Cold pressure fix toner compositions based on crystalline polyester and amorphous organic compound mixtures

SECRETARY OF ECONOMY

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IMPI

GE MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

2021: Year of Independence

PATENT TITLE No. 378665

<td>Headlines):</td><td>XEROX CORPORATION</td>

<td>Home:</td><td>45 Glover Avenue, Norwalk, Connecticut, 06856-4505, USA</td>

<td>Denomination:</td><td>COMPOSITIONS OF ORGANIC PIGMENT FOR COLD PRESS FIXATION BASED ON CRYSTALLINE POLYESTER AND MIXTURES OF AMORPHOUS ORGANIC COMPOUNDS.</td>

<td>Classification:</td><td>CIP: G03G9/087; C08L21/02; G03G9/00; G03G13/20 CPC: G03G9/08755; C08L21/02; G03G9/00; G03G9/0821; G03G9/08775; G03G9/08797; G03G13/20</td>

<td>Inventor(s):</td><td>RICHARD PHILIP NELSON VEREGIN; KENTARO MORIMITSU; GUERINO G. SACRIPANTE; KE ZHOU; NAN-XING HU</td>

REQUEST

<td>Number: Filing Date: MX/a/2016/008592 June 28, 2016</td><td>Hour: 13:47</td>

PRIORITY

Country: US

Date: July 17, 2015

Number:

14/802,932

Validity: Twenty years

Maturity Date: June 28, 2036

Issue Date: January 6, 2021

The reference patent is granted based on articles 1^either, 2^either fraction V, 6^either section III, and 59 of the Industrial Property Law.

In accordance with article 23 of the Industrial Property Law, this patent is valid for twenty years, non-renewable, counted from the date of filing of the application and will be subject to the payment of the fee to keep the rights in force.

Whoever signs this title does so based on the provisions of articles 5^either section I, 9, 10 and 119 of the Federal Law for the Protection of Industrial Property; items 1^either, 3^either fraction V item a), sub item i), 4^either and 12th sections I and III of the Regulations of the Mexican Institute of Industrial Property; items 1^either, 3^either, 4^either, 5^either section V item a), sub item ii), 16 items I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property; 1^either, 3^either and 5^either section I and antepenultimate paragraph of the Agreement Delegating Powers of the Mexican Institute of Industrial Property.

This electronic document has been signed through the use of the advanced electronic signature by the competent public servant, protected by a digital certificate in force at the date of its preparation, and is valid in accordance with the provisions of articles 7 and 9 section I of the Advanced Electronic Signature Law and article 12 of its Regulations. Its integrity and authorship can be verified at www.qob.mx/impi.

Likewise, it was issued in accordance with the provisions of articles 1^either fraction III; two^either fraction VI; 37, 38 and 39 of the Agreement establishing guidelines on Electronic Services of the Mexican Institute of Industrial Property.

DIVISIONAL DEPUTY DIRECTOR OF SUBSTANTIVE EXAMINATION OF PATENT AREAS BIOTECHNOLOGY, PHARMACEUTICAL AND CHEMICAL

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EMELIA HERNANDEZ PRIEGO

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in

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

COMPOSITIONS OF ORGANIC PIGMENT OF PRESSURE FIXATION IN

COLD BASED ON CRYSTALLINE POLYESTER AND MIXTURES OF COMPOUNDS

AMORPHOUS ORGANIC

FIELD OF THE INVENTION The present description is organic pigment compositions for

In particular, cold compositions.

use relates to in xerography.

The present description relates to pressure-fixing organic pigment in

BACKGROUND OF

INVENTION

Cold-press fixation organic pigments typically work in a system that uses a pair of high-pressure rollers to fix organic pigment to paper, without heating.

Among the advantages of these systems is the use of little energy and little heating of the paper. An example of a pressure setting organic pigment in polyamide softening cold copolymer

An example of an American organic present such as comprises ethylene-acetate of a

Nope.

99°C solution point

4,935,324, reference.

predominantly a vinyl polymer with wax, thermoplastic softening point which is shown

Another is in the incorporates example of a a of

120°C

patent in the cold-press fixation pigment is made of

Ref. No.: 266641

IMPI £

is a copolymer of styrene with l-tert-butyl-2-ethenylbenzene and a polyolefin wax exemplified, for example, as Xerox 4060 organic cold-press setting pigment.

Other cold-fixing organic pigments have been based on a long-chain acrylate core produced by suspension polymerization, such as lauryl acrylate.

Examples of these compositions are described in US Patent Nos.

5,013,630 and 5,023,159, which are incorporated herein by reference.

These systems are designed to have a core with a

Tg less than room temperature.

A hard coating, eg polyurethane prepared by interfacial polymerization, is placed around the core in order to keep the liquid content in the core in the organic pigment particle.

Performance issues with high wax content designs include operating only at high pressure, for example at approximately 14 MPa (2000 psi) even 28 MPa (4000 psi), which are respectively

140 kgf/cm² and 280 kgf/cm² and even image robustness can be poor. In the case of long chain acrylate core designs the coating needs to be very thin to rupture under pressure, but it can be very challenging to prevent capsules from leaking as the core is usually liquid at room temperature.

£ in

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

SUMMARY OF THE INVENTION

In some aspects, embodiments herein relate to cold-press-setting organic pigment compositions comprising at least one crystalline polyester material having a melting point in a range from about

30°C to approx.

130°C and at least one C16 to C80 amorphous organic material having a Tg of from about

-30°C to approximately 70°C.

In other aspects, embodiments herein relate to methods of applying cold-press setting organic pigment comprising providing a cold-press setting organic pigment composition comprising at least one crystalline polyester material having a melting point in a range from about

30°C to approx.

130°C and at least one ester of C16 to C80 amorphous organic material having a Tg of from about 0°C to about

60°C, place the organic cold-press setting pigment composition on a substrate and apply pressure to the composition placed on the substrate under cold-press setting conditions.

In still other aspects, the embodiments herein relate to latexes formed from a pressure-setting organic pigment composition£

IMPI's

cold forming comprising at least one crystalline polyester having a melting point in a range from about

30°C to approx.

130°C and at least one amorphous C16 to C80 rosin ester having a

Tg from about -30°C to about 60°C.

BRIEF DESCRIPTION OF THE FIGURES

Various embodiments of the present description will be described in the following with reference to the figures.

where:

Figure 1 shows a Shimadzu flowmeter plot with temperature for an exemplary blend of crystalline distearyl terephthalate ester and an amorphous SYLVARES polyterpene resin.^MR TR A25

79/21% cold.

in a weight ratio for pressure fixing application low pressure kgf/cm², the transition temperature to reach a viscosity of 10⁴ Pa-s is 77°C, while a high pressure

0 kgf/cm², the transition temperature to reach a viscosity of 10⁴

country is

38°C

The shift in transition temperature to reach a viscosity of 10⁴ Pa-s is 39°C between a pressure of 10 kgf/cm² and 100 kgf/cm².

Figure 2A shows Shimadzu flowmeter transition temperatures for an exemplary mixture of a variable crystalline amorphous ester of distearyl terephthalate with a Tg for different organic materials.

IMPI £

OI small amorphous molecules in a ratio of 79/21% by weight.

Transition temperatures are shown to reach 10⁴

Pa-s kgf/cm²,

100 kgf/cm² and the difference in transition temperatures to reach 10⁴ Pa-s at 10 kgf/cm² less than 10kgf/cm².

Figure 2B shows a plot with the same materials as in Figure 2A and transition temperatures as in Figure 1, but showing the effect of different

Ts of the different small amorphous molecules.

Figure 3 shows Shimadzu's results for an exemplary blend of a crystalline polyester polymer with an amorphous small molecule polyterpene resin.

SYLVARES^ TR A25 in a ratio of 79/21% by weight.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments herein provide organic cold-press setting pigments comprising at least one crystalline organic compound which may be a small molecule or an organic polymer, either organic molecule.

which attaches small organic amorphous or

The components with at least one crystalline amorphous oligomeric resin are bonded by mixing to provide a material that undergoes a phase change from solid to liquid at a modest temperature, such as about 20°C to about 70°C at a pressure as low as 25 kgf/cm² at approx £100

IMPI kgf/cm² about 400kgf/cm².

In embodiments, organic cold-press setting pigments are provided which comprise at least one crystalline small molecule, eg a crystalline small molecule ester, for example, and at least one amorphous organic molecule or resin composition, or in embodiments at least one amorphous organic small molecule or organic oligomeric resin composition.

Small crystalline and amorphous molecules come together by mixing to provide a material that undergoes a phase change from solid to liquid at modest temperature, say about

20°C to about 70°C a pressure as low as kgf/cm² about

100 kgf/cm² about

400 kgf/cm².

In some embodiments, the organic cold press setting pigments may comprise a solid ink pattern used in solid ink jet printing.

Although solid inkjet inks typically operate by heating above 100°C, it has surprisingly been found that under pressure these materials exhibit desirable flow at near room temperature and are therefore ideal for organic fixation pigment applications. by cold pressure.

In embodiments, organic cold-press fixation pigments are provided which comprise at least one crystalline polyester resin of at least one £

in

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY Amorphous organic small molecule or an organic oligomeric resin composition.

The crystalline polyester resin and small amorphous molecules bind by mixing to provide a material that undergoes a phase change from solid to liquid at modest temperature, for example about 20°C to about 70°C at pressure as low as kgf/ cm² about

100 kgf/cm² about 400kgf/cm².

small

As used herein, an oligomeric molecule or resin has less than about 100 carbon atoms and less than about 100 combined carbon and oxygen atoms.

In embodiments, organic pigment cold-pressed fixing compositions are provided that comprise at least one crystalline organic material, for example a crystalline ester or such as a crystalline polyester, having a melting point in a range from about

30°C to about 130°C and at least one Cie to Cso amorphous small molecule or one oligomeric having one from about resin

-30°C to approximately 70°C.

In embodiments, cold-press setting organic pigment compositions are provided comprising at least one Ci6 crystalline organic material, such as a crystalline ester, having a

IMPI £

Ul melting point in a to about range from about 30°C

130°C and po^r at least one amorphous molecule or resin having a Tg of from about

-30°C to about 70°C, or in embodiments at least one small amorphous molecule of Ci₆ a Ceo or oligomeric resin having a

Tg from approx.

30°C to about 70°C.

small

As used herein, a molecule refers to an organic compound, that is, one that contains at least carbon and hydrogen atoms and has

1,500 a molecular weight less than 2,000 daltons, daltons

500 daltons.

organic organic substrate material less than less than

1,000 daltons less than

As used herein, a pigment

CPF pigment cold-press fixation refers to an organic pigment designed for application to a and which is fixed to the substrate primarily by application using pressure.

Although heating can optionally be used to aid in the fixation of a CPF organic pigment, a benefit of the compositions described herein is heating heating.

is the ability to use reduced or, in modalities, without applying fixation for application of pressure can be obtained by a wide range of pressures, such as by r

£

IMPI example from about 50 kgf/cm² to approximately

100 kgf/cm² at about 200 kgf/cm². If necessary, it is possible to use higher pressures up to approx.

00 kgf/cm²however, these high pressures are generally undesirable, causing calendering and even corrugating of the paper which distorts the look and feel of the paper and requires more robust pressure setting rollers and spring assemblies.

In embodiments, the CPF organic pigment comprises at least one crystalline ester.

In some of these embodiments, the organic pigment

CPF comprises a crystalline diester.

In embodiments, it comprises a substituted.

ester of at least one crystalline benzyl phenyl ester optionally

In embodiments, the at least one crystalline ester comprises distearyl terephthalate (DST).

In embodiments, suitable crystalline esters can be diesters from about Ci6 to Ceo / with melting points ranging from about 30°C to about 130°C, such as those shown in the examples below in Table 1.

In embodiments, it may be desirable to incorporate one or more acid groups, such as carboxylate or sulfonate, into these materials to provide a negative charge to enhance the performance of the organic pigment.

These groups £

σ> σ> σι

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY Acids may also be useful so that the materials can be used in organic pigment processing by emulsion/aggregation.

In embodiments, the acid moiety can be placed at any position on aromatic residues of the compounds in Table 1. In other embodiments, the acid can be provided by including some amount of monoester in place of the diester so that one end of the molecules contain an acid portion.

TABLE 1 structure

Tf usion (“O

IT crys (°C) 47g (°C) n/a

115 n/an/a

102 n/an/a £

IMPI n/an/a

127 n/a

20-26 na

100 n/an/a

119 n/an/a £

H₃C(H₂c)

H₃C(H₂c)

in compounds

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Ü1

80, na

OH n/an/a (CH₂) Yo₇CH “DST” n/an/an/a (CH₂)₂₁CH₃ “DBT”n/a

110 n/

Oh "DPT" modalities, diester the crystalline compound are made from Reaction Scheme 1 below.

IMPI £

yes

REACTION SCHEME 1 catalyst

R—OH + 2H₃CO

OCR wherein is a saturated ethylenically unsaturated aliphatic group in one embodiment with at least about 6 carbon atoms, and in another embodiment with at least about 8 carbon atoms, and in one embodiment with no more than about

100 carbon atoms, in another embodiment with no more than about 80 carbon atoms, and in a further embodiment with no more than about 60 carbon atoms, although the number of carbon atoms may be outside these ranges. In a specific embodiment, the crystalline compound is derived from naturally occurring fatty alcohols such as octanol, stearyl alcohol, lauryl alcohol, behenyl alcohol, myristyl alcohol, and the like.

capric alcohol,

The above linoleyl alcohol reaction can be carried out by combining dimethyl terephthalate and alcohol in the melt, in the presence of a tin catalyst, such as dibutyltin dilaurate (Fascat

4202), dibutyltin oxide (Fascat 4100);

a zinc catalyst such as Bi cat

Z, example Bi cat 8124;

a bismuth catalyst

Bi cat 8108, as per a titanium catalyst £

IMPI such as titanium dioxide.

Only trace amounts of catalyst are required for the process.

In embodiments, the catalyst is present in an amount of from about 0.01 weight percent to 2 weight percent or from about 0.05 weight percent to about 1 weight percent of the total product.

The reaction can be carried out at an elevated temperature of from about 150°C to about 250°C or from about

160°C solvent-free is approx.

210°C.

The process is environmentally sustainable and eliminates by-product problems and also means higher reactor throughput.

In embodiments, the crystalline component may have a structure of formula A:

-0 pi ' where pi is approximately approximately qi is approximately approximately

40.

In certain embodiments, pl is from about 8 to about 26, from about 14 to about about .

In certain modalities, qi is from about 8 to about 26, from about 14

IMPI £

approximately approximately approximately 18.

In certain embodiments, pl is the same as ql.

Yes

In embodiments, the crystalline component is present in an amount of from about 95 percent by weight, from about 60 percent to about 95 percent by weight, or from about 65 percent to about 95 percent by weight, or from about 70 percent to about 90 percent by weight of the total weight of the CPF organic pigment composition.

Typically crystalline about about the same as

50:50

60:40 weight ratio of the amorphous component component is about about

95:5,

95:5 is from about 70:30 to about 90:10.

In embodiments, the crystalline component is a polyester resin.

Examples of diols can be prepared by crystalline polyester resins from organics which diacid is a diol.

select for

The preparation of crystalline polyester resins include aliphatic diols with from about to about 36 carbon atoms, such as

1,2- ethanediol,

1,3-propanediol,

1,4-butanediol,

1,5-pentanediol,

1,6- hexanediol,

1,7-heptanediol,

yes

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

1,8- octanediol,

1,9-nonanediol,

1,10-decanediol,

similar 1,12-dodecanediol;

alkali metal sulfo- or aliphatic diols such as sodium 2-sulfo-l,2-ethanediol,

2-sulfo-l,2-ethanediol

Potassium 2-sulfo-1,2-ethanediol,

sodium 2-sulfo-l,3-propanediol,

Lithium 2-sulfo-l,3-propanediol,

Potassium 2-sulfo-1,3-propanediol, similar mixtures thereof.

The aliphatic diol is selected, for example, in an amount of from about 45 to about 50 mole percent of the resin, the alkali aliphatic sulfo diol can be selected in an amount of from about 1 to about 10 mole percent of the resin.

Examples of selected organic diester diacids for the preparation of the crystalline polyester resins include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, italic acid, isophthalic acid, naphthalene- 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid and mesaconic acid, a diester or anhydride thereof; and an alkaline sulfo-organic diacid such as sodium, dimethyl, natalic italate, lithium or potassium salt of 5-sulfo-isophthalate dialkyl, dimethyl, anhydride

5-sulfo-isophthalate-4-sulfo-l,8 acid

4-sulfo-italic,

4-soulium italate

-sulfodialkyl, £

IMPI

4-sulfophenyl-3,5-dicarbomethoxybenzene,

6-sulfo-2-naphthyl-3,5-dicarbometh-oxybenzene, sulfo-terephthalic acid, dimethyl sulfo-terephthalate, acid

5-sulfo-isophthalic, dialkyl sulfo-terephthalate, sulfo-p-hydroxybenzoic acid, dialkyl sulfonate

N,N-bis(2-hydroxyethyl)-2-aminoethane or mixtures thereof.

The organic diacid can be selected in an amount, for example, from about 40 to about 50 mole percent of the resin and the alkali aliphatic sulfo diacid can be selected in an amount from about 1 to about 10 mole percent of the resin. resin.

As an example, crystalline 1,12-dodecanedioic acid resins have been prepared with diols starting from C3 (1,315 propylene glycol)

C12 crystalline polyesters (1,12-dodecanediol) with one to provide

Tm from approx.

60°C to about 90°C.

The properties of the crystalline polyesters used in connection with the embodiments herein are shown in Table 2 below.

Acid ID: diol

TABLE 2

av

tm

GPC resin

mg

KOH/g (°C) lst

C12:C9

10.3

C12:C6

14.5

72.3

C12: C3

66.1g/m X 1000

MW

24.2

14.3

13.4

min

6.1

6.6

Organic pigments for pressure fixing £

Cold IMPI comprised of a mixture of a crystalline polyester resin with a melting point of about 30°C about 90°C, and at least one mono-, di-.

amorphous tetra-ester, including rosin esters, based on glycerol, propylene glycol, dipropylene glycol, tartaric acid, citric acid, or pentaerythritol, or a terpene oligomer, with from about 16 to about carbons, with a

Tg from approx.

0°C to about 40°C.

In embodiments, the crystalline polyester can have an acid value of from about 6 to about 30, a

Mn from about 1,000 to about 10,000, and Mw from about 2,000 to about 30,000.

Organic pigments can be prepared by any means, including conventional extrusion and milling, suspension,

SPSS, incorporated in an organic pigment of

N-Cap, incorporated in an EA organic pigment, optionally with a coating.

Latexes can be prepared, by, but not limited to, solvent distillation or phase inversion emulsification, including by solvent-free methods.

In embodiments, the cold-press setting organic pigment composition comprises at least one ester with rosin or of rosin which may be

IMPI £

ΟΊ based on mono-, tetra-ester on an alcohol such as methanol, glycerol (1,2,3-trihydroxypropane), diethylene glycol, dipropylene glycol, ethylene glycol, propylene glycol, menthol, neopentyl glycol, pentaerythritol (2,2-bis(hydroxymethyl) 1,3-propanediol), and an acid, for example tartaric acid, oxalic acid, succinic acid, suberic acid, maleic acid, with phenol acid, tert-butylphenol, citric acid, glutaric acid, azelaic acid, adipic acid, fumaric acid, dodecanedioic acid and sebacic acid.

Suitable rosin esters include, without limitation, those with about about carbon atoms, including those with a number average molecular weight Mn of from about 300 to about 1200, and with a weight average molecular weight of

Mw from about 300 to about 2000.

Suitable rosins have, without limitation, acid about

Asters with a number of approximately

300.

Optionally, monoesters, including monoesters with some acid functionality, may be incorporated, including rosin acids with an acid value of about 400.

synonymous Rosin,

These

As used herein, an ester with rosin ester refers to rosin acids that have been esterified.

rosin acids may include resinous acids

IMPI £

OI as found naturally exuded by various species of trees, mainly pine and other conifers.

Rosin can be separated from essential oil spirit or turpentine by distillation.

Tall oil rosin is produced during the distillation of crude tall oil or by side production from the kraft papermaking process. Additionally, landfill waste from pine trees can be distilled or solvent extracted to separate rosin, which has been referred to as wood rosin. The rosin used in the rosin ester may be partially or fully hydrogenated to remove some or essentially all of the double bonds from the rosin, resulting in a lighter color and significantly improved stability of the rosin and rosin ester. rosin.

As an example, abietic acid can be partially dehydrogenated to form dihydroabietic acid, it can be completely dehydrogenated to form tetrahydroabietic acid.

Again, it may be desirable to incorporate some acid groups into the cold-setting organic pigment materials in the amorphous component to provide a negative charge for organic pigment performance and emulsion/aggregation processing.

of

For pigment these organic purposes a certain amount of the amorphous material that has had a free acid end, instead of terminating in an ester, can be used.

alternative.

some of the ester groups substituted by ester groups with acid functionality.

They're available

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

So they can be additionally include

Suitable rosin esters commercially include ABALYN^MR, a rosin methyl ester,

PENTALYN^MR, a pentaerythritol ester of rosin,

PEXALYN^MR 9085, a glycerol ester of rosin,

PEXALYN^mr T, a pentaerythritol ester of rosin, PINOVA^MR

Ester Gum 8BG, a glycerol ester of rosin, FORAL^MR 85, a hydrogenated glycerol ester of rosin, FORAL^MR 105, a pentaerythritol ester of hydroabietic acid (from rosin),

STATUTORY^MR

3085, a hydrogenated glycerol ester of rosin,

HERCOLYN^MR D, a hydrogenated rosin methyl ester,

PENTALY^

H, a pentaerythritol ester of rosin, all commercially available from Pinova; ARAKAWA^MR Ester Gum G.

ARAKAWA^MR Ester Gum

ARAKAWA^MR Ester Gum AAV ARAKAWA^MR Ester Gum AT commercially available rosin esters from

arakawa

chemicals

Industries,

Ltd., ARAKAWA^MR Ester Gum HP, ARAKAWA^MR Ester Gum

H,

ARAKAWA^MR Ester Gum HT commercially available hydrogenated rosin esters from Arakawa Chemical

Industries,

Ltd.,

ARAKAWA^MR

S-80,

ARAKAWA^MR

S-100,

ARAKAWA^MR

S-115,

ARAKAWAMR a-75,

ARAKAWAMR A-10 0,

ARAKAWA^MR A-115,

ARAKAWAMR

A-125,

ARAKAWAMR

L,

ARAKAWA^MR

A-18 commercially available stabilized rosin esters from Arakawa Chemical £

IMPI

Industries,

Ltd.;

ARAKAWA^MR resins

KE-100, hydrogenated abietic acid triglycerides (from rosin) commercially available from Arakawa Chemical

Industries,

ARAKAWA^MR KE - 3 5 9, a hydrogenated rosin ester

ARAKAWA^MR D-6011, a commercially available disproportionate rosin ester from Arakawa

chemicals

Industries,

Ltd.; and SYLVALITE^MR

RE 10L, SYLVALITE^MR RE 80HP, SYLVALITE^MR

RE 85L, SYLVALITE^MR RE 100XL, SYLVALITE^MR RE 100L, SYLVALITE^MR

RE 105L, SYLVALITE^MR RE 110L. SYLVATAC^MR

RE 25,

SYLVATAC^MR RE 40,

SYLVATAC^MR RE 85,

SYLVATAC^MR RE 98, all available from Arizona Chemical; and PERMALYN^MR 5095, a glycerol ester of rosin, PERMALYN^MR 5095-C, a glycerol ester of rosin,

PERMALYN^MR

5110, a pentaerythritol ester of rosin,

PERMALYNMR_TM 5110-C, a pentaerythritol ester of rosin,

PERMALYN^MR₆₁₁₀ a pentaerythritol ester of rosin,

PERMALYN™ 6110-M, a pentaerythritol ester of rosin,

PERMALYN™ 812 0, a pentaerythritol ester of rosin,

STAYBELITE^MR Ester

3-E of a partially hydrogenated rosin ester,

STAYBELITE^MR

Ester 5-E of a partially hydrogenated rosin ester and

STAYBELITE™ Ester 10-E, a partially hydrogenated rosin ester all available from Eastman Kodak; and ARAKAWA^MR

ESTER

E-720

SUPER

ESTER

E-730-55 commercially available rosin ester latex from

arakawa

chemicals

Industries, Ltd. Table 3 shows examples of other asters

IMPI £

Yes amorphous suitable for organic cold press setting pigments described herein.

TABLE 3 structure

Tfusion

crys

Tg

OH (°C) (°C) (°C)

TMC mixtures of suitable limit

ooh

ooh

DMT

ooh

ooh

TBCT

Other amorphous materials include other rosins rosin esters.

n/an/an/an/an/an/a modified molecule

Examples of small do not know other suitable small molecule amorphous modified rosins

IMPI £

They do include UNI-TAC^MR 70 commercially available from

Arizona

Chemicals, and ABITOL^MR E, a hydroabiethyl alcohol commercially available from Eastman Kodak;

and POLY-PALE^MR, a commercially available dimerized rosin from Eastman Kodak.

Other suitable small molecule amorphous materials include terpene resins, for example resins from α-pinene including PICCOLYTE^MR A25,

PICCOLYTE^MR

A115, and PICCOLYTE^MR Pinova Al25;

and β-pinene resins.

PICCOLYTE^MRS25, PICCOLYTE^MR S85, PICCOLYTE^MR S115, and PICCOLYTE^MR

s125 gauge

Pinova;

d-limonene resins, including

PICCOLYTE^MR C85, PICCOLYTE^MR C105, PICCOLYTE^MR C115, PICCOLYTE^MR

C115,

PICCOLYTE^MR Pinova D115; and mixed terpene resins such as PICCOLYTE^MR F105 IG and PICCOLYTE^MR F115 IG's

Pinova;

and others

SYLVARES^MR TR A2 5,

SYLVARES^MR

TR resins

7125, based on terpenes that

SYLVARES^MR TR B115,

SYLVAGUM^MR

TR

90, include

S YLVARES^MR TR 7115,

SYLVAGUM^MR

TR

105,

ZONATAC^MR NG 98 a styrene-modified terpene resin from Arizona Chemicals; and synthetic polyterpene resins for example NEVTAC^MR 23 00,

NEVTAC^MR 100, and NEVTAC^MR 80 commercially available from Neville Chemical Company;

PICCOLYTE^MR

HM106

Ultra, a d-limonene styrenated polyterpene resin from Pinova; and hydrogenated terpene resins such as CLEARON^MR P115,

CLEARON*® P105,

CLEARED^MR p85 gauge

Yasuhara Chemical Co.,

Ltd.; hydrogenated aromatic modified terpene resins such as CLEARON^MR MI 15, £

CLEARED^MR MIO 5, CLEARON*® K10 0,

CLEARED^MR K4100,

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY TO115 aromatic modified terpene polymer YS resin, YS resin

Ü1

TO105, YS resin TO85, YS TR105 resin from Yasuhara Chemical

Co., and terpene phenolic resins including YS

Polyster U130,

YS Polyster

U115,

YS Polyster

T115,

YS

Polyester T100,

YS Polyster T80 all from Yasuhara Chemical

Co., Ltd., and SYLVARES^MR TP 96, SYLVARES^MR TP 3 00, SYLVARES^MR PT

2040,

SYLVARES^MR TP 2 019,

SYLVARES^MR TP 2040HM, SYLVARES^MR PT

105,

SYLVARES^MR TP115 from Arizona Chemicals.

Other Amorphous Molecule Materials

A* small suitable include rosin acids including but not limited to FORAL^MR AX, produced by synthetic resin hydrogenation

STATUTORY^MR NC one of that partial of one

STATUTORY^MR AX, thermoplastic wood rosin acid resin and is the resinate of highly hydrogenated wood rosin sodium, both commercially available from

Pinova;

ARAKAWA^MR KE-604, ARAKAWA^MR KE-604B, ARAKAWA^MR KR-610, ARAKAWA^MR

KR-612,

ARAKAWA^MR

KR-614, commercially available hydrogenated rosins from Arakawa Chemical

Industries,

Ltd.

Other suitable small molecule amorphous materials include the class of materials known as adhesion enhancers, a category in which many of the amorphous materials herein typically fall.

Other adhesion improvers are also known and can be

in

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY may be suitable as the small molecule amorphous material used herein or may be added in effective amounts up to about 40%. Examples of other potentially effective adhesion improvers include C5 aliphatic monomer resin,

PICCOTAC^MR 1095, EASTOTAC Hydrogenated C5 Monomer Resin^MR H-100R, EASTOTAC resin^MR

H-100L, resin

KRISTALEX^MR 112 0,

EASTOTAC^MR H-100W,

PICCOTEX®^MR 75, hydrocarbon resin,

PICCOLASTIC^MR

A5, monomer resins

C9

PICCOTEX®^MR LC,

PICCOTEX®^MR 10 0 C8 monomer resins

PICCOLASTIC^MR

A75, REGALITE hydrogenated C9 aromatic monomer styrenic resins^MR S1100, aromatic monomer resins

partially hydrogenated C9

GIFT^MR S5100,

GIFT^MR S7125, GIFT^MR R1100, GIFT^MR R7100, GIFT^MR

R1090,

GIFT^MR R1125, GIFT^MR R9100, PICCOTAC Mixed C5 Aliphatic and C9 Aromatic Monomer Resins^MR 8095, PICCOTAC^MR

9095,

PICCOTAC^MR

7050, aromatic hydrocarbon resins,

REGARD^MR 1094, monomer aromatic hydrocarbon resins

Hydrogenated C9, REGALREZ^MR 1085, aromatic monomer resin

Partially Hydrogenated C9 REGALREZ^MR, modified petroleum resin

C5 all of

Eastman;

al if Attic WINGTACK^MR

10,

WINGTACK^MR 95, WINGTACK^MR 98, WINGTACK^MR 86, WINGTACK Aromatically Modified Petroleum Resin^MR ET and aromatically modified petroleum resin

WINGTACK^MR

STS, all of

cray

Valley.

In the composition of organic fixation pigment £

IMPI by cold pressing, an acid functionality may be present on at least one crystalline ester, at least one amorphous rosin ester, or both.

In these embodiments, the acid functionality is incorporated as a monoester of a diacid.

In other embodiments, the acidic functionality is incorporated as a separate functional group present on at least one crystalline ester.

In still other embodiments, the acid functionality is incorporated as a separate functional group present on at least one amorphous rosin ester.

In embodiments, a molecule component

A/ small amorphous can have an acid value from about 0 to about 30.

In s modes, the temperature for the viscosity of the material to be reduced from about 10,000 Pa-s to about 100 kgf/cm² of applied pressure is from approx.

0°C to approx.

50°C, in other modes from about 10°C to about 40°C, in further modes from about 0°C to about

30°C

In other embodiments, the applied pressure for the flow of organic pigment materials is from about 25 to about 400 kgf/cm.², and in additional embodiments of approximately approximately

200 kgf/cm².

For organic pigment that can be set by cold pressing it may be desirable to have a flow of pigment material £

organic RO close to

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY room temperature under the applied pressure of the cold-press fixing system, to allow the organic pigment to flow over the surface of the substrate and into the pores or fibers in the substrate as well as allow particles of organic pigment flow into each other, thus providing a continuous and uniform organic pigment layer that effectively adheres to the substrate.

It may be desirable for the applied pressure to be relatively low compared to the prior art, e.g. approx.

100 kgf/cm².

However, in embodiments, the pressure can be higher up to about 400 kgf/cm² or smaller, as small as

5 kgf/cm², provided that the conditions described above for the initiation of organic pigment flow and flow viscosity are satisfied.

In embodiments, some of the heat may be applied to preheat the organic pigment or paper prior to entry into the cold press fixing system which may enable cold press fixing for temperatures slightly above room temperature.

In modalities it may be desirable to fix cold press under low pressures, for example about 10 kgf/cm² of applied pressure, the organic cold-press fixation pigment does not flow significantly so that the pigment particles £

σ > in in

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY adhere to each other, for example, in the organic pigment cartridge, in the printer, including in the developer housing or on imaging surfaces such as the photoreceptor, or in modalities in an intermediate transfer belt.

In transport or in the printer the temperature can temperature modalities, flow of particles kgf/cm².

as high as

50°C may be desirable for the organic pigment to increase significantly so that these organic pigments are not allowed to adhere together until 50°C at about

Thus, in modalities, the temperature for the viscosity of the approximately fixing material

10,000 pressure approximately will reduce a value of

Pa-s, for the organic pigment of cold a pressure less than kgf/cm² of applied pressure, the temperature is approximately

50°C approximately

70°C, in modes, approx.

55°C approximately 70°C, in modes, approximately 60°C approximately

90°C in additional modes approximately 20 kgf/cm² at about 40 kgf/cm².

Thus, it may be desirable to have a high temperature for material flow at low pressures representative of storage and use in the printer and a low temperature for material at higher than desired cold pressure fixing pressure.

In modalities, there is £

in

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY a calculated temperature shift in the range from approximately 10 °C to approximately

60°C, where the flow viscosity of the cold press setting composition is approximately equal to

10,000 pascal-seconds, when the pressure applied on the cold-press setting composition is increased from 10

100 kgf/cm².

In these modalities, the temperature shift can be calculated as,

10000 = Τη = íoooo (10 kgf/cm²) - Τη = íoooo (100 kgf/cm²) where Τη = íoooo (10 kgf/cm²) is the temperature for flow viscosity η of 10000 Pa-s at kgf/cm² of applied pressure and Τη íoooo (100 kgf/cm²) is the temperature for flow viscosity η of 10000 Pa-s at

100 kgf/cm².

In other embodiments, the low pressure for storage and printer use applied may be in the range of about 10 kgf/cm² at about 40 kgf/cm², and the high pressure for applying cold pressure fixing may be in the range of about 25 kgf/cm² at about 400 kgf/cm².

In embodiments, methods of applying cold press setting organic pigment are provided comprising providing a cold pressing setting organic pigment composition comprising: at least one crystalline material and a crystalline ester small molecule amorphous material from Cie to Ceo who has a £

I HEARD

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY melting point in a range from approximately 30°C to approximately

130°C and at least one amorphous ester having one from about

30°C to about 70°C, depositing the organic cold pressure setting pigment composition onto a substrate, and applying pressure to the composition placed on the substrate under cold pressure setting conditions.

In some embodiments, the applied pressure is in a range from about 25 kgf/cm² about 400kgf/cm².

In embodiments, cold pressure fixing is carried out by applying pressure in the aforementioned range between two fixing rollers which may be selected from known fixing rollers above, US Patent 8,541,153, for reference.

for example as incorporated herein

Examples of fixing rollers are cylindrical metal rollers which may optionally be coated with fluorine-containing resins, such as polytetrafluoroethylene resins.

TEFLON^MR

PTFE, TEFLON perfluoroalkoxy resins^MR PFA, flucrated ethylene and propylene

TEFLON^MR

FEP, amorphous fluoroplastic resins

DUPONT^MR TEFLON^MR AF and silicone resins, or a combination of the different resins.

The two fixing rollers can be made of the same materials or they can be different.

In embodiments, the fixing step is cold press fixing without any direct application of heat in £

IMPI

Ü1 the fixing stage.

Nevertheless.

due to heat from printer components, frictional heating between the rollers, the temperature can rise above room temperature at the fusing nip.

Also, the paper and/or the organic pigment layer on the paper, in embodiments, can be heated, for example, with a heat lamp before the cold-press fixing apparatus.

In embodiments, latexes are provided formed from a cold-press-setting organic pigment composition comprising at least one crystalline Cie to Ceo ester having a melting point in a range from about 30°C to about 30°C.

130°C and at least one amorphous rosin aster from Cíe a

Cso you have a

Tg from approx.

0°C to approximately 60°C.

The organic pigments may be prepared from the cold-pressed organic pigment composition described herein by any means, including the conventional forms of extrusion and milling, suspension,

SPSS (Spherical Polyester Organic Pigment by Polymer Suspension/Pigment Solution Solvent Removal Method, as described in

Journal of Imaging

Society of Japan, Vol. 43, 1, 48-53, 2004), incorporated in an organic pigment N-Cap (encapsulated organic pigment, such as £

IMPI σι is described, for example, in US patent

5,283,153 and incorporated into an organic emulsion aggregation pigment, optionally with a coating.

needed for organic pigment applications,

When latexes can be made by incorporating crystalline and/or amorphous mixtures, prepared by solvent separation, by solvent inversion emulsification.

They can phase including by methods free of being present other additives in CPF organic pigments described herein.

The organic pigment compositions of

CPF of the present embodiments may optionally associate conventional may to further include one or more additives to take advantage of the known functionality with these conventional additives.

These additives include, for example, colorants, antioxidants, defoamers, brighteners, plasticizers, slip release agents, similar modifiers.

of viscosity, adhesives,

When present, the optional additives may each, or in combination, be present in the organic pigment in the desired or effective amount,

1% about about about 5

either.

of

CPF in

10%, be any for example from approximately

10%, from approx.

Or, *6 from approx.

either.

by weight of the organic pigment CPF.

In a common composition of organic pigment CPF £

in

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY antioxidants are added to prevent the color change of the small molecule composition.

In modalities.

the antioxidant material

NAUGARD^MR 7 6, may include

IRGANOX^MR

1010;

NAUGARD^MR 44 5,

NAUGARD^ 512, and NAUGARD^MR 524.

In modalities, the antioxidant is NAUGARD^MR 44 5.

In other embodiments the antioxidant material may include MAYZO^MR

BNX^MR 1425 a calcium salt of phosphoric acid and MAYZO^MR BNX^MR

358 a thiophenol both commercially available from MAYZO^MR, as ETHANOX^MR 32 3A, a commercially available nonylphenol disulfide from SI Group.

described

In in plasticizer.

Uniplex

250 embodiments, the organic pigments present may comprise of

CPF plus a

Exemplary plasticizers may include (commercially available from

Unitex), commercially available phthalate ester plasticizers from

Ferro under the trade name

SANTICIZER^MR, such as dioctyl phthalate, diundecyl phthalate, alkylbenzyl phthalate (SANTICIZER^MR 2 78), triphenyl phosphate (commercially available from Ferro), tributoxyethyl (available

KP-140, a phosphate of

chemicals

Corporation), commercially

MORFLEX^MR

150, of a

Great

Lakes dicyclohexyl phthalate (commercially available from Morflex Chemical

Company

Inc.), trioctyl trimellitate (commercially available from

Sigma Aldrich

Co.), similar

Plasticizers may be present in an amount from £

σ> CD σι

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY approximately 0.1 to approximately percent, from approximately

0.1 to about percent, from about 1 to about 20 percent by weight of the organic pigment CPF.

In embodiments, the organic cold pigment press-fix compositions described herein also include a colorant.

Any desired or effective colorant can be used in the cold-press setting organic pigment compositions, including dyes, pigments, mixtures thereof.

Any dye or pigment can be selected as long as it is capable of being dispersed or dissolved in the organic pigment.

CPF and that organic organic pigment pigment is compatible with other components of the

CPF.

of

Any conventional cold-press dye fixation material such as solvent color (CI) dyes, disperse dyes, direct dyes, acid-modified dyes, basic dyes, fluorescent sulfur dyes, vat dyes, the like.

Examples of suitable dyes include NEOZAPON^MR Network 492 (BASF); ORASOL^MR Red G (Pylam Products);

Direct Brilliant Pink B (Oriental Giant

dyes);

Direct

Net

3BL (Classic

Dyestuffs);

SUPRANOL^MR

Brilliant

Net

3BW (Bayer AG);

Lemon

Yellow

6G (United

Chemie);

Light Fast Yellow 3G (Shaanxi); Aizen Spilon Yellow

C-GNH (Hodogaya Chemical); Bemachrome Yellow GD Sub (Classic £

IMPI

Dyestuffs);

CARTASOL^MR

Brilliant

Yellow

4GF (Clariant):

Cibanone Yellow 2G (Classic Dyestuffs);

ORASOL^MR Black Rll (BASF); ORASOL^MR Black CN (Pylam Products); Savinyl Black RLSN (Clariant);

Pyrazol Black BG (Clariant); MORFAST^MR Black 101 (Rohm &amp; Haas); Diaazol Black RN (ICI); THERMOPLAST^MR Blue 670 (BASF); ORASOL^MR Blue GN (Pylam Products); Savinyl Blue GLS (Clariant);

Blue

5GMF

KEYPLAST^MR

Black

X51

Dyestuffs);

LUXOL^MR Fast Blue MBSN (Pylam Products) ;

(Classic Dyestuffs);

BASICID^MR Blue 750

Blue (Keystone (BASF) ;

Sevron (BASF);

Aniline Corporation);

classical

solvent

Black

NEOZAPON^MR (Classic

SUDAN^MR Blue

670

61554) (BASF);

SUDAN^MR

Yellow 146 (CI 12700) (BASF); SUDAN^MR Red 462 (CI 26050) (BASF);

(BASF,

IQ

IQ

Disperse Yellow 238;

Solvent Red 49);

Fatsol Black BR ​​(CI

Neptune Red Base NB543

Neopen Blue FF-4012

Solvent Black 35) (BASF);

(Chemische Fabriek

Triad BV); Morton Morplas Magenta 36 (CI Solvent Red 172);

metal phthalocyanine dyes such as described in US Patent No. 6,221,137, the disclosure of which is referenced, incorporated by and the like.

can use, for example, patent on as complete

Dyes herein as polymeric also for example those described, US Pat.

Nope.

I know for

5,621,022 US No.

each of which is used in its entirety for reference,

5,231,135, the descriptions of which are incorporated herein by their and commercially available, for £

in

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY For example, by Milliken &amp; Company as Milliken Ink Yellow 869,

Milliken Ink Blue 92,

Milliken Ink Red 357,

Milliken Ink

Yellow 1800, Milliken Ink Black 8915-67, Reactint Orange X-38 Uncut, Reactint Blue X-17 Uncut, Solvent Yellow 162,

Acid Red 52,

Solvent Blue 44, and Reactint Violet X-80 without cut.

Pigments are also suitable colorants for organic pigments examples

5100 cold pressure fixing.

Suitable pigments include PALIOGEN^MR Violet (BASF);

PALIOGEN^MR Violet 5890 (BASF); HELIOGEN*® Green

L8730 (BASF);

LITHOL^MR Scarlet D3700 (BASE);

SUNFAST^MR Blue

15:4 (Sun

Chemical);

HOSTAPERM^MR

Blue

B2G-D (Clariant);

HOSTAPERM^MR

Blue

B4G (Clariant);

Permanent

Net

P-F7RK;

HOSTAPERM^MR

violet

BL (Clariant);

LITHOL^MR

Scarlet

4440 (BASF); Bon Red C (Dominion Color Company); ORACET^MR Pink RF (BASF); PALIOGE^_Re¿ _{3871 K} (BASF); SUNFAST^MR Blue 15:3 (Sun

Chemical);

PALIOGEN^MR Network 334 0 (BASF) ;

SUNFAST^MR carbazole

Violet 23 (Sun Chemical); LITHOL^MR Fast Scarlet L4300 (BASF)-,

SUNBRITE^MR Yellow 17 (Sun Chemical),

HELIOGEN^MR Blue L6900,

L7020 (BASF); SUNBRITE^MR Yellow 74 (Sun Chemical); SPECTRA PAC

C Orange 16 (Sun Chemical);

HELIOGEN^ Blue K6902,

K6910 (BASF); SUNFAST^MR Magenta 122 (Sun Chemical); HELIOGEN^MR Blue

D6840,

D7080 (BASF);

SUDAN™ Blue OS (BASF);

NEOPEN Blue

FF4012 (BASF); PV Fast Blue B2G01 (Clariant);

IRGALITE Blue

GLO (BASF);

PALIOGEN™ Blue

6470 (BASF);

SUDANMR orange G £

IMPI (Aldrich) ; SUDAN^MR Orange 220 (BASF) : PALIOGEN^MR Orange 3040 (BASF);

PALIOGEN™

Yellow

152,1560 (BASF);

LITHOL^MR

Fast

Yellow 0991K (BASF);

PALIOTOL Yellow 1840 (BASF); NOVOPERM

Yellow FGL (Clariant);

Ink Jet Yellow 4G VP2532 (Clariant),

Yellow HG Toner

Suco-Yellow L1250

Fast

Yellow (Clariant);

(Clariant);

(BASF);

D1355,

hansa

D1351

Lumogen Yellow D0790

Suco-Yellow Di (BASF);

Brilliant

Permanent Yellow GRL 02 (Clariant);

PONT);

355

HOSTAPERM

Yellow

5GX03 (BASF);

(BASF);

Pink

Suco (Clariant);

(Clariant);

Permanent Rubine L6B 05

FANAL Pink D4830 (BASF); CINQUASIA^MR Magenta (DU

PALIOGEN^MR Black

L0084 (BASF);

Pigment Black K801 (BASF); and carbon blacks such as REGAL 330MR (Cabot), Nipex

150 (Evonik) Carbon Black 5250 and Carbon Black 5750 (Columbia

Chemical), and the like,

the organic

dispersant CPF.

as well as mixtures thereof.

pigment dispersions can be stabilized

Generally, in pigment by synergistics suitable pigments may be organic or inorganic materials. Pigments based on magnetic materials are also suitable, for example, for the manufacture of robust magnetic ink character recognition (MICR) inks.

Magnetic pigments include magnetic nanoparticles such as ferromagnetic nanoparticles.

The dyes described in £

IMPI United States Patent No.

6,476,219, patent the

6,726,755, United States Patent No.

6,755,902, patent the

6,472,523, U.S. Patent No.

American

Nope.

6,576,747, the

Nope.

6,663,703, United States Patent No.

6,646,111, patent the

6,713,614, U.S. Patent No.

American

Nope.

6,590,082, the

Nope.

6,696,552, patent

6,576,748, United States Patent No.

7,053,227, US Patent No.

American

Nope.

6,673,139, the

Nope.

6,958,406, patent

6,821,327, U.S. Patent No.

American

Nope.

7,381,831 US Patent No.

7,427,323, the description of each of which is incorporated herein by reference in its entirety.

In embodiments, solvent dyes are used.

An example of a solvent dye suitable for use herein may include spirit soluble dyes due to their compatibility with the CPF organic pigment carriers described herein.

Examples of suitable spirit solvent dyes include NEOZAPON”¹* Network 4 92 (BASF); ORASOL^MR Red G (Pylam Products); Direct Brilliant Pink

B (Global Colors); Aizen Spilon Red C-BH (Hodogaya Chemical);

Kayanol Red 3BL (Nippon Kayaku); Spirit Fast Yellow 3G; Aizen

Spilon Yellow C-GNH (Hodogaya Chemical); CARTASOL^MR Brilliant£

IMPI

Yellow

4GF (Clariant);

PERGASOL^MR Yellow (Classic

Dyestuffs); ORASOL^MR Black RLI (BASF); ORASOL^MR Blue GN (Pylam

Products)i

Savinyl Black RLS (Clariant); MORFAST^MR Black 101 (Rohm and Haas); THERMOPLAST^MR Blue 670 (BASF); Savinyl Blue GLS (Sandoz);

LUXOL^MR Fast Blue MSSN (Pylam);

Sevron Blue 5GMF (Classic Dyestuffs);

BASICID^MR Blue

750 (BASF);

KEYPLAST^MR

Blue (Keystone Aniline Corporation);

NEOZAPON^MR Black X5I (CI

Solvent Black,

IQ

12195) (BASF);

SUDAN^MR Blue 670 (CI 61554) (BASF), SUDAN® yellow 146 (CI

12700) (BASF);

SUDAN¹® _Red₄₆₂ (CI 260501) (BASF), mixtures thereof and the like.

The colorant may be present in the organic cold press setting pigment in any amount desired or effective to obtain the desired color or hue, such as from at least about 0.1 percent by weight of the CPF organic pigment to about 50 percent. by weight of the organic pigment CPF, from at least about 0.2 percent by weight of the organic pigment

CPF to about 20 percent by weight of the organic pigment CPF and from at least about 0.5 percent by weight of the organic pigment CPF to about percent by weight of the organic pigment CPF. The colorant may be included in the CPF organic pigment in an amount of, for example, about 0.1 to about

15% by weight of the organic pigment

CPF, from £

IMPI about 0.5 to about 6

O, Ό by weight of organic pigment CPF.

The following examples are presented to illustrate embodiments of the present description. These examples are intended to be illustrative only and are not intended to limit the scope of the present description.

Also, parts and percentages are by weight, unless otherwise indicated.

As used herein, room temperature refers to a temperature from about

20°C to about 25°C.

EXAMPLES

Example 1 - C16 to C80 crystalline organic material

This example describes testing of exemplary cold-pressed organic pigments according to embodiments herein.

Evaluation of Cold Press Fixability with Shimadzu Flow Tester: In order to test the ability of materials to flow under pressure as required by cold press fixation, a Shimadzu flow tester also known as Shimadzu Flow Tester was used. as a capillary rheometer (available from

Shimadzu

Scientific

Instruments).

The solid samples were scalloped apart and fractured into pieces with a rubber mallet. The samples were not dried or ground.

All materials are pressed into an ingot with a pressure

2268 kg £

IMPI (5000lbs) a hold for seconds.

Samples are run on Shimadzu CTF 500/100 equipment.

All samples are extruded through a 1.0 x 1.0 mm cone die using a piston with a cross-sectional area of ​​1 cm.².

Typical sample weights are between approximately 1.5 g and 2.5 grams. The process conditions are: approximately 23 to 26 °C to start, 10 kg to

100 kg,

180 seconds of preheating and a gradual increase of 3°C/minute. Then the two pressures tested are kgf/cm² as a low pressure control and

100 kgf/cm² high fixation is like a high pressure for compositions, the latter pressure representative of the target pressure for cold.

table shows the results

Shimadzu for two organic control pigments.

TABLE 4 shows transition temperature polymer formulation 10⁴ Pa-s) of (°C,

ΔΤ (°C) control 1 control 2 copolymer of styrene and l-tertbutyl-2ethenylbenzene 50:50 ratio 46:46:8 of

100 kgf/cm²

Ϊ13 kgf/cm²123

10-100kgf/cm²10

100

100 amorphous resin A:

resin

amorphous B: crystalline C resin

Control 1 is an example of an organic pigment £

IMPI

Ü1 cold-press fixing pigment which is made of a copolymer of styrene with l-tert-butyl-2-ethenylbenzene and a polyolefin wax, Xerox 4060 cold-press fixing organic pigment.

Table 4 shows that the organic pigment cold pressure fixation flow of control organic pigment 1, the transition from high to low viscosity approximately

10⁴

Pa-s occurs about 10°C lower at high pressure than at low pressure, and even at high pressure it has a higher flow transition temperature

100°C

Note that the control is designed to set approximately

00 kgf/cm², about 3X higher than what applies here.

But clearly not suitable for cold press fixing at 100 kgf/cm².

Control is an organic emulsion/aggregation pigment about about 8 g, or

O, *O o, o black particle size μm consisting of a core of each of polyester A and polyester B, of crystalline polyester C, approximately of polyethylene wax, approximately 6

a.

carbon black

either. or cyan pigment, a coating of about 14 each of polyester A and polyester B, wherein polyester A has a number average molecular weight (Mw) of about 86,000 and a number average molecular weight (Mn) of about 5,600, and a start of £

IMPI

Ü1 transition temperature (beginning of

Tg) of about 56°C, where polyester B has a Mw of about 19,400 and an Mn of about 5,000, starting Tg of about 60°C, and where crystalline polyester resin C has a Mw of about 23,300, an Mn of about 10,500, and a melting temperature (Tm) of about 71°C, where the polyethylene wax has a Tm of about 90°C.

Both amorphous resins are of the formula where m is about 5 about

1000. The crystalline resin is of the formula (CH₂)_1st (CH₂)₉ where is approximately approximately 2000.

As shown in Table 4, the organic pigment £

I HEARD

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY control

2, which is a mixture of crystalline and amorphous polymer resins, shows no difference in rheology at any pressure, also has a very high transition temperature of 100°C at a low viscosity, itself not a candidate. for cold pressing fixation at this pressure.

for

Table 5 shows the sample compositions and results with small molecule crystalline amorphous materials.

TABLE 5 shows small crystalline molecule structure distearyl terephthalate ester (II) distearyl terephthalate distearyl terephthalate distearyl terephthalate distearyl terephthalate b by weight

Too amorphous small molecule structure no mixed benzoate ester (III) rosin ester SYLVATAC^MR

RE40 polyterpene SYLVARES^MR

TR A25 rosin ester

SYLVALITE RE

85L polyterpene phenolic SYLVARES^MR

TP 96

O, b by weight

Tg (°C) NA

NA amorphous properties

Ts

min

MW

Av (°C)

NA

NA

NA

NA

850

330

810

520

NA

NA

1275

462

1053

676

NA

NA transition temperature (°C, 10⁴Pa-s)

100

ΔΤ (°C) kgf/cm²78 kgf/cm²83

10-100kgf/cm² £

IMPI distearyl terephthalate distearyl terephthalate modified rosin UniTac 70 hydrogenated rosin ester

Arakawa Esther

Gum H

315

756

140 no data no data distearyl terephthalate distearyl terephthalate polyterpene SYLVARES^MR

TR A25 rosin ester

SYLVALITE^MR

RE 10L

The distearyl sample, or DST, h₃c(h₂c) liquid liquid liquid

330

330

680

680

680

462

462

748

748

748 is made up of diester terephthalate (I):

(CH₂)ch₃

Sample 2 is comprised primarily of a 70:30 weight ratio of a crystalline diester (II) with a short chain amorphous oligomer mixture consisting of an amide and an ester in the main chain, terminated as benzoate esters (III) .

CH h₃c(II) £

OI sample has η=0,1,2 (III) a relationship

79:21 crystalline distearyl terephthalate (DST;

compound

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY of the

SYLVATAC^MR RE40 an amorphous mixture of esters with rosin (IV), the major component a diester of diethylene glycol, and minor components a monoester of diethylene glycol and di-, tri- and tetra-esters of pentaerythritol.

81%

2%

OH £

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY in

<img file="MX378665B_D0003.tif" />

EITHER

<img file="MX378665B_D0004.tif" />

ooh

EITHER

7%

2.2%

<img file="MX378665B_D0005.tif" />

EITHER

EITHER

The organic pigment

ooh

ooh

4.7% (IV) standard cold press setting (control 1 in table 4) transition of 10⁴ Pa-s a temperature of about 113°C which is too high in temperature to be useful for high pressure fixing.

with cold, and a displacement of 10°C

The organic pigment based on amorphous pressured crystalline polyester resins (control 2) does not have £

I HEARD

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY temperature displacement with pressure and therefore it is not suitable as main components for cold pressure fixing.

The crystalline/amorphous designs of esters example the ink sample solid ink sample using mixtures of small molecules, solid and in particular (table

5) are suitable cold pressing fixing materials.

Sample 3, in particular, has a larger displacement with pressure than the standard pressure fixation organic pigment (control 1), much less than cold but with a transition temperature approaching room temperature.

Thus, the samples represent an advantage over currently used organic cold-press setting pigments.

EXAMPLE 2 -CRYSTALLINE POLYESTER

Flow Meter Evaluation of Cold Press Fixability – To test the ability of materials to flow under pressure for cold press fix (CPF) flow meter

Shimadzu.

detached by scalloping or in English),

The samples were used solid, fractured into pieces with a rubber hammer. All materials were pressed into an ingot with a pressure of 2668 kg (5,000 pounds) of pressure a hold ran in a set for seconds.

Shimadzu

CFT

The samples

500/100.

all the £

Ü1

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY samples were extruded through a cone die of

1.0x

1.0 mm using a piston with a cross-sectional area of ​​cm^.

The procedural conditions were:

27.7°C to start, either 10 kg

100 kg,

180 seconds of warm-up and a gradual change of

3°C/minute. Thus, the two pressures tested were kgf/cm² and 100 kgf/cm². The latter is a particularly useful target pressure for CPF. The results were tabulated in Table 6.

Useful designs generally have a transition temperature to reach a viscosity of

10⁴ Pa-s from about 0°C to

50°C

100 kgf/cm² to allow melting at room temperature, one of about 55°C to 70°C at low pressure, for good blocking of organic pigment.

The example uses a crystalline small molecule, distearyl terephthalate, and an amorphous small molecule, SYLVARES^MR TR A25, an oligomeric alpha-pinene like small pressure molecule.

this approximately environment,

temperature gives material

38°C, at the beginning example of is high from just above the temperature while the transition to low pressure is still high enough at about

73°C to potentially provide reasonable blocking.

In contrast, in the present example which is a mixture of the C12:C9 crystalline form of diacid:diol (CPE) of £

IMPI

OI resin and amorphous resins.

instead of small crystalline and amorphous molecules, no displacement with pressure is perceived and therefore it is a very high transition temperature to high pressure.

The CPE polyester resin, alone, also does not show any displacement with pressure and therefore has a very high transition temperature at high pressure.

Note also that the CPE low-pressure transition temperature is about 73°C, close to the CPE melting point, but when an amorphous resin with T_g from about 55°C to 60°C is added, the transition temperature actually increases.

Thus unexpectedly an organic pigment

CPF based on a mixture of these amorphous and crystalline polyester resins is not suitable for CPF.

Therefore it is very surprising that the same CPE C12:C9 resin mixed with SYLVARES^MR TR A25 (a small molecule oligomeric alpha pinene resin) shifts the glass transition temperature to less than about 54°C at high pressure, a temperature shift of 15°C. The CPE with diol chain lengths of C3

C6 also has a similar high pressure transition of about

54°C

transition from low to pressure in all cases is very close to the melting point of the CPE. So in all cases at low pressure this will pass the blocking criterion while providing a much smaller transition to high pressure compared to £

the control material.

show comment

79% DST/21

SYLVARES^MR TR A25 (from example 1) 46:46:8 wt% ratio of amorphous resin A:amorphous resin B:crystalline C resin C12:C9 qcid:diol CPE (from example 1) C12:C9 acid:diol CPE

79:21

C12:C3/SYLVARES^MR

TR A25

79:21

C12:C6/SYLVARES^MR

TR A25

79:21

C12:C9/SYLVARES^MR

TR A25

73:30

C12:C6/SYLVARES^MR

TR A25

60:40

C12:C6/SYLVARES^MR

TR A25

50:50

C12:C6/SYLVARES^MR

TABLE 6 properties of crystalline material melting point (°C)

72.5

MW

min

15.7

22.9

22.9

13.4

14.3

6.5

10.4

10.4

6.6

6.1

22.9

10.4

15.7

15.7

15.7

6.5

6.5

6.5

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY phase change transition temperature T_pc (°C) at 1x10⁴Paσ > CD σι

Tpc at 100 kgf/cm²

Tpc to kgf/cm²

ΔTpc (10 kgf/cm²100 kgf/cm²)

100

100 £

IMPI

I HEARD

TRA25 70:30 C12:C6/SYLVATAC^MRRE25

72.6

16.9

7.6

70:30

C12:C6/SYLVALITE^MR

RE 10L

72.6

16.9

7.6

70:30

C12:C6/SYLVALITE^MR

RE 10L

72.7

17.0

7.5

As shown in sample 7 to sample 12, increasing the amount of amorphous small molecule lowers the high pressure transition temperature even more.

low pressure transition is generally not affected by the addition of amorphous resin, the low pressure transition temperature remains close to the CPE melting point, so it is possible to reduce the high pressure transition temperature while leaving the low pressure temperature. pressure high enough for a good lock.

There are some important advantages of using resin

CPE for organic pigment

CPF, instead of a small molecule crystalline material.

Because CPE is a polymer, compared to a small molecule DST, /V there is increased toughness and elasticity, which can be very important in producing a robust organic pigment particle.

Furthermore, because CPE resins have previously been designed for organic pigment control of £

I HEARD

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY emulsion aggregation (EA), the acid number to obtain the required acid value is well known.

Adjustment of the acid value of a small molecule crystalline material is not as straightforward.

Since DST is a small molecule which places an acid group on each molecule it can make the acid value too high to produce organic pigment.

Thus, only a small number of DST molecules, for example, can potentially have an acid group, to allow the elaboration of a functional EA organic pigment.

- the acid number affects both the elaboration of the organic pigment and the performance of the organic pigment in the filler. Also, one of the easiest ways to add an acid group to the small molecule DST, for example, is to have only one stearate group and have the other terephthalate functional group as a free acid group. However, this will change the baroplastic melting behavior of those acid and monostearyl terephthalate molecules compared to those DSTs. Another small molecule with acidic groups can be added, but again, this has an impact on baroplastic performance.

These problems do not arise with polymeric CPE.

EXAMPLE 3

ORGANIC PIGMENT PRODUCTION

Latex preparation:

a latex with a size

1920 nm is prepared by coemulsification of a ratio 79/21 £

σ> CD σι

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY of C10/C6 CPE (AV = 10.2) and SYLVARES^ TR A25 (AV = 0) . 79 grams of C10/C6 CPE resin and 21 g of SYLVARES^ TR are measured

A25 in a liter beaker containing approximately 1000 grams of ethyl acetate. The mixture is stirred at approximately 300 rpm at 65°C to dissolve the resin and CCA in the ethyl acetate.

measure 6.3 8 grams of Dowfax (approximately 47 precipitates by weight) in a

Used glass cup

1000 liters containing grams of deionized water.

Homogenization of the aqueous solution in the liter glass beaker is started with an IKA Ultra Turrax T50 homogenizer at 4,000 revolutions per minute.

Mixing solution slowly into the solution becoming homogeneous, increases it

8,000 of resin then aqueous revolutions the mixture is poured continuously homogenizer speed per minute if homogenization is carried out under these conditions for approximately 30 minutes. Upon completion of homogenization, the glass flask reactor and its contents are placed in a heating mantle and connected to a distillation device.

mixture is stirred approx.

250 revolutions per minute and the temperature of the mixture increases

80°C approximately

1°C per minute to distill off ethyl acetate from the mixture.

The stirring of the mixture continues

80°C during £

IMPI

OS approximately

120 minutes followed by cooling at about 2°C per minute to room temperature.

The product is analyzed through a micrometer sieve.

resulting resin emulsion is made up of approximately

13.84 weight percent solids in water and has a volume average diameter of approximately 196.2 nanometers as measured by the HONEYWELL MICROTRAC particle size analyzer^MR UPA 150. Two additional latexes are also prepared in a similar manner, except that 70 grams of C10/C6 CPE resin are used with g of SYLVARES^MR TR A25 to prepare latex with a size of

183.1 nm with a solids content of 17.52

O, Ό by weight and grams of C10/C6 CPE resin with 30 g of SYLVATAC^MR RE25 are used to prepare another latex with a size of 139.6 nm with a solid content of 17.44 by weight.

Preparation of organic pigment:

In a 2-liter glass reactor equipped with an overhead stirrer, add 33.95 g of PB 15:3 dispersion (17.89

726.26 g of the previous latex with

O, Ό

9 grams of se by weight) resin

CPE

C10/C6 and 21 g of SYLVARES^MR TR A25. The previous mixture has a pH of 3.71, then 20.17 grams of solution of

A1₂(SW₄)₃ by weight) as a flocculant under homogenization.

The temperature of the mixture is increased to 55°C at 250 rpm.

The particle size is monitored with a Coultier counter until the core particles average £

IMPI

RO volume particle size of 7.42 gm. Subsequently, the pH of the reaction suspension is increased to 9.5 using

15.81 g of EDTA (39% by weight) and NaOH (4 q, 'o by weight) to stop the growth of organic pigment.

After quenching, the reaction mixture is heated

70°C

The organic pigment is suspended after coalescence and has a final particle size of 9.64 microns.

Room temperature filtration, pigment suspension, organic is then separated by sieving followed by washing and lyophilized.

cools (25 μm),

Preparation of organic pigment B:

34.18 g of PB 15:3 dispersion (17.89 q, or by weight) are added to a 2-liter glass reactor equipped with an overhead stirrer.

577.61 g (17.52 q, Ό wt) of latex with a CPE ratio

C10/C6 compared to SYLVARES^MR TR A25 from about 70 to

30.

above mixture has a pH of

3.70, after

56.15 grams of AI2 (804)3 solution (1?

by weight) is added as a flocculant under homogenization.

The temperature of the mixture increases

60.5°C

250 rpm.

Particle size is monitored with a Coultier counter until the core particles reach a volume average particle size of 6.48 gm.

Subsequently, the pH of the reaction suspension is increased to 9.5 using 13.08 g of EDTA (39% by weight) and NaOH (4% growth of organic pigment.

by weight) to stop the

After the arrest, the £

IMPI

Ü1 reaction mixture is heated to 67.9°C.

The organic pigment is suspended after coalescence and has a final particle size of

8.24 micrometers.

organic pigment suspension is then cooled to room temperature, separated by sieving (25 μm), filtration, followed by washing and freeze-drying.

Preparation of organic pigment C:

In a 2-liter glass reactor equipped with an overhead stirrer, add

38.70 g of dispersion PB15:3 (16.00

Or, by weight)

571.97 g of latex with CPE C10/C6 compared to SYLVATAC^MR RE25.

The above mixture has a pH of 4.07 and then add

61.71 grams of solution

Al2(SO4)3 (1 by weight) as flocculant under homogenization.

The temperature of the mixture is increased to 60.8°C at 250 rpm.

Particle size is monitored with a Coultier counter until the core particles reach a volume average particle size of 6.75 µm.

Subsequently, the pH of the reaction suspension is increased to 9.01 using NaOH (4 o, o by weight) to stop the growth of organic pigment. After quenching, the reaction mixture is heated to 68°C. The organic pigment is suspended after coalescence and has a size

The temperature filtration, ambient pigment particle suspension is separated from organic

7.90 after by micrometers.

sieving (25 μm) is cooled, followed by washing and lyophilization.

£

IMPI σι

Table 7 shows the Shimadzu phase change transition temperature difference which is not as large in the organic pigment samples as that obtained in the simple mixtures of CPE and small amorphous molecule in Table 6. For example, table 6, the mixture of sample 5 with a 79/21 ratio of CPE CIO:C6/SYLVARES^MR

TR

A2 5 has temperature of a shift transition from con

53°C pressure

100 of

17°C kgf/cm², compared to a displacement with pressure sample of organic pigment A, with a of

3°C the glass transition temperature of 68°C at 100 kgf/cm².

Also in the table the mixture of sample 1 with a 70/30 ratio of CPE

CIO:C6/SYLVARES^MR TR A25 has a pressure displacement of 25°C at a transition temperature of 45°C at 100 kgf/cm², compared to the organic pigment sample B with a displacement with a pressure of

4°C transition temperature of 68 °C at 100 kgf/cm².

Also in Table 6, the mixture of the sample relative to

70/30 off

CPE

CIO:C6/SYLVATAC^MR RE40 has a displacement with pressure of

17°C at 45°C transition temperature at 100 kgf/cm², compared to organic pigment sample C with the same formulation, with a pressure shift of 7°C at sample transition temperature in table 7,

62°C the phase transition reduction and the increase in

100 kgf/cm².

As I know in the temperature of the displacement with £

IMPI

Yes pressure can be obtained with a further increase in amorphous content.

TABLE 7 sample of

Material ID CPE properties transition temperature of

ΔΤ pigment phase change (°C, 10⁴ Pa-s)

Mn(k)

Mw(k)

Mp (°C)

100 (°C) kgf/cm² kgf/cm²

10-100kgf/cm²

79/21

25.6

10.7

75.5

C12:C6/

SYLVARES^MR

TR A25

70/30

25.6

10.7

75.5

C12:C6/

SYLVARES^MR

TR A25

70/30

16.9

72.6

C12:C6/

SYLVATAC^MR

RE25

It is stated that in relation to this date.

the best method known by the applicant to carry out the aforementioned invention is the one that is clear from the present description of the invention.

<img file="MX378665B_D0006.tif" />

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY