CH621006A5 - Toner for electrostatic printing of sheet materials - Google Patents

Description

The present invention relates to a toner 2o for electrostatically printing sheet materials, which contains an antistatic substance which has a polar group and is capable of controlling the build-up of static electricity, and this toner is particularly suitable for electrostatic printing on Textile material. 2s

Recently, electrophotography, electrostatic electrography and the like have been significantly developed, and there has been no lack of attempts to transfer these operations to other areas of technology. For example, so-called electrostatic printing has been proposed, in which a toner image is transferred onto a paper, a textile structure or similar substrates directly or with the interposition of a printing medium. The toner image mentioned can be obtained by various methods, for example by electrophotography such as xerography or electrofax, by electrostatic recording or electrostatic printing, for example xeroprinting or electrostatic gravure printing, or else by the so-called TESI technology.

The toner used in this electrostatic printing generally consists of a fine powder of a mixture of a synthetic resin such as styrene resin, acrylic resin or epoxy resin or a natural resin such as rosin or Dammar, and a colorant such as a dye or pigment . In an improved toner 45, special resins and colorants are used in specific proportions, or a third substance is added. However, the use of known toners gives unsatisfactory prints because these prints have little build-up, show fogging and the color 50 is uneven. In particular, with electrostatic printing on textile fabrics, it has been very difficult to achieve satisfactory results because of the unevenness and the roughness of the surface and the high porosity of the fabric. 55

The object of the invention was therefore to create a new type of toner for electrostatic printing, which behaves permanently in the case of repeated printing processes and is capable of being applied to a textile fabric 60 easily, uniformly and with a high build-up capacity and without soiling the fabric, which also gives better coverage during development and is easier and more uniform to transfer, and which can also be used without difficulty in multiple printing, giving multicolored prints, or as a mixture of toners containing b5 different colorants.

The invention now proposes a toner for electrostatically printing a sheet material with a

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Toner base containing at least one resin and at least one colorant, and which is characterized in that it contains an antistatic agent having a polar group capable of controlling the accumulation of static electricity, which antistatic agents are present on the surface of the toner particles or in a mixture with the toner base substance.

The term "toner base substance" refers to a mixture which contains at least one resin and at least one colorant. The basic toner substance can also contain the usual known additives such as iron powder, coloring aids and finishing agents.

The resins are those which are commonly used in toner technology, and they consist, for example, of homopolymers or copolymers of monoolefinically unsaturated monomers such as ethylene, propylene, vinyl chloride, vinyl acetate, styrene, aminostyrene, methyl methacrylate or butyl methacrylate, and of modified polymers such as poly vinyl formal or mixtures thereof. In addition, polycarbonates and ethyl cellulose or polyacrylamide and polyvinyl alcohol can be used. Resins based on styrene monomers or methacrylate monomers and the polycarbonates or modified resins are particularly advantageously used.

The type of colorant is not critical to the present invention. Examples of such colorants are disperse dyes such as Diacelliton Fast Scarlet R (Misubishi Kasei Co., CI. 11150), Miketon Fast Pink FF3B (Mitsui Toatsu Co., CI. 62015), Celliton Fast Yellos RR (BASF Co., C.1.10345), Miketon Fast Orange GR (Mitsui Toatsu Co., CI. 11005), Kayaion Fast Scarlet B (Nippon Kayaku Co, C.1.11110), Kiacelliton Red RM / D (Mitsubishi Kasei Co, CI. 11210), Celliton Fast Violet B (BASF Co., CI. 62030), Cibacet Blue F3R (Ciba-Geigy Co, CI. 61505), Miketon Fast Turquoise Blue G (Mitsui Toatsu Co, CI 62500) and Kayaion Diazo Black B (Nippon Kayaku Co, CI 11365); Acid dyes such as Suminol Fast Yellow R (Sumitomo Kagaku Co, CI. 18835), Coomassie Fast Orange G (ICI Co, C.1.24780), Kayaku Acid Red 3B (Nippon Kayaku Co, CI. 24810), Acid Violet 5B (CI. 42640 ), Diacid Light Blue 2A (Mitsubishi Kasei Co, CI. 62055), Alizarine Fast Green G (Ciba-Geigy Co, CI 61570 and Supranol Fast Black VLG (Bayer Co, CI 27070); basic dyes such as Sumiacryl Orange G (Sumitomo Kagaku Co, C.1.48035), Auramine extra 0-125 (Sumitomo Kagaku Co, CI 41000), Astrazon Pink FG (Bayer Co, CI 48015), Diabasic Magenta (Mitsubishi Kasei Co, CI. 42510), Serron Blue 5G (EI Dupont Co, CI 51005) and Aizen Cathilon Gray BLH (Hodogaya Kagaku Co, C.1.11825); direct dyes such as Direct Fast Yellow GC (Mitsui Toatsu Co, CI. 2900), Benzo Scarlet GS (Bayer Co, CI. 29165), Diacotton Violet X (Mitsubishi Kasei Co, CI 22550), Direct Blue 2B (Nippon Kayaku Co, CI. 22610), Sumilight Supra Brown G (Sumitomo Kagaku Co, C.1.36200) and Direct Fast Black AB (Mitsubishi Kasei Co , C.I. 35440); Reactive dyes such as Procion Blue HB (ICI Co, CI. 61211), Diamira Golden Yellow G (Mitsubishi Kasei Co, CI. 18852), Procion Brilliant Yellow H-5G (ICI Co, CI. 18972), Cibacron Brilliant Orange GE (Ciba- Geigy Co, CI 17865), Mikacion Rubine BS (Nippon Kayaku Co, CI 17965), Cibacron Violet F2R-A (Ciba-Geigy Co, C.1.18157), Cibacron Brown 3GR-A (Ciba-Geigy Co, C.1.26440) and Procion Black HG (ICI Co, C.1.17916); oil-soluble dyes such as Zapon Fast Yellow CGG (BASF Co, C.1.18820), Ciaresin Red J (Mitsubishi Kasei Co, CI. 12715), Victoria Blue F4R (BASF Co, CI. 42563) and Nigrosine Base GB (Bayer Co, C. 1.50415), and pigments such as Brilliant Carmine 3B (C.1.16015), Benzidine Yellow G (C.1.21090), Benzidine Orange (C.1.21110), Lake Red 4R (CI 12120), Permanent Carmine FB (CI 12490), Fanal Violet R supra (CI. 42535), Phthalocyanine Blue (CL 74160), Fanal Green G Supra (CI. 42040), Permanent Brown FG (C.1.12480),

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Diamond Black (CI. 50440), Zinc White (CI. 77947), Titanium White (CI. 77891) and Russ (C.1.77265).

The antistatic substance used in the practice of the invention has a polar group and controls the build-up of static electricity on the toner. 5 In other words, the antistatic substance acts as a conductor and diffuser of the accumulated electrical charge or to limit the task of the electrical charge and thus limits the retention of the electrical charge on the toner. ok

It has been found that certain inorganic substances such as metals, metal oxides and inorganic salts, surface-active agents, polar organic compounds of low molecular weight and tri-azine derivatives can be suitably used for this purpose. Preferred anti-static agents are those which have an electrification factor from 100 to 2000, in particular from 200 to 1500.

The term “electrification factor” refers to an absolute value of the surface potential, which is determined as follows 20. A test sample is made

by processing a polystyrene, which had previously been mixed with 2% by weight of the antistatic agent to be tested, into a sheet with a thickness of 30 μm on an aluminum foil. This test sample is subjected to an inversion 25 of a positive corona discharge with a Bias current of 2.8 [iA if the antistatic agent is to be used in a positively charged toner or negative corona discharge with a bias current of 2.8 {iA if the toner is to be negatively charged, for a total of 20 30 seconds at 20 ° C and a relative humidity of 65%, then the surface potential of the test sample is determined.

Examples of inorganic substances are metals in the form of powder, for example Cu, Zn, Al, Si, Sb, W, Mn, Fe, Co and 35 Ni; Metal oxides such as ZnO, FezOî, AI2O3, CaO, BaO, MgO and TÌO2 as well as inorganic salts such as LiCl, NaCl, KBr, CuS04, Mg (N03) 2, CaF2, Al (OH) 3 and (NH4) 2S04. Metals such as Al, Si and Fe, metal oxides such as ZnO, AI2O3 and TÌO2 and salts such as LiCl and NaCl are preferably used. 40

The surfactants can be anionic, cationic, nonionic and ampholytic. Examples of anionic surface-active agents are the carboxylic acid salts such as soaps, salts of acidic sulfuric acid esters such as the salts of acidic sulfuric acid esters with higher alcohols, sulfated oils, sulfated fatty acid esters and sulfated olefins; Sulfonates such as alkylbenzenesulfonates, alkylnaphthalenesulfonates and alkylsulfonates and phosphoric acid ester salts such as salts of acidic phosphoric acid esters with higher alcohols. Among these substances, the sulfonates and the ester salts of phosphoric acid 50 are particularly preferred.

The cationic surface-active agents used are expediently, for example, amine salts such as the salts of primary amines, secondary amine salts, tertiary amine salts and salts of esters of ethanolamine and quaternary salts such as 55 tetraalkylammonium salts and pyridinium salts. Among these substances, the quaternary salts are particularly preferred.

Nonionic surfactants are, for example, alkylphenol ethers such as polyoxyethylene octylphenol ether,

higher alcohol ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; Sorbitan esters of higher fatty acids such as sorbitan monooleate, sorbitan distearate and polyoxyethylene sorbitan monooleate; Esters of pentaerythritol with higher fatty acids such as pentaerythritol monostearate; Esters of trimethylolpropane with higher fatty acids such as trimethylolpropane b5 monooleate; Esters of polyethylene glycol with higher fatty acids such as polyethylene glycol monooleate and polyethylene glycol distearate as well as nitrogenous substances such as polyoxyethylene

len laurylamine ether. Among these substances, preference is given to those whose HLB value is 3 to 19 and in particular those with an HLB value of 6 to 14.

Examples of ampholytic surface-active agents are carboxylic acid compounds such as betaines and amino acids, salts of acidic sulfuric acid esters such as the salts of aminoalkyl sulfates, sulfonates such as aminoalkane sulfonates and salts of acidic phosphoric acid esters, for example the salts of acidic esters of phosphoric acid with amino alcohols. Among these agents, the sulfonates and the salts of acidic phosphoric esters are preferred.

Polar, low molecular weight organic compounds are also suitable as antistatic agents for carrying out the invention. Compounds which can be used include the following: carboxylic acids such as aromatic carboxylic acids, for example benzoic acid, p-hydroxybenzoic acid and anthranilic acid, pyrrolidone carboxylic acid and N-acyl sarcosinate; Sulfonic acids such as alkanesulfonic acids, for example butane-2-sulfonic acid, salts of diethanolamine with alkylsulfonic acids, dialkylsulfosuccinic acids and their sodium salts and aromatic sulfonic acids, for example benzenesulfonic acid, sulfanilic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, the acidic salt of ethylenediaminate acid and the sodium salt of phenolsulfonic acid; Phosphoric acid esters such as the metal salts of dialkyl phosphoric acid esters, pentaalkyl tripolyphosphates and hexaalkyl tetrapolyphosphates; Phosphonic acids such as ethylmethylphosphonic acid salts, benzenephosphonic acid salts, methoxyphosphonic acid salts, ethoxyphosphonic acid salts, alkylallylphosphonic acid and alkoxyphosphonic acid salts; Amines such as alkylamines, for example the salts of phosphoric acid with tributylamine, hexamethylene diamine, dicyanoethylamine, diethanolamine and 2,5-dichloroaniline, amidoamines such as fatty acid hexamethylene diamine monoamide and N-monoacetylethylene diamine, cyclic amines such as alkylimidazoline and alkylmorpholine; and esters; and esters Ammonium salts such as quaternary ammonium salts, for example methylammonium chloride, ethyldimethylphenylammonium bromide and N-methylpyridinium chloride, tertiary ammonium salts such as triethylammonium chloride, secondary ammonium salts such as dipropylammonium chloride and primary ammonium salts such as n-butylammonium chloride; Halides such as ethyl bromide, o-dichlorobenzene, octyl chloride, chlorostyrene, chlorotoluene, dichloronaphthalene, 1,2,4-trichlorobenzene and o-dibromobenzene; Esters such as methyl acetate, methyl n-propionate, ethyl benzoate, terephthalic acid ester, octyl adipate and butyl adi-pat; Ethers such as ethoxypropane, methoxypropane, 1,3-dimethoxy-benzene, diethylene glycol dimethyl ether and glycidol; Epoxy compounds such as epichlorohydrin, propyl monoglycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and ethylene glycol diglycol diglycidyl ether; Alcohols and hydroxy compounds such as ethylene glycol, glycerin, 1,4-butanediol, cyclohexanol, sorbitol, mannitol, benzyl alcohol and octyl alcohol; Phenols such as phenol, cresol, xylenol, catechin, resorcinol, ethylphenol, chlorophenol and a-naphthol; Nitro compounds such as chloronitrobenzene, dinitrobenzene and nitrotoluene; Amides such as acetamide, propionamide, stearic acid amide, a-phenylamide and N, N'-dimethyl urea as well as semiconducting compounds such as carbazole complexes and thiazine complexes.

Tri-azine derivatives can also be used expediently to carry out the invention. Examples of the triazine derivatives that can be used correspond to the following formulas x x

^ H ^

n n and n n

"AÂ

5

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in which: X is halogen, Y is a radical of the formula -A— (SO ^ M), -A— (GOOM),

/ -R

—A— (PO M) or —TT

V 3 ^ -CH COOK,

whereA for —ÎJH (CH2) m, * -CH3N (CH2)

m;

-NH- (Ö). -NH- ^ rCH3,

-nh — IQJ or -nh 40j (>

Cl n

5 Na03S- ^ ~ ^) - HN-4> ^ -Q ^ Na

10th

h17C

, 5 h00ch

-i 7 c o n n / 7 ~ \\ 17 "^ N- ^ JJ — NH-w \ -i ch0c n \ /

so3h is, R is hydrogen or alkyl having 1 to 18 carbon atoms, M is hydrogen or an alkali metal atom and m is an integer from 12o to 5.

The triazine derivatives, which correspond to the above formulas, can be obtained in a known manner by reacting cyanuric halide with another reagent, for example sulfonic acids such as taurine, methyl taurine, aniline sulfonic acid, phenol-25 sulfonic acid, tolidine sulfonic acid, toluidine disulfonic acid, aniline disulfonic acid, naphthionic acid, l -Naphthylamine-3,6-disulfonic acid, Koch acid, H-acid, l-naphthylamine-3,7-disulfonic acid, 7-acid from Cleve, 8-acid from Cleve, amino-R-acid, y-di sulphonic acid, RM acid, tar acid, M acid, amino J acid, 30 Tobias acid and phenol disulfonic acid and their alkali metal salts; Carboxylic acids such as glycine, phenylglycine, aminobenzoic acid, aminobutyric acid, aminocaproic acid, aminopropionic acid and aminophthalic acid and their alkali salts and phosphoric acids such as aminomethanephosphonic acid, hydroxy-35 methanephosphonic acid, aminoethylphosphonic acid, aminobutylphosphonic acid and anilinephosphonic acid and anilinephosphonic acid and their anilinephosphonic acid.

The reaction can conveniently be carried out by reacting 1 or 2 moles of an acid or its salt as indicated above 40 with a mole of cyanuric halide in the presence of an acid binder and in an aqueous, organic or aqueous-organic medium at 0 to 5 ° C. If different groups Y are to be introduced, the reaction can be carried out in two steps. In the second step 45, the reaction is expediently carried out at 20 to 40 ° C. For example, acetone, methyl ethyl ketone and dioxane serves as the organic medium and, for example, potassium and sodium hydroxide, potassium and sodium carbonate, calcium, magnesium and barium hydroxide 50 and sodium acetate and bicarbonate serve as acid binders.

Some important representatives of the triazine derivatives that can be used are given in the following formulas:

cl 55

Cl n n

Cl— ^ -S03Na hooc sq3H

Cl

H0.Cnc- N N Cnc.HQ, 31 1 ^ n_ì ^^ jl_n / 15 31

h00ch2c / n xch2cooh

H21C10-hooch2C ^

Cl n n / r ~ ^ N — t ^ jl-m-S /

H

Cl n n n— ^> y-n;

h03pch2ch2 / n

, ch-

ch2ch2p03h n

Cl hcc „n n 5 ^ N-l ^ | i-ci

60

h00ch2c n

The toner according to the invention contains the aforementioned toner base substance and the antistatic, and it can be classified into one of the following three classes depending on its composition. The first class consists of a toner in which the antistatic agent is applied to the surface of the basic toner substance (this class is hereinafter referred to as type A); a further class is formed by a toner in which the antistatic is incorporated into the basic toner substance itself (called type B toner), and the third class comprises the toners which are composed of a mixture of the

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Type A and Type B exist (Type C toner). All three classes of toner fall within the scope of the invention and can be made as follows.

Type A toner

The constituents of the basic toner substance are dissolved and / or dispersed in a liquid medium such as dioxane, trichlorethylene, dimethylformamide, benzene or water. The mixture is then prepared so that a toner base substance is obtained which is in the form of particles or powder, for example by pouring the liquid mixture into a non-solvent, precipitation and drying, for example by spray drying, by gelation at low temperature, grinding and Drying, or by melt grinding. Then an antistatic agent is added to the basic toner substance in a suitable manner and according to procedures known per se. The application of the toner can, for example, expediently be carried out by dissolving or dispersing the antistatic in a liquid medium such as water, acetone or methanol, the liquid medium forming a non-solvent or a poor solvent for the basic toner substance, and the solution or Apply dispersion to the toner base by spraying or dipping, then filtering or centrifuging until an appropriate liquid content is reached and then drying. The antistatic agent is preferably applied to the toner base in an amount of not less than 0.01% based on the weight of the toner base.

Type B toner

With this type, the antistatic is incorporated into the basic toner substance. This incorporation can be carried out, for example, and expediently by dissolving and / or dispersing the constituents of the basic toner substance and an antistatic in a suitable medium, such as dioxane, trichlorethylene, dimethylformamide, benzene or water, and then working up the mixture into particles in a suitable manner , as described above, or by melting the constituents of the toner base substance, mixing an antistatic in the melt and then producing the particle shape by grinding. Other known and customary working methods can also be used for this training. The antistatic agent is preferably incorporated into the toner base in an amount of not less than 0.1% based on the weight of the toner base.

Type C toner

A toner of this class can be produced according to the procedures described above for types A and B.

The toner according to the invention may optionally also contain other substances, such as additives, and these substances can expediently be added during the production of the toner. The toner is preferably in a particle size of less than 80 (i, in particular less than 30 p) and can be appropriately classified in a liquid medium.

The toner can be applied to a textile structure, for example woven, knitted, crocheted or non-woven textile structures, all of which consist of natural fibers such as cotton, silk or wool or of semi-synthetic fibers such as viscose or cellulose acetate, and also of synthetic fibers such as polyesters, polyacrylonitrile or polyamide . The toner can also be used on paper, leather,

Films or metallic substrates are applied.

A toner image can be obtained by the usual suitable methods of electrophotography, electrostatic printing or electrostatic recording, as described above. The toner image can then be transferred to the textile structure by means of the known corona discharge, furthermore by means of bias transfer or repulsion transfer, after which it is fixed in a known manner.

When printing on a textile structure using the toner according to the invention, it is preferred, in view of the uniformity of the color, its structure and to avoid fogging and contamination of the rear surface, that the transfer is carried out by using a sheet with a smooth surface such as paper or film on the back surface of the textile structure to be printed on, or by using a textile structure which has been treated beforehand with a surface-active agent or a water-soluble polymer to give a surface resistance of IO6 to IO14 Q. receive.

The colorant, which is contained in the toner and has been transferred to the textile structure in this way, can be fixed by subjecting the textile material to a heat treatment or a 20 ° solvent vapor treatment. However, the colorant can also be fixed in a conventional way. If desired, the fabric can then be washed with a solvent to remove the resin.

The toner according to the invention can also be used to print a textile structure or leather by means of so-called transfer printing, using an auxiliary carrier such as paper or film on which the toner is deposited. In addition, the toner can also be used in multicolor printing if you want to print on the textile in multicolor. In this case, two or more toners containing different colored colorants are transferred to the textile in succession.

After development, the toner according to the invention gives significantly better hiding colorings compared to the prior art. The known toners result in a coverage of at most 0.6 to 0.7 mg / cm 2 and accordingly a poor color build-up. If a known toner is transferred in large quantities, excessive toner accumulation occurs and the surface areas of the plate which are not covered by the toner 40 are soiled by the excess of the toner. This results in the well-known formation of fog. When the toner according to the invention is used, however, the color density is significantly increased, and printing with high color intensities is obtained in this way without soiling due to unfixed toner.

With the toner according to the invention, the transfer of the developed toner to the substrate to be printed is greatly increased. When using the known toners, a degree of transfer of only about 40% results if one works in this way with a textile substrate. With the toner according to the invention, however, transfer values of up to 80% are obtained, even if a textile material is selected as the substrate.

Furthermore, the toner according to the invention does not soil the rear surface of the printed textile structure. In general, textile materials have a high porosity, and accordingly, when the developed toner is transferred, it passes through the pores and diffuses onto the rear surface of the fabric. As a result, this area of the printed textile material is contaminated by the toner which passes through the pores. However, the toner according to the invention does not soil the rear surface of such a textile material.

Furthermore, the use of the toner according to the present invention gives a uniform color as well as an intensity 65 of the tone, even if two or more toners are used in a mixture. However, when using the known toners, it was difficult to achieve such a uniform color. Especially when using the

7

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Known toners as a mixture of several toners with different colored colorants produce prints which are not only uneven in their coloring as a whole, but whose individual colored areas are also non-uniform, these areas appearing stippled with countless dots of other colors.

Finally, the toner according to the invention is excellently suitable for durability in the case of repeated printing. This means that the hue of the prints obtained and the flow properties of the toner do not change over long periods of time when printed repeatedly.

The features according to the invention will now be explained in detail by means of the following, illustrative and non-limiting examples. In these examples, all parts are to be understood as parts by weight. The test results given in the examples were obtained as follows.

A. Color intensity

According to the evaluation basis given below, an evaluation in five stages was carried out by 10 experts, and their evaluations were averaged.

1: very low color intensity 2: low color intensity 3: medium color intensity 4: high color intensity 5: very high color intensity

B. Uniformity of color

According to the following standard, the evaluation was carried out as described under A above.

1: significant unevenness 2: strong unevenness 3: weak unevenness 4: low unevenness 5: no unevenness

C. Soiling of the rear surface

According to the following standard, the evaluation was carried out as described under A above.

1: heavy pollution 2: moderate pollution 3: weak pollution 4: very low pollution 5: no pollution

D. Hue

According to the following standard, the color differences of a sample with that of the first printed sample were assessed in the same way as described under A.

1: very large color difference 2: strong color difference 3: medium color difference 4: small color difference 5: small to no color difference

E. Angle of rest (fluidity)

A sample of the toner was placed in a transparent plastic vessel 5 cm in diameter and 2 cm in thickness up to about half of the volume of the vessel, and then the vessel was closed. The vessel is now placed on a base such that the circular walls are vertical and the surface of the powder layer is horizontal. Then the container is rolled slowly so that the surface of the toner layer is inclined. The angle of inclination at the moment when the surface of the toner layer starts to slide was determined.

F. Fogging

According to the following standard, the evaluation was carried out as described under A above.

1: strong fog 2: medium fog 3: weak fog 4: very weak fog 5: no fog

example 1

In the dark, a photoconductive layer of zinc oxide was uniformly charged by corona discharge and then exposed through a monochromatic film with a stripe pattern to form a corresponding electrostatic latent image.

A mixture of a copolymer of diethylaminoethyl methacrylate and styrene and diacelliton Fast Scarlet R (a disperse dye from Mitsubishi Kasei Co., C.1.11150) in methyl ethyl ketone was poured into a large amount of water with stirring, with fine particles precipitating out. These particles were then filtered off and dried to obtain a toner base in the form of a fine powder. The toner base was then placed in a solution or dispersion of the various low molecular weight antistatic agents based on organic and inorganic compounds shown in Table I. The basic substance was then filtered and dried in vacuo. In this way an electrostatic printing toner was obtained which had an antistatic on the surface of its particles.

The latent image was developed using the toner by the magnetic brush method. Thereafter, a polyester fabric was placed on the developed surface of the photoconductive layer, and the toner was transferred to the fabric by corona discharge and then heat set there. The dye contained in the toner was then fixed by steaming and the fabric was washed with trichlorethylene. In this way, a printed fabric was obtained.

The uniformity of the coloring and the soiling of the back surface were assessed and the assessments are given in Table I. For the purpose of comparison, Table I also shows the results obtained by working in the same way with a toner which has no antistatic.

Table I

No.

Antistatic

Uniformity of color

Soiling the back

1

Benzoic acid

4.2

4.1

2nd

Sulfanilic acid

4.3

4.2

3rd

2,5-dichloroaniline

4.1

4.3

4th

p-nitrotoluene

4.2

4.1

5

Lithium chloride

4.3

4.2

6

Calcium fluoride

4.1

4.2

7

-

2.7

2.8

The antistatic agents used here all have an electrification factor which falls within the range designated as preferred above. The table above shows that a toner which is provided with a low molecular weight organic or inorganic compound is extremely suitable for electrostatic printing.

Table II below shows the uniformity of the dyeing and the soiling of the back of fabrics which had been printed in the above manner. Here

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

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8th

the printing was carried out on a polyester fabric which had previously been treated with a solution of a nonionic surfactant, namely polyoxyethylene nonylphenol ether in trichlorethylene, such that the fabric had taken up 0.5% by weight of the surfactant used, or by placed a paper 0.15 mm thick on the back of a polyester fiber.

Table II

No.

tissue

Antistatic

Color equality

Soiling the back

1

With

Benzoic acid

4.6

4.5

Wetting agent

treated

2nd

do

Sulfanilic acid

4.5

4.5

3rd

do

Lithium chloride

4.6

4.6

4th

on paper

Benzoic acid

4.4

4.3

hung up

5

do

Sulfanilic acid

4.4

4.4

6

do

Lithium chloride

4.4

4.5

contains nonionic surfactant, is very suitable for electrostatic printing.

1 part of the toner obtained and used as above was mixed with 2 parts of a toner which was produced in the same manner as described, but which was used as the dye Diamira Golden Yellow G (a reactive dye from Mitsubishi Kasei Co, C. 1.18852). A cotton fabric was printed with this toner mixture in the same way as described. The evaluation results can be found in Table IV below.

A cotton fabric was printed in the same manner, but without using an antistatic in the toner, and these comparative values are also given in Table IV.

Table IV

From the above results, in conjunction with those of Table I, it can be seen that the pretreatment of the fabric or the use of sheet material on the back of the fabric greatly improves the pressure.

Example 2

Printed fabrics were produced according to Example 1, with the exception that the nonionic wetting agents listed in Table III were used as antistatic agents, Procion Blue H-B (a reactive dye of I.C.I. Co, C.1.61211) and a cotton fabric as the printing substrate. The printed fabrics were then assessed. The results can be found in Table III.

For comparison, the evaluations of the same fabric are listed, but no antistatic agent was used when printing.

Table III

25th

35

40

No.

Antistatic

HLB

Levelness of

coloring

Soiling the back

1

Polyoxyethylene cetyl ether (5 moles of ethylene oxide)

9.5

4.3

4.3

2nd

Polyethylene glycol monolaurate (average molecular weight 4000)

13.3

4.2

4.4

3rd

Sorbitan monostearate

6.8

4.5

4.0

4th

Polyoxyethylene nonyl phenol ether (5 moles of ethylene oxide)

8.9

4.4

4.1

5

-

-

2.8

2.9

50

55

The antistatic agents used here all have b5 values for the electrification factor and the HLB, which fall within the ranges previously designated as preferred. The table above shows that a toner which is a

No.

Antistatic

Levelness of coloring

Soiling the back

1

Polyoxyethylene cetyl ether (5 moles of ethylene oxide)

4.3

4.3

2nd

Polyethylene glycol monolauate (average molecular weight 4000)

4.2

4.4

3rd

Sorbitan monostearate

4.4

4.1

4th

Polyoxyethylene nonylphenyl ether (5 moles of ethylene oxide)

4.4

4.2

5

-

2.2

2.5

This table shows that the color level and soiling of the back are much poorer when using a toner mixture without an antistatic agent compared to the values that can be obtained with a single toner. When using a toner mixture with an antistatic, excellent printing is again achieved.

Example 3

An electrostatic latent image was formed on a zinc oxide photoconductive layer in the same manner as in Example 1.

A mixture of polystyrene and phthalocyanine blue (an organic pigment, C.1.74160) in trichlorethylene was spray dried to obtain a toner base. This base substance was treated with the various wetting agents listed in Table V as an antistatic in the same way as described in Example 1. This gave an electrostatic printing toner containing a surface active agent on the surface of its particles.

The latent image was then cascaded with the toner. A mixed fabric made of polyester and cotton was placed on the developed surface and the toner was transferred to the fabric using the cross-roll method and fixed there in trichlorethylene vapor. In this way, a printed fabric was obtained.

The evaluation of the printed fabric is shown in Table V. This table also lists the values obtained after printing the same fabric, but with a toner that did not contain an antistatic.

9

621006

Table V

No.

Antistatic

Levelness of coloring

Soiling the back

1

Trimethylolpropane mono-oleate

4.3

4.4

2nd

Pentaerythritol monostearate

4.4

4.0

3rd

Polyoxyethylene laurylamine ether (10 moles of ethylene oxide)

4.5

4.1

4th

Sodium dodecylbenzenesulfonate

4.2

4.3

5

Sodium salt of octyl phosphate

4.5

4.1

6

Sodium salt of the ester of sulfuric acid with octyl alcohol

4.1.

4.4

7

Octadecyltrimethylammonium chloride

4.4

4.1

8th

Octadecylamine acetate

4.4

4.0

9

Dodecylimidazoline

4.3

4.2

10th

-

2.9

2.7

Table VI

20th

25th

The antistatic agents used all had an electrification factor in the range designated above as preferred. The table shows that a toner which contains a surface-active agent with the stated properties on the surface of its particles is excellently suitable for electrostatic printing.

Polyethylene terephthalate films cut into strips were placed on an aluminum plate at regular intervals and fixed thereto, thereby obtaining a xerographic printing plate. The film surface on the plate was positively charged by corona discharge. A fabric was printed with this plate and a toner composed as described above, but which had included one of the antistatic agents described in Table VI. The evaluation of the printed fabric is shown in Table VI. For comparison, this table also shows a pressure in which the toner contained no antistatic.

No.

Antistatic

Levelness of

Scum

Coloring tongue

the back

1

Lauryldimethylbetaine

4.3

4.1

2nd

Polyethylene glycol monosteal

4.2

4.4

advice (middle

Molecular weight 4000)

3rd

-

2.8

2.7

The table shows that toners according to the invention are well suited for xeroprinting.

Example 4

A photoconductive plate made of cadmium sulfide as the photo-conductive layer and polyethylene terephthalate as the insulation layer was evenly positively charged by means of corona discharge. Then the plate was exposed to the light reflected from an object equipped with a monochromatic vertical stripe pattern and simultaneously subjected to an AC corona discharge. Then the plate was exposed evenly to form a latent image.

A mixture of one of the resins shown in Table VII, the dye Brilliant Carmine 3B (organic pigment, CI. 16015) and one of the antistatic agents listed in Table VII in trichlorethylene was spray-dried to obtain a toner, the toner base of which was an antistatic contained.

Then the latent image was developed using this toner by means of a magnetic brush. The developed surface was subjected to a positive corona discharge. A blend of polyester and cotton was placed on this surface and then the toner was transferred to the fabric by rollers which acted on the back of the fabric. Finally the toner was heat set and a printed fabric was obtained.

The evaluation of the results on the tissue obtained are summarized in Table VII. This table also shows results of tests in which the toner did not contain an antistatic.

Table VII

No resin

Antistatic

Color uniformity Soiling of the back

1 copolymer of diethylaminoethyl methacrylate and styrene

2 copolymer of methyl methacrylate and aminomethyl methacrylic lat

3 polystyrene

4 copolymer of diethylaminoethyl methacrylate and styrene

5 copolymer of methyl methacrylate and aminomethyl methacrylic lat

6 polystyrene

N-methylpyridinium chloride

phenol

Trichlorobenzene

4.1

4.4

4.2 2.8

2.6

2.6

4.5

4.2

4.3 2.9

2.8

2.7

i

621006

10th

This table shows that a good print is obtained, which does not depend on the type of resin, but depends on whether an antistatic agent is incorporated into the basic toner substance.

A printed fabric was made in the same manner, except that a toner was used in which an antistatic was applied to the surface of the toner particles according to the procedure of Example 1, using the same resins, organic pigments and antistatic agents were used as indicated above. The results of the evaluations are shown in Table VIII. There are also comparative values in which no antistatic was used.

Table VIII

No resin

Antistatic

Color uniformity Soiling of the back

1 copolymer of diethylaminoethyl methacrylate and styrene

2 copolymer of methyl methacrylate and aminomethyl methacrylate

3 polystyrene

4 copolymer of diethylaminoethyl methacrylate and styrene

5 copolymer of methyl methacrylate and aminomethyl methacrylate

6 polystyrene

N-methylpyridinium chloride

phenol

Trichlorobenzene

4.3

4.4

4.3 2.9

2.7

2.8

4.4 4.3

4.4 2.7

2.8

2.8

The table above shows that you also get a good print, which does not depend on the type of resin, if you put an antistatic on the surface of the toner particles.

Example 5

A light-sensitive plate made of selenium was positively charged in the dark by corona discharge. Then this plate was exposed to light reflected from an object that had a horizontal stripe pattern. In this way, a latent electrostatic image was obtained.

A mixture of polystyrene, the dye Miketon Fast Pink FF3B (a disperse dye from Mitsui Toatsu Co., CI. 62015) and one of the antistatic agents according to Table IX in trichlorethylene was spray-dried, and a toner was obtained, the particles of which contained an antistatic agent.

Then the latent image was developed with this toner by the magnetic brush method and the toner was transferred to paper according to the procedure of Example 4 and heat-set there. A polyester fabric was then placed on the surface of the paper, which contained fixed toner, and the dye present in the toner was transferred to the fabric by heating and fixed there.

The values of the evaluation of the thus printed fabric are shown in Table IX. For comparison, a test is given in which the toner contained no antistatic.

Table IX

30th

No antistatic

Color intensity

Soiling the back

1

2nd

3rd

4th

5

Aluminum powder Copper powder Calcium oxide Titanium dioxide

4.4

4.5 4.1 4.3 2.9

4.1

4.2

4.3

4.4 2.7

The table shows that when using a metal powder or metal oxide as an antistatic in the toner, good printing is achieved.

35 Example 6

A photoconductive layer of zinc oxide was evenly charged in the dark by corona discharge. The layer was then exposed through a monochromatic film with a stripe pattern to form a corresponding 40 latent electrostatic image.

A mixture of a copolymer of styrene and 1-hydroxy-2-N, N -diethylaminopropyl methacrylate and Kayaku Acid Red 3B (an acid dye from Nippon Kayaku Co, CI. 24810) in trichlorethylene was spray dried to give 45 a toner base . This was placed in an aqueous solution of a nonionic wetting agent, namely polyoxyethylene nonylphenol ether (containing 4 moles of ethylene oxide, HLB 8.9), the mixture was filtered and dried in vacuo. In this way, a red-colored toner for electrostatic printing was obtained, the particles of which contained a surface-active agent on the surface.

A yellow-colored toner was obtained in the same way, except that instead of the red dye mentioned, Suminol Fast Yellow R (acid dye from Sumitomo 55 Kagaku Co, CI. 18835) was used as the colorant.

Three parts of the red colored toner were mixed with seven parts of the yellow toner. Then the latent image was developed with this toner mixture according to the magnetic brush method and then a 60 nylon fabric was placed on the developed surface. The toner mixture was transferred to the fabric by corona discharge and heat-set there. The dyes contained in the toners were fixed by steaming and the fabric was washed with trichlorethylene. This gave a printed fabric. 65 The evaluation results of the printed fabric are summarized in Table X. This table also shows the results of a corresponding print, but the toner contained no surfactant.

Table X

No.

Covering with

Levelness of

Pollution

Wetting agent%

Coloring the back

1

0.005

2.8 1

3.0

2nd

0.03

4.0

4.1

3rd

0.09

4.3

4.3

4th

1.03

4.5

4.6

5

2.01

4.7

4.4

6

4.97

4.7

4.2

7

9.68

4.8

4.1

8th

-

2.1

2.7

As can be seen from the table, color uniformity without soiling the back of the fabric is achieved if at least 0.01%, based on the weight of the toner base substance, of a nonionic surface-active agent is applied to the surface of the toner particles. :

Example 7

A mixture of a copolymer described in Example 6, Cibacet Blue F3R (a disperse dye from Ciba-Geigy Co., CI. 61505), and a nonionic surfactant, namely sorbitan monopalmitate (HLB 6.7) in the amounts given in Table XI in trichlorethylene was spray dried to produce a particulate toner. The printing was then carried out in the same manner as described in Example 6, but using a paper made of straw instead of a nylon fabric. Printed paper with a blue stripe pattern was obtained.

A polyester fabric was placed on the printed surface of the paper and the blue stripe pattern was transferred by heating on a «Pantex» apparatus and fixed in the fabric.

The results of the evaluation of the printed fabric are shown in Table XI. There is also a result with a toner that does not contain a surfactant.

kept table XI

No.

Wetting agent content%

Color intensity

1

0.05

3.2

2nd

0.3

4.0

3rd

1.0

4.4

4th

5.0

4.5

5

10.0

4.6

6

-

2.2

11 621006

This table shows that if you incorporate 0.1%, based on the weight of the toner, of a nonionic surfactant into the base toner, and the color intensity continues to increase, a great increase in color intensity will be obtained. if you increase the surfactant content.

Example 8

A photosensitive plate with cadmium sulfide as the photo-10 conductive layer and polyethylene terephthalate as the insulating layer was uniformly positively charged by means of a corona discharge. Then, this plate was exposed to the light reflected from an object with a monochromatic vertical stripe pattern and simultaneously subjected to an AC corona discharge. Then the plate was exposed evenly, creating a latent image.

A mixture of a copolymer of styrene and 2-hydroxyethyl methacrylate and diacelliton Red R M / D (a disperse dye from Mitsubishi Kasei Co., CI. 11210) in methyl ethyl ketone was poured into a large amount of water, with fine particles precipitating out. These were dried, and a toner base was obtained in the form of a fine powder. This was placed in an aqueous solution of a nonionic surfactant, namely polyethylene glycol monooleate (average molecular weight 300, HLB 10.3), the mixture was filtered and the residue was dried. A red toner for electrostatic printing was obtained.

A yellow toner was produced in the same way, but with Celliton Fast Yellow RR (disperse dye from BASF Co, CI. 10345) as the colorant.

1 part of the red toner was mixed with 2 parts of the yellow toner. Then said latent image was developed by the magnetic brush method using this toner. The developed area was subjected to a positive corona discharge. A polyester fabric was then placed on this surface and pressure rollers were passed over the back of the fabric in order to transfer the toner mixture onto the fabric. The toners were then heat set and the dyes contained in toners were fixed by steaming. After a trichlorethylene wash, a printed fabric with an orange stripe pattern was obtained.

25th

30th

45

50

The above-mentioned printing process was repeated ten thousand times, and the durability of the toners was examined in terms of color intensity, color uniformity, soiling by unfixed toner, soiling of the back of the fabric and color tone. The results are shown in Table XII.

Table XII

No. of color in-dyeing veils soiling color

Print intensity level formation of the back

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 1000 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 10000 4.4 4.1 4.0 4.2 4.7

621006 12

From this table it can be seen that when an Example 9 nonionic surfactant was applied to the particles of toner, the base fabric was printed in the same manner as described in Example 6 even when using a toner mixture, but instead of the polyoxyethylene, the fabric was printed Color intensity, color levelness, absence of the Verlen-nonylphenoläther as antistatic one of the table dirt caused by unfixed toner and absence of the 5 XIII derivatives shown was used. The soiling of the back, as well as the color of the print results, are also listed in Table XIII. There is also a trial over a very large number of successive tissues in which no triazine derivative printed very uniformly. was applied.

Table XIII

medium colored strings for.

N ° 'triazine derivative toner coverage back level ci

N / - \ 1.96 4.7 4.3

Na03s ^ §) -H, ', - ^ N> NH- (O) rS03Na

Cl

H01Cnc: M / C, cH0, 2.05 1.5 4.4

5 3

H00CH2C CH2C00H

Cl

H ~ C N N .CI-L

3 3

H03PH2CH2C ^ W XCH2CH2P03H Cl

/ K so H

^ 21 ^ 10-- ^ * 1 r ~ K 2.18 4.6 4.2

1.99 4.7 4.2

H00CH2C ^ w "

ci -S03H

C1 ~ ^ N ^ m ~ ^ 0 /) - SQ3Ha '1.88' ^ '3

Cl

2'01 "'5 ^

"CH2C00H Cl

H17C8 ^ m ï '„T / CT \ 1.95 4.4 4.4

hoxh? C ^> NH ^ / S03h 3X CH

JN N -. 1.91 J | .5 1 | .3

N K ^.

so3h

1.3 2.7

13

621006

The triazine derivatives described above all had an electrification factor in the range designated as preferred. The table also shows that a toner whose particles on the surface contain a triazine derivative with these properties is very suitable for electrostatic printing.

The same effects are achieved if the triazine derivative is incorporated into the basic toner substance.

Example 10

A basic toner substance was prepared by mixing polystyrene with Diacelliton Fast Scarlet R (a dispersion material from Mitsubishi Kasei Co., C.1.11150) on a roller mill with heated rollers, the mixture first being coarse and then finely ground. This basic toner substance was dissolved in an aqueous solution of a triazine derivative of the formula Cl

Cl ^ N NH ^ QVSO Na h '- \ 5>

10th

Surface contained said triazine derivative.

In the same manner as in Example 8, a latent image was formed on a sensitive plate made of cadmium sulfide and polyethylene terephthalate, developed with a mixture of the above-mentioned toner and iron powder by the magnetic brush method, and then the developed image was transferred by the transfer printing method according to Example 8. The remaining mixture of toner and iron powder was circulated in a stream of compressed air, the toner was separated off and its flowability was examined. The results are shown in Table XIV.

Table XIV

No.

15

Number of consecutive prints

Angle of rest (degrees)

1

0

36

2nd

1000

38

20 ^

5000

35

4th

10,000

37

introduced, the whole then filtered and the residue dried. A toner was obtained, the particles on the

The table shows that the fluidity of the toner, the particles of which contain a triazine derivative, remains stable even after an extraordinarily large number of prints.

G

Claims (11)

621006 2nd PATENT CLAIMS 1. Toner for electrostatically printing a sheet material with a toner base substance which contains at least one resin and at least one colorant, characterized in that it contains an antistatic agent which has a polar group capable of preventing the accumulation of static electricity to control, said antistatic agent being present on the surface of the toner particles or in admixture with the toner base substance. 2. Toner according to claim 1, characterized in that the antistatic agent is an inorganic substance, a surface-active substance, a polar low-molecular organic compound or a triazine derivative. 3. Toner according to claim 2, characterized in that the inorganic substance is a powdered metal, a metal oxide or an inorganic salt. 4. Toner according to claim 2, characterized in that the surface-active substance is anionic, cationic, nonionic or ampholytic. 5. Toner according to claim 4, characterized in that the nonionic surface-active substance has an HLB value of 3 to 19. 6. Toner according to claim 2, characterized in that the triazine niyate corresponds to the following formulas: 10th i X n n N \ or n n nA where X for halogen and Y for a radical of the formulas -a - ("so-.h), -a— (ccom), Cl hr-c ,. n n 5 JJ — Cl h00ch2c / n NaO ^ S Cl h, 7cp n n 17 ■ n— ^ ji — nh h00ch2c ^ n Cl • SO ^ Na hooc so3h R -A (PO- ^ f-i) or ^ Qp ^ coori, where cil. i 3 A -NH (CH2) m, -N (CK2) m> k31c15- c1 n n / c h h00ch2c- ^ n ^ chgcooh -nh n! oh h ~, c h00ch2c Cl N N 21 10-N-V N so3h means R is hydrogen or an alkyl radical having 1 to 18 carbon atoms, M is hydrogen or an alkali metal atom and m is an integer from 1 to 5. 7. The toner according to claim 6, characterized in that the triazine derivative corresponds to one of the following formulas: Cl N Cl- ^ —NH N -SO ^ na 60 or H03PCH2CH2 '/ n so3h Cl h ^ n n ch-N-t ^ N 5 'ch2CH2PO3H 8. Toner according to claim 1, characterized in that the antistatic agent has an absolute value of the surface potential, measured in the case of corona discharge at a layer 30 | x thick, of 100 to 2000. 9. The toner according to claim 1, wherein the antistatic agent 5 is present on the surface of the particles, characterized in that its amount is at least 0.01% based on the weight of the toner base substance. 10. The toner according to claim 1, wherein the antistatic agent is incorporated into the basic toner substance, characterized in that the latter contains at least 0.1%, based on the weight of the basic substance, of antistatic. 11. The toner according to claim 1 having a particle size of less than 80 p ..