JP2000029238A - Toner composition for use in textile printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain dry toner particles contg. a sublimable dye and a toner resin for suitable textile printing by making the viscosity and tgδ of a resin within a specified range when the resin is measured at a specified temp. SOLUTION: Toner particles contain a toner resin and a heat sublimable dye. The resin has 30-100 mPa.s viscosity η and tg δsatisfying 0.010<=tgδ/η<=0.20, preferably 0.010<=tgδ/η<=0.03 in the measurement at 190 deg.C. The sublimable colorant is e.g. diarylaminoanthraquinone, monoacylamino- arylaminoanthraquinone, phenylamide of 1-phenylazo-2-hydroxynaphthalene-3- carboxylic acid, phenyl- or naphthylamide of acetyl- or benzoylacetic acid or an alkylamide of 1,4-diaminoanthraquinone-2,3-dicarboxylic acid carrying a phenoxy or phenylamino group in which an aliphatic chain is one or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to toner particles containing a toner resin and a thermosublimable dye or pigment for use in textile printing.

[0002]

BACKGROUND OF THE INVENTION Toner particles containing thermosublimable dyes or pigments for use in sublimation transfer printing are very well known in the art. When the toner is used, a method for textile printing is as follows. A toner image is formed on an intermediate support (eg, paper, plastic sheet, etc.) and the intermediate support carrying the toner image is brought into contact with the fabric (short).
Heat for hours. During this process, the sublimable dye or pigment evaporates and enters the fabric to be printed, where the dye or pigment molecules diffuse into the fibers. After the dye sublimates from the toner image to the fibers, the intermediate support carrying the toner image is removed. This system is particularly well suited for printing on synthetic fibers, for example polyester.

In such a method, it is important that a large amount of dye can be sublimated in a short time, and that a very small amount of toner resin is transferred to the fabric while the toner image is in contact with the fabric and heated. When a large amount of toner resin is transferred,
The fabric becomes stiff and the feel of the fabric is changed where the image is printed. This is especially true when printing high quality fabrics.
The presence of the toner resin is very undesirable because it has a negative effect on the pleasure of wearing the printed fabric or its drapeability.

Some proposals for toner particles containing sublimable dyes have been made to improve toner particles for use in textile printing using toner particles containing sublimable dyes.

For example, in US Pat. No. 4,251,611, 1
A method for producing a monochromatic or multicolor permanent copy by developing an electrostatic latent image with a magnetic brush using toner particles and a ferromagnetic material comprising polymer particles having a dye subliming or evaporating at 00 to 250 ° C. Has been described. It is said that only the pure dye is transferred, while the other components of the toner remain on the latent image and do not undergo opacity or bleaching.

In US Pat. No. 4,391,893, spherical magnetic toner particles are made from magnetic compounds, polymers, and waxes. The dye used sublimates at 100-200 ° C. and the wax is preferably montan wax.

[0007] US Pat. No. 4,251,616 discloses a dry electrophotographic developer consisting of a single type of particles containing a conductive substance, a magnetic substance and a binder. Typically, the developer is carbon black (2-20%), 130-
Contains dyes, waxes and plasticizers that sublime or evaporate at 240 ° C. Binders are polymers, especially PVC, polystyrene or copolymers of styrene and butadiene and acrylic resins.

In GB-A 2095585, 60-1
Develop an electrostatic latent image comprising a solid polymeric thermoplastic material having a ball-ring of 40 ° C and fine toner particles and carrier particles containing a thermosublimable dye sublimating at 100-220 ° C at atmospheric pressure A two-component toner composition is disclosed.

In EP-A 0 821 163, a binder which can be heated to 230 ° C. without easily discernible decomposition, optionally conductive or ultrafine magnetic particles, and an amount of at least 60% at 210 ° C. and 100 hPa for 30 seconds. Heat or pressure fixable spherical particles comprising at least 5% of at least one sublimable or evaporable dye which becomes vapor in 30 seconds at the same temperature and atmospheric pressure at the same temperature and atmospheric pressure. An electrostatic single component developer in the form of a dry fluid powder is disclosed. Binders having a softening point between 100 and 160 ° C. are in particular cellulose esters, vinyl resins, vinyl copolymers, polyamides or polystyrenes and contain waxes selected from polyethylene waxes, aliphatic waxes or hydroxylated fatty acids.

[0010] EP-A 561313 describes a method for textile printing in which a printing pattern on a transfer material is formed using colored powders. Transfer printing on synthetic fabrics or similar materials is performed by sublimation of a pigment, a finely divided powder contained in a finely divided heat-sensitive synthetic resin. The resin has a melting point around 120 ° C.

Although the toner particles according to the cited documents can be used for indirect printing, there is still room for improvement.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to contact a fabric with a toner image made of fused toner particles, whereby a large amount of dye is transferred to the fabric, and only a very small amount of toner resin with the dye. It is an object of the present invention to provide a dry toner particle containing a sublimable dye for transfer printing and a toner resin.

It is a further object of the present invention to provide a non-magnetic monolithic device in which when a toner image made of toner particles is brought into contact with a fabric, a large amount of dye is transferred to the fabric and only a very small amount of toner resin is transferred with the dye. It is to provide dry non-magnetic toner particles for textile printing, which can be used as a component developer or in a multi-component developer together with magnetic carrier particles.

[0014] Further objects and advantages of the present invention will become apparent from the following detailed description.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner particle containing a toner resin and a heat sublimable dye, wherein the resin is measured at 190.degree. This is achieved by providing toner particles characterized by having a viscosity η of s and a tgδ such that 0.015 ≦ tgδ / η ≦ 0.20.

Preferably, the toner resin is 0.02 ≦ t
It has tgδ such that gδ / η ≦ 0.06.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In indirect printing using toner particles containing a sublimable dye, toner particles containing a sublimable dye (a full-color image can be used) are applied to the transfer material in accordance with an image, and after being fused. Place the transfer paper with the colorant on the fabric to be printed (woven, non-woven or knitted polyester or similar synthetic fibers, or a mixture of such synthetic fibers and up to 33% of natural or regenerated fibers) This is basically done by printing a pattern on the transfer material. 30 fabrics and transfer paper
Pass on a calender heated to 180-260 ° C. at low pressure for seconds to 1 minute. The toner image comprising the toner particles according to the present invention is not only advantageous for decorating textile materials, but also for decorating polymer sheets or web materials (such as polyvinyl chloride sheets or webs, polyester sheets or webs, etc.). is there. Objects coated with a polymer layer can also be decorated using an indirect printing method using toner particles according to the present invention.

It is known from the prior art that for toner particles containing sublimable dyes and useful for print printing, the toner resin must have a softening point below the dye sublimation temperature. In most cases the polymer is at 60-160 ° C
Is said to have a softening point of From the prior art, once this condition is met, most of the known resins appear to be useful.

It has been found that satisfying only these conditions is not enough for a toner resin to be useful for textile printing using a sublimable dye. For example, Atlas Chemical describes a sublimable dye and a linear polyester of propoxylated bisphenol A and fumaric acid having a softening point near 100 ° C.
Industries Inc. Wilmington, Del. US registered trademark name
It has been found that toner particles containing known toner resins such as ATLAC T500 are not useful for indirect printing. Although a good intermediate toner image could be formed on the transfer foil, it was found that a large amount of resin was transferred instead of sublimed dye during transfer from the intermediate image to the fabric. The properties of the resin are within the range of the prior art.

Specific viscosity η and tgδ at 190 ° C.
It has been found that only toner resins having a specific ratio between η and η can be used advantageously. The viscosity η at 190 ° C. is 30 to 100 mPa. s, and tgδ / η at 190 ° C must be 0.010 to 0.20, preferably 0.010 ≦ tgδ / η ≦ 0.06. Most preferably, the resin used in the toner particles according to the present invention has a viscosity η at 190 ° C. of 30 to 100 mPa.s. s
Where tgδ at 190 ° C. is 0.010 ≦ tgδ / η
≦ 0.03.

The rheological parameter of the toner resin is CLS ²
Measured with a 500 RHEOMETER (TA Instruments, Newcastle, US trademark).

It has been found that a variety of known toner resins can be used to produce toners useful in the present invention as long as they meet the conditions just described. The toner resin used can be a polycondensation polymer or a mixture of various polycondensation polymers and an addition polymer or a mixture of addition polymers. Mixtures of polycondensation polymers and addition polymers and their composites are suitable as toner resins for the toner particles useful in the present invention.

The sublimable dye for incorporation into the toner particles can be any known dye having a sublimation temperature of 100-220 ° C. at atmospheric pressure.

Sublimable colorants include, for example, (a) diarylaminoanthraquinone; (b) monoacylamino-arylaminoanthraquinone; (c) 1-phenylazo-2.
Phenylamide of -hydroxynaphthalene-3-carboxylic acid (particularly, the phenyl group does not include an N-containing substituent);
(D) phenyl or naphthylamide of acetyl or benzoylacetic acid (particularly the phenyl group does not contain N-containing substituents); or (e) a phenoxy group having one or more aliphatic chains as disclosed in WO-A83 / 00235. Or 1,4-diaminoanthraquinone having a phenylamino group
It can be an alkylamide of 2,3-dicarboxylic acid. EP-A 773976 and EP-A 7910
The dyes disclosed in No. 34 can also be used advantageously.

Further important dyes for use in the toner particles according to the invention are GB-A 231430, GB
-A 231431, GB-A 231432, G
BA 231433, GB-A 231434,
GB-A 231435, GB-A 231436
And GB-A 2312437.

The toner particles according to the present invention may contain a fluorescent whitening agent.

The toner particles according to the present invention can be manufactured by any of known toner manufacturing means.

The toner particles according to the present invention can be prepared in a melt kneader at an appropriate temperature for 30 minutes at a suitable temperature depending on the toner resin and the sublimation dye used. Etc.) by melt blending or by extrusion. After cooling, the solidified mass is ALPINE Fliessbettgegenst
Finely pulverized using rahlmuehle type 100AFG (trade name), and further ALPINE multiplex zig-zag classifier ty
Classified using pe 100MZR (brand name). Milling and classification can also be performed by other commercially available equipment. Classification can be performed by a classifier using the "Coanda" effect, for example as described in EP-A 608902. The average particle size of the classified toner is
It was measured by model MULTISIZER (trade name).

The toner particles according to the present invention can also be produced by the "emulsion polymerization" method. Such a method limited to addition polymers is described, for example, in U.S. Pat. No. 2,923,629, U.S. Pat.
SP 4148741, U.S. Pat. No. 4,314,932 and EP-A 255,716. In this method, the non-water-miscible polymerizable liquid is converted into a toner component (eg, a pigment,
Pigments, charge control agents, release agents, etc.) to form droplets that are emulsified in aqueous solution and polymerize the monomer droplets in the presence of the emulsifier. Initially, the polymerizable monomer is in liquid form and only at the end of the polymerization is a suspension of solid polymer particles in the aqueous phase obtained.

[0030] The toner particles according to the present invention can also be produced by the "suspension polymerization" method. In such a method, the preformed polymer is dissolved in a suitable low boiling organic solvent that is immiscible with water and the toner components (eg, pigments, charge control agents, release agents, etc.) are dispersed in the solution. . The resulting solution is dispersed in an aqueous medium containing a stabilizer, the organic solvent is evaporated and the resulting particles are dried. Evaporation of the solvent is by raising the temperature, by vacuum evaporation,
For example, US-P 3,166,510, US-P 33389
Spray drying as described in 91, GB-A 2121
203, etc. can be performed by electrostatic fine grinding.

The toner particles useful in the present invention have a particle size of 3 to 20 μm.
m, preferably 5 to 15 μm, more preferably 5 to 7 μm
m can have an average volume diameter ( _dv50 ) of m. The particle size distribution of the toner particles may be of any type. However, it is preferred to have essentially a Gaussian or normal particle size distribution by number or volume, with a coefficient of variation (standard deviation divided by the average) (v) of less than 0.5, more preferably 0.3. Positive or negative skew is acceptable, but positive skew, which gives less particles than the unskewed distribution, is preferred.

The toner particles of the present invention may be any of known toner components,
For example, it may further include a charge control agent, a filler, a release agent, and the like. It can be magnetic or non-magnetic particles, the latter type being the preferred type. When the toner particles are non-magnetic, they can be used in multi-component and non-magnetic single-component developers in combination with magnetic carrier particles.

The toner particles can be used in any electrostatic printing device, in electrophotographic devices where the toner particles are used to develop an electrostatic latent image, and where the electrostatic printing is directly received from the toner carrier. Used in direct electrostatic printing performed on a support. The latter has no electrostatic latent image following the image by the electrically addressable printhead structure. Apparatuses for direct electrostatic printing are, for example, EP-A 740224, EP-A 7807
40, EP-A 731394, EP-A 81269
6 and the like. When the toner particles according to the present invention are intended to be used for direct electrostatic printing (DEP), it is preferred that the toner particles are manufactured to satisfy the following conditions (i) and (ii): i) The toner particles have a ratio of the major axis length to the minor axis length of the projected microscope image of the particles of 1.00 to 1.00.
The topological criterion of 1.40
n); and (ii) the toner particles are 260 m ^2.
Of fumed hydrophobic silica having a specific surface area of 0.1 g / g.
After the addition of 5% by weight, the following real density (ρr
eal) to the apparent density (ρapp):

(Equation 2) Such toner particles are disclosed in EP-A 715 218.

The true density (ρreal) of the toner particles is determined by Beck
mann Instruments, Chemin des Bourdon nr. 52-54, 93
BECKMANN AIR COM available from 220 Gagny, France
Measured according to conventional techniques in an instrument such as PARIMETER. It measures the volume of an accurately weighed amount of toner particles.

The apparent density (ρapp) of the toner particles was determined according to the following procedure: 50 g of a mixture of 0.5% by weight of fumed hydrophobic silica having a specific surface area of 260 m ² / g and 50 g of toner particles were weighed and measured at 35 mm. It was introduced into a graduated glass cylinder having a diameter. Cylinders with "tapping" equipment available from JEL, J. Engelmann AG, Ludwigshafen, Germany, ST
AV 2003, placed above STAMPFVOLUMETER (product name). The device taps at a rate of 250 cycles per minute. The mixture of toner particles and hydrophobic silica is 2000
Tapped during cycle. Then, the volume is cm ³
(Xcm ³ for 50 g of mixture), ρ
app was calculated as follows:

(Equation 3)

The toner particles according to the present invention can be applied to known transfer papers for textile printing. Such transfer materials are for example EP-A 146504, EP-A 479
882, EP-A 684337, EP-A 6830
57, EP-A 692742 and the like.

The present invention provides a method for indirect textile printing comprising the steps of: forming a toner image on an intermediate support with toner particles containing a thermosublimable dye; the thermosublimation contained in the image. Contacting the image with the fabric under elevated pressure to transfer a sex dye to the fabric; and-separating the image from the fabric, wherein the toner particles comprise a toner resin and a thermosublimable dye. 30 to 10 when the resin is measured at 190 ° C
0 mPa. viscosity η of s and 0.010 ≦ tgδ / η ≦
A method characterized by having a tgδ such that it is 0.20 is also included.

In this method, the toner particles used are preferably dry toner particles.

The support can be any support known in the art of electrostatic printing, but preferably a paper support is used.

[0040]

EXAMPLES General Procedure for Producing Toner Particles 90 parts by weight of a toner resin was added to a RESIRN RED TB (Colour Index).
10 parts by weight of Disperse Red 60, Bayer AG (German name) were melt-blended in an experimental kneader at 110 ° C. for 30 minutes. After cooling, the solidified mass is removed from the ALPINE Fliessbettgegen
Finely pulverized using strahlmuehle type 100AFG (trade name), and further ALPINE multiplex zig-zagclassifier typ
e Classified using 100MZR (brand name). Coulter Counter model Multisizer
When measured by (product name), the volume average is 12 μm
It turned out to be.

Table 1 shows the used toner resins.

[Table 1] ATLAC T500: Atlas Chemical Industries Inc. Wilming
ton, Del. US registered trademarks DIANAL FB1431, DIACRON FC043 and DIACRON FC433: Mi
tsubishi Rayon, Toyohashi-shi, Japan EPIKOTE 1009: Shell Chemicals, Rotterdam, Dutch brand name ALMACRYL XPE1676: Image Polymers Europe, Stirling
house, Scotland AG28 and AG4: Experimental compounds provided by KAO corp. Wakayama, Japan

Developer Composition Using toners made from resins T1 to T8, 0.5% by weight of each toner was used for fumed hydrophobic silica (AEROSIL R97).
2, Degussa German trade name) to produce a multi-component developer, coated on a ferrite carrier having a volume average particle size of 50 mm at a toner concentration of 5% by weight with respect to the carrier and activated for 30 minutes And a stable charge level was obtained.

Printing Example Printing was performed with an X35 copying machine (Agfa-Gevaert NV Mortsel, trade name of Belgium), and transfer paper (Agfa paper 1001, Agfa
-Gevaert NV Mortsel (brand name in Belgium) with uniform concentration of spots.

The paper print contained three toner layers, as in multicolor printing.

The print was contacted with the nonwoven polyester, the print and the polyester were maintained under a pressure of 4 bar for 20 seconds, and then the print was immediately separated from the fabric. The contact area was 10.5 × 2.4 cm.

[0046] After separation of the printed matter, to determine the concentration D _p remaining on the transfer paper like the concentration D _t on the fabric. Both concentrations were measured by reflection using a Gretag D19C densitometer.

The ratio D _t / D _p is taken as a measure of the quality of the dye transfer and is indicated by the ratio.

On the fabric spots, post-transfer stiffness, which is a measure for resin transfer, was measured using the cantilever method according to ASTM D-1388. The percentage increase BL in the bending length between the unprinted fabric and the printed fabric is measured.

The overall quality of the toner particles is determined by dividing the ratio by BL, the higher the number the better the result. Because when the ratio is high and BL is low,
This is because toner particles give high color transfer to low resin transfer.

A BL of 50% or less is acceptable because the feel of the fabric (generally referred to as the hand) is acceptable compared to the hand of the unprinted fabric. A value of ratio / BL of 0.02 or more gives acceptable color transfer. T2 to T5 satisfy these conditions and are acceptable. T6 is the borderline quality. Table 2 shows the results.

[Table 2]

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Paul Sterk Septetrat, Mozère, Belgium 27 Inside Agfa Gevaert Namloze Bennacht Chap

Claims (4)

[Claims] 1. A toner particle comprising a toner resin and a thermo-sublimable dye, wherein the resin has a particle diameter of 30.degree.
１００100 mPa. s viscosity η and 0.010 ≦ tgδ /
A toner particle having tgδ such that η ≦ 0.20. 2. tgδ is 0.010 ≦ tgδ / η ≦ 0.
3. The method according to claim 1, wherein the value has a value such as 03.
The toner particles according to the above. 3. A toner particle according to claim 1, wherein the toner particle has the following conditions (i) and (ii): (i) the toner particle is a minor axis of a projected microscope image of the particle; The ratio of the length of the major axis to the length of the
And (ii) the toner particles have the following apparent density after addition of 0.5% by weight of a fumed hydrophobic silica having a specific surface area of 260 m ² / g to the following true density (ρreal): Shows the ratio of density (ρapp): 4. A method for indirect textile printing comprising the steps of:-forming a toner image on an intermediate support with toner particles containing a thermosublimable dye;-the thermosublimation contained in said image. Contacting the image with the fabric under high pressure to transfer dye to the fabric; and-separating the image from the fabric; wherein the toner particles comprise a toner resin and a thermosublimable dye;
When the resin is measured at 190 ° C., 30 to 100 mPa.s.
A method characterized by having a viscosity η of s and a tgδ such that 0.010 ≦ tgδ / η ≦ 0.20.