BE548062A - - Google Patents

Description

       

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   The main object of the present invention is a printing composition suitable for textiles, papers and other absorbent materials.



   Another object of the invention is to provide a textile printing composition in inexpensive emulsion form.



   Another object is an emulsion or print which gives extraordinarily high color yields when used as a vehicle with pigments or dye dispersions or dyestuff solutions.



   A further object of the invention is a printing composition in emulsion form which can be fixed at low temperatures to give films which are resistant to water.

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 "crocking" (baring the fabric by rubbing) and machine washing.



   The objects of the present invention are achieved. using an emulsion of a solvent, immiscible in water, with a starch dispersion containing a surfactant and a colorant and other additions as will be seen below.



   Starch-based pastes have long been used for printing with coloring materials. The disadvantage of using these water-dispersed starch pastes as a vehicle or as a thickener is that in order to obtain the suitable paste it is necessary to add quantities as high as 15 to 20 µl. unmodified starch and correspondingly higher amounts of modified starch resulting in lower pulp viscosities to obtain pulps of the consistency suitable for printing use.



   With high solids contents in the printing paste, prints with poor feel are usually obtained. Natural gums such as tragacanth, sodium alginate or soluble cellulose gums such as methylcellulose or carboxy-methylcellulose / capable of giving thick pasta at lower concentrations than starch. However, their price is several times that of starch and the color yield obtained with these gums is much lower than in the case of starch pastes. For this reason, combinations of starch with other natural gums or modified cellulose products have been used for printing on textiles, although this entails some sacrifices in color yield.



   When printing with pigments, starch is used in the form of an aqueous dispersion both as a vehicle and as a binder. Starch alone, however, does not give wash-resistant films, and the prints are extremely stiff.

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   A starch product, which was mixed with about 3% tetravalent antimony salt, was used as a thickener and binder capable of being dispersed in water. Prints made using this binder are, after drying, completely insoluble in hot water, but are very badly damaged when washed in cold water.



   Since starch based pastes do not form stable emulsions with most hydrocarbon liquids, starch emulsions have not generally been used either in printing with dyes, either in printing with pigments, although in printing with dyes sometimes small amounts have been used, i.e. up to 1 or 2% oil mineral or kerosene especially as a lubricant.



   For printing with pigments, the most suitable vehicle pastes, also called filler pastes, have been prepared using cellulose gums such as methylcellulose or carboxy-methylcellulose and processed or modified starches. chemically, such as carboxy-methylated locust bean gum or carboxy-methylated corn starch.



  One of the most satisfactory vehicles for printing with pigments is based on a methyl cellulose solution in which a water-immiscible hydrocarbon solvent, such as mineral spirits, has been emulsified, using a suitable emulsifier. The printing compositions thus prepared with methylcellulose generally have a good feel and a good color index. Because of the relatively large percentage of solvent which it was necessary to use with these compositions in order to obtain a satisfactory color yield and because of the high cost of methylcellulose, such compositions are relatively expensive.



   In accordance with the present invention, it has been found that if water-immiscible solvents are emulsified in aqueous starch dispersions using suitable emulsifiers, and if dispersions are

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 sions of pigments are incorporated in these emulsions, the? prints made with these compositions give colors with a much higher color index and gloss than can be obtained with the well known starch pastes or
 EMI4.1
 vehicle pastes based on methylcellulose-h emulsions; drocabure.



  In fact, the starch emulsion vehicles according to the invention have made it possible to exceed the color index obtainable with water-in-oil type printing products using the color index. same concentration of coloring matter. When used in combination with suitable resin emulsions or water-soluble resin solution, the fastness of prints prepared with the starch-based emulsion carriers of the present invention is highly critical. satisfactorily and fulfills the conditions imposed on the textile industry.



   Common properties, that is, application characteristics of printing compositions using machines, such as roller or screen printing machines or using stencils, are described below. 'of extreme importance to the industry. Common properties are generally dependent to a large extent on the consistency of the printing pastes.



  The consistency of a paste, as is commonly understood in this industry, is controlled by two factors, true viscosity and thixotropic structure. To obtain printing with fine lines, sharp pattern and smooth surfaces, using the printing paste, in general, it is considered advantageous that it has a structure which is truly thixotropic or the like. Also in order to give smooth impressions and to remain on the surface of the printed fabric, the printing pastes must have a relatively high true viscosity. The combination of high viscosity and thixotropic structure is a factor determining the penetration and sharpness of the design as well as the gloss and color intensity of the prints.

   Starch-based emulsion vehicles prepared according to the invention are readily available.

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 mixtures to give the particular properties most desired for printing.



   Due to? starch is a weak protective colloid, starch deplets prepared according to the invention tend to allow a film of organic liquid to form on the surface of the pasta. The film protects the underlying pastes from the formation of unwanted skin when exposed to air for several hours or days.

   This is a great advantage in textile printing in view of the skin formation usual with solvent-free starch dispersions or even with certain emulsions containing solvents, prepared according to the prior art, for example those which are based on cellulose ether, involves an expenditure of dye and if the skin is not completely removed, the latter causes streaks on the prints. In addition, the solvent or liquid organic film acts as a lubricant which enables the spatula to clean the unetched parts of the rollers completely and easily. The thin film of solvent formed by the starch emulsion paste appears to have a favorable action for the rapid and complete departure of the printing paste from the gravure.



   Generally, the oil-in-water emulsion vehicles of the present invention are suitable for disperse pigments and colorants and can be used in printing textiles in conjunction with pigments and colorants. These vehicles generally have the consistency of a paste and 1. ' water is found in the continuous phase of the emulsion. The starch dispersed in the vehicle can be about 2 to 20% by weight, with about 4 to 10% being a particularly satisfactory amount; the weight of surfactant which exhibits the emulsifying properties may be of the order of 0.05 to 10%, the preferred range ranging from approximately 0.2 to 2%;

   the organic liquid insoluble in water, volatile, can represent about 5 to 67%

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 by weight, the preferred range being about 10 to 50%. The water to starch ratio can range from 3: 1 to 99: 1, with values from 5: 1 to 25: 1 being particularly satisfactory. The percentages and ratios are by weight and the percentages are calculated on the total weight of the emulsion vehicle. In general, the vehicle comprises three components, one of which is a dispersion, in water, of a starch, which dispersion comprises about 1 to 25% starch, these percentages being calculated on the total weight of the starch. aqueous dispersion, the preferred range being about 4 to 15% starch.



  The second component of the emulsion vehicle is the volatile, water-insoluble organic liquid which may be present in an amount ranging from 5 to 150 parts by weight, or preferably between 10 and about 100 parts per 100 parts. , by weight, of starch dispersion. A surfactant is present, as a component having emulsifying properties, generally in the amount of 0.09 to 10% of the total vehicle weight, the preferred range being about 0.2 to 2%.



   Differences in the surfactants used in the preparation of starch emulsions largely control the degree of separation of the solvent or organic liquid from the starch emulsion pastes and also are critical. from the standpoint of the adhesion of the starch paste to the metal surface of the printing roller.

   Starch-based vehicles or starch-based printing pastes can furthermore be modified to achieve specific effects by including one or more protective colloids such as methylcellulose, carboxy-methylcellulose, casein, water soluble alginates, such as sodium alginate, polyvinyl alcohol, polyvinyl-pyrolidone, or dextran or a combination of these and other protective colloids.



   The vehicle emulsions of the present invention mainly comprise the following ingredients: starch, water, solvent

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 organic liquid, volatile, immiscible with water, and emulsifier. The resulting printing paste comprises repellant vehicle and the dispersion or solution of dyes.



   The dye used for practicing the invention can be either a pigment dispersion or a coloring matter dispersion or a coloring matter solution. In addition to the above components, other materials can be incorporated to achieve certain desired properties. These include protective colloids, other surfactants, resins, elastomers, catalysts, salts and other products which are indicated below. When using pigments in the printing paste, a resinous binder should be used.



  STARCH. -
Starches suitable for the invention are starches derived mainly from cereals and root crops.



  Among the most important raw materials providing starch are corn, wheat, potato, tapioca or cassava, waxy corn, sago, arrowroot, rice, barley. pearl, waxy sorghum, potato and guar gum *
The starches used according to the invention may be pure starches or they may contain small amounts of fibrous or protein impurities and the moisture usually present in industrial starches. The starches used should be of the high viscosity starch type or of the type which gives thick emulsions by heating to boiling; however, partially degraded starches or starches giving fluid starches can also be used although they are less economical.

   Pregelatinized starches, preferably those which do not retrograde to a significant extent during gelatinization can also be used for the purpose of the invention. Starches suitable according to the invention

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 EMI8.1
 are those (him swell and di3F2rS2-nt; in Cllan "'L3 .31i e. and 1C' C. water.

   Starches can also, as is well known: in these techniques, be swollen and dispersed in mechanical nuclei such as ball mills, roller mills, or supersonic vibrators or by means of vibrators. agents
 EMI8.2
 chemicals such as caustic alkali or inorganic salts such as sodium chloride or oi-g = inE swelling agents, such as urea or dispersing agents such as copper O "1'TloniAcal. The pre-41atinized starches which can be used can also undergo swelling and be dispersed in cold 1 ml. The starch, used in the invention, is in the swollen state in the continuous phase or phase. emulsion water.



   The term "disperse starch" used herein refers to
 EMI8.3
 the state of the starch in the aqueous dispersions in the water: l¯1: the starch granules are partly or completely swollen or burst and the term excludes the state of the essentially unswollen raw starch granules suspended in the starch. Cold water.



  WATER. -
The water used in the invention should preferably be of low hardness. If the water is hard, it is preferable to add a softening agent in an amount sufficient to eliminate the detrimental effects of the polyvalent metal ions. Water softened by the use of a deionizing agent such as zeolites is also suitable.
 EMI8.4
 



  LIQUIDS T1PIT '? TTS.-
The organic liquids used according to the invention are volatile, essentially insoluble in water, for example they have a solubility in water of less than 3%, by weight The organic liquid provides the vehicle emulsion and the paste
 EMI8.5
 For printing, desirable structural features which improve the color index and feel of the final print obtained by solvent evaporation. The organic liquids are preferably hydrocarbons derived from petroleum,

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 such as naphtha derived from petroleum, mineral spirits or others.

   Other liquids, such as aromatic hydrocarbons
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 ticks, such as toluene, xylene and soldant n.;: ph1ï ::; !.;:, possibly high flash, or terp <5nic hydrocarbons, such as turpentine, can also be used.



  We have found that liquids like this, with clues
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 tTriGux: ï.-3utanoht (K-B index) between 30 and 96-1 / 2 are quite satisfactory. The printing properties and the color index of the printing pastes are influen-
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 These to some extent by the rate of evaporation of the solvents used. Low boiling point solvents have a low flash point, can be used but this
 EMI9.4
 causes risk of fire. Solvents with a medium 5blill-j-- tion point, having a flash point greater than? , 9 are pi- <fl ... fired for continuous printing operations.

   High boiling a .vra: zt; s, such as kerosene or pine oil, can be used; however, due to their low evaporation rate, they require special treatment
When using, in the printing paste of the
 EMI9.5
 ktelrosene, the latter may remain in the print itself,: \ prf1: 3 drying and heat curing and may somewhat retard the curing of some resins. The residual odor of
 EMI9.6
 kerosene is sometimes detrimental but can be caused by prolonged heating with good ventilation or by 1: J1 /; ',?'; ' : v Can be used:

     - aliphatic hydrocarbons with the following properties specific gravity at 15/15 C 0.6900 to 0.8100 section flash point 'covered with a cloth above - 17 C to 52 C Initial boiling point 65 C to 177 C
 EMI9.7
 End point 65aC to 21.c K-B value (ASTM D 1133-50T) 30 to 50

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 - aromatic hydrocarbons with the following properties:

   Specific weight at 15/15 C 0.8650 to 0.9250 Flash point (at cloth-covered cup) 4.4 C to 71 C Starting boiling point 80 C to 188 C final boil 80 C to 288 C KB index (ASTM D 1133-50T) 80 to 110
 EMI10.1
 j "3 T ^" T; 3I-riGTIF. -.



     Starches have been found to be relatively weak protective colloids for the intended purpose; It has been found advantageous to employ suitable emulsifying agents to form stable emulsions with organic liquids immiscible with water. Thus, aqueous starch dispersions used in accordance with the invention gradually retrograde, if protective agents used herein are not incorporated into the starch dispersions to prevent or block retrogradation. Such agents include fatty acid soaps such as sodium stearate, non-innate surfactants, such as some ethylene oxide condensation products, and others.



   Retrogradation of starch in an aqueous starch dispersion can be avoided by the use of small amounts of stearic resolves. In order to obtain satisfactory emulsification of the organic liquids present, stearic acid, for example in the form of sodium or ammonium stearate, is used according to the invention. The presence of other surfactants, in particular those which are capable of preventing the precipitation of stearic acid by the calcium and magnesium usually present in water, is desirable in order to impart satisfactory qualities to the product. paste for printing.



  However, the maximum color index and the greatest economy are obtained if a soap alone, such as ammonium oleate, stearate or palmitate, is used as the emulsifying agent in

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 pastes for printing. The following surfactants are representative members of the group which have been found: suitable for use in preparations according to the invention!
Ammonium, morpholine, (mono-, di-, or tri-) ethanolamine, or alkali metal salts of the following fatty acids:

   oleic, stearic, lauric, undecylenic and palmitic acids, in general fatty acids with a straight or branched chain comprising from 10 to 22 carbon atoms ;,
Fatty acids with one or more hydroxyl groups in the chain, such as alpha-hydroxy-stearic, di-hydroxy-stearic acids and fatty acids derived from castor oil,
Unsaturated fatty acids with one double bond such as oleic acid, with several double bonds such as fatty acids derived from linseed oil, soybean oil, fish oil;
The ammonium or alkali metal salts of the monosulfuric esters of fatty alcohols prepared by reduction of the carboxyl groups of the fatty acids indicated above.

   The preferred compounds are lauryl-cetyl-stearyl and oleyl-sulfuric acids, the salts of monosulfuric esters of straight-chain or branched fatty alcohols having from 8 to 22 carbon atoms;
Ammonium or alkali metal salts of benzene - or naphthalene - sulfonic acids with one or more aliphatic chains on the aromatic ring. Among these compounds
 EMI11.1
 preferred are the ulf onified alCOy1-'benzeaae-sulfonic acids 8lcog.-naphtaine-s;
Nonionic agents: poly-oxyethylene derivatives of fatty acids, fatty alcohols and substituted phenols.



    Examples of such products are condensate products.
 EMI11.2
 sati.on ethylene oxide with nonylphenol which are well

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 known under the trademark "Igépals".



   Nonionic and anionic surfactants are preferred, but of course, a cationic surfactant can be employed in a cationic pulse system under suitable conditions.



    RESI @ ES. -
The starch film after printing, in the case of pigment printing, is insolubilized using a resin which can act as a crosslinking agent. Among the preferred resins, there will be mentioned amino-aldehyde resins of the solvent-soluble type which are incorporated into the starch paste in emulsion form. These resins are capable of insolubilizing the starch films under the influence of heat alone and more fully in the presence of an acid catalyst. The amino-aldehyde resins included in the spirit of the invention are the condensation products of urea or formaldehyde or of melamine and formaldehyde.



  Substituted ureas and melamines and aldehydes other than formaldehyde can also be used for the formation of these resins. The resins are preferably modified to make them soluble in a solvent, for example by “butylation” (reaction with a butyl alcohol). Thus, satisfactory products are, for example, butylated dimethylol-urea or trimethylol-melamine. These resins dissolved in an organic solvent or an organic liquid are emulsified in water using an emulsifying agent and protective colloids.



  Such emulsions are then incorporated into the starch pastes in an amount sufficient to bind or insolubilize the starch film. Other resins or resinous products can be used, either alone or in admixture with the amino aldehyde resins to bind the starch in the prints. Resins give prints wet and dry abrasion resistance, resistance to mild alkalis,

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 EMI13.1
 1;: \ i [J,: "E: 'and dry cleaning.



  The starch film can also be used. ; 'u .ti ;; s, i 3 using straight chain ester resins or: ;; <:.; li. ± 5.F, is at 1 q hts11. ethers or p?: nol> condensation products. fornaldehyde and a:;! "3.! ld. number dl é 12.8 t.01;: èJ.'es. E.ai>: i; 1 L: ± 3 1 <s i.:h" .: appropriate, we will mention the condensation products, i, ioài, j.'i-; 1 ;, 1.



  11 oil, bisphenol with epichlorohydrin, 1'8: Li'.C; S i:; lye / J. '". Oil modified phthalates, phthalate resins of P21.1" L! .M erythrytol modified in oil, and the alkyl resins tf4;. i ': i = t: v with maleic acid.



   The above resins and analogous resins are of
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 p1 = ± ± ôrence dissolved in suitable immiscible solvents ?. 1 T Ge1U, then emulsified in water using # ajgeiits (H11 st- fiants and protective colloids before incorporating them into the starch paste.
 EMI13.3
 t.Ll. 'J lr: (!. L..lJ a "' Elastomers can be incorporated into the cos - ,. os: īt: .e:; ... preferably in the form of latex or in the form of solvents which are absorbed in water with the aid of an emulsifier and protective colloids.

   The natural or synthetic rubbery elastomers are: rubber, acrylic nitrile copolymers
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 butadiene ,. butadiene-styrene copolymers, polychlox'o1d; 'È :: n {:. vinyl chloride-vinyl acetate copolymers,
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 vinyl chloride-vinylidene chloride copolymers, rolyvinyl chloride, polyvinylidene chloride and mixtures thereof, 2lSF1SIOr L1; 5 Tl '.T, r
Suitable materials for printing with emulsion pastes are fine particles of solids
 EMI13.6
 cui colors are mainly ins ..., ln11.,; s in water, mild ilcalis, hydrocarbon solvents as well as solvents

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 Usually used in the dry cleaning of textiles.



  Some of these pigments are materials, but most are organic compounds, usually insolubilized coloring materials, metal complexes and the like. The preferred pigments are those which have a high dyeing power.

   Some of the pigments which can be used according to the invention are: Smoky black pigments B green pigments Iron oxides Benzidine orange Titanium dioxide Molybdate orange Zinc oxides Red coupling ITR / AS-ITR Chromium june Rhodamine Toner Y Phthalocyanine blue Red coupling PNOA / AS-P3 Chlorinated phthalocyanine blue Red coupling PNOT / AS-D Indanthrene blue CE Salt coupling Scarlet G / ASD Dianisidene blue Scarlet coupling PNOT / AS Overseas blue Indanthrene red violet RHN Azo brown metallic Indomarcon (Harmon) Indantrene brown RRD Violet bright indanthrene RR Phthalocyanine green Benzidine yellow
Solid yellow lithosol 3 GD
Pigments are generally used in aqueous dispersion.

   The dispersions are preferably prepared by treating the dry pigment or pigment press cake with suitable surfactants and protective colloids to achieve the desired dispersion and paste characteristics. Coarse pigments are generally ground in suitable mills such as ball mills, roller mills or colloid mills in the presence of surfactants and protective colloids to achieve the desired particle size and dispersion. To be suitable, the pigment dispersion must contain sufficient surfactant to make it miscible with resin emulsions and resin.

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 EMI15.1
 <?; \ 1Ulsions vehicles without ocuLItion of peppers or coagulation of lq: rulsion.



    COLORANTS.-
The colorants can be incorporated into the carrier emulsions of the invention, either as a solution or as a dispersion. Suitable dyes are, for example: Violet 6R for tank printing Paste Golden orange Ponsol YL (DuPont) Double paste blue Ponsol BF (DuPont) Double paste blue Indanthrene BFF, (G.D.C) Double paste Fonsol black direct, (DuPont)
 EMI15.2
 Brilliant violet paste Indanthrene y RL (Colo! 'Index 1101 ..) Sulfanthrene paste 3B (Color index 1212) Orange Sulfanthrene paste R (Color index 1217) Double paste Ponsol Vert-Jade (Color index 1101) Indanthrene yellow GK (Color index 1132 )

     
 EMI15.3
 Indanthrene brown R (Color index 1151) Indanthrene brown RRD (A.A.'r.C.c. Prototype 121) Ruby indanthrene double paste R (A.A.T.C.C. prototype 12y) Indanthrene blue CE (Color index 1112) Sol. Scarlet Rapidogene RS (A.A.T.C.C. prototype 170) Sol. Rapidogene R.S. (A.A.T.C.C. prototype 1'70)
 EMI15.4
 Ground. Rapidogenated R (A.A.T.C.C. prototype 169) Rapidogene Blue DN (A.A.T.C.C. prototype 164) Red Algosol IFBB-CF (.t.? .'L '. C.

   VS . prototype 296) Algosol Blue IDC (Color index If 1113) Algosol Brown IRR (A.A.T.G.C. prototype 118) Scarlet Diamine BA-CF (Color index 382)
 EMI15.5
 Blue Fastusol BA-CF (... 'f.C.C. Prototype 356) 3rurlfastuso1 LBRA

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 Tests. -
The printing pastes shown in the examples are tested, whenever possible, following the American Association of Textile Chemist and Colorists (AATCC) test methods described in the Association's Technical Manual and Yearbook. . The expressions and nomenclature used are generally consistent with those adopted by the A.A.T.C.C. Accordingly, when "satisfactory wash resistance" is indicated, the printed fabrics after drying and curing are subjected to accelerated wash resistance tests No. 3 or 4.

   By "abrasion resistance" is meant that the dried and heat cured prints have passed the "A.A.T.C.C. Standard Test Method 8-52" for resistance of color to rubbing off. The tests were carried out with a usual "crockmeter" abrasion indicator from the A.A.T.C.C.



   The examples below illustrate the invention.
EXAMPLES Example 1-A.- Starch dispersion
 EMI16.1
 
<tb> Parts <SEP> in <SEP> '.weight
<tb>
<tb> Water <SEP> 89.0
<tb>
<tb> Starch <SEP> from <SEP> but <SEP> 10.0
<tb>
<tb> Ammonia <SEP> 0.5
<tb>
<tb> Oleic acid <SEP> <SEP> 0.5
<tb>
<tb> 100.0
<tb>
 
The water and corn starch are placed in a jacketed tank, mixed so as to obtain a uniform suspension of starch, then the temperature is brought to 95 C. The mass is maintained for 15 minutes at this temperature and then allowed to cool. at 85 ° C. Ammonia is added and the temperature is maintained at 85 ° C. for a further 5 minutes. The oleic acid is then added. Mixing is continued and the mass is cooled to about 65 C. The starch paste is then cooled.

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 extracted from the container.

   This paste can, if desired, be combined with pigments or dyes to form a printing paste but preferably, it is worked as described in Example 1-B so as to form the carrier emulsion.
 EMI17.1
 



  Example 1-B¯ ¯.- Vehicle emulsion
 EMI17.2
 
<tb> Parts <SEP> in <SEP> weight <SEP>
<tb>
<tb> Starch <SEP> dispersion <SEP> Example <SEP> 1-A <SEP> 50.5
<tb>
<tb>
<tb> Petrol <SEP> mineral <SEP> 31.2
<tb>
<tb>
<tb> Water <SEP> 18.3
<tb>
<tb>
<tb> 100.0
<tb>
 
The starch dispersion is placed in a mixing vessel equipped with a turbine mixer. Water is then added to lower the viscosity of the dispersion to the point where the mixture can be handled, then mineral spirits are added while the mixer is set in motion and the mixing operation is continued until to obtain a homogeneous and uniform emulsion suitable as a vehicle for pigments and dyes.
 EMI17.3
 



  Example 2-A.- Preparation of starch dispersion
 EMI17.4
 
<tb> Parts <SEP>, in <SEP> weight
<tb>
<tb> Water <SEP> 1 <SEP> 70.56
<tb>
<tb> Starch <SEP> from <SEP> but <SEP> 6.59
<tb>
 
 EMI17.5
 ¯¯¯¯..¯¯¯..¯¯¯¯¯¯¯ .......,. ¯¯¯, .. ¯ ......, ...,. W¯¯¯ ., ¯ .., ¯, ¯¯¯¯., ...,
 EMI17.6
 
<tb> Ammonia <SEP> 0.32
<tb>
<tb> Ammonium <SEP> stearate <SEP> to <SEP> 15 <SEP>%
<tb> (Solution <SEP> aqueous <SEP> to <SEP> 15 <SEP>%:
<tb>
 
 EMI17.7
 Stearic acid content> .22
 EMI17.8
 
<tb> Water <SEP> II <SEP> '<SEP> 12,18
<tb>
<tb> Petrol <SEP> mineral <SEP> 9.13
<tb>
 
 EMI17.9
 .0 $ tt
 EMI17.10
 Starch and water (I) are cold mixed in a suitable jacketed mixing tank * 'The temperature of the dis-
 EMI17.11
 aqueous starch persion is then = .. 'to 85 0.

   We add

 <Desc / Clms Page number 18>

 
 EMI18.1
 l rB, ;; '1oni2que and the temperature is maintained at;, i5 0 penJ2nt 15 1¯in; tes. We add the stearate of e! L "onÍW'1 at, '5 C and the remainder <1'> mu (II) is added during ue lE: n;, i # intj # uz" is in Motion t finalA " First, mineral spirits are added with a c4cifinue weight of 0.7854, a trigger point of 4C'C and a boiling point co ::::::! Ençf1nte of 152 C, dt 8bulli, ending tion lc5oC, a KB index of 35.1 U..ST.2'i: II..33-50'l) at 16.2 dtaronatinous, although mineral spirits are not essential for the dispersion of starch it has been found to be advantageous for the preservation and stabilization of the starch dispersion.



   Ammonium stearate is used in this example and prepared as follows: 6.8 kg of stariac acid is melted on a hot pan and water is heated to a boil in a separate container and stearic acid is added to hot water while mixing then introduced 6.8 kg
 EMI18.2
 el '{)' l1l11onia oue and mix until a homogeneous creamy product is obtained. This soap dispersion is then used in the preparation of the above starch dispersion.



  Example 2-B. Vehicle emulsion
 EMI18.3
 
<tb> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb> Starch dispersion <SEP> <SEP> of <SEP> Example <SEP> 2-A <SEP> 61.50
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Ammonium <SEP> stearate <SEP> to <SEP> 15 <SEP>% <SEP> 2.60
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Water <SEP> 11.2-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Petrol <SEP> mineral <SEP> 24.10
<tb>
<tb>
<tb>
<tb>
<tb> 100.00
<tb>
 
The starch dispersion is then poured into a mixing vessel equipped with a high speed turbine mixer. Water is added to reduce the viscosity of the starch dispersion so that the mixer can agitate.



  The ammonium stearate paste is then added and mixed.



  Finally, mineral spirits are added in small quantities at the rate at which the mixer can incorporate them into the mixture.

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 mass. The resulting emulsion is uniform and viscous. The ulcer is a suitable vehicle for pigments and dyes for printing.



  Example 3-A.- Starch dispersion
 EMI19.1
 
<tb> Parts <SEP> in <SEP> weight
<tb>
<tb> Water <SEP> 82.00
<tb>
<tb>
<tb> Starch <SEP> from <SEP> but <SEP> 7.70
<tb>
 
 EMI19.2
 -------------------------------------------------- ----------- Arnmonique oe4o Lauryl ammonium sulphate
 EMI19.3
 
<tb> (aqueous <SEP> solution <SEP> to <SEP> 30 <SEP>%) <SEP> 2.25
<tb>
<tb>
<tb>
<tb> Essence <SEP> mineral <SEP> 7.65
<tb>
<tb>
<tb>
<tb> 100.00
<tb>
 
Water and starch are mixed in a jacketed mixing tank. Then the temperature of the suspension is brought to 90 ° C. while mixing. The mass is maintained at 85 C
 EMI19.4
 for about 15 minutes. Ammonium is then added, maintained for a further 9 minutes at this temperature and ammonium lauryl sulfate is added while mixing.

   The temperature drops to 65 ° C and mineral spirits are added with the mixer running. This starch dispersion is then used in the preparation of the vehicle for printing with pigments and dyes.
 EMI19.5
 



  Example J3-B. Vehicle emulsion
 EMI19.6
 
<tb> Parts <SEP> in <SEP> weight
<tb>
<tb> Starch dispersion <SEP> <SEP> of <SEP> Example <SEP> 3-A <SEP> 71.00
<tb>
<tb>
<tb> Essence <SEP> mineral <SEP> 29.00
<tb>
<tb>
<tb> r <SEP> 100.00
<tb>
 
The starch dispersion is placed in a mixing vessel provided with a turbine mixer. Mineral spirits are gradually added to the starch dispersion while the mixer is in motion. Mixing was continued until a homogeneous emulsion was obtained. This emulsion is a

 <Desc / Clms Page number 20>

 suitable vehicle for printing with dispersions of pigments and dyes.



  Example 4-A.- Starch dispersion based on wheat starch
The starch dispersion is prepared in the same manner as that of Example 3-A except that the wheat starch replaces the corn starch.



  Example 4-B. Vehicle emulsion
 EMI20.1
 
<tb> Parts <SEP> in <SEP> weight <SEP>
<tb>
<tb> Starch <SEP> from <SEP> wheat <SEP> from <SEP> Example <SEP> 4-a <SEP> 71.00
<tb>
<tb> Essence <SEP> mineral <SEP> 29.00
<tb>
<tb> 100.00
<tb>
 
The vehicle is prepared in the same manner as in Example 3-B.



  Example 5-A. Vehicle emulsion based on pregelatinized maize starch
 EMI20.2
 
<tb> Parts <SEP> in <SEP> weight <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> ;; to <SEP> 4450
<tb>
<tb>
<tb>
<tb>
<tb> Petrol <SEP> mineral <SEP> 1 <SEP> 5.50
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Starch <SEP> of <SEP> but <SEP> pregelatinized <SEP> 5.50
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Ammonia <SEP> 1.30
<tb>
<tb>
<tb>
<tb>
<tb>
Ammonium <tb> Lauryl-sulfate <SEP>
<tb>
<tb>
<tb> (solution <SEP> to <SEP> 30 <SEP>%) <SEP> 1.60
<tb>
<tb>
<tb>
<tb>
<tb> Petrol <SEP> mineral <SEP> II <SEP> 41.60
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100.00
<tb>
 
The water is placed in a mixing vessel equipped with a high speed turbine mixer.

   The pregelized starch is first wetted with an equal weight of mineral spirits I to avoid gumming and is then introduced into the water while the mixer is in motion. It is not necessary to heat. After 5 minutes of stirring, ammonia is added.



  Stirring is continued for a further 5 minutes, then the ammonium lauryl sulfate and then mineral spirits II are introduced in small fractions. We continue brewing until

 <Desc / Clms Page number 21>

 one obtains a homogeneous emulsion. This emulsion vehicle is suitable for printing using dispersion of pigments and dyes.



   The pregelatinized starch used in this example is obtained by gelatinizing the starch in boiling water and then drying the gelatinized starch for a tumble dryer so as to obtain a product with a little less than 10% water.



  Example 5-B.-
The vehicle emulsion is prepared as in Example 5-A except that the pregelatinized corn starch used in this example is a commercial product called Amijol-B-001 sold by the Corn Products Refining Company. Other pregelatinized starches can be used in Examples 5A and 5-B, for example potato starch, tapioca starch or rice starch.



  Example 6.- Polyester resin emulsion
An emulsion of polyester resinous binder of the type described in French patent 1,080,028 of May 4, 1948 (Example 1) is prepared from an alcohol component which is the condensation product of epichlorohydrin with bis-phenol and having a melting point of between 95 and 105 C (resin 2) and an acidic component which is, as indicated above, an acid contained in natural fatty oils.



   This polyester E is prepared as follows:
Kg Alcohol resin component 2 with a combined weight
 EMI21.1
 of 174 .................................. If ... 15. It e 500 Rosin, type 1Y.0 .............. * .........> ...., 110 Fatty acid from linseed oil .. .................. 558 Aromatic solvent derived from petroleum with
 EMI21.2
 a boiling zone of 15900 'at 205 C, a yC flash point of 38 C .......................... 308.5 Mineral spirits ................................ ¯¯3P9 ¯.¯, Total ...... ,, , 1.785.5 Water loss during. ix'1..4 .Cat3.Onm s e s e a a s e. ¯¯¯¯¯¯¯¯¯¯ Return ..... 1.692.5

 <Desc / Clms Page number 22>

 the resin component alkoc-rent, the fatty acids and the rosin are heated to 204 ° C. and one mainbient for one hour and jusou'à this due one obtains the suitable viscosity and is diluted.

   Preferably, an integer is passed through the reaction mass during heating. We dilute. The yield is 1.77 liters, 0.945 kg / liter, non-volatile product content 65 acid number 12, viscosity Z-Z2 on the Gardner scale. The resin is emulsified in the retort water described in the aforementioned French patent 1,080,028 so as to create a homogeneous oil-in-water emulsion. The emulsion can be used as an adduct to the starch-based carrier emulsions of the invention, which has the particular advantage, when used with pigments, of obtaining resistant prints. in washing.



  Example 7.- Melamine formaldehyde resin emulsion prepared as follows:
 EMI22.1
 
<tb> Parts <SEP> in <SEP> weight
<tb>
<tb> Butylated <SEP> melamine-formaldehyde <SEP> resin
<tb> (solution <SEP> to <SEP> 65% <SEP> in <SEP> the <SEP> xylene) <SEP> 47.0
<tb>
<tb> Protective <SEP> colloid <SEP> (methyl cellulose) <SEP> 2.9
<tb>
<tb> Water <SEP> 46.6]
<tb>
<tb> Agent <SEP> surfactant <SEP> alkyl-aryl-sulfonate
<tb> of <SEP> sodium <SEP> 2.5
<tb>
<tb> Ammonia <SEP> 1.0
<tb>
<tb> 100.0
<tb>
 
The above reagents are mixed so as to obtain a homogeneous emulsion. This emulsion is suitable for incorporation into vehicle emulsions. After drying and curing, it is able to bind the starch film and pigments to give solid impressions in washing.



    Example 8 - Stabilized Elastomer Dispersion
A) First, a stabilizing composition is prepared with the reagents below.

 <Desc / Clms Page number 23>

 
 EMI23.1
 



  Start:, s ert..P9.i.d.ê Water 5, 3 ..w: or¯i; aue 1,2
 EMI23.2
 
<tb> Protective <SEP> colloid <SEP> (casein) <SEP> 5.3
<tb>
<tb> Xylene <SEP> 6.0
<tb>
 
 EMI23.3
 : ment surfactant (sodium Leury1-sulfate) ¯¯22¯
 EMI23.4
 
<tb> 100.0
<tb>
 The protective colloid may be casein or algi-
 EMI23.5
 sodium nate or methylcellulose or other suitable stabilizing agent.



  B) A stabilized elastomer dispersion is prepared CU: Il! J0 follows:
 EMI23.6
 p ..! ll2 ... P2 id! Butadiene-nitrile acrylic copolymer (1+. Of solid resin) tex 66.0 Stabilizing composition {8-A} 31j. 0 ¯¯
 EMI23.7
 
<tb> 100.0
<tb>
 
Composition A is placed in an open container with a turbine launcher (120-160 rpm), the mixture is added.
 EMI23.8
 elastomer latex and mixed jusou'à that: a homogeneous composition is obtained.

   Butadiene copolymer latex -
 EMI23.9
 nitrile EJ crylioue used in this composition is a product obtained by emulsion polymerization of butadiene and acrylic nitrile in the butadiene: acrylic nitrile ratio of about 75 to 25 and containing about 4% ammonium oleate as
 EMI23.10
 Cmul i.i.nt for monomers during polymerization.



    Normally this latex has a low stability to actions
 EMI23.11
 mcpnioues, but, after mixing with the stabilizing composition in the proportions indicated above, the stability to
 EMI23.12
 m canial actions of the composition is excellent. The latex stabilized with the stabilizing composition is suitable for use with the: ulsions vehicles for plasticizing and binding the starch film and serving as a binder for pigments.

 <Desc / Clms Page number 24>

 



   The stabilized elastomer dispersions can be prepared as described in Examples 2 and 13, in which the elastomer is a butadiene-acrylic nitrile copolymer with a butadiene: acrylic nitrile ratio of 60 to 35 and a solids content of 40% and containing sodium stearate as an emulsifier and emulsion stabilizer. If desired, the emulsifier used in the emulsion polymerization of the monomers can be a nonionic surfactant. The latex thus prepared is supplied under the tradename Chemigum 245 CHS, by the Goodyear Chemical Co.

   The stabilized elastomer dispersion can be prepared from an emulsion of vinyl chloride-vinyl acetate copolymer and mixed with a butadiene-acrylic nitrile copolymer in the ratio of about 55 to 45. The latter is sold as denominated it. Geon 552 nation by the B. F. Goodrich Chemical Co.



  Example 9. Schematic formula of urea-formaldehyde resin emulsion prepared as in Example 7 from the following components.
 EMI24.1
 
<tb>



  Parts <SEP> in <SEP> weight
<tb>
<tb> Butylated <SEP> urea-formaldehyde <SEP> resin
<tb> (solution <SEP> to <SEP> 65 <SEP>% <SEP> in <SEP> the <SEP> xylene) <SEP> 47.0
<tb>
<tb> Colloid <SEP> protective <SEP> methyl-cellulose <SEP> 2.9
<tb>
<tb> Water <SEP> 46.6
<tb>
<tb> Aent <SEP> surfactant <SEP> (lauryl-sulfate <SEP> of
<tb> sodium) <SEP> 2.5
<tb>
<tb> Ammonia <SEP> 1.0
<tb>
<tb> 100.0
<tb>
 Example 10. Vehicle emulsion with melamine-formaldehyde resin having the following composition.
 EMI24.2
 
<tb>



  Parts <SEP> in <SEP> weight <SEP>
<tb>
<tb> Emulsion <SEP> vehicle <SEP> from <SEP> example <SEP> 2-B <SEP> 99.0
<tb>
<tb> Melamine-formaldehyde <SEP> resin <SEP> <SEP> emulsion <SEP>
<tb> the <SEP> Example <SEP> 7 <SEP> 1.0
<tb>
<tb> the <SEP> 0,0 <SEP>
<tb>
 

 <Desc / Clms Page number 25>

 
 EMI25.1
 1 ll.- ::; Julsion vehicle containing melanin resins: Jld8hYlle with the following composition:
 EMI25.2
 Pa r: t i .., s¯s:.! L .. ±? ..: h t1, 2'.1: IÙ.3i, we carry from Example 3 -B 95, Ô 1 <: iil -iiJn of mslaEline-formalëhyde resin
 EMI25.3
 
<tb> of <SEP> example <SEP> 7 <SEP> 5.0
<tb>
<tb> 100.0
<tb>
 
 EMI25.4
 ? 12 ...

   Vehicle emulsion containing urea-formaldehyde resins with the following composition:
 EMI25.5
 Parts in Doids: m111sion véii # rule example 5-A 9g, 0 iE; ni> 1, sîon of urea-formaldehyde resin of
 EMI25.6
 
<tb> the example <SEP> 9 <SEP> 2.0
<tb>
<tb> 100.0
<tb>
 
The carrier emulsions of Examples 10, 11 and 12 are suitable for use as fillers in printing with pigments *
The prints obtained exhibit superior wash fastness.
 EMI25.7
 



  :: m, pe 13.- Vehicle emulsion containing an elastomer, stabilized, having the following composition:
 EMI25.8
   rt i e s¯.! l ... 12.Q..i d Ii
 EMI25.9
 
<tb> Emulsion <SEP> vehicle <SEP> from <SEP> example <SEP> 2-B <SEP> 95.0
<tb>
 
 EMI25.10
 Elastomer dispersion of Example 8 .JLtJ3 ...
 EMI25.11
 
<tb> 100.0
<tb>
 
This composition is suitable as a filler for printing pigment compositions, the elastomer serving as a plasticizer and binder for the pigments. The impressions made with this filler are superior in abrasion resistance (Crocking) and feel.



  Example 14. Vehicle emulsion containing a polyester resin having the following composition:

 <Desc / Clms Page number 26>

 
 EMI26.1
 
<tb> Parts <SEP> in <SEP> weight
<tb>
<tb> Emulsion <SEP> vehicle <SEP> from <SEP> example <SEP> 2-B <SEP> 85.0
<tb>
<tb> Emulsion <SEP> of <SEP> resin <SEP> of <SEP> example <SEP> 6 <SEP> 15.0
<tb>
<tb> 100.0
<tb>
 
This composition is suitable for use as a filler for printing onto textiles with pigments and dyes, however, in order to achieve superior fastness, it has been found desirable to heat the printed textile at elevated temperatures. The prints obtained show superior wash fastness.



    Example 15.- Vehicle emulsion with an elastomer and a melamine-formaldehyde resin having the following composition:
 EMI26.2
 
<tb> Parts <SEP> in <SEP> weight
<tb>
<tb> Emulsion <SEP> vehicle <SEP> from <SEP> example <SEP> 2-B <SEP> 85.0
<tb>
<tb> Dispersion <SEP> of elastomer <SEP> of <SEP> example <SEP> 6-B <SEP> 13.5
<tb>
<tb> Melamine-formaldehyde <SEP> emulsion <SEP> of <SEP> example <SEP> 7 <SEP> 1.5
<tb>
<tb> 100.0
<tb>
 
This composition is suitable for printing on. tiles with pigments and dyes. The prints are glossy, exhibit good washfastness, excellent feel and experience very low abrasion.

   The properties of these prints are improved by exposure to high temperatures, for example 3 minutes at 150 C.



  Example 16. Vehicle emulsion with elastomer and a melanin-formaldehyde resin with the following composition:
 EMI26.3
 
<tb> parts <SEP> in <SEP> poias
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Emulsion <SEP> vehicle <SEP> 90.0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Elastomer <SEP> Dispersion <SEP> from <SEP> Example <SEP> 8-B
<tb>
<tb>
<tb> using <SEP> the <SEP> chemigum <SEP> 245 <SEP> CHS <SEP> 9.0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Melamine-formaldehyde <SEP> resin <SEP> from <SEP> example <SEP> 7 <SEP> 1.0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100.0
<tb>
 

 <Desc / Clms Page number 27>

 
This emulsion gives prints with excellent washfastness, good feel and excellent abrasion resistance and can be set at lower temperatures and in a shorter time than the composition of Example 15.

   



  Example 17.- Vehicle emulsion with elastomer, melamine-formaldehyde and polyester resins with the following composition:
 EMI27.1
 
<tb> Parts <SEP> in <SEP> weight <SEP>
<tb>
<tb> Vehicle <SEP> emulsion <SEP> of <SEP> example <SEP> 3-B <SEP> 80.0
<tb>
<tb> Dispersion <SEP> of <SEP> elastomer <SEP> of <SEP> Example <SEP> 8-B <SEP> 12.0
<tb>
<tb> Emulsion <SEP> of <SEP> resin <SEP> melamine-formaldehyde <SEP> of
<tb> the example <SEP> 7 <SEP> 3.0
<tb>
<tb> <SEP> polyester resin <SEP> of <SEP> example <SEP> 6 <SEP> 5.0
<tb>
<tb> 100.0
<tb>
 
The above composition gives excellent fastness when used as a filler in printing with chillies or printing with dyes.

   After heat curing, printed textiles exhibit excellent wash, machine wash and abrasion fastness.



  Example 18. Vehicle emulsion for curing at low temperature.
 EMI27.2
 
<tb>



  <SEP> parts in <SEP> oids <SEP>
<tb>
<tb> Emulsion <SEP> vehicle <SEP> from <SEP> example <SEP> 3-B <SEP> 88.0
<tb>
<tb> <SEP> elastomer dispersion <SEP> stabilized <SEP> of <SEP> example <SEP> 8-B <SEP> 9.0
<tb>
<tb> Emulsion <SEP> of <SEP> resin <SEP> melamine-formaldehyde <SEP> of
<tb> the example <SEP> 7 <SEP> 1.0
<tb>
<tb> Solution <SEP> of <SEP> resin <SEP> melamine-formaldehyde <SEP> methylated <SEP> 2, -
<tb>
<tb> 100.0
<tb>
 
The methylated melamine-formaldehyde resin used in this example is Resloom M-75 sold by Onsanto Chemical Co. and contains about 60% dry resinous solids in aqueous solution. The prints obtained with this composition are converted into resistant films. machine wash at relatively low temperature.

 <Desc / Clms Page number 28>

 



  Example 10. Vehicle emulsion for heat curing at low temperature.
 EMI28.1
 
<tb>



  Parts <SEP> in <SEP> weight <SEP>
<tb>
<tb> mulsion <SEP> vehicle <SEP> of <SEP> example <SEP> 3-B <SEP> 88.0
<tb>
<tb> Dispersion <SEP>, of elastomer <SEP> stabilized <SEP> of
<tb> Example <SEP> 8-B <SEP> 9.0
<tb>
<tb> <SEP> solution <SEP> melamine-formaldehyde <SEP> resin <SEP>
<tb> methylated <SEP> (solution <SEP> aqueous <SEP> to <SEP> 60 <SEP>%) <SEP> 3 <SEP>, it <SEP>
<tb> 100. <SEP> 0
<tb>
 Example 20.- Vehicle emulsion for low curing
 EMI28.2
 
<tb> temperature.

   <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> Emulsion <SEP> vehicle. <SEP> example <SEP> 3-B <SEP> 80.0
<tb>
<tb>
<tb>
<tb>
<tb> Elastomer <SEP> dispersion <SEP> stabilized <SEP> of
<tb>
<tb> example <SEP> 6-B <SEP> 15.0
<tb>
<tb>
<tb>
<tb> Solution <SEP> of <SEP> resin <SEP> urea-formaldehyde
<tb>
<tb> methylated <SEP> (aqueous <SEP> to <SEP> 50 <SEP>%) <SEP> 5.0
<tb>
<tb>
<tb>
<tb>
<tb> 100.0
<tb>
 Example 21.- Vehicle emulsion for curing at low temperature.
 EMI28.3
 
<tb>



  Parts <SEP> in <SEP> weight
<tb>
<tb> Emulsion <SEP> vehicle <SEP> from <SEP> example <SEP> 3-B <SEP> 90.0
<tb>
<tb> <SEP> solution <SEP> melamine-formaldehyde <SEP> resin <SEP>
<tb> methylated <SEP> (aqueous <SEP> solution <SEP> to <SEP> 60 <SEP>%) <SEP> 10.0
<tb>
<tb> 100.0
<tb>
 Example 22 Vehicle emulsion for low temperature heat curing.
 EMI28.4
 
<tb>



  Parts <SEP> in <SEP> weight
<tb>
<tb> Emulsion <SEP> vehicle <SEP> from <SEP> example <SEP> 3-B <SEP> 93.0
<tb>
<tb> Solution <SEP> of <SEP> resin <SEP> urea-formaldehyde
<tb> methylated <SEP> (aqueous <SEP> to <SEP> 50 <SEP>%) <SEP> 7.0
<tb>
<tb> 100.0
<tb>
 
Suitable commercial amino-formaldehyde resin solutions mentioned in Examples 19, 20,21 and 22 are: Resloom M-75, Aerotex resin M3, Rhonite R-21, Zeset S and Lyofix CH. In the specification, the expression resin in aqueous dispersion includes both solutions and emulsions of resin soluble in organic solvents.

 <Desc / Clms Page number 29>

 
 EMI29.1
 



  1> F.V¯1¯IQE] ligl D: iCx f'Ï, GOnIJr ^ z I-'OI :. L t. ': LAW .VïC Iai.S! : UL: :(: c;.



  Y'I ('': i'I7S 1.ITÎiLE-D%]? 3-L'E ± 1U DESCRIBED HERE. Mx mple 23.- The following reagents are combined to give a pigment dispersion as described in French patent 1.080.28:
Pigment .................... 17.22
Surfactant ......... 4.00
Protective colloid ........ 4.00
Mineral spirits ........... 5.44
Ammonia ................. 1.20
 EMI29.2
 Water ............................ $ 68 'J 1.4: ..- 100.00: l: 4, Inle 1.- Phthalocyanin blue pigment dispersion $ Tja pigment dispersion is prepared according to 1 t .X8:

  11 - ple 23, the pigment being a filter cake, in prasse, of phthalocyanine blue at 30.1% dry pigment. This cake
 EMI29.3
 Press filtration of pigment is sold under the name "Blue Heliogen BKA" by General Dyestuff Corp.
 EMI29.4
 4i; rr?. Green pigment dispersion of phthalocyanine
The filter cake, in the press, of phthalocyanine green with approximately 36% dry pigment is dispersed according to Example 23.



     Water is used to adjust the composition to the same pigment content as for blue. The ratio of pigment to surfactant and protective colloid is maintained the same as in the case of the blue of Example 24.
 EMI29.5
 



  = rT-¯p) ¯g¯g6.- Dispersion of yellow pigment.



   The yellow press filter cake (the benzidine is dispersed in the same manner using the same adducts and in the same ratios as in Example 23.



  Example 27.- Dispersion of blue pigment
The procedure is analogous to that of Example 24 except that sodium lauryl sulfate is used in place of lauryl-

 <Desc / Clms Page number 30>

 ammonium sulfate.



  Example 28. Dispersion of pigments containing ammonium borate
The procedure is analogous to that of Example 24, except that in part B, 1% boric acid is dissolved in water and ammonia to give a solution of tetraborate d. 'ammonium. The preparation of the composition takes place, for the rest, as for Example 24.



  Example 29. Usual oil-in-water vehicle emulsion used as a control in the comparative tests and which shows the value of the vehicle exhaustions according to the invention.



   Parts by weight
 EMI30.1
 .L. Eci.u .... a ..... .... 1 ........ ..., a .. s t s. 20.50 Ammonia ............................... 0.25 Glycerin ........... ..................... 0,) 0 II. Methyl cellulose powder (4,000 cps) dry3 0.30
Mineral spirits ......................... 1.20
 EMI30.2
 .... ¯¯¯¯¯¯ .... ¯..¯ .... ¯¯¯..¯¯¯¯¯¯¯¯¯¯¯¯, .¯¯¯¯¯..¯¯. .¯¯..¯¯¯¯¯¯..¯¯¯¯¯¯..¯ .... ¯¯ ....... III. Water ...................., ................. 26.05
Mineral spirits ......................... 49.75
 EMI30.3
 -------------------------------------------------- ----, IV. Sodium lauryl sulfate ................. 1.65 / 100.00
100.00
I- Water, ammonia and glycerin are measured in a mixing vessel of suitable dimensions. We turn on the mixer.



   II - Mixing, in a bucket, with a spatula or a stick, the methyl cellulose powder in mineral spirits until the dry powder is completely wet. Mixture "II" is then poured into the mixing vessel, containing mixture "I", with the mixer in motion. We blend

 <Desc / Clms Page number 31>

 for 2 to 3 minutes until the methylcellulose is well dispersed in water and forms a viscous lump free solution.



   III - Water and mineral spirits "I" are added while mixing.



     IV - Add sodium lauryl sulfate to "I" while mixing, then mix for 5-10 minutes to obtain a uniform homogeneous emulsion.
 EMI31.1
 



  PATE FOi3 IPJ.'RBSSION AV'C DBS PIGi :. NTS PPE USING Eli? JL3TQjg VEHICLES, FREE OF RESIN.



  Example 30 - Printing pastes are prepared containing 5 parts of the pigment dispersion of Example 24 in 95 parts of the vehicle emulsion of the following examples: n 1-B n 4-B n 2-B n 5-A n 3-B n 5-B (all)
The pastes are used to make prints with a laboratory machine, dried and cured. All the pastes have a satisfactory consistency for working with the printing machine and give higher color indices than the control pastes based on vehicle emulsion of Example% 9.

   The above pastes are less satisfactory from the standpoint of wash fastness and abrasion fastness than similar printing pastes containing an effective binder such as resin *
 EMI31.2
 'AT' '0L INJURIES WITH FIGPN'S GONTErlATïT A BIWLSION' 'V "HTCtILB WITH IANT iSTPP1Y FORGETTING ELASTOMER.



  Example 31. -
Printing pastes are prepared using 5 parts of the pigment dispersion of Example 24 with a carrier emulsion of Example 2-B and incorporating resinous binders and elastomer dispersions, respectively. where the elastomers are used in quantity

 <Desc / Clms Page number 32>

 such that there is approximately 2 parts by weight of dry resin to one part of dry pigment, and the carrier emulsion makes up the balance to 100 parts by weight. One of the following resin emulsions or dispersions of elastomers is introduced into each paste:
Polyester resin emulsion of Example 6.



   Melamine-formaldehyde resin emulsion of Example 7.



   Elastomer dispersion of Example 8-B (all)
Urea-formaldehyde resin emulsion of Example 9.



   Resin emulsion of Examples 21 and 22.



   The printing pastes containing the different resins are used for printing with a laboratory machine, dried and cured. The pastes exhibit satisfactory properties and give higher color indices than those of the control vehicle emulsion-based emulsions of Example 29. All of these pastes give wash fastness and strength.
 EMI32.1
 abrasion resistances superior to those of eXf'11ple 30a PASTA FOR FR ESSiOTTS USING PIGi7, IENTS, ¯ CONTENADTT DES 'E.rIT, S'n'T> V "-HICIJLES WITH A COI. '#INATION OF LIAMTS R2SIF% OEX AND ELASTOMERS Example 32.-
Printing pastes were prepared using 5 parts of the pigment dispersion of Example 24 and the emulsion vehicle of Example 3-B.

   The resins are modified to obtain a series of different strengths. In each paste, the pigment to binder ratio is adjusted so as to have for one part by weight of dry pigment, two parts by weight of dry binder and the vehicle emulsion is present to make the remainder to 100 parts by weight. The term binder covers the resins and elastomers present. The binders are formed by the following emulsions in the indicated weight ratio.

 <Desc / Clms Page number 33>

 



  A / Polyester emulsion of example 6 50
Melamine-formaldehyde resin emulsion of Example 7 50 B / Polyester resin emulsion of Example 6 90
Melamine-formaldehyde resin emulsion of example 7 10 C / polyester emulsion of example 6 90
Urea-formaldehyde resin emulsion of Example 9 10 D / Elastomer dispersion of Example 8-B 50
Polyester emulsion of Example 6 50 E / Elastomer dispersion of Example 8-B 90
 EMI33.1
 Melamine-formaldehyde resin emulsion of Example 7 10
F / Elastomer dispersion of example 8-B 95
Aqueous solution of methylated melamine-formaldehyde resin (Resloom M-75) of Example 21 5
G / Elastomer dispersion of example 8-B 93
Aqueous solution of methylated urea-formaldehyde resin (Rhonite R-1)

   As in the example
22 7
H / Elastomer dispersion of example 8-B 90
Urea-formaldehyde resin emulsion of Example 9 10
I / 'Elastomer dispersion of Example 8-B 60
Polyester emulsion of Example 6 20
Melamine-formaldehyde resin emulsion of Example 7.20
The printing pastes having the above compositions are used for printing, using a laboratory machine, on cotton fabrics. The prints are dried and cured under the action of heat for 3 minutes at 149 C. The control tests are carried out by replacing the vehicle emulsion of Example 3-B with the vehicle emulsion of Example 29. .

   The color index of the prints made with the vehicle emulsion of Example 3-B is each time much higher than that of the corresponding control tests. The exceptional fastness properties combined with a very high color index4 are obtained with the pastes containing an elastomer dispersion of Example 8-B and

 <Desc / Clms Page number 34>

 a melamine-formaldehyde resin of Example 7 in the 90:10 ratio.
 EMI34.1
 



  FIT ± 5 PQIQ BTR33SIO WITH Fhs¯ "'., 5 to. L'2ja (1 D'E: UL3IOFi 7¯IHß. JI L ¯t 3¯¯E DZ DIFF ± RZ] [T3 µGiIpz'5 J¯ h -. ... L.1. :: ;; ....



  Example 33. -
Printing pastes were prepared using 5 parts of the pigment dispersion of Example 24. As the binder in each case, a combination of elastomer and resin was employed.



   Elastomer dispersion of Example 8-B 90 parts
Melamine-formaldehyde resin emulsion of Example 7 part
The pigment to binder ratio is maintained at approximately 1: 2 and the carrier emulsion makes up the balance at 100 parts by weight.



   The starch carrier emulsions and the emulsifier combinations given below are used in this example.
 EMI34.2
 
<tb>



  Emulsion <SEP> vehicle <SEP> Starch <SEP> Emulsifier
<tb>
<tb> Example <SEP> 2-B <SEP> but <SEP> Ammonium <SEP> stearate
<tb>
<tb> Example <SEP> 3-B <SEP> but <SEP> Ammonium lauryl sulfate <SEP>
<tb>
<tb> Example <SEP> 1-B <SEP> but <SEP> Oleic acid <SEP>
<tb>
<tb> Example <SEP> 4-B <SEP> wheat <SEP> Ammonium lauryl sulfate <SEP>
<tb>
<tb> Example <SEP> 5-A <SEP> but <SEP> pregelatinized <SEP> Ammonium lauryl sulfate <SEP>
<tb>
<tb> Example <SEP> 5-B <SEP> but <SEP> pregelatinized <SEP> Ammonium lauryl sulfate <SEP>
<tb>
<tb> Example <SEP> 5-B <SEP> apple <SEP> from <SEP> earth <SEP> Ammonium lauryl sulfate <SEP>
<tb>
<tb> Example <SEP> 5-B <SEP> tapioca <SEP> Lauryl-sulfate <SEP> dtammonium
<tb>
<tb> Example <SEP> 5-B <SEP> rice <SEP> Ammonium lauryl sulfate <SEP>
<tb>
 
All printing pastes prepared with 'mulsions

  above vehicles, applied with the laboratory printing machine to cotton fabric, give good results. Impressions made with carrier emulsions containing corn starch are somewhat superior in strength properties to impressions made.

 <Desc / Clms Page number 35>

 with vehicle damage based on other types of starch.
 EMI35.1
 I-r: 3SI0Y] ¯tV-SC) ":; 9 P" ¯TTS CC1'IT "'I \:! \:' L! I .a:,., 3C: .Ic-ü:

  at
Printing pastes composed of a dispersion of pigments or of dye and emulsion solutions to be conveyed must have a minimum viscosity to exhibit the best printing properties and color index when applied with any device. standard used in textile printing. The viscosity of the carrier emulsion controls the viscosity of the final printing pastes, especially when low concentrations of pigment dispersion or dye solution are used.

   When pigment dispersions or dye solutions form a significant part of the printing paste, which is the case with dark shades, the viscosity of the pigment dispersion or dye solution used has a considerable effect on the color. the consistency and characteristics of the final paste. Pigment dispersions and colorant dispersions generally have relatively low viscosities. This is important to ensure ease of preparation and processing of pigments and coloring materials.

   In dark shades, therefore, dispersions of pigments and solutions of ordinary coloring matters act as diluents for emulsion vehicles, causing a serious drop in viscosity with a corresponding decrease in properties from the point of view of the vehicle. printing and color index. In practice, it is not possible to increase the viscosity of the carrier emulsion to the point where it gives a satisfactory viscosity in dark shades. This is because, while the carrier emulsions are viscous enough to withstand dilution, they are much too viscous to be used in light shades where the percentage of pigments or colorants present is very low.

 <Desc / Clms Page number 36>

 



   It has been found that boric acid or compounds which may give boric acid ions in solution when introduced into carrier emulsions cause an increase in viscosity of carrier emulsions. Since the lowering of the viscosity is caused by the dilution of the carrier emulsion by the dispersion of pigments or the solution of dyestuffs and is in direct relation with the amount of these diluents, depending on the amount. In accordance with the invention, the boric ion yielding compounds are introduced into the pigment dispersion and the coloring matter solution, which automatically adjusts the amount of boric ions present in relation to that of starch.

   As the amount of boric ions increases with the increased amounts of pigment dispersion present, they cause the viscosity of the starch-based carrier emulsion to increase accordingly. By this means it is possible to adjust the viscosity of the printing pastes at will, even if they contain considerable amounts of dispersion of pigments or solutions of dyestuffs.



   In each case, the quantity of boric ion donor compounds introduced is calculated so as to give the paste a satisfactory consistency for printing at the maximum concentration of dispersion of pigments or of solution of dyestuffs required to give tints. dark with vehicle emulsion. When smaller amounts of these boric ions are used to obtain pastel shades, the effect of increasing viscosity due to boric ions is reduced accordingly.



    Example 31 + .-
To the pigment dispersion of Example 24 was added in one case (A) 0.1 part and in another case (B) 5 parts of boric acid in the form of an aqueous solution of ammonium tetraborate. We use, for the preparation of pasta for

 <Desc / Clms Page number 37>

 prints, as a binder, the elastomer dispersion of Example 8-B and the melamine-formaldehyde resin emulsion of Example 7 by mixing these products in the 90:10 ratio. The mixed binder is applied in proportions such that there is, in the paste, for one part of dry pigment, 2 parts of dry binder. Series of printing pastes were made using the carrier emulsions of Examples 2-B, 3-B, 4-B, 5-A and 5-B.

   In a similar way, pastes are prepared in which boric acid is introduced in the form of sodium tetraborate and in another series, in the form of potassium tetraborate respectively.



   By using pigment dispersions in the ratio of one part pigment dispersion to 3 parts carrier emulsion, a very pronounced viscosity increasing effect is obtained even when using very small amounts of boric acid. . The optimum viscosity effects are obtained when the ratio of dry starch to dry boric acid is between 8: 1 and 20: 1.

   Similar results are obtained when boric acid is introduced in the form of glycol boriborate or glyceryl borate.
Good results are obtained by using, in this example, instead of 0.1 and 5% boric acid, 1 and 2% respectively, calculated on the weight of the pigment dispersion of Example 24,
Printing pastes containing pigment dispersions with boric ions invariably give prints with a better color index and dry and wet crack resistance than similar printing pastes containing pigment and borate dispersions.
 EMI37.1
 fi.rPFS71O'IS OF COLORING MATERIALS WITH U1 \:

  'E EI1JLSIOT VEHICULE -, Tr Dr RESINE¯

 <Desc / Clms Page number 38>

   In the examples below, a "double
 EMI38.1
 :: t. bl) u indanthrene 3! i'pn (color-index 613) in ë.jOUèUt 5 'v c .t, r {ite dye with irdic vehicle emulsions, uss.



  J-: yl 35: u1¯: we see example 2-B. , ¯le 36 Enulsion support of example 3-B
 EMI38.2
 <: 1}) the 37 L2mlsion support of example 1-B
The pastes are used to make prints using a laboratory machine, then dried; after
 EMI38.3
 :>! cr-! ± :: 8 they are wetted with a 15: 1 solution of carbonate, 1; lotassiun1, 10 1.1 sodium formaldehyde sulfoxylate, 7 = 'glycerin and 68% water. Then it is aged for 10 minutes in a vaporizer, oxidized with a dilute solution of sodium dichromate and acetic acid.



  The prints are washed and dried.
 EMI38.4
 



  % ry¯p1; 3E t;. (. Moill A paste for impressions, control, is prepared following
 EMI38.5
 before the usual "Golloresine" process also called "Cellapret" process. The vehicle in this case has the following composition:
 EMI38.6
 
<tb> parts <SEP> in <SEP> weight <SEP>
<tb>
<tb> Starch <SEP> paste <SEP> from <SEP> wheat <SEP> to <SEP> 8 <SEP>% <SEP> 30.0
<tb>
<tb> Solution <SEP> to <SEP> 3 <SEP>% <SEP> of <SEP> methyl cellulose <SEP> 4000 <SEP> cps. <SEP> 30.0
<tb>
<tb> Water <SEP> 35.0
<tb>
<tb> Glycerin <SEP> 5.0
<tb>
<tb> 100.0
<tb>
 
Control doughs are processed in exactly the same way as doughs prepared with the emulsion vehicle. The conclusions below emerge from the results.

   Prints made with emulsion vehicles have a higher color intensity and gloss than prints made.
 EMI38.7
 with "colloresine" vehicles.
The carrier emulsions of the invention are suitable for printing with stabilized azo dyes which

 <Desc / Clms Page number 39>

 are well known in the industry of coloring mat @@ eres under the name "Rapidogene" The examples below illustrate the use of these supports with dyes of the Rapidogene type.



  Rapidogene dyes are introduced into vehicle emulsions in the form of their solution. The most suitable solutions are those which are prepared with caustic soda and in the absence of lower alcohols. The solutions prepared with 2-methyl-2,4 pentanediol are the most satisfactory. A typical solution contains 10 dyestuffs, 5-10% of the above glycol and sufficient sodium hydroxide to effect dissolution of the dye. The dye solution prepared as indicated above can be introduced into the emulsion vehicles.

   A solution of Rapidogene RS scarlet (prototype 170), 10% solution, prepared in the above manner is introduced into the following vehicles: Example 39 Vehicle emulsion of Example 1-B Example 40 Vehicle emulsion of Example 5-A
The dye is added to the above vehicles so as to have a 2% dye concentration in the printing paste. The colorant may be added in the form of an aqueous dispersion, which term denotes either a dye suspension or a dye dispersion. The impressions made with these pastes are good and are "set" after the usual acid aging and soaping.

   The consistency of the pastes is increased and the properties are improved by the introduction of a small amount of ammonium borate without detrimental effect from the point of view of fixing the dyes.



   Although the description and the examples above illustrate various preferred embodiments of the invention, it is understood that the latter is not limited to the latter.


    

Claims (1)

ABSTRACT A composition for printing fabrics or other materials in which the carrier for pigments and dyestuffs comprises, as components: (A) a dispersion of starch in water, said dispersion comprising 1 to about 25 of starch dispersed in water, the percentages being calculated on the total weight of the starch dispersion in water; (B) an organic liquid, insoluble in water, volatile present in an amount ranging from 5 to 150 parts by weight of organic acid per 100 parts by weight of starch dispersion; (C) a surfactant having emulsifying properties, the latter being present in the proportion of about 0.5 to 1% of the total weight of the vehicle, this vehicle being an emulsion in which water constitutes the phase. keep on going. II - The vehicle of the composition comprises approximately 4 to 15% of component A starch dispersed in water, approximately 10 to 100 parts by weight of organic liquid per 100 parts of starch dispersion and from 0.2 to 2%, by weight, of the vehicle consisting of a surfactant, the vehicle constituting an emulsion in which water is the continuous phase. III - The vehicle of the pigments or coloring matters is also characterized by the following points, separately or in combination: 1) the starch is selected from the class comprising cereal starch, starch from root crops and guar gum; 2) the starch is corn starch; 3) the starch is pregelatinized starch; 4) the starch is pre-gelated corn starch; <Desc / Clms Page number 41> EMI41.1 5) the surfactant Eo.5t chosen from C1: ': 53,' ;: comprising anionic and nonionic surfactants; 6) the surfactant is a water-soluble salt of a fatty acid having a chain comprising between 10 and 22 carbon atoms approximately; 7) the surfactant is ammonium stearate; 8) the surfactant is a water soluble salt of a monosulfuric acid ester of a fatty alcohol having a chain with 8 to 22 carbon atoms; EMI41.2 9) the surfactant is lauryl sulfate c.g; -.:. ¯a- nium; 10) the surfactant is an al; .ay..arr .--; ū¯ ... Ex: = ::. ammonium; 11) the surfactant is a product of coiÂdc: ;. vc: t, .rF. ethylene oxide with a phenol comprising as StlL;:; 'v: .¯, 1:, f; "' - a long chain alkyl radical; 12) phenol with a c-sb alkyl substituent zl.- ,; r.- phenol; 13) the organic liquid is chosen from the group EMI41.3 comprising petroleum hydrocarbons, hydrocarbons; -Qx ': "0C a-o" matics and terpene hydrocarbons; 14) the organic liquid is a hydrocarbon derived from petroleum; EMI41.4 15) the organic liquid is a mixture of aliphatics derived from petroleum and known as mineral spirits; 16) the organic liquid is an aromatic hydrocarbon; 17) the organic liquid is xylene; 18) Starch represents approximately 5%, the surfactant approximately 0.5%, organic fluid approximately 27%, water approximately 67.5%, all the percentages being understood by weight and being related to the weight. total weight of the composition; <Desc / Clms Page number 42> 19) the starch is corn starch, the surfactant is ammonium stearate and the organic liquid is mineral spirits; 20) the starch is corn starch, the surfactant is ammonium lauryl sulfate and the organic liquid is the linear essence; 24) the organic liquid is a terpene hydrocarbon: 22) the composition further contains from about 0.1 to 15 parts, by weight, of an amino-aldehyde resin dispersed per 100 parts of vehicle; 23) the amino-aldehyde resin is selected from the group comprising butylated melamine-formaldehyde resins, soluble in organic solvents, botylated urea-formaldehyde resins, soluble in organic solvents, methylated melamine-formaldehyde resins, soluble in l ' water and water soluble methylated urea-formaldehyde resins; 24) it further comprises about 0.1 to 25% by weight of an elastomer dispersed per 100 parts of vehicle; 25) the elastomer is chosen from the group comprising rubber, acrylic nitrile-butadiene copolymers, butadiene-styrene copolymers, polychloroprene, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloride copolymers, polyvinyl chloride, polyvinylidene chloride and mixtures thereof; 26) it further contains from 0.1 to 25 parts by weight of a polyester resin derived from a fatty acid per 100 parts of vehicle; 27) the polyester resin is selected from the group comprising oil-modified alkyd resins and oil-modified epichlorohydrin-bisphenol condensates, emulsified; <Desc / Clms Page number 43> 28) it contains a portect @ ur IV colloid - For the decoration of textile fabrics 3 in discontinuous patterns by printing, use of a printing paste comprising the following vehicle I and II and a coloring agent, and in which: 1) the colorant is selected from the class of aqueous dispersions of pigments and / or aqueous cols; 2) the carrier emulsion is that of I) and the dispersion is an aqueous dispersion of an elamomer, optionally supplemented with an aqueous dispersion of an amino-aldehyde resin; 3) the aqueous dispersion is a soft dispersion of an amino-aldehyde resin free of fatty acid ester resin; 4) the paste contains a dispersion of chili peppers in water and boric ions. V - An oil-in-water emulsion vehicle for dispersed pigments and dyes suitable for printing on textiles, comprising about 2 to 20% by weight of dispersed starch, about 0.05 to 10% by weight of surfactant with emulsifying properties and about 3 to 67% of a volatile, water-insoluble organic liquid, the ratio, by weight, of water to starch being between 3: 1 and 99: 1 approximately, the percentages being calculated on the total weight of the emulsion vehicle and the water being the continuous phase of the emulsion. VI .- The following oil-in-water emulsion vehicle V is also characterized by the following) points, separately or in combination: 1) It comprises from 4 to 10% by weight of starch, from 0.2 to 2% by weight of surfactant with emulsifying properties of about 10 to 50% by weight of an organic liquid. '' water insoluble, volatile, the ratio, by weight of water to <Desc / Clms Page number 44> the starch being between 5: 1 and 25: 1; 2) The organic liquid insoluble in water is dispersed evenly.