resin and thermoreversible polymer. According to the procedure described above, about 250 grams of the clear ink base formulated in Example 1 was used. About 125 grams of the cyan urethane resin prepared in Example 3 and about 125 grams of the clear urethane / urea resin described in US Pat. No. 5,782,966. When the resulting ink is evaluated by the print performance test method described above, it has the predictive function of a polymer.

Example 5: Yellow Ink Made from Polyethylene Wax, Mixed Urethane / Urea Resin, and Yellow Colored Urethane Resin Using the standard procedure described above, about 250 grams of the ink base of Example 1 was obtained from Tektronix, USA. About 125 grams of the yellow urethane resin described in U.S. Pat. No. 5,780,528, and about 125 grams of the urethane / urea resin of Example 2 of this patent, plus Baker Petrofile, Tulsa, Oklahoma, USA
ofile) PE850 polyethylene commercially available from
Combine with about 25 grams of wax. These inks exhibit the desired performance properties.

Example 6: bis-difufuryl
rfuryl) dimer acid ester Henkel (He in Cincinnati, Ohio, USA
nkel) One mole of hydrogenated timer acid EMPOL 1008, commercially available from Corporation, is reacted with a catalytic amount of furfuryl alcohol (2.2 moles) and 12N hydrochloric acid to convert to bis difurfuryl ester. The excess furfuryl alcohol is removed by vacuum distillation, leaving a clear to amber yellow residue. This material acts as a diene on the Diels-Alder reaction product and is subsequently prepared into a phase change ink.

Example 7: Formulation of a bis-acrylate ester of a polymeric colorant. One mole of the yellow colorant "A" in Table I of US Pat.
Treat with equivalents. This reaction is affected by heating and the evolution of methanol to give a diacrylate derivative of an alkyleneoxy substituted colorant. The excess methyl acrylate is removed in vacuo to produce a dark yellow material suitable as a dienophile reactant in the Diels-Alder type chemistry of the present invention.

Example 8: Formulation of Bisacrylate Esters of Epoxy Resins The material defined in column 5 of US Pat. No. 4,310,644 is rated as a dienophile for Diels-Alder products useful in phase change inks. Thermal and mechanical stability, chemical resistance, tackiness and reactive sites can be applied to obtain excellent performance phase change inks.

The bisphenol A is reacted with 2 equivalents of ethylene oxide and the subsequent 10 equivalents of propylene oxide. A further 6 equivalents of ethylene oxide are added to the alkoxylated material. The reaction with catalytic KOH is carried out in anhydrous toluene at a temperature suitable for carrying out the reaction. The hydroxyl number of this reaction material ranges from 104 to 115. This material is treated with two equivalents of glycidyl chloride in the presence of sodium acetate. Under reduced pressure, the material is filtered and stripped to produce bisphenol A alkoxylated glycidyl ether. This ether reacts with two equivalents of acrylic acid to form a bisacrylate derivative suitable as the dienophile reactant of the present invention.

Example 9 Preparation of Diels-Alder Adducts from Reaction of the Products of Examples 6 and 8 Heated to 110 ° C. for 2 hours in a stainless steel beaker with mechanical stirring function To complete the theoretical reaction of the dienophile of Example 8 and the diene of Example 6. The polymer material, ie, the result of the Diels-Alder polymerization reaction, is used to formulate an ink base suitable for use in a phase change ink.

Example 10: Phase Change Ink-Based Formulation Approximately 25% by weight of the Diels-Alder-Adducts of Example 9 and Tektronix US Pat.
About 25% by weight of the urethane / urea resin made by the procedure of Example 4 of 784966, about 50% by weight of stearyl stearamide, and 2% by weight of the antioxidant of Uniroyal Naugard 445. Prepare a phase change ink base. These components are combined to form an ink base according to the standard methods described above.

Example 11: About 35 grams of Cyan Ink Millijet Blue 28 containing a thermally reversible polymer and 500 grams of the clear ink base of Example 10 containing Diels-Alder Adducts. , Prepare cyan ink. This ink is processed and prepared according to standard procedures, and is manufactured by Tektronix Phasor Color Co., Ltd.
Generate a solid ink stick for testing on the printer. The properties of the print head operation, the transfer fixation process, and the final printed product exhibit additional properties that are attributed to the presence of the thermally reversible polymer.

Example 12: Yellow ink prepared from the dienophile Diels-Alder-Adducts and a diene resin. The dienophile yellow bisacrylate ester prepared in Example 7 was prepared in Example 6. A yellow phase change ink is prepared by blending a diene resin with a stoichiometric ratio. Heat the mixture to 100 ° C. for about 1 hour,
Produce a thermally reversible polymer material. About 25% by weight of this yellow colored polymer is about 50% by weight of stearyl stearamide (US Pat. No. 57).
An ink is prepared by combining about 25% by weight of the urethane / urea resin (described in Example 4 of No. 82966). In addition, about 2% by weight of the antioxidant of Uniroyal Nowgard 445 is added. According to the standard procedure described above,
The ink is processed and rated.

Example 13: Formulation of a diene-containing yellow ink for use in bonding with a dienophile added to a sacrificial print layer. About 5% by weight (about 5% by weight) of Milliken Chemical Yellow 869; About 50% by weight of stearyl stearamide and about 25% by weight of the diene described in Example 6
And Example 4 of US Pat. No. 5,782,966.
About 25% by weight of the urethane / urea resin described in
A phase change ink is prepared by mixing about 2% by weight of Uniroyal Nowgard 445 antioxidant. The sacrificial silicone oil used as the intermediate transfer surface in the transfer fixation process is formulated with 0.5 to 5% by weight of the bisphenol-based dienophile of Example 8. The ink is printed using the drum of a Tektronix Phaser 350 type phase change color printer prepared with dienophile-containing silicone oil. Upon contact with the heated drum, the ink / oil system reacts to produce a polymeric material. It is mainly located at the ink-oil interface. By transferring and fixing this image to the substrate, a polymer material is formed on the print surface. This material gives the substrate the desired mechanical properties (durability), as assessed by standard procedures.

Example 14: Preparation of N stearyl maleimide 1.05 equivalents of maleic anhydride and stearyl amine (1) at 90 ° C for 2.5 hours in an inert atmosphere.
Equivalent) to produce N stearyl maleimide. This material is used as a chain stopper in the phase change inks of the present invention to control the molecular weight of Diels-Alder Adducts. While the maleimide derivative is a dienophile, it does not have the bis-functionality required to form the Diels-Alder reaction polymer of the present invention, so it acts as a chain terminator. Stearyl maleimide is adjusted to be infinitely soluble in the phase change ink base.

Example 15: N, N7-bis-maleimide Jeffamine D-2000 1 mol of Jeffamine D-2000 was added to Amoc (Amoc).
o) Maleic anhydride commercially available from Chemicals
The reaction is carried out with one equivalent at 90 ° C. for 2.5 hours in an inert atmosphere. The reaction is monitored by FTIR to ensure that all free amide functionality is converted to bisimide.

This material acts as a dienophile capable of chain extension polymerization in a thermally reversible Diels-Alder reaction. In addition, the soft alkoxyl section of the Jeffamine component imparts elastomeric properties to the initial Diels-Alder polymer. The choice of different MW Jeffamine diamine can tailor the physical properties of the desired ultimate polymer.

Example 16 Use of Dienophiles with Variable Reaction Limits and Preparation for Phase Change Inks Propoxylated Allyl Methacrylate (CD-513) (Sartomer, Exton, PA, USA) (Commercially available from The Company) with the diene of Example 6 to produce a polymer material suitable for phase change ink preparation. About 25% by weight of Diels-Alder-Adducts
And a urethane / urea resin (US Patent No. 57
And about 50% by weight of stearyl stearamide (available from Witco Chemical Company, Memphis, Tenn., USA) and about 50% by weight of Naugard 445. An oxidizing agent (available from Uniroyal Chemical Company of Oxford, Conn., USA) is compounded with 2% by weight) to formulate the phase change ink. These components are combined to form an ink base for use in the standard methods described above. This ink
The base is formulated with Acid Red 52 (1.5% by weight) to produce a magenta colored phase change ink.

Example 17: Commercial Phasor 340 Ink Modified by Thermally Reversible Diels Alder Adduct Commercial Tektronix Phasor 340 Type Ink Stick (6 pieces, each about 40 grams) Are melted at 125 ° C. in a stainless steel beaker. To this are added, as theoretical amounts, the dimer acid based diene of Example 6 and the dienophile prepared in Example 14. The total mass of these two reaction components is about 80
Equal in grams. An additional amount of dye is added to maintain spectral intensity. The modified ink is processed according to standard procedures, with mechanical stirring of the modified ink at the temperatures described above for about one hour. This new ink formulation, compared to inks without the Diels-Alder thermoreversible reactant,
The durability characteristics are improved.

Example 18: Preparation of polymer dienophile from Jeffamine D-2000 and diacetone acrylamide Ketone compound part of diacetone acrylamide (2.05
Equivalent. Jeffamine Diamine D-2000 (available from Huttsman, Houston, Texas, USA) was obtained from Kyowa Hakko USA, Inc., New York, NY.
US Patent No. 46651 assigned to DeSoto Incorporated, Des Plaines, Ill., United States of America.
Experimental procedure described in No. 46). The reaction is monitored by the disappearance of the ketone component in the infrared spectrum and the appearance of the imine absorption band. Continuous azeotropic removal of water with toluene provides an equilibrium for this reaction. The final product contains the reactive acrylamide units from the Diels-Alder polymerization reaction described above with respect to the present invention.

The values for this material can vary widely. Acrylamide bonds are important for their thermal stability,
It is known for its ability to hydrogen bond to substrates (paper). Furthermore, when used as a dienophile in the above described invention, the resulting polymer becomes biodegradable by hydrolysis of the imine functionality. The polymer is
Stable in non-aqueous phase change ink formulations. By hydrolyzing the Diels-Alder polymer, inks printed with these inks can be recycled.

2,5-furandimethanol (furandimet)
Preparation of a cross-linked (cross-linked / cross-linked) diene by the reaction of furanol, furfuryl alcohol and a dibasic fatty acid. Aldrich, Milwaukee, AL
drich) (available from Chemical Company) to give intermediates for further reaction. This material is treated with 2 moles of furfuryl alcohol (available from Ashland Chemical Company of Columbus, Ohio, USA) to give a diene component having reactive sites at the ends and center of the molecule. The central diene is available for cross-linking or to make dendrimeric polymers from the Diels-Alder chemistry of the present invention.

Example 20: The dienophile of Example 18,
Formulation of yellow phase change ink from diene of Example 19 and yellow polymer colorant dienophile of Example 7 Formulation of dienophiles of Examples 18 and 7 in Example 19 with stoichiometry based on diene and dienophile content And the yellow phase change ink. The mixture is reacted at 90 ° C. for 1 hour in an inert atmosphere to produce a yellow polymer. About 25% (about 25%) by weight of the yellow colored polymer.
Wt.) To about 50 wt.% Of stearyl stearamide (Kemami, available from Witco Chemical Company of Memphis, TN, USA).
de) S-180) and about 25% by weight of a urethane / urea resin (described in Example 4 of U.S. Pat. No. 5,782,966) to form an ink. Also add about 2% by weight of Nowgard 445 antioxidant (available from Uniroyal Chemical Company, Oxford, Conn., USA). The ink is processed and rated according to the standard procedures described herein. The additional cross-linking ability of the diene gives the ink improved physical properties. Since a mixed dienophile system is generally appropriate, a different stoichiometric amount of dienophile is treated with a mixture of dienes to obtain a phase change ink component of the resin.

Although the present invention has been described with reference to specific embodiments, various modifications can be made without departing from the spirit of the invention.

[0104]

As described above, according to the phase change ink carrier composition of the present invention, it has a small molecular weight and a low viscosity in a liquid state, and is thermally reversible between a liquid state and a solid state. It has the properties of a polymer in the solid state.

 ──────────────────────────────────────────────────の Continued on front page (72) Inventor Michael B. Minehart 97306 Oregon, USA 97306 Serham South East Springwood Avenue 5541

Claims (9)

[Claims] 1. A composition comprising a component selected from the group consisting of a thermally reversible Diels-Alder polymerization reaction product, a Diels-Alder polymerization precursor, and mixtures thereof, wherein the temperature is between about 90 ° C and at least about 160 ° C. It becomes a low-viscosity liquid at a temperature in the range, and becomes a highly viscous malleable substance at a temperature in the range of about 40 ° C. to about 80 ° C.
A phase change ink carrier composition characterized by becoming a solid at a temperature below. 2. The phase change ink carrier composition according to claim 1, wherein the reaction product comprises a polymer formed by a Diels-Alder reaction between difurfuryl adipate and bismaleimidodiphenylmethane. 3. The phase change ink carrier composition of claim 1, wherein said Diels-Alder polymerization precursor comprises a bisdiene. 4. The Diels-Alder-reacted bisdiene has 5- to 8-membered rings containing conjugated dienes, wherein all of these ring portions are carbon or carbon and nitrogen, oxygen, sulfur 4. The phase change ink carrier composition according to claim 3, wherein the composition is a mixture with a heteroatom selected from a mixture thereof. 5. The phase change ink according to claim 1, further comprising at least one amide compound.
Carrier composition. 6. The phase change ink carrier according to claim 1, further comprising at least one compound selected from the group consisting of urethane resins, urea resins, mixed urethane / urea resins, and mixtures thereof. Composition. 7. The phase change ink carrier composition of claim 1, further comprising a Diels-Alder precursor that is a bisfurfuryl ester. 8. The phase change ink carrier composition according to claim 1, further comprising a Diels-Alder precursor, which is a diacrylate derivative of an alkylene oxide-substituted colorant. 9. The phase change ink carrier composition according to claim 1, further comprising a Diels-Alder precursor which is a reaction product of propoxylate allyl methacrylate and bisfurfuryl ester.