CA1067742A - Toner consisting of a resin, colorant and a triazine derivative - Google Patents

Abstract

TONER FOR ELECTROSTATIC PRINTING
OF SHEET LIKE MATERIALS

ABSTRACT OF THE DISCLOSURE

A toner for the electrostatic printing of a sheet like material, which comprises a toner substrate con-sisting essentially of a resin and a coloring matter, and an antistatic agent, containing a polar group capable of regulating the accumulation of static electricity, said antistatic agent being applied to the surface of or incorporated in the toner substrate.

Description

~o67'74z The invention relates to a toner for the electrostatic printing of a sheet like material. More particularlyg the lnvention relates to a toner comprising an antistatic ~ agent containing a polar group capable of regulatin~ the - 5 accumulation of static electricity 9 which is particularlyuseful for electrostatically printing a textile material.
; Recentlyg techniques such as electrophoto~raphy, electrostatlc electrography and the like have been greatly developed and, thus, many attempts have been made to apply such techniques to other technical fields. For example, there has been proposed so called electrostatic printing wherein a toner image which may be obtained by varlous methods, such as electrophotography, for example xerography ; or electrofax, electrostatic recording, or electrostatic printing, for example xeroprlnting or electrostatic gravure printlng, or TESI technique, is transfered utilizing electrostatic force, directly or through a printing medium, to a paper or textile fabric or the like.
The toner to be used in such electrostatic printing generally consists of a fine powder of a blend of a synthetic resin such as a styrene, acrylic or epoxy resin or a natural resin such as rosin or dammar and a coloring matter such as dye or pigmentO In the improved toner, specific resins and coloring matters are used in a speciflc amount or a third material is added. Howeverg the use of a known toner gives unsatisfactory printings, because the ; printings result in low build-up, fog and non-uniformity of color. Particularly, in the electrostatic printing of textile fabrics, it has been very difficult to obtain satisfactory results due to the unevenness and non-

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smoothness of the sur~ace, and high porocity o~ the fabric.
It is, therefore, an ob~ect of the present invention to provide a novel toner for electrostatic printing which is durable in repeated printing and capable of being applied to a textile fabric easily, uniformly and in high build-up without any staining of the fabric.
Another ob~ect of the invention is to provide a toner superior in the coverage upon development, as well as superior in transference and uniform transferability : 10 upon trans~er.
A further ob~ect of the invention is to provide a toner which can be used, without any trouble, for cross printing to obtain a multicolor effect or as a blend of toners containing different coloring matter.
Additional ob~ects of the invention will become apparent from the ~ollowing description.
The invention provides a toner for the electrostatic -: printing of a sheet like material, which comprises a toner substrate consisting essentially of a resin and a coloring matter, and an antistatic agent, containing a polar group capable of regulating the accumulation of static electricity, which antistatic agent is applied to the surface of or incorporated in the toner substrate.
The term "toner substrate" as used herein, refers to a composition comprising at least one resin and at least one coloring matter. The toner substrate may further comprise conventional additives such as iron powder, dyeing aids and finishing agents.
Resins such as those which are conventionally used

3 in the art are usable for the toner substrate and they .
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includeg for example, homopolymers and copolymers of monoethylenically unsaturated monomers such as ethylene, propylene, vlnyl chloride, vinyl acetate, styrene, aminostyrene, methyl methacrylate and butyl methacrylate, and the modified polymers such as polyvinyl formal as well ~
as their mixtures. In addltion, polycarbonates and ethyl 7:
cellulose as well as polyacrylamide and polyvinyl alcohol are also usable. Particularly, resins based on the styrene monomers and the methacrylate monomers, and the polycarbonates or the modi~ied resins can suitably be employed.
The exact nature of the coloring matter is not crltical to the invention. Examples of the coloring matters are disperse dyes such as Diacelliton Fast Scarlet R (Misubishi Kasel Co., C. I. 11150), Mlketon Fast Pink , 15 FF3B (Mltsul Toatsu Co., C. I. 62015), Celliton Fast .
Yellow RR (BASF Co., C. I. 10345), Miketon Fast Orange GR
(Mltsui Toatsu Co., C. I. 11005), Kayalon Fast Scarlet B
(Nlppon Kayaku Co., C. I. 11110), Diacelliton Red R M/D
;' (Mltsublshl Kasei Co., C. I. 11210)9 Celliton Fast Violet B (BASF Co., C. I. 62030)9 Cibacet Blue F3R (Ciba-Geigy Co., C. I. 61505), Miketon Fast Turquoise Blue G (Mitsui Toatsu Co., C. I. 62500) and Kayalon Diazo Black B (Nippon Kayaku Co., C. I. 11365)~ acld dyes such as Suminol Fast Yellow R (Sumitomo Kagaku Co., C. I. 18835)9 Coomassie Fast Orange G (I.C.I. Co., C. I. 247~0), Kayaku Acid Red 3B (Nippon Kayaku Co., C. I. 24810), Acid Violet 5B (C. I.
42640), Diacld Light Blue 2A (Mitsubishi Kasei Co., C. I.
62055), Alizarine Fast Green G (Ciba-Geigy Co.g C. I.
61570) and Supranol Fast Black VLG (Bayer Co., C. I.
27070); basic dyes such as Sumiacryl Orange G (Sumltomo ~
' '' "

4 -Kagaku CO~g C. I. 48035), Auramine extra 0-125 (Sumitomo Kagaku Co., C. I. 41000) 9 Astrazon Pink FG (Bayer Co., C.
I. 48015)~ Diabasic Magenta (Mitsubishi Kasei Co., C. I. -42510), Serron Blue 5G (E.I. Dupont Co., C. I. 51005) and ~

- 5 Aizen Cathilon Grey BLH (Hodogaya Kagaku Co., C. I. 11825) 5 .
direct dyes such as Direct Fast Yellow GC (Mitsui Toatsu Co., C. I. 2900), Benzo Scarlet GS (Bayer Co., C. I.
29165)g Diacotton Vlolet X (Mitsubishi Kasei Co., C. I.
22550), Direct Blue 2B (Nippon Kayaku Co., C. I. 22610), Sumlllght Supra Brown G (Sumitomo Ka~aku Co., C. I. 36200) ~.
. and Direct Fast Black AB (Mitsublshi Kasei Co., C. I.
35440); reactive dyes such as Procion Blue H-B (I~C.I.
Co., C. I. 61211), Diamira Golden Yellow G (Mltsubishi Kasel Co., C. I. 18852), Procion Brllllant Yellow H-5G
(I.C.I. Co., C. I. 18972), Cibacron Brilliant Orange G-E
(Ciba-Geigy Co., C. I. 17865), Mikacion Rubine BS (Nippon Kayaku Co., C. I. 17965), Cibacron Vlolet F2R-A (Clba-~elgy Co., C. I. 18157), Clbacron Brown 3GR-A (Ciba-Geigy Co., C. I. 26440) and Proclon Black H-G (I.C.I. Co. 3 C. I.
17916); Oil-sluble dyes such as Zapon Fast Yellow CGG . .
(BASF Co., C. I. 18820), Diaresin Red J (Mltsubishi Kasei Co., C. I. 12715)) Victoria Blue F4R (BASF Co., C. I.
42563) and Nigrosine Base GB (Bayer CO~g C. I. 50415), and; plgments such as Brllliant Carmine 3B (C. I. 16015), ' 25 Benz$dine Yellow G (C. I. 21090), Benzidine Orange (C. I.
; 21110)g Lake Red 4R (C. I. 12120), Permanent Carmine FB
; (C. I. 12490), Fanal Violet R supra (C. I. 42535), Phthalo-cyanine Blue (C. I. 74160), Fanal Green G Supra (C. I.
42040), Permanent Brown ~G (C. I. 12480)~ Diamond Black 3o (C. I. 50440)g zinc white (C. I. 77947), titanium white :: - 5 -1067~4Z
.7 .
(C. I. 77891) and carbon black (C. I. 77265).
The antistatic agent usable for the invention ;~
contains a polar group and regulates the accumulation of static electricity onto the toner. In other words, the antistatlc agent acts to conduct and diffuse the electrical charge accumulated, or to limit the yield Or the electrical charge, and thus, limits the retention of the electrical charge on the toner.
It has been found that for this purpose, certain inorganic substances such as metals, metal oxides and lnorganic salts, sur~ace active agents, polar organic compounds of low molecular weight and triazine derivatives can suitably employed. Preferred antistatic agents are those which have an electrificatlon factor of from 100 to 2,000, particularly from 200 to 1,500.
The term "electrification factor" as used herein, refers to an absolute value of the surface potential determlned as follows. A test sample is prepared by formlng polystyrene, blended with 2~ by weight of an antistatic agent to be tested, into a sheet of a 30 ,u thickness on an aluminum foil. The test sample is inter-mittently sub~ected to positive corona discharge of a , . .
leakage current of 2.8 ,uA, in the case where the antistatic agent is to be employed in a positively charged toner, or ; 25 to negative corona discharge of a leakage current of 2.8 -~uA, in the case where it is to be employed in a negatively charged toner, for 20 seconds in total under conditions of ~ -20'C and 65% RH. Then, the surface potential of the test - sample is determined. ;
3~ Examples of the inorganic substances are metals, in .

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the form of powder, such as Cu, Zng Al, Si, Sb, W, Mn, ~e, Co and Ni; metal oxides such as ZnO, Fe2O3 9 A12O3g CaO, BaO, MgO and Ti02, and; inorganic salts such as LiCl, NaCl, KBr, CuSO4~ Mg(NO3)2a CaF2, Al(OH)3 and (NH4)2S04.
O~ these compounds, metals such as Al, Si and Fe, metal oxides such as ZnOg A12O3 and TiO2 and salts such as LiCl and NaCl are particularly preferred.
The surface active agents include anionic9 cationic~ nonionic and ampholytic agents. As examples of the anionic surface active agents 9 there are carboxylates such as soap, sulfuric acid ester salts such as salts of higher alcohol sulfuric acid esters, sulfated oils, sulfated fatty acid esters and sulfated olefins~ sulfonates such as alkyl benzene sulfonates, alkyl naphthalene sulfonates and alkyl sulfonates, and; phosphoric acid ester salts such as salts of higher alcohol phosphoric acid esters. Of these agents, the sulfonates and the phosphoric acid ester salts are particularly preferred.
As the cationic surface active agents, there are suitably employed, for example, amine salts such as primary amine salts, secondary amine salts, tertiary amine salts and salts of ethanolamine esters, and; quaternary salts such as tetraalkylammonlum salts and pyridinium salts.
Among these~ the quaternary salts are particularly preferred.
As the nonionlc surface active agentæ, there are, for example, alkylphenol ethers such as polyoxyethylene octylphenol ether; higher alcohol ethers such as poly-oxyethylene lauryl ether and polyoxyethylene oleyl ether;
higher fatty acid sorbitan esters such as solbitan monooleate, 3o sorbitan distearate and polyoxyethylene sorbitan monooleate;

. . .
higher fatty acid pentaerythritol esters such as penta-erythritol monostearate; higher fakty acid trimethylolpropane ;
esters such as trlmethylolpropane monooleate, higher fatty -; acid polyethylene glycol esters such as polyethylene glycol monooleate and polyethylene ~lycol distearate/ and;
nitrogen-containing agents such as polyoxyethylene laurylamine ether. Among these, those having a HLB value of from 3 to 19 are preferred and those having a HLB value of from 6 to 14 are e~en more preferred.

As examples of the ampholytlc surfaoe active agents, carboxylates such as betaine and amino acid, suIfuric acld ester salts such as salts of aminoalkyl sulfate esters, sulfonates such as aminoalkane sulfonates and phosphoric acid ester salts such as salts of amlnoalkyl phosphoric ; 15 acld esters are suitably employed. Of these, the sulfonates and the phosphoric acid ester salts are preferred.
In the invention, polar low molecular weight organic compounds are also suitably employed as the antistatic agent. The represnat~ves of such organic compounds are as follows: carboxylic acids such as aromatic carboxylic acids, e.g. benzoic acid, p-hydroxybenzoic acid and en-thranilic acid, pyrrolidonecarboxylic acid and N-acyl sarcoslnate; sulfonic aclds such as alkanesulfonic acids, e.~. butane-2-sulfonic acid, alkylsulfonic acid diethanolamine salts, dialkylsulfosuccinic acids and their sodium salts, and aromatic sulfonic acids such as benzenesulfonic acid, sulfanilic acid, p~toluenesulfonic acid, naphthalenesulfonic acid, ethylenediamine acidic salt of benzenesulfonic acid and sodium salt of phenolsulfonic acid; phosphoric acid ~ 30 esters such as metal salts of dlalkyl phosphoric acid ; - 8 -.. ~ .

~067'74Z
esters, pentaalkyl tripolyphosphate and hexaalkyl tetra-polyphosphate; phosphonic acids such as ethylme~hylphosphonic acid salts, benzenephosphonic acid salts, methoxyphosphonic acid salts, ethoxyphosphonic acid salts, alkylallylphosphonic acid and alkoxyphosphonic acid salts; amines such as alkylamines, e.g. tributylamine phosphoric acid salts, hexamethylenediamine, dlcyanoethylamine, diethanolamine and 2,5-dichloroaniline, amidoamines, e.g. fatty acid hexamethylenediamine monoamlde and N-monoacetylethylene- ;
diamine, cyclic amines, e.g. alkylimidazoline and alkyl-morpholine, and ester amines; ammonium salts such as quaternary ammonium salts, e.g. methylammonium chloride, ethyl dimethylphenylammonium bromide, and N-mothylpyridinium chloride, tertiary ammonium salts, e.g. triethylammonium chloride, secondary ammonium salts, e.g. dipropylammonium chloride, and primary ammonium salts, e.g. n-butylammonium chloride; halides such as ethyl bromlde, o-dichlorobenzene, octyl chloride, chlorostyrene, chlorotoluene, dichloro-naphthalene, 1,2,4-trichlorobenzene and o-dibromobenzene;
esters such as methyl acetate, methyl n-propionate, ethyl benzoate, terephthalic acid ester, octyl adipate and butyl adipate; ethers such as ethoxypropane, methoxypropane, 4 1,3-dlmethoxybenzene, diethylene glycol dimethyl ether and glycidol; epoxy compounds such as epichlorohydrin, propyl-monoglycidyl ether, methylglycidyl ether, phenylglycidyl ether and ethylene glycol diglycidyl ether; alcohols and hydroxy compounds such as ethylene glycol, glycerine, 1,4-butanediol, cyclohexanol, sorbitol, mannitol, benæyl alcohol and octyl alcohol; phenols such as phenol, cresol, xylenol, catechol, resorcin, ethylphenol, chlorophenol and ~ .
_ g _ ~06774'~ ~;
~-naphthol; nitro compounds such as chloronitrobenzene, dinitrobenzene and nitrotoluene~ amides such as acetoamide, propionamide, stearic acid amide, ~-phenylamide and N,N'-dimethylurea, and~ semiconducting compounds such as carbazole -complex and thiazine complex. -Further, in the invention, triazine derivatlves are suitably employed as the antistatic agent. Examples of the usable triazlne derivatives are those of the formulae, X X
; N ~ and N ~ ~
X N Y Y N Y ~:

wherein X is halogen, Y is a radical of the formula -A-~SO3M), -A-~COOM)9 -A-~PO3M) or -N ~CH2COOM wherein . A is ~NH(C~I2)m, ~CH3N(CH2)m' N ~ , -NH ~ 3~
-NH ~ ~ Q ¦ or -NH ~ ) ~ OH, R is hydrogen or alkyl having 1 to 18 carbon atoms9 M ls hydrogen or an alkall :~:
metal atom, and m is an integer of 1 to 5.
The triazine derivatives of the above formulae may be prepared, in a known manner, by reacting cyanuric halide with a member selected from the group consisting of sulfonic acids such as taurine, methyltaurine9 anilinesulfonic . acid, phenolsulfonic acid, toluidinesulfonic acid, tolu- ~.
. 25 idinedisulfonic acid, anilinedisulfonic acid, naphthionic acid, l-naphthylamine-3~6-disulfonic acid, Koch's acidg H-acld, l--naphthylamine -3,7-disulfonic acid3 Cleve's 7-:
acid, Cleve's 8-acid, amino R-Acid, ~-disulfonic acid, RM-acid tar acids, M-acid9 amino J-acid9 Tobias' acid and : 3 phenoldisulfonic acid and their alkali metal saltsg carboxylic ,' :.

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acids such as glycine, phenylglycine, aminobenzoic acid, aminobutyric acidg aminocaproic acid~ aminopropionic acid and aminophthalic acid and thelr alkali metal salts a and phosphoric acids such as aminomethanephosphonic acid, hydroxymethanephosphonic acidg aminoethylphosphonic acidg aminobutylphosphonic acid and aniline phosphonic acid and their alkali metal salts.
The reaction may convenlently be carried out usin~
approximately 1 or 2 mols of an acid or its salt as mentioned above per mol of cyanuric halide~ in the presence of an acid binding agentg in an aqueousg organic or aqueous-organic medium at 0 to 5-C. Where different groups Y are to be introduced, the reaction may be carried out in two steps. At the second step, the reaction may conveniently be carried out at 20 to 40-C. As the organ~c medium, for example, acetone, methyl ethyl ketone and dioxane are preferred and as the acid binding agent, for example, potassium and sodium hydroxides, potassium and sodium carbonates, calcium, magnesium and barium hydroxides, and sodium acetate and bicarbonate are conveniently employed.
~ epresentatives of the triazine derivatives are exemplified below.

:'." , ~0~;7742 Cl N~ T
Cl~ NH~--S03Na N ~;/

Cl --- N--~L C 1 Cl NaO3S~--HN~ ,~LNH~S03Na H17C8 M N /~\
.~ ~N--~ ,U--NH G~ \~--SO H
, HOOCH2C ` ~7/ 3 Cl CH CH
3 N ~ N 3 --HN~ ~--NH-~
)=J N

'' ~
Cl ~\ ~. ! i H31C15 N ,~N~C15H31 HOOCH2c~ N \CH2COOH
.: :
., Çl H C N N ~ 3 21 10--N--~ "~1--NH~ b HOOCH2C ~ N \SJ

\~ 3 .
Cl H N N ~ C H
N--~ ,~J--N

HO3PCH2CH2/ N CH2CH2PO3~1 ~067 The toner according to the invention is composed of the hereinbefore mentioned toner substrate and antistatic agent, and can be classified as one of thw following three types depending upon its construction. One type is a toner wherein the antistatic agent is applied to the surface of the toner substrate (hereinafter referrèd to as A type toner); another type is a toner wherein the antistatic agent is incorporated in the toner substrate (hereinafter referred to as B type toner), and; the other type is a blend of the A type and B type toners (hereinafter referred , to as C type toner). All of these three types of toners are included in the scope of the invention and they may be prepared as follows.
A Type Toner Toner substrate ingredients are dissolved and/or dispersed in a medlum such as dioxane, trichlene, dimethyl-formamide, ben~ene or water. The mixture is then formulated to obtain a toner substrate ln a particle or powder formg in a proper manner such as by pouring it into a non-solvent, precipitating and drying, b~ spray drying, by gelating it at a low temperature, grinding and drying, or by melt grinding. Then, an antistatic agent is applied to the toner substrate in a proper manner by any conventional methods. The application may conveniently be carried out, ` 25 for example, by dissolving or dispersing the antistatic agent ln a medium æuch as water~ acetone or methanolg which is a non-solvent or poor solvent of the toner substrate, applying the solution or dispersion to the toner substrate by spraying or dippingg then filtering or centrifugating to a proper llquid content, and finally drying. The :, .
antistatic agent is preferably applied to the toner substrate in an amount of not less than 0.01% based on the weight of the toner substrate.
B Type Toner An antistatic agent is incorporated in a toner substrate. The incorporation may conveniently be carried out, for example, by dissolving and/or dispersin~ the -~ toner substrate lngredients and an antistatic a~ent in a proper medium such as dioxane, trichleneg dimethyl formamide~
benzene or water and, then, formulating the mixture into a particle form in a proper manner as mentioned above7 or by heat melting the toner substrate in~redien~s, blending the melt with an antistatic a~ent and~ then, formulating the blend lnto a particle form by grinding. F~r the incorporation, any other conventional methods may also be employed. The antistatic agent is preferably incorporated in the toner substrate in an amount of not less than 0.1~ based on the weight of the toner substrate.
C Type Toner ;~ 20 A toner of this type may be prepared in accordance with the procedures mentioned above for the A type and B
~ type toners.
; The toner according to the invention may optionally comprise other third materials, such as additives 7 and ; 25 such materials may conveniently added at the time of -preparation of the toner. The toner is preferably in a ;, particle size of less than 80 ~, particularly less than 30 ~, and may conveniently be classified by the fluid sizing method-.
The toner may conveniently be applied to a textile .

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fabric, such as woven, knitted or non-woven fabric, consisting of or comprising a natural fibrous materlal such as cotton, silk or wool; semi-synthetic fibrous material such as of viscose or cellulose acetate, and~
synthetic fibrous material such as those of polyester9 polyacrylonitrile or polyamide. The toner may also con--- veniently applied to a paper, leather, film or metallic substrates.
A toner image may be formed by a proper method of electrophotography 3 electrostatic printing or electrostatic recording as hereinbefore mentioned. Then, the toner image may conveniently be transferred onto the textile fabric by the known corona dischar~e transfer, bias transfer or repulsion transfer, and then fixed in a conventional manner.
When a textile fabric is printed using the toner of the invention, it is preferred, in view of uniformity of color, build-up and avoidance of fog and stain of the back surface, that the transfer be carried out by placing a sheet having a smooth surface such as paper or film upon the back surface of the textile fabric to be printedg or by using a textile fabric preliminarily treated with a surface actlve agent or water-soluble polymer to give a surface resistivity of lx106 to lx1014 Q .
The coloring matter contained in the toner thus transferred onto the fabric may be fixed by sub~ecting the fabric to a heat or solvent steam treatment. Alternatively, the colorin~ matter may be fixed by a conventional dyeing technique. If desired, the fabric may then be washed with a solvent to eliminate the resin.

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; The toner of the invention may also be employed to print a textile fabric or leather by so called transfer printing using a support such as paper or film, onto which the toner is applied. Further, the toner may be employed for cross printing to obtain a multicolor effect on the ~ -printed fabric. In such a case, two or more toners con-taining different coloring matters of different shades ~ay be sequentially transferred to the fabric.
- The toner of the invention is excellent in coverage upon development in comparison with toners of the prior art. The known toners give a coverage of at most 0.6 to 0.7 mg/cm2 and, thus, result in low build-up. If a known toner is applied in a large amount, an excess accumulation of the toner occurs and the area of the plate which is not to be covered by the toner is stained by the excess of the toner. Thus, this stain yields so called fog. However, if the toner of the invention is used, the coverage of the toner is greatly increased and, thus, a printlng of high ;~
color intensity with no stain by unfixed toner can be obtained.
According to the toner of the invention, the trans-ference of the developed toner to the material to be printed is remarkably increased. The use of the prior art toners gives a transference of only about 40~, in the transfer to a textile fabric. However, a transference of the toner of the invention of up to about 80% can be attained even in the transfer to a textile material.
Further, the toner of the invention does not stain the back surface of the printed fabric. Textile fabrics generally have a high porosity and, therefore, upon the - 1~67742 transfer of the developed toner, the toner is passed through the 70res and ~iffused onto the back surface of the fabric. Thus~ the back surface of the printed fabric is stained by the toner passed through the pores. However~
the toner of the invention does not stain the back sur~ace of such a fabric.
Furthermore, the use of the toner Or the invention results in a uniformity of color such as of intensity and tone even when two or more toners are used as a blend.
However, in the use of the conventional toners, it has been difficult to obtain such uniformity of color. Parti-cularly, when the prior art toners are used as a blend of toners containing coloring matters of different shades, printings result which are not only non-uniform in co~lor as a whole but also of non-uniform color in portions, which portions are dotted with innumerable points of different shades.
Still further, the toner of the invention is excellent in durability in repeated printing. That is, the tone of the color of the obtained printings and the flowability of the toner are very durable in repeated printing for a long time of period.
The features of the invention will now be more distinctly illustrated by the following illustrative, but not limitative examples. In the examples, all parts are by weight. The evaluation results given in the examples were obtained as follows.
A. Color Intensity Under the evaluation standard shown below, a ~ 30 five step evaluation was effected by 10 panelists skilled .' :
17 ~

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1067~42 in the art and their evaluation values were averaged.
.
1: ~7ery low in color intensity 2: Low in color intensity 3: Medium in color intensity 4: High in color intensity 5: Very high in color intensity -.
B. Uniformity of Color :
Under the followin~ standard 3 evaluation was carried out in the same manner as mentioned in A~ above.

1: Remarkable non-uniformity observed 2: Fair non-uniformity observed 3: Some non-uniformity observed 4: Little non-uniformity observed 5: No non-uniformity observed C. Stain of Bac~ Surface Under the followin~ standard, evaluation was carried out in the same manner as mentioned in A, above.

1: Remarkable stain observed 2: Fair stain observed 3: Some stain observed 4: Little stain observed 5: No stain observed D. Tone of Color Under the followin~ standard, the difference .. :

- 1 ~ - . .

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of tone of color of a sample with that o~ the first printed sample was evaluated in the same manner as ment~oned in A, above.

1: Great remarkable difference observed 2: Remarkable difference observed 3: Fair difference observed 4: Some difference observed 5: Little difference observed E. Angle of Repose (Flowability) A toner sample was charged in a transparent plastic vessel of a diameter of 5 cm and a thickness of 2 cm, up to the half volume of the yessel and the vessel was . 15 closed. The vessel was placed on a desk so that the circular sides thereof became vertical and the surface of the powder layer of the toner was horizontal. Then, the vessel was slowly rolled so that the surface of the toner layer was inclined. Thus, the angle of inclination at the time the surface of the toner layer began to slide was determined.
F. Fog Under the following standard, evaluation was carried out in the same manner as mentioned in A, above.

1: Remarkable fog observed 2: Fair fog observed 3: Some fog observed 4: Little fog observed 5: No fog observed - 19 - ~.

, , , . : . :

Example 1 , .
A zinc oxide photoconductive layer was uniformly charged by corona discharge in the dark and, then~ exposed to light through a monochromatic film of stripe-Patter to form a corresponding electrastatic latent image. ;
A mixture of a copolymer of diethylaminoethyl methacrylate and styrene, and Diacelliton Fast Scarlet R
(a disperse dye from Mitsubishi ~asei Co.~ C. I. 11150) in methyl ethyl ketone was poured, with stirring, lnto a large amount of water to form fine particles. The particles were then filtered and dried, and thus~ a toner substrate was obtained in a fine powder form. Then~ the toner substrate was immersed into a solut~on or dispersion of each of the various antistatic agents of low molecular weight organic compounds and inoreanic compounds as shown in Table 1 below. The substrate was then filtered and dried in a vacuum. Thus, a toner for electrostatic printing which had an antistatic agent applied to the surface of the toner substrate, was obtained.
Then, the latent imape was developed with the toner by magnetic brush method. Thereafter, a polyester fabric was placed upon the developed surface of the photoconductive layer and the toner was transferred onto the fabric by corona discharge and fixed by heat. The dye contained in the toner was then fixed by steaminp and the fabric was washed with trichlene. Thus, a printed fabric was obtained.
Uniformity of color and stain of back surface -evaluated with respect to the obtained fabric were as shown in Table 1. ~or comparison purposes, evaluation results of a fabric obtained as above but not using an ~:

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antistatic agent are also shown in Table 1.

Table 1 Uniformity Stain of No. Antistatic Agent of Color Back Surface 1 Benzoic acid 4.2 4.1 2 Sulfanilic acid 4.3 4.2 3 2 9 5-dichloroaniline 4.1 4.3 4 p-nitrotoluene Ll . 2 4 .1 5 Lithium chloride 4,3 I~,z

6 Calciu~ fluoride 4.1 4 . 2

7 - 2.7 2.8 15The antistatic agents used herein all have an electrification factor within the ran~e mentioned hereinbefore as preferable. From the above table, it is apparent that a toner to which a low molecular wel~ht organic compound or an inorganic salt having such a property has been ' applied is very effective for electrostatic printing.
Table 2 below shows unifor~.ity of color and back surface stain evaluated with respect to fabrics printed in a manner as described above. The printing was carried out by using a polyester fabric treated with a solution of a nonionic surface active agent, polyoxyethylene nonylphonol ether~ in trichlene so that the fabric had 0.5% by wei~ht of the surface active a~ent applied, or by placing a paper of a 0.15 mm thickness upon the back surface of a polyester fiber.

3o ~ 21 --:~ .
', . . , , ~ ' 106774Z -:

Table 2 - .:
Uni~ormity Stain of -~
No. Fabric Antistatic Agent of Color Back Surface 1 Treated wlth Benzoic acld 4.6 4.5 surfactant .~ 2 - do - Sulfanillc acld 4.5 4.5 3 - do - Llthium chloride 4.6 4.6 4 Placed upon Benzoic acid 4.4 4.3 paper - do - Sulfanilic acid 4.~ 4.4 6 - do - Lithium chloride 4.4 4.5 .: .
. ' From the above results, ln comparison wlth the ; results shown ln Table 1, it ls apparent t~at the printing ...~
, effect i5 increased by the pretreatment of the fabric to be printed or the use of a sheet material place on the t', ~ back surface of the fabrlc.

; Example 2 ,, .
,; Prlnted fabrics were obtained in a manner as described in Example 1, except that the nonionic surface active agents shown in Table 3 below were used as an antistatic agent, Proclon Blue H-B (a reactive dye from I.C.I. Co., C. I. 61211) was used as a coloring matter and a cotton fabric was used as a material to be printed. The printed fabrics were then evaluated. The results are shown in ~,l Table 3.
For comparison purposes, the evaluation results of a fabric obtained as above but not using an antistatic agent are also shown in Table 3.
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Table 3 Uniformity Stain of No. Antistatic Agent HLB o~ Color Back Surface 1 Polyoxyethylene cetyl ether 9.5 4.3 4.3 (5 mols of ethylene oxide) 2 Polyethylene glycol 13.3 4.2 4.4 monolaurate (average molecular weight of 4000) 3 Sorbitan monostearate6.8 4,5 4.0 4 Polyoxyethylene nonylphenol 8.9 4.4 4.1 ether (5 mols of ethylene oxide) ~ ~ 2.8 2.9 The antlstatlc agents used herein all have an ~;
electrification factor and HLB within the ranges mentioned hereinbefore as preferable. From the above table, it is apparent that a toner to whlch a nonionlc surface active agent having such a property has been applied is very effective for electrostatic printing.
1 part of the toner obtained above was blended with 2 parts of a toner which was prepared in the same manner as described above, except that Diamira Golden Yellow G
(a reactive dye from Mitsubishi Kasei Co. 9 C. I. 18852) was used as a coloring matter. A cotton fabric was printed using the toner blend in the same manner as described -above. ~he evaluation results are shown in Table 4 below.
Results obtained for a cotton fabric printed in the same manner as described above using a toner blend as described above9 but to which an antistatic agent was not applied, are also shown in Table 4.

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Table 4 Uniformity Stain of No. Antistatic A~ent of Color Back Surface 1 Polyoxyethylencetyl ether 4.3 4.3 (5 mols of ethylene oxide) 2 Polyethylene glycol monolaurate 4.2 4.4 (average molecular weight of 4000) 3 Sorbitan monostearate 4.4 4.1 -i 4 Polyoxyethylene nonylphenyl ether 4.4 4.2 (5 mols o~ ethylene oxide) _ 2.2 2.5 From the above table, it is seen that uniformity of color and back surface stain where a toner blend which does not have an antistatic agent applied thereto is used are very inferior in comparison with those where a single toner is used. However~ the use of a toner blend to which an ;' antistatic agent has been applied can resultln good printing.
Example 3 An electrostatic latent lmage was formed on a zinc oxlde photoconductive layer ln the same manner as descrlbed .~:
in Example 1.
'~l A mixture of polystyrene and Phthalocyanine Blue (an ., ~
~, organic pigment, C. I. 74160) in trichlene was spray dried to produce a toner substrate. The toner substrate was , treated using, as an antistatic agent, each of the various surface active agents shown in Table 5 below in the same ; manner as described in ~xample 1. Thus, a toner for electrostatic printing whereln a surface active agent was 3 applied to the surface of the toner substrate was obtained.
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10-67'74Z

Then, the latent image was developed with the toner by cascade method. Thereafter, a polyester-cotton fabric was placed upon the developed surface, and the toner was transferred onto the fabric by the bias roll method and fixed in trichlene steam. Thus, a printed fabric was obtained. .
Evaluation results for the printed fabric are shown J
in Table 5. In the table, results obtained for a fabric printed in the same manner as described above but using a ~:
10 toner to which a surface active agent was not applied are .
also shown. .
.
Table 5 Uniformity Stain cf 15 No. Antistatic Agent of Color Bac~ Surface 1 ~rimethylolpropane monooleate 4.3 4.4 2 Pentaerythrltol monostearate 4.4 4.0 :
3 Polyoxyethylene laurylamine ether 4.5 4.1 (10 mols of ethylene oxide) 4 Sodium dodecylbenzenesulfonate 4.2 4.3 5 Sodium salt of octyl phosphate 4.5 4.1 6 Sodium salt of octyl alcohol sulfaric 4.1 4.4 acid ester , 7 Octadecyltrimethyla~imoniwm chloride 4.4 4.1

8 Octadecylamine acetate 4.4 4.0 ~ .

9 Dodecylimidazoline 4.3 4.2 lO - 2.9 2.7 The antistatic agents used herein all have an . 3O electrification factor within the range mentioned hereinbefore .~ :
- 2~ ~ .
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as prePerable. From the above tableg it is seen that a toner9 to which has been applied a surface active agent having such a property is very effective for electrostatlc printing.
Polyethylene terephthalate films cut in a ribbon shape were arranged and bonded onto an aluminlum plate at `-regular intervals to produce a xerographic printing plate.
The film area on the plate was positively charged by corona discharge. A fabric was printed uslng the plate and a toner as described above but to whlch each of the antistatic '~ agents shown in Table 6 below had been applled. Evaluatlon results for the printed fabric are shown in Table 6. In the table, evaluation results rOr a printed fabrlc obtained , as mentloned above but to which an antistatic agent had not been applied are also shown.
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Table 6 Uniformity Staln of No. Antistatic Atent of Color Back Surface 1 Lauryldlmethylbetaine 4.3 4.1 ~ 2 Polyethylene glycol monostearate 4.2 4.4 ; (average molecular welght of 4000) 3 - 2.8 2.7 As is apparent from the above table, toners accord-ing to the invention are useful for xeroprinting method.
Example 4 A photoconductive plate consistlng of cadmium sulfide as a photoconductive layer and polyethylene terephthalate - 30 as an insulating layer was uniformly and positively charged ; 26 -by corona discharge. Then~ the plate was exposed to light reflected from an ob~ect having monochromatic vertical stripe patterns and concurrently sub~ected to alternating current corona discharge. Therea~terg the plate was -uniformly exposed to light to form a latent image.
A mixture of one Or the resins shown in Table 7 ;-below, Brilliant Carmine 3B (an organic pigment 9 C~ I. ;
16015) and one of the antistatic a~ents shown in Table 7 in trichlene was spray dried to obtain a toner wherein an antistatic agent was incorporated in the toner substra~.
Then, the latent image was developed using the toner by magnetic brush method. The developed surface was sub~ected to positive corona dischar~e. A polyest~r-cotton fabrlc was placed upon the surface and, then, grounding rolls were rolled over the back surface of the fabric to transfer the toner onto the ~abric. Theng the toner composltion was fixed by heat and a printed fabric was obtained.
'~Evaluation results for the obtained fabric are shown ln Table 7. In the table~ results where an antistatic agent was not used are also sho~n.

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;, - 27 -Table 7 Color Stain of No. Resin Antistatic ~r,ent Intensity ~ ck Surface 1. Copolymer of N-methylpyridinium 4.1 4.5 diethylaminoethyl chloride methacrylate and styrene 2. Copolymer of methyl Phenol 4.4 4.2 methacrylate and aminomethyl me~hacrylate 3. Polystyrene ~richlorobenzene 4.2 4.3 4. Copolymer of - 2.8 2.9 `
diethylaminoethyl -methacrylate and ;I styrene 5. Copolymer of methyl - 2.6 2.8 methacrylate and aminomethyl methacrylate 6. Polystyrene - 2.6 2.7 , : ,, As is seen from the above table, a ~ood printlng ¦; can be obtained, which does not depenc~ upon the type of l' resin by incorporating an antistatic agent in a toner 1 20 substrate.

i A printed fabric was obtained as mentioned above, .i except that a toner was used which was prepared by applying an antistatlc agent to the surface of the toner substrate in the same manner as described in Example 1 9 but using the resins~ organic pigments and antistatic agent mentioned above. The evaluation results are shown in Table 8 below.
Results obtained where no antistatic agent was used are also shown in the table.

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: 1067~4Z
Table 8 ~
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~Tniformity Stain of .
No. Resin Antistatic Agent of Color ~ack Surface 1. Copolymer of N ~thylpyridinium 4.3 4.4 ;~
diethylaminoethyl chloride .
methacrylate and - -~
5 styrene 2. Copolymer of methyl Phenol 4.4 4.3 methacrylate and .
aminomethyl methacrylate 3. Polystyrene Trichlorobenzene 4.3 4.4 4. Copolymer of - 2.9 2.7 :: 10dlethylaminoethyl . methacrylate and styrene 5. Copolymer of methyl - 2.7 2.8 methacrylate and .
aminomethyl .. , methacrylate 156. Polystyrene - 2.8 2.8 ~ .
:, From the above table, it is seen that a good prlnting can also be obtained, which does not depens~ upon the type .
... .
' of the resin, by applying an antlstatic agent to the .
:; 20 surface of the toner substrate. ~ :
Example 5 . A selenlum sensitlve plate was unlformly and posltively .
charged by corona discharge in the dark. Then, the plate was exposed to light reflected from an object having -l 25 lateral stripe patterns to form an electrostatic latent ~ image.
1 A mixture of polystyrene, Miketon Fast Pink FF3B (a disperse dye from Mltsui Toatsu Co. C.I. 62015) and one of the antistatic agents shown in Table 9 below in trichlene was spray dried to obtain a toner with an antistatic agent ':
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incorporated in the toner substrate.
Then, the latent image was developed using the toner by magnetic brush method and the toner was transferred onto a paper in the same manner as described in Example 4 and fixed by heat. A polyester fabric was then placed upon the surface of the paper fixed with the toner and the -dye contalned in the toner was transferred and fixed onto the fabric by heating. Thus 9 a printed fabric was obtained.
Evaluation results for the printed fabric are shown ln Table 9. Results obtained where no antistatic agent was used are also shown in the Table.
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Table 9 Color Stain of No. Antistatic Ag,ent IntensityBack Surface 1. Aluminium powder 4.4 4.' 2. Copper powder 4.5 4.2 ; 3. Calcium oxlde 4.1 4.3 i;l 4. Titanium dioxide 4.3 4.4 5. _ 2.7 !~

From the above table9 it is apparent that a good printing can be obtained by applying a metal powder or , . .
metal oxide as an antistatic agent to the toner substrate.
Example 6 A zlnc oxide photoconductive layer was uniformly charged by corona discharge in the dark. Then9 the sheet was exposed to light through a monochromatic film of stripe-patterns to form a corresponding electrostatic latent image.
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A mixture of a copolymer of styrene and l-hydroxy-2~ diethylaminopropyl methacrylate and ~ayaku Acid Red 3B (an acid dye from Nippon Kayaku Co., C.I. 24810) in trichlene was spray dried to obtain a toner substrate.
The toner substrate was dipped lnto an aqueous solution of a nonionic surface active agent/ polyoxyethylene nonylphenol ether (containing 4 mols of ethylene oxide,HLB of 8.9), ~ -filtered and dried in vacuum. Thus, a red shaded toner~ ~-for electrostatlc printing was obtained which had a surface active agent applied to the surface of the toner substrate.
A yellow shaded toner was obtained in the same -~
manner as described above~ except that Suminol Fast Yellow R (an acid dye from Sumitomo Kagaku Co., C.I. 18835) was used as a coloring matter.
Three parts of the red shaded toner was blended wlth 7 parts of the yellow shaded toner. Then, a latent '` image was developed using the toner blend by magnetlc brush method and, thereafter 9 a nylon fabric was placed upon the developed surface. The toner blend was transferred ,~ onto the fabric by corona discharge and fixed by heat.
The dyes contained in the toners were then fixed by steaming and the fabric was washed with trichlene. Thus, a prlnted , fabric was obtained.
Evaluation results for the obtained fabrlc are shown in Table 10 below. Results obtained for a printed fabric where no surface active agent was used are also shown in the Table.

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Table 10 Coverage of Sur~actant Uniformity Stain of No, (%) of Color Back Surface -1 0.0~5 2.8 3-2. 0.03 4.0 4.1 3. 0.09 4.3 4.3 4. 1.03 4.5 ~.6 5. 2.01 4-7 4-4 6. 4.97 4.7 4.2 9.68 4.8 4.1 8. - 2.1 2.7 :' i As seen from the above tableg uniformity of color and avoidance of back surface stain are obtained when at least 0.01~, based on the welght of the toner substrate, of a nonlonlc surface active agent is applied to the surface of the toner substrate.
Example 7 A mixture of a copolymer as described in Example 6, Cibacet Blue F3R (a disperse dye from Ciba-Geigy Co., C.I. 61505) and a nonionic surface active agentl sorbitan monopalmltate (HLB of 6.7), of the amount shown in Table 11 below in trichlene was spray dried to obtain a toner.
Prlnting was then carried out in the same manner as descrlbed ln Example 6, except that a straw paper was used instead of a nylon fabric. Thus, a printed paper of blue shaded stripe patterns was obtained.
Then, a polyester fabric was placed on the printed surface of the paper and the blue shaded stripe patterns . ' 106~742 -:

were transferred and fixed by heatinf, on a pantex.
Evaluation results for the obtained fabric are shown in liable 11. Results obtained where no sur~ace active agent was used are also shown in the table.

Table 11 `

Content Or Surfactant Color I~O. (%) Intensity 1. 0.05 3.2 2. 0.3 4.0 3. 1.0 4.4 4. 5.0 4.5 5. 10.0 4.6 6. - 2.2 As is apparent from the above table, an increase of the color intensity is obtained when 0.1,'" based on the weight of the toner, of a nonionic surface active agent is incorporated in the toner substrate and the color intensity is increased further as the content of the surface active agent is increased.
Example 8 A sensitive plate consisting of cadmium sulfide as a photoconductive layer and polyethylene terephthalate as an insulating layer was uniformly and positively charged by corona discharge. Then the plate was exposed to light reflected from an object having monochromatic vertical stripe patterns and9 concurrently, sub~ected to alternat-ing current corona discharge. Thereafter~ the plate was `: . 106774Z
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uniformly exposed to light to form a latent image.
A mixture o~ a copolymer of styrene and 2-hydroxyethyl methacrylate and Diacelliton Red R l~/D (a disperse dye from Mitsubishi Kasei Co.~ C.I. 11210) in methyl ethyl ketone was poured into a large amount of water to form fine particles. The particles were then dried. Thus a toner substrate was obtained in a fine powder form. Then, the toner substrate was dipped into an aqueous solution of -a nonionic surface active agent, polyethylene glycol monooleate (average molecular weight of 300 9 HLB of 10~3)y flltered and dried. Thus, a red shaded toner for electro-static printing was obtained.
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A yellow shaded toner was also prepared in the same manner as described above but using Celliton Fast Yellow RR (a disperse dye from BASF Co., C.I. 10345) as a color-ing matter.
1 part of the red shaded toner was blended with 2 ~arts of the yellow shaded toner. Then, a latent image was developed using the toner blend by magnetlc brush method. The developed surface was subjected to positive - corona discharge. A polyester fabric was placed upon the surface and, then, grounding rolls were rolled over the back surface of the fabrlc to transfer the toner blend onto the fabrlc. The toners were then flxed by heat and the dyes contained in the toners were fixed by steaming.
After washing wlth trichlene~ a printed fabric having orange shaded stripe patterns was obtained.
The printing mentioned above was repeated ten thousands times and the durability of the toners in color intensity, uniformity of color, avoidance of stain by .
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unfixed toner, avoidance of back surface stain and tone of --.:. :' .
color was evaluated. The results are shown in Table 12 below.

5Table 12 Stain of Repeated Color Uniformity Back Tone of No. No. Intensity of Color Fog Surface Color 1. 1 4.3 4.3 4.1 4.3 -2.100 4.3 4.3 4.2 4.3 5.0 3.500 4.3 4.3 4.2 4.3 4.9 4.loOo 4.3 4.2 4.2 4.2 4.9 5.2000 4.4 4.2 4.1 4.2 4.8 6.5000 4.4 4.2 4.0 4.2 4-7 7.1000 4.4 4.1 4.0 4.2 4.7 ' .`
~ As ls seen from the above table, when a nonionlc . .
, surface actlve agent is applied to the toner substrate, ..
' even where two toners are used as a blend, the color lntensitya uniformity of color, avoidance of stain by unfixed toner and avoidance of back surface stain, as ` well as the tone of color are very consistant over a very large number fabric prlntings.
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Example 9 -A prlnted fabrlc was obtalned ln the same manner as descrlbed in Example 6, except that a triazine derivative as shown in Table 13 below was used instead of polyoxyethylene nonylphenol ether. The evaluation results are shown in Table 13. Evaluation results obtalned where no triazine dervative was used are also shown in the table.
,,: , Table 13 Stain of Coverage in Uniformity Back No. qriazine Derivative Average (%) of Color Surface N ~ N 1.96 4.7 4.3 NaO3S~ -HN-~N~-NH~so3Na Cl 2 H31C15 - N ~ ~N N ~515 31 2.05 4.5 4.4 ..HOOCH2C ~ CH2COOH

Cl 3H3C ~ ~ N JN N ~C 3 1.99 4.7 4.2 H03PH2CH2C CH2CH2P3H .-Cl 4H21C10 N N S03H 2.18 4.6 4.2 N ~NJ N
HOOCH2C ' ~ S03H

Cl 5N ~ N - ~ 1.88 4.7 4.3 cl-~NJLNH~)~so3Na Cl 6Cl ~ ~ N ~ 4 5 2.01 4.5 4.4 Cl :
7Hl C N N 1.95 4.4 4.4 7 8~ N~ N ~-NH ~ so3H
HOOCH2C / ---~

Cl : CH ~ CH
:, 8~-~~ 3N N 3~r--~ 1.91 4.5 4-3 '' ,~/-HN-~N~-NH~

: S03H

_ - 1.3 2.7 . ..
: ... . ,, . :, . . .

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106774Z : -:.
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The triazine derivatives used as described above ; all had an electrification factor within the range mentioned hereinbefore as preferable. From the above table, it is seen that a toner to which has been applied a triazine ~, derivative having such a property is very effective for electrostatic printing.
The same effects were obtained where the triazine derlvatives were incorporated in the toner substrate.
` ~xample 10 ~ ' A toner substrate was prepared by blending polystyrene and Diacelliton Fast Scarlet R (a disperse dye from Mitsubishi Kasei Co., C.I. 11150) in a hot roll mlll, grinding the blend roughly and then grinding it finely. ;
The toner substrate was dipped into an aqueous solution of -~
a triazine derlvative of the formulag .'' :~
Cl N ~ N
Cl ~ N NH ~ ~S3Na ' 20 and then filtered and dried. Thus, a toner wherein the trlazine derivative was applied to the surface of the - toner substrate was obtained.
Then, in the same manner as described in Example 8, a latent image formed on a sensitive plate consisting of cadmium sulfide and polyethylene terephthalate was developed using a mixture of the toner and iron powder by magnetic brush method~ and then transfer printing was repeated in the same manner as described in Example 8. Theng the 3 remaining mixture of the toner and the iron powder was ... ~ . .... . . .. . ... . ..

1067'742 agitated in a current of compressed air, the toner separated was collected and the flowability thereof was determined.
The results are shown in Table 14 below.

Table 14 No. Repeated No. Angle of Repose ~degree 1. 0 36 - 2. 1000 38 ; 10 3. 5000 35 4.10000 37 From the above table, it is apparent that the flowability of the toner to which has been applied a triazine derivative is stable during repeated printing.

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Claims (6)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A toner for the electrostatic printing of a sheet-like material, which comprises a toner consisting essentially of at least one resin and at least one coloring matter, and a triazine derivative applied to the surface of or incorporated in said toner said triazine derivative being selected from those of the formulae:

and wherein X is a halogen; and Y is a radical of the formula:
- A ?SO3M) - A ?COOM) - A ?PO3M) or wherein A is -NH(CH2)m- or R is hydrogen or alkyl having 1 to 18 carbon atoms;
M is hydrogen or an alkali metal atom;
m is an integer of 1 to 5.

2. A toner according to claim 1, wherein said triazine derivative is selected from those consisting of and . 40

3. A toner according to claim 1, wherein said triazine derivative has an electrification factor of from 100 to 2,000.

4. A toner according to claim 1, wherein said triazine derivative is applied to the toner in an amount of not less than 0.01% based on the weight of said toner.

5. A toner according to claim 1, wherein said triazine derivate is incorporated in the toner in an amount of not less than 0.1% based on the weight of said toner.

6. A toner according to claim 1 having a particle size of less than 80 µ.